CN117946508A - Double-ring cage-shaped phosphate phosphazene derivative flame-retardant PC/ABS composition and preparation method thereof - Google Patents
Double-ring cage-shaped phosphate phosphazene derivative flame-retardant PC/ABS composition and preparation method thereof Download PDFInfo
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- CN117946508A CN117946508A CN202311802060.0A CN202311802060A CN117946508A CN 117946508 A CN117946508 A CN 117946508A CN 202311802060 A CN202311802060 A CN 202311802060A CN 117946508 A CN117946508 A CN 117946508A
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- flame retardant
- retardant
- phosphazene derivative
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 97
- 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 title claims abstract description 93
- 229920007019 PC/ABS Polymers 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 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 title claims abstract description 31
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 21
- 239000010452 phosphate Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 15
- -1 phosphate phosphazene derivative Chemical class 0.000 claims abstract description 29
- 125000002619 bicyclic group Chemical group 0.000 claims abstract description 19
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000004595 color masterbatch Substances 0.000 claims abstract description 6
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 6
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 239000004005 microsphere Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- SBKRBXBQFDKYSO-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C)=C(O)C(C(C)(C)C)=C1 SBKRBXBQFDKYSO-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006222 acrylic ester polymer Polymers 0.000 claims description 2
- 230000002902 bimodal effect Effects 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical group C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical group P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- BKLGNGGEJNHIQT-UHFFFAOYSA-N prop-2-enoic acid;silicon Chemical compound [Si].OC(=O)C=C BKLGNGGEJNHIQT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001741 organic sulfur group Chemical group 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 10
- 150000003254 radicals Chemical class 0.000 abstract 4
- 239000003112 inhibitor Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 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
- C08L2201/22—Halogen free composition
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)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a double-ring cage-shaped phosphate phosphazene derivative flame-retardant PC/ABS composition and a preparation method thereof, wherein the double-ring cage-shaped phosphate phosphazene derivative flame-retardant PC/ABS composition comprises the following raw materials in parts by weight: polycarbonate resin: 52-99.96%; acrylonitrile-butadiene-styrene copolymer: 0.01-20%; and (3) a compatilizer: 0.01-5%; flame retardant: 0.01-15%; char-forming agent: 0.01-4%; an antioxidant: 0-1%; processing aid: 0-2%; color master batch: 0-1%. The invention has the advantages that according to the combustion characteristics of the PC/ABS composition and the principle of the molecular assembly design of the flame retardant, the dicyclic cage-shaped phosphate phosphazene derivative is introduced into the flame retardant PC/ABS formula design to serve as the flame retardant, the free radical inhibitor released by the flame retardant can capture the free radical released by the material in the combustion reaction, and the free radical can react with the free radical to generate incombustible materials to destroy the chain growth of the combustion reaction, so that the flame retardance is realized. The flame-retardant PC/ABS composition prepared by the invention can be applied to the fields of automobile industry, electric appliance and instrument industry, mechanical industry and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a double-ring cage-shaped phosphate phosphazene derivative flame-retardant PC/ABS composition and a preparation method thereof.
Background
PC/ABS is thermoplastic plastics formed by blending Polycarbonate (PC) and acrylonitrile-butadiene-styrene terpolymer (ABS), combines the characteristics of the two materials, and is the property of combining three components, wherein the acrylonitrile has high hardness and strength, heat resistance and corrosion resistance; butadiene has impact resistance and toughness; styrene has high surface glossiness, easy coloring property and easy processing property, but ABS has poor heat resistance and strength, PC melt viscosity is high, processing property is poor, the sensitivity of internal stress and impact strength of products to the thickness of the products is large, PC/ABS alloy material has a certain improvement on heat resistance and strength compared with ABS, and compared with PC material, the processing property is improved, the internal stress of the products is reduced, and PC/ABS can be applied to the fields of thin-wall products such as mobile phone shells, automobile sound and image systems, screw hole burst prevention, electronic appliances, sports products and the like.
The flame-retardant PC/ABS has excellent mechanical properties, high thermal deformation temperature, high dielectric strength, good electrical insulation and good flame-retardant effect. Therefore, the LED lamp can be widely applied to products such as high-end chargers, lamp holders, switch panels and the like. In recent years, the flame-retardant PC/ABS alloy needs to meet the requirements of environmental protection regulations such as RoHS, REACH and the like, meets the requirements of environmental protection regulations while meeting the flame-retardant performance, and is also a factor to be considered in the development of the flame-retardant PC/ABS technology.
Chinese patent CN102153590a discloses a dicyclo-cage-like phosphate siloxane flame retardant and a method for preparing the same, and the desired product can be obtained by reacting 1-oxyphosphino-4-hydroxymethyl-2, 6, 7-trioxabicyclo [2, 2] octane with chlorosilane or alkoxysilane. The prepared double-ring caged phosphate siloxane flame retardant contains a plurality of rigid double-ring caged phosphate groups and silicon elements, plays a role in synergistic flame retardance, has higher thermal stability and char formation performance, and can effectively reduce smoke generated in combustion. The Chinese patent CN109735080A selects the organic phosphorus flame retardant with a specific polycyclic aromatic hydrocarbon structure from the formula design to be matched with the efficient functional auxiliary agent, and the low-dosage and efficient weather resistance auxiliary agent is used as auxiliary agent to cooperatively improve the stability of the flame-retardant PC/ABS blend material under the influence of comprehensive environmental factors such as outdoor, long-period high humidity, high heat, illumination and the like, so that the rigidity, toughness, flame retardance and electrical insulation stability of the material are greatly improved. Chinese patent CN107474510A discloses a high-fluidity high-rigidity halogen-free flame-retardant PC/ABS mixture and a preparation method thereof, wherein polyarylphosphate, phenyl rare earth phosphate and metal hybridization polysilsesquioxane are used as flame retardants, and the prepared PC/ABS mixture has the advantages of good fluidity, high strength, excellent antistatic and flame-retardant properties and the like, and is suitable for preparing ultrathin products. The invention disclosed at present has more researches on the influence of different flame retardants on the performance of flame retardant PC/ABS through formula design, and has relatively less researches on the performance of flame retardant PC/ABS of a novel structure flame retardant or a novel form flame retardant based on the principle of molecular assembly design. The flame retardant efficiency and the performance of the flame retardant PC/ABS material are improved, and the flame retardant PC/ABS material has important significance for expanding the application field of PC/ABS.
Disclosure of Invention
In order to fill the blank of the prior art, the invention provides a double-ring cage-shaped phosphate phosphazene derivative flame-retardant PC/ABS composition and a preparation method thereof, wherein the double-ring cage-shaped phosphate phosphazene derivative is introduced into the formula design as a flame retardant to prepare the flame-retardant PC/ABS composition according to the molecular assembly design principle of the flame retardant, and the flame-retardant PC/ABS composition prepared by the method can be applied to the fields of automobile industry, electric appliance and instrument industry, mechanical industry and the like.
The invention is realized by the following technical scheme:
The double-ring cage-shaped phosphate phosphazene derivative flame-retardant PC/ABS composition comprises the following raw materials in parts by weight:
The polycarbonate resin has a number average molecular weight of 17000-40000, a weight-to-relative molecular weight of 20000-50000, and a melt flow rate (test conditions: 300 ℃ C. 1.2 kg): 10-25g/10min.
The acrylonitrile-butadiene-styrene copolymer can be prepared by an emulsion graft-blending polymerization method or a continuous bulk polymerization method, the melt flow rate (the test condition is that the temperature is 220 ℃ and the weight is 10 kg) is 5-25g/10min, the butadiene content is 15-20%, the particle size of the butadiene is 0.1-1.0 mu m, the particle size is in bimodal distribution, and the content and the particle size of the butadiene in the acrylonitrile-butadiene-styrene copolymer are limited to be excellent in surface performance and toughness.
The compatilizer can be one or a mixture of a plurality of methyl methacrylate/butadiene/styrene copolymer, methyl methacrylate/acrylic ester polymer, ethylene/acrylic ester/glycidyl methacrylate terpolymer, ethylene-butyl acrylate, acrylic acid-silicon rubber toughening agent and the like.
The invention is preferable: methyl methacrylate-butadiene-styrene terpolymers.
The flame retardant is a dicyclic caged phosphate phosphazene derivative, the molar ratio of dicyclic caged phosphate phosphorus groups to phosphazene groups is 6:1, and the phosphorus content is as follows: 9-12%, nitrogen content: 3-5%, the structural general formula is as follows:
wherein the structural formula of B is as follows:
The char former is an ultrathin hollow zinc aluminate microsphere with a diameter (D50): 1-30 mu m, the thickness of the spherical shell is 20-60nm, and the moisture is less than 0.3%.
The antioxidant is 3- (dodecylthio) propionic acid-2, 2-bis [ [3- (dodecylthio) -propionyloxy ] methyl ] -1, 3-propanediol ester, CAS No.29598-76-3; n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, CAS No.2082-79-3; triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, CAS No.36443-68-2; pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 6683-19-8; tris [ 2.4-di-t-butylphenyl ] phosphite, cas No.31570-04-4; one or more of hindered phenols such as bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, 154862-43-8, and the like, organosulfur compounds or phosphites;
The invention is preferable: tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite
The processing aid is one or more of silicone, pentaerythritol stearate, ethylene bisstearamide, erucamide and polyethylene wax.
Silicone is preferred in the present invention.
The color master batch can be one or more of carbon black, zinc sulfide, ferric oxide and the like according to the color requirement, the content of the toner is 20-99%, and the carrier is AS or the color master batch of the lubricant.
The preparation method of the flame-retardant PC/ABS composition comprises the following steps:
(1) Weighing various raw materials according to the formula proportion; the acrylonitrile-butadiene-styrene copolymer, the polycarbonate resin, the compatilizer, the flame retardant, the char forming agent, the antioxidant, the processing aid, the masterbatch and the like are uniformly mixed by a high-speed stirrer for standby.
(2) The above resin and auxiliary agent mixed raw materials are added through a main feeding port of a double-screw extruder, and the flame-retardant PC/ABS composition is obtained after the procedures of melt extrusion, granulation, drying treatment and the like at 220-240 ℃.
The flame-retardant PC/ABS composition can be applied to the fields of automobile industry, electric appliance and instrument industry, mechanical industry and the like.
The invention has the advantages that the dicyclo cage-shaped phosphate phosphazene derivative is selected as the flame retardant in the flame retardant PC/ABS formula design according to the molecular assembly design principle of the flame retardant, the phosphate and phosphazene groups in the molecular structure can play a role in flame retardance, the phosphate and phosphazene are decomposed in the combustion process to generate substances such as phosphoric acid, metaphosphoric acid, carbon dioxide, ammonia, nitrogen, water vapor and the like, the phosphoric acid is a non-flammable liquid film and plays a role in blocking combustible substances, the polymetaphosphoric acid can dehydrate and carbonize PC/ABS resin, the formed carbon layer can isolate air to further play a stronger flame retardant effect, and the non-flammable gas such as nitrogen and the like can dilute the concentration of oxygen to block the supply of oxygen. PO groups generated in the combustion process of the flame retardant react with H.HO.active groups in a flame area to play a role in inhibiting flame, and the capturing free radicals of the free radicals stop the combustion chain reaction, so that the double-ring caged phosphazene derivative can play a good flame retardant effect when used as the flame retardant of the PC/ABS material. Meanwhile, zinc aluminate is introduced into the formula design as a char forming agent, the thickness of the carbon layer can be increased, the effect of blocking combustible gas is better, the zinc aluminate is in the form of ultrathin hollow microspheres, the wall thickness and the particle size of the microspheres are limited, the char forming efficiency of the zinc aluminate can be increased by utilizing the characteristics of the microspheres, and the flame retardant efficiency of the zinc aluminate is further improved.
The beneficial effects of the invention are as follows:
1) According to the invention, the dicyclo cage-shaped phosphate phosphazene derivative is selected as a flame retardant of PC/ABS materials, phosphate and phosphazene groups in a molecular structure can play a role in flame retardance, phosphate and phosphazene are decomposed in the combustion process to generate substances such as phosphoric acid, metaphosphoric acid, polymetaphosphoric acid, carbon dioxide, ammonia, nitrogen, water vapor and the like, the phosphoric acid is a non-flammable liquid film, the flame retardant plays a role in blocking combustible substances, the polymetaphosphoric acid can dehydrate and carbonize PC/ABS resins, a formed carbon layer can isolate air and further play a stronger flame retardant effect, and non-flammable gases such as nitrogen and the like can dilute the concentration of oxygen to block the supply of oxygen. PO groups generated in the combustion process of the flame retardant react with H.HO.active groups in the flame area, so that the free radicals are captured to stop the combustion chain reaction.
2) According to the invention, the ultrathin hollow zinc aluminate microsphere is selected as a char forming agent, and the zinc aluminate can effectively increase the thickness and hardness of a carbon layer and has a better effect of blocking combustible gas.
3) According to the invention, when the flame retardant is selected, the proportion of the double-ring cage-shaped phosphate and the phosphazene structure in the flame retardant is limited to be 6:1 through the selection of the structure, the contents of phosphorus element and nitrogen element are further limited, and the synergistic effect is better achieved.
4) The form of the selected carbon forming agent zinc aluminate is an ultrathin hollow microsphere, the wall thickness and the particle size of the microsphere are limited, the shape of the microsphere is ensured by limiting the wall thickness, and the characteristic of hollowness can further increase the carbon forming efficiency of the zinc aluminate and improve the flame retardant efficiency of the zinc aluminate.
5) The flame-retardant PC/ABS composition has excellent mechanical properties while realizing the flame retardance of UL 94V-0@1.6mm through limiting the proportion of each component in the flame-retardant PC/ABS composition and limiting the performances of PC resin and ABS resin.
The flame-retardant PC/ABS composition has the advantages of excellent mechanical property and flame retardance, and endows the flame-retardant PC/ABS composition with the characteristics of halogen-free environment protection concept and high performance.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention will be further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The examples and comparative examples of the present invention use the following materials, but are not limited to:
PC, trade name 2800, Produced by kestosis;
ABS, trade name PA-726M, produced from Qimei;
MBS, trade name EM500, produced from LG;
bicyclic caged phosphazene derivative flame retardants, commercially available;
ultra-thin hollow zinc aluminate microspheres, commercially available;
Bisphenol A bis (diphenyl phosphate) BDP, trade name WSFR-BDP, produced by Zhejiang Wansheng;
Drip PTFE, trade name DB105, available from Suzhou Pr Le Fei;
organosiloxane flame retardants, trade name ADDITIVE 40-001, produced from dakaning;
Phenoxy polyphosphazene flame retardant, commercially available;
lubricants, silicone powders, commercially available;
antioxidant 1010, commercially available;
An antioxidant 168, commercially available;
Color master batches, commercially available;
the preparation methods of examples 1-4 and comparative examples 1-8:
preparation method of flame-retardant PC/ABS composition
(1) Weighing various raw materials according to the formula proportion; the acrylonitrile-butadiene-styrene copolymer, the polycarbonate resin, the compatilizer, the flame retardant, the char forming agent, the antioxidant, the processing aid, the masterbatch and the like are uniformly mixed by a high-speed stirrer for standby.
(2) The above resin and auxiliary agent mixed raw materials are added through a main feeding port of a double-screw extruder, and the flame-retardant PC/ABS composition is obtained after the procedures of melt extrusion, granulation, drying treatment and the like at 220-240 ℃.
Preparation of flame retardant PC/ABS composition test bars:
the above materials were dried in a forced air drying oven at 120 ℃ for 4 hours and then injection molded into standard bars at an injection molding temperature of 240-270 ℃. The prepared mechanical property sample is subjected to state adjustment for 24 hours in a laboratory standard environment (23 ℃ and 50% RH).
The testing method of each performance index comprises the following steps:
tensile properties: spline size according to ISO 527 method: 170 x 10 x 4mm, test speed 5mm/min. Bending properties: spline size according to ISO 178 method: 80.10.4 mm, test speed 2mm/min. Notched impact properties: spline size according to ISO 179 method: 80 x 10 x 4mm.
Flame retardant properties: spline size according to UL94 method: 127 x 12.7 x 1.6mm.
Limiting oxygen index LOI; according to GB/T2406.1, spline size: 50 x 10 x 4mm.
Table 1: flame retardant PC/ABS compositions and Properties of examples 1-4 and comparative examples 1-8
As can be seen from the results of examples and comparative examples in Table 1, the dicyclic cage-shaped phosphazene derivative and the ultrathin hollow zinc aluminate microsphere used in the invention have better mechanical properties and oxygen index (example 1, comparative example 1-2) than the conventional BDP and PTFE or BDP and organosilane systems as the flame retardant under the same flame retardant addition amount, the content of the flame retardant can be greatly reduced on the basis of meeting the flame retardant requirement of UL 94.6mmV0, the mechanical properties of the flame retardant PC/ABS composition can be further improved (examples 2-3), and the flame retardant efficiency of the dicyclic cage-shaped phosphazene derivative flame retardant is obviously higher than that of BDP or BDP and phosphazene blend system under the same flame retardant addition amount by examples 2 and comparative examples 3-6, which is due to the performance advantage brought by the cooperation of dicyclic cage-shaped phosphazene and phosphazene groups. It can be seen from example 3 and comparative examples 7 to 8 that the flame retardant efficiency of the char-forming agent used in the present invention is higher than that of conventional PTFE and siloxane, and the improvement of the flame retardant efficiency can reduce the addition amount of the flame retardant, and improve the mechanical properties of the flame retardant PC/ABS composition, and the PC/ABS composition prepared in the present invention shows excellent mechanical properties and flame retardant properties. The flame-retardant PC/ABS composition prepared by the invention can be applied to the fields of automobile industry, electric appliance and instrument industry, mechanical industry and the like.
Claims (10)
1. The dicyclic caged phosphazene derivative flame-retardant PC/ABS composition is characterized in that: the material comprises the following raw materials in parts by weight:
The flame retardant is a dicyclic caged phosphate phosphazene derivative, the molar ratio of dicyclic caged phosphate phosphorus groups to phosphazene groups is 6:1, and the phosphorus content is as follows: 9-12%, nitrogen content: 3-5%, the structural general formula is as follows:
wherein the structural formula of B is as follows:
2. The dicyclic caged phosphazene derivative flame retardant PC/ABS composition according to claim 1, wherein: the polycarbonate resin has a number average molecular weight of 17000-40000, a weight-to-relative molecular weight of 20000-50000, and a melt flow rate (test conditions: 300 ℃ C. 1.2 kg): 10-25g/10min.
3. The dicyclic caged phosphazene derivative flame retardant PC/ABS composition according to claim 1, wherein: the acrylonitrile-butadiene-styrene copolymer can be prepared by an emulsion graft-blending polymerization method or a continuous bulk polymerization method, the melt flow rate is 5-25g/10min under the test condition of 220 ℃ and 10kg, the butadiene content is 15-20%, the particle size of butadiene is 0.1-1.0 mu m, the particle size is in bimodal distribution, and the content and the particle size of butadiene in the acrylonitrile-butadiene-styrene copolymer are limited to be excellent in surface performance and toughness.
4. The dicyclic caged phosphazene derivative flame retardant PC/ABS composition according to claim 1, wherein: the compatilizer is one or a mixture of more than one of methyl methacrylate/butadiene/styrene copolymer, methyl methacrylate/acrylic ester polymer, ethylene/acrylic ester/glycidyl methacrylate terpolymer, ethylene-butyl acrylate, acrylic acid-silicon rubber toughening agent and the like;
The processing aid is one or more of silicone, pentaerythritol stearate, ethylene bisstearamide, erucamide and polyethylene wax.
5. The dicyclic caged phosphazene derivative flame retardant PC/ABS composition and the preparation method thereof according to claim 4, wherein the composition is characterized in that: the compatilizer is selected from methyl methacrylate-butadiene-styrene terpolymer; the processing aid is selected from silicones.
6. The dicyclic caged phosphazene derivative flame retardant PC/ABS composition and the preparation method thereof according to claim 1, wherein the composition is characterized in that: the char former is an ultrathin hollow zinc aluminate microsphere, the diameter (D 50) of the microsphere is as follows: 1-30 mu m, the thickness of the spherical shell is 20-60nm, and the moisture is less than 0.3%.
7. The dicyclic caged phosphazene derivative flame retardant PC/ABS composition and the preparation method thereof according to claim 1, wherein the composition is characterized in that: the antioxidant is 3- (dodecylthio) propionic acid-2, 2-bis [ [3- (dodecylthio) -propionyloxy ] methyl ] -1, 3-propanediol ester, CAS No.29598-76-3; n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, CAS No.2082-79-3; triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, CAS No.36443-68-2; pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 6683-19-8; tris [2, 4-di-t-butylphenyl ] phosphite, CAS No.31570-04-4; bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, 154862-43-8 hindered phenol, organic sulfur, or one or more of the phosphites.
8. The dicyclic caged phosphazene derivative flame retardant PC/ABS composition and the preparation method thereof according to claim 7, wherein the composition is characterized in that: the antioxidant is as follows: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite.
9. The dicyclic caged phosphazene derivative flame retardant PC/ABS composition and the preparation method thereof according to claim 1, wherein the composition is characterized in that: the color master batch can be one or more of carbon black, zinc sulfide, ferric oxide and the like according to the color requirement, the content of the toner is 20-99%, and the carrier is AS or the color master batch of the lubricant.
10. The method for preparing a dicyclic caged phosphazene derivative flame retardant PC/ABS composition according to any one of claims 1 to 9, characterized in that: the method comprises the following steps:
(1) Weighing various raw materials according to the formula proportion; uniformly mixing an acrylonitrile-butadiene-styrene copolymer, polycarbonate resin, a compatilizer, a flame retardant, a char forming agent, an antioxidant, a processing aid, masterbatch and the like through a high-speed stirrer for later use;
(2) The above resin and auxiliary agent mixed raw materials are added through a main feeding port of a double-screw extruder, and the flame-retardant PC/ABS composition is obtained after the procedures of melt extrusion, granulation, drying treatment and the like at 220-240 ℃.
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