CN115181392B - Metal spraying-free ABS material with low humidity and heat aging resistance and low precipitation and preparation method thereof - Google Patents
Metal spraying-free ABS material with low humidity and heat aging resistance and low precipitation and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 238000001556 precipitation Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
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- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010556 emulsion polymerization method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
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- 150000003384 small molecules Chemical class 0.000 description 5
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
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- 238000001746 injection moulding Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
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- 238000004945 emulsification Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940075529 glyceryl stearate Drugs 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
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- 239000012860 organic pigment Substances 0.000 description 2
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/08—Metals
- C08K2003/0812—Aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a metal spraying-free ABS material with low humidity and heat aging resistance and low precipitation and a preparation method thereof, wherein the material comprises the following components in parts by weight: 100 parts of ABS resin, 0.1-1.5 parts of antioxidant, 0.1-1 part of lubricant, 0.1-0.5 part of weather-proof agent, 0.1-2 parts of metal powder and 1-10 parts of pigment; according to the weight portions, the ABS resin, the antioxidant, the lubricant, the metal powder and the pigment are uniformly mixed in a high-speed mixer, the uniformly mixed materials are added into a double-screw extruder to be melted, blended and extruded, and finally the ABS resin, the antioxidant, the lubricant, the metal powder and the pigment are obtained after granulating and drying. The metal spraying-free ABS material with low humidity and heat aging resistance and precipitation has the appearance effect of metal spraying imitation, has very excellent humidity and heat aging resistance, greatly improves the precipitation condition in the practical application process, has simple formula components and lower process requirements, and has good economic benefit.
Description
Technical Field
The invention relates to the technical field of metal spraying-free materials, in particular to a metal spraying-free ABS material with low humidity resistance and heat aging resistance and precipitation and a preparation method thereof.
Background
Along with the gradual implementation of environmental protection policies in recent years, the traditional post-treatment process for the surface of a workpiece such as spraying, water transfer printing and the like is gradually resisted by more and more enterprises due to the defects of large smell, toxicity, poor production environment and the like, and the spraying-free material formed by one-step injection molding is slowly accepted and adopted by more enterprises. By adding aluminum powder with a certain proportion and particle size in the injection molding process, metal texture similar to aluminum alloy can be formed on the surface of plastic, and meanwhile, the convenience of processing, designability of surface appearance effect and cost advantage compared with the traditional spray product make research on spray-free materials more and more important.
In the use process of the metal spraying-free ABS material, the phenomenon of performance reduction caused by wet heat aging deformation or color change and the like is often encountered, the phenomenon of precipitation of small molecular substances on the surface occurs along with the change of temperature or humidity, the phenomenon is generated because the wet heat aging resistance level of the ABS is poor, the precipitation of the small molecules is caused by more small molecular substances brought in the synthesis or processing process, and the small molecules migrate out of a matrix along with the change of the external temperature and humidity.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a metal spraying-free ABS material with low humidity resistance and heat aging resistance and low precipitation and a preparation method thereof.
The invention aims at realizing the following scheme:
The invention relates to a metal spraying-free ABS material with low humidity and heat aging resistance and precipitation, which comprises the following components in parts by weight:
As one embodiment, the ABS resin is synthesized by an emulsion polymerization method, and the particle size of rubber is 200-700 mu m.
As one embodiment, the ABS resin has a butadiene content of 12-15% and a melt flow rate of 15-30 g/10min measured under a melt index test condition of 220 ℃ and 10 kg.
As one embodiment, the lubricant is one or more of magnesium stearate, ethylene bisstearamide EBS, glyceryl stearate. The selected lubricant has few residual small molecules.
As an embodiment, the weather-resistant agent is one or more of a weather-resistant agent 3033P, a weather-resistant agent 234, and a weather-resistant agent 329. Preferably 0.6 to 1 part.
As one embodiment, the metal powder is one or more of aluminum powder, copper powder and silver powder.
As one embodiment, the metal powder has a particle size of 60 μm to 140. Mu.m. The addition amount decreases with the increase of the pigment particle size.
As one embodiment, the antioxidant is one or more of antioxidant 1076, antioxidant 168, antioxidant 1010.
As one embodiment, the pigment is carbon black. Most of the toner can play a role of covering a matrix, the higher the content of the toner, the less detailed the color change of the material is caused by environmental test, while the carbon black has the best effect and also has the effect of a weather-proof agent.
The invention also relates to a preparation method of the metal spraying-free ABS material with low humidity and heat aging resistance and precipitation, which comprises the following steps:
S1, weighing raw materials according to parts by weight; uniformly mixing ABS resin, an antioxidant, a lubricant, a weather-resistant agent, metal powder and pigment;
S2, adding the uniformly mixed materials in the step S1 into a double-screw extruder, and finally granulating and drying.
As one embodiment, the twin-screw extruder is operated at a temperature of 180℃to 235℃and a screw speed of 400 to 500 revolutions per minute.
As one embodiment, the temperature of the drying is 75-85 ℃ and the time is 4-8h.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention selects the antioxidant with better heat resistance to cooperate with the high-efficiency weather-proof agent, so that the heat stability of the matrix resin is improved, and the change of the internal molecular structure of the material caused by damp-heat condition is restrained, thereby solving the problems of obvious reduction of impact performance and precipitation of small molecules of the metal spraying-free ABS in damp-heat environment
2) According to the invention, the lubricant with poor migration is selected, the content is adjusted, the precipitation amount under the processing and damp-heat conditions is reduced, and the problem that the small molecules of the metal spraying-free ABS are easy to precipitate under the damp-heat environment is solved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The raw materials used in examples and comparative examples are described below, but are not limited to these materials:
ABS resin # 1: commercial emulsion process ABS, MI20;
ABS resin # 2: commercial emulsion process ABS, MI30;
ABS resin 3#: commercial bulk ABS, MI21;
an antioxidant: antioxidants 107, 168 and 1010, all of which are commercially available products;
And (3) a lubricant: magnesium stearate, EBS and glyceryl stearate, commercially available products;
weather-resistant agent: 3033P, 234 and 329, commercially available products;
metal powder: aluminum powder, MP100-20B, bohuai chemical industry, particle size of 100um;
examples 1 to 7
ABS resin, antioxidant, weather-proof agent, lubricant, aluminum pigment and organic pigment are fully mixed according to the proportion of the table 1 (examples 1-7), and then the metal spraying-free ABS material with low moisture and heat aging resistance and precipitation is prepared through twin-screw extrusion, bracing, granulating and drying. The temperature of each section of the double-screw extruder body is 180-190 ℃, 190-200 ℃, 210-220 ℃, 220-230 ℃ and the temperature of the machine head is 230-235 ℃ in sequence; the screw speed of the extruder is 500 revolutions per minute, the cooling water temperature is 25 ℃, the vacuum degree is 1.0MPa, the drying temperature is 80 ℃, and the time is 6 hours.
Comparative examples 1 to 15
ABS resin, antioxidant, weather-proof agent, lubricant, aluminum pigment and organic pigment are fully mixed according to the proportion of the table 1 (comparative examples 1-15), and then the metal spraying-free ABS material with low moisture and heat aging resistance and precipitation is prepared through twin-screw extrusion, bracing, granulating and drying. The temperature of each section of the double-screw extruder body is 180-190 ℃, 190-200 ℃, 210-220 ℃, 220-230 ℃ and the temperature of the machine head is 230-235 ℃ in sequence; the screw speed of the extruder is 400-500 rpm, the cooling water temperature is 25 ℃, the vacuum degree is 1.0MPa, the drying temperature is 80 ℃ and the time is 6 hours.
Performance evaluation mode and implementation standard:
The notch impact strength is tested according to the D256-10 (2018) standard, and the notch type is V-shaped;
The accelerated aging test is carried out according to the ASTM D4459-2006 standard, the xenon lamp is continuously irradiated for 60 hours, then the test is carried out by aging for 60 hours in a constant temperature and humidity box with the speed of 85 ℃/85%RH, the color difference is tested according to the GB/T7921-2008 standard, and the test is carried out by adopting a D65 light source;
The retention of impact properties is the ratio of the notched impact strength after accelerated aging to the notched impact strength before aging; the color difference Δe is a color difference value between the color after the accelerated aging test and the color before aging.
Table 1 specific proportions (parts by weight) of the components in each example and comparative example
TABLE 2 Performance test data for samples of examples and comparative examples
As can be seen from examples 1 to 7, the impact retention rate of the spray-free ABS material for metals with low resistance to wet heat aging after aging is more than 80%, the color difference DeltaE is less than or equal to 2, the spray-free ABS material has excellent resistance to wet heat aging, no obvious precipitation on the surface and good metal texture. As can be seen from examples 1 to 7, the emulsion ABS has a high impact toughness retention rate and maintains good resistance to humid heat aging under a certain content of auxiliary agents; as can be seen from comparative examples 1, 10,11, 12 and example 7, the types and contents of antioxidants affect the stability of the materials after the materials are subjected to wet heat aging, the impact retention rate is reduced to a certain extent by increasing the contents, the chromatic aberration is gradually increased, and meanwhile, precipitation is more likely to occur; as can be seen from comparative examples 2, 13, 14 and example 7, too high a lubricant content results in a large number of residual monomers, the color difference of the materials after accelerated aging is relatively poor, precipitation occurs, while other types of lubricants are precipitated to a certain extent, but the impact is less influenced; as seen from comparison of comparative example 3 and example 7, an increase in the content of the weathering agent also affects the appearance of the material after wet heat aging, resulting in an increase in color difference, and the condition after accelerated aging depends on the kind of the weathering agent; as can be seen from comparative example 4 and example 7, too high a content of aluminum powder reduces the retention of impact properties after aging of the material, increasing the color difference. From comparative examples 6,7 and example 7, it can be seen that the increase of the extruder vacuum degree, the retention rate of impact strength after accelerated aging of the material is slightly improved, the chromatic aberration is significantly increased, the precipitation condition of the surface of the material is greatly improved, and the method is mainly attributed to the increase of the extruder vacuum degree, so that the method is beneficial to removing small molecular monomers in ABS, the unstable migration of the small molecular monomers in the processing process is one of the main reasons for the precipitation of the material after humid heat aging, the precipitation improvement further reduces the chromatic aberration, and meanwhile, the better retention rate of impact performance is maintained. As can be seen from comparative examples 8,9 and example 7, the impact retention rate of the bulk ABS is better, but the color difference change caused by aging degradation is larger, and the comprehensive performance is inferior to that of the emulsion ABS (preferably MI20 emulsion ABS); in conclusion, small molecular assistants (antioxidant, lubricant and weather resistant agent) are important reasons for influencing the wet heat aging performance of ABS, and different kinds of assistants are selected, so that the dosage of the different assistants is adjusted, and the wet heat aging resistance of the material is improved. The auxiliary agent has low molecular weight, can migrate out of a matrix more easily in extrusion and injection molding, and can be exposed on the surface of a material easily due to instability under a humid heat aging experiment. While the impact of the substrate, filler and process cannot be neglected.
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the application. The embodiments of the application and the features of the embodiments may be combined with each other arbitrarily without conflict.
Claims (6)
1. The metal spraying-free ABS material with low humidity and heat aging resistance and precipitation is characterized by comprising the following components in parts by weight:
The ABS resin is synthesized by an emulsion polymerization method; the lubricant is Ethylene Bis Stearamide (EBS); the weather resistant agent is one or more of weather resistant agent 3033P and weather resistant agent 234; the antioxidants are antioxidant 1076 and antioxidant 168; the metal spraying-free ABS material is prepared by a method comprising the following steps:
S1, weighing raw materials according to parts by weight; uniformly mixing ABS resin, an antioxidant, a lubricant, a weather-resistant agent, metal powder and pigment;
S2, adding the uniformly mixed materials in the step S1 into a double-screw extruder, and finally granulating and drying; the vacuum degree of the double-screw extruder is 1.0MPa.
2. The low heat and humidity aging resistant low precipitation metal spray free ABS material according to claim 1 wherein the ABS resin rubber particle size is 200-700 μm and butadiene content is 12-15% and melt flow rate measured under 220 ℃ 10kg melt index test conditions is 15-30 g/10min.
3. The low-aging, wet heat resistant, low-precipitation, metal spray-free ABS material of claim 1 wherein the metal powder is one or more of aluminum powder, copper powder, silver powder.
4. The spray-free ABS material for metals with low precipitation resistance to wet heat aging according to claim 3, wherein the particle size of the metal powder is 60 μm to 140. Mu.m.
5. The low wet heat aging resistant, low precipitation metal spray free ABS material of claim 1 wherein the pigment is carbon black.
6. The spray-free ABS material for metals with low humidity and heat aging resistance and precipitation according to claim 1, wherein the working temperature of the twin-screw extruder is 180-235 ℃ and the screw rotating speed is 400-500 rpm; the temperature of the drying is 75-85 ℃ and the time is 4-8h.
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| CN108276718A (en) * | 2017-12-28 | 2018-07-13 | 深圳市富恒新材料股份有限公司 | A kind of bloom is exempted to spray ASA/PMMA air-inlet grille for automobile composite material specials and preparation method thereof |
| CN109836764A (en) * | 2019-03-04 | 2019-06-04 | 广州科苑新型材料有限公司 | A kind of silver color is exempted to spray ABS material and the preparation method and application thereof |
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| CN114276639A (en) * | 2021-12-02 | 2022-04-05 | 金发科技股份有限公司 | Weather-resistant high-temperature-resistant high-humidity-resistant ABS (acrylonitrile butadiene styrene) composition and preparation method thereof |
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