PMMA-ASA composite material as well as preparation method and application thereof

Abstract

The invention provides a PMMA (Polymethyl Methacrylate)-ASA (Acrylonitrile Styrene Acrylate) composite material as well as a preparation method and application thereof. The PMMA-ASA composite material is prepared from the following components in parts by mass: 33 to 70 parts of PMMA resin, 20 to 45 parts of ASA rubber powder, 5 to 30 parts of styrene-N-phenylmaleimide-MMA copolymer and 0.1 to 2 parts of coloring agent. The ASA rubber powder comprises a combination of small-particle-size ASA rubber powder and large-particle-size ASA rubber powder, the particle size of the small-particle-size ASA rubber powder is smaller than or equal to 150 nm, and the particle size of the large-particle-size ASA rubber powder is 180-400 nm. Through the design of the ASA rubber powder with bimodal particle size distribution and the styrene-N-phenylmaleimide-MMA copolymer and the compounding of the ASA rubber powder and the styrene-N-phenylmaleimide-MMA copolymer with the PMMA resin, the PMMA-ASA composite material has the advantages of excellent heat resistance, good chromaticity, excellent toughness and impact resistance, and no appearance defect on the surface of a product.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a PMMA-ASA composite material and a preparation method and application thereof. Background Art

[0002] In recent years, high-gloss black automotive interior and exterior decoration parts have been loved by more and more consumers. The high gloss and black appearance of plastic parts are usually achieved by surface spray painting, but the cost of spray painting is high, and the large amount of organic solvents used in the painting process will cause environmental pollution. Therefore, high-gloss spray-free polymer materials are used. Spray-free high-gloss black polymer materials are widely used in automotive grilles, door pillar trims, fog lamp trims, etc. due to their green and environmental protection, easy recycling, and cost reduction.

[0003] PMMA (polymethyl methacrylate), also known as organic glass, has excellent optical properties, weather resistance, mechanical strength, heat and sound insulation, strong tinting power, and scratch resistance. It is one of the most widely used plastics, but its impact toughness is relatively low, it is sensitive to notches, and it is prone to assembly cracking. ASA (acrylonitrile-styrene-acrylate copolymer) resin has excellent performance in mechanical properties, weather resistance, and processing performance. It is widely used in packaging materials, electronic appliances, toys, instruments, transportation, and machinery manufacturing. However, the surface hardness of ASA resin is insufficient and its scratch resistance is weak. In order to make up for the performance defects of PMMA and ASA, the industry has developed PMMA / ASA alloy, which has gradually become the main product of spray-free high-gloss black materials.

[0004] CN110256798A discloses a PMMA / ASA alloy material, which includes the following components by mass: 20-30 parts of PMMA, 60-70 parts of ASA, 1-5 parts of compatibilizer, 1-3 parts of nano zirconium oxide, 1-3 parts of SAN base silicone masterbatch, 0.1-1 parts of antioxidant, 0.1-1 parts of weathering agent, and 0.1-2 parts of black dye; the material can achieve the effects of high gloss black, high hardness and spray-free. CN109181193A discloses a spray-free PMMA / ASA material, comprising the following components: 50-75% PMMA, 10-20% ASA, 0-20% SAN, 5-10% toughening agent, 2-5% flame retardant, 1-2% coupling agent, 0.1-0.4% antioxidant, 0.3-1% light stabilizer, 1-5% black masterbatch; the material has good performance in scratch resistance, dimensional stability, chemical resistance and weather resistance.

[0005] With the widespread application of PMMA / ASA alloy materials, people have found that the Vicat softening temperature of PMMA / ASA is usually around 85°C, and the heat resistance is poor. In the process of high temperature resistance test of parts, deformation and failure often occur. In order to improve the heat resistance of the material, a heat-resistant agent can be added to the PMMA / ASA system. For example, the high gloss black scratch-resistant PMMA / ASA composite material disclosed in CN112552614A includes the following raw materials in parts by weight: 25-60 parts of SAN resin, 5-15 parts of toughening agent, 15-35 parts of PMMA resin, 5-15 parts of heat-resistant agent, 1-10 parts of inorganic nanoparticles, 1-5 parts of auxiliary agent, and 1-5 parts of colorant; wherein the heat-resistant agent is at least one of maleimide, α-alkyl styrene copolymer, and styrene-maleic anhydride copolymer. Although the addition of heat-resistant agent can improve the Vicat softening temperature of the material, it also leads to a decrease in the impact resistance of the material. In addition, due to compatibility issues, the glossiness and blackness of PMMA / ASA decrease, and the surface of the parts is prone to appearance defects such as pitting and silver wire. CN115490979A discloses a spray-free, high-toughness, high-heat-resistant, and high-laser transmittance ASA / PMMA for laser welding, comprising PMMA resin, ASA resin and heat-resistant agent, wherein the ASA resin is a composite of large and small particle size rubber powder, the large particle size of the ASA resin is 300-500μm, and the small particle size of the ASA resin is 100-200μm; however, the disclosed micron-grade ASA rubber powder is difficult to be commercially available or self-produced, and the blackness of the ASA / PMMA material cannot meet the requirements.

[0006] Therefore, developing a spray-free PMMA / ASA material with high heat resistance, good chroma, good appearance and impact resistance is an urgent problem to be solved in this field. Summary of the invention

[0007] In view of the deficiencies in the prior art, the object of the present invention is to provide a PMMA-ASA composite material and a preparation method and application thereof. By designing ASA rubber powder with a bimodal particle size distribution and a styrene-N-phenylmaleimide-MMA copolymer and compounding them with PMMA resin, the PMMA-ASA composite material has high heat resistance, excellent chromaticity and appearance effects, good toughness and impact resistance, and excellent mechanical properties.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a PMMA-ASA composite material, wherein the PMMA-ASA composite material comprises the following components in parts by mass:

[0010]

[0011] The ASA rubber powder comprises a combination of small-diameter rubber powder and large-diameter rubber powder, the particle size of the small-diameter rubber powder is ≤150nm, and the particle size of the large-diameter rubber powder is 180-400nm.

[0012] In the present invention, the term "PMMA" means polymethyl methacrylate, "ASA" means acrylonitrile-styrene-acrylate copolymer, and "MMA" means methyl methacrylate.

[0013] The PMMA-ASA composite material of the present invention adopts ASA rubber powder with bimodal particle size distribution, that is, a combination of specific small-particle ASA rubber powder and large-particle ASA rubber powder, thereby taking into account both high impact strength and excellent chromaticity. The styrene-N-phenylmaleimide-MMA copolymer has good compatibility with the PMMA-ASA system, and while effectively improving the heat resistance of the material, it also allows the material to maintain excellent chromaticity, toughness and impact resistance. The present invention, through the design of ASA rubber powder with bimodal particle size distribution and styrene-N-phenylmaleimide-MMA copolymer and their compounding with PMMA resin, makes the PMMA-ASA composite material have high Vicat softening temperature, good heat resistance, good chromaticity, excellent toughness and impact resistance, and the product has no appearance defects, achieving the effect of comprehensively improving heat resistance, mechanical properties, chromaticity and appearance effects.

[0014] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0015] In the PMMA-ASA composite material of the present invention, the mass parts of the PMMA resin are 33-70 parts, for example, 34 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts or 68 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0016] The mass proportion of the ASA rubber powder is 20-45 parts, for example, it can be 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts or 44 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0017] The mass parts of the styrene-N-phenylmaleimide-MMA copolymer are 5-30 parts, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts or 28 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0018] The mass fraction of the colorant is 0.1-2 parts, for example, it can be 0.2 parts, 0.4 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts or 1.8 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0019] In the present invention, the particle size of the small-particle ASA rubber powder is ≤150nm, for example, it can be 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 145nm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively enumerates the specific point values ​​included in the range, preferably 50-140nm, and more preferably 80-120nm.

[0020] In the present invention, the particle size of the large-particle ASA rubber powder is 180-400nm, for example, it can be 190nm, 200nm, 220nm, 240nm, 250nm, 260nm, 280nm, 300nm, 320nm, 350nm or 380nm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, preferably 200-350nm.

[0021] In the present invention, the particle size of the small-size ASA rubber powder and the large-size ASA rubber powder can be understood as the "average particle size" (D 50 Particle size), for example, the particle size can be measured by a laser particle size analyzer with reference to the standard GB / T 19077-2016.

[0022] Preferably, the density of the ASA rubber powder is 1.04-1.1 g / cm 3 , for example, it can be 1.05 g / cm 3 , 1.06g / cm 3 , 1.07g / cm 3 , 1.08g / cm 3 or 1.09 g / cm 3, as well as specific point values ​​between the above point values, due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0023] Exemplarily, in the present invention, the "density" parameter of each component can be obtained by testing using the method in standard ISO 1183-2019.

[0024] Preferably, the mass percentage of the acrylonitrile-based structural units in the ASA rubber powder is 15-35%, for example, it can be 16%, 18%, 20%, 22%, 25%, 28%, 30%, 32% or 34%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0025] Preferably, the mass percentage of the acrylate-based structural units in the ASA rubber powder is 40-70%, for example, it can be 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65% or 68%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0026] Preferably, the mass percentage of small-particle ASA rubber powder in the ASA rubber powder is 30-70%, for example, it can be 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60% or 65%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 40-60% is further preferred.

[0027] In the present invention, the more energy the large-particle ASA rubber powder absorbs during impact, the more effectively the impact strength of the PMMA-ASA composite material can be improved; the small-particle ASA rubber powder has weak absorption of light, which is conducive to maintaining the excellent chromaticity characteristics of the PMMA-ASA composite material. The present invention compounds the small-particle ASA rubber powder and the large-particle ASA rubber powder to form an ASA rubber powder with a bimodal particle size distribution. By designing the dosage of the two rubber powders, the mass content of the small-particle ASA rubber powder is preferably 30-70%, more preferably 40-60%. The two are compounded with each other, so that the PMMA-ASA composite material obtains an excellent balance effect between high heat resistance, excellent chromaticity, high toughness and high impact strength. If the mass content of the small-particle ASA rubber powder is too high, it will affect the toughness and impact resistance of the PMMA-ASA composite material. If the mass content of the small-particle ASA rubber powder is too low, it will affect the chromaticity effect of the material.

[0028] Preferably, the density of the PMMA resin is 1.16-1.19 g / cm 3 , for example, it can be 1.162 g / cm 3 , 1.165g / cm 3 , 1.168g / cm 3 , 1.17g / cm 3 , 1.172g / cm 3 , 1.175g / cm 3 , 1.178g / cm 3 , 1.18g / cm 3 , 1.182g / cm 3 , 1.185g / cm 3 or 1.188 g / cm 3 , as well as specific point values ​​between the above point values, due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0029] Preferably, the melt index of the PMMA resin at 220°C and 10kg is 2-10g / 10min, for example, it can be 2.5g / 10min, 3g / 10min, 3.5g / 10min, 4g / 10min, 4.5g / 10min, 5g / 10min, 5.5g / 10min, 6g / 10min, 6.5g / 10min, 7g / 10min, 7.5g / 10min, 8g / 10min, 8.5g / 10min, 9g / 10min or 9.5g / 10min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0030] In the present invention, the term "melt index" is also called "melt flow rate", abbreviated as "MFR", and the unit is g / 10min. The MFR in the present invention can be measured by the method in ISO 1133-1-2011.

[0031] Preferably, the density of the styrene-N-phenylmaleimide-MMA copolymer is 1.1-1.3 g / cm 3 , for example, it can be 1.12 g / cm 3 , 1.15g / cm 3 , 1.18g / cm 3 , 1.2g / cm 3 , 1.22g / cm 3 , 1.25g / cm 3 or 1.28 g / cm 3, as well as specific point values ​​between the above point values, due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0032] The present invention has no special limitation on the colorant, and the present invention is applicable to any colorant known in the art that can be used in polymer materials. The color of the colorant can be selected according to the appearance requirements of the product, and exemplarily includes but is not limited to: any one of black colorant, white colorant, red colorant, yellow colorant, blue colorant, green colorant, purple colorant, and orange colorant, or a combination of at least two thereof.

[0033] Preferably, the colorant is a black colorant, thereby making the PMMA-ASA composite material present a spray-free, high-gloss black appearance.

[0034] Preferably, the colorant includes toner and / or masterbatch.

[0035] In the present invention, the toner includes organic toner and / or inorganic toner.

[0036] It should be noted that the PMMA-ASA composite material of the present invention may also include any other additives that are added with motivation in the art.

[0037] Preferably, the PMMA-ASA composite material further comprises any one of an antioxidant, a light stabilizer, and a lubricant, or a combination of at least two of them.

[0038] Preferably, the PMMA-ASA composite material further includes 0.1-2 parts of an antioxidant by mass, and the mass proportion of the antioxidant may be 0.2 parts, 0.4 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts or 1.8 parts, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0039] Preferably, the antioxidant includes any one of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants, and thioether antioxidants, or a combination of at least two of them.

[0040] Preferably, the PMMA-ASA composite material further includes 0.1-2 parts of light stabilizer by weight, and the weight of the light stabilizer can be 0.2 parts, 0.4 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts or 1.8 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0041] Preferably, the light stabilizer includes any one of a benzotriazole light stabilizer, a triazine light stabilizer, a benzophenone light stabilizer, a salicylate light stabilizer, and a hindered amine light stabilizer, or a combination of at least two thereof.

[0042] Preferably, the PMMA-ASA composite material further includes 0.1-2 parts of lubricant by mass, and the mass proportion of the lubricant may be 0.2 parts, 0.4 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts or 1.8 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0043] Preferably, the lubricant includes any one of silicone lubricants, vinyl polymer lubricants, and ester lubricants, or a combination of at least two of them.

[0044] As a preferred technical solution of the present invention, the PMMA-ASA composite material comprises the following components in parts by mass:

[0045]

[0046]

[0047] The ASA rubber powder comprises a combination of small-diameter ASA rubber powder and large-diameter ASA rubber powder, wherein the particle size of the small-diameter ASA rubber powder is ≤150nm, and the particle size of the large-diameter ASA rubber powder is 180-500nm; the mass percentage of the small-diameter ASA rubber powder in the ASA rubber powder is 30-70%, preferably 40-60%.

[0048] Preferably, the mass percentage of PMMA resin in the PMMA-ASA composite material is 33-70%, for example, it can be 35%, 40%, 45%, 50%, 55%, 60% or 65%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0049] Preferably, the mass percentage of ASA rubber powder in the PMMA-ASA composite material is 18-45%, for example, it can be 19%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42% or 44%, and specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range. The PMMA resin and ASA rubber powder are compounded in a specific ratio, which can better balance the comprehensive effects of high toughness, high impact performance and excellent chromaticity of the PMMA-ASA composite material.

[0050] Preferably, the mass percentage of styrene-N-phenylmaleimide-MMA copolymer in the PMMA-ASA composite material is 5-30%, for example, it can be 8%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0051] In a second aspect, the present invention provides a method for preparing the PMMA-ASA composite material as described in the first aspect, the preparation method comprising:

[0052] The PMMA resin, ASA rubber powder, styrene-N-phenylmaleimide-MMA copolymer and a colorant are melt-blended and then extruded to obtain the PMMA-ASA composite material.

[0053] Preferably, the preparation method comprises the following steps:

[0054] PMMA resin, ASA rubber powder, styrene-N-phenylmaleimide-MMA copolymer and colorant are mixed to obtain a premix;

[0055] The premix is ​​melt-blended and then extruded to obtain the PMMA-ASA composite material.

[0056] Preferably, the mixed material further comprises any one of an antioxidant, a light stabilizer, and a lubricant, or a combination of at least two of them.

[0057] Preferably, the mixing is carried out in a high mixer.

[0058] Preferably, the mixing time is 1-20 min, for example, it can be 2 min, 5 min, 8 min, 10 min, 12 min, 15 min or 18 min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 2-10 min is further preferred.

[0059] Preferably, the mixing temperature is 15-40°C, for example, it can be 18°C, 20°C, 22°C, 25°C, 28°C, 30°C, 32°C, 35°C or 38°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and room temperature / normal temperature is further preferred.

[0060] Preferably, the melt blending is carried out in a screw extruder, and the screw extruder is preferably a twin-screw extruder.

[0061] Preferably, the temperature of the screw extruder is 80-270°C, for example, it can be 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C or 260°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0062] Preferably, the aspect ratio of the screw extruder is (38-60):1, for example, it can be 40:1, 42:1, 44:1, 48:1, 50:1, 52:1, 55:1, 56:1, 58:1, etc.

[0063] Preferably, the screw speed of the screw extruder is 200-800r / min, for example, it can be 250r / min, 300r / min, 350r / min, 400r / min, 450r / min, 500r / min, 550r / min, 600r / min, 650r / min, 700r / min or 750r / min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0064] Preferably, the extrusion further includes the steps of granulation, cooling and drying.

[0065] In a third aspect, the present invention provides a use of the PMMA-ASA composite material as described in the first aspect in automobile parts.

[0066] Preferably, the PMMA-ASA composite material is applied to a grille, a door pillar trim or a fog lamp trim of an automobile.

[0067] In a fourth aspect, the present invention provides an automobile component, comprising the PMMA-ASA composite material as described in the first aspect.

[0068] Preferably, the automobile component includes an automobile grille, a door pillar trim or a fog lamp trim.

[0069] Compared with the prior art, the present invention has the following beneficial effects:

[0070] In the PMMA-ASA composite material provided by the present invention, by designing ASA rubber powder with bimodal particle size distribution and styrene-N-phenylmaleimide-MMA copolymer and compounding them with PMMA resin, the PMMA-ASA composite material has a high Vicat softening temperature, excellent heat resistance and chromaticity, high impact strength, excellent toughness and impact resistance, and no appearance defects on the surface of the product, thereby achieving the effect of comprehensively improving the Vicat softening temperature, impact strength, chromaticity and appearance effect. DETAILED DESCRIPTION

[0071] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0072] As used herein, the terms "comprises," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0073] In the following specific embodiments of the present invention, the materials for which the preparation methods are not provided are all commercially available chemicals, and the specific information is as follows:

[0074]

[0075]

[0076] The PMMA-ASA composite material and the preparation method thereof of the present invention will be described in detail below by taking a plurality of embodiments as examples, but the PMMA-ASA composite material and the preparation method thereof are not limited to these embodiments.

[0077] Examples 1-7, Comparative Examples 1-8

[0078] A PMMA-ASA composite material, the types and amounts of the components are shown in Table 1 and Table 2, and the units of the amounts of the components are all "parts by mass".

[0079] The preparation method of the PMMA-ASA composite material is as follows:

[0080] (1) According to the formula amounts shown in Table 1 and Table 2, PMMA resin, ASA rubber powder, styrene-N-phenylmaleimide-MMA copolymer, color powder, antioxidant, light stabilizer and lubricant are placed in a high-speed mixer and mixed uniformly to obtain a premix;

[0081] (2) adding the premix obtained in step (1) into a twin-screw extruder, wherein the screw speed of the twin-screw extruder is 350 rpm, the aspect ratio is 55:1, the temperatures of zones 1-9 are 90° C., 120° C., 200° C., 240° C., 250° C., 255° C., 255° C., 250° C., and 250° C., respectively, and the die temperature is 250° C., and the PMMA-ASA composite material is obtained by melt mixing and extrusion granulation.

[0082] The following performance tests were performed on PMMA-ASA composite materials:

[0083] (1) Impact strength: tested according to the method in standard ISO 179-2023, injection molded into standard specimens, pendulum energy of 4J, and test temperature at room temperature;

[0084] (2) Vicat softening temperature: tested according to the method in standard ISO 306-2022, with the test conditions of 5 kg and 50 °C / h;

[0085] (3) L value: Tested using a colorimeter with D65 light source SCI mode; L value represents blackness and is used to characterize the degree of high gloss black effect. The lower the L value, the darker the color and the more prominent the high gloss black effect.

[0086] The test data are shown in Table 1 and Table 2.

[0087] Table 1

[0088]

[0089]

[0090] Table 2

[0091]

[0092]

[0093] According to the data in Table 1, the present invention adopts ASA rubber powder with bimodal particle size distribution and adopts styrene-N-phenylmaleimide-MMA copolymer as a heat-resistant agent. Through the design and compounding of components, the Vicat softening temperature of the PMMA-ASA composite material is ≥98°C, and it has excellent heat resistance; at the same time, the impact strength of the PMMA-ASA composite material is ≥8kJ / m 2, has high toughness and excellent impact resistance, its L value is ≤23.5, has outstanding high gloss black effect, and the surface of the product has no appearance defects. Further, according to the comparison between Example 2 and Examples 6-7, it can be seen that the present invention can achieve the balance and optimization of the comprehensive properties of PMMA-ASA composite materials in high gloss black, toughness and impact resistance by adjusting the content of rubber powder with different particle sizes in ASA rubber powder.

[0094] The present invention adopts ASA rubber powder with a bimodal particle size distribution at the nanoscale, and compounded with PMMA resin and styrene-N-phenylmaleimide-MMA copolymer, so that the PMMA-ASA composite material has high impact strength, excellent chromaticity and high heat resistance. According to the performance data in Table 2, although ASA rubber powder with a bimodal particle size distribution is used in Comparative Examples 1-2, the particle size of the ASA rubber powder is too large, resulting in weaker light reflected by the material and poor high-gloss black effect. In Comparative Example 3, there is only small-particle ASA rubber powder, and its impact strength is significantly reduced; in Comparative Example 4, there is only large-particle ASA rubber powder, and its chromaticity performance decreases and the L value increases. The amount of ASA rubber powder used in Comparative Example 7 is low, resulting in deterioration of the impact performance of the material; the amount of ASA rubber powder used in Comparative Example 6 is too high, which increases the L value of the material and significantly loses chromaticity.

[0095] The present invention adopts styrene-N-phenylmaleimide-MMA copolymer as a heat-resistant agent, which not only effectively improves the heat resistance of the material, but also maintains excellent chromaticity and impact performance. In Comparative Example 5, styrene-N-phenylmaleimide-maleic anhydride copolymer is used as a heat-resistant agent. Due to the poor compatibility between different components, the impact performance and chromaticity are significantly reduced. In Comparative Example 8, the content of styrene-N-phenylmaleimide-MMA copolymer is too low, resulting in a decrease in the Vicat softening temperature of the material.

[0096] The applicant declares that the present invention illustrates the PMMA-ASA composite material and its preparation method and application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A PMMA-ASA composite material, characterized in that: The PMMA-ASA composite material comprises the following components in parts by mass: The ASA rubber powder comprises a combination of small-diameter ASA rubber powder and large-diameter ASA rubber powder, the particle size of the small-diameter ASA rubber powder is ≤150nm, and the particle size of the large-diameter ASA rubber powder is 180-400nm.

2. The PMMA-ASA composite material according to claim 1, characterized in that The particle size of the small-particle ASA rubber powder is 50-140nm; Preferably, the particle size of the large-particle ASA rubber powder is 200-350nm; Preferably, the density of the ASA rubber powder is 1.04-1.1 g / cm 3 .

3. The PMMA-ASA composite material according to claim 1, characterized in that The mass percentage of small-particle ASA rubber powder in the ASA rubber powder is 30-70%, preferably 40-60%.

4. The PMMA-ASA composite material according to claim 1, characterized in that The density of the PMMA resin is 1.16-1.19 g / cm 3 ; Preferably, the PMMA resin has a melt index of 2-10 g / 10 min at 220° C. and 10 kg.

5. The PMMA-ASA composite material according to claim 1, characterized in that: The density of the styrene-N-phenylmaleimide-MMA copolymer is 1.1-1.3 g / cm 3 .

6. The PMMA-ASA composite material according to claim 1, characterized in that: The colorant includes toner and / or masterbatch.

7. The PMMA-ASA composite material according to claim 1, characterized in that: The PMMA-ASA composite material further comprises any one or a combination of at least two of an antioxidant, a light stabilizer, and a lubricant; Preferably, the PMMA-ASA composite material further comprises 0.1-2 parts by weight of an antioxidant; Preferably, the PMMA-ASA composite material further comprises 0.1-2 parts by weight of a light stabilizer; Preferably, the PMMA-ASA composite material further comprises 0.1-2 parts by mass of a lubricant.

8. A method for preparing the PMMA-ASA composite material according to any one of claims 1 to 7, characterized in that: The preparation method comprises: The PMMA resin, ASA rubber powder, styrene-N-phenylmaleimide-MMA copolymer and a colorant are melt-blended and then extruded to obtain the PMMA-ASA composite material.

9. Use of the PMMA-ASA composite material according to any one of claims 1 to 7 in automobile parts; Preferably, the PMMA-ASA composite material is applied to a grille, a door pillar trim or a fog lamp trim of an automobile.

10. An automobile component, characterized in that: The automobile component comprises the PMMA-ASA composite material according to any one of claims 1 to 7.

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