CN114479401A - Halogen-free flame-retardant PC/ABS composition and preparation method and application thereof - Google Patents
Halogen-free flame-retardant PC/ABS composition and preparation method and application thereof Download PDFInfo
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- CN114479401A CN114479401A CN202011148839.1A CN202011148839A CN114479401A CN 114479401 A CN114479401 A CN 114479401A CN 202011148839 A CN202011148839 A CN 202011148839A CN 114479401 A CN114479401 A CN 114479401A
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- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 109
- 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 59
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 229920007019 PC/ABS Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 14
- 229920001971 elastomer Polymers 0.000 claims abstract description 64
- 239000005060 rubber Substances 0.000 claims abstract description 64
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 54
- 239000004417 polycarbonate Substances 0.000 claims abstract description 49
- 239000012745 toughening agent Substances 0.000 claims abstract description 44
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 40
- 230000009477 glass transition Effects 0.000 claims abstract description 34
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000001125 extrusion Methods 0.000 claims description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- KLIYQWXIWMRMGR-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate Chemical compound C=CC=C.COC(=O)C(C)=C KLIYQWXIWMRMGR-UHFFFAOYSA-N 0.000 claims description 7
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 6
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 4
- MPAHZJBGSWHKBJ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octaphenoxy-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene 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(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 MPAHZJBGSWHKBJ-UHFFFAOYSA-N 0.000 claims description 3
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 claims description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- FGDAXMHZSNXUFJ-UHFFFAOYSA-N ethene;prop-1-ene;prop-2-enenitrile Chemical group C=C.CC=C.C=CC#N FGDAXMHZSNXUFJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims 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 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 3
- HWXBQOWZWWYBLY-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)OS(=O)(=O)C=1C=CC=CC1.[K] Chemical compound C1(=CC=CC=C1)S(=O)(=O)OS(=O)(=O)C=1C=CC=CC1.[K] HWXBQOWZWWYBLY-UHFFFAOYSA-N 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920005668 polycarbonate resin Polymers 0.000 claims description 2
- 239000004431 polycarbonate resin Substances 0.000 claims description 2
- XKTHNXOWFFIVIF-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octahydro-1,3,5,7,9,2,4,6,8,10-pentazapentaphosphecine Chemical compound n1p[nH][pH][nH][pH][nH][pH][nH][pH]1 XKTHNXOWFFIVIF-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000001746 injection moulding Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 39
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 33
- 238000002844 melting Methods 0.000 description 25
- 230000008018 melting Effects 0.000 description 25
- 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 description 24
- 239000000155 melt Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 229920000578 graft copolymer Polymers 0.000 description 14
- 239000012994 photoredox catalyst Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005520 cutting process Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000008187 granular material Substances 0.000 description 12
- 238000004806 packaging method and process Methods 0.000 description 12
- 239000008188 pellet Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 phosphazenes Chemical class 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- AYBQEWUIMBWDHL-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N.COC(=O)C(C)=C AYBQEWUIMBWDHL-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- GGRIQDPLLHVRDU-UHFFFAOYSA-M potassium;2-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 GGRIQDPLLHVRDU-UHFFFAOYSA-M 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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 provides a halogen-free flame-retardant PC/ABS composition, which comprises polycarbonate, ABS resin, a halogen-free flame retardant, a toughening agent and an optional functional modification auxiliary agent, wherein the rubber phase glass transition temperature of the ABS resin is not higher than-90 ℃. The halogen-free flame-retardant PC/ABS composition provided by the invention improves the low-temperature impact property of the composition, is easy to obtain raw materials, and is beneficial to subsequent injection molding and other applications.
Description
Technical Field
The invention relates to a halogen-free flame-retardant PC/ABS composition, a preparation method and application thereof.
Background
Polycarbonates are high molecular polymers containing carbonate groups in the molecular chain, and are classified into various types, such as aliphatic, aromatic, aliphatic-aromatic, and the like, depending on the structure of the ester group. Among them, aromatic polycarbonates are excellent in mechanical properties and are widely used in the fields of glass assembly industry, automobile industry, electronic and electric appliance industry, and the like.
The ABS resin is one of five synthetic resins, is formed by ternary polymerization of acrylonitrile, butadiene and styrene, and has the comprehensive properties of high chemical stability, oil resistance and surface hardness of polyacrylonitrile, toughness and cold resistance of polybutadiene, good dielectric property, gloss, processability and the like of polystyrene. In addition, ABS resin is easy to coat and color, can be subjected to secondary processing such as surface metal spraying, electroplating, welding, hot pressing, bonding and the like, and is widely applied to the industrial fields of machinery, automobiles, electronic appliances, instruments, textile, buildings and the like.
The PC/ABS alloy is a mixture of polycarbonate and acrylonitrile-butadiene-styrene copolymer. Combines the excellent characteristics of the two materials (such as formability of ABS and mechanical property, impact strength, temperature resistance, ultraviolet resistance and the like of PC), improves the fluidity compared with PC, improves the processing performance, and reduces the sensitivity of products to stress, thereby being widely applied to the fields of automobiles, household appliances, electronics and electricity and the like. Among them, the demand for lightweight parts such as housings and panels in the fields of electronics and electrical requires that PC/ABS have flame retardancy and also have good mechanical properties when the parts are thin. In recent years, there has been an increasing demand for halogen-free flame retardant PC/ABS due to the requirements of environmental protection policies. Among them, phosphate flame retardants are most commonly used. However, the addition of phosphate flame retardants has a large effect on the properties of PC/ABS alloys, especially impact properties. This is a big hot spot for developing halogen-free flame retardant PCA/BS alloy. US 9018286B discloses a method of using phosphazene flame retardant instead of phosphate flame retardant and using special PC such as silicone-containing copolymerized PC to improve the impact property at-40 ℃, which is high in cost and raw materials are not easy to obtain. CN 109749392A discloses a preparation method of low-warpage high-flame-retardant low-temperature-resistant glass fiber reinforced PC/ABS, however, the impact strength of the PC/ABS is only 9kJ/m2 at the maximum at the temperature of-30 ℃. CN 102746631A reports that PC/ABS prepared by bulk ABS has better low-temperature impact property, the effect of adding a compatilizer styrene-maleic anhydride copolymer is better, and the influence of rubber types and flame retardants is not discussed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the halogen-free flame-retardant PC/ABS composition with improved low-temperature impact property, so as to improve the low-temperature impact property.
The invention provides a halogen-free flame-retardant PC/ABS composition, which comprises polycarbonate, ABS resin, a halogen-free flame retardant, a toughening agent and an optional functional modification auxiliary agent, wherein the rubber phase glass transition temperature of the ABS resin is not higher than-90 ℃.
According to some embodiments of the invention, the halogen-free flame retardant PC/ABS composition comprises, in parts by mass:
(a)50-99 parts of a polycarbonate;
(b)1-49 parts of an ABS resin;
(c)0.1-20 parts of a toughening agent;
(d)0.1-30 parts of halogen-free flame retardant; and optionally
(e)0.1-5 parts of functional modification auxiliary agent.
According to a preferred embodiment of the present invention, the halogen-free flame retardant PC/ABS composition comprises, in parts by mass:
(a)55-95 parts of polycarbonate;
(b)5-45 parts of ABS resin;
(c)0.2-10 parts of a toughening agent;
(d)0.5-20 parts of halogen-free flame retardant; and optionally
(e)0.2-3 parts of functional modification auxiliary agent.
According to some embodiments of the present invention, the polycarbonate resin is obtained by melt polycondensation of bisphenol a and diphenyl carbonate and/or by direct esterification polymerization of bisphenol a and phosgene.
According to some embodiments of the invention, the rubber content of the ABS resin is 8 wt% to 20 wt%.
According to some embodiments of the invention, the ABS resin is obtained by continuous bulk polymerization.
According to some embodiments of the invention, the toughening agent has a rubber phase glass transition temperature of no more than-70 ℃.
According to some embodiments of the invention, the rubber content of the toughening agent is from 40 wt% to 90 wt%.
According to some embodiments of the invention, the toughening agent is obtained by emulsion polymerization.
According to some embodiments of the invention, the toughening agent is selected from at least one of styrene-acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene-styrene, methyl methacrylate-butadiene, acrylonitrile-ethylene propylene copolymer-styrene, and acrylonitrile-styrene-butyl acrylate copolymer.
According to some embodiments of the invention, the halogen-free flame retardant is selected from at least one of phosphate flame retardants, phosphazene flame retardants, phosphine oxide flame retardants, and sulfonate flame retardants.
According to some embodiments of the present invention, the phosphate-based flame retardant is selected from at least one of triphenyl phosphate, bisphenol a bis (diphenyl phosphate), resorcinol (diphenyl phosphate), and resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ].
According to some embodiments of the invention, the phosphazene-based flame retardant is selected from at least one of hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene and decaepoxycyclopentaphosphazene.
According to some embodiments of the invention, the phosphine oxide based flame retardant is selected from at least one of monophenyl phosphine oxide, diphenyl phosphine oxide and triphenyl phosphine oxide.
According to some embodiments of the invention, the sulfonate-based flame retardant is selected from at least one of potassium perfluorobutane sulfonate and potassium benzenesulfonyl benzenesulfonate.
According to some embodiments of the invention, the functional modification aid is selected from at least one of anti-drip agents, antioxidants, light stabilizers and lubricants.
The second aspect of the invention provides a preparation method of the halogen-free flame retardant PC/ABS composition, which comprises the steps of mixing the polycarbonate, the ABS resin, the halogen-free flame retardant, the toughening agent and the optional functional modification auxiliary agent in a molten state, extruding and granulating to obtain the halogen-free flame retardant PC/ABS composition.
According to some embodiments of the invention, the halogen-free flame retardant PC/ABS composition is prepared by a melt blending process.
According to some embodiments of the invention, the melt blending process employs a twin screw continuous extrusion process.
According to some embodiments of the invention, the melt blending method comprises the steps of uniformly mixing the polycarbonate, the ABS resin, the halogen-free flame retardant, the toughening agent and the optional functional modification auxiliary agent according to a required proportion, and then carrying out continuous extrusion granulation to obtain the halogen-free flame retardant PC/ABS composition.
According to some embodiments of the invention, the melt blending method comprises the step of respectively metering the polycarbonate, the ABS resin, the halogen-free flame retardant, the toughening agent and the optional functional modification auxiliary agent into a double-screw extruder according to a certain feeding proportion for extrusion granulation, so as to obtain the halogen-free flame retardant PC/ABS composition.
According to some embodiments of the invention, in the melt blending process, the screw speed is from 50rpm to 1500 rpm.
According to some embodiments of the invention, the temperature in the melt blending process is from 160 ℃ to 260 ℃.
The third aspect of the invention provides an application of the halogen-free flame-retardant PC/ABS composition according to the first aspect or the halogen-free flame-retardant PC/ABS composition obtained by the preparation method according to the second aspect in flame-retardant materials for electric use.
The fourth aspect of the invention provides a preparation method of a halogen-free flame retardant PC/ABS material, which comprises the steps of melt extruding, cooling and orientation drafting the halogen-free flame retardant PC/ABS composition according to the first aspect or the halogen-free flame retardant PC/ABS composition obtained by the preparation method according to the second aspect to obtain the halogen-free flame retardant PC/ABS material.
The halogen-free flame-retardant PC/ABS composition provided by the invention improves the low-temperature impact property of the composition, is easy to obtain raw materials, and is beneficial to subsequent injection molding and other applications. The halogen-free flame-retardant PC/ABS composition can be used for preparing electronic and electrical parts and the like by injection molding.
Detailed Description
The materials and preparation methods used in the present invention are briefly described below:
1. polycarbonate (PC)
In the present invention, PC is a high molecular polymer containing carbonate groups in its molecular chain, and is generally obtained by melt polycondensation of bisphenol A and diphenyl carbonate or direct esterification of bisphenol A and phosgene.
ABS resin
The ABS resin in the invention is a graft copolymer of acrylonitrile, 1, 3-butadiene and styrene, and is generally a mixture of a graft copolymer containing butadiene and an acrylonitrile-styrene copolymer, wherein the acrylonitrile accounts for 15% -35%, the butadiene accounts for 5% -30% and the styrene accounts for 40% -60%. Commercial continuous bulk processes generally employ rubber dissolved in acrylonitrile, styrene and a small amount of solvent followed by copolymerization. The rubber can be butadiene rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene rubber, acrylate rubber, isoprene rubber, etc. or their mixture. Butadiene rubber is preferred.
3. Toughening agent
The toughening agent is a core-shell structure copolymer obtained by emulsion polymerization, and comprises at least one of styrene-acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene-styrene, methyl methacrylate-butadiene, acrylonitrile-ethylene propylene copolymer-styrene and acrylonitrile-styrene-butyl acrylate copolymer. The toughening agent is preferably at least one of styrene-acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene-styrene and methyl methacrylate-butadiene.
4. Flame retardant
The flame retardant of the present invention contains at least one of phosphoric esters, phosphazenes, phosphine oxides, and sulfonates. Wherein the phosphate ester comprises at least one of triphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol (diphenyl phosphate) and resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ]; the phosphazene comprises at least one of hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene and decacycloxycyclopentaphosphonitrile; the phosphine oxides include at least one of monophenyl phosphine oxide, diphenyl phosphine oxide and triphenyl phosphine oxide; the sulfonate comprises at least one of potassium perfluorobutylsulfonate and potassium benzenesulfonylbenzenesulfonate.
5. Functional modification auxiliary agent
The functional processing aid is at least one of an anti-dripping agent, an antioxidant, a lubricant and a light stabilizer. Wherein the anti-dripping agent comprises polytetrafluoroethylene coated by styrene-acrylonitrile copolymer, etc.; the antioxidant comprises hindered phenol compounds, phosphite compounds and the like and mixtures thereof; the light stabilizer includes benzotriazoles, benzophenones and the like; lubricants include mineral oil, wax, stearate, pentaerythritol stearate, silicone oil, and the like.
6. Method for preparing halogen-free flame-retardant PC/ABS composition
The method for preparing the halogen-free flame-retardant PC/ABS composition comprises the steps of uniformly mixing the required amount of PC, the required amount of ABS, the required amount of flame retardant, the required amount of toughening agent and the optional required amount of functional modification auxiliary agent in a molten state in a continuous process, and extruding and granulating. The continuous melting preparation method of the invention uniformly mixes the PC particles, the ABS particles, the flame retardant, the toughening agent and the functional modification auxiliary agent according to a certain proportion, and then adds the mixture into a feeding port of a double-screw extruder according to a certain feeding rate by using a feeding machine. The feeder can be a weight loss feeder or a volume feeder. And the other concrete embodiment is that a plurality of feeders are adopted to respectively meter the PC particles, the ABS particles, the flame retardant, the toughening agent and the functional modification auxiliary agent into a double-screw extruder according to a certain feeding proportion for reaction and extrusion, and extruded sample bars are cut into particles through a water tank or underwater to prepare the composition particles. The extrudate can also be air cooled by an anhydrous process and then pelletized.
Extrusion temperatures suitable for the present invention are preferably from 140 ℃ to those having low thermal decomposition temperatures for PC, ABS and flame retardants, tougheners, more preferably from 160 ℃ to 260 ℃. The rotation speed of the extruder is preferably 50rpm to 1200rpm, more preferably 100rpm to 800 rpm.
Melt blending devices suitable for use in the present invention include a variety of mixers, Farrel continuous mixers, Banbury mixers, single screw extruders, twin screw extruders, multiple screw extruders (more than two screws), reciprocating single screw extruders such as Buss Ko-kneaders (Buss Ko-kneaders), and the like. Preferred processes are continuous melt blending extrusion processes including twin screw extrusion processes. Continuous twin-screw extruders suitable for use in the present invention include twin-screw extruders of different designs, such as the ZSK Mc from Coperion, Germany18Co-rotating parallel twin screw extruders and the like.
The halogen-free flame-retardant PC/ABS composition can be used for preparing electronic and electrical parts and the like by injection molding.
The invention carries out performance measurement according to the following method:
melt index (MFR) determination method: measured according to ISO 1133 standard by using a Lloyd Davenport MFI-10/230 melt index meter, the cylinder temperature is 250 ℃, the weight load is 5.0kg, the diameter of a die is 2.095mm, the length is 8mm, the preheating time is 4min, samples are automatically cut at set time intervals, 5 times of averaging is carried out, and the measurement result is expressed by grams per 10 minutes (g/10 min).
Notched impact strength test: the measurement was carried out according to ISO 179/1eA using a model 6957 materials tester from CEAST.
Glass transition temperature test: a Q800 type dynamic thermal mechanical analyzer manufactured by TA company is adopted, the heating rate is 2.5 ℃/min, and the temperature scanning range is-120 ℃ to 150 ℃. The glass transition temperature is defined as the loss tangent peak position of the glass transition.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
[ example 1 ]
Weighing the following raw materials in proportion: 75 parts of PC (Mitsubishi product of Mitsubishi petrochemical industry, the melting index is 6g/10min), 8 parts of ABS (high-bridged petrochemical product, the melting index is 7g/10min, the glass transition temperature of a rubber phase is-91 ℃, and the mass percentage is 13 percent of the rubber content), 10 parts of a flame retardant (phosphate esters, Nippon Daba product), 3 parts of a toughening agent (styrene-butadiene-acrylonitrile graft copolymer, the rubber content is 65 percent, the glass transition temperature of the rubber phase is-90 ℃, Korea brocade lake product), 0.3 part of an anti-dripping agent and 0.8 part of an antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 17g/10min at 250 ℃ and 5.0 kg.
[ example 2 ] A method for producing a polycarbonate
Weighing the following raw materials in proportion: 76 parts of PC (Mitsubishi petrochemical, melting means 10g/10min), 13 parts of ABS (high-bridging petrochemical, melting means 7g/10min, rubber phase glass transition temperature of-91 ℃, and rubber content accounting for 13% by mass), 9 parts of flame retardant 1 (phosphate, Nippon Daba), 2 parts of flexibilizer (styrene-butadiene-acrylonitrile graft copolymer, rubber content of 65%, rubber phase glass transition temperature of-90 ℃, Korea brocade lake product), 0.3 part of anti-dripping agent and 0.8 part of antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 16g/10min at 250 ℃ and 5.0 kg.
[ example 3 ]
Weighing the following raw materials in proportion: 76 parts of PC (Mitsubishi petrochemical, melting index is 10g/10min), 13 parts of ABS (high-bridging petrochemical, melting index is 10g/10min, rubber phase glass transition temperature is-90 ℃, and the mass percentage is 10 percent of rubber content), 9 parts of flame retardant (phosphate esters, Nippon Daba), 2 parts of toughening agent (methyl methacrylate-butadiene-styrene graft copolymer, rubber content is 80 percent, rubber phase glass transition temperature is-74 ℃, Nippon Dayun), 0.3 part of anti-dripping agent and 0.8 part of antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 16g/10min at 250 ℃ and 5.0 kg.
[ example 4 ]
Weighing the following raw materials in proportion: 76 parts of PC (Mitsubishi petrochemical, melting index is 20g/10min), 13 parts of ABS (high-bridging petrochemical, melting index is 7g/10min, rubber phase glass transition temperature is-91 ℃, and the mass percentage is 13 percent of rubber content), 9 parts of flame retardant 1 (phosphate, Nippon Daba), 2 parts of flexibilizer (methyl methacrylate-butadiene-styrene graft copolymer, rubber content is 80 percent, rubber phase glass transition temperature is-74 ℃, Nippon Dayun), 0.3 part of anti-dripping agent and 0.8 part of antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 25g/10min at 250 ℃ and 5.0 kg.
[ example 5 ]
Weighing the following raw materials in proportion: 70 parts of PC (Mitsubishi petrochemical, melting means 10g/10min), 18 parts of ABS (high-bridging petrochemical, melting means 10g/10min, rubber phase glass transition temperature of-90 ℃, and rubber content accounting for 10% by mass), 10 parts of flame retardant 1 (phosphate, Nippon Daba), 2 parts of flexibilizer (methyl methacrylate-butadiene graft copolymer, rubber content of 80%, rubber phase glass transition temperature of-74 ℃, Nippon Daba), 0.3 part of anti-dripping agent and 0.8 part of antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 18g/10min at 250 ℃ and 5.0 kg.
[ example 6 ]
Weighing the following raw materials in proportion: 70 parts of PC (Mitsubishi product of Mitsubishi petrochemical industry, melting means 10g/10min), 18 parts of ABS (high petrochemical product, melting means 7g/10min, rubber phase glass transition temperature of-91 ℃, and rubber content accounting for 13% by mass), 10 parts of flame retardant 1 (phosphate ester, Nippon Daba product), 2 parts of flexibilizer (styrene-butadiene-acrylonitrile graft copolymer, rubber content of 65%, rubber phase glass transition temperature of-90 ℃, Korea brocade lake product), 0.3 part of anti-dripping agent and 0.8 part of antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 18g/10min at 250 ℃ and 5.0 kg.
[ example 7 ]
Weighing the following raw materials in proportion: 75 parts of PC (produced by SABIC, the melting index is 10g/10min), 8 parts of ABS (high-bridged petrochemical product, the melting index is 7g/10min, the glass transition temperature of a rubber phase is-91 ℃, and the mass percentage is 13 percent of the rubber content), 10.25 parts of a flame retardant (phosphate esters, produced by Daba Japan), 3 parts of a toughening agent (methyl methacrylate-butadiene graft copolymer, the rubber content is 80 percent, the glass transition temperature of the rubber phase is-74 ℃, produced by Dayun Japan), 0.3 part of an anti-dripping agent and 0.8 part of an antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 22g/10min at 250 ℃ and 5.0 kg.
[ example 8 ]
Weighing the following raw materials in proportion: 75 parts of PC (Mitsubishi product of China petrochemical industry, the melting index is 6g/10min), 8 parts of ABS (high petrochemical product, the melting index is 7g/10min, the glass transition temperature of a rubber phase is-91 ℃, and the mass percentage is 13 percent of the rubber content), 10 parts of a flame retardant (phosphate esters, Nippon Daba product), 3 parts of a toughening agent (methyl methacrylate-butadiene graft copolymer, the rubber content is 80 percent, the glass transition temperature of the rubber phase is-74 ℃, Nippon Dayun product), 0.3 part of an anti-dripping agent and 0.8 part of an antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 19g/10min at 250 ℃ and 5.0 kg.
[ example 9 ]
Weighing the following raw materials in proportion: 75 parts of PC (Mitsubishi product of Mitsubishi petrochemical industry, the melting index is 6g/10min), 8 parts of ABS (high-bridged petrochemical product, the melting index is 10g/10min, the glass transition temperature of a rubber phase is-90 ℃, the mass percentage is 10 percent of the rubber content), 10 parts of a flame retardant (phosphate esters, Nippon Daba product), 3 parts of a toughening agent (styrene-butadiene-acrylonitrile graft copolymer, the rubber content is 65 percent, the glass transition temperature of the rubber phase is-90 ℃, Korea brocade lake product), 0.3 part of an anti-dripping agent and 0.8 part of an antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 17.5g/10min at 250 ℃ and 5.0 kg.
Comparative example 1
Weighing the following raw materials in proportion: 70 parts of PC (Mitsubishi product of Mitsubishi petrochemical industry, melting means 10g/10min), 18 parts of ABS (high petrochemical product, melting means 18g/10min, rubber phase glass transition temperature of-88 ℃, and rubber content accounting for 13% by mass), 10 parts of flame retardant (phosphate esters, Nippon Daba product), 2 parts of toughening agent (styrene-butadiene-acrylonitrile graft copolymer, rubber content of 65%, rubber phase glass transition temperature of-90 ℃, Korea brocade lake product), 0.3 part of anti-dripping agent and 0.8 part of antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 20g/10min at 250 ℃ and 5.0 kg.
Comparative example 2
Weighing the following raw materials in proportion: 75 parts of PC (Mitsubishi product of China petrochemical industry, melting means 10g/10min), 8 parts of ABS (Nippon sumitomo product, melting means 40g/10min, rubber phase glass transition temperature of-82 ℃, and rubber content of 17% in percentage by mass), 10 parts of flame retardant (phosphate ester, Nippon Daba product), 3 parts of toughening agent (styrene-butadiene-acrylonitrile graft copolymer, rubber content of 65%, rubber phase glass transition temperature of-90 ℃, Korea brocade lake product), 0.3 part of anti-dripping agent and 0.8 part of antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 25.2g/10min at 250 ℃ and 5.0 kg.
Comparative example 3
Weighing the following raw materials in proportion: 75 parts of PC (Mitsubishi petrochemical, the melting index is 6g/10min), 8 parts of ABS (high-bridge petrochemical, the melting index is 7g/10min, the glass transition temperature of a rubber phase is-91 ℃, and the mass percentage is 13 percent of the rubber content), 10 parts of flame retardant (phosphate, Nippon Daba), 3 parts of toughening agent (methyl methacrylate-butadiene-acrylonitrile graft copolymer, the rubber content is 80 percent, the glass transition temperature of the rubber phase is-51 ℃, 0.3 part of anti-dripping agent and 0.8 part of antioxidant 1010. Feeding PC, ABS, a flame retardant, a toughening agent, an anti-dripping agent and an antioxidant 1010 into a double-screw extruder through different feeders, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 150rpm, the feeding speed is 6kg/h, and the temperature of each section of the extruder is 200-. Drying the prepared granules at 90 ℃ for 4h, and packaging for later use. The pellets had a melt index of 16.5g/10min at 250 ℃ and 5.0 kg.
[ test example 1 ]
The 8 blend particles of examples 1 to 7 and comparative examples 1 to 3 were injection-molded in an injection molding machine set at 240 ℃, 250 ℃, 255 ℃, 260 ℃ and 60 ℃ to prepare specimens of prescribed sizes for testing impact strength.
The above 10 compositions of examples 1 to 7 and comparative examples 1 to 3 were subjected to the impact strength test using test bars prepared in test example 1, and the results are shown in Table 1.
TABLE 1
As is apparent from the test results in Table 1, the low temperature impact strength of the composition using bulk ABS with a low glass transition temperature of the rubber phase is significantly increased by 78% compared with the composition using ABS with a glass transition temperature of the rubber phase higher than-90 ℃. Also, the molecular weight of PC affects the low temperature impact strength. According to the scheme of the invention, under the condition that other modifiers such as a compatilizer and the like are not added, the technical effect of further improving the low-temperature impact performance is obtained through the adjustment of rubber varieties.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A halogen-free flame-retardant PC/ABS composition comprises polycarbonate, ABS resin, a halogen-free flame retardant, a toughening agent and an optional functional modification auxiliary agent, wherein the rubber phase glass transition temperature of the ABS resin is not higher than-90 ℃.
2. The halogen-free flame retardant PC/ABS composition according to claim 1, wherein the halogen-free flame retardant PC/ABS composition comprises, in parts by mass:
(a)50-99 parts of a polycarbonate;
(b)1-49 parts of an ABS resin;
(c)0.1-20 parts of a toughening agent;
(d)0.1-30 parts of halogen-free flame retardant; and optionally
(e)0.1-5 parts of functional modification auxiliary agent.
3. The halogen-free flame retardant PC/ABS composition according to claim 1 or 2, wherein the polycarbonate resin is obtained by melt polycondensation of bisphenol A and diphenyl carbonate and/or by direct esterification polymerization of bisphenol A and phosgene.
4. The halogen-free flame retardant PC/ABS composition according to any of claims 1-3, wherein the rubber content of the ABS resin is 8-20 wt%; preferably, the ABS resin is obtained by continuous bulk polymerization.
5. The halogen free flame retardant PC/ABS composition according to any of claims 1-4, wherein the rubber phase glass transition temperature of the toughening agent is not higher than-70 ℃ and/or the rubber content of the toughening agent is 40-90 wt%; preferably, the first and second electrodes are formed of a metal,
the toughening agent is obtained by emulsion polymerization; more preferably, the toughening agent is selected from at least one of styrene-acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene-styrene, methyl methacrylate-butadiene, acrylonitrile-ethylene propylene copolymer-styrene, and acrylonitrile-styrene-butyl acrylate copolymer.
6. Halogen free flame retardant PC/ABS composition according to any of claims 1-5, wherein the halogen free flame retardant is selected from at least one of phosphate based flame retardants, phosphazene based flame retardants, phosphine oxide based flame retardants and sulfonate based flame retardants, preferably,
the phosphate flame retardant is at least one selected from triphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol (diphenyl phosphate) and resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ]; the phosphazene flame retardant is selected from at least one of hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene and decaepoxy cyclopentaphosphazene; the phosphine oxide flame retardant is selected from at least one of monophenyl phosphine oxide, diphenyl phosphine oxide and triphenyl phosphine oxide; the sulfonate flame retardant is at least one of potassium perfluorobutyl sulfonate and potassium benzenesulfonyl benzenesulfonate.
7. The halogen-free flame retardant PC/ABS composition according to any of claims 1-6, wherein the functional modification aid is selected from at least one of anti-dripping agents, antioxidants, light stabilizers and lubricants.
8. The preparation method of the halogen-free flame retardant PC/ABS composition according to any one of claims 1-7, which comprises mixing the polycarbonate, the ABS resin, the halogen-free flame retardant, the toughening agent and the optional functional modification auxiliary agent in a molten state, and performing extrusion granulation to obtain the halogen-free flame retardant PC/ABS composition.
9. Use of the halogen-free flame retardant PC/ABS composition according to any one of claims 1-7 or the halogen-free flame retardant PC/ABS composition obtained by the preparation method according to claim 8 in flame retardant materials for electrical applications.
10. A preparation method of a halogen-free flame retardant PC/ABS material, which comprises the steps of melt extruding, cooling and orientation drawing the halogen-free flame retardant PC/ABS composition according to any one of claims 1-7 or the halogen-free flame retardant PC/ABS composition obtained by the preparation method according to claim 8 to obtain the halogen-free flame retardant PC/ABS material.
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|---|---|---|---|---|
| CN117447828A (en) * | 2023-11-24 | 2024-01-26 | 东莞市国亨塑胶科技有限公司 | Light PC-ABS flame-retardant composite material and preparation method thereof |
| CN117447828B (en) * | 2023-11-24 | 2024-05-24 | 东莞市国亨塑胶科技有限公司 | Light PC-ABS flame-retardant composite material and preparation method thereof |
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