Glass fiber modified PBT / ASA alloy material, and preparation method and use therefor

Abstract

Provided in the present invention are a glass fiber modified PBT / ASA alloy material, and a preparation method and use therefor. The glass fiber modified PBT / ASA alloy material comprises specific parts of polybutylene terephthalate, styrene-acrylonitrile-acrylate rubber, flat fiberglass, an inorganic filler, a silane coupling agent, a compatibilizer and a surface improver. The inorganic filler and the silane coupling agent are used to generate a synergistic effect, such that the interface bonding force between PBT and ASA is enhanced, and warping of the PBT / ASA alloy material is reduced. In addition, the flat fiber is used to reinforce and modify the PBT / ASA alloy material, and the compatibilizer and the surface improver are added for assistance, so that the obtained PBT / ASA alloy material has high tensile property and low warping property, and is suitable for manufacturing products such as high-end electronic and electrical components, automobile interior and exterior decorative components, and mechanical components.

Description

A glass fiber modified PBT / ASA alloy material and its preparation method and application Technical Field

[0001] The present invention belongs to the technical field of composite materials, and in particular relates to a glass fiber modified PBT / ASA alloy material and a preparation method and application thereof. Background Art

[0002] Polybutylene terephthalate (PBT) is a crystalline, linear, saturated polyester resin. Due to its mature production process and low investment costs, it has seen rapid growth in the engineering plastics sector. However, when used alone, PBT exhibits low notched impact strength and significant molding shrinkage, which limits its application to some extent. Styrene-acrylonitrile-acrylate rubber (ASA), with its excellent dimensional stability and weather resistance, is a commonly used material for outdoor products.

[0003] Currently, to improve the performance of polymer materials, a common method is to compound two or more of the aforementioned polymer materials to form a PBT / ASA alloy material, thereby leveraging the respective advantages of the two materials. CN101838443A discloses a PBT / ASA alloy with good interfacial compatibility. Calculated by weight, it is prepared from 100 parts of PBT, 0-100 parts of ASA, and 0-7 parts of epoxy resin. The invention uses epoxy resin as a compatibilizer to improve the interfacial adhesion of the PBT / ASA alloy, significantly improving the interfacial compatibility of the resulting PBT / ASA alloy. The notched impact strength of the expanded material is increased by approximately 150% compared to the pre-expansion material.

[0004] However, the PBT / ASA alloy materials provided in the prior art, including the above invention, still have relatively low rigidity and are prone to warping, which limits the application of PBT / ASA alloy materials in high-end electronic products, high-end automobiles and other fields.

[0005] Therefore, developing a glass fiber modified PBT / ASA alloy material with low warpage and high rigidity is a technical problem that needs to be solved urgently in this field.

[0006] Summary of the Invention

[0007] In response to the shortcomings of the existing technology, the purpose of the present invention is to provide a glass fiber modified PBT / ASA alloy material and its preparation method and application. By adding flat glass fiber and inorganic filler, and supplemented with silane coupling agent, compatibilizer and surface improver, it helps to promote the modified crystallization of PBT / ASA alloy material, so that the obtained glass fiber modified PBT / ASA alloy material has low warpage and high rigidity, and is suitable for the production of high-end electronic and electrical components, automotive interior and exterior parts, mechanical components and other products.

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

[0009] In a first aspect, the present invention provides a glass fiber modified PBT / ASA alloy material, wherein the glass fiber modified PBT / ASA alloy material comprises the following components in parts by weight:

[0010] The glass fiber-modified PBT / ASA alloy material provided by the present invention comprises specific proportions of polybutylene terephthalate (PBT), styrene-acrylonitrile-acrylate rubber (ASA), flat glass fiber, inorganic filler, silane coupling agent, compatibilizer and surface modifier. Specifically, on the one hand, the inorganic filler and the silane coupling agent produce a synergistic effect, which can enhance the interfacial bonding strength between PBT and ASA and reduce the warping of the PBT / ASA alloy material. On the other hand, the flat fiber is used to reinforce and modify the PBT / ASA alloy material, and a compatibilizer and a surface modifier are added to assist. Thus, the obtained PBT / ASA alloy material has high tensile properties, low warpage, high rigidity and good appearance, and is suitable for use in preparing products such as high-end electronic and electrical components, automotive interior and exterior parts, and mechanical components.

[0011] Among them, the polybutylene terephthalate can be 23 parts by weight, 26 parts by weight, 29 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, 42 parts by weight, 45 parts by weight or 48 parts by weight, 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.

[0012] The styrene-acrylonitrile-acrylate rubber can be 17 parts by weight, 19 parts by weight, 21 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight or 29 parts by weight, 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.

[0013] The flat fiber can be 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, 21 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight or 29 parts by weight, 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 said range.

[0014] The inorganic filler can be 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight or 14 parts by weight, 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.

[0015] The silane coupling agent can be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight, 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.

[0016] The compatibilizer can be 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight or 5.5 parts by weight, 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.

[0017] The surface improver can be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight, 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.

[0018] Preferably, the polybutylene terephthalate is selected from Changchun Chemical (Jiangsu) Co., Ltd., 11D0-211M.

[0019] Preferably, the styrene-acrylonitrile-acrylate rubber is selected from LG Chemical Co., Ltd. of South Korea, L1911.

[0020] Preferably, the length of the cross section of the flat glass fiber is 25 to 28 μm, for example, 25.5 μm, 26 μm, 26.5 μm, 27 μm or 27.5 μm, 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.

[0021] Preferably, the width of the cross section of the flat glass fiber is 6 to 8 μm, for example, 6.2 μm, 6.4 μm, 6.6 μm, 6.8 μm, 7 μm, 7.2 μm, 7.4 μm, 7.6 μm or 7.8 μm, 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.

[0022] Preferably, the flat glass fiber has an aspect ratio of 3 to 4, such as 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8 or 3.9, 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.

[0023] Preferably, the flat fiber is selected from Chongqing International Composite Materials Co., Ltd., ECS301HP.

[0024] Preferably, the inorganic filler includes any one of talc powder, needle-shaped wollastonite or glass microspheres, or a combination of at least two of them.

[0025] Preferably, the particle size of the talc is 1250-2500 mesh, for example, 1300 mesh, 1500 mesh, 1700 mesh, 1900 mesh, 2100 mesh or 2300 mesh, 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.

[0026] Preferably, the aspect ratio of the needle-shaped wollastonite is (5-15):1, such as 7:1, 9:1, 11:1 or 13:1.

[0027] Preferably, the particle size of the glass microspheres is 3000-10000 mesh, for example, 4000 mesh, 5000 mesh, 6000 mesh, 7000 mesh, 8000 mesh or 9000 mesh, 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.

[0028] Preferably, the inorganic filler is selected from Jiangxi Guangyuan Chemical Co., Ltd.

[0029] Preferably, the silane coupling agent includes silane coupling agent KH560.

[0030] Preferably, the silane coupling agent is selected from Momentive, A1100.

[0031] Preferably, it is characterized in that the compatibilizer is an epoxy compatibilizer.

[0032] Preferably, the epoxy compatibilizer includes styrene-acrylonitrile-glycidyl methacrylate (SAG).

[0033] Preferably, the epoxy compatibilizer is selected from Nantong Rizhisheng and SAG001.

[0034] Preferably, the surface improver comprises oxidized polyethylene wax (O-PE).

[0035] Preferably, the surface improver is selected from BASF, Germany, OA6 or OA9.

[0036] In a second aspect, the present invention provides a method for preparing a glass fiber-modified PBT / ASA alloy material as described in the first aspect, the preparation method comprising: mixing polybutylene terephthalate and styrene-acrylonitrile-acrylate rubber, adding an inorganic filler, flat glass fiber, a silane coupling agent, a compatibilizer and a surface improver, and extruding to obtain the glass fiber-modified PBT / ASA alloy material.

[0037] Preferably, the mixing time is 2 to 4 minutes, for example, 2.2 minutes, 2.4 minutes, 2.6 minutes, 2.8 minutes, 3 minutes, 3.2 minutes, 3.4 minutes, 3.6 minutes or 3.8 minutes, 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.

[0038] Preferably, the extrusion is carried out in a twin-screw extruder.

[0039] Preferably, the extrusion temperatures in different zones of the twin-screw extruder are: the extrusion temperatures in zone 1 and zone 2 are each independently 95-105°C (e.g., 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C or 104°C, etc.), and the extrusion temperatures in zones 3 to 11 are each independently 195-205°C (e.g., 196°C, 197°C, 198°C, 199°C, 200°C, 201°C, 202°C, 203°C or 204°C, etc.).

[0040] Preferably, the screw speed of the twin-screw extruder is 500-700 r / min, for example, 520 r / min, 540 r / min, 560 r / min, 580 r / min, 600 r / min, 620 r / min, 640 r / min, 660 r / min or 680 r / 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.

[0041] In a third aspect, the present invention provides an application of the glass fiber modified PBT / ASA alloy material as described in the first aspect in preparing electronic and electrical components, automotive interior components or mechanical components.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] The glass fiber-modified PBT / ASA alloy material provided by the present invention comprises specific proportions of PBT, ASA, flat glass fibers, an inorganic filler, a silane coupling agent, a compatibilizer, and a surface modifier. On the one hand, the inorganic filler and the silane coupling agent produce a synergistic effect, which can enhance the interfacial bonding strength between PBT and ASA and reduce the warping of the PBT / ASA alloy material. On the other hand, the flat fiber-reinforced and modified PBT / ASA alloy material is supplemented by the addition of a compatibilizer and a surface modifier, so that the obtained PBT / ASA alloy material has high rigidity and good appearance and morphology, and is suitable for use in the preparation of high-end electronic and electrical components, automotive interior and exterior parts, mechanical components, and other products. DETAILED DESCRIPTION

[0044] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0045] Some of the raw material information involved in the specific implementation of the present invention is as follows:

[0046] (1) Polybutylene terephthalate (PBT): from Changchun Chemical (Jiangsu) Co., Ltd., 11D0-211M;

[0047] (2) Styrene-acrylonitrile-acrylate rubber (ASA): from LG Chemical Co., Ltd., South Korea, L1911;

[0048] (3) Flat glass fiber: the cross-section length is about 28 μm, the width is about 7 μm, the flatness ratio is about 4, from Chongqing International Composite Materials Co., Ltd., ECS301HP;

[0049] (4) Inorganic fillers: specifically wollastonite and GY6000, sourced from Jiangxi Guangyuan Chemical Co., Ltd.;

[0050] (5) Silane coupling agent (KH560): from Momentive, A1100;

[0051] (6) Styrene-acrylonitrile-glycidyl methacrylate (SAG): from Nantong Rizhisheng, SAG001;

[0052] (7) Oxidized polyethylene wax (O-PE): from BASF, Germany, OA6.

[0053] Examples 1 to 7

[0054] A glass fiber modified PBT / ASA alloy material, the specific components of which are shown in Table 1, and the amounts of each component in Table 1 are all in parts by weight;

[0055] Table 1

[0056] The preparation methods of the glass fiber modified PBT / ASA alloy materials provided in Examples 1 to 7 include:

[0057] PBT and ASA are mixed in a high-speed mixer for 3 minutes, and the mixed raw materials are added to the main feeder of a twin-screw extruder. Flat glass fiber, inorganic filler, KH560, SAG and O-PE are mixed evenly and then added from the side feeder of the twin-screw extruder for melt co-extrusion. The extruder temperatures are as follows: zone 1 temperature is 100° C., zone 2 temperature is 100° C., zone 3 temperature is 200° C., zone 4 temperature is 250° C., zone 5 temperature is 250° C., zone 6 temperature is 250° C., zone 7 temperature is 250° C., zone 8 temperature is 250° C., zone 9 temperature is 250° C., zone 10 temperature is 250° C., zone 11 temperature is 245° C.; the speed of the extruder screw is 600 rpm, the speed of the side electrode is 300 rpm, and after screw extrusion, the material is cooled, blown dry and pelletized to obtain the glass fiber modified PET / ASA alloy material.

[0058] Comparative Examples 1 to 7

[0059] A modified PBT / ASA alloy material, the specific components of which are shown in Table 2, where the amounts of the components in Table 2 are all in parts by weight;

[0060] Table 2

[0061] The preparation methods of the modified PBT / ASA alloy materials provided in Comparative Examples 1 to 7 refer to Example 1.

[0062] Performance testing:

[0063] (1) Tensile strength and tensile modulus: Tested according to the test method provided in ISO-527;

[0064] (2) Room temperature notched impact strength and low temperature notched impact strength: Tested in accordance with the test method provided in ISO-179;

[0065] (3) Melt index: Tested according to the test method provided in ASTM D 1238, under the following conditions: 250°C, 2.16 kg;

[0066] (4) Warpage: The glass fiber modified PBT / ASA alloy material was made into a square plate using a mold with a size of 100×100×4 mm. The square plate was then placed at room temperature for 24 h. A weight was used to press one corner of the square plate, and the height of the diagonal corner was measured with a ruler to characterize the warpage deformation of the material.

[0067] Among them, the warping height is lower than 1.5mm, which is good; the warping height is higher than 1.5mm but lower than 3mm, which is better; the warping height is higher than 3mm but lower than 5mm, which is average; and the warping height is higher than 5mm, which is poor.

[0068] The PBT / ASA alloy materials provided in Examples 1 to 7 and Comparative Examples 1 to 7 were tested according to the above test method. The test results are shown in Table 3:

[0069] Table 3

[0070] According to the data in Table 3, it can be seen that the PBT / ASA alloy material provided by the present invention has high rigidity and good appearance;

[0071] Specifically, the glass fiber modified PBT / ASA alloy materials provided in Examples 1 to 7 have a tensile strength of 117 to 135 MPa, a tensile modulus of 7400 to 12000 MPa, a room temperature notched impact strength of 46 to 62 MPa, a low temperature notched impact strength of 43 to 55 MPa, a melt index of 16.6 to 20.5 g / 10 min, and a warpage test of good or good.

[0072] The warpage performance of the modified PBT / ASA alloy materials provided in Comparative Examples 1 to 7 is only average or poor, indicating poor rigidity and appearance.

[0073] In summary, the present invention can make the glass fiber modified PBT / ASA alloy material have excellent tensile properties and rigidity by using specific proportions of PBT, ASA, flat glass fiber, inorganic filler, silane coupling agent, compatibilizer and surface modifier.

[0074] The applicant states that while the present invention uses the aforementioned embodiments to illustrate a glass fiber-modified PBT / ASA alloy material, its preparation method, and its applications, the present invention is not limited to these embodiments, nor does it necessarily rely on these embodiments for implementation. Persons skilled in the art should understand that any improvements to the present invention, equivalent substitutions for various raw materials in the present invention's products, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A glass fiber modified PBT / ASA alloy material, characterized in that: The glass fiber modified PBT / ASA alloy material comprises the following components in parts by weight:

2. The glass fiber modified PBT / ASA alloy material according to claim 1, characterized in that: The length of the cross section of the flat glass fiber is 25 to 28 μm; Preferably, the width of the cross section of the flat glass fiber is 6 to 8 μm; Preferably, the flatness ratio of the flat glass fiber is 3-4.

3. The glass fiber modified PBT / ASA alloy material according to claim 1 or 2, characterized in that: The inorganic filler includes any one of talc, needle-shaped wollastonite or glass microspheres, or a combination of at least two of them; Preferably, the particle size of the talc is 1250-2500 mesh; Preferably, the aspect ratio of the needle-shaped wollastonite is (5-15):1; Preferably, the particle size of the glass microbeads is 3000-10000 mesh.

4. The glass fiber modified PBT / ASA alloy material according to any one of claims 1 to 3, characterized in that: The silane coupling agent includes silane coupling agent KH560.

5. The glass fiber modified PBT / ASA alloy material according to any one of claims 1 to 4, characterized in that: The compatibilizer includes an epoxy compatibilizer; Preferably, the epoxy compatibilizer includes styrene-acrylonitrile-glycidyl methacrylate.

6. The glass fiber modified PBT / ASA alloy material according to any one of claims 1 to 5, characterized in that: The surface improver includes oxidized polyethylene wax.

7. A method for preparing the glass fiber modified PBT / ASA alloy material according to any one of claims 1 to 6, characterized in that: The preparation method comprises: mixing polybutylene terephthalate and styrene-acrylonitrile-acrylate rubber, adding inorganic filler, flat glass fiber, silane coupling agent, compatibilizer and surface improver, and extruding to obtain the glass fiber modified PBT / ASA alloy material.

8. The preparation method according to claim 7, characterized in that: The mixing time is 2 to 4 minutes.

9. The preparation method according to claim 7 or 8, characterized in that: The extrusion is carried out in a twin-screw extruder; Preferably, the extrusion temperatures of different zones in the twin-screw extruder are: the extrusion temperatures of zone 1 and zone 2 are independently 95-105° C., and the extrusion temperatures of zones 3 to 11 are independently 195-205° C.; Preferably, the screw speed of the twin-screw extruder is 500-700 r / min.

10. Use of the glass fiber modified PBT / ASA alloy material according to any one of claims 1 to 6 in preparing electronic and electrical parts, automobile interior parts or mechanical components.

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