Good appearance and high performance mineral reinforced PC / ABS alloy and preparation method thereof

Abstract

This invention discloses a high-performance, aesthetically pleasing mineral-reinforced PC / ABS alloy and its preparation method, comprising: 40-70 parts PC resin, 5-25 parts ABS resin, 15-40 parts ABS masterbatch, 2-5 parts toughening agent, 0.5-5 parts compatibilizer, 0.1-2 parts antioxidant, and 0.1-2 parts lubricant. In preparation, the PC resin, ABS resin, ABS masterbatch, compatibilizer, toughening agent, antioxidant, and lubricant are mixed; the resulting mixture is blended using a twin-screw extruder, melt-extruded, and granulated to obtain the final product. This invention utilizes an anti-dripping agent to form a fiber network in the ABS mineral masterbatch, weakening the flow of minerals to the surface during PC / ABS injection molding to prevent precipitation, while simultaneously reducing the degradation reaction between minerals and PC, resulting in a high-performance, aesthetically pleasing mineral-reinforced PC / ABS alloy.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to a mineral-reinforced PC / ABS alloy with good appearance and high performance, and its preparation method. Background Technology

[0002] PC / ABS alloys possess excellent mechanical and thermal properties and are currently widely used in automobiles, home appliances, and digital products. Especially in recent years, with the increasing intelligence of automotive interior and exterior trim, the demand for PC / ABS alloys with good appearance, high performance, and good dimensional stability has been growing. The coefficient of linear expansion is a reference indicator for characterizing the dimensional stability of a material. Mineral and glass fiber fillers can meet the requirement of a low coefficient of linear expansion, but the anisotropy of glass fiber fillers can easily lead to warping and fiber floating problems. Isotropic mineral-reinforced PC / ABS can simultaneously meet the requirements of excellent dimensional stability and appearance performance.

[0003] Taking automobiles as an example, the increasing demand for larger displays and larger rear spoilers necessitates a lower linear expansion coefficient, requiring higher proportions of mineral-filled PC / ABS alloys to meet size requirements. However, due to the poor compatibility between inorganic minerals and PC / ABS, high content can lead to agglomeration, resulting in defects such as mineral precipitation on the material's appearance. Furthermore, the presence of alkali metal ions (Mg) in inorganic minerals further complicates matters. 2+ Fe 3+ Ca 2+ These substances significantly promote PC degradation, affecting the overall performance of the material. Existing technologies only address the compatibility between minerals and the substrate through mineral masterbatch or mineral modification to improve the performance of PC / ABS alloys, but the results are unsatisfactory. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects of the prior art and provide a mineral-reinforced PC / ABS alloy with good appearance and high performance, as well as a method for its preparation.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] This invention provides a mineral-reinforced PC / ABS alloy with good appearance and high performance, the alloy comprising the following components in parts by weight:

[0007]

[0008] As one embodiment of the present invention, the PC resin is a bisphenol A type polycarbonate resin with a melt index of 8 to 20 g / 10 min at 300°C / 1.2 kg.

[0009] As one embodiment of the present invention, the ABS resin has a weight-average molecular weight of 120,000 to 160,000 g / mol, a rubber content of 5 to 30 wt.%, an acrylonitrile content of 20 to 30 wt.%, a styrene content of 40 to 70 wt.%, and a melt index of 10 to 15 g / min under the condition of 220℃*10kg.

[0010] In one embodiment of the present invention, the ABS masterbatch is a composite of acrylonitrile-butadiene-styrene (ABS), talc, lubricant, antioxidant, compatibilizer, and anti-dripping agent. Each component is weighed according to the following weight percentages: ABS resin with a weight-average molecular weight of 120,000–160,000 g / mol, weighing 40–70 parts; talc, 25–55 parts; lubricant, 0.1–1 part; antioxidant, 0.1–2 parts; compatibilizer, 1–5 parts; and anti-dripping agent, 0.1–1.1 parts. This addition ratio was obtained through internal verification. If too little anti-dripping agent is added, its fiber-forming network in the alloy is low, insufficient to weaken the flow and precipitation of minerals. Conversely, if too much anti-dripping agent is added, its fiber-forming network in the alloy is high, easily causing a sharp increase in the viscosity of the alloy system, resulting in screw slippage and preventing normal extrusion of particles from the barrel.

[0011] The antioxidant is one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-tert-butyl)phosphite, and dioctadecyl pentaerythritol diphosphite. The lubricant includes one or more of silicone oil, silicone powder, pentaerythritol ester, and ethylene bis-stearamide. The compatibilizer is one or more of styrene-acrylonitrile-glycidyl acrylate, ethylene-vinyl acetate copolymer-functionalized maleic anhydride, and styrene-maleic anhydride-acrylonitrile. The anti-dripping agent is one or more of polytetrafluoroethylene powder, polytetrafluoroethylene emulsion, and polytetrafluoroethylene coating.

[0012] As one embodiment of the present invention, the method for preparing the ABS masterbatch includes the following steps:

[0013] (1) Mix ABS resin, talc, lubricant, antioxidant, compatibilizer and anti-dripping agent in a mixer for 5 to 30 minutes according to the specified ratio;

[0014] (2) Place the mixture obtained in step (1) into a twin-screw extruder with a barrel temperature of 180-240°C and a screw speed of 200-600 rpm to granulate and obtain ABS masterbatch.

[0015] As one embodiment of the present invention, the twin-screw extruder includes 10 temperature control zones, with temperature control zones 1-2 having a temperature of 180-210°C, temperature control zones 3-4 having a temperature of 190-220°C, temperature control zones 5-6 having a temperature of 190-220°C, temperature control zones 7-8 having a temperature of 190-230°C, and temperature control zones 9-10 having a temperature of 200-240°C.

[0016] As one embodiment of the present invention, the compatibilizer is one or more of styrene-acrylonitrile-glycidyl acrylate, ethylene-vinyl acetate copolymer-functionalized maleic anhydride, and styrene-maleic anhydride-acrylonitrile.

[0017] As one embodiment of the present invention, the anti-dripping agent is one or more of polytetrafluoroethylene pure powder, polytetrafluoroethylene emulsion, and polytetrafluoroethylene coating.

[0018] As one embodiment of the present invention, the toughening agent is one or more of methyl methacrylate, butadiene, styrene terpolymer, and acrylate copolymer.

[0019] As one embodiment of the present invention, the antioxidant is one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl alcohol 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-tert-butyl)phosphite, and dioctadecyl pentaerythritol diphosphite.

[0020] As one embodiment of the present invention, the lubricant includes one or more of silicone oil, silicone powder, pentaerythritol ester, and ethylene bis-stearamide.

[0021] This invention also provides a method for preparing a high-performance mineral-reinforced PC / ABS alloy with good appearance. The method involves mixing PC resin, ABS resin, ABS masterbatch, compatibilizer, toughening agent, antioxidant, and lubricant; adding the mixture to a twin-screw extruder for melt blending and extrusion, controlling the extrusion temperature at 220–260°C, the screw speed at 200–500 rpm, and the pressure at 2–3 MPa; and obtaining the product after underwater pelletizing and drying.

[0022] In one embodiment of the present invention, the mixing is carried out in a high-speed mixer with a speed of 100-300 r / min and a mixing time of 10-30 min.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1) This invention uses an anti-dripping agent to form a fiber network in ABS mineral masterbatch, which weakens the flow of minerals to the surface during PC / ABS injection molding and thus reduces precipitation. At the same time, it reduces the degradation reaction between minerals and PC, resulting in a mineral-reinforced PC / ABS alloy with good appearance and high performance.

[0025] 2) The mineral-reinforced PC / ABS alloy with good appearance and high performance obtained by the present invention is particularly suitable for complex parts and multi-point injection molds. For the home appliance and automotive industries with complex shapes, it will not only not affect the overall performance of the material, but also obtain products with excellent appearance. Detailed Implementation

[0026] The present invention will be described in detail below with reference to embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make several adjustments and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.

[0027] The raw materials used in the comparative examples and embodiments are as follows:

[0028] Bisphenol A type polycarbonate with a weight-average molecular weight of 40,000–80,000 g / mol was selected, specifically Mitsubishi Gas S-3000F, which has a melt index of 17 g / 10 min at 300℃*1.2 kg. The ABS resin had a weight-average molecular weight of 120,000–160,000 g / mol, a rubber content of 5–30%, an acrylonitrile content of 20–30%, and a styrene content of 40–70%, specifically ABS 8434 from Gaoqiao Petrochemical. The ABS masterbatch was self-made. The talc powder was commercially available PT-559 with a D50 of 2.6–3.2 μm. The compatibilizer was Nantong Rizhisheng's SAG-001. The toughening agent was LG's EM500. The anti-dripping agent was commercially available SN3300B7, the coating layer was SAN, and the antioxidant was BASF's IRGANOX. 1010 (antioxidant in Table 2); lubricant is PETS (pentaerythritol stearate); antioxidants are 168 and 245 (Table 1).

[0029] The ABS masterbatch is a complex of acrylonitrile-butadiene-styrene (ABS), talc, lubricant, antioxidant, compatibilizer and anti-dripping agent; each component is weighed by weight, and the prepared masterbatches are ABS masterbatch 0#, ABS masterbatch 1#, ABS masterbatch 2# and ABS masterbatch 3#, as shown in Table 1 below.

[0030] The above-mentioned method for preparing ABS masterbatch includes the following steps:

[0031] (1) Mix the ABS resin, talc, lubricant, antioxidant, compatibilizer and anti-dripping agent in Table 1 in a mixer for 10 min according to the weight parts;

[0032] (2) Place the mixture obtained in step (1) into a twin-screw extruder. The barrel temperature is 180°C in temperature control zone 1-2, 200°C in temperature control zone 3-4, 210°C in temperature control zone 5-6, 230°C in temperature control zone 7-8, and 240°C in temperature control zone 9-10. The screw speed is 400 rpm. Granulation yields ABS masterbatch.

[0033] Table 1

[0034] Components ABS Masterbatch 0# ABS Masterbatch #1 ABS Masterbatch #2 ABS Masterbatch #3 ABS resin 50 50 50 50 talcum powder 50 50 50 50 lubricant 0.3 0.3 0.3 0.3 Antioxidant 168 0.15 0.15 0.15 0.15 Antioxidant 245 0.15 0.15 0.15 0.15 compatibilizer 2 2 2 2 Anti-dripping agent 0 0.1 0.6 1.1

[0035] In Tables 1 and 2, the selection of lubricant, compatibilizer, and anti-dripping agent is the same.

[0036] The preparation method of PC / ABS alloy includes the following steps:

[0037] (1) Mix the substances in Table 2 according to their weight proportions in a high-speed mixer at a speed of 150 r / min for 10 min.

[0038] (2) Place the mixture obtained in step (1) into a twin-screw extruder. The barrel temperature is 220°C for temperature control zone 1-2, 230°C for temperature control zone 3-4, 240°C for temperature control zone 5-6, 250°C for temperature control zone 7-8, and 260°C for temperature control zone 9-10. The screw speed is 400 rpm. Granulation yields PC / ABS alloy.

[0039] Table 2

[0040]

[0041]

[0042] Performance testing

[0043] After the composition particles prepared in the above comparative examples and embodiments were thoroughly dried, they were injection molded into specimens and subjected to various performance tests. Large high-gloss plates were also injection molded to compare the appearance effects.

[0044] Table 3

[0045]

[0046]

[0047] Note: The more "☆" marks there are, the better the appearance of the injection molded product.

[0048] The test results for each comparative example and embodiment are shown in Table 3. Tensile strength was tested according to ISO 527 standard, with a specimen size of 135*10*4 mm and a tensile speed of 5 mm / min. Bending performance was tested according to ISO 178 standard, with a specimen size of 80*10*4 mm and a tensile speed of 2 mm / min. Notched impact strength was tested according to ISO 179 standard, with a specimen size of 80*10*4 mm, a notch type of A, a remaining width at the bottom of the notch of 8 ± 0.2 mm, and test conditions of 5.5 J and 23℃. Heat distortion temperature was tested according to ISO 75 standard, with a specimen size of 80*10*4 mm and test conditions of 1.80 MPa and 120℃ / h. Appearance evaluation was conducted by injection molding a large high-gloss plate to assess defects such as mineral precipitation on the surface. The large high-gloss plate size was 100*90*3 mm.

[0049] Comparing Comparative Example 1 and Comparative Example 2, it can be found that the two-step method (first preparing ABS masterbatch, then preparing PC / ABS alloy) increases the notched impact strength from 15 to 28.1 KJ / m compared to the one-step method. 2 Furthermore, the injection-molded appearance is relatively good; comparing Comparative Example 1 with Examples 1, 2, and 3, it can be found that when the anti-dripping agent in the ABS masterbatch is increased to 0.1, 0.6, and 1.1 parts by weight, respectively, the impact strength increases from 28.1 KJ / m 2 Increased to 36.4 KJ / m 2 and 38.1 KJ / m 2 It then dropped to 26.2 KJ / m 2 Moreover, the injection molding appearance gradually improves first, and then deteriorates. Comparing Comparative Example 3 with Examples 4 and 5, it can be found that when the PC content is high, the injection molding appearance and impact performance are poor. To obtain a product with better appearance and performance, it is recommended to use 40-70 parts of PC resin, 5-25 parts of ABS resin, 15-40 parts of ABS masterbatch, 2-5 parts of toughening agent, 0.5-5 parts of compatibilizer, 0.1-2 parts of antioxidant, and 0.1-2 parts of lubricant.

[0050] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A mineral-reinforced PC / ABS alloy, characterized in that, The alloy comprises the following components in parts by weight: The ABS masterbatch is a composite of acrylonitrile-butadiene-styrene ABS, talc, lubricant, antioxidant, compatibilizer, and anti-dripping agent; wherein the ABS resin has a weight average molecular weight of 120,000 to 160,000 g / mol and a weight percentage of 40 to 70 parts, talc 25 to 55 parts, lubricant 0.1 to 1 part, antioxidant 0.1 to 2 parts, compatibilizer 1 to 5 parts, and anti-dripping agent 0.1 to 1.1 parts.

2. The mineral-reinforced PC / ABS alloy according to claim 1, characterized in that, The PC resin is a bisphenol A type polycarbonate resin with a melt index of 8 to 20 g / 10 min at 300℃ / 1.2 kg.

3. The mineral-reinforced PC / ABS alloy according to claim 1, characterized in that, The ABS resin has a weight-average molecular weight of 120,000–160,000 g / mol, a rubber content of 5–30 wt.%, an acrylonitrile content of 20–30 wt.%, a styrene content of 40–70 wt.%, and a melt index of 10–15 g / min at 220℃*10 kg.

4. The mineral-reinforced PC / ABS alloy according to claim 1, characterized in that, The compatibilizer is one or more of the following: styrene-acrylonitrile-glycidyl acrylate, ethylene-vinyl acetate copolymer-functionalized maleic anhydride, and styrene-maleic anhydride-acrylonitrile.

5. The mineral-reinforced PC / ABS alloy according to claim 1, characterized in that, The toughening agent is one or more of methyl methacrylate, butadiene, styrene terpolymer, and acrylic copolymer.

6. The mineral-reinforced PC / ABS alloy according to claim 1, characterized in that, The antioxidant is one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl alcohol 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-tert-butyl)phosphite, and dioctadecyl pentaerythritol diphosphite; the lubricant is one or more of silicone oil, silicone powder, paraffin wax, stearic acid, butyl stearate, oleamide, and ethylene bis-stearamide.

7. A method for preparing a mineral-reinforced PC / ABS alloy as described in any one of claims 1-6, characterized in that, The PC resin, ABS resin, ABS masterbatch, compatibilizer, toughening agent, antioxidant, and lubricant are mixed; the mixture is added to a twin-screw extruder for melt blending and extrusion, with the extrusion temperature controlled at 220-260℃, the screw speed at 200-500rpm, and the pressure at 2-3MPa. After underwater pelletizing and drying, the product is obtained.

8. The method for preparing the mineral-reinforced PC / ABS alloy as described in claim 7, characterized in that, The mixing is carried out in a high-speed mixer with a speed of 100-300 r / min and a mixing time of 10-30 min.

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