CN118006104A - Halogen-free flame-retardant polycarbonate material and preparation method thereof - Google Patents
Halogen-free flame-retardant polycarbonate material and preparation method thereof Download PDFInfo
- Publication number
- CN118006104A CN118006104A CN202311818459.8A CN202311818459A CN118006104A CN 118006104 A CN118006104 A CN 118006104A CN 202311818459 A CN202311818459 A CN 202311818459A CN 118006104 A CN118006104 A CN 118006104A
- Authority
- CN
- China
- Prior art keywords
- percent
- flame retardant
- halogen
- gato
- free flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 141
- 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 118
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 116
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000002250 absorbent Substances 0.000 claims abstract description 59
- 230000002745 absorbent Effects 0.000 claims abstract description 59
- -1 polysiloxane Polymers 0.000 claims abstract description 46
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 45
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 42
- 125000003118 aryl group Chemical group 0.000 claims abstract description 40
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 39
- 238000009413 insulation Methods 0.000 claims abstract description 35
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 35
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 35
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims description 28
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 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 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000012757 flame retardant agent Substances 0.000 claims description 4
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- 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 3
- 239000004698 Polyethylene 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
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 3
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 30
- 239000000779 smoke Substances 0.000 description 21
- 230000003287 optical effect Effects 0.000 description 17
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- BGVIOMZXEIPKTI-UHFFFAOYSA-N [In].[Cs] Chemical compound [In].[Cs] BGVIOMZXEIPKTI-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000004595 color masterbatch Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 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 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000110847 Kochia Species 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical group [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 239000007799 cork Substances 0.000 description 2
- VPXSRGLTQINCRV-UHFFFAOYSA-N dicesium;dioxido(dioxo)tungsten Chemical compound [Cs+].[Cs+].[O-][W]([O-])(=O)=O VPXSRGLTQINCRV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 description 1
- 150000005857 PFAS Chemical class 0.000 description 1
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012754 barrier agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 208000030533 eye disease Diseases 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- HYERJXDYFLQTGF-UHFFFAOYSA-N rhenium Chemical compound [Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re] HYERJXDYFLQTGF-UHFFFAOYSA-N 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 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)
Abstract
The invention discloses a halogen-free flame-retardant polycarbonate material which is prepared from the following components in percentage by weight: 85 to 96.15 percent of branched polycarbonate resin, 3 to 10 percent of nanometer GATO heat insulation master batch, 0.1 to 1 percent of near infrared absorbent, 0.05 to 0.5 percent of blue light absorbent, 0.1 to 1 percent of aromatic sulfonate flame retardant, 0.1 to 1 percent of polysiloxane flame retardant and 0.5 to 1.5 percent of auxiliary agent. The invention adopts the nano GATO heat insulation master batch and the near infrared absorbent to compound, not only ensures the high transparency and low haze of PC, but also blocks more than 95 percent of near infrared rays of 780-1650nm, and obtains good near infrared blocking effect.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a halogen-free flame-retardant polycarbonate material and a preparation method thereof.
Background
Polycarbonate (PC) is widely used in the technical fields of electronics, automobiles, machine manufacturing, computers and the like because of the characteristics of heat resistance, flame retardance, good shock resistance, easiness in processing and molding, low cost and the like. Along with the development of scientific technology, the application of the PC has been developed towards the directions of multifunction, specialization and serialization, especially the demand of optical fiber communication and various sunlight plates, eyeglass lenses, automobile windows and the like in recent years is rapidly increased, and new performance requirements are put forward for the PC, especially the requirements for the performances of flame retardance, heat insulation, blue light absorption and the like. In particular, with the increasing demands of energy conservation and emission reduction by replacing steel with plastic, higher heat insulation requirements are put forward for the application of PC in the fields. The common PC has no selectivity on the transmission of sunlight, has obvious thermal effect on infrared light in the sunlight while enough visible light is transmitted, and is easy to cause the increase of the ambient temperature, in particular to cause the increase of the indoor temperature. The service time of the cooling electric appliance is prolonged, and although the indoor temperature can be reduced, the energy burden is greatly increased. The blue light wave band can increase the toxin amount of the macular region in eyes, seriously threaten the eye fundus health and even induce blinding eye diseases, and if the illumination light is used for a long time, the rhythm and sleep of the human stethocarpon are affected, and biological clock disorder is caused, so that the immunity is reduced.
The polycarbonate resin has a certain flame retardance, is only UL 94V-2 grade, cannot meet the flame retardant requirement of vehicle interior materials, releases smoke in the combustion process, and is easy to cause choking of human bodies. There is a need to improve its low smoke, flame retardant properties. Traditional brominated flame retardants are known for high flame retardant efficiency, but flame retardant materials generate a large amount of smoke and carcinogens such as tetrabromodibenzodioxane, tetrabromobisbenzofuran and the like in the combustion and thermal cracking processes; although the phosphate flame retardant avoids harmful substances generated in the combustion process of a brominated flame retardant system, the melting point of the phosphate flame retardant is low, the volatility of the phosphate flame retardant is high, and the heat resistance of the PC composite material is easily reduced greatly and the volatilization loss in the molding process is easily caused; the sulfonate flame retardant commonly used in PC is KSS, PPFBS, STB. STB is commonly used for flame retardant opaque PC materials, which have good flame retardant effect, but are limited to use because STB contains halogen. The KSS accelerates the carbon forming rate of the PC during combustion, promotes the molecular crosslinking of the polymer, has the characteristics of small addition amount, high efficiency and capability of keeping the transparency of the PC material, is widely applied, but cannot meet the flame retardant requirement of the thin-wall workpiece, and is easy to absorb moisture to cause yellowing of the material; PPFBS is also a highly effective flame retardant for PC, but applications of PPFBS have been limited as the european union has identified fluorine-containing substances such as PFAS, PFOA, PFOS as highly interesting substances. Polysiloxane flame retardants are regarded as important by researchers because of their excellent processability, flame retardancy and good mechanical properties, in particular, being environmentally friendly, but they have a large amount of added materials when used alone and affect the transparency of PC. In recent years, high-efficiency mixed metal salts of aromatic sulfonates have been increasingly paid attention to, and not only are flame retarding efficiency high, but also transparency is less affected.
Patent application publication number WO2023134404A1 discloses a polycarbonate composition, a method for its preparation and its use; the polycarbonate composition comprises polycarbonate, micron-sized porous ceramic and the like. The polycarbonate composition takes specific porous ceramic as an infrared blocking functional material, has good infrared blocking performance, good heat insulation effect, low cost, good stability and environmental protection; also has better weather resistance. Although the blocking rate of the composition to infrared rays is 80% or more, the composition has a high infrared blocking effect; the temperature difference is not higher than 12 ℃ after heat insulation test treatment, and the heat insulation effect is good; after weather-resistant aging treatment of the xenon lamp, the color difference is not higher than 3.7, and the xenon lamp has better weather resistance and is not easy to fade. However, the addition of the micron-sized porous ceramic seriously affects the light transmittance of the material, and can only be used for the requirements of the opaque PC field. And the patent does not improve blue light absorption, does not modify flame retardance, and cannot meet the situation with higher requirements on flame retardance and blue light absorption.
The patent application with publication number CN113024853A discloses a preparation method of high-infrared-transmission barrier polycarbonate color master batch, stannous salt is dissolved in strong acid, a very small amount of tin powder is slowly added in the stirring process, and then carbonate is added until no bubbles are generated, so that suspension is obtained; adding indium salt, cesium salt and hydrogen peroxide into the suspension, stirring, washing and drying to obtain powder; pressing the powder into a rod shape by uniaxial pressure and cold isostatic pressing, heating by a current field of 15-25V/cm, heating by a program until the limited current reaches 0.8-8A, maintaining the temperature of 200-240 ℃ for 6-12 min, and stopping electrifying to obtain indium-cesium co-doped tin oxide; mixing indium cesium co-doped tin oxide with polycarbonate and lubricant paraffin, adding auxiliary materials of rhenium heptaoxide, an organic phosphorus flame retardant, tea polyphenol and rosin resin, uniformly mixing, adding into a double-screw extruder, extruding, cooling, drawing, air-drying and granulating to obtain the high-transparency infrared barrier polycarbonate color master batch. The master batch can absorb sunlight in an infrared band after being stretched and molded at high temperature, has the heat insulation and sun protection functions, and has the infrared blocking rate of more than 97% at the wavelength of 950 nm. The color master batch takes indium cesium co-doped tin oxide powder as an infrared blocking material, and simultaneously combines with a lubricant to improve the infrared blocking capability of a polycarbonate product. However, the method has high cost, poor stability and weather resistance, large chromatic aberration in the extrusion processing process and the substance is harmful to human bodies and the environment.
The patent application with publication number CN109575550A discloses an antimony tin oxide reinforced polycarbonate heat insulation material, which uses nano Antimony Tin Oxide (ATO) as an infrared barrier agent by a sol-gel method to prepare a series of silane coupling agent KH-X70 modified nano ATO/PC composite materials so as to improve the heat insulation performance of polycarbonate and maintain higher transparency. The particle size distribution of the nano ATO and the dispersion condition of the nano ATO in a PC matrix are researched through a laser particle size distribution meter and an SFM, and the mechanical property, the transmission property and the heat insulation effect of the composite material are measured by a tensile testing machine, a spectrophotometer and a heat insulation effect simulation device. The results show that: the silane modified nano ATO is uniformly dispersed in the PC matrix; with the increase of the mass fraction of the nanometer ATO, the infrared resistance and heat insulation performance of the nanometer ATO/PC composite material are improved; when the nano ATO content is 0.5wt%, the visible light transmittance of the nano ATO/PC composite material is higher than 80%. The temperature difference between the inside and the outside of the heat insulation effect simulation device reaches 3.9 ℃. When the content of the nano ATO is 0.3-0.5 wt%, the transmissivity of the nano ATO/PC composite material is reduced to about 80%, which shows that the addition of the nano ATO influences the visible light transmissivity of the PC to a certain extent, but the visible light transmissivity of the composite material is still maintained at a higher level; when the nano ATO content is increased to 0.6wt% to 0.7wt%, the transmittance of the nano ATO/PC composite material is further reduced. Also, the patent does not improve blue light absorption, does not modify flame retardancy, and cannot meet the requirements of high flame retardance and blue light absorption.
Therefore, it is very necessary to develop an infrared blocking, blue light absorbing, halogen-free flame retardant, transparent polycarbonate material for use in the field of vehicle interior.
Disclosure of Invention
The invention aims to provide an infrared-blocking, blue light-absorbing, halogen-free flame-retardant and transparent halogen-free flame-retardant polycarbonate material.
The invention also aims to provide a preparation method of the halogen-free flame-retardant polycarbonate material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The invention provides a halogen-free flame-retardant polycarbonate material, which is prepared from the following components in percentage by weight: 85 to 96.15 percent of branched polycarbonate resin, 3 to 10 percent of nanometer GATO heat insulation master batch, 0.1 to 1 percent of near infrared absorbent, 0.05 to 0.5 percent of blue light absorbent, 0.1 to 1 percent of aromatic sulfonate flame retardant, 0.1 to 1 percent of polysiloxane flame retardant and 0.5 to 1.5 percent of auxiliary agent.
More preferably, the halogen-free flame retardant polycarbonate material is prepared from the following components in percentage by weight: 88.3 to 95.3 percent of branched polycarbonate resin, 3 to 10 percent of nanometer GATO heat insulation master batch, 0.2 to 0.5 percent of near infrared absorbent, 0.05 to 0.2 percent of blue light absorbent, 0.2 to 1 percent of aromatic sulfonate flame retardant, 0.2 to 1 percent of polysiloxane flame retardant and 0.5 to 1 percent of auxiliary agent.
Most preferably, the halogen-free flame retardant polycarbonate material is prepared from the following components in percentage by weight: 91.3 to 95.3 percent of branched polycarbonate resin, 3 to 6 percent of nanometer GATO heat insulation master batch, 0.2 to 0.5 percent of near infrared absorbent, 0.1 to 0.2 percent of blue light absorbent, 0.2 to 0.5 percent of aromatic sulfonate flame retardant, 0.2 to 0.5 percent of polysiloxane flame retardant and 0.5 to 1 percent of auxiliary agent.
The halogen-free flame-retardant polycarbonate material is prepared from the following components in percentage by weight: 95.3% of branched polycarbonate resin, 3% of nano GATO heat insulation master batch, 0.2% of near infrared absorbent, 0.1% of blue light absorbent, 0.2% of aromatic sulfonate flame retardant, 0.2% of polysiloxane flame retardant and 1% of auxiliary agent.
The halogen-free flame-retardant polycarbonate material is prepared from the following components in percentage by weight: 92.3% of branched polycarbonate resin, 6% of nano GATO heat insulation master batch, 0.2% of near infrared absorbent, 0.1% of blue light absorbent, 0.2% of aromatic sulfonate flame retardant, 0.2% of polysiloxane flame retardant and 1% of auxiliary agent.
The halogen-free flame-retardant polycarbonate material is prepared from the following components in percentage by weight: 92% of branched polycarbonate resin, 6% of nano GATO heat insulation master batch, 0.5% of near infrared absorbent, 0.1% of blue light absorbent, 0.2% of aromatic sulfonate flame retardant, 0.2% of polysiloxane flame retardant and 1% of auxiliary agent.
The halogen-free flame-retardant polycarbonate material is prepared from the following components in percentage by weight: 92.2% of branched polycarbonate resin, 6% of nano GATO heat insulation master batch, 0.2% of near infrared absorbent, 0.2% of blue light absorbent, 0.2% of aromatic sulfonate flame retardant, 0.2% of polysiloxane flame retardant and 1% of auxiliary agent.
The halogen-free flame-retardant polycarbonate material is prepared from the following components in percentage by weight: branched polycarbonate resin 92.35%, nano GATO heat insulation master batch 6%, near infrared absorbent 0.2%, blue light absorbent 0.05%, aromatic sulfonate flame retardant 0.2%, polysiloxane flame retardant 0.2% and auxiliary agent 1%.
The halogen-free flame-retardant polycarbonate material is prepared from the following components in percentage by weight: 91.5% of branched polycarbonate resin, 6% of nano GATO heat insulation master batch, 0.2% of near infrared absorbent, 0.1% of blue light absorbent, 1% of aromatic sulfonate flame retardant, 0.2% of polysiloxane flame retardant and 1% of auxiliary agent.
The halogen-free flame-retardant polycarbonate material is prepared from the following components in percentage by weight: 91.5% of branched polycarbonate resin, 6% of nano GATO heat insulation master batch, 0.2% of near infrared absorbent, 0.1% of blue light absorbent, 0.2% of aromatic sulfonate flame retardant, 1% of polysiloxane flame retardant and 1% of auxiliary agent.
The halogen-free flame-retardant polycarbonate material is prepared from the following components in percentage by weight: 88.3% of branched polycarbonate resin, 10% of nano GATO heat insulation master batch, 0.2% of near infrared absorbent, 0.1% of blue light absorbent, 0.2% of aromatic sulfonate flame retardant, 0.2% of polysiloxane flame retardant and 1% of auxiliary agent.
The branched polycarbonate resin is bisphenol A type aromatic branched polycarbonate resin, the relative molecular weight of the resin is 25000-32000, and the branched polycarbonate resin is obtained by adding a branching agent with more than 3 functional groups in the polymerization process and is manufactured by Kochia company, and the model is PC ET3137.
The nanometer GATO heat-insulating master batch is prepared from the following components in percentage by mass:
PC 87.6％；
10% of PC powder;
2.4 percent of nanometer GATO heat insulating agent.
The model of the PC is PC ET3137.
The PC powder is bisphenol A type aromatic linear polycarbonate resin, the relative molecular weight of the PC powder is 25000-32000, and the PC powder is manufactured by the Cork company and is PC 3100.
The nanometer GATO heat insulating agent is GATO ethanol dispersion liquid, wherein the content of GATO nanometer cesium tungsten oxide is 25%, the pH value is 6-8, the particle size is less than or equal to 70nm, and the viscosity is less than or equal to 10 mPa.s. Preferably, it is a GATO ethanol dispersion manufactured by Kagaolon nanoindustry Co., ltd.
The preparation method of the nanometer GATO heat-insulating master batch comprises the following steps: according to the following proportion, PC 3100 powder and a nano GATO heat insulating agent are firstly weighed, added into a mixer for premixing for 1 minute, then added with PC ET3137 particles, mixed in a high-speed mixer for 3 minutes, extruded by a double screw extruder at the temperature of 250-260 ℃, cooled and granulated, and the obtained particles are sealed by an aluminum foil bag for later use, so that the nano GATO heat insulating master batch is obtained.
PC ET3137 particles 87.6%;
10% of PC 3100 powder;
2.4 percent of nanometer GATO heat insulating agent.
The near infrared absorbent is N, N' -2, 5-cyclohexadiene-1, 4-diylbis [4- (dibutylamino) -N- [4- (dibutylamino) phenyl ] anilium, and bis [ (OC-6-11) -hexafluoroantimonate (1-) ], and the structural formula is shown as follows:
Preferably, R006, manufactured by Shanghai Kai Bi Cui chemical technologies Co., ltd.
The blue light absorber is a spiro-ring compound, can absorb the whole blue light range of 400-450 nm, and has the following structural formula:
wherein R 1 and R 2 are each independently selected from methyl (CH 3). Preferably manufactured by Shanghai Kai Bi Cui chemical technology Co., ltd., model B004.
The aromatic sulfonate flame retardant is an efficient mixed metal salt of aromatic sulfonate, and is a mixture of sulfonate and sulfonic acid derivatives. Preferably manufactured by Sloss, model HES2-FR.
The polysiloxane flame retardant is at least one of branched polysiloxane, linear polysiloxane and branched phenyl silicone oil flame retardant, preferably methyl series liquid organosilicon containing Si-H bonding bond, and has good halogen-free flame retardant performance while not affecting the original optical transparency of PC. Preferably manufactured by Japanese Kossa, model KP-2710.
The auxiliary agent is prepared from an antioxidant, an ultraviolet-proof additive, a processing auxiliary agent and toner in a mass ratio of 3:3:3:1.
The antioxidant is at least one selected from phosphite antioxidant 168, high molecular weight phosphite antioxidant S-9228 (manufactured by the company Dover), hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 and hindered phenol antioxidant 1076 (manufactured by the company BASF); preferably an antioxidant S-9228 and an antioxidant 1076 in a mass ratio of 2:1.
The ultraviolet-proof additive is benzotriazole ultraviolet absorber, preferably at least one of UV234, UV-329 and UV 360. More preferably UV360, manufactured by BASF corporation.
The processing aid is at least one selected from polyethylene wax (manufactured by BASF corporation), oxidized polyethylene wax (manufactured by BASF corporation), pentaerythritol stearate; more preferably pentaerythritol stearate, manufactured by american dragon sand.
The toner is prepared from pigment and lubricant EBS in a mass ratio of 1:10, wherein the pigment is selected from phthalocyanine blue, phthalocyanine green, BR red, HG yellow, 3R blue and the like (phthalocyanine green is selected in the embodiment of the invention), and can be purchased from Coryn chemical (China) Co.
In a second aspect of the present invention, there is provided a method for preparing the halogen-free flame retardant polycarbonate material, comprising the steps of:
Mixing polysiloxane flame retardant and dried branched polycarbonate resin, mixing in a high-speed mixer, sequentially adding nano GATO heat-insulating master batch, near infrared absorbent, blue light absorbent, aromatic sulfonate flame retardant and auxiliary agent into the high-speed mixer, mixing at high speed for 6-8 minutes, uniformly mixing, feeding into a double-screw extruder through a main feeder, granulating after melt blending, and drying to obtain the halogen-free flame-retardant polycarbonate material.
Drying conditions of the branched polycarbonate resin: drying in a forced air dryer at a temperature of 120℃for 4h.
The temperature of the 11 region of the twin-screw extruder is respectively set to 250 ℃, 260 ℃, 270 DEG C270 ℃, 260 ℃ and 260 ℃.
In a third aspect of the invention, there is provided the use of the halogen-free flame retardant polycarbonate material in the preparation of an interior material for a vehicle.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
the invention adopts the nano GATO heat insulation master batch and the near infrared absorbent to compound, not only ensures the high transparency and low haze of PC, but also blocks more than 95 percent of near infrared rays of 780-1650nm, and obtains good near infrared blocking effect.
The invention adopts the spiral ring-shaped blue light absorbent, not only resists the temperature and meets the processing temperature requirement of PC materials, but also can absorb all blue light of 400-450 nm.
The invention adopts branched polycarbonate resin, and is compounded with aromatic sulfonate flame retardant and polysiloxane flame retardant, so that the transparency is not affected on the basis of guaranteeing the flame retardance, and the smoke density is very low in the combustion process test.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The materials used in the embodiment of the invention are as follows:
The branched polycarbonate resin is bisphenol A type aromatic branched polycarbonate resin, the relative molecular weight of the resin is 25000-32000, and the branched polycarbonate resin is obtained by adding a branching agent with more than 3 functional groups in the polymerization process and is manufactured by Kochia company, and the model is PC ET3137.
The nanometer GATO heat-insulating master batch is prepared from the following components in percentage by mass:
PC 87.6％；
10% of PC powder;
2.4 percent of nanometer GATO heat insulating agent.
The model of the PC is PC ET3137.
The PC powder is bisphenol A type aromatic linear polycarbonate resin, the relative molecular weight of the PC powder is 25000-32000, and the PC powder is manufactured by the Cork company and is PC 3100.
The nanometer GATO heat insulating agent is GATO ethanol dispersion liquid, wherein the content of GATO nanometer cesium tungsten oxide is 25%, the pH value is 6-8, the particle size is less than or equal to 70nm, and the viscosity is less than or equal to 10 mPa.s. Preferably, it is a GATO ethanol dispersion manufactured by Kagaolon nanoindustry Co., ltd.
The preparation method of the nanometer GATO heat-insulating master batch comprises the following steps: according to the following proportion, PC 3100 powder and a nano GATO heat insulating agent are firstly weighed, added into a mixer for premixing for 1 minute, then added with PC ET3137 particles, mixed in a high-speed mixer for 3 minutes, extruded by a double screw extruder at the temperature of 250-260 ℃, cooled and granulated, and the obtained particles are sealed by an aluminum foil bag for later use, so that the nano GATO heat insulating master batch is obtained.
PC ET3137 particles 87.6%;
10% of PC 3100 powder;
2.4 percent of nanometer GATO heat insulating agent.
The near infrared absorbent is N, N' -2, 5-cyclohexadiene-1, 4-diylbis [4- (dibutylamino) -N- [4- (dibutylamino) phenyl ] anilium, and bis [ (OC-6-11) -hexafluoroantimonate (1-) ], and the structural formula is shown as follows:
Preferably, R006, manufactured by Shanghai Kai Bi Cui chemical technologies Co., ltd.
The blue light absorber is a spiro-ring compound, can absorb the whole blue light range of 400-450 nm, and has the following structural formula:
wherein R 1 and R 2 are each independently selected from methyl (CH 3). Preferably manufactured by Shanghai Kai Bi Cui chemical technology Co., ltd., model B004.
The aromatic sulfonate flame retardant is an efficient mixed metal salt of aromatic sulfonate, and is a mixture of sulfonate and sulfonic acid derivatives. Preferably manufactured by Sloss, model HES2-FR.
The polysiloxane flame retardant is at least one of branched polysiloxane, linear polysiloxane and branched phenyl silicone oil flame retardant, preferably methyl series liquid organosilicon containing Si-H bonding bond, and has good halogen-free flame retardant performance while not affecting the original optical transparency of PC. Preferably manufactured by Japanese Kossa, model KP-2710.
The auxiliary agent is prepared from an antioxidant, an ultraviolet-proof additive, a processing auxiliary agent and toner in a mass ratio of 3:3:3:1.
The antioxidant is at least one selected from phosphite antioxidant 168, high molecular weight phosphite antioxidant S-9228 (manufactured by the company Dover), hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 and hindered phenol antioxidant 1076 (manufactured by the company BASF); preferably an antioxidant S-9228 and an antioxidant 1076 in a mass ratio of 2:1, manufactured by BASF corporation.
The ultraviolet-proof additive is benzotriazole ultraviolet absorber, preferably at least one of UV234, UV-329 and UV 360. More preferably UV360, manufactured by BASF corporation.
The processing aid is at least one selected from polyethylene wax (manufactured by BASF corporation), oxidized polyethylene wax (manufactured by BASF corporation), pentaerythritol stearate; more preferably pentaerythritol stearate, manufactured by american dragon sand.
The toner is prepared from pigment and lubricant EBS in a mass ratio of 1:10, wherein the pigment is selected from phthalocyanine blue, phthalocyanine green, BR red, HG yellow, 3R blue and the like (phthalocyanine green is selected in the embodiment of the invention), and can be purchased from Coryn chemical (China) Co.
The materials used in the comparative examples are as follows:
branched polysiloxane flame retardant: manufactured by the company us doucorning, model FCA-107; ordinary sulfonate flame retardants: manufactured by SLOSS company, U.S. Pat. No. F535.
The preparation method of the halogen-free flame-retardant polycarbonate material in the embodiment of the invention comprises the following steps:
Firstly, drying branched polycarbonate resin in a blast drier at 120 ℃ for 4 hours, then mixing polysiloxane flame retardant and the branched polycarbonate resin in a high-speed mixer for 1 minute, then sequentially adding nano GATO heat insulation master batch, near infrared absorbent, blue light absorbent, aromatic sulfonate flame retardant and auxiliary agent into the high-speed mixer, mixing at high speed for 6-8 minutes, uniformly mixing, feeding the mixture into a double-screw extruder through a main feeder, granulating after melt blending, drying the obtained granules at 120 ℃ for 4 hours, and injection molding the granules at 280-290 ℃ into standard sample bars to obtain the halogen-free flame retardant polycarbonate material.
The temperature of the 11 region of the twin-screw extruder was set at 250 ℃, 260 ℃, 270 ℃ respectively 270 ℃, 260 ℃ and 260 ℃.
The components and proportions of the inventive examples 1 to 4 and comparative examples 1 to 5 are shown in Table 1:
TABLE 1 comparative examples 1-5 and examples 1-4 Components and proportions
The components and proportions of examples 5 to 8 and comparative examples 6 to 8 of the present invention are shown in Table 1:
TABLE 2 comparative examples 6-8 and examples 5-8 Components and proportions
The preparation method of comparative examples 1 to 5 is as follows:
According to the proportion in Table 1, firstly, branched polycarbonate resin is dried for 4 hours in a blast drier at 120 ℃, then polysiloxane flame retardant and the branched polycarbonate resin are mixed, after being mixed in a high-speed mixer for 1 minute, nanometer GATO heat insulation master batch, near infrared absorbent, blue light absorbent, aromatic sulfonate flame retardant and auxiliary agent are sequentially added into the high-speed mixer, high-speed mixing is carried out for 6-8 minutes, after uniform mixing, the mixture is fed into a double-screw extruder through a main feeder, and after melt blending, pelleting is carried out, the obtained granules are dried for 4 hours at 120 ℃, and are injection molded into standard sample bars at 280-290 ℃, thus obtaining the halogen-free flame retardant polycarbonate material.
The temperature of the 11 region of the twin-screw extruder was set at 250 ℃, 260 ℃, 270 ℃ respectively 270 ℃, 260 ℃ and 260 ℃.
Preparation method of comparative example 6:
According to the proportions in Table 2, PC is dried for 4 hours at 120 ℃ in a blast drier, then branched polysiloxane flame retardant is mixed with the PC, and the mixture is mixed in a high-speed mixer for 1 minute; sequentially adding the nanometer GATO heat-insulating master batch, the near infrared absorbent, the blue light absorbent, the sulfonate flame retardant and the auxiliary agent into a high-speed mixer, mixing at a high speed for 6-8 minutes, uniformly mixing, feeding into a double-screw extruder through a main feeder, and granulating after melt blending.
The temperature of the 11 region of the twin-screw extruder was set at 250 ℃, 260 ℃, 270 ℃ respectively 270 ℃, 260 ℃ and 260 ℃. The obtained granules are dried for 4 hours at 120 ℃ and then are subjected to injection molding at 280-290 ℃ to form standard sample bars, thus obtaining the composite material.
Comparative example 7 preparation method:
According to the proportions in Table 2, PC is dried for 4 hours at 120 ℃ in a blast drier, then polysiloxane flame retardant is mixed with the PC, and the mixture is mixed in a high-speed mixer for 1 minute; sequentially adding the nanometer GATO heat-insulating master batch, the near infrared absorbent, the blue light absorbent, the sulfonate flame retardant and the auxiliary agent into a high-speed mixer, mixing at a high speed for 6-8 minutes, uniformly mixing, feeding into a double-screw extruder through a main feeder, and granulating after melt blending.
The temperature of the 11 region of the twin-screw extruder was set at 250 ℃, 260 ℃, 270 ℃ respectively 270 ℃, 260 ℃ and 260 ℃. The obtained granules are dried for 4 hours at 120 ℃ and then are subjected to injection molding at 280-290 ℃ to form standard sample bars, thus obtaining the composite material.
Preparation method of comparative example 8:
According to the proportions in Table 2, PC is dried for 4 hours at 120 ℃ in a blast drier, then polysiloxane flame retardant is mixed with the PC, and the mixture is mixed in a high-speed mixer for 1 minute; sequentially adding the nanometer GATO heat-insulating master batch, the near infrared absorbent, the blue light absorbent, the aromatic sulfonate flame retardant and the auxiliary agent into a high-speed mixer, mixing at a high speed for 6-8 minutes, uniformly mixing, feeding into a double-screw extruder through a main feeder, and granulating after melt blending.
The temperature of the 11 region of the twin-screw extruder was set at 250 ℃, 260 ℃, 270 ℃ respectively 270 ℃, 260 ℃ and 260 ℃. The obtained granules are dried for 4 hours at 120 ℃ and then are subjected to injection molding at 280-290 ℃ to form standard sample bars, thus obtaining the composite material.
Evaluation of the effects of the inventive examples and comparative examples
The samples obtained in examples 1-8 and comparative examples 1-8 were tested for mechanical properties according to the American Society for Testing and Materials (ASTM) standard, for flame retardant properties according to the UIC 564-2:1991 standard, according to GB/T8323.2-2008 Plastic-Smoke Generation-part 2: single chamber method measurement smoke density test method the specific optical density of smoke is tested, total light transmittance and haze are tested according to ASTM D1003. Near infrared ray blocking rate test method: the samples were injection molded into 2mm plaques and scanned with an ultraviolet-visible infrared spectrophotometer over the infrared wavelength range 780-1650nm to test for near infrared blocking. The blue light transmittance testing method comprises the following steps: the sample was injection molded into a 2mm color plate, and the blue light transmittance was measured by scanning the wavelength range of 400-450nm blue light with an ultraviolet-visible infrared spectrophotometer.
The test results of examples 1 to 4 and comparative examples 1 to 5 are shown in Table 3:
TABLE 3 Properties of examples 1-4 and comparative examples 1-5
Remarks: ds1.5—smoke specific optical density at 1.5min from the start of the test;
ds4.0—smoke specific optical density at 4.0min from the start of the test.
The test results of examples 5 to 8 and comparative examples 6 to 8 are shown in Table 4:
TABLE 4 Properties of examples 5-8 and comparative examples 6-8
Remarks: ds1.5—smoke specific optical density at 1.5min from the start of the test;
ds4.0—smoke specific optical density at 4.0min from the start of the test.
The test performance results of tables 3 and 4 show that:
(1) Comparative examples 1-4 and comparative examples 3 and 8 found that the use of the nano-GATO heat-insulating master batch and the near infrared absorbent for compounding not only ensures high transparency and low haze of PC, but also blocks more than 95% of near infrared rays of 780-1650nm, and good near infrared blocking effect is obtained. Haze is well known as an irregular state that characterizes the appearance of clouds or chaos in transparent materials. When light irradiates the transparent material, the light transmitted through the material (transmitted light) is divided into two parts: a straight transmitted light portion parallel to the incident light, a scattered transmitted light portion offset from the incident light by a distance other than 2.5 °. Haze is the ratio of the scattered transmitted light flux to the total transmitted light flux; the lower the haze, the lower the amount of light transmitted by the diffuser, the higher the amount of light transmitted directly, and the better the transparency. The comparison result shows that with the increase of the addition of the nanometer GATO heat insulation master batch and the near infrared absorbent, the near infrared blocking rate is slightly increased, the haze is obviously increased, the transparency of the material is greatly influenced, the specific optical density of the smoke is also increased, and the comprehensive performance of the material is influenced. Example 1 has low haze and good transparency but poor near infrared barrier properties. The optimum formulation should therefore be example 2.
(2) Comparative example 2, example 4, example 5 found that: the adopted spiral ring-shaped blue light absorbent not only can meet the requirement of high processing temperature of PC materials, but also can absorb all blue light of 400-450 nm. When the blue light absorber addition ratio is 0.05%, the blue light transmittance is reduced, but the blue light transmittance is not disappeared, which indicates that part of blue light remains; when the adding proportion is increased to 0.1%, blue light completely disappears, the blue light transmittance is 0, which indicates that the energy absorption of the short wave high energy section is complete, and the blue light absorbent has effectively absorbed the high energy short wave and converted into low energy radiation; when the addition ratio was increased to 0.2%, the blue light transmittance was 0, but the haze was remarkably increased, which had a large effect on the transparency of the material, so that the optimum ratio was to be example 2.
(3) Comparative example 2 and comparative examples 1,2, 6, 7 and 8 have found that the use of the combination of aromatic sulfonate flame retardant and polysiloxane flame retardant, and the selection of branched PC as the base material, not only ensures high transparency and low haze of PC, but also ensures easy char formation and self-extinguishment during combustion, the flame retardance can reach class A, and the smoke ratio optical density is lower, meeting the requirements of interior materials of vehicles. Compared with branched polysiloxane flame retardants, the polysiloxane flame retardants containing Si-H bond in methyl series have excellent compatibility with PC resin, and the polysiloxane flame retardants not affecting the original optical transparency of PC, but also endowing the material with good halogen-free flame retardant property. In addition, it was found in the study that: as the aromatic sulfonate flame retardant is a halogen-free high-efficiency mixed metal salt, the water absorbability of the aromatic sulfonate flame retardant is far lower than that of a common sulfonate flame retardant, and the flame retardant efficiency of the aromatic sulfonate flame retardant in PC resin is also better than that of the common sulfonate flame retardant.
(4) Comparative example 2, example 6, example 7 found that: with the increase of the addition amount of the aromatic sulfonate flame retardant and the polysiloxane flame retardant, although the material can obtain lower smoke specific optical density, the haze is obviously increased, the transparency of the material is greatly influenced, and the comprehensive performance of the material is influenced. The optimum formulation should therefore be example 2.
(5) When the polysiloxane flame retardant in comparative example 1 is zero, the flame retardant rating is only B-class, and the specific optical density of smoke is higher than that of example 2, so that the requirements of the interior material of the vehicle on flame retardance and specific optical density of smoke cannot be met.
When the aromatic sulfonate flame retardant in comparative example 2 is zero, the flame retardant rating is only C-grade, the smoke specific optical density is remarkably higher than that in comparative example 2, and the requirements of the vehicle interior material on flame retardance and smoke specific optical density cannot be met.
When both the nano-GATO heat-insulating master batch and the near infrared absorbent in comparative example 3 were zero, the near infrared ray blocking rate was low as compared with example 2.
In comparative example 4, when the near infrared absorbent was added and the nano-GATO heat-insulating master batch was zero, the near infrared blocking rate was only 63, and the near infrared blocking rate was not as high as that of example 2.
When the near infrared absorbing agent of comparative example 5 was zero, the near infrared blocking rate was only 71, and the near infrared blocking rate was not as high as that of example 2. When the nanometer GATO heat insulation master batch and the near infrared absorbent are matched for use, the near infrared blocking rate is obviously improved, and the nanometer GATO heat insulation master batch and the near infrared absorbent have obvious synergistic effect.
When both the aromatic sulfonate flame retardant and the polysiloxane flame retardant in comparative example 6 were zero, the haze was remarkably increased, the total light transmittance was decreased, and the transparency of the material was poor, as compared with example 2, by replacing the aromatic sulfonate flame retardant and the polysiloxane flame retardant with the sulfonate flame retardant and the branched polysiloxane flame retardant.
When the aromatic sulfonate flame retardant in comparative example 7 was zero, the flame retardant was replaced with sulfonate flame retardant, and the flame retardant rating was class B and the smoke specific optical density was also higher as compared with example 2.
When the branched polycarbonate resin in comparative example 8 was zero, the flame retardant rating was B-rated and the smoke specific optical density was high, as compared with example 2, instead of the linear PC ET 3117. Obviously, the branched polycarbonate resin, the aromatic sulfonate flame retardant and the polysiloxane flame retardant are matched for use, so that the flame retardant has obvious synergistic effect, the material is easier to char and self-extinguish in the combustion process, the flame retardance reaches A level, the smoke density is lower, and the requirements of the interior material of the vehicle are met.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (10)
1. The halogen-free flame-retardant polycarbonate material is characterized by being prepared from the following components in percentage by weight: 85 to 96.15 percent of branched polycarbonate resin, 3 to 10 percent of nanometer GATO heat insulation master batch, 0.1 to 1 percent of near infrared absorbent, 0.05 to 0.5 percent of blue light absorbent, 0.1 to 1 percent of aromatic sulfonate flame retardant, 0.1 to 1 percent of polysiloxane flame retardant and 0.5 to 1.5 percent of auxiliary agent.
2. The halogen-free flame retardant polycarbonate material of claim 1, wherein the halogen-free flame retardant polycarbonate material is made of the following components in weight percent: 88.3 to 95.3 percent of branched polycarbonate resin, 3 to 10 percent of nanometer GATO heat insulation master batch, 0.2 to 0.5 percent of near infrared absorbent, 0.05 to 0.2 percent of blue light absorbent, 0.2 to 1 percent of aromatic sulfonate flame retardant, 0.2 to 1 percent of polysiloxane flame retardant and 0.5 to 1 percent of auxiliary agent.
3. The halogen-free flame retardant polycarbonate material of claim 2, wherein the halogen-free flame retardant polycarbonate material is made of the following components in weight percent: 91.3 to 95.3 percent of branched polycarbonate resin, 3 to 6 percent of nanometer GATO heat insulation master batch, 0.2 to 0.5 percent of near infrared absorbent, 0.1 to 0.2 percent of blue light absorbent, 0.2 to 0.5 percent of aromatic sulfonate flame retardant, 0.2 to 0.5 percent of polysiloxane flame retardant and 0.5 to 1 percent of auxiliary agent.
4. The halogen-free flame retardant polycarbonate material of claim 3, wherein the halogen-free flame retardant polycarbonate material is made of the following components in weight percent: 92.3% of branched polycarbonate resin, 6% of nano GATO heat insulation master batch, 0.2% of near infrared absorbent, 0.1% of blue light absorbent, 0.2% of aromatic sulfonate flame retardant, 0.2% of polysiloxane flame retardant and 1% of auxiliary agent.
5. The halogen-free flame retardant polycarbonate material of claim 1, wherein the nano-GATO heat insulation master batch is prepared from the following components in percentage by mass:
PC 87.6％；
10% of PC powder;
2.4 percent of nanometer GATO heat insulating agent.
6. The halogen-free flame retardant polycarbonate material of claim 1, wherein the auxiliary agent is prepared from an antioxidant, an ultraviolet-proof additive, a processing auxiliary agent and toner in a mass ratio of 3:3:3:1.
7. The halogen-free flame retardant polycarbonate material of claim 6, wherein the antioxidant is selected from at least one of phosphite antioxidant 168, high molecular weight phosphite antioxidant S-9228, hindered phenol antioxidant 1010, hindered phenol antioxidant 1098, hindered phenol antioxidant 1076;
the ultraviolet-proof additive is benzotriazole ultraviolet absorber;
The processing aid is at least one selected from polyethylene wax, oxidized polyethylene wax and pentaerythritol stearate;
the toner is prepared from pigment and lubricant EBS in a mass ratio of 1:10.
8. A method of preparing the halogen-free flame retardant polycarbonate material of any one of claims 1 to 7, comprising the steps of:
Mixing polysiloxane flame retardant and dried branched polycarbonate resin, mixing in a high-speed mixer, sequentially adding nano GATO heat-insulating master batch, near infrared absorbent, blue light absorbent, aromatic sulfonate flame retardant and auxiliary agent into the high-speed mixer, mixing at high speed for 6-8 minutes, uniformly mixing, feeding into a double-screw extruder through a main feeder, granulating after melt blending, and drying to obtain the halogen-free flame-retardant polycarbonate material.
9. The method for preparing a halogen-free flame retardant polycarbonate material according to claim 8, wherein, the temperature of the 11 region of the twin-screw extruder is respectively set to 250 ℃, 260 ℃, 270 DEG C270 ℃, 260 ℃ and 260 ℃.
10. Use of the halogen-free flame retardant polycarbonate material of any one of claims 1 to 7 for the preparation of vehicle interior materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311818459.8A CN118006104A (en) | 2023-12-27 | 2023-12-27 | Halogen-free flame-retardant polycarbonate material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311818459.8A CN118006104A (en) | 2023-12-27 | 2023-12-27 | Halogen-free flame-retardant polycarbonate material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118006104A true CN118006104A (en) | 2024-05-10 |
Family
ID=90941900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311818459.8A Pending CN118006104A (en) | 2023-12-27 | 2023-12-27 | Halogen-free flame-retardant polycarbonate material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118006104A (en) |
-
2023
- 2023-12-27 CN CN202311818459.8A patent/CN118006104A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103571037B (en) | Preparation method of polypropylene resin | |
| CN102786787A (en) | Anti-glare flame-retardant polycarbonate material, and preparation method and application thereof | |
| CN110698836B (en) | High-strength polycarbonate composite material for plastic-coated aluminum and preparation method thereof | |
| CN106566104B (en) | A kind of high flow flame-proof masterbatch and preparation method thereof | |
| CN111019316B (en) | Polycarbonate composition with light diffusion performance, preparation method and application | |
| CN104744865A (en) | Environment-friendly cable shield material with high flame resistance and preparation method of environment-friendly cable shield material | |
| CN111171547B (en) | High-weather-resistance black polycarbonate material capable of selectively transmitting visible light and preparation method thereof | |
| WO2024011848A1 (en) | Highly-weather-resistant black thermal insulation asa resin and preparation method therefor | |
| CN107286461B (en) | Antibacterial weather-resistant flame-retardant V0-grade polypropylene material and preparation method thereof | |
| CN109337330B (en) | Halogen-free flame-retardant high-shading PC composite material and preparation method thereof | |
| CN110776688A (en) | Antioxidant and anti-UV color master batch and preparation method thereof | |
| CN113121906A (en) | Wear-resistant flame-retardant plastic and preparation method thereof | |
| CN118006104A (en) | Halogen-free flame-retardant polycarbonate material and preparation method thereof | |
| CN111303602A (en) | Master batch, polycarbonate cooling film, and preparation method and application thereof | |
| CN104130569B (en) | A kind of daiamid composition improving light-heat aging performance | |
| CN109679184A (en) | A kind of corrosion resistant modified plastics and preparation method thereof | |
| CN105733233A (en) | PC optical material filtering biological blue light and being halogen-free and flame retarding, and preparation and application thereof | |
| CN113637191A (en) | PMMA-based flame-retardant shading anti-aging master batch, preparation method and PC sheet | |
| JP5764851B2 (en) | Light absorbing composition and light absorbing device comprising the same | |
| CN112322019A (en) | High-hardness transparent flame-retardant PC material and preparation method thereof | |
| CN107857948A (en) | A kind of modified ASA polymeric compositions | |
| CN111205584A (en) | Preparation method of flame-retardant ultraviolet radiation-resistant polycarbonate material | |
| JP4752525B2 (en) | Resin composition | |
| CN108546387A (en) | A kind of flame-proof anti-aging cable material and preparation method thereof | |
| CN114031921B (en) | Green weather-resistant halogen-free flame-retardant PC composition and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |