CN114276639B - Weather-resistant high-temperature-resistant high-humidity-resistant ABS (acrylonitrile butadiene styrene) composition and preparation method thereof - Google Patents
Weather-resistant high-temperature-resistant high-humidity-resistant ABS (acrylonitrile butadiene styrene) composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a weather-resistant high-temperature and high-humidity resistant ABS composition and a preparation method thereof. The invention has excellent weather resistance, high temperature and high humidity resistance and good molding processing performance, can stand the harsh environment of illumination and high temperature and high humidity, and meets the requirement of office equipment for ten years without color change.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a weather-resistant high-temperature high-humidity resistant ABS composition and a preparation method thereof.
Background
The acrylonitrile, butadiene and styrene terpolymer (ABS) has the advantages of excellent mechanical property, high gloss appearance effect, good creep resistance, stable size retention rate, good processability and the like, and is widely applied to the product fields of household appliances, electronic appliances, toys, automobile traffic and the like. However, the ABS resin has butadiene double bonds, has general weather resistance, is limited by an emulsion process of a main flow synthesis process, has more contents of residual emulsifier, monomer and the like, and causes that the ABS product has poor light, heat, oxygen, water vapor and other corrosion resistance.
At present, material suppliers continuously search corresponding modification upgrading solutions for the problem of insufficient weather resistance and wet-heat-aging resistance of ABS, for example, the technical scheme disclosed in patent No. CN101638503B selects an ultraviolet absorber and a light stabilizer to improve the weather resistance of flame-retardant ABS, but does not solve the problem of discoloration in high-temperature and high-humidity environments; the technical scheme disclosed in patent No. CN104403291B is to add 1-5% of EMA resin to improve the high temperature and high humidity resistance of PC/ABS material, but the light resistance is general.
Disclosure of Invention
The invention aims to solve the technical problem of providing a weather-resistant high-temperature high-humidity resistant ABS composition and a preparation method thereof, and the composition overcomes the defect that the existing product cannot simultaneously achieve weather resistance, high-temperature high-humidity resistance.
The invention provides a weather-resistant high-temperature-resistant high-humidity-resistant ABS composition which comprises the following components in parts by weight:
wherein the melt flow rate of the EMMA resin is 15-50g/10min (test standard: ISO 1133-1. Preferably, the EMMA resin has a melt flow rate of 15 to 25g/10min.
The acrylonitrile content of the SAN resin is 20-25wt%.
The ABS resin is high rubber powder with 50-65wt% of butadiene content, and the high rubber powder with high butadiene content is prepared by emulsion graft polymerization. ABS high-rubber powder with a butadiene content of 60 wt.% is preferred.
The PMMA resin has a melt flow rate of 15 to 30g/10min (test standard: ISO 1133-1; test conditions: 230 ℃, 3.8kg load). Preferably, the PMMA resin has a melt flow rate of 20 to 25g/10min.
The MMA content in the EMMA resin is 15-32wt%.
The weather-resistant agent is a compound of a hindered amine light stabilizer and a benzotriazole ultraviolet light absorber.
The composition further comprises: 0.1 to 2 portions of antioxidant and 0.1 to 2 portions of lubricant.
Preferably, the antioxidant is one or more of hindered phenol antioxidant and phosphite antioxidant, such as antioxidant 1010 and antioxidant 168; the lubricant is one or more of vinyl bis stearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, PE wax and PP wax, and specifically is vinyl bis stearamide EBS.
The invention also provides a preparation method of the weather-resistant high-temperature high-humidity resistant ABS composition, which comprises the following steps:
uniformly mixing SAN resin, ABS resin and organic modified montmorillonite according to a ratio, carrying out melt blending extrusion on a double-screw extruder, extracting small molecular gas by adopting a double-vacuumizing system, and carrying out underwater grain cutting and drying to obtain a one-step material of the ABS composition; and uniformly mixing the obtained ABS composition raw material with PMMA resin, EMMA resin and weather-resistant agent, performing melt blending extrusion on a double-screw extruder, and performing underwater granulation and drying to obtain the weather-resistant, high-temperature and high-humidity resistant ABS composition.
The processing temperature of the double-screw extruder is 120-240 ℃, the temperature of the first zone to the second zone is 120-190 ℃, the temperature of the third zone to the fifth zone is 200-240 ℃, the temperature of the fifth zone to the tenth zone is 200-240 ℃, and the rotating speed of the screw is 350-450 rpm.
The invention also provides application of the weather-resistant high-temperature-resistant high-humidity-resistant ABS composition in office equipment and warehouse logistics.
Montmorillonite (MMT) is a natural layered aluminosilicate clay material, has the advantages of high specific surface area, excellent adsorption capacity, good environmental compatibility, low price and the like, and can be used as an effective adsorbent for resin impurity residues through compounding modification of a cationic surfactant and a coupling agent.
Ethylene-methyl methacrylate copolymer (EMMA) has a molecular structure in which a plurality of methyl groups are present in the side chain in comparison with EMA (ethylene-vinyl acetate), and is excellent in heat stability, water barrier properties, adhesion properties, and heat sealability.
Experimental research shows that the content of residual impurities and monomers in the resin synthesis process can be reduced by adding the organic modified montmorillonite into the ABS resin, a protective layer can be formed on the surface by adding the high-flow EMMA, and the ABS resin is compounded with the light stabilizer and the absorbent, so that the negative effects of illumination, heat, oxygen and water vapor on the material are reduced, the color change degree of the material is reduced, and the performance retention rate is improved. Meanwhile, by compounding PMMA, the compatibility of EMMA and ABS can be effectively improved, and the comprehensive performance of the compound is improved.
Advantageous effects
According to the invention, the organic modified montmorillonite is introduced into the ABS system, and the high-efficiency adsorption performance of the montmorillonite is utilized to reduce the content of residual impurities and monomers in SAN and ABS high-adhesive powder, so that the negative influence of subsequent illumination, heat, oxygen and water vapor on the color change of the material is reduced. The EMMA resin is an ethylene-methyl methacrylate copolymer, ethylene has good high temperature and high humidity resistance, methyl methacrylate and ABS have certain compatibility, and the EMMA resin with ethylene and methyl methacrylate can improve the high temperature and high humidity resistance of the ABS; generally, the melt flow rate of ABS under the condition of 200 ℃/5KG is 1-8g/10min, which is far lower than the fluidity of EMMA, EMMA flows faster during molding, and can be enriched to the surface of a workpiece to form a similar skin-core structure, and the EMMA skin layer can effectively prevent water vapor from contacting ABS, thereby reducing the discoloration risk of ABS in a high-temperature and high-humidity environment. Meanwhile, the introduction of high-flow PMMA can further improve the compatibility of ABS and EMMA and improve the performance of the composition. The hindered amine light stabilizer and the benzotriazole ultraviolet light absorber are preferably selected, so that the light resistance of the ABS composition is improved, the prepared weather-resistant high-temperature high-humidity resistant ABS composition has good compatibility, excellent weather-resistant high-temperature high-humidity resistance and good forming processability, can stand the harsh environment of illumination and high-temperature high-humidity, and meets the requirement of office equipment for ten years of color fastness.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The raw materials used in the examples and comparative examples are illustrated below, but are not limited to these materials:
SAN resin 1: SAN 310N TR, korean brocade lake, acrylonitrile content 21wt%;
SAN resin 2: SAN 350, korean brocade lake, acrylonitrile content 32wt%;
1 part of ABS high rubber powder: ABS POW HR181, korea brocade lake, butadiene content 60wt%;
ABS high rubber powder 2: WD-133, chemical industry of Wanda, shandong, butadiene content 70wt%;
PMMA resin 1: PMMA IF870, LX MMA, melt flow rate 23g/10min;
PMMA resin 2: PMMA CM-207, chimei, taiwan, melt flow rate 8g/10min;
PMMA resin 3: PMMA BA410, LX MMA, melt flow rate 45g/10min;
EMMA resin 1: EMMA WK402, nippon Sumitomo chemical, melt flow rate 20g/10min, MMA content 25wt%;
EMMA resin 2: EMMA M28N430, enlish, melt flow rate 8g/10min, MMA content 8.3wt%;
organically modified montmorillonite: i.31ps, nanocor, usa;
weather resisting agent: a light stabilizer and an ultraviolet light absorber in a mass ratio of 1; wherein, the light stabilizer and the ultraviolet light absorber are all commercial products;
antioxidant: antioxidant 1010 and antioxidant 168, both commercially available;
lubricant: EBS lubricant, commercially available product.
The preparation of examples 1 to 9 was as follows:
uniformly mixing SAN resin, ABS resin, organic modified montmorillonite, antioxidant and lubricant according to the proportion shown in Table 1 (example 1-9), carrying out melt blending extrusion on a double-screw extruder, extracting small molecular gas by adopting a double-vacuumizing system, and carrying out underwater granulation and drying to obtain the ABS composition one-step material; and uniformly mixing the obtained ABS composition raw material with PMMA resin, EMMA resin and weather-resistant agent, performing melt blending extrusion on a double-screw extruder, and performing underwater granulation and drying to obtain the weather-resistant high-temperature and high-humidity resistant ABS composition.
The processing temperature of the double-screw extruder is 120-240 ℃, the temperature of the first zone to the second zone is 120-190 ℃, the temperature of the third zone to the fifth zone is 200-240 ℃, the temperature of the fifth zone to the tenth zone is 200-240 ℃, and the rotating speed of the screw is 350-450 rpm.
Comparative examples 1 to 4 were prepared as follows:
uniformly mixing SAN resin, ABS resin, organic modified montmorillonite, antioxidant and lubricant according to the proportion of table 1 (comparative example 1-4), performing melt blending extrusion on a double-screw extruder, extracting small molecular gas by adopting a double-vacuum-pumping system, and performing underwater granulation and drying to obtain a primary material of the ABS composition; and uniformly mixing the obtained ABS composition raw material with PMMA resin, EMMA resin and weather-resistant agent, performing melt blending extrusion on a double-screw extruder, and performing underwater granulation and drying to obtain the weather-resistant, high-temperature and high-humidity resistant ABS composition.
The processing temperature of the double-screw extruder is 120-240 ℃, the temperature of the first zone to the second zone is 120-190 ℃, the temperature of the third zone to the fifth zone is 200-240 ℃, the temperature of the fifth zone to the tenth zone is 200-240 ℃, and the rotating speed of the screw is 350-450 rpm.
Performance evaluation method and implementation standard:
the notch impact strength is tested according to ISO 180-2000 standard, and the notch type is A type;
the accelerated aging is tested according to the ASTM D4459-2006 standard, a xenon lamp continuously irradiates for 60 hours, then the aging is carried out for 60 hours in a constant temperature and humidity box with the RH being 85 ℃/85 percent, the color difference is tested according to the GB/T7921-2008 standard, and a D65 light source is adopted for measurement;
the impact property retention rate is the ratio of the notched impact strength after accelerated aging to the notched impact strength before aging;
the total color difference delta E is the difference value between the color after accelerated aging and the color before aging.
TABLE 1 concrete compounding ratio (parts by weight) of each component in each example and comparative example
TABLE 2 Performance test data for each of the examples and comparative samples
As can be seen from examples 1-9, the weather-resistant, high temperature and high humidity resistant ABS composition has good compatibility, the retention rate of impact property after aging is more than 85%, the color difference Delta E is less than 2, and the composition has excellent weather-resistant, high temperature and high humidity resistant property and good molding processability. From examples 1 and 2, it can be seen that SAN with a higher AN content has a poor compatibility with PMMA and EMMA, which slightly reduces the retention of impact toughness after accelerated aging of the composition. As can be seen from examples 3 and 4, the ABS high rubber powder with too high a butadiene content has relatively poor impact toughness retention and color difference after accelerated aging of the composition due to more residual monomers. From the comparison between example 5 and example 6, the melt flow rate of PMMA is too low, and the melt viscosity difference with the composition system is too large, so that the compatibility of the system is affected, and the impact property retention rate and the color difference of the composition after accelerated aging are relatively poor. In comparison between examples 5 and 10, the melt flow rate of PMMA is too high, which reduces the impact retention and color difference of the composition. From examples 7 and 8, it can be seen that when the melt flow rate of EMMA is relatively low, EMMA is not easily enriched on the surface of the product during injection molding, and the barrier effect on light, heat, oxygen and water vapor is reduced during accelerated aging, thereby affecting the impact retention rate and color difference. As can be seen from comparative examples 1 and 5, the introduction of the organically modified montmorillonite improves certain weather resistance, high temperature resistance and high humidity resistance. As can be seen from comparative example 2 and example 1, the addition ratio of the organic modified montmorillonite is too high, and the weather resistance, high temperature resistance and high humidity resistance of the composition are reduced. As can be seen from the comparison of comparative example 3 and example 1, EMMA resin can improve the high temperature and high humidity resistance of ABS. As can be seen from the comparison between comparative example 4 and example 1, PMMA can further improve the compatibility between ABS and EMMA, and improve the weather resistance, high temperature resistance and high humidity resistance of the composition.
Claims (10)
1. An ABS composition with weather resistance, high temperature resistance and high humidity resistance is characterized in that: the paint comprises the following components in parts by weight:
wherein the melt flow rate of the EMMA resin at 190 ℃ under the load of 2.16KG is 15-50g/10min.
2. The ABS composition according to claim 1, wherein: the acrylonitrile content of the SAN resin is 20-25wt%.
3. The ABS composition according to claim 1, wherein: the ABS resin is high rubber powder with 50-65wt% of butadiene content.
4. The ABS composition according to claim 1, wherein: the melt flow rate of the PMMA resin at 230 ℃ under the load of 3.8KG is 15-30g/10min.
5. The ABS composition according to claim 1, wherein: the MMA content in the EMMA resin is 15-32wt%.
6. The ABS composition according to claim 1, wherein: the weather-resistant agent is a compound of a hindered amine light stabilizer and a benzotriazole ultraviolet light absorber.
7. The ABS composition according to claim 1, wherein: the composition further comprises: 0.1 to 2 portions of antioxidant and 0.1 to 2 portions of lubricant.
8. The ABS composition according to claim 7, wherein: the antioxidant is one or more of hindered phenol antioxidant and phosphite antioxidant; the lubricant is one or more of vinyl bis stearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, PE wax and PP wax.
9. A method for preparing the ABS composition with weather resistance, high temperature and high humidity resistance according to claim 1, comprising:
uniformly mixing SAN resin, ABS resin and organic modified montmorillonite according to a ratio, carrying out melt blending extrusion on a double-screw extruder, extracting small molecular gas by adopting a double-vacuumizing system, and carrying out underwater grain cutting and drying to obtain the ABS composition one-step material; and uniformly mixing the obtained ABS composition raw material with PMMA resin, EMMA resin and weather-resistant agent, performing melt blending extrusion on a double-screw extruder, and performing underwater granulation and drying to obtain the weather-resistant, high-temperature and high-humidity resistant ABS composition.
10. Use of a weather-resistant, high temperature and high humidity resistant ABS composition according to claim 1 in office equipment, warehouse logistics.
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