CN114276639A

CN114276639A - Weather-resistant high-temperature-resistant high-humidity-resistant ABS (acrylonitrile butadiene styrene) composition and preparation method thereof

Info

Publication number: CN114276639A
Application number: CN202111458019.7A
Authority: CN
Inventors: 官焕祥; 陈平绪; 叶南飚; 付锦锋; 杨霄云
Original assignee: Kingfa Science and Technology Co Ltd
Current assignee: Kingfa Science and Technology Co Ltd
Priority date: 2021-12-02
Filing date: 2021-12-02
Publication date: 2022-04-05
Anticipated expiration: 2041-12-02
Also published as: CN114276639B

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 forming 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 discoloration.

Description

Weather-resistant high-temperature-resistant high-humidity-resistant ABS (acrylonitrile butadiene styrene) composition and preparation method thereof

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, the weather resistance is general, the content of residual emulsifier, monomer and the like is more due to the limitation of the emulsion process of the main flow synthesis process, so that the corrosion resistance of ABS products to light, heat, oxygen, water vapor and the like is poorer, and when the ABS resin is applied to light-color or color appearance parts, the parts are easily subjected to a long-time high-temperature and high-humidity marine transportation environment, obvious color change is easy to occur, and the sale of the ABS resin is influenced.

At present, material suppliers continuously search corresponding modification upgrading solutions for the problem of insufficient weather resistance and resistance to wet heat and aging 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 under high-temperature and high-humidity environments; according to the technical scheme disclosed by the patent number CN104403291B, 1-5% of EMA resin is added to improve the high-temperature and high-humidity resistance of a PC/ABS material, but the light-resistant performance 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: 2011; test conditions: 190 ℃ and load of 2.16 KG). Preferably, the EMMA resin has a melt flow rate of 15 to 25g/10 min.

The acrylonitrile content of the SAN resin is 20-25 wt%.

The ABS resin is high rubber powder with 50-65 wt% of butadiene content, and the high rubber powder with high butadiene content is prepared by emulsion graft polymerization. ABS high-rubber powder having a butadiene content of 60 wt.% is preferred.

The melt flow rate of the PMMA resin is 15-30g/10min (test standard: ISO 1133-1: 2011; test conditions: 230 ℃ and load: 3.8 kg). Preferably, the PMMA resin has a melt flow rate of 20-25g/10 min.

The MMA content in the EMMA resin is 15-32 wt%.

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, PP wax and ethylene bis stearamide, specifically 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 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.

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 compound modification of a cationic surfactant and a coupling agent.

Ethylene-methyl methacrylate copolymer (EMMA) has a molecular structure with a plurality of methyl groups in the side chain than EMA (ethylene-vinyl acetate), and is excellent in thermal 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, brocade lake korea, acrylonitrile content 21 wt%;

SAN resin 2: SAN 350, korean brocade lake, acrylonitrile content 32 wt%;

1 part of ABS high rubber powder: ABS POW HR181, Korea brocade lake, butadiene content 60 wt%;

ABS high rubber powder 2: WD-133, chemical industry, Shandong Wanda, butadiene content 70 wt%;

PMMA resin 1: PMMA IF870, LX MMA, melt flow rate 23g/10 min;

PMMA resin 2: PMMA CM-207, Taiwan Chimei, melt flow rate 8g/10 min;

PMMA resin 3: PMMA BA410, LX MMA, melt flow rate 45g/10 min;

EMMA resin 1: EMMA WK402, Nippon Sumitomo chemical, melt flow rate 20g/10min, MMA content 25 wt%;

EMMA resin 2: EMMA M28N430, Enlish, melt flow rate 8g/10min, MMA content 8.3 wt%;

organically modified montmorillonite: 31PS, Nanocor, USA;

weather resisting agent: a light stabilizer and an ultraviolet light absorber in a mass ratio of 1: 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.

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 shown in Table 1 (comparative example 1-4), performing melt blending extrusion on a double-screw extruder, extracting small molecular gas by adopting a double-vacuumizing system, and performing 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.

Performance evaluation method and implementation standard:

the notch impact strength is tested according to ISO 180-2000-plus-one 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 is aged for 60 hours in a constant temperature and humidity box with the temperature of 85 ℃/85% RH, the color difference is tested according to the GB/T7921-2008 standard, and the D65 light source is adopted for determination;

the impact property retention rate is the ratio of the notch impact strength after accelerated aging to the notch 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 examples

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. As can be seen from examples 1 and 2, SAN having a higher AN content has a poor compatibility with PMMA and EMMA, and the impact toughness retention of the composition after accelerated aging is slightly reduced. 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 poor 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 example 1 and comparative example 5, the introduction of the organic 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

1. An ABS composition with weather resistance, high temperature resistance and high humidity resistance, which 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/10 min.

2. The ABS composition according to claim 1, wherein: the acrylonitrile content of the SAN resin is 20-25 wt%.

3. The ABS composition according to claim 1, wherein: the ABS resin is high rubber powder with 50-65 wt% of butadiene content.

4. The ABS composition according to claim 1, wherein: the melt flow rate of the PMMA resin at 230 ℃ and under the load of 3.8KG is 15-30g/10 min.

5. The ABS composition according to claim 1, wherein: the MMA content in the EMMA resin is 15-32 wt%.

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, PP wax and ethylene bis stearamide.

9. A method for preparing the weather-resistant, high temperature and high humidity resistant ABS composition of claim 1, comprising:

10. Use of the weather-resistant, high temperature and humidity-resistant ABS composition according to claim 1 in office equipment, warehouse logistics.