Gasoline-resistant highlight black ASA material and preparation method thereof

Abstract

The invention discloses a gasoline-resistant highlight black ASA material and a preparation method thereof, and belongs to the technical field of high polymer material modification. The ASA material is prepared from the following raw materials in parts by weight: 60 to 75 parts of AS resin, 20 to 35 parts of ASA high rubber powder, 5 to 10 parts of thermoplastic polyamide elastomer, 0.2 to 0.4 part of antioxidant and 0.5 to 1 part of toner. Wherein the ASA high rubber powder is of a core-shell structure, an inner core of the ASA high rubber powder is butyl acrylate, the content of the butyl acrylate is 50-60%, and a shell graft is styrene and acrylonitrile. By embedding the thermoplastic polyamide elastomer, the material can be prevented from being damaged by highly corrosive gasoline components, meanwhile, the highlight black effect of the material is not affected by the addition of the thermoplastic polyamide elastomer, and the problem that the glossiness of the highlight surface is degraded after the automotive exterior ASA material is in contact with gasoline is solved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer material modification, and in particular to a gasoline-resistant high-gloss black ASA material and a preparation method thereof. Background Art

[0002] ASA resin is an iterative material based on ABS material. Because there is no unsaturated double bond in its structure, its weather resistance is far better than ABS resin. In addition, the particle size of ASA rubber powder in ASA resin can be small, easy to dye, and has good colorability and surface gloss. ASA resin is widely used in automotive exterior parts, such as radiator grilles, spoilers, pillar outer panels, etc.

[0003] During the use of cars, they will inevitably come into contact with gasoline, which tests the gasoline resistance of the car's exterior parts. There are two common solutions to solve gasoline resistance: one is to apply corrosion-resistant paint on the surface of the parts. This solution increases the cost due to the increase in processes and is restricted by environmental issues; the other is to make the surface rough leather-grained. This solution mainly reduces the surface gloss. After gasoline corrosion, the surface contrast is low and it is not easy to attract customers' attention. However, this solution loses the high gloss effect and the application scenarios are limited. From the above, the key to improving the gasoline resistance of high-gloss ASA materials is to improve the gasoline resistance of the material itself. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a gasoline-resistant high-gloss black ASA material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A gasoline-resistant ASA material comprises the following raw materials in parts by weight:

[0007] 60-75 parts of AS resin,

[0008] ASA high glue powder 20-35 parts,

[0009] Thermoplastic polyamide elastomer 5-10 parts,

[0010] Antioxidant 0.2-0.4 parts,

[0011] Color powder 0.5-1 part;

[0012] The ASA high-rubber powder is a core-shell structure, wherein the core is butyl acrylate with a content of 50-60%, and the grafted material of the shell is styrene and acrylonitrile.

[0013] Optionally, the ASA resin particle size is 150-300 nm.

[0014] Optionally, the thermoplastic polyamide elastomer is a polyester and polyamide block copolymer.

[0015] Optionally, the hard segment of the thermoplastic polyamide elastomer is polyamide, and the soft segment is polyester.

[0016] Optionally, the antioxidant includes hindered phenols and phosphites.

[0017] Optionally, the hindered phenols and phosphites are compounded in a mass ratio of 1:1-1:1.5.

[0018] Optionally, the color powder is carbon black masterbatch.

[0019] Optionally, in the carbon black masterbatch, carbon black accounts for 45% of its total mass, and the characteristic particle size of the carbon black is 18 nm.

[0020] A method for preparing a gasoline-resistant ASA material comprises the following steps:

[0021] Weigh the raw materials described in claim 1, mix them evenly, add them to a screw extruder for melting and extrusion; the temperatures of each zone of the screw extruder are set to 180°C, 240°C, 240°C, 240°C, 230°C, 230°C, 230°C, 230°C, 230°C, 240°C, 240°C, and the speed is 500 rpm.

[0022] The above-mentioned ASA material is used in preparing gasoline-resistant products or improving the gasoline-resistant performance of products.

[0023] Another aspect of the present invention discloses a gasoline-resistant high-gloss black ASA material as described in any one of the above items and a preparation method thereof, comprising the following steps:

[0024] AS resin, ASA high-rubber powder, thermoplastic polyamide elastomer, antioxidant and color powder are weighed according to the ratio, and fully mixed to obtain a uniform mixture; the mixture is added into a twin-screw extruder for melting, extrusion and granulation to obtain a gasoline-resistant high-gloss black ASA material;

[0025] The temperatures of the twin-screw extruder zones were set to 180°C, 240°C, 240°C, 240°C, 230°C, 230°C, 230°C, 230°C, 240°C, and the main engine speed was 500 rpm.

[0026] Beneficial effects of the present invention:

[0027] Thermoplastic polyamide elastomer is evenly dispersed in ASA resin by co-extrusion. The soft segment polyester in the thermoplastic polyamide elastomer is first connected with the base material ASA resin to ensure compatibility; the hard segment polyamide in the thermoplastic polyamide elastomer is in a crystalline state in the ASA matrix, which can prevent the material from being damaged by highly corrosive gasoline components. At the same time, the addition of thermoplastic polyamide elastomer does not affect the high gloss black effect of the material. This invention solves the problem of gloss deterioration of the high gloss surface of the ASA material of the automobile exterior after contact with gasoline. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0030] AS resin, produced by Chi Mei Company;

[0031] ASA high-rubber powder, produced by Mitsubishi Rayon Co., Ltd. of Japan, brand SX-006;

[0032] Thermoplastic polyester amide elastomer, produced by Zhejiang Xinyuan Company, brand UPAE series C155;

[0033] Thermoplastic polyether polyamide elastomer, produced by Arkema, brand name Pebax series;

[0034] Antioxidant 1076 and Antioxidant 168, both produced by BASF, Germany;

[0035] Toner, high pigment carbon black masterbatch;

[0036] All materials are commercially available conventional products.

[0037] It is to be understood that the above raw materials and reagents are only examples of some specific embodiments of the present invention, so that the technical solution of the present invention is clearer, and it does not mean that the present invention can only use the above reagents, and the specific scope in the claims shall prevail. In addition, the "parts" described in the examples and comparative examples, unless otherwise specified, refer to parts by weight.

[0038] Any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0039] Weigh each component according to the proportion in Table 1, mix them thoroughly, and obtain a uniform mixture; add the mixture into a twin-screw extruder, melt, extrude, and granulate to obtain a gasoline-resistant high-gloss black ASA material;

[0040] Among them, the screw diameter of the twin-screw extruder is 40mm, the aspect ratio L / D=36, the screw combination is cooperated with a high-dispersion thread block to help ASA high rubber powder and thermoplastic polyester amide elastomer to be fully dispersed, and the barrel temperature is controlled in sections at 180℃, 240℃, 240℃, 240℃, 230℃, 230℃, 230℃, 230℃, 240℃, 240℃, the main engine speed is 500 rpm, and the feeding rate is 130-150kg / h.

[0041] Table 1

[0042]

[0043]

[0044] The ASA materials prepared in Examples 1-3 and Comparative Examples 1-3 were first placed in a blast oven at 80-90° C. and dried for 3-4 hours to fully dry the moisture, and then injection molded the specimens and the sample plates on an injection molding machine. After adjusting the state for 24 hours under a standard environment, the performance test was carried out. The test standards and test conditions are as follows:

[0045] Density test: according to ISO 1183-1 standard, the sample size is 40*10*4mm;

[0046] Tensile strength test: according to ISO 527-2 standard, the sample size is 135*10*4mm, and the tensile speed is 50mm / min;

[0047] Bending strength and bending modulus test: According to ISO 178 standard, the sample size is 80*10*4mm, the bending speed is 2mm / min, and the span is 64mm;

[0048] Simple supported beam notched impact strength test: according to ISO 179-1 standard, the sample size is 80*10*4mm, A-type notch, 4J pendulum;

[0049] Vicat softening temperature test: according to ISO 306 standard, the sample size is 10*10*4mm, the load is 50N, and the heating rate is 50℃ / h;

[0050] Gasoline resistance test: add 92# ethanol gasoline to the high-gloss board, cover the test liquid with a petri dish, and place it at room temperature for 24 hours; use the GB / T-250 gray sample card for evaluation, where level 1 represents the worst and level 5 represents the best. Generally speaking, customers judge that levels ≥4 are qualified.

[0051] The performance test results are shown in Table 2.

[0052] Table 2

[0053]

[0054]

[0055] From the comparison of the test results of Examples 1-3 and Comparative Examples 1-3, it can be seen that the gasoline resistance of the ASA material is greatly improved; the mechanical properties and thermal properties are less affected and can still meet customer requirements.

[0056] From the comparison between Examples 1-3 and Comparative Example 1, it can be found that the improvement effect on gasoline resistance in the present invention is obvious, the gray card grade is significantly improved, and customer requirements are met; in the system, the polyester end has good compatibility with the matrix, ensuring uniform dispersion of the polyamide; the crystallization of the polyamide component effectively resists the invasion of gasoline.

[0057] Comparative Example 2 is a different type of thermoplastic polyamide elastomer than Example 2, wherein Comparative Example 2 is polyetheramide, the soft segment is polyether, and the hardness is polyamide; it cannot be well dispersed in the system and cannot achieve the effect of gasoline resistance.

[0058] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0059] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A gasoline-resistant ASA material, characterized in that: It includes the following raw materials in parts by weight: 60-75 parts of AS resin, ASA high glue powder 20-35 parts, Thermoplastic polyamide elastomer 5-10 parts, Antioxidant 0.2-0.4 parts, Color powder 0.5-1 part; The ASA high-rubber powder is a core-shell structure, wherein the core is butyl acrylate with a mass ratio of 50-60%, and the outer shell grafts are styrene and acrylonitrile.

2. The gasoline resistant ASA material according to claim 1, characterized in that: The ASA resin particle size is 150-300nm.

3. The gasoline resistant ASA material according to claim 1, characterized in that: The thermoplastic polyamide elastomer is a polyester and polyamide block copolymer.

4. The gasoline resistant ASA material according to claim 1, characterized in that: The hard segment of the thermoplastic polyamide elastomer is polyamide, and the soft segment is polyester.

5. The gasoline resistant ASA material according to claim 1, characterized in that: The antioxidants include hindered phenols and phosphites.

6. The gasoline resistant ASA material according to claim 5, characterized in that: The hindered phenols and phosphites are compounded in a mass ratio of 1:1-1:1.

5.

7. The gasoline resistant ASA material according to claim 1, characterized in that: The toner is carbon black masterbatch.

8. The gasoline resistant ASA material according to claim 7, characterized in that: In the carbon black masterbatch, carbon black accounts for 45% of the total mass, and the characteristic particle size of the carbon black is 18 nm.

9. A method for preparing a gasoline-resistant ASA material, characterized in that: The following steps are involved: Weigh the raw materials described in claim 1, mix them evenly, add them to a screw extruder for melting and extrusion; the temperatures of each zone of the screw extruder are set to 180°C, 240°C, 240°C, 240°C, 230°C, 230°C, 230°C, 230°C, 230°C, 240°C, 240°C, and the speed is 500 rpm.

10. Use of the ASA material according to any one of claims 1 to 8 in preparing gasoline-resistant products or improving the gasoline-resistant performance of products.

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