CN110643165A - High-performance ultraviolet-resistant environment-friendly flame-retardant PC/ABS composite material and preparation method thereof - Google Patents
High-performance ultraviolet-resistant environment-friendly flame-retardant PC/ABS composite material and preparation method thereof Download PDFInfo
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- CN110643165A CN110643165A CN201910983523.5A CN201910983523A CN110643165A CN 110643165 A CN110643165 A CN 110643165A CN 201910983523 A CN201910983523 A CN 201910983523A CN 110643165 A CN110643165 A CN 110643165A
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 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 74
- 239000003063 flame retardant Substances 0.000 title claims abstract description 74
- 229920007019 PC/ABS Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title description 13
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 39
- 239000004417 polycarbonate Substances 0.000 claims abstract description 39
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 29
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 19
- 239000006096 absorbing agent Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 19
- 239000012745 toughening agent Substances 0.000 claims description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 13
- 239000002250 absorbent Substances 0.000 claims description 9
- 230000002745 absorbent Effects 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 8
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 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 7
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 239000011145 styrene acrylonitrile resin Substances 0.000 claims description 5
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 3
- 238000005034 decoration Methods 0.000 abstract description 7
- 230000006750 UV protection Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 4
- 238000004383 yellowing Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 15
- 239000000779 smoke Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
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- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- -1 pentaerythritol ester Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
-
- 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
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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 belongs to the technical field of composite materials, and particularly relates to a PC/ABS composite material, which comprises the following raw material components in percentage by mass based on 100% of the total mass of the PC/ABS composite material: 20-80% of polycarbonate, 10-60% of acrylonitrile-butadiene-styrene graft copolymer, 2-11% of compatilizer, 2-10% of flexibilizer, 1-10% of compound efficient flame retardant, 0.3-1% of antioxidant and 0.3-2% of light absorber. The PC/ABS composite material improves the ultraviolet resistance of the PC/ABS composite material through the action of each component, overcomes the defect of quick yellowing of the PC/ABS composite material, simultaneously ensures that a PC/ABS composite material product has good mechanical property and low divergence, and meets the requirements of national standard interior decoration flame retardance of new-edition commercial vehicles (JT/T1095-2016) and the like.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a high-performance, anti-ultraviolet, environment-friendly and flame-retardant PC/ABS composite material and a preparation method thereof.
Background
Polycarbonate (PC) has many advantages such as high heat resistance, high transparency, excellent mechanical properties, and good flame retardancy, and is widely used in automobile materials and other industries, but it also has significant disadvantages such as: the sensitivity to the notch is higher, the stress cracking phenomenon is easier to occur, and the viscosity is higher, so that the processing is not facilitated. In order to better utilize the advantages of the alloy and effectively improve the disadvantages of the alloy, the alloy material prepared by blending and modifying the alloy material with other resins is found to be easier to realize. For example, PC/ABS alloy material prepared by blending PC and acrylonitrile-butadiene-styrene graft copolymer (ABS) can effectively improve the defects of notch sensitivity and high viscosity, and the PC/ABS alloy has low viscosity, easy processing and good toughness and is widely applied to automobiles and other industries.
However, due to the action of butadiene double bonds in the ABS, the double bonds of the ABS in the PC/ABS alloy material are easily broken under the irradiation of ultraviolet rays, the molecular weight is reduced, yellowing is caused, and the ultraviolet resistance is poor. In addition, with the issuance of the national standard interior decoration flame retardant requirement JT/T1095-2016 for new-edition commercial vehicles, the flame retardant requirement for the interior decoration material of the common commercial vehicles reaches a new step, and the requirements of smoke density and oxygen index are increased compared with the flame retardant requirement of the old edition. Specifically, the method comprises the following steps: the horizontal combustion in a combustion test project required by the flame retardance of the interior trim of the old-version commercial vehicle is less than or equal to 100mm/min, and vertical combustion, oxygen index, smoke density grade and the like are not involved to the index requirements; in a combustion test project of the special school bus flame retardant requirement (GB 24407), the horizontal combustion is less than or equal to 70mm/min, the oxygen index is greater than or equal to 22%, and the smoke density grade is less than or equal to 75. The national standard interior decoration flame retardant requirement of the new version of commercial vehicle requires JT/T1095-2016, and in the combustion test project, the horizontal combustion is less than or equal to 50mm/min, the vertical combustion is less than or equal to 100mm/min, the oxygen index is more than or equal to 24%, and the smoke density grade is less than or equal to 70. Also, when a fire occurs, a large amount of toxic gas is a cause of secondary damage. Meanwhile, with the enhancement of environmental awareness, the quality of air in the passenger car is also the focus of attention of people, and particularly, the emission requirement of interior trim materials which are in close contact with drivers is higher and higher.
Disclosure of Invention
The invention aims to provide a PC/ABS composite material, aiming at solving the problem that the existing PC/ABS composite material can not meet the following requirements at the same time: ultraviolet resistance and discoloration resistance, meets the national standard requirement of flame retardance of the new-edition commercial vehicle, and has the technical problems of environmental protection, high performance and the like.
The invention also aims to provide a preparation method of the PC/ABS composite material.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the PC/ABS composite material comprises the following raw material components in percentage by mass based on 100% of the total mass of the PC/ABS composite material:
preferably, the polycarbonate is selected from: bisphenol a type aromatic polycarbonate; and/or the presence of a gas in the gas,
the weight average molecular weight of the polycarbonate is 20000-35000.
Preferably, the acrylonitrile-butadiene-styrene graft copolymer is selected from: at least one resin synthesized by a continuous bulk method, emulsion rubber, graft-bulk styrene acrylonitrile resin blending method.
Preferably, the compound efficient flame retardant is a mixed flame retardant of magnesium hydroxide, zinc borate and an organic phosphorus flame retardant.
Preferably, the mass ratio of the magnesium hydroxide, the zinc borate and the organic phosphorus flame retardant in the compound efficient flame retardant is (2-6): (3-7): (1-5).
Preferably, the antioxidant is selected from hindered phenolic and/or phosphate antioxidants; and/or the presence of a gas in the gas,
the light absorber is selected from benzotriazole light absorbers; and/or the presence of a gas in the gas,
the organophosphorus flame retardant comprises: ammonium polyphosphate and bisphenol a-bis (diphenyl phosphate).
Preferably, the antioxidant is selected from: antioxidant 619F and/or antioxidant 1010; and/or the presence of a gas in the gas,
the light absorber is selected from UV 5411.
Preferably, the compatibilizer is selected from styrene-N-phenylmaleimide-maleic anhydride copolymers; and/or the presence of a gas in the gas,
the toughening agent is selected from methyl methacrylate/butadiene/styrene copolymer.
The preparation method of the PC/ABS composite material comprises the following steps:
obtaining polycarbonate, acrylonitrile-butadiene-styrene graft copolymer, compatilizer, toughening agent, compound efficient flame retardant, antioxidant and light absorbent in formula amount;
mixing the polycarbonate, the acrylonitrile-butadiene-styrene graft copolymer, the compatilizer, the toughening agent, the compound efficient flame retardant, the antioxidant and the light absorbent, and then extruding and granulating the mixture by a double-screw extruder; wherein the working temperature in the double-screw extruder is 200-250 ℃, and the rotating speed of the double screws is 250-350 r/min.
Preferably, the working temperature of a main machine cylinder of the double-screw extruder from a feeding port to a machine head outlet is controlled in nine sections of 200-220 ℃, 225-235 ℃, 235-250 ℃ and 225-235 ℃.
The PC/ABS composite material provided by the invention comprises 20-80% of polycarbonate, 10-60% of acrylonitrile-butadiene-styrene graft copolymer, 2-11% of compatilizer, 2-10% of toughening agent, 1-10% of compound high-efficiency flame retardant, 0.3-1% of antioxidant and 0.3-2% of light absorbent, improves the ultraviolet resistance of the PC/ABS composite material through the action of each component, overcomes the defect of quick yellowing of the PC/ABS composite material, simultaneously ensures that a PC/ABS composite material product has good mechanical property and low divergence, meets the advantages of the national standard interior decoration flame retardant requirement (JT/T1095-2016) of a new edition of commercial vehicle and the like, wherein the limit oxygen index is more than or equal to 24%, the smoke density level SDR is less than or equal to 70, the total carbon content is less than 50 mu gC/g, the flame retardant property is high, the environment is protected, and the flame retardant can be directly applied to manufacturing automobile interior parts such as automobile instrument boards, air conditioner panels and the like.
According to the preparation method of the PC/ABS composite material, the raw material components with the formula amount are mixed, and the mixture is extruded and granulated by a double-screw extruder under the conditions that the working temperature is 200-250 ℃ and the double-screw rotating speed is 250-350 r/min to prepare the PC/ABS composite material.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a PC/ABS composite material, which comprises the following raw material components in percentage by mass based on 100% of the total mass of the PC/ABS composite material:
the PC/ABS composite material provided by the embodiment of the invention comprises 20-80% of polycarbonate, 10-60% of acrylonitrile-butadiene-styrene graft copolymer, 2-11% of compatilizer, 2-10% of toughening agent, 1-10% of compound efficient flame retardant, 0.3-1% of antioxidant and 0.3-2% of light absorbent, improves the ultraviolet resistance of the PC/ABS composite material through the combined action of the components, overcomes the defect of quick yellowing of the PC/ABS composite material, simultaneously enables a PC/ABS composite material product to have good mechanical property and low divergence, meets the requirements of national standard interior decoration flame retardance of new edition commercial vehicles (JT/T1095-2016) and the like, wherein the limiting oxygen index is more than or equal to 24%, the smoke density grade is less than or equal to 70, the total carbon content is less than 50 mu gC/g, the flame retardant property is high, the environment is protected, and the flame retardant can be directly applied to manufacturing automobile interior parts such as automobile instrument boards, air conditioner panels and the like.
In a further embodiment, the polycarbonate is selected from the group consisting of: bisphenol A type aromatic polycarbonate. The bisphenol A type aromatic polycarbonate adopted in the embodiment of the invention has aromatic main chains, mainly contains bisphenol A polycarbonate phenol, has stronger impact resistance, and has the characteristics of good stability, stable size, good heat resistance, low water absorption, no toxicity, excellent dielectric property and the like.
In a further embodiment, the weight average molecular weight of the polycarbonate is 20000-35000. The embodiment of the invention adopts the polycarbonate with the weight-average molecular weight of 20000-35000, the thermal stability of the composite material is influenced by the molecular weight of the polycarbonate, the breaking temperature is determined by the molecular weight of the PC, and the higher the molecular weight is, the higher the breaking temperature of the main chain is; the broader the molecular weight distribution, the higher the small molecular weight content, and the greater the unstable terminal group content, the lower the PC initial decomposition temperature. The polycarbonate with the weight-average molecular weight of 20000-35000 in the embodiment of the invention has the best decomposition temperature, is beneficial to processing and application, and simultaneously ensures the mechanical properties and the like of the composite material.
In some embodiments, the polycarbonate is selected from: a bisphenol A type aromatic polycarbonate having a weight average molecular weight of 20000-35000.
In a further embodiment, the acrylonitrile-butadiene-styrene graft copolymer is selected from the group consisting of: at least one resin synthesized by a continuous bulk method, emulsion rubber, graft-bulk styrene acrylonitrile resin blending method. According to the embodiment of the invention, at least one of the resins synthesized by adopting a continuous bulk method, emulsion rubber and a graft-bulk styrene acrylonitrile resin blending method, namely acrylonitrile-butadiene-styrene graft copolymer (ABS), improves the heat resistance, impact resistance and tensile strength of the ABS on the one hand and reduces the cost and melt viscosity of PC on the other hand through the mutual doping and coaction of the polycarbonate and the ABS, so that the PC/ABS composite material has good mechanical and other physical and chemical properties and good processability.
In a further embodiment, the compound efficient flame retardant is a mixed flame retardant of magnesium hydroxide, zinc borate and an organic phosphorus flame retardant. The mixed flame retardant of magnesium hydroxide, zinc borate and organic phosphorus flame retardant adopted by the embodiment of the invention is a novel filling type flame retardant, and the magnesium hydroxide releases bound water when being heated and decomposed, absorbs a large amount of latent heat, so as to reduce the surface temperature of a synthetic material filled with the magnesium hydroxide in flame, and has the effects of inhibiting the decomposition of a polymer and cooling generated combustible gas. The zinc borate is an environment-friendly non-halogen flame retardant, has the characteristics of no toxicity, low water solubility, high thermal stability, small granularity, small specific gravity, good dispersibility and the like, can effectively improve the flame retardant property and reduce the generation of smoke during combustion as a multifunctional synergistic additive, and can adjust the chemical, mechanical, electrical and other properties of rubber and plastic products. The organic phosphorus flame retardant has double functions of flame retarding and plasticizing, can replace halogenated flame retardants, has the functions of flame retarding, heat insulation and oxygen isolation, generates less smoke and is not easy to form toxic gas and corrosive gas. According to the embodiment of the invention, the composite material has good flame retardant performance through the mixed flame retardant of magnesium hydroxide, zinc borate and organic phosphorus flame retardant, and meets the national standard interior decoration flame retardant requirement (JT/T1095-2016) of a new-edition commercial vehicle, wherein the limited oxygen index is more than or equal to 24 percent, the smoke density level SDR is less than or equal to 70, and the total carbon content is less than 50 mu gC/g, so that the composite material not only has good flame retardant performance, but also is environment-friendly.
In a further embodiment, the mass ratio of the magnesium hydroxide, the zinc borate and the organic phosphorus flame retardant in the compound efficient flame retardant is (2-6): (3-7): (1-5). The embodiment of the invention adopts the following components in mass ratio (2-6): (3-7): and (1) the compound flame retardant formed by mixing the magnesium hydroxide, the zinc borate and the organic phosphorus flame retardant has the optimal flame retardant performances of limited oxygen index, smoke density grade, total carbon and the like through the interaction among the components, and simultaneously the mechanical performance of the composite material is effectively improved.
In a further embodiment, the organophosphorus flame retardant comprises: ammonium polyphosphate and bisphenol A-bis (diphenyl phosphate), in particular to an organic phosphorus flame retardant which is prepared by compounding and granulating the ammonium polyphosphate and the bisphenol A-bis (diphenyl phosphate). Wherein, the bisphenol A-bis (diphenyl phosphate) (BDP) is a halogen-free environment-friendly organic phosphorus flame retardant, and has the characteristics of large molecular weight, strong thermal stability, lower volatility, high-efficiency flame retardant performance and the like; the ammonium polyphosphate is nontoxic and tasteless, does not generate corrosive gas, has small hygroscopicity and high thermal stability, is a non-halogen flame retardant with excellent performance, has high flame retardance, dimensional stability, hydrolysis resistance and heat resistance, and has an expansion flame-retardant function, thereby being beneficial to smoke reduction and dripping resistance. The embodiment of the invention adopts the organic phosphorus flame retardant prepared by compounding and granulating ammonium polyphosphate and bisphenol A-bis (diphenyl phosphate), which not only can effectively improve the flame retardant effect of the compounded efficient flame retardant, but also can reduce the smoke density grade, so that the composite material is more environment-friendly.
In a further embodiment, the antioxidant is selected from hindered phenolic and/or phosphate antioxidants. In some embodiments, the antioxidant is selected from: antioxidant 619F and/or antioxidant 1010, wherein the antioxidant 619F (dioctadecyl pentaerythritol diphosphite) is a phosphate antioxidant, so that the composite material has excellent color stability during processing, finished product preparation and use, and polymer degradation during processing is prevented; the polymer fading is reduced, and the polymer and the benzotriazole light stabilizer can play a role in synergism. Wherein, the antioxidant 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester) is a phosphate antioxidant, is a hindered phenol antioxidant with high molecular weight, has low volatility, is not easy to migrate, is extraction resistant, has high thermal stability, long lasting effect, no coloring, no pollution and no toxicity, can effectively prevent the thermal oxidative degradation of the polymer material in the long-term aging process, is also an efficient processing stabilizer, and can improve the discoloration resistance of the polymer material under the high-temperature processing condition.
In a further embodiment, the light absorber is selected from benzotriazole-based light absorbers. In some embodiments, the light absorber is selected from UV 5411. The UV 5411 adopted by the embodiment of the invention is a hydroxyphenyl benzotriazole ultraviolet absorbent, so that the composite material has obvious ultraviolet absorption performance, is a high-efficiency light stabilizer and can effectively overcome the defect that the PC/ABS composite material is easy to yellow under the irradiation of ultraviolet light. And the composite material is combined with antioxidants such as hindered phenols and the like, so that the composite material has an obvious composite synergistic effect, and the stability, the discoloration resistance, the service life and the like of the composite material are better improved.
In some embodiments, the antioxidant is selected from hindered phenolic 619F and/or phosphate ester antioxidant 1010; the light absorber is selected from a benzotriazole light absorber UV 5411.
In a further embodiment, the compatibilizing agent is selected from styrene-N-phenylmaleimide-maleic anhydride copolymers. The styrene-N-phenylmaleimide-maleic anhydride copolymer compatilizer adopted in the embodiment of the invention can obviously improve the compatibility among materials such as PC, ABS, antioxidant, flame retardant and the like, and the N-phenylmaleimide in the compatilizer can effectively improve the glass transition temperature of ABS, so that the heat resistance and the processability of the PC/ABS composite material are effectively improved.
In a further embodiment, the toughening agent is selected from methyl methacrylate/butadiene/styrene copolymers. The embodiment of the invention adopts methyl methacrylate/butadiene/styrene copolymer (MBS) as a toughening agent, has a typical core-shell structure, can effectively improve the impact strength of a PC/ABS composite material product, and simultaneously improves the cold resistance and the processing fluidity of the composite material product.
In some embodiments, the compatibilizing agent is selected from styrene-N-phenylmaleimide-maleic anhydride copolymers; the toughening agent is selected from methyl methacrylate/butadiene/styrene copolymer.
The PC/ABS composite material provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, the embodiment of the invention also provides a preparation method of the PC/ABS composite material, which comprises the following steps:
s10, obtaining polycarbonate, acrylonitrile-butadiene-styrene graft copolymer, compatilizer, toughening agent, compound efficient flame retardant, antioxidant and light absorbent in formula amount;
s20, mixing the polycarbonate, the acrylonitrile-butadiene-styrene graft copolymer, the compatilizer, the toughening agent, the compounded efficient flame retardant, the antioxidant and the light absorbent, and then extruding and granulating the mixture by a double-screw extruder; wherein the working temperature in the double-screw extruder is 200-250 ℃, and the rotating speed of the double screws is 250-350 r/min.
According to the preparation method of the PC/ABS composite material provided by the embodiment of the invention, the raw material components with the formula amount are mixed, and then the mixture is extruded and granulated by a double-screw extruder under the conditions that the working temperature is 200-250 ℃ and the double-screw rotating speed is 250-350 r/min, so that the PC/ABS composite material can be prepared.
Specifically, in the step S10, the polycarbonate, the acrylonitrile-butadiene-styrene graft copolymer, the compatibilizer, the toughening agent, the compounded efficient flame retardant, the antioxidant and the light absorber are obtained according to the formula amounts. According to the preparation method of the PC/ABS composite material provided by the embodiment of the invention, the raw materials comprise, by taking the total mass of the PC/ABS composite material as 100%, 20-80% of polycarbonate, 10-60% of acrylonitrile-butadiene-styrene graft copolymer, 2-11% of compatilizer, 2-10% of toughening agent, 1-10% of compound efficient flame retardant, 0.3-1% of antioxidant and 0.3-2% of light absorber.
In some embodiments, the polycarbonate is selected from the group consisting of: a bisphenol A type aromatic polycarbonate having a weight average molecular weight of 20000-35000.
In some embodiments, the acrylonitrile-butadiene-styrene graft copolymer is selected from the group consisting of: a resin synthesized by at least one of a continuous bulk method, an emulsion rubber or a graft-bulk styrene acrylonitrile resin blending method.
In some specific embodiments, the compound efficient flame retardant is prepared from the following components in percentage by mass (2-6): (3-7): (1-5) mixing magnesium hydroxide, zinc borate and an organic phosphorus flame retardant to prepare the compound flame retardant.
In some embodiments, the antioxidant is selected from: antioxidant 619F and/or antioxidant 1010.
In some embodiments, the light absorber is selected from UV 5411.
In some embodiments, the compatibilizing agent is selected from styrene-N-phenylmaleimide-maleic anhydride copolymers.
In some embodiments, the toughening agent is selected from methyl methacrylate/butadiene/styrene copolymers.
Specifically, in the step S20, the polycarbonate, the acrylonitrile-butadiene-styrene graft copolymer, the compatibilizer, the toughening agent, the compounded high-efficiency flame retardant, the antioxidant and the light absorber are mixed and then extruded by a twin-screw extruder for granulation; wherein the working temperature in the double-screw extruder is 200-250 ℃, and the rotating speed of the double screws is 250-350 r/min. In a further embodiment, the working temperature of the main barrel of the double-screw extruder from the feeding port to the outlet of the machine head is controlled in nine sections of 200-220 ℃, 225-235 ℃, 235-250 ℃ and 225-235 ℃, and the temperature of the main barrel of the double-screw extruder is controlled in sections, so that all raw material components are uniformly heated at all positions and stages in the barrel, and all raw material components are uniformly mixed. In some embodiments, the working temperature in the main barrel of the twin-screw extruder is controlled in nine stages of 200 ℃, 230 ℃, 235 ℃ and 230 ℃ from the feeding port to the outlet of the head.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the progress of the PC/ABS composite material and the preparation method thereof remarkably obvious, the above technical solution is illustrated by a plurality of examples below.
The embodiment of the invention uses the following raw materials:
polycarbonate PC: bisphenol A resin type resin with molecular weight of 25000-35000, Sanxingdian Korea;
acrylonitrile-butadiene-styrene graft copolymer ABS: resin synthesized by a continuous bulk method, China petrochemical Shanghai high bridge division.
A compatilizer: styrene-N-phenylmaleimide-maleic anhydride copolymer (SMI): japanese Electrochem, MS-NA.
A toughening agent: methyl methacrylate/butadiene/styrene copolymer (MBS), commercially available.
Antioxidant 1010: hindered phenol antioxidants, commercially available.
Antioxidant 619F: phosphate antioxidants, commercially available.
Light absorber UV 5411: benzotriazole-based light absorbers, Cytec, USA.
Magnesium hydroxide: technical grade, commercially available.
Zinc borate: anhydrous zinc borate, technical grade, commercially available.
Organic phosphorus flame retardant: ammonium polyphosphate APP and bisphenol A-bis (diphenyl phosphate) BDP are compounded and granulated, and are sold in the market.
The preparation method of the PC/ABS composite material comprises the following steps:
uniformly mixing the dried PC, ABS, SMI, MBS, compound flame retardant and antioxidant according to the formula amount, passing the mixture through a double-screw extruder (the diameter of a screw is 35mm, and the length-diameter ratio L/D is 36) in a main machine cylinder, controlling the temperature (from a feed inlet to a machine head outlet) of the main machine cylinder to be 200 ℃, 230 ℃, 235 ℃, 230 ℃ and 300 revolutions per minute, cooling an extruded material strip through a water tank, and then pelletizing the cooled extruded material strip to obtain the PC/ABS composite material.
The preparation method of the PC/ABS composite material plastic product comprises the following steps:
and drying the PC/ABS composite material in a blast oven at 95 ℃ for 5 hours, then using a plastic injection molding machine to injection mold the PC/ABS composite material into a standard sample strip and a standard light plate (150 x 100 x 3.2mm), placing the injection molded sample strip and the injection molded light plate into a glass drier at the injection temperature of 240 ℃ and standing at room temperature for at least 24 hours to obtain the PC/ABS composite material plastic product.
Examples 1 to 8
The PC/ABS composite material and the rate product thereof provided by the embodiments 1-8 of the invention are prepared by the method, and the component ratios of the raw materials are shown in the following tables 1 and 2:
comparative examples 1 to 2
The PC/ABS composite material and the rate product thereof provided by the comparative examples 1-2 of the invention are prepared by the method, and the component ratios of the raw materials are shown in the following tables 1 and 2:
TABLE 1
The formula components of the compound flame retardant 1-4 are shown in the following table 2:
TABLE 2
Further, in order to verify the advancement of the PC/ABS composite material prepared by the embodiment of the present invention, the embodiment of the present invention performs a performance test on a plastic product of the PC/ABS composite material.
The performance test method comprises the following steps:
charpy notched impact strength: according to ISO 179-1 method, the specification of the test specimen is as follows: 80 x 10 x 4 mm.
Accelerated aging of a xenon lamp: energy value according to SAE J2412 standard: 600KJ/m2And measuring the color difference delta E value.
Limiting oxygen index LOI: test specimens with a thickness of 4mm were tested according to the GB/T2406.2 standard.
Smoke density rating SDR: test according to GB/T8627 standard, 25X 3.2mm sample, propane gas, gas pressure 276 kPa.
Total carbon VOC test: according to VDA 277: the test value is less than or equal to 50 mu gC/g, and the product is qualified.
The test results are shown in table 3 below:
TABLE 3
From the test results of the examples 1-4 and the comparative example 1, the plastic product made of the PC/ABS composite material added with the compound flame retardant 3 has good mechanical properties, can meet the requirements of the smoke density and the oxygen index of a new national standard, and has a total carbon content of less than 50 mu gC/g and reaches 17.8.
From the test results of the examples 5-8 and the comparative example 2, the PC/ABS composite material prepared by adding the compound flame retardant 3 obtains ideal notch impact, the limited oxygen index and the smoke density level can also meet the requirements of new national standards, and the total carbon content meets the requirements of less than 50 mu gC/g and is below 25 mu gC/g, which shows that the PC/ABS composite material provided by the embodiment of the invention has excellent mechanical properties, excellent weather resistance and meets the strict requirements of new national standards for environmental protection.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The PC/ABS composite material is characterized by comprising the following raw material components in percentage by mass based on 100% of the total mass of the PC/ABS composite material:
2. the PC/ABS composite of claim 1 wherein the polycarbonate is selected from the group consisting of: bisphenol a type aromatic polycarbonate; and/or the presence of a gas in the gas,
the weight average molecular weight of the polycarbonate is 20000-35000.
3. The PC/ABS composite of claim 1 or 2 wherein the acrylonitrile-butadiene-styrene graft copolymer is selected from the group consisting of: at least one resin synthesized by a continuous bulk method, emulsion rubber, graft-bulk styrene acrylonitrile resin blending method.
4. The PC/ABS composite material according to claim 3, wherein the compounded efficient flame retardant is a mixed flame retardant of magnesium hydroxide, zinc borate and an organic phosphorus flame retardant.
5. The PC/ABS composite material according to claim 4, wherein the mass ratio of the magnesium hydroxide, the zinc borate and the organic phosphorus flame retardant in the compounded efficient flame retardant is (2-6): (3-7): (1-5).
6. The PC/ABS composite material according to claim 4 or 5, wherein the antioxidant is selected from hindered phenolic and/or phosphate antioxidants; and/or the presence of a gas in the gas,
the light absorber is selected from benzotriazole light absorbers; and/or the presence of a gas in the gas,
the organophosphorus flame retardant comprises: ammonium polyphosphate and bisphenol a-bis (diphenyl phosphate).
7. The PC/ABS composite material according to claim 6, wherein the antioxidant is selected from the group consisting of: antioxidant 619F and/or antioxidant 1010; and/or the presence of a gas in the gas,
the light absorber is selected from UV 5411.
8. The PC/ABS composite material of any of claims 1, 2, 4, 5, or 7, wherein the compatibilizer is selected from the group consisting of styrene-N-phenylmaleimide-maleic anhydride copolymers; and/or the presence of a gas in the gas,
the toughening agent is selected from methyl methacrylate/butadiene/styrene copolymer.
9. A method for preparing the PC/ABS composite material as claimed in any one of claims 1 to 8, comprising the steps of:
obtaining polycarbonate, acrylonitrile-butadiene-styrene graft copolymer, compatilizer, toughening agent, compound efficient flame retardant, antioxidant and light absorbent in formula amount;
mixing the polycarbonate, the acrylonitrile-butadiene-styrene graft copolymer, the compatilizer, the toughening agent, the compound efficient flame retardant, the antioxidant and the light absorbent, and then extruding and granulating the mixture by a double-screw extruder; wherein the working temperature in the double-screw extruder is 200-250 ℃, and the rotating speed of the double screws is 250-350 r/min.
10. The method for preparing a PC/ABS composite material according to claim 9, wherein the working temperature in the main barrel of the twin-screw extruder from the feed port to the head outlet is controlled in nine stages of 200 to 220 ℃, 225 to 235 ℃, 235 to 250 ℃ and 225 to 235 ℃.
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