CN115772325B - PC/ABS composition with good electrostatic spraying performance, and preparation method and application thereof - Google Patents
PC/ABS composition with good electrostatic spraying performance, and preparation method and application thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 229920007019 PC/ABS Polymers 0.000 title claims abstract description 45
- 238000007590 electrostatic spraying Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 amino activated carbon nano tube Chemical class 0.000 claims abstract description 39
- 239000011231 conductive filler Substances 0.000 claims abstract description 31
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims abstract description 15
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 13
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 54
- 239000002048 multi walled nanotube Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007921 spray Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
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- 229910021641 deionized water Inorganic materials 0.000 claims description 8
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- 238000001914 filtration Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
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- 125000003277 amino group Chemical group 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
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- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
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- 239000002530 phenolic antioxidant Substances 0.000 claims 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 3
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 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 2
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- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
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- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- JBTXGEJRJCNRLU-UHFFFAOYSA-N [2-(dihydroxyphosphanyloxymethyl)-3-hydroxy-2-(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OP(O)OCC(CO)(CO)COP(O)O JBTXGEJRJCNRLU-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a good electrostatic spraying PC/ABS composition, a preparation method and application thereof. The PC/ABS composition comprises the following components: 50-70 parts of polycarbonate resin, 10-30 parts of ABS resin, 3-8 parts of spraying modifier, 2-4 parts of conductive filler, 0.1-0.3 part of antioxidant and 0.3-0.8 part of lubricant. The invention introduces the branched styrene-acrylonitrile copolymer grafted by maleic anhydride into PC/ABS composition system, so that the copolymer reacts with the mixture composed of the amino activated carbon nano tube and the amino activated conductive carbon black to realize good dispersion of the conductive filler, the PC/ABS composition has extremely low surface resistance, and meanwhile, the constructed physical isolation layer can greatly improve the capability of resisting solvent erosion.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a good electrostatic spraying PC/ABS composition, a preparation method and application thereof.
Background
Along with the continuous enhancement of greenhouse effect and natural environment deterioration, the state formally proposes a green concept of realizing carbon peak in 2030 and carbon neutralization in 2060, and makes related action plans, and green environmental protection has become a mainstream concept and trend of society. The surface spraying of the plastic part can obviously improve the properties of impact resistance, scratch resistance, solvent resistance, aging resistance and the like of the material, greatly prolongs the service life of the part, and achieves the aims of carbon reduction and emission reduction in the whole life cycle. Different spraying processes have obvious difference on the paint coating rate, the traditional air spraying paint coating rate is only 30% -60%, the electrostatic spraying is mainly adsorbed on the surface of a workpiece by the electrostatic adsorption force of the paint, the paint coating rate can be up to 70% -90%, the utilization rate of the paint can be improved by 30% -40%, further saving and energy saving and emission reduction are realized, and therefore, the electrostatic spraying is more and more concerned and selected in the market.
Polycarbonate resin (PC) has the performance characteristics of high gloss, high heat resistance, high strength and high impact resistance, and is very important engineering plastic; the acrylonitrile-butadiene-styrene terpolymer resin (ABS) has the advantages of three components, excellent chemical stability, impact strength and good processing performance, and the PC/ABS composite material prepared from PC and ABS has the advantages of both performances, thus being an excellent paint spraying base material. However, the surface resistance of the traditional PC/ABS composition is higher and generally exceeds 10 14 omega, the painting rate is extremely low when the traditional PC/ABS composition is directly subjected to electrostatic spraying, and the traditional PC/ABS composition has no practical significance and has to be subjected to conductive property improvement. In the prior art, a conductive matrix is prepared by using PC resin, barium titanate ceramic powder and a siloxane coupling agent, and then a bicontinuous structure is prepared by blending with ABS, so that the conductivity of the material is improved; the conductive performance of the material is improved by adding a composite antistatic agent formed by mixing a plurality of inorganic salts, so that the antistatic effect is realized; and the conductive performance of the PC/ABS composite material is improved by adding a large amount of conductive carbon black. However, the degree of improving the conductivity is insufficient in the scheme, the electrostatic spraying paint rate is not high enough, and the impact resistance and the flowability of the material are greatly reduced due to a large amount of conductive carbon black. There is therefore a need for a PC/ABS composition suitable for electrostatic spraying processes that combines good electrical conductivity and spray paint application rates with good resistance to paint cracking.
Disclosure of Invention
Based on this, the present invention aims to overcome the above-mentioned disadvantages of the prior art and provide a good electrostatic spraying PC/ABS composition and a preparation method thereof. The PC/ABS composition can have very low surface resistance under the condition of small addition amount of conductive filler, has excellent solvent resistance, can meet the requirements of an electrostatic spraying process for products produced by injection molding, and has the characteristics of higher spraying and painting rate and paint cracking resistance.
In order to achieve the aim, the invention provides a good electrostatic spraying PC/ABS composition, which comprises the following components in parts by weight: 50-70 parts of polycarbonate resin, 10-30 parts of ABS resin, 3-8 parts of spraying modifier, 2-4 parts of conductive filler, 0.1-0.3 part of antioxidant and 0.3-0.8 part of lubricant. The spraying modifier is maleic anhydride grafted branched styrene-acrylonitrile copolymer.
Preferably, the good electrostatic spray PC/ABS composition comprises the following components in parts by weight: 60 parts of polycarbonate resin, 25 parts of ABS resin, 5 parts of spraying modifier, 3 parts of conductive filler, 0.1-0.3 part of antioxidant and 0.3-0.8 part of lubricant.
Further, the maleic anhydride graft ratio of the maleic anhydride-grafted branched styrene-acrylonitrile copolymer (test method reference ASTM D3644-2006) is 0.6 to 2.4wt%, preferably 1.5wt%.
Further, the preparation method of the maleic anhydride grafted branched styrene-acrylonitrile copolymer comprises the following steps: the branched styrene-acrylonitrile copolymer, maleic anhydride and dicumyl peroxide are mixed according to the mass ratio (96-99): (1-3): (0.1-0.4), adding into a double-screw extruder, and carrying out melt extrusion, wherein the mass ratio of the branched styrene-acrylonitrile copolymer, the maleic anhydride and the dicumyl peroxide is (98:2:0.2) to obtain the maleic anhydride grafted branched styrene-acrylonitrile copolymer; the length-diameter ratio of the double-screw extruder is 52:1, the extrusion temperature is set to 170-200 ℃, and the screw rotating speed is set to 200-300rpm.
Further, the conductive filler is a mixture of amino-activated multi-wall carbon nanotubes and amino-activated conductive carbon black, wherein the mass ratio of the amino-activated multi-wall carbon nanotubes to the amino-activated conductive carbon black is 1 (1-3), preferably 1:2.
Further, the amino group-activated multi-walled carbon nanotubes have an amino group content of 2 to 6wt%, preferably 5wt%. The average resistivity is 0.07 to 0.09. Omega. Cm, preferably 0.08. Omega. Cm.
Further, the amino group-activated conductive carbon black has an amino group content of 1 to 4wt%, preferably 2wt%. The average resistivity is 0.17 to 0.20. Omega. Cm, preferably 0.19. Omega. Cm.
Further, the preparation method of the amino activated multiwall carbon nanotube comprises the following steps:
S1: adding the multiwall carbon nanotube and concentrated nitric acid with the mass fraction of 68% into a reaction flask, stirring and refluxing at 70 ℃ for reaction for 24 hours, cooling to room temperature, adding deionized water for dilution, filtering, continuously washing with the deionized water until the pH value of the filtrate is=7, finally freeze-drying the filter cake for 8 hours, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the carboxyl-activated multiwall carbon nanotube;
S2: adding the carboxyl activated multiwall carbon nanotube obtained in the first step, ethylenediamine and DCC condensing agent into a reaction flask, stirring and refluxing at 120 ℃ for reaction for 96 hours, washing off excessive amine, DCC condensing agent and other byproducts by using absolute ethyl alcohol under the condition of ultrasonic oscillation after the reaction is completed, filtering, finally performing freeze drying on a filter cake for 8 hours, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the amino activated multiwall carbon nanotube.
Further, the preparation method of the amino activated conductive carbon black comprises the following steps:
S1: adding conductive carbon black and 68 mass percent of concentrated nitric acid into a reaction flask, stirring and refluxing at 70 ℃ for reaction for 24 hours, cooling to room temperature, adding deionized water for dilution, filtering, continuously washing with deionized water until the pH value of the filtrate is=7, finally freeze-drying the filter cake for 8 hours, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain carboxyl-activated conductive carbon black;
S2: adding the carboxyl activated conductive carbon black obtained in the first step, ethylenediamine and DCC condensing agent into a reaction flask, stirring and refluxing at 120 ℃ for reaction for 96 hours, washing off excessive amine, DCC condensing agent and other byproducts by using absolute ethyl alcohol under the condition of ultrasonic oscillation after the reaction is completed, filtering, finally performing freeze drying on a filter cake for 8 hours, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the amino activated conductive carbon black.
Further, the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant, preferably any one or more of 2, 6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis (2, 4-di-tert-butyl) quaternium diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol bisphosphite dioctadecyl alcohol.
Further, the lubricant is any one or more of silane polymer, butyl stearate, stearic acid, fatty acid salt, fatty acid amide, ethylene bis-stearamide and polyethylene wax. Further, the melt flow rate of the polycarbonate tree is 10-30g/10min, the test standard is ISO 1133-1-2011, the temperature is 300 ℃, and the load is 1.2kg; the melt flow rate of the ABS resin is 16-38g/10min, and the test standard is ISO 1133-1-2011, the temperature is 220 ℃, and the load is 10kg.
The invention also provides a preparation method of the good electrostatic spraying PC/ABS composition, which comprises the following steps:
Weighing polycarbonate resin, ABS resin, spraying modifier, conductive filler, antioxidant and lubricant according to parts by weight, and uniformly mixing to obtain premix, and obtaining a good electrostatic spraying PC/ABS composition through melting, dispersing, blending, extruding, bracing, cooling, drying and granulating; the adopted extrusion processing equipment is a double-screw extruder, the screw rotating speed is 500-600 revolutions per minute, and the processing temperature is 190-250 ℃; double vacuum is adopted, and the vacuum degree is minus 0.075 to minus 0.08MPa.
The invention also provides application of the good electrostatic spraying PC/ABS composition in the field of electrostatic spraying decoration parts. Such as paint parts of automobile spoilers, luggage racks, license plates and the like.
Compared with the prior art, the invention has the following beneficial effects:
The good electrostatic spraying PC/ABS composition provided by the invention can have very low surface resistance under the condition of small addition amount of conductive filler, and meanwhile, the solvent resistance is excellent, and the product produced by injection molding can meet the requirements of an electrostatic spraying process and has the characteristics of higher spraying paint rate and paint cracking resistance. According to the invention, the branched styrene-acrylonitrile copolymer grafted by maleic anhydride is introduced into a PC/ABS composition system, and simultaneously, the amino activated multiwall carbon nano tube and the amino activated conductive carbon black are mixed to obtain a novel conductive filler, active amino groups carried by the novel conductive filler can react with the active anhydride of the branched styrene-acrylonitrile copolymer grafted by maleic anhydride respectively to be combined, the conductive filler is mutually supported by a unique dendritic branched structure, so that the conductive filler is not easy to disperse caused by aggregation, and meanwhile, the amino activated multiwall carbon nano tube with a one-dimensional structure and the amino activated conductive carbon black with a zero-dimensional structure in the system are organically combined in a proper formula ratio, so that the conductive carbon black can be filled in a connecting gap of the multiwall carbon nano tube to strengthen the connection, a conductive network is further formed in the PC/ABS composition in a boosting way, the conduction and migration of charges are accelerated, the PC/ABS composition has extremely low surface resistance, and is very suitable for the requirements of an electrostatic spraying process, and the produced product has higher painting rate. In addition, the combination formed by the reaction connection of the branched styrene-acrylonitrile copolymer grafted by maleic anhydride, the amino activated multiwall carbon nano tube and the amino activated conductive carbon black can build a uniform, continuous and compact physical isolation layer inside the PC/ABS composition by means of the geometrical structure of the multiwall carbon nano tube and the conductive carbon black, can avoid cracking phenomenon caused by excessively corroding the PC/ABS composition due to too strong solvent corrosion in paint, and improves the paint cracking resistance.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, shall fall within the scope of the invention.
Examples
The present invention will be further described with reference to the following specific examples, which are all preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples, and are not particularly limited to the types of the raw materials of the components used in the following specific examples.
1. The raw materials of each component used are as follows:
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
Polycarbonate resin: bisphenol A type, wanhua chemical group Co., ltd., brand PC 2220, melt flow rate (300 ℃ C./1.2 kg) of 20g/10min;
ABS resin: the Shanghai high-bridge petrochemical Co., ltd, with the brand ABS 8434, and the melt flow rate (220 ℃/10 kg) of 19g/10min;
Branched styrene-acrylonitrile copolymer: the best Yi Rong compatibilizer Shanghai Co., ltd., brand EMI-230B, weight average molecular weight 250000, branching degree: the average number of branches per 1000 carbon atoms was 70.
And (3) spraying an improver:
maleic anhydride grafted branched styrene-acrylonitrile copolymer 1 (bSAN-g-MAH 1), self-made, maleic anhydride grafting ratio of 1.5wt%;
Maleic anhydride grafted branched styrene-acrylonitrile copolymer 2 (bSAN-g-MAH 2), self-made, maleic anhydride grafting ratio is 0.6wt%;
maleic anhydride grafted branched styrene-acrylonitrile copolymer 3 (bSAN-g-MAH 3), self-made, maleic anhydride grafting ratio is 2.4wt%;
Maleic anhydride grafted branched styrene-acrylonitrile copolymer 4 (bSAN-g-MAH 4), self-made, maleic anhydride grafting ratio is 0.3%;
maleic anhydride grafted branched styrene-acrylonitrile copolymer 5 (bSAN-g-MAH 5), self-made, maleic anhydride grafting ratio is 3.2%;
Multiwall carbon nanotubes: the Shandong Dazhan nanomaterial Co., ltd., brand GC-21, average resistivity of 0.08Ω & cm;
Conductive carbon black: the product was acetylene BLACK DENKA BLACK, available from Kagaku Kogyo Co., ltd, and had an average resistivity of 0.19. Omega. Cm;
conductive filler 1: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:2;
conductive filler 2: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:1;
conductive filler 3: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:3;
Conductive filler 4: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:0.5;
conductive filler 5: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:4;
Conductive filler 6: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 2 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:2;
conductive filler 7: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 6 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:2;
conductive filler 8: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 1 wt%) with the mass ratio of 1:2;
conductive filler 9: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 4 wt%) with the mass ratio of 1:2;
Conductive filler 10: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 1 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:2;
Conductive filler 11: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 8 wt%) and amino activated conductive carbon black (the amino content is 2 wt%) with the mass ratio of 1:2;
Conductive filler 12: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 0.5 wt%) with the mass ratio of 1:2;
conductive filler 13: self-made, namely, a mixture of amino activated multi-wall carbon nano tubes (the amino content is 5 wt%) and amino activated conductive carbon black (the amino content is 5 wt%) with the mass ratio of 1:2;
conductive filler 14: self-made, unactivated multiwall carbon nanotubes and unactivated conductive carbon black mixture in a mass ratio of 1:2;
conductive filler 15: homemade, amino activated multi-walled carbon nanotubes (amino content 5 wt%);
conductive filler 16: homemade, amino activated conductive carbon black (amino content 5 wt%);
an antioxidant: hindered phenol antioxidants, 2, 6-di-tert-butyl-4-methylphenol, commercially available; phosphite antioxidants, tris (2, 4-di-t-butylphenyl) phosphite, commercially available; the mass ratio of the two is 1:1, the same substances are used in parallel experiments;
And (3) a lubricant: stearate, commercially available, used the same species in parallel experiments;
the PC/ABS compositions of examples 1-17 and comparative examples 1-9 were selected as shown in tables 1 and 2.
The preparation method of the PC/ABS compositions of examples 1-17 and comparative examples 1-9 comprises the following steps: weighing polycarbonate resin, ABS resin, spraying modifier, conductive filler, antioxidant and lubricant according to parts by weight, adding into a high-speed mixer, mixing for 8 minutes, and melting, dispersing, blending, extruding, bracing, cooling, drying and granulating the obtained premix to obtain a good electrostatic spraying PC/ABS composition; the adopted extrusion processing equipment is a double-screw extruder, the screw rotating speed is 500-600 revolutions per minute, and the processing temperature is 190-250 ℃; double vacuum is adopted, and the vacuum degree is minus 0.075 to minus 0.08MPa.
Table 1 example formulation (parts by weight)
Table 2 comparative example formulation (parts by weight)
2. Performance testing
The PC/ABS compositions of examples 1-17 and comparative examples 1-9 were dried in a forced air oven at 100deg.C for 4 hours, injection molded into standard ISO bars and 100 x 3mm plaques using an injection molding machine, and the molded bars and plaques were subjected to performance testing after being placed in a temperature environment of 50.+ -. 5% relative humidity and 23.+ -. 2 ℃ for 24 hours.
The testing method comprises the following steps:
(1) Notched impact strength of simply supported beams: with reference to ISO 179/1eA-1-2010 standard, type A notch, pendulum energy 4J, test temperature 23 ℃;
(2) Melt flow rate: with reference to ISO 1133-1-2011 standard, testing temperature 260 ℃ and load 5kg;
(3) Surface resistance: testing with reference to ISO 3915-1981 standard;
(4) Paint application rate: paint application rate = (weight of template after electrostatic spraying-weight of template before electrostatic spraying)/weight of total loss paint × 100%;
(5) Number of cracks: the method comprises the steps of self-building, firstly performing an electrostatic spraying process, selecting templates with the size of 200 x 140 x 3mm and no defects in appearance, and 10 templates are combined into a group, and performing pretreatment (degreasing, ash removal and drying), electrostatic spraying (electrostatic high voltage of 60-90kV, current of 10-20 mu A, atomization pressure of 0.3-0.5MPa, nozzle distance of 150-300mm, conveying speed of 4.5-5.5 m/min), surface curing (temperature of 90 ℃ and time of 60 min), checking and counting (visual observation and counting of average value of surface cracks of 10 templates after electrostatic spraying).
The results of the PC/ABS composition performance tests of examples 1-17 and comparative examples 1-9 are shown in tables 3 and 4.
Table 3 example performance test results
Table 4 comparative example performance test results
The detection data result shows that the good electrostatic spraying PC/ABS composition has excellent comprehensive properties such as notch impact strength, melt flow rate, surface resistance, paint rate, crack number and the like, and is very suitable for the field of electrostatic spraying decoration. The good electrostatic spraying PC/ABS composition has notch impact strength up to 52-62kJ/m 2, melt flow rate up to 15-25g/10min, surface resistance up to 10E6-10E9 omega and electrostatic spraying paint rate up to 80-92wt%.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (11)
1. The PC/ABS composition for good electrostatic spraying is characterized by comprising the following components in parts by weight:
50-70 parts of polycarbonate resin;
10-30 parts of ABS resin;
3-8 parts of spraying modifier;
2-4 parts of conductive filler;
0.1-0.3 part of antioxidant;
0.3-0.8 parts of lubricant;
the spraying modifier is maleic anhydride grafted branched styrene-acrylonitrile copolymer with grafting rate of 0.6-2.4 wt%;
The conductive filler is a mixture of amino-activated multi-wall carbon nanotubes and amino-activated conductive carbon black, wherein the mass ratio of the amino-activated multi-wall carbon nanotubes to the amino-activated conductive carbon black is 1 (1-3);
the amino group content of the amino group activated multi-wall carbon nano tube is 2-6wt% and the amino group content of the amino group activated conductive carbon black is 1-4wt%.
2. The fine electrostatic spray PC/ABS composition according to claim 1 wherein the maleic anhydride grafted branched styrene-acrylonitrile copolymer is prepared by the following method: the branched styrene-acrylonitrile copolymer, maleic anhydride and dicumyl peroxide are mixed according to the mass ratio (96-99): (1-3): (0.1-0.4) and then adding the mixture into a double-screw extruder for melt extrusion, thus obtaining the maleic anhydride grafted branched styrene-acrylonitrile copolymer.
3. The fine electrostatic spray PC/ABS composition according to claim 1 wherein the amino activated multiwall carbon nanotubes have an average resistivity of 0.07 to 0.09 Ω -cm.
4. The fine electrostatic spray PC/ABS composition according to claim 1 wherein the average resistivity of the amino activated conductive carbon black is from 0.17 to 0.20 Ω -cm.
5. The fine electrostatic spray PC/ABS composition according to claim 1 wherein the amino activated multiwall carbon nanotubes are prepared by the process comprising:
S1: adding the multiwall carbon nanotube and concentrated nitric acid with the mass fraction of 68% into a reaction flask, stirring and refluxing at 70 ℃ for reaction for 24 hours, cooling to room temperature, adding deionized water for dilution, filtering, continuously washing with the deionized water until the pH value of the filtrate is=7, finally freeze-drying the filter cake for 8 hours, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the carboxyl-activated multiwall carbon nanotube;
S2: adding the carboxyl activated multiwall carbon nanotube obtained in the first step, ethylenediamine and DCC condensing agent into a reaction flask, stirring and refluxing at 120 ℃ for reaction for 96 hours, washing off excessive amine, DCC condensing agent and other byproducts by using absolute ethyl alcohol under the condition of ultrasonic oscillation after the reaction is completed, filtering, finally performing freeze drying on a filter cake for 8 hours, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the amino activated multiwall carbon nanotube.
6. The fine electrostatic spray PC/ABS composition according to claim 1 wherein the process for the preparation of the amino activated conductive carbon black is as follows:
S1: adding conductive carbon black and 68 mass percent of concentrated nitric acid into a reaction flask, stirring and refluxing at 70 ℃ for reaction for 24 hours, cooling to room temperature, adding deionized water for dilution, filtering, continuously washing with deionized water until the pH value of the filtrate is=7, finally freeze-drying the filter cake for 8 hours, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain carboxyl-activated conductive carbon black;
S2: adding the carboxyl activated conductive carbon black obtained in the first step, ethylenediamine and DCC condensing agent into a reaction flask, stirring and refluxing at 120 ℃ for reaction for 96 hours, washing off excessive amine, DCC condensing agent and other byproducts by using absolute ethyl alcohol under the condition of ultrasonic oscillation after the reaction is completed, filtering, finally performing freeze drying on a filter cake for 8 hours, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the amino activated conductive carbon black.
7. The fine electrostatic spray PC/ABS composition according to claim 1 wherein the antioxidant is a hindered phenolic antioxidant and/or a phosphite antioxidant.
8. The fine electrostatic spray PC/ABS composition according to claim 1 wherein the lubricant is any one or more of a silane polymer, butyl stearate, stearic acid, fatty acid salts, fatty acid amides, ethylenebisstearamide, polyethylene wax.
9. The fine electrostatic spray PC/ABS composition according to claim 1 wherein the polycarbonate resin melt flow rate is 10-30g/10min and the ABS resin melt flow rate is 16-38g/10min.
10. A method of preparing a good electrostatic spray PC/ABS composition according to any one of claims 1 to 9 comprising the steps of: weighing the raw materials according to the parts by weight, uniformly mixing, and carrying out melting, dispersing, blending, extrusion, bracing, cooling, drying and granulating on the obtained premix to obtain the good electrostatic spraying PC/ABS composition.
11. Use of a good electrostatic spray PC/ABS composition according to any one of claims 1 to 9 in the field of electrostatic spray decorative parts.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230211A (en) * | 2007-12-27 | 2008-07-30 | 同济大学 | A kind of preparation method of small molecule imide modified carbon nanotube |
| CN102430121A (en) * | 2011-11-18 | 2012-05-02 | 广东工业大学 | A kind of preparation method of aminated carbon nanotube |
| CN102604299A (en) * | 2012-02-20 | 2012-07-25 | 金发科技股份有限公司 | Thermoplastic resin blend with weather resistance, scratch resistance, high gloss and high heat resistance and preparation method of the resin blend |
| CN103214881A (en) * | 2013-04-15 | 2013-07-24 | 苏州大学 | Ionic liquid grafted modified carbon black and preparation method thereof |
| CN109622011A (en) * | 2018-12-06 | 2019-04-16 | 浙江工业大学 | A kind of amino multi-wall carbon nanotube supported ruthenium catalyst and its preparation and application |
| CN111087800A (en) * | 2019-12-28 | 2020-05-01 | 会通新材料股份有限公司 | Matte PA/ABS composite material with good touch feeling and preparation method thereof |
| CN114702811A (en) * | 2022-03-31 | 2022-07-05 | 上海金发科技发展有限公司 | Antistatic piano black PC/ABS alloy and preparation method and application thereof |
| CN115124842A (en) * | 2022-07-15 | 2022-09-30 | 东莞市润银实业有限公司 | Storage-resistant silicone rubber used at wide temperature and preparation method thereof |
| CN115260626A (en) * | 2022-06-30 | 2022-11-01 | 广东九彩新材料有限公司 | Blue-biased high-content pigment carbon black coloring polyethylene master batch and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009521535A (en) * | 2005-08-08 | 2009-06-04 | キャボット コーポレイション | Polymer composition comprising nanotubes |
-
2022
- 2022-11-29 CN CN202211505753.9A patent/CN115772325B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230211A (en) * | 2007-12-27 | 2008-07-30 | 同济大学 | A kind of preparation method of small molecule imide modified carbon nanotube |
| CN102430121A (en) * | 2011-11-18 | 2012-05-02 | 广东工业大学 | A kind of preparation method of aminated carbon nanotube |
| CN102604299A (en) * | 2012-02-20 | 2012-07-25 | 金发科技股份有限公司 | Thermoplastic resin blend with weather resistance, scratch resistance, high gloss and high heat resistance and preparation method of the resin blend |
| CN103214881A (en) * | 2013-04-15 | 2013-07-24 | 苏州大学 | Ionic liquid grafted modified carbon black and preparation method thereof |
| CN109622011A (en) * | 2018-12-06 | 2019-04-16 | 浙江工业大学 | A kind of amino multi-wall carbon nanotube supported ruthenium catalyst and its preparation and application |
| CN111087800A (en) * | 2019-12-28 | 2020-05-01 | 会通新材料股份有限公司 | Matte PA/ABS composite material with good touch feeling and preparation method thereof |
| CN114702811A (en) * | 2022-03-31 | 2022-07-05 | 上海金发科技发展有限公司 | Antistatic piano black PC/ABS alloy and preparation method and application thereof |
| CN115260626A (en) * | 2022-06-30 | 2022-11-01 | 广东九彩新材料有限公司 | Blue-biased high-content pigment carbon black coloring polyethylene master batch and preparation method thereof |
| CN115124842A (en) * | 2022-07-15 | 2022-09-30 | 东莞市润银实业有限公司 | Storage-resistant silicone rubber used at wide temperature and preparation method thereof |
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