PA / ABS (polyamide / acrylonitrile-butadiene-styrene) alloy material as well as preparation method and application thereof

Abstract

The invention relates to a PA / ABS (polyamide / acrylonitrile-butadiene-styrene) alloy material as well as a preparation method and application thereof, and belongs to the technical field of high polymer materials. The PA / ABS alloy material provided by the invention is prepared from the following components in parts by weight: 39 to 71 parts of PA6 resin, 29 to 56 parts of ABS resin, 4 to 31 parts of polyimide fiber and 0.05 to 5.5 parts of processing aid, the relative viscosity of the PA6 resin is 2.0 to 3.0. The polyimide fiber is introduced into the PA / ABS alloy material, so that the tensile strength and bending strength of the material can be improved, the affinity of the polyimide fiber and a resin matrix is higher than that of inorganic fiber, and the impact resistance of the material can be improved. The polyimide fiber and the PA6 resin with the relative viscosity of 2.0-3.0 are compounded, so that the mechanical property and the appearance of the material are effectively improved, and the application range of the PA / ABS alloy material is widened.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a PA / ABS alloy material and a preparation method and application thereof. Background Art

[0002] PA has excellent mechanical properties, corrosion resistance and wear resistance, but its water absorption is high and its dimensional stability is relatively poor; while acrylonitrile-styrene-butadiene (ABS) is an amorphous material with good dimensional stability, rigidity-toughness balance and low water absorption. Therefore, the PA / ABS alloy material prepared by compounding the two can take into account the advantages of both and has a wide range of applications in the fields of automobiles, electronics, sporting goods, etc.

[0003] However, since PA has a strong polarity and is a crystalline material, while ABS has a weak polarity and is an amorphous material, the compatibility between the two is poor. Therefore, more compatibilizers are needed in the preparation of the alloy to improve the compatibility between the two. At the same time, in some special application fields, there are higher requirements for the mechanical strength and toughness of the materials. In order to improve the strength of the materials, the most commonly used method is glass fiber filling and reinforcement. Since the polarity difference between inorganic fibers and resin matrix is ​​also relatively large, coupling agents are generally required to improve compatibility. Although the addition of coupling agents improves the tensile and bending strength of the material, it will affect the impact strength performance of the material. This is because peeling is prone to occur between the phase interfaces, resulting in poor comprehensive mechanical properties of the material.

[0004] Therefore, it is of great significance to prepare a PA / ABS alloy material with excellent mechanical properties. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems existing in the above-mentioned prior art and to provide a PA / ABS alloy material and a preparation method and application thereof.

[0006] The present invention is achieved through the following technical solutions:

[0007] In a first aspect, the present invention provides a PA / ABS alloy material, comprising the following components by weight: 39-71 parts of PA6 resin, 29-56 parts of ABS resin, 4-31 parts of polyimide fiber, and 0.05-5.5 parts of processing aid; the relative viscosity of the PA6 resin is 2.0-3.0.

[0008] Polyimide is a type of polymer containing an imide ring (-CO-NR-CO-) on the main chain, which has extremely high heat resistance and high self-strength. The present invention introduces polyimide fiber into PA / ABS alloy material, which can not only improve the tensile and bending strength of the material, but also has stronger affinity with the resin matrix than inorganic fiber, and can also improve the impact resistance of the material. The present invention compounds polyimide fiber with PA6 resin with a relative viscosity of 2.0-3.0, effectively improving the mechanical properties and appearance of the material, and broadening the application range of PA / ABS alloy material.

[0009] Specifically, the test method for the relative viscosity of the PA6 resin refers to ISO 307-2007, wherein the solvent used for the PA6 resin is 96% concentrated sulfuric acid at 25°C.

[0010] More preferably, the relative viscosity of the PA6 resin is 2.5-3.0.

[0011] In the PA / ABS alloy material of the present invention, the weight proportion of the PA6 resin is any one of 39 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, and 71 parts, or both of the range values; the weight proportion of the ABS resin is any one of 29 parts, 30 parts, 35 parts, 39 parts, 40 parts, 45 parts, 50 parts, 55 parts, and 56 parts, or both of the range values.

[0012] Preferably, in the PA / ABS material, the mass percentage of the PA6 resin is not less than 30%.

[0013] Preferably, the PA / ABS alloy material comprises the following components by weight: 40-70 parts of PA6 resin, 30-55 parts of ABS resin, 5-30 parts of polyimide fiber, and 0.1-5 parts of processing aid.

[0014] Preferably, the acrylonitrile content in the ABS resin is 15%-35%.

[0015] ABS resin is the base resin that accounts for a relatively large proportion in the product of the present invention. The content of its components has an impact on the performance and surface appearance of the product. It has been verified that when the content of each component in the ABS resin in the product is preferably within the above range, the obtained product can obtain better mechanical properties and good appearance.

[0016] The ABS resin used in the present invention may be either emulsion method ABS or bulk method ABS.

[0017] Preferably, the ABS resin has a melt index of 5-20 g / 10 min at 220° C. and 10 kg weight according to ISO 1133-2012.

[0018] Preferably, the polyimide fibers are chopped fibers.

[0019] Preferably, the average length of the polyimide fibers is 2 mm to 8 mm; more preferably, the average length of the polyimide fibers is 3 mm to 6 mm.

[0020] Preferably, the average diameter of the polyimide fiber is 6 μm-16 μm, more preferably 6 μm-10 μm.

[0021] Preferably, the processing aid includes at least one of an antioxidant, a lubricant, a light stabilizer, and a compatibilizer.

[0022] Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant, the primary antioxidant comprises a hindered phenol antioxidant and / or an aromatic amine antioxidant, and the secondary antioxidant comprises a phosphite antioxidant and / or a thioether secondary antioxidant.

[0023] Preferably, the lubricant comprises pentaerythritol stearate (PETS).

[0024] Preferably, the compatibilizer comprises ABS-g-MAH.

[0025] More preferably, the processing aid includes an antioxidant, a lubricant and a compatibilizer; wherein the mass ratio of the antioxidant, the lubricant and the compatibilizer is (0.005-0.015):(0.5-1.5):(1-3).

[0026] In a second aspect, the present invention provides a method for preparing the PA / ABS alloy material, comprising the following steps:

[0027] (1) uniformly mixing PA6 resin, ABS resin and processing aid according to the above-mentioned parts by weight to obtain a premix;

[0028] (2) placing the premix obtained in step (1) at the main feed port of a twin-screw extruder, feeding the polyimide fiber to the side, melt-extruding, granulating and drying, thereby obtaining the PA / ABS alloy material.

[0029] The components of the PA / ABS material of the present invention are transported, heated and sheared in a twin-screw extruder, so that the materials are fully melted and compounded, and then extruded, granulated and dried to obtain a polyimide fiber reinforced PA / ABS alloy material. The preparation method of the present invention is simple and can realize industrial-scale production.

[0030] Preferably, in step (2), the screw temperature of the twin-screw extruder is 80°C-300°C, the screw speed is 200-400 rpm, and the aspect ratio is (38-50):1; more preferably, the screw temperature of the twin-screw extruder is 80°C-270°C.

[0031] Although polyimide has excellent heat resistance, extremely high processing temperatures should not be used to prevent fiber damage. At the same time, the thermal decomposition of PA and ABS can be effectively reduced. The temperature should be controlled within 300°C, preferably within 270°C. The dispersion of polyimide fiber should be ensured before adding it to the twin-screw extruder for granulation. If necessary, some solution can be used to pre-disperse the fiber.

[0032] In a third aspect, the present invention provides applications of the PA / ABS alloy material in automotive parts, electrical and electronic equipment, and sports equipment.

[0033] The PA / ABS alloy material of the present invention can be used in the fields of automobile parts, electrical and electronic equipment, sports equipment, etc., for example, it can be used in automobile interior and exterior parts such as automobile speaker grilles.

[0034] The present invention has the following beneficial effects: the polyimide fiber in the material of the present invention has better compatibility with the PA / ABS resin matrix, and coupling agent may not be used, effectively avoiding the disadvantage of decreased impact strength of the material after filling due to interface peeling, so that the material has high tensile strength, bending strength and impact strength; in addition, compared with the defects such as floating fibers generated when inorganic fibers are added, the appearance of the parts after injection molding using polyimide reinforced resin is more excellent, and the material fluidity is better and the formability is better. Furthermore, since no inorganic components are introduced into the material system of the present invention, it is convenient to directly recycle the resin by physical methods in the future. DETAILED DESCRIPTION

[0035] To better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be understood by those skilled in the art that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0036] Unless otherwise specified, the experimental methods used in the examples are all conventional methods; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.

[0037] Examples 1-10

[0038] The composition of the PA / ABS alloy material described in the embodiment of the present invention is shown in Table 1.

[0039] The preparation method of the PA / ABS alloy material comprises the following steps:

[0040] (1) premixing PA6 resin, ABS resin and processing aid according to the weight proportions and then transferring the mixture into a high-speed mixer for stirring and mixing uniformly to obtain a premix;

[0041] (2) placing the premix obtained in step (1) at the main feed port of a twin-screw extruder, feeding the polyimide fiber to the side, melt-extruding, granulating and drying, thereby obtaining the PA / ABS alloy material.

[0042] The melt extrusion conditions are as follows: the temperature of zone 1 is 90°C, the temperature of zone 2 is 120°C, the temperature of zone 3 is 200°C, the temperature of zone 4 is 240°C, the temperature of zone 5 is 250°C, the temperature of zone 6 is 255°C, the temperature of zone 7 is 255°C, the temperature of zone 8 is 250°C, the temperature of zone 9 is 250°C, and the head temperature is 250°C; the screw speed is 300 rpm; and the aspect ratio of the twin-screw extruder is 40:1.

[0043] Comparative Examples 1-5

[0044] The difference between Comparative Examples 1-5 and the embodiment is only in the types and proportions of components, as shown in Table 2.

[0045] Among the components described in each embodiment and comparative example,

[0046] The PA6 resin-1 is: PA6 HY2500A, Haiyang, Jiangsu; relative viscosity is 2.5;

[0047] The PA6 resin-2 is: PA6 HY2800A, Haiyang, Jiangsu; relative viscosity is 2.8;

[0048] The PA6 resin-3 is: PA6 VOLGAMID27, Kuibyshev nitrogen; relative viscosity is 3;

[0049] The PA6 resin-4 is: PA6 J2000, Hangzhou Polymerization; relative viscosity is 1.9;

[0050] The PA6 resin-5 is: PA6 M3400, Xinhui Meida; relative viscosity is 3.3;

[0051] The ABS resin-1 is: ABS 8434, Sinopec Gaoqiao; the melt index is 16g / 10min at 220°C and 10kg weight; the acrylonitrile content is 20%, the butadiene content is 30%, and the styrene content is 50%; the average particle size of the butadiene rubber phase is about 250nm;

[0052] The ABS resin-2 is: ANC100, Taiwan Chemical Corporation; the melt index is 5g / 10min at 220°C and 10kg weight; wherein the acrylonitrile content is 30%, the butadiene content is 20%, and the styrene content is 50%;

[0053] The ABS resin-3 is: ABS PA-757, Taiwan Chimei; the melt index is 20g / 10min at 220°C and 10kg weight; wherein the acrylonitrile content is 35%, the butadiene content is 20%, and the styrene content is 55%;

[0054] The fiber length of the polyimide fiber-1 is 3.0 mm, Shilon, Jiangsu Xiannuo;

[0055] The fiber length of the polyimide fiber-2 is 6.0 mm; Shilon, Jiangsu Xiannuo;

[0056] The fiber length of the polyimide fiber-3 is 2.0 mm; Shilon, Jiangsu Xiannuo;

[0057] The fiber length of the polyimide fiber-4 is 8.0 mm; Shilon, Jiangsu Xiannuo;

[0058] The glass fibers are: chopped glass fibers (3 mm), with a diameter of 13 μm, from Jushi Group;

[0059] The auxiliary agent is compounded by an antioxidant, a lubricant, and a compatibilizer in a mass ratio of 0.01:1:2, wherein the antioxidant is composed of a primary antioxidant 1010 and an auxiliary antioxidant 168 in a mass ratio of 1:2; the lubricant is PETS; and the compatibilizer is ABS-g-MAH:KT-2H;

[0060] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0061] Table 1 Content of each component in the materials of Examples 1-10 (parts)

[0062]

[0063] Table 2 Content of each component in the materials of Comparative Examples 1-5 (parts)

[0064]

[0065]

[0066] The PA / ABS alloy materials prepared in the embodiments and comparative examples were subjected to the following performance tests, as follows:

[0067] 1. Tensile strength: tested according to ISO 527, injection molded into standard specimens, tensile rate is 50mm / min;

[0068] 2. Flexural strength: tested according to ISO 178, injection molded into standard specimens, bending rate is 2mm / min;

[0069] 3. Charpy notched impact strength (room temperature and -30°C): tested according to ISO 179, injection molded into standard specimens, pendulum energy of 5J;

[0070] 4. Tensile strength retention rate: UV xenon lamp aging, irradiance (1.2±0.02)W / (m2·nm)@420nm, aging time 168h, after aging, test according to ISO 527, tensile rate 50mm / min;

[0071] 5. Appearance evaluation: The appearance evaluation adopts the visual observation evaluation method of injection molded 100*100*3mm square plates; Appearance evaluation description: 5: There are no floating fibers on the surface of the square plate; 4: There are fine floating fibers on the surface of the square plate; 3: The floating fibers on the surface of the square plate are relatively serious and spread all over the surface of the square plate; 2: The floating fibers on the surface of the square plate are serious, and you can feel obvious bumps and depressions when you touch it; 1: The floating fibers on the surface of the square plate are very serious, and the bumps and depressions of the plate surface can be seen visually.

[0072] The test results are shown in Tables 3 and 4.

[0073] Table 3 Material performance test results of Examples 1-10

[0074]

[0075] Table 4 Material performance test results of comparative examples 1-5

[0076]

[0077] The test results in Tables 3-4 show that the PA / ABS alloy material of the present invention has excellent mechanical properties and good appearance, with a tensile strength of more than 65 MPa, a bending strength of not less than 79 MPa, and a room temperature impact strength of not less than 55 kJ / m 2 , -30℃ impact strength is not less than 34kJ / m 2 , the tensile strength retention rate after aging is not less than 89%, and the appearance evaluation is not less than level 4.

[0078] It can be seen from Comparative Examples 1 and 2 that if the viscosity of PA6 resin is too low or too high, the appearance of the material after injection molding will be poor. Comparative Example 3 is compared with Example 1. It can be seen that when the fiber content is the same, the glass fiber has a greater increase in tensile strength and bending strength than the polyimide fiber, but the impact strength will not increase but will decrease. In addition, since the aging strength attenuation of the glass fiber-filled PA / ABS system mainly comes from the interface peeling between the resin and the glass fiber, the root cause is the lack of compatibility between the two, so its retention rate after aging is lower; and the polyimide fiber with better compatibility has a better retention rate due to the better compatibility and almost no interface peeling. In Comparative Example 4, the amount of polyimide fiber added is too low, resulting in a significant decrease in the mechanical properties of the material. In Comparative Example 5, the amount of polyimide fiber added is too high. Although it can improve the mechanical properties of the material, it will cause the appearance rating of the material to be significantly reduced.

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A PA / ABS alloy material, characterized in that: The invention comprises the following components by weight: 39-71 parts of PA6 resin, 29-56 parts of ABS resin, 4-31 parts of polyimide fiber and 0.05-5.5 parts of processing aid; the relative viscosity of the PA6 resin is 2.0-3.

0.

2. The PA / ABS alloy material according to claim 1, characterized in that: The acrylonitrile content in the ABS resin is 15%-35%.

3. The PA / ABS alloy material according to claim 1, characterized in that: The ABS resin has a melt index of 5-20 g / 10 min at 220° C. and a weight of 10 kg according to ISO 1133-2012.

4. The PA / ABS alloy material according to claim 1, characterized in that: The average length of the polyimide fiber is 2 mm to 8 mm.

5. The PA / ABS alloy material according to claim 1, characterized in that: The processing aid includes at least one of an antioxidant, a lubricant, a light stabilizer, and a compatibilizer.

6. The PA / ABS alloy material according to claim 5, characterized in that: The antioxidant includes a primary antioxidant and an auxiliary antioxidant. The primary antioxidant includes a hindered phenol antioxidant and / or an aromatic amine antioxidant, and the auxiliary antioxidant includes a phosphite antioxidant and / or a thioether auxiliary antioxidant.

7. The PA / ABS alloy material according to claim 5, characterized in that: The lubricant includes pentaerythritol stearate; and / or the compatibilizer includes ABS-g-MAH.

8. The PA / ABS alloy material according to claim 1, characterized in that: The processing aid includes an antioxidant, a lubricant and a compatibilizer; the mass ratio of the antioxidant, the lubricant and the compatibilizer is (0.005-0.015):(0.5-1.5):(1-3).

9. The method for preparing the PA / ABS alloy material according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) uniformly mixing PA6 resin, ABS resin and processing aid according to the above-mentioned parts by weight to obtain a premix; (2) placing the premix obtained in step (1) at the main feed port of a twin-screw extruder, feeding the polyimide fiber to the side, melt-extruding, granulating and drying, thereby obtaining the PA / ABS alloy material.

10. Application of the PA / ABS alloy material according to any one of claims 1 to 8 in automobile parts, electrical and electronic equipment, and sports equipment.

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