CN110256829B - High-fluidity polycarbonate composition, and preparation method and application thereof - Google Patents
High-fluidity polycarbonate composition, and preparation method and application thereof Download PDFInfo
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- CN110256829B CN110256829B CN201910446509.1A CN201910446509A CN110256829B CN 110256829 B CN110256829 B CN 110256829B CN 201910446509 A CN201910446509 A CN 201910446509A CN 110256829 B CN110256829 B CN 110256829B
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 64
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000005060 rubber Substances 0.000 claims abstract description 32
- 239000004611 light stabiliser Substances 0.000 claims abstract description 25
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 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 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000002745 absorbent Effects 0.000 claims abstract description 9
- 239000002250 absorbent Substances 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 57
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000001746 injection moulding Methods 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 12
- 230000032683 aging Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000011257 shell material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 239000012745 toughening agent Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000010998 test method Methods 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
- 229920007019 PC/ABS Polymers 0.000 description 2
- 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 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 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 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-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
- 229920001296 polysiloxane Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical group C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 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
- 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention discloses a high-fluidity polycarbonate composition, which comprises the following raw materials in part by weight of 100: 65-90 parts of polycarbonate, 5-15 parts of high rubber powder, 5-15 parts of a flame retardant, 0.3-1 part of an anti-dripping agent, 0.3-1 part of an ultraviolet absorber, 0.2-1 part of a light stabilizer and 0.1-2.5 parts of other additives. The invention also discloses a preparation method of the high-fluidity polycarbonate composition, which comprises the following steps: uniformly mixing polycarbonate, high rubber powder, an anti-dripping agent, an ultraviolet absorbent, a light stabilizer and other auxiliaries, feeding the mixture through a main feeding port of a double-screw extruder, independently feeding a flame retardant through feeding equipment, and performing extrusion, granulation and drying to obtain the high-fluidity polycarbonate composition. The high-flow polycarbonate composition has the characteristics of excellent flame retardance, weather resistance, cracking resistance, low-temperature toughness, high flow, high cost performance and the like. The invention also discloses an application of the high-fluidity polycarbonate composition in preparation of a charging pile shell.
Description
Technical Field
The invention relates to the technical field of polycarbonate materials, in particular to a high-fluidity polycarbonate composition, and a preparation method and application thereof.
Background
At present, with the aggravation of energy problems and environmental pollution problems, new energy automobiles come into operation, and China, which is the first major automobile production and consumption country in the world, is supporting the development of new energy automobiles greatly. The new energy automobile completely accords with the strategies of energy continuous utilization and environmental friendliness, becomes the main direction of the development of the modern automobile, and is certainly the most potential vehicle in the 21 st century.
Automobile companies such as BMW, Shanghai, Dongfeng and BYD have deeply developed research work on new energy automobiles, so with implementation of national energy conservation and emission reduction and environmental friendly policies and improvement of technical level, the new energy automobiles have wide development prospects, and the matched charging pile industry also comes up to the period of high-speed development.
According to filling electric pile's in-service use environment complicacy, be used for coastal city some, the shell material need face high temperature, high ultraviolet irradiation, the influence of complex environment such as seashore salt fog corruption, fills electric pile surface temperature and probably rises to 85 ℃, if the material temperature resistance is not enough, the material softening can appear, creepage distance and electric clearance reduce, induce the quality accident. The long-term ultraviolet irradiation can lead the material to be seriously faded, even reduce the mechanical property, and cause the safety problems of material aging, cracking and the like. Meanwhile, when the charging pile is used in extremely cold northern climates, the shell material needs to withstand the low temperature of-40 ℃, and the problems of material brittleness, cracking and the like can also cause product failure. Therefore, according to different use environments of the charging pile, the shell material of the charging pile needs to meet the characteristic requirements of flame retardance, weather resistance, low temperature resistance, cracking resistance, easiness in injection molding, shell insulation and the like.
Aiming at a series of performance requirements of a charging pile shell material, Polycarbonate (PC) materials are preferably selected in the industry for modification, in order to improve the properties of low-temperature toughness, stress cracking and the like of polycarbonate, one mode is to modify siloxane copolycarbonate with better molecular chain flexibility by adopting the siloxane copolycarbonate disclosed in Chinese patents with application publication numbers of CN 108102328A (application number of 201711066583.8) and CN 106398234A (application number of 201610806227.4), but the defects of the siloxane copolycarbonate are that the price of the siloxane copolycarbonate is extremely high, the material cost is high, the material is not suitable for large-area popularization in the market, and meanwhile, the injection molding flowability of the modified material is not enough, and the material is not suitable for large-scale injection molding shells.
The other method is that as disclosed in chinese patent application publication nos. CN 104448749 a (application No. 201310414007.3) and CN 109385062 a (application No. 201710650880.0), a PC/ABS alloy is selected to improve the properties of the material, such as low temperature and stress cracking resistance, and at the same time, ABS can improve the flowability of the material during injection molding to a greater extent.
Disclosure of Invention
Aiming at the defects in the field, the invention provides the high-fluidity polycarbonate composition, which has the characteristics of high fluidity, excellent flame retardance, weather resistance, cracking resistance, low-temperature toughness, high cost performance and the like, and can be popularized and applied to different parts such as charging pile shells and the like.
A high-fluidity polycarbonate composition comprises the following raw materials by weight of 100 parts:
preferably, the polycarbonate is bisphenol A type linear polymer, the melt flow rate is 10-20 g/10min under the conditions of 300 ℃ and 1.2Kg, and the weight average molecular weight is 3.0-5.0 ten thousand. Preferably, polycarbonate prepared by a phosgene method can be selected, the proportion distribution of high molecular weight components of PC polymerized by the phosgene method is larger, so that the aging life of the material is better, and LG 1201-10 can be selected particularly.
Preferably, the high rubber powder is selected from core-shell polymers consisting of styrene, acrylonitrile and butadiene rubber, and the butadiene content is 55 wt% -70 wt%. The high rubber powder has a structure similar to that of ABS, but the butadiene content of the high rubber powder is far higher than that of ABS, and the high rubber powder can be used as a toughening agent to obviously improve the low-temperature toughness of a PC material due to the extremely high rubber content, and can also improve the stress cracking resistance and injection molding fluidity of the PC material; compared with silane copolymerization PC with extremely high price to improve the low-temperature toughness of PC materials, the high rubber powder has excellent cost advantage, and the injection molding flowability is better than that of the silane copolymerization PC, but the weather resistance is poorer, so that the weather resistance of the materials needs to be improved. More preferably, the high rubber powder is Korean Jinhu HR181 or Taiwan national arbor 60P.
Preferably, the flame retardant is an aromatic phosphate flame retardant, and can be one or two of triphenyl phosphate, resorcinol-bis (diphenyl phosphate), bisphenol a-bis (diphenyl phosphate) and resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ]. The phosphorus flame retardant is a halogen-free, low-smoke and low-toxicity environment-friendly flame retardant, has good compatibility with high polymers, can endow the material with better weather resistance and injection molding fluidity compared with bromine flame retardants, is particularly suitable for selecting a flame-retardant scheme for injection molding of larger parts, and can be particularly used for selecting BDP, TPP, RDP, PX220 and the like of the ten thousand prosperous shares in Zhejiang.
Preferably, the anti-dripping agent is selected from acrylonitrile-styrene copolymer (SAN) coated anti-dripping agents, and SAN coated PTFE, i.e., SAN resin coated polytetrafluoroethylene, such as products using Korean Hanna FS-200(HANNANOFS-200), is used, and the coated shell of SAN imparts a good dispersion effect to PTFE.
Preferably, the ultraviolet absorbent is selected from one or two of benzophenone ultraviolet resistant agents and benzotriazole ultraviolet resistant agents.
The benzophenone ultraviolet resistant agent is selected from 2-hydroxy-4-n-octoxy benzophenone and/or 2-hydroxy-4-methoxy benzophenone.
The benzotriazole ultraviolet inhibitor is at least one selected from 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-5 '- (1,1,3, 3-tetramethylbutyl) phenyl) benzotriazole, and 2- (2' -hydroxy-3 ',5' -bis (a, a-dimethylbenzyl) phenyl) benzotriazole.
Preferably, the light stabilizer is a high molecular weight hindered amine light stabilizer with a special structure, and the molar mass is 3000-4000 g/mol. The light stabilizer has higher molecular weight, and the alkyl molecular chain of the molecular chain side group is longer, so that the light stability is weaker than that of the conventional light stabilizer in alkalinity, and the problem that the physical and mechanical properties of the PC resin are greatly reduced due to the molecular chain degradation of the conventional light stabilizer in the extrusion processing process due to the higher alkalinity can be solved. The structural formula of the hindered amine light stabilizer is shown as the following formula (I):
preferably, the other auxiliaries include antioxidants and lubricants.
The antioxidant is selected from a compound consisting of antioxidant 1076 and antioxidant 168 according to the weight ratio of 1: 1.
The lubricant is at least one selected from calcium stearate, ethylene bis stearamide and silicone powder.
Because the addition amount of the high rubber powder is mutually restricted for the low-temperature toughness, the flame retardant property, the weather resistance and the like of the material, preferably, the high-fluidity polycarbonate composition comprises the following raw materials by weight of 100 parts:
the invention also provides a preparation method of the high-fluidity polycarbonate composition, which comprises the following steps:
(1) uniformly mixing polycarbonate, high rubber powder, an anti-dripping agent, an ultraviolet absorbent, a light stabilizer and other auxiliaries to obtain a mixed material;
(2) and (2) feeding the mixed material obtained in the step (1) through a main feeding port of a double-screw extruder, feeding the flame retardant through a feeding device separately, and performing extrusion, granulation and drying to obtain the high-fluidity polycarbonate composition.
Preferably, in the step (2), the temperature of each temperature zone from feeding to extrusion discharging of the double-screw extruder is set as follows: a first area: 245-255 ℃ and two zones: 250-260 ℃ and three zones: 250-260 ℃ and four regions: 250-260 ℃ and five regions: 240-250 ℃ and six zones: 220-230 ℃ and seven regions: 220-230 ℃ and eight zones: 220-230 ℃ and nine zones: 220-230 ℃ and die head: 245-255 ℃ and the screw rotating speed of 350-450 rpm.
The invention also provides an application of the high-flow polycarbonate composition in preparing a charging pile shell.
Compared with the prior art, the invention has the main advantages that:
(1) the invention adopts the high rubber powder with ultrahigh butadiene content as the toughening agent to modify the PC material, can obviously improve the low-temperature toughness of the PC material, and can also improve the stress cracking resistance and the injection molding fluidity of the PC material. Compared with silane copolymerization PC with extremely high price, the low-temperature toughness of the PC material is improved, the high rubber powder has excellent cost advantage, and the injection molding flowability is better than that of the silane copolymerization PC; on the other hand, the content of butadiene in the high rubber powder is obviously higher than that of the ABS material, so that better low-temperature toughness can be obtained, and the PC/ABS material needs more ABS components or toughening agent components to obtain the same low-temperature performance effect, so that the weather resistance and the flame retardant property are greatly influenced. Therefore, the polycarbonate composition prepared by the invention has excellent performance and ultrahigh cost performance, and is convenient for large-area popularization in the market.
(2) Aiming at the problem of poor weather resistance of high rubber powder, the comprehensive weather resistance of the material is obviously improved by adopting a compounding mode of a conventional ultraviolet absorbent and a high molecular weight hindered amine light stabilizer with a special molecular structure, and compared with the problem that the physical and mechanical properties of a PC material are seriously attenuated due to the obvious degradation in the processing process of the PC material because the conventional low molecular weight hindered amine has higher alkalinity, the high molecular weight hindered amine adopted in the invention can form an excellent synergistic effect with the ultraviolet absorbent due to extremely low alkalinity, and can obviously improve the defect of poor weather resistance caused by butadiene components in the high rubber powder.
(3) The prepared polycarbonate material has the characteristics of excellent flame retardance, weather resistance, cracking resistance, low-temperature toughness, high fluidity, high cost performance and the like, and can be popularized and applied to different parts such as charging pile shells and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
In each embodiment and comparative example of the invention, the following brands of raw materials are specifically selected:
polycarbonate was obtained from a melt flow rate of 10g/10min at 300 ℃ under 1.2Kg using a Korean LG 1201-10 product.
The high-gel powder is HR181 from Korea brocade lake.
The fire retardant is RDP phosphorus fire retardant with ten thousand shares in Zhejiang.
The anti-dripping agent was obtained from Korean Hanna FS-200 (HANNAOFS-200).
The ultraviolet absorber is selected from benzotriazole UV-329 (basf, Germany).
The light stabilizer is selected from UVINUL5050H from basf, Germany.
The antioxidant is a compound of antioxidant 1076 and antioxidant 168, and the weight ratio is 1: 1.
The lubricant is pentaerythritol stearate (PETS).
In the following examples and comparative examples, unless otherwise specified, parts are by weight and the specific process for preparing the polycarbonate composition is as follows:
(1) uniformly mixing the raw materials except the flame retardant by using a high-speed mixer to obtain a mixed material;
(2) and (2) feeding the mixed material obtained in the step (1) through a main feeding port of a double-screw extruder, feeding the flame retardant through a feeding device separately, and performing extrusion, granulation and drying to obtain the high-fluidity polycarbonate composition.
In the step (2), the temperature of each temperature zone from feeding to extruding and discharging of the double-screw extruder is set as follows: a first area: 245-255 ℃ and two zones: 250-260 ℃ and three zones: 250-260 ℃ and four regions: 250-260 ℃ and five regions: 240-250 ℃ and six zones: 220-230 ℃ and seven regions: 220-230 ℃ and eight zones: 220-230 ℃ and nine zones: 220-230 ℃ and die head: 245-255 ℃ and the screw rotating speed of 350-450 rpm.
Examples 1 to 6
The amounts of the respective raw material components added to the high flow polycarbonate compositions of examples 1 to 6 are shown in Table 1.
TABLE 1 ingredient component ratios of the high flow polycarbonate compositions of examples 1 to 6
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| PC | 86 | 80 | 74 | 68 | 79.8 | 79.8 |
| High rubber powder | 5 | 8 | 12 | 15 | 8 | 8 |
| RDP | 7 | 10 | 12 | 15 | 10 | 10 |
| FS-200 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| UV-329 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.5 |
| 5050H | 0.2 | 0.2 | 0.2 | 0.2 | 0.4 | 0.2 |
| Antioxidant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| PETS | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The test method of the material performance is as follows:
physical and mechanical properties: the tensile property test refers to GB/T1040.2-2006 standard; the elongation at break test refers to GB/T1040.2-2006 standard, and the stretching speed is 10 mm/min; the bending property test refers to the GB/T9341-2008 standard, and the bending speed is 2 mm/min; the impact performance test refers to the GB/T1043.1-2008 standard; the heat distortion temperature (0.45Mpa) refers to GB/T1634.2-2004 standard; the flame-retardant vertical combustion test refers to the GB/T2408 + 2008 standard; the melt flow rate was determined in accordance with GB/T3682-2000, test conditions were selected at 300 ℃ C. 1.2 kg.
And (3) testing weather resistance: the prepared material is subjected to injection molding on an injection molding machine (the injection molding temperature is 250 ℃, 240 ℃ and 230 ℃) to form a conventional physical and mechanical property sample strip, then the sample strip is placed in a xenon lamp aging box to be subjected to an aging test according to GB/T16422.2-2014, the sample strip exposure condition is carried out by adopting the condition of a cycle method 1, the impact property of the simply supported beam notch of the material is tested after the sample strip is aged for 1000 hours, and the corresponding property retention rate is (the performance after the aging/the performance without aging) 100%.
The materials respectively prepared in examples 1 to 6 were tested according to the test method, and the initial material performance and the retention rate of the notch impact performance of the simply supported beam after 1000-hour xenon lamp aging are shown in table 2 below.
TABLE 2 results of the Performance test of the high flow polycarbonate compositions of examples 1-6
As can be seen from the table, the high-molecular-weight hindered amine light stabilizer and the ultraviolet absorber are compounded, so that the problem of poor weather resistance of butadiene on a high-molecular-weight rubber powder chain is well solved, and the high-flow high-cost-performance polycarbonate composition for the charging pile shell is obtained. Compared with the examples 1-3, the low-temperature toughness of the material is gradually enhanced along with the increase of the addition amount of the high rubber powder, and particularly, when the high rubber powder is added to 10%, the low-temperature impact performance is mutated; in the aspect of weather resistance of the material, the notch impact retention rate of the material is gradually reduced along with the increase of the addition amount of the high rubber powder, but due to the good synergistic effect of the light stabilizer and the ultraviolet absorber, the performance retention rate can be kept over 75% after the material is aged for 1000 hours. Comparing the performances of the embodiment 4 and the embodiments 1 to 3, when the content of the high rubber powder reaches 15%, the mechanical strength and the impact property of the material are rapidly reduced, and the aging property retention rate of the material is also reduced to a great extent, which may be related to the fact that the ultrahigh rubber content is difficult to form better dispersion in a polycarbonate matrix. Therefore, the preferable amount of the high rubber powder is 8 to 12 parts.
Comparing example 2 with example 5, increasing the addition of the light stabilizer causes little change in the conventional mechanical properties of the material, slightly decreases the notch impact performance, but increases the retention rate of the aged performance, so that the light stabilizer has a better improvement effect on the weather resistance of the material; comparing example 2 with example 6, increasing the content of the ultraviolet absorbent, the mechanical property and the weather resistance of the material are basically not changed, and the effect of the visible ultraviolet absorbent is basically saturated when more than 0.3 part.
Comparative examples 1 to 5
The purpose of comparative examples 1 to 5 is to study the influence of the synergistic effect of the high rubber powder, the light stabilizer and the ultraviolet absorber on the performance of the polycarbonate composition. The specific preparation method and the extrusion processing technology are the same as those in the embodiments 1 to 6. The addition amounts of the raw material components in comparative examples 1-5 are shown in Table 3, wherein S2001 is a silicon-based toughening agent and has a good low-temperature toughening effect; 944 is a high molecular weight hindered amine light stabilizer with a molecular weight of 2100-3000.
TABLE 3 polycarbonate compositions of comparative examples 1 to 5 with respect to the compounding ratio of the respective raw material components
| Material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| PC | 98 | 80 | 80 | 80 | 80 |
| High rubber powder | 0 | 0 | 8 | 8 | 8 |
| S2001 | 0 | 8 | 0 | 0 | 0 |
| RDP | 0 | 10 | 10 | 10 | 10 |
| FS-200 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| UV-329 | 0.3 | 0.3 | 0.5 | 0 | 0.3 |
| 5050H | 0.2 | 0.2 | 0 | 0.5 | 0 |
| 944 | 0 | 0 | 0 | 0 | 0.2 |
| Antioxidant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| PETS | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The polycarbonate compositions prepared in comparative examples 1 to 5 were tested according to the test methods described above, and the initial material properties and the retention rate of the notched impact properties of the simply supported beam after 1000-hour xenon lamp aging are shown in table 4 below.
TABLE 4 results of Performance test of the polycarbonate compositions of comparative examples 1 to 5
Compared with a pure PC system, the addition of the high rubber powder obviously improves the low-temperature impact toughness and the injection molding fluidity of the material, compared with a silicon-based toughening agent S2001, under the condition of the same addition amount, although the normal-temperature impact resistance of S2001 is slightly higher, the notch impact strength at minus 40 ℃ is obviously better than that of the high rubber powder, and the fluidity of the embodiment 2 is better than that of the comparative example 2. Although the high rubber powder has slightly poor weather resistance, the weather resistance notch performance retention of the material obtained in example 2 is only slightly lower than that of comparative example 1 due to the synergistic effect of the high molecular weight hindered amine light stabilizer with a special structure and the ultraviolet absorber.
Compared with the data in the comparative examples 3-5, the data in the example 2 show that the aging performance of the material is greatly different when the light stabilizer and the ultraviolet absorber are added independently and the two auxiliary agents are added simultaneously, so that the two auxiliary agents have excellent synergistic effect on the aging performance of the material. In comparative example 5, hindered amine light stabilizer 944 is used, and although the molecular weight of the hindered amine light stabilizer 944 is above 2000, the hindered amine light stabilizer added to a PC matrix can cause processing degradation of the material, and further cause the material to have extremely high fluidity and poor mechanical impact property. In addition, the retention rate of the aging notch impact performance of the comparative example 5 is obviously lower than that of the example 2, which shows that the high molecular weight hindered amine light stabilizer with a special structure adopted by the invention has better matching property and compatibility with high rubber powder, and can effectively improve the weather resistance of the polycarbonate composition.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (4)
1. The high-fluidity polycarbonate composition suitable for preparing the charging pile shell is characterized by comprising the following raw materials in parts by weight of 100 parts:
the polycarbonate is prepared by adopting a phosgene method;
the high rubber powder is selected from core-shell polymers consisting of styrene, acrylonitrile and butadiene rubber, and the butadiene content is 55-70 wt%;
the flame retardant is an aromatic phosphate flame retardant;
the anti-dripping agent is selected from SAN coated anti-dripping agents;
the ultraviolet absorbent is benzotriazole UV-329;
the light stabilizer is UVINUL 5050H.
2. The high flow polycarbonate composition of claim 1, wherein the polycarbonate has a weight average molecular weight of 3.0 to 5.0 ten thousand.
3. A method of making the high flow polycarbonate composition of claim 1 or 2, comprising the steps of:
(1) uniformly mixing polycarbonate, high rubber powder, an anti-dripping agent, an ultraviolet absorbent, a light stabilizer and other auxiliaries to obtain a mixed material;
(2) and (2) feeding the mixed material obtained in the step (1) through a main feeding port of a double-screw extruder, feeding the flame retardant through a feeding device separately, and performing extrusion, granulation and drying to obtain the high-fluidity polycarbonate composition.
4. Use of the high flow polycarbonate composition of claim 1 or 2 in the preparation of a charging post housing.
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| CN112375365A (en) * | 2020-11-30 | 2021-02-19 | 重庆普利特新材料有限公司 | Preparation method of PC/ABS high-brightness black material with high heat resistance, scratch resistance and high weather resistance for automotive interior |
| CN114316555A (en) * | 2021-12-03 | 2022-04-12 | 上海金山锦湖日丽塑料有限公司 | Fatigue-resistant flame-retardant PC/ABS alloy and preparation method thereof |
| CN115433447A (en) * | 2022-08-04 | 2022-12-06 | 青岛国恩科技股份有限公司 | Weather-resistant charging pile shell material and preparation method thereof |
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