PA / ABS alloy material, preparation method and application thereof

Abstract

The application relates to a PA / ABS alloy material and a preparation method and application thereof, and belongs to the technical field of polymer materials. The PA / ABS alloy material provided by the application comprises the following components in proportion 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. The polyimide fiber is introduced into the PA / ABS alloy material, so that the tensile strength and the bending strength of the material can be improved, the affinity of the inorganic fiber with the resin matrix is stronger, and the impact resistance of the material can be improved. The polyimide fiber is compounded with the PA6 resin with the relative viscosity of 2.0-3.0, so that the mechanical properties 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] This invention belongs to the field of polymer materials technology, specifically relating to a PA / ABS alloy material, its preparation method, and its application. Background Technology

[0002] PA possesses excellent mechanical properties, corrosion resistance, and wear resistance, but it has high water absorption and relatively poor dimensional stability. Acrylonitrile-styrene-butadiene (ABS), on the other hand, is an amorphous material with good dimensional stability, a good balance of rigidity and toughness, and low water absorption. Therefore, PA / ABS alloy materials prepared by combining the two can combine the advantages of both and have wide applications in the automotive, electronics, and sporting goods industries.

[0003] However, because PA is highly polar and a crystalline material, while ABS is less polar and amorphous, their compatibility is poor. Therefore, a large amount of compatibilizer is needed during alloy preparation to improve their compatibility. Furthermore, in some specialized applications, higher requirements are placed on the mechanical strength and toughness of the material. To improve strength, glass fiber reinforcement is commonly used. Since the polarity difference between inorganic fibers and the resin matrix is ​​significant, coupling agents are generally required to improve compatibility. While the addition of coupling agents improves the tensile and flexural strength of the material, it affects its impact strength due to the ease of delamination at the phase interface, resulting in poor overall mechanical properties.

[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 this invention is to overcome the problems existing in the prior art and to provide a PA / ABS alloy material, its preparation method, and its application.

[0006] This invention is achieved through the following technical solution:

[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; wherein 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-) in its main chain. It possesses extremely high heat resistance and inherent strength. This invention introduces polyimide fibers into PA / ABS alloy materials, which not only improves the tensile and flexural strength of the material but also exhibits stronger affinity with the resin matrix compared to inorganic fibers, thus enhancing the material's impact resistance. This invention further refines the polyimide fibers with PA6 resin of a relative viscosity of 2.0-3.0, effectively improving the material's mechanical properties and appearance, and broadening the application range of PA / ABS alloy materials.

[0009] Specifically, the test method for the relative viscosity of the PA6 resin is in accordance with 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 parts of PA6 resin are any one or a combination of 39 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, and 71 parts; and the weight parts of ABS resin are any one or a combination of 29 parts, 30 parts, 35 parts, 39 parts, 40 parts, 45 parts, 50 parts, 55 parts, and 56 parts.

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

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

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

[0015] ABS resin is the matrix resin with a large proportion in the product of this invention. Its component content affects 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 product can obtain better mechanical properties and good appearance.

[0016] The ABS resin used in this invention can be either emulsion ABS or bulk ABS.

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

[0018] Preferably, the polyimide fiber is a short-cut fiber.

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

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

[0021] Preferably, the processing aid includes at least one of antioxidants, lubricants, light stabilizers, and compatibilizers.

[0022] Preferably, the antioxidant includes a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant includes hindered phenolic antioxidants and / or aromatic amine antioxidants, and the secondary antioxidant includes phosphite antioxidants and / or thioether secondary antioxidants.

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

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

[0025] More preferably, the processing aids include antioxidants, lubricants and compatibilizers; wherein the mass ratio of the antioxidants, lubricants and compatibilizers is (0.005-0.015):(0.5-1.5):(1-3).

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

[0027] (1) Mix PA6 resin, ABS resin and processing aids evenly according to the weight proportions to obtain a premix;

[0028] (2) Place the premixed material obtained in step (1) into the main feed port of a twin-screw extruder, and feed the polyimide fiber from the side. Then, melt-extrude, granulate and dry to obtain the PA / ABS alloy material.

[0029] The components of the PA / ABS material described in this invention are conveyed, heated, and sheared in a twin-screw extruder, allowing the material to be fully melted and compounded. The resulting material is then extruded, granulated, and dried to obtain a polyimide fiber-reinforced PA / ABS alloy material. The preparation method of this invention is simple and can be mass-produced industrially.

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

[0031] Although polyimide has excellent heat resistance, extremely high processing temperatures should be avoided to prevent fiber damage. It can also effectively reduce the thermal decomposition of PA and ABS; the temperature should be controlled below 300℃, preferably below 270℃. Before adding it to a twin-screw extruder for granulation, the dispersibility of the polyimide fibers should be ensured. If necessary, some solution can be used to pre-disperse the fibers.

[0032] Thirdly, the present invention provides the application of the PA / ABS alloy material in automotive parts, electrical and electronic products, and sporting goods.

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

[0034] The present invention has the following beneficial effects: the polyimide fibers in the material of the present invention have better compatibility with the PA / ABS resin matrix, eliminating the need for coupling agents and effectively avoiding the disadvantage of decreased impact strength of the filled material due to interfacial delamination, resulting in high tensile strength, flexural strength, and impact resistance. Furthermore, compared to defects such as loose fibers that occur when inorganic fibers are added, the appearance of parts injection molded using polyimide-reinforced resin is superior, while the material has better flowability and moldability. Moreover, since no inorganic components are introduced into the material system of the present invention, the resin can be easily recycled directly using physical methods. Detailed Implementation

[0035] To better illustrate the objectives, technical solutions, and advantages of this invention, the invention will be further described below with reference to specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0036] Unless otherwise specified, the experimental methods used in the examples are conventional methods; the materials and reagents used are commercially available unless otherwise specified.

[0037] Examples 1-10

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

[0039] The method for preparing the PA / ABS alloy material includes the following steps:

[0040] (1) PA6 resin, ABS resin and processing aids are premixed according to the weight proportions and then transferred to a high-speed mixer for stirring. The mixture is stirred evenly to obtain a premix.

[0041] (2) Place the premixed material obtained in step (1) into the main feed port of a twin-screw extruder, and feed the polyimide fiber from the side. Then, melt-extrude, granulate and dry to obtain the PA / ABS alloy material.

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

[0043] Comparative Examples 1-5

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

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

[0046] The PA6 resin-1 is: PA6 HY2500A, from Haiyang, Jiangsu; with a relative viscosity of 2.5.

[0047] The PA6 resin-2 is: PA6 HY2800A, from Haiyang, Jiangsu; with a relative viscosity of 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 Juhua Shun; 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, manufactured by Sinopec Gaoqiao; its melt flow index at 220℃ and with a 10kg weight is 16g / 10min; it contains 20% acrylonitrile, 30% butadiene, and 50% styrene; the average particle size of the butadiene rubber phase is approximately 250nm.

[0052] The ABS resin-2 is ANC100, manufactured by Formosa Plastics; its melt flow index is 5 g / 10 min at 220°C and with a 10 kg weight; and it contains 30% acrylonitrile, 20% butadiene, and 50% styrene.

[0053] The ABS resin-3 is: ABS PA-757, from Chi Mei Corporation of Taiwan; its melt flow index is 20 g / 10 min at 220°C and with a 10 kg weight; and it contains 35% acrylonitrile, 20% butadiene, and 55% styrene.

[0054] The polyimide fiber-1 has a fiber length of 3.0 mm, is manufactured by Shilon and Jiangsu Xiannuo.

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

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

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

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

[0059] The additives are composed of antioxidants, lubricants, and compatibilizers in a mass ratio of 0.01:1:2. The antioxidants consist of primary antioxidant 1010 and secondary antioxidant 168 in a mass ratio of 1:2. The lubricant is PETS. The compatibilizer is ABS-g-MAH:KT-2H.

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

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

[0062]

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

[0064]

[0065]

[0066] The PA / ABS alloy materials prepared in each embodiment and comparative example were subjected to the following performance tests, as detailed below:

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

[0068] 2. Bending strength: Tested according to ISO 178, injection molded into a standard specimen, bending rate is 2 mm / min;

[0069] 3. Notched impact strength of simply supported beam (room temperature and -30℃): Tested according to ISO 179, injection molded into a standard specimen, with a pendulum energy of 5J;

[0070] 4. Tensile strength retention rate: After aging under ultraviolet xenon lamp with an irradiance of (1.2±0.02) W / (m2·nm)@420nm and an aging time of 168h, the tensile rate was 50mm / min after testing according to ISO 527.

[0071] 5. Appearance Evaluation: The appearance evaluation adopts the visual observation evaluation method of injection molded 100*100*3mm square plate; Appearance evaluation description: 5: 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 are spread all over the surface of the square plate; 2: The floating fibers on the surface of the square plate are serious, and the unevenness can be felt by hand; 1: The floating fibers on the surface of the square plate are very serious, and the unevenness of the plate surface can be seen by visual inspection.

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

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

[0074]

[0075] Table 4. Material property test results for Comparative Examples 1-5

[0076]

[0077] As can be seen from the test results in Table 3-4, the PA / ABS alloy material of the present invention has excellent mechanical properties and a good appearance. The tensile strength can reach more than 65 MPa, the flexural strength is not less than 79 MPa, and the room temperature impact strength is not less than 55 kJ / m. 2 Impact strength at -30℃ not less than 34kJ / m 2 After aging, the tensile strength retention rate shall not be less than 89%, and the appearance evaluation shall not be less than level 4.

[0078] As can be seen from Comparative Examples 1 and 2, both excessively low and excessively high viscosity of PA6 resin lead to poor appearance of the material after injection molding. Comparing Comparative Example 3 with Example 1, it can be seen that at the same fiber content, glass fiber provides a greater increase in tensile and flexural strength compared to polyimide fiber, but the impact strength not only does not increase but actually decreases. Furthermore, since the aging strength decay of the glass fiber-filled PA / ABS system mainly originates from interfacial delamination between the resin and glass fiber, the root cause is insufficient compatibility between the two, resulting in a lower retention rate after aging; while polyimide fiber, with better compatibility, hardly produces interfacial delamination and therefore has a better retention rate. In Comparative Example 4, the addition of too little polyimide fiber leads to a significant decrease in the mechanical properties of the material; in Comparative Example 5, the addition of too much polyimide fiber, although improving the mechanical properties, leads to a significant decrease in the appearance rating of the material.

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A PA / ABS alloy material, characterized in that, The product comprises the following components by weight: 39-65 parts PA6 resin, 29-50 parts ABS resin, 4-10 parts polyimide fiber, and 0.05-5.5 parts processing aids; the relative viscosity of the PA6 resin is 2.0-3.0; and the average length of the polyimide fiber is 2mm-6mm.

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, according to ISO 1133-2012, has a melt flow index of 5-20 g / 10 min at 220°C and with a 10 kg weight.

4. The PA / ABS alloy material according to claim 1, characterized in that, The processing aids include at least one of antioxidants, lubricants, light stabilizers, and compatibilizers.

5. The PA / ABS alloy material according to claim 4, characterized in that, The antioxidants include primary antioxidants and secondary antioxidants. The primary antioxidants include hindered phenolic antioxidants and / or aromatic amine antioxidants, and the secondary antioxidants include phosphite antioxidants and / or thioether secondary antioxidants.

6. The PA / ABS alloy material according to claim 4, characterized in that, The lubricant comprises pentaerythritol stearate; and / or, the compatibilizer comprises ABS-g-MAH.

7. The PA / ABS alloy material according to claim 1, characterized in that, The processing aids include antioxidants, lubricants, and compatibilizers; the mass ratio of the antioxidants, lubricants, and compatibilizers is (0.005-0.015):(0.5-1.5):(1-3).

8. The method for preparing the PA / ABS alloy material according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Mix PA6 resin, ABS resin and processing aids evenly according to the stated weight proportions to obtain a premix; (2) Place the premix obtained in step (1) into the main feed port of a twin-screw extruder, feed the polyimide fiber from the side, melt extrude, granulate and dry to obtain the PA / ABS alloy material.

9. The application of the PA / ABS alloy material according to any one of claims 1-7 in automotive parts, electrical and electronic products, and sporting goods.

Images