CN115772325A - Good electrostatic spraying PC/ABS composition and preparation method and application thereof - Google Patents
Good electrostatic spraying PC/ABS composition and preparation method and application thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 229920007019 PC/ABS Polymers 0.000 title claims abstract description 46
- 238000007590 electrostatic spraying Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 amino activated carbon nano tube Chemical class 0.000 claims abstract description 38
- 239000011231 conductive filler Substances 0.000 claims abstract description 30
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims abstract description 17
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 55
- 239000002048 multi walled nanotube Substances 0.000 claims description 37
- 239000012065 filter cake Substances 0.000 claims description 16
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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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 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
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- 238000005034 decoration Methods 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
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
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- 238000010422 painting Methods 0.000 description 11
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- 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 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
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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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 241000872198 Serjania polyphylla Species 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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000013022 formulation composition Substances 0.000 description 2
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- 229920005989 resin Polymers 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 150000008064 anhydrides Chemical class 0.000 description 1
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- 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
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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
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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
Landscapes
- 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 maleic anhydride grafted branched styrene-acrylonitrile copolymer into the PC/ABS composition system, so that the branched styrene-acrylonitrile copolymer reacts with the mixture consisting 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 corrosion.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a good electrostatic spraying PC/ABS composition, and a preparation method and application thereof.
Background
With the continuous enhancement of greenhouse effect and natural environment deterioration, environmental protection has further become the mainstream concept and trend of society. The surface spraying of the plastic part can obviously improve the performances of impact resistance, scratch resistance, solvent resistance, aging resistance and the like of the material, greatly prolong the service life of the part and realize the purposes of carbon reduction and emission reduction in the whole life cycle. The different spraying processes have obvious difference on the painting rate of the coating, the painting rate of the traditional air spraying is only 30% -60%, the electrostatic spraying is mainly absorbed on the surface of a workpiece by virtue of the electrostatic adsorption force of the coating, the painting rate can reach 70% -90%, the utilization rate of the coating can be improved by 30% -40%, the saving, energy saving and emission reduction are further realized, and therefore the electrostatic spraying is paid more and more attention and choices in the market.
The polycarbonate resin (PC) has the characteristics of high gloss, high heat resistance, high strength and high impact resistance, and is a very important engineering plastic; the acrylonitrile-butadiene-styrene terpolymer resin (ABS) has the excellent performances of three components, has excellent chemical stability resistance, impact strength and processability, and the PC/ABS composite material prepared from PC and ABS has the performance advantages of the PC/ABS composite material and the ABS, and is an excellent paint spraying base material. However, conventional PC/ABS compositions have a high surface resistance, generally in excess of 10 14 Omega, the direct electrostatic spraying has extremely low painting rate and no practical significance, and the conductivity of the conductive coating needs to be improved. In the prior art, a conductive matrix is prepared by using PC resin, barium titanate ceramic powder and a siloxane coupling agent, and then the conductive matrix and ABS are mixed to prepare a bicontinuous structure, 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 conductivity of the PC/ABS composite material is improved by adding a large amount of conductive carbon black. However, the above solutions have insufficient degree of conductivity improvement, the electrostatic spraying painting rate is not high enough, and a large amount of conductive carbon black can also cause great attenuation of the impact resistance and fluidity of the material. Therefore, a PC/ABS composition which is suitable for an electrostatic spraying process and has the advantages of excellent conductivity, spraying painting rate and good oil paint cracking resistance is needed.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a good electrostatic spraying PC/ABS composition and a preparation method thereof. The PC/ABS composition has very low surface resistance and excellent solvent resistance under the condition of less conductive filler addition, and the injection-molded product can meet the requirements of an electrostatic spraying process and has the characteristics of high spraying and painting rate and oil-resistant paint cracking.
In order to achieve the purpose, 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 spraying 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 graft-branched styrene-acrylonitrile copolymer (test method is referred to 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: mixing a branched styrene-acrylonitrile copolymer, maleic anhydride and dicumyl peroxide according to a mass ratio of (96-99): (1-3): (0.1-0.4), adding the mixture into a double-screw extruder for melt extrusion, wherein the mass ratio of the branched styrene-acrylonitrile copolymer to the maleic anhydride to the dicumyl peroxide is preferably 98; the length-diameter ratio of the twin-screw extruder is 52, the extrusion temperature is set to be 170-200 ℃, and the screw rotating speed is set to be 200-300rpm.
Furthermore, 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), and is preferably 1:2.
Furthermore, the amino-activated multi-walled carbon nanotube has an amino 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 multi-wall carbon nanotube comprises the following steps:
s1: adding a multi-walled carbon nanotube and concentrated nitric acid with the mass fraction of 68% into a reaction flask, stirring and refluxing at 70 ℃ for 24h, cooling to room temperature, adding deionized water for dilution, filtering, continuously washing with deionized water until the pH of the filtrate is =7, finally freeze-drying a filter cake for 8h, and then placing the filter cake in a vacuum oven for drying at 60 ℃ for 24h to obtain a carboxyl activated multi-walled carbon nanotube;
s2: adding the carboxyl activated multi-walled carbon nano-tube, ethylenediamine and DCC condensing agent obtained in the first step into a reaction flask, stirring and refluxing for 96h at 120 ℃, after the reaction is finished, washing off redundant amine, DCC condensing agent and other byproducts by absolute ethyl alcohol under the ultrasonic oscillation condition, filtering, finally freeze-drying the filter cake for 8h, and then placing the filter cake in a vacuum oven for drying for 24h at 60 ℃ to obtain the amino activated multi-walled carbon nano-tube.
Further, the preparation method of the amino activated conductive carbon black comprises the following steps:
s1: adding conductive carbon black and concentrated nitric acid with the mass fraction of 68% into a reaction flask, stirring and refluxing at 70 ℃ for 24h, cooling to room temperature, adding deionized water for dilution, filtering, continuously washing with deionized water until the pH of the filtrate is =7, finally performing freeze drying on a filter cake for 8h, and then placing the filter cake in a vacuum oven for drying at 60 ℃ for 24h 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 for 96h at 120 ℃, washing off redundant amine, DCC condensing agent and other byproducts by using absolute ethyl alcohol under the condition of ultrasonic oscillation after the reaction is finished, filtering, finally freeze-drying the filter cake for 8h, and then placing the filter cake in a vacuum oven for drying for 24h at 60 ℃ to obtain the amino activated conductive carbon black.
Further, the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant, preferably 2,6-di-tert-butyl-4-methylphenol, pentaerythrityl tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis (2,4-di-tert-butyl) Ji Sichun diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, or dioctadecyl pentaerythritol diphosphite.
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 refers to 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, the test standard refers to 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, a spraying modifier, conductive filler, an antioxidant and a lubricant according to the weight parts, uniformly mixing, 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 rotating speed of a screw is 500-600 revolutions per minute, and the processing temperature is 190-250 ℃; double vacuum is adopted, and the vacuum degree is-0.075 to-0.08 MPa.
The invention also provides application of the good electrostatic spraying PC/ABS composition in the field of electrostatic spraying decoration parts. Such as painted 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 has very low surface resistance and excellent solvent resistance under the condition of a small addition amount of conductive filler, and a product produced by injection molding can meet the requirements of an electrostatic spraying process and has the characteristics of high spraying and painting rate and oil cracking resistance. The invention introduces maleic anhydride grafted branched styrene-acrylonitrile copolymer into a PC/ABS composition system, and simultaneously obtains a novel conductive filler by mixing amino activated multi-walled carbon nanotubes and amino activated conductive carbon black, active amino groups of the novel conductive filler can respectively react with active anhydride of the maleic anhydride grafted branched styrene-acrylonitrile copolymer to be combined, the conductive filler is mutually supported by a unique dendritic branched structure to avoid difficult dispersion caused by agglomeration, and meanwhile, the conductive carbon black can be filled in a connecting gap of the multi-walled carbon nanotubes to strengthen the linkage by organically combining the amino activated multi-walled carbon nanotubes with one-dimensional structures and the amino activated conductive carbon black with zero-dimensional structures in the system in a proper formula proportion, so that a conductive network is further formed in the PC/ABS composition by assistance, the conduction and the migration of charges are accelerated, the PC/ABS composition has extremely low surface resistance, is very suitable for the requirements of an electrostatic spraying process, and the produced products have high lacquering rate. In addition, a branched styrene-acrylonitrile copolymer grafted by maleic anhydride, an amino activated multi-walled carbon nanotube and amino activated conductive carbon black are reacted and connected to form a combined body, and by means of the geometrical structures of the multi-walled carbon nanotube and the conductive carbon black, a uniform, continuous and compact physical isolation layer can be constructed in the PC/ABS composition, so that the cracking phenomenon caused by excessive erosion of the PC/ABS composition due to too strong corrosion of a solvent in paint can be avoided, and the cracking performance of the oil-resistant paint is improved.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
Examples
The present invention will be further described with reference to the following specific examples and comparative examples, which are preferred embodiments of the present invention, but the present invention is not limited to the following examples, and is not particularly limited to the types of the component materials used in the following specific examples.
1. The raw materials of the components used are as follows:
in the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Polycarbonate resin: bisphenol A, wanhua chemical group, inc., brand PC 2220, melt flow rate (300 ℃/1.2 kg) 20g/10min;
ABS resin: shanghai Gaoqiao petrochemical Co., ltd, the trademark is ABS 8434, and the melt flow rate (220 ℃/10 kg) is 19g/10min;
branched styrene-acrylonitrile copolymer: good easy compatibility agent Shanghai Limited, under the trade designation EMI-230B, weight average molecular weight 250000, degree of branching: the average number of branches per 1000 carbon atoms was 70.
And (3) spraying a modifier:
maleic anhydride grafted and branched styrene-acrylonitrile copolymer 1 (bSAN-g-MAH 1), which is prepared by self, wherein the grafting rate of maleic anhydride is 1.5wt%;
maleic anhydride grafted and branched styrene-acrylonitrile copolymer 2 (bSAN-g-MAH 2), which is prepared by self, wherein the grafting rate of maleic anhydride is 0.6wt%;
maleic anhydride grafted and branched styrene-acrylonitrile copolymer 3 (bSAN-g-MAH 3), which is prepared by self, wherein the grafting rate of maleic anhydride is 2.4wt%;
maleic anhydride grafted and branched styrene-acrylonitrile copolymer 4 (bSAN-g-MAH 4), which is prepared by self, wherein the grafting rate of maleic anhydride is 0.3%;
maleic anhydride grafted and branched styrene-acrylonitrile copolymer 5 (bSAN-g-MAH 5), which is prepared by self, wherein the grafting rate of maleic anhydride is 3.2%;
multi-walled carbon nanotubes: shandong Dazhu nanometer materials, inc., having a GC-21 designation and an average resistivity of 0.08 Ω & cm;
conductive carbon black: manufactured by Nippon Denka chemical industry Co., ltd., acetylene BLACK DENKA BLACK having an average resistivity of 0.19. Omega. Cm;
conductive filler 1: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 5 wt%) and amino activated conductive carbon black (amino content is 2 wt%), and mass ratio is 1:2;
conductive filler 2: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 5 wt%) and amino activated conductive carbon black (amino content is 2 wt%), and mass ratio is 1:1;
conductive filler 3: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 5 wt%) and amino activated conductive carbon black (amino content is 2 wt%), and mass ratio is 1:3;
conductive filler 4: self-made mixture of amino activated multi-walled carbon nanotubes (amino content 5 wt%) and amino activated conductive carbon black (amino content 2 wt%), wherein the mass ratio is 1;
conductive filler 5: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 5 wt%) and amino activated conductive carbon black (amino content is 2 wt%), and mass ratio is 1:4;
conductive filler 6: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 2 wt%) and amino activated conductive carbon black (amino content is 2 wt%), and the mass ratio is 1:2;
conductive filler 7: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 6 wt%) and amino activated conductive carbon black (amino content is 2 wt%), and mass ratio is 1:2;
conductive filler 8: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 5 wt%) and amino activated conductive carbon black (amino content is 1 wt%), and the mass ratio is 1:2;
conductive filler 9: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 5wt percent) and amino activated conductive carbon black (amino content is 4wt percent), and the mass ratio is 1:2;
conductive filler 10: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 1 wt%) and amino activated conductive carbon black (amino content is 2 wt%), and mass ratio is 1:2;
conductive filler 11: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content 8 wt%) and amino activated conductive carbon black (amino content 2 wt%), with the mass ratio of 1:2;
conductive filler 12: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 5 wt%) and amino activated conductive carbon black (amino content is 0.5 wt%), and the mass ratio is 1:2;
conductive filler 13: self-made mixture of amino activated multi-walled carbon nano-tubes (amino content is 5 wt%) and amino activated conductive carbon black (amino content is 5 wt%), and the mass ratio is 1:2;
conductive filler 14: self-made mixture of unactivated multi-wall carbon nano-tubes and unactivated conductive carbon black with the mass ratio of 1:2;
conductive filler 15: self-made amino activated multi-wall carbon nano-tubes (the amino content is 5 wt%);
conductive filler 16: self-made, amino activated conductive carbon black (amino content 5 wt%);
antioxidant: hindered phenol antioxidant 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 substance is used in the parallel experiment;
lubricant: stearate, commercially available, used in parallel experiments with the same material;
the PC/ABS composition components and parts by weight selections for examples 1-17 and comparative examples 1-9 are 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, a spraying modifier, conductive filler, an antioxidant and a lubricant according to the parts by weight, adding the weighed materials into a high-speed mixer, mixing for 8 minutes, and melting, dispersing, blending, extruding, drawing strips, 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 rotating speed of a screw is 500-600 revolutions per minute, and the processing temperature is 190-250 ℃; double vacuum is adopted, and the vacuum degree is-0.075 to-0.08 MPa.
TABLE 1 examples formulation composition (parts by weight)
TABLE 2 comparative example formulation composition (parts by weight)
2. Performance testing
The PC/ABS compositions of examples 1 to 17 and comparative examples 1 to 9 were dried in a forced air oven at 100 ℃ for 4 hours, injection-molded into standard ISO test bars and 100X 3mm test pieces using an injection molding machine, and the injection-molded test bars and test pieces were subjected to a performance test after being left for 24 hours in an atmosphere of 50. + -. 5% relative humidity and 23. + -. 2 ℃.
The test method comprises the following steps:
(1) Impact strength of the simply supported beam notch: referring to ISO 179/1eA-1-2010 standard, type A notch, pendulum energy 4J, test temperature 23 ℃;
(2) Melt flow rate: according to ISO 1133-1-2011 standard, the test temperature is 260 ℃, and the load is 5kg;
(3) Surface resistance: the test is carried out by referring to the ISO 3915-1981 standard;
(4) The painting rate is as follows: lacquering rate = (weight of sample after electrostatic spraying-weight of sample before electrostatic spraying)/weight of total lost paint 100%;
(5) The number of cracks: the method is self-established, firstly, an electrostatic spraying process is carried out, samples with the size of 200 x 140 x 3mm and no defect in appearance are selected, 10 samples are taken as a group, and pretreatment (oil removal, ash removal and drying) → electrostatic powder spraying (electrostatic high voltage 60-90kV, current 10-20 muA, atomization pressure 0.3-0.5MPa, nozzle distance 150-300mm, conveying speed 4.5-5.5 m/min) → surface curing (temperature 90 ℃, time 60 min) → inspection statistics (the average value of the surface crack number of 10 samples after electrostatic spraying is observed and counted by naked eyes).
The results of the performance tests of the PC/ABS compositions of examples 1-17 and comparative examples 1-9 are shown in tables 3 and 4.
Table 3 results of performance testing of examples
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, painting rate, crack number and the like, and is very suitable for the field of electrostatic spraying decorative parts. The notch impact strength of the good electrostatic spraying PC/ABS composition can reach 52-62kJ/m 2 The melt flow rate reaches 15-25g/10min, the surface resistance reaches 10E6-10E9 omega, and the electrostatic spraying painting rate reaches 80-92wt%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (13)
1. A good electrostatic spraying PC/ABS composition 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 a spraying modifier;
2-4 parts of conductive filler;
0.1-0.3 part of antioxidant;
0.3-0.8 part of lubricant;
the spraying modifier is maleic anhydride grafted branched styrene-acrylonitrile copolymer.
2. The good electrostatic spray PC/ABS composition of claim 1 wherein the spray modifier has a maleic anhydride grafting of 0.6 to 2.4wt%.
3. The good electrostatic spraying PC/ABS composition of claim 1, wherein the maleic anhydride grafted branched styrene-acrylonitrile copolymer is prepared by the following method: mixing a branched styrene-acrylonitrile copolymer, maleic anhydride and dicumyl peroxide according to a mass ratio of (96-99): (1-3): (0.1-0.4) and adding the mixture into a double-screw extruder for melt extrusion to obtain the maleic anhydride grafted branched styrene-acrylonitrile copolymer.
4. The good electrostatic spraying PC/ABS composition as claimed in claim 1, wherein the conductive filler is a mixture of amino-activated multi-walled carbon nanotubes and amino-activated conductive carbon black, and the mass ratio of the amino-activated multi-walled carbon nanotubes to the amino-activated conductive carbon black is 1 (1-3).
5. The good electrostatic spraying PC/ABS composition of claim 4, wherein the amino group-activated multi-walled carbon nanotubes have an amino group content of 2 to 6 wt.% and an average resistivity of 0.07 to 0.09 Ω -cm.
6. The good electrostatic spraying PC/ABS composition of claim 4, wherein the amino activated conductive carbon black has an amino group content of 1-4wt% and an average resistivity of 0.17-0.20 Ω -cm.
7. The good electrostatic spraying PC/ABS composition of claim 5, wherein the amino activated multi-walled carbon nanotubes are prepared by the following method:
s1: adding a multi-walled carbon nanotube and concentrated nitric acid with the mass fraction of 68% into a reaction flask, stirring and refluxing at 70 ℃ for 24h, cooling to room temperature, adding deionized water for dilution, filtering, continuously washing with deionized water until the pH of the filtrate is =7, finally freeze-drying a filter cake for 8h, and then placing the filter cake in a vacuum oven for drying at 60 ℃ for 24h to obtain a carboxyl activated multi-walled carbon nanotube;
s2: adding the carboxyl activated multi-walled carbon nanotube, ethylenediamine and DCC condensing agent obtained in the first step into a reaction flask, stirring and refluxing for 96 hours at 120 ℃, washing off redundant amine, DCC condensing agent and other byproducts by using absolute ethyl alcohol under the condition of ultrasonic oscillation after the reaction is finished, filtering, finally freeze-drying the filter cake for 8 hours, and then placing the filter cake in a vacuum oven for drying for 24 hours at 60 ℃ to obtain the amino activated multi-walled carbon nanotube.
8. The good electrostatic spray PC/ABS composition of claim 6 wherein the amino activated conductive carbon black is prepared by the following method:
s1: adding conductive carbon black and concentrated nitric acid with the mass fraction of 68% into a reaction flask, stirring and refluxing at 70 ℃ for 24h, cooling to room temperature, adding deionized water for dilution, filtering, continuously washing with deionized water until the pH of the filtrate is =7, finally performing freeze drying on a filter cake for 8h, and then placing the filter cake in a vacuum oven for drying at 60 ℃ for 24h to obtain carboxyl activated conductive carbon black;
s2: and adding the carboxyl activated conductive carbon black, ethylenediamine and DCC condensing agent obtained in the first step into a reaction flask, stirring and refluxing for 96 hours at 120 ℃, after the reaction is finished, washing off redundant amine, DCC condensing agent and other byproducts by absolute ethyl alcohol under the ultrasonic oscillation condition, filtering, finally freeze-drying the filter cake for 8 hours, and then placing the filter cake in a vacuum oven for drying for 24 hours at 60 ℃ to obtain the amino activated conductive carbon black.
9. The good electrostatic spraying PC/ABS composition as claimed in claim 1, wherein the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant.
10. The good electrostatic spraying PC/ABS composition of claim 1, wherein the lubricant is any one or more of silane polymer, butyl stearate, stearic acid, fatty acid salt, fatty acid amide, ethylene bis-stearamide, polyethylene wax.
11. The good electrostatic spraying PC/ABS composition of claim 1, wherein the polycarbonate resin has a melt flow rate of 10-30g/10min and the ABS resin has a melt flow rate of 16-38g/10min.
12. A process for the preparation of a good electrostatic spray PC/ABS composition according to any of claims 1 to 11, characterized in that it comprises the following steps: weighing the raw materials according to the parts by weight, uniformly mixing, and carrying out melting, dispersing, blending, extruding, bracing, cooling, drying and granulating on the obtained premix to obtain the good electrostatic spraying PC/ABS composition.
13. Use of a good electrostatic spray PC/ABS composition according to any of claims 1 to 11 in the field of electrostatic spray decoration.
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