CN114933792B - Polycarbonate alloy material and preparation method and application thereof - Google Patents
Polycarbonate alloy material and preparation method and application thereof Download PDFInfo
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 48
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 43
- 239000000956 alloy Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 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 claims abstract description 27
- 239000003063 flame retardant Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 13
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012964 benzotriazole Substances 0.000 claims abstract description 7
- 241000872198 Serjania polyphylla Species 0.000 claims abstract description 3
- 238000013329 compounding Methods 0.000 claims abstract 2
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 4
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical group C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 claims description 3
- OJUVOJCIHNPHSA-UHFFFAOYSA-N bis(2,6-dimethylphenyl) (3-hydroxyphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=CC=CC(O)=C1 OJUVOJCIHNPHSA-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
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- VHKFLUVQGQCGNO-UHFFFAOYSA-N buta-1,3-diene oxiran-2-ylmethyl 2-methylprop-2-enoate styrene Chemical compound C(C(=C)C)(=O)OCC1CO1.C=CC=C.C=CC1=CC=CC=C1 VHKFLUVQGQCGNO-UHFFFAOYSA-N 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004945 silicone rubber Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 19
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 206010051246 Photodermatosis Diseases 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008845 photoaging Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polycarbonate alloy material, which comprises the following components in parts by weight: 65-75 parts of PC resin; 5-20 parts of ASA resin; 8-16 parts of flame retardant; 0.1-4 parts of toughening agent; 0.1-3 parts of antioxidant; 0.1-5 parts of weather-proof agent; 0.1-3 parts of light shielding agent. According to the invention, a proper kind of flame retardant is added into a PC/ASA material system, a special auxiliary antioxidant and a main antioxidant are adopted for compounding, benzotriazole and triazine weather resistant agents are matched for use, and simultaneously, carbon black with a super structure is selected as a light shielding agent, so that the performance retention of the material after the material is subjected to the action of dry heat weather conditions can be greatly ensured through the synergistic effect of the components, the polycarbonate alloy material with high weather resistance is prepared, the UL94V-0 flame retardant grade can be still achieved after the material is subjected to the aging condition of PV3929, the color change is small, and the retention rate of impact strength is more than 80%.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polycarbonate alloy material and a preparation method and application thereof.
Background
Polycarbonate (PC) has various advantages in transparency, impact resistance, heat resistance, dimensional stability, and the like, and is widely used in fields of automobiles, electronics, and the like, and has become a general-purpose engineering plastic with the fastest growing speed among five engineering plastics. Many engineering plastics must be operated outdoors for a long time, and often face complex and changeable natural environments such as sunlight, wind blowing, rain, and the like, which requires special attention to the weather resistance of the materials.
The dry heat environment is widely distributed in the world from the tropical zone to the temperate zone, and a large-area dry heat desert environment exists in the western region of China. The high temperature and high irradiation characteristics of the polymer material in the dry heat environment are easy to generate the phenomena of deformation, aging and the like of the polymer material, so that the product performance is deteriorated and the service life is shortened. The outdoor products (such as charging facilities, communication equipment and the like) in a dry-heat environment have strict weather resistance requirements on materials, and can have better performance maintenance (flame retardant performance, mechanical performance and color) under the condition of long-term dry-heat photo-aging.
The dry heat aging test of the material, using the PV3929 standard, corresponds to an atmospheric exposure test of nonmetallic materials in dry-hot climates, simulating artificial weathering in dry-hot climates, such as the dry-hot climates in karrahali, south Africa and Arizona, with average ultraviolet radiation doses (300-385 nm) associated with annual cycles. It is more severe than other aging conditions, and presents a serious challenge for PC materials. At present, relatively few related researches on the improvement of the dry heat resistance of PC materials are carried out, which limits the application of the PC materials to a certain extent.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a polycarbonate alloy material with high weather resistance, which can ensure that the polycarbonate alloy material has better flame retardant property, mechanical property and color retention under the condition of long-term dry heat photo-aging.
Another object of the present invention is to provide a method for preparing the above polycarbonate alloy material.
The invention is realized by the following technical scheme:
the polycarbonate alloy material comprises the following components in parts by weight:
65-75 parts of PC resin;
5-20 parts of ASA resin;
8-16 parts of flame retardant;
0.1-4 parts of toughening agent;
0.1-3 parts of antioxidant;
0.1-5 parts of weather-proof agent;
0.1-3 parts of light shielding agent.
Preferably, the viscosity average molecular weight of the PC resin is 10000-40000; more preferably, the PC resin has a viscosity average molecular weight of 18000-32000.
The viscosity average molecular weight is measured by an Ubbelohde viscometer to determine limiting viscosity number [ ƞ ], methylene dichloride is used as a solvent of the polycarbonate, and the solution is assisted by a constant-temperature water bath at 20 ℃. The viscosity average molecular weight M is calculated by a Mark-Hou-wink equation, and [ ƞ ] =KMalpha, wherein K is a proportionality constant; alpha-expansion factor.
Preferably, the ASA resin has a rubber content of 30-80%; more preferably, the ASA resin has a rubber content of 40 to 70%.
The rubber content of the ASA resin is measured by adopting an infrared spectrum method, and the method refers to GB/T7764-2001 dissolution film-making method, a small amount of sample is taken to be dissolved in 1, 2-dichlorobenzene, the sample is heated to be partially dissolved and filtered, the filtrate is coated on a salt sheet to be dried and film-formed, and the infrared spectrum is measured, and an acrylic ester peak and a styrene peak are taken as reference peaks.
The flame retardant is at least one selected from hydroquinone bis (diphenyl phosphate) or resorcinol-bis (2, 6-xylyl) phosphate.
The toughening agent is selected from any one or more of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic ester-glycidyl methacrylate terpolymer, maleic anhydride functionalized ethylene-vinyl acetate copolymer, acrylic acid toughening agent, styrene-butadiene-glycidyl methacrylate or organic silicon rubber graft toughening agent.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant. The primary antioxidant is selected from at least one of hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 or hindered phenol antioxidant 1076; the secondary antioxidant is selected from benzofuranones.
Preferably, the weight ratio of the main antioxidant to the auxiliary antioxidant in the antioxidants is 1: (1-4).
The weather resistant agent is compounded by benzotriazole weather resistant agent and triazine weather resistant agent; preferably, the weather-proof agent is benzotriazole weather-proof agent and triazine weather-proof agent according to the weight ratio of (0.5-2): 1.
The light shielding agent is selected from super-structure carbon black; the oil absorption value of the super-structure carbon black is 1.6-2.4ml/g.
The oil absorption value of the carbon black refers to the volume of the dibutyl phthalate of the carbon black per unit mass, and is used for representing the structural degree of the carbon black. The oil absorption value is tested by the A method in the standard GB/T3780.2-2003 determination of the absorption value of dibutyl phthalate of the second part of carbon black.
According to the invention, the research shows that the carbon black with the super structure is selected, so that the polycarbonate alloy material can be effectively prevented from being damaged by hot dry weather, the performance retention of the aged material, especially the performance retention of the aged material after long-term aging under the condition of PV3929, is greatly ensured.
The invention also provides a preparation method of the polycarbonate alloy material, which comprises the following steps: according to the proportion, the components are put into a mixer to be blended until uniform, and a premix is obtained; then, the premix is put into a double-screw extruder for melt mixing and extrusion granulation, and the polycarbonate alloy material is prepared; wherein, the length-diameter ratio of the screw of the double screw extruder is (38-48): 1, the temperature of the screw barrel is 240-260 ℃, and the rotating speed of the screw is 400-500 rpm.
The invention also provides application of the polycarbonate alloy material, which is particularly suitable for products used outdoors under the dry heat condition, such as charging facilities, communication equipment and the like.
The invention has the following beneficial effects:
according to the invention, a proper kind of flame retardant is added into a PC/ASA material system, special auxiliary antioxidants are adopted to compound with main antioxidants, benzotriazole and triazine weather resistant agents are matched, and simultaneously, super-structure carbon black is selected as a light shielding agent, so that the performance retention of the material after the material is subjected to the action of dry and hot weather conditions can be greatly ensured through the synergistic effect of the components, and the high-weather-resistance polycarbonate alloy material can be prepared, can still reach the UL94V-0 flame retardant grade after being subjected to the aging condition of PV3929, and has small color change and high retention rate of impact strength of more than 80%.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
PC resin 1: the viscosity average molecular weight is 28000, PC E-3000F, mitsubishi Japanese;
PC resin 2: the viscosity average molecular weight is 35000, PC E-1000F, mitsubishi Japanese;
ASA resin 1: the rubber content is 60%, A600N, UMG;
ASA resin 2: rubber content is 35%, LP2065X, entropy energy;
flame retardant 1: hydroquinone bis (diphenyl phosphate), PX-220, mo Cheng;
flame retardant 2: resorcinol-bis (2, 6-xylyl) phosphate, RXP, octa chemistry
Flame retardant 3: bisphenol a-bis (diphenyl phosphate), BDP-H, mo Cheng;
toughening agent: an organosilicon rubber graft toughening agent, SX-005, mitsubishi Li yang;
and (3) a main antioxidant: hindered phenol antioxidant 1010,Irganox 1010,BASF;
auxiliary antioxidant 1: benzofuranone, revolox 501, chitec;
auxiliary antioxidant 2: irgafos 168, BASF;
weather-resistant agent 1: benzotriazole weather-resistant agent, tinuvin 234, BASF;
weather-resistant agent 2: triazine weather-proofing agents, tinuvin 1577, BASF;
light-shielding agent 1: the oil absorption value of the super-structure carbon black is 1.9ml/G,250G and beneficial rayleigh stone;
light-shielding agent 2: carbon BLACK having an oil absorption of 2.7ml/g, DENKA BLACK, DENKA;
light-shielding agent 3: carbon black, oil absorption of 1.2ml/g, M717, CABOT;
preparation methods of examples and comparative examples:
according to the proportion, the components are put into a mixer to be blended until uniform, and a premix is obtained; then, the premix is put into a double-screw extruder for melt mixing and extrusion granulation, and the polycarbonate alloy material is prepared; wherein, the screw length-diameter ratio of the double screw extruder is 45:1, screw barrel temperature was 240℃and screw speed was 450rpm.
The related performance testing method comprises the following steps:
(1) Notched Izod impact Strength (Normal temperature): the notched Izod impact strength was measured using a 4.0mm thick molded notched Izod impact bar, measured in kJ/m according to ISO 180-2010 2 The results were recorded and the test was performed at room temperature (23 ℃).
(2) Flame retardant properties: flammability testing was performed following the protocol "flammability test of plastics materials, UL 94". Flame retardant rating is derived based on the burn rate, the extinguishing time, the ability to resist dripping, and whether or not dripping (drop) is burning. Sample for testing: bars with dimensions 125mm length by 13mm width by no more than 13mm thickness were selected for the thickness of the bars at the time of testing according to the invention to be 2.0mm.
(3) Dry heat aging resistance test:
aging conditions: using the PV3929 standard, weather-Ometer CI3000, black standardThe temperature of the sample space in the drying stage was 50.+ -. 2 ℃ at 90.+ -. 2 ℃ and the relative humidity (20.+ -. 10)%, the spectral irradiance was 0.6W/m 2 （340nm）。
(1) Notch impact strength (normal temperature) of the aged cantilever beam: placing a molded cantilever beam notch impact bar with the thickness of 4.0mm in a xenon lamp aging box, aging for 3000 hours, taking out, and then testing according to the step (1); the retention of impact strength after aging was calculated.
(2) Flame retardant properties after aging: the 2.0mm thick combustion sample strip is placed in a xenon lamp aging box, aged for 3000 hours, taken out and then tested according to (2).
(3) Color change: placing a color plate with the size of 60mm length multiplied by 40mm width multiplied by 2mm thickness in a xenon lamp aging box for 3000 hours, grading according to GB/T250-2008 gray card after aging, and dividing the color difference into five integer color fastness grades according to the appearance and feel, namely 5, 4, 3, 2 and 1. And supplementing one half of the grades in every two grades, namely 4-5, 3-4, 2-3 and 1-2, and expanding into 9 grades. When the observed color difference between the original sample and the test sample corresponds to the observed color difference of a certain grade of the gray sample card, the grade is taken as the color-changing fastness grade of the sample, and if the observed color difference between the original sample and the test sample corresponds to the middle of the two grades of the gray sample card, the color-changing grade of the sample is rated as the middle grade, such as 4-5 grade and 3-4 grade. Grade 5 can be rated only when there is no perceived color difference between the sample and the original after the test.
Table 1: the proportions (in parts by weight) of the components of examples 1 to 6 and the results of the performance test
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| PC resin 1 | 75 | 75 | 70 | 65 | 70 | |
| PC resin 2 | 75 | |||||
| ASA resin 1 | 10 | 10 | 15 | 20 | 5 | |
| ASA resin 2 | 10 | |||||
| Flame retardant 1, PX-220 | 12 | 12 | 12 | 8 | ||
| Flame retardant 2, RXP | 16 | 10 | ||||
| Toughening agent | 1 | 1 | 1 | 3 | 1 | 2 |
| Primary antioxidant, 1010 | 0.2 | 0.2 | 0.2 | 0.3 | 0.4 | 0.2 |
| Auxiliary antioxidants 1, 501 | 0.5 | 0.5 | 0.5 | 0.6 | 0.4 | 0.8 |
| Weather-proof agent 1 | 0.6 | 0.6 | 0.6 | 0.8 | 0.6 | 0.6 |
| Weather-proof agent 2 | 0.6 | 0.6 | 0.6 | 0.4 | 0.6 | 0.6 |
| Light shielding agent 1, 250G | 0.5 | 0.5 | 0.5 | 1 | 0.8 | 0.5 |
| Izod notched impact strength, kJ/m, before aging 2 | 60.6 | 63.5 | 56.4 | 61.8 | 60.3 | 59.2 |
| Izod notched impact strength after aging, kJ/m 2 | 57.1 | 57.3 | 45.7 | 58.5 | 56.1 | 49.6 |
| Impact strength retention | 94.2% | 90.2% | 81.0% | 94.7% | 93.0% | 83.8% |
| Flame retardant rating before aging, 2mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Flame retardant rating after aging, 2mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Color change rating of test specimen after aging | 4-5 grade | 4-5 grade | 4-5 grade | 4-5 grade | 4-5 grade | 4-5 grade |
Table 2: comparative examples 1 to 6 the ratio of the amounts of the respective components (in parts by weight) and the results of the performance test
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| PC resin 1 | 75 | 75 | 75 | 75 | 75 | 75 |
| ASA resin 1 | 10 | 10 | 10 | 10 | 10 | 10 |
| Flame retardant 1, PX-220 | 12 | 12 | 12 | 12 | 12 | |
| Flame retardant 3, BDP-H | 12 | |||||
| Toughening agent | 1 | 1 | 1 | 1 | 1 | 1 |
| Primary antioxidant, 1010 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Auxiliary antioxidants 1, 501 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| Auxiliary antioxidant 2, 168 | 0.5 | |||||
| Weather-proof agent 1 | 0.6 | 0.6 | 1.2 | / | 0.6 | 0.6 |
| Weather-proof agent 2 | 0.6 | 0.6 | / | 1.2 | 0.6 | 0.6 |
| Light shielding agent 1, 250G | 0.5 | 0.5 | 0.5 | 0.5 | ||
| Light shielding agent 2, DENKA BLACK | 0.5 | |||||
| Light-shielding agent 3, M717 | 0.5 | |||||
| Izod notched impact strength, kJ/m, before aging 2 | 60.3 | 60.5 | 61.3 | 61.5 | 60.3 | 60.1 |
| Izod notched impact strength after aging, kJ/m 2 | 12.3 | 7.7 | 8.1 | 9.8 | 19.6 | 7.8 |
| Impact strength retention | 20.4% | 12.7% | 13.2% | 15.9% | 32.5% | 13.0% |
| Flame retardant rating before aging, 2mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Flame retardant rating after aging, 2mm | V-2 | V-2 | V-2 | V-2 | V-2 | V-2 |
| Color change rating of test specimen after aging | Grade 4 | Level 2 | Level 2 | Level 2 | 3 grade | Level 2 |
According to the invention, a proper kind of flame retardant is added into a PC/ASA material system, a special auxiliary antioxidant is adopted to compound with a main antioxidant, benzotriazole and triazine weather resistant agents are matched, and simultaneously, super-structure carbon black is selected as a light shielding agent, and all the components are synergistic to prepare the polycarbonate alloy material with high weather resistance, and after being treated for 3000 hours under the ageing condition of PV3929, the polycarbonate alloy material still can reach the UL94V-0 flame retardant level, and has small color change and high impact strength retention rate of more than 80%.
Claims (8)
1. The polycarbonate alloy material is characterized by comprising the following components in parts by weight:
65-75 parts of PC resin;
5-20 parts of ASA resin;
8-16 parts of flame retardant;
0.1-4 parts of toughening agent;
0.1-3 parts of antioxidant;
0.1-5 parts of weather-proof agent;
0.1-3 parts of light shielding agent;
the flame retardant is at least one selected from hydroquinone bis (diphenyl phosphate) or resorcinol-bis (2, 6-xylyl) phosphate;
the weight ratio of the main antioxidant to the auxiliary antioxidant in the antioxidants is 1: (1-4), wherein the primary antioxidant is selected from at least one of a hindered phenol antioxidant 1010, a hindered phenol antioxidant 1098, or a hindered phenol antioxidant 1076; the secondary antioxidant is selected from benzofuranone;
the weather-resistant agent is benzotriazole weather-resistant agent and triazine weather-resistant agent according to the weight ratio of (0.5-2): 1, compounding;
the light shielding agent is selected from super-structure carbon black with an oil absorption value of 1.6-2.4ml/g.
2. The polycarbonate alloy material according to claim 1, wherein the PC resin has a viscosity average molecular weight of 10000 to 40000.
3. The polycarbonate alloy material of claim 1, wherein the PC resin has a viscosity average molecular weight of 18000-32000.
4. The polycarbonate alloy material according to claim 1, wherein the ASA resin has a rubber content of 30 to 80%.
5. The polycarbonate alloy material according to claim 1, wherein the ASA resin has a rubber content of 40 to 70%.
6. The polycarbonate alloy material according to claim 1, wherein the toughening agent is selected from any one or more of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-glycidyl methacrylate terpolymer, maleic anhydride functionalized ethylene-vinyl acetate copolymer, acrylic toughening agent, styrene-butadiene-glycidyl methacrylate, or silicone rubber graft toughening agent.
7. The method for producing a polycarbonate alloy material according to any one of claims 1 to 6, comprising the steps of: according to the proportion, the components are put into a mixer to be blended until uniform, and a premix is obtained; then, the premix is put into a double-screw extruder for melt mixing and extrusion granulation, and the polycarbonate alloy material is prepared; wherein, the length-diameter ratio of the screw of the double screw extruder is (38-48): 1, the temperature of the screw barrel is 240-260 ℃, and the rotating speed of the screw is 400-500 rpm.
8. The use of a polycarbonate alloy material according to any of claims 1-6, for products used outdoors under dry heat conditions.
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| CN101263198A (en) * | 2005-09-12 | 2008-09-10 | 三菱化学株式会社 | Resin compositions and resin moldings |
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| CN105164203A (en) * | 2013-05-20 | 2015-12-16 | 三菱工程塑料株式会社 | Polycarbonate resin composition, molded article comprising same, and method for manufacturing same |
| CN105324421A (en) * | 2013-06-26 | 2016-02-10 | 三菱瓦斯化学株式会社 | Flame retardant sheet or film, product using same, and method for manufacturing same |
| CN107383829A (en) * | 2017-08-16 | 2017-11-24 | 江苏金发科技新材料有限公司 | Ageing-resistant hydrolysis halogen-free flame-retardant polycarbonate composition and preparation method thereof |
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| CN101263198A (en) * | 2005-09-12 | 2008-09-10 | 三菱化学株式会社 | Resin compositions and resin moldings |
| CN104684995A (en) * | 2012-09-25 | 2015-06-03 | 东丽株式会社 | Natural rubber-containing thermoplastic resin composition and molded article thereof |
| CN105164203A (en) * | 2013-05-20 | 2015-12-16 | 三菱工程塑料株式会社 | Polycarbonate resin composition, molded article comprising same, and method for manufacturing same |
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