CN108129825B - high-CTI high-heat-resistance halogen-free flame-retardant PC/ABS composition and preparation method thereof - Google Patents
high-CTI high-heat-resistance halogen-free flame-retardant PC/ABS composition and preparation method thereof Download PDFInfo
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- CN108129825B CN108129825B CN201711468638.8A CN201711468638A CN108129825B CN 108129825 B CN108129825 B CN 108129825B CN 201711468638 A CN201711468638 A CN 201711468638A CN 108129825 B CN108129825 B CN 108129825B
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- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 229920007019 PC/ABS Polymers 0.000 title claims abstract description 50
- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 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 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 8
- 239000004417 polycarbonate Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 6
- 239000012745 toughening agent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 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 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 4
- 150000002367 halogens Chemical class 0.000 claims 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 4
- 230000005684 electric field Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010621 bar drawing Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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 high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition and a preparation method thereof, wherein the composition of the raw materials in parts by weight is as follows: 65-90 parts by weight of polycarbonate; 3-10 parts of ABS resin; 4-10 parts of self-made phosphorus-silicon polymer; 3-10 parts of modified porous material; 1-5 parts of a toughening agent; 0.1 to 0.3 weight portion of antioxidant; 0.3-0.7 part by weight of anti-dripping agent; 0.2 to 0.5 weight portion of lubricant. The invention overcomes the defects of low CTI value, large addition amount of phosphorus flame retardant, poor flame retardance and low thermal deformation temperature of the traditional halogen-free flame-retardant PC/ABS resin, and adopts a compound system of self-made phosphorus-silicon polymer and porous material to form a discontinuous reticular carbon layer structure under the action of an electric field and electrolyte, so that the resin has high CTI value and high thermal deformation temperature, the thermal deformation temperature of the PC/ABS composition prepared by the invention can reach 113 ℃, and the CTI value can reach 450V.
Description
Technical Field
The invention belongs to the technical field of alloy materials, relates to a halogen-free flame-retardant modified resin composition, and more particularly relates to a high-CTI high-heat-resistance halogen-free flame-retardant PC/ABS composition and a preparation method thereof.
Background
At present, PC/ABS alloy is widely applied to the fields of electronic appliances, automobile industry, office equipment, communication equipment, household appliances and the like. However, with the importance of safety, the requirements of electronic and electrical products on the heat resistance and CTI value of materials are higher and higher. The tracking resistance is the ability of the material surface to form a conductive path under the action of an electric field and electrolyte, and the CTI value is an important index for measuring the tracking resistance of the material. As the traditional halogen-free flame-retardant PC/ABS mostly adopts phosphate as a flame retardant, a continuous carbon layer is easily formed under the action of an electric field and electrolyte, the CTI value is low, and the halogen-free flame-retardant PC/ABS has the characteristics of large addition amount, low thermal deformation temperature and the like, is difficult to meet the requirements of electric leakage tracking resistance and heat resistance of electronic and electric products, and limits the application of the halogen-free flame-retardant PC/ABS in the aspects of electric switches, high-temperature relays, transformers and other products needing electric leakage tracking resistance and high-temperature resistance. Therefore, how to develop the halogen-free flame-retardant PC/ABS composition with high CTI and high heat resistance has important practical significance.
Patent 201510323598.2 discloses a flame retardant PC compound with high CTI and high light diffusivity, the CTI value of the resin composition is improved by adding polyethylene glycol, but the melting point of polyethylene glycol is low, the polyethylene glycol is easy to melt and block a feeding port during feeding, and the continuity and stability of production are poor; patent 201610495534.5 discloses a PC plastic alloy material and its preparation method, wherein the resin composition contains melamine cyanurate, which has poor heat resistance, easy decomposition during processing and poor processability.
Disclosure of Invention
The invention aims to overcome the defects of low CTI value, large addition amount of phosphorus flame retardant, poor flame retardance and low heat deformation temperature of halogen-free flame retardant PC/ABS resin in the prior art, and provides a high CTI and high heat-resistant halogen-free flame retardant PC/ABS composition.
The technical scheme adopted by the invention is as follows:
a high CTI, high heat-resistant halogen-free flame-retardant PC/ABS composition comprises the following raw materials in parts by weight:
further, the polycarbonate is melt produced by a transesterification method or a phosgene method, and is one or a mixture of more of 5g/10min, 10g/10min, 15g/10min, 20g/10min and 30g/10 min.
Further, the ABS resin is ABS resin with glue content of 10% -30%.
Further, the self-made phosphorus-silicon polymer is synthesized by phosphorus oxychloride, pentaerythritol and diphenyl dichlorosilane through a two-step method.
Further, the synthesis method of the self-made phosphorus-silicon polymer comprises the following steps:
(1) preparing an intermediate product: dissolving pentaerythritol in dioxane solvent, heating to 80 deg.C, and dissolving in N2Dropping phosphorus oxychloride with the molar ratio of pentaerythritol to phosphorus oxychloride being 1:1 in the atmosphere, heating to 100 ℃, reacting for 6 hours under mechanical stirring, then cooling to room temperature, separating out white solids, filtering, washing twice with dioxane and n-hexane respectively, and drying in vacuum for later use;
(2) preparing a phosphorus-silicon copolymer: adding the intermediate product and triethylamine into acetonitrile, heating to 60 ℃, and reacting under N2Dropwise adding diphenyldichlorosilane under the atmosphere, wherein the molar ratio of the intermediate product to the diphenyldichlorosilane is 2:1, heating to 70 ℃ for reaction for 2h, heating to 90 ℃ for reaction for 12h, cooling to room temperature, separating out white solid, filtering, washing twice with acetonitrile and ethanol respectively, and drying in vacuum to obtain the phosphorus-silicon copolymer.
The specific synthetic route is as follows:
the phosphorus-silicon polymer contains 11.97% of phosphorus and 5.4% of silicon, and during combustion, the phosphorus can generate phosphoric acid or polyphosphoric acid with strong dehydration property to promote the generation of a carbon layer, while the silicon can generate an oxygen-insulating and heat-insulating protective layer containing-Si-O-bond or-Si-C-bond to increase the thermal stability of the carbon layer, and the phosphorus-silicon polymer has a synergistic flame-retardant effect. Compared with a phosphate flame retardant, the flame retardant has the advantages that the flame retardant can be obviously reduced by reaching the same flame retardant grade, the phosphorus-silicon copolymer has a highly symmetrical chemical structure, and a molecular chain contains two benzene rings, so that the phosphorus-silicon copolymer has better thermal stability, and the heat resistance of the PC/ABS composition is obviously improved.
Further, the modified porous material is one or a mixture of two of silicon oxide and aluminosilicate, the surface of which is pretreated by an amino alkyl silane coupling agent. The modified porous material after surface pretreatment can improve the compatibility with the PC/ABS composition.
The porous material is subjected to surface pretreatment by the silane coupling agent, and because the silane coupling agent simultaneously has an organic functional group capable of being combined with a high-molecular polymer and a hydrophilic group capable of reacting with the surface of an inorganic substance, the compatibility of the porous material and a PC/ABS composition is improved, the porous material can be better dispersed in the PC/ABS composition, the risk of agglomeration of the porous material is reduced, the mechanical property is improved, and meanwhile, the uniform discontinuous reticular structure carbon layer is more favorably formed, and the CTI value of the composition is improved.
Further, the toughening agent is one or a mixture of a plurality of methyl methacrylate-butadiene-styrene copolymer, butyl acrylate-methyl methacrylate copolymer and organic silicon-acrylic acid-methyl methacrylate copolymer.
Furthermore, the antioxidant is one or a mixture of two of Irganox 1010, Irganox 1076, Irganox 1098 and Irganox 168.
Furthermore, the anti-dripping agent is one or the mixture of polytetrafluoroethylene raw powder or polytetrafluoroethylene coated by acrylonitrile-styrene copolymer (AS).
Further, the lubricant is one or a mixture of pentaerythritol stearate, PE wax and OP wax.
The preparation method of the halogen-free flame-retardant PC/ABS composition with high CTI and high heat resistance comprises the following steps:
(1) preparing a modified porous material: firstly, mixing an amino-hydrocarbon silane coupling agent and ethanol according to the mass ratio of 1:200 to prepare a solution, then mixing the solution and a porous material according to the mass ratio of 2:1, stirring for 10min by using a mechanical stirrer at 50 ℃, and then placing the mixture into a 100 ℃ oven to be dried for two hours for later use;
(2) mixing materials: weighing the self-made phosphorus-silicon polymer and the modified porous material according to a set proportion, stirring for 3-5 min at a high speed by a mixer, adding the polycarbonate, the ABS resin, the toughening agent, the antioxidant, the anti-dripping agent and the lubricant according to the proportion, and stirring by the high-speed mixer to uniformly mix the materials to obtain a mixed material;
(3) preparation of PC/ABS composition: and (3) putting the prepared mixed material into a screw extruder with a small screw barrel gap, fully melting and mixing under the conditions of shearing, conveying and mixing of double screws, extruding by a machine head, bracing, watering, granulating, drying and finally packaging to obtain a finished product.
The screw extruder is a double-screw extruder, the length-diameter ratio of a screw of the double-screw extruder is 40, the temperature of the front section is 200-fold, the interruption temperature is 250-fold, the extrusion temperature of a machine head is 240 ℃, and the rotating speed of the screw is 600 revolutions per minute.
The double-screw extruder selects the neck ring die with small aperture and less hole number, sets lower die head temperature (240 ℃), increases die head pressure, and reduces the risk of broken bars caused by adding PTFE in the bar-drawing process.
The invention has the beneficial effects that:
the self-made phosphorus-silicon polymer has the advantages that a carbon layer formed by the self-made phosphorus-silicon polymer is fluffy under the action of an electric field and an electrolyte, the porous material has holes due to the addition of the porous material, when the porous material is compounded with the silicon-phosphorus polymer, the generated carbon layer is uniformly dispersed around the porous material to form a discontinuous net structure, the probability of open fire in the electrolytic process is greatly reduced, a conductive path is difficult to form, the CTI value of the PC/ABS resin is greatly improved, meanwhile, the self-made phosphorus-silicon polymer simultaneously contains phosphorus element and silicon element, the flame retardant efficiency is high, the addition amount is low, the PC/ABS resin has high thermal deformation temperature, the defects of low CTI value, poor heat resistance and the like of the traditional halogen-free flame retardant PC/ABS resin are overcome, and the self-made phosphorus-silicon polymer has a wide application.
Detailed Description
The synthesis method of the self-made phosphorus-silicon polymer comprises the following steps:
(1) preparing an intermediate product: dissolving pentaerythritol in dioxane solvent, heating to 80 deg.C, and dissolving in N2Dropping phosphorus oxychloride with the molar ratio of pentaerythritol to phosphorus oxychloride being 1:1 in the atmosphere, heating to 100 ℃, reacting for 6 hours under mechanical stirring, then cooling to room temperature, separating out white solids, filtering, washing twice with dioxane and n-hexane respectively, and drying in vacuum for later use;
(2) preparing a phosphorus-silicon copolymer: adding the intermediate product and triethylamine into acetonitrile, heating to 60 ℃, and reacting under N2Dropwise adding diphenyldichlorosilane under the atmosphere, wherein the molar ratio of the intermediate product to the diphenyldichlorosilane is 2:1, heating to 70 ℃ for reaction for 2h, heating to 90 ℃ for reaction for 12h, cooling to room temperature, separating out white solid, filtering, washing twice with acetonitrile and ethanol respectively, and drying in vacuum to obtain the phosphorus-silicon copolymer.
The preparation method of the halogen-free flame-retardant PC/ABS composition with high CTI and high heat resistance comprises the following steps:
(1) preparing a modified porous material: firstly, mixing an amino-hydrocarbon silane coupling agent and ethanol according to the mass ratio of 1:200 to prepare a solution, then mixing the solution and a porous material according to the mass ratio of 2:1, stirring for 10min by using a mechanical stirrer at 50 ℃, and then placing the mixture into a 100 ℃ oven to be dried for two hours for later use;
(2) mixing materials: weighing the self-made phosphorus-silicon polymer and the modified porous material according to a set proportion, stirring for 3-5 min at a high speed by a mixer, adding the polycarbonate, the ABS resin, the toughening agent, the antioxidant, the anti-dripping agent and the lubricant according to the proportion, and stirring by the high-speed mixer to uniformly mix the materials to obtain a mixed material;
(3) preparation of PC/ABS composition: and (3) putting the prepared mixed material into a screw extruder with a small screw barrel gap, fully melting and mixing under the conditions of shearing, conveying and mixing of double screws, extruding by a machine head, bracing, watering, granulating, drying and finally packaging to obtain a finished product.
The screw extruder is a double-screw extruder, the length-diameter ratio of a screw of the double-screw extruder is 40, the temperature of the front section is 200-fold, the interruption temperature is 250-fold, the extrusion temperature of a machine head is 240 ℃, and the rotating speed of the screw is 600 revolutions per minute.
The double-screw extruder selects the neck ring die with small aperture and less hole number, sets lower die head temperature (240 ℃), increases die head pressure, and reduces the risk of broken bars caused by adding PTFE in the bar-drawing process.
The present invention will be described in detail with reference to specific examples.
The flame-retardant PC/ABS resins prepared in the examples and comparative examples were injection molded according to ASTM standards into various standard bars to test the mechanical properties and flame-retardant properties of the resins, and the physical properties and test methods are shown in Table 1.
TABLE 1
Example 1
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
example 2
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
example 3
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
example 4
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
example 5
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
comparative example 1
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
comparative example 2
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
comparative example 3
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
comparative example 4
The embodiment relates to a high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition, which comprises the following components in percentage by weight:
the physical properties of the flame retardant PC/ABS resins prepared in the respective examples and comparative examples are shown in Table 2.
TABLE 2
The results of the physical property tests of examples 1 to 5 and comparative examples 1 to 4 are shown in table 2, and the test results of examples 1 to 5 and comparative examples 1 to 4 show that the addition of the modified porous material can obviously improve the CTI value of the PC/ABS composition, and the CTI value of the PC/ABS composition increases with the increase of the content of the modified porous material, and when the modified porous material is compounded with the self-made phosphorus-silicon polymer, the CTI value is obviously improved, and the addition of the untreated porous material can also improve the CTI value of the composition, but the effect is not obvious, and the impact strength of the composition is seriously influenced; meanwhile, under the same experimental conditions and formula system, the flame retardant effect and CTI value of the self-made phosphorus-silicon polymer are higher than that of the BDP flame retardant. The prepared halogen-free flame-retardant PC/ABS composition has the CTI value of 450V and the thermal deformation temperature of 113 ℃. Has wide application prospect in electronic and electric products with high requirements on the heat resistance and the electrochemical resistance of the material.
The above description is not meant to be limiting, it being noted that: it will be apparent to those skilled in the art that various changes, modifications, additions and substitutions can be made without departing from the true scope of the invention, and these improvements and modifications should also be construed as within the scope of the invention.
Claims (10)
1. The halogen-free flame-retardant PC/ABS composition with high CTI and high heat resistance is characterized by comprising the following raw materials in parts by weight:
the self-made phosphorus-silicon polymer is synthesized by phosphorus oxychloride, pentaerythritol and diphenyldichlorosilane through a two-step method; the modified porous material is one or a mixture of silicon oxide and aluminosilicate.
2. The PC/ABS composition with high CTI, high heat resistance, halogen-free and flame retardant properties as claimed in claim 1, wherein the polycarbonate is one or a mixture of 5g/10min, 10g/10min, 15g/10min, 20g/10min and 30g/10min in melt index produced by transesterification or phosgene method.
3. The high CTI, high heat resistant, halogen free, flame retardant PC/ABS composition of claim 1, wherein the ABS resin is an ABS resin having a gum content of 10% -30%.
4. The high CTI, high heat-resistant, halogen-free, flame retardant PC/ABS composition of claim 1, wherein the two-step synthesis method of the self-made phosphorus silicon polymer comprises:
(1) preparing an intermediate product: dissolving pentaerythritol in dioxane solvent, heating to 80 deg.C, and dissolving in N2Dropping phosphorus oxychloride with the molar ratio of pentaerythritol to phosphorus oxychloride of 1:1 in the atmosphere, heating to 100 ℃, reacting under mechanical stirring, cooling to room temperature to precipitate white solid, filtering, washing twice with dioxane and n-hexane respectively,vacuum drying for later use;
(2) preparing a phosphorus-silicon copolymer: adding the intermediate product and triethylamine into acetonitrile, heating to 60 ℃, and reacting under N2Dropwise adding diphenyldichlorosilane under the atmosphere, wherein the molar ratio of the intermediate product to the diphenyldichlorosilane is 2:1, heating to 70 ℃ for reacting for a certain time, heating to 90 ℃ for reacting for a certain time, cooling to room temperature, separating out a white solid, filtering, washing twice with acetonitrile and ethanol respectively, and drying in vacuum to obtain the phosphorus-silicon copolymer.
5. The high CTI, high heat resistant, halogen free, flame retardant PC/ABS composition of claim 1 wherein the modified porous material is one or a mixture of two of silica or aluminosilicate surface pretreated with an amino silane coupling agent.
6. The high CTI, high heat resistant, halogen free, flame retardant PC/ABS composition of claim 1 wherein the toughening agent is one or a mixture of methyl methacrylate-butadiene-styrene copolymer, butyl acrylate-methyl methacrylate copolymer, silicone-acrylic acid-methyl methacrylate copolymer.
7. The PC/ABS composition as claimed in claim 1, wherein the antioxidant is one or a mixture of Irganox 1010, Irganox 1076, Irganox 1098, and Irganox 168.
8. The high CTI, high heat resistant, halogen free, flame retardant PC/ABS composition of claim 1, wherein the anti-dripping agent is one or a mixture of polytetrafluoroethylene raw powder or acrylonitrile-styrene copolymer coated polytetrafluoroethylene.
9. The PC/ABS composition as claimed in claim 1, wherein the lubricant is one or a mixture of pentaerythritol stearate, PE wax and OP wax.
10. The preparation method of the high CTI, high heat-resistant, halogen-free and flame-retardant PC/ABS composition according to claim 1, which is characterized by comprising the following steps:
(1) preparing a modified porous material: firstly, mixing an amino-hydrocarbyl silane coupling agent and ethanol according to the mass ratio of 1:200 to prepare a solution, then mixing the solution and a porous material according to the mass ratio of 2:1, stirring for a plurality of minutes by using a mechanical stirrer at 50 ℃, and then putting the mixture into an oven to be dried for later use;
(2) mixing materials: firstly, weighing the self-made phosphorus-silicon polymer and the modified porous material according to a set proportion, stirring at a high speed by a mixer, adding the polycarbonate, the ABS resin, the toughening agent, the antioxidant, the anti-dripping agent and the lubricant according to the proportion, and stirring by the high-speed mixer to uniformly mix the materials to obtain a mixed material;
(3) preparation of PC/ABS composition: and (3) putting the prepared mixed material into a screw extruder with a small screw barrel gap, fully melting and mixing under the conditions of shearing, conveying and mixing of double screws, extruding by a machine head, bracing, watering, granulating, drying and finally packaging to obtain a finished product.
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| CN112341694A (en) * | 2020-11-24 | 2021-02-09 | 杭州富通通信技术股份有限公司 | Tracking-resistant optical cable and preparation method thereof |
| CN115819945A (en) * | 2022-11-30 | 2023-03-21 | 中广核俊尔(浙江)新材料有限公司 | Flame-retardant PC plastic with high CTI (comparative tracking index) and high ultrasonic welding strength and preparation method thereof |
| CN118530641B (en) * | 2024-07-25 | 2024-11-22 | 安徽神舟飞船胶业有限公司 | A method for preparing modified polyacrylic acid fire retardant coating |
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| CN102070886A (en) * | 2010-12-29 | 2011-05-25 | 上海日之升新技术发展有限公司 | PBT (polybutylene terephthalate)/PC (polycarbonate) alloy material with high CTI (comparative tracking index) value and high flame retardance and preparation method thereof |
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