Carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material and preparation method thereof

Abstract

The invention discloses a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material and a preparation method thereof, and relates to the technical field of high polymer materials. The PA56 / PPO composite material comprises the following components in percentage by mass: 20%-40% of PA56 resin, 20%-30% of PPO resin, 20%-40% of modified carbon fibers, 10%-20% of silane modified glass beads, 0.5%-5% of a toughening agent and 0.5%-5% of a compatilizer. Through compound use of the modified carbon fibers and the silane modified glass beads, the addition amount of a single carbon fiber material can be reduced, and weight reduction is realized while the cost is reduced; the toughening agent has good compatibility with matrix resin and can generate a better toughness modification effect after being added into a PA56 / PPO system, and the added compatilizer can improve the interfacial effect among the components so as to effectively improve the mechanical properties and antistatic properties of the composite material. The carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material provided by the invention is balanced in rigidity, toughness and antistatic property, and can be used in automotive electronic and electrical products with requirements on high strength, high toughness and antistatic property.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material and a preparation method thereof. Background Art

[0002] PA56 (polyamide 56) is a new type of bio-based polyamide. It contains carboxyl and amino groups at the end of the molecular chain and has high hygroscopicity. However, high water absorption will lead to a decrease in the electrical properties of the material, poor dimensional stability and deterioration of mechanical properties. At the same time, PA56 exhibits great brittleness in dry and low-temperature environments. These defects seriously limit its application in automotive electronics and other fields.

[0003] PPO (polyphenylene ether) is a high-performance engineering plastic characterized by high rigidity, high impact resistance, and low water absorption. In theory, its toughness can be improved by blending it with PA56. However, PA56 is a polar crystalline resin, while PPO is a non-polar, amorphous resin. The two have poor compatibility, making it difficult to achieve good interfacial bonding with simple blending. Consequently, the alloy cannot achieve both toughness and strength, making it difficult to meet the demands of high-performance applications.

[0004] As the automotive electronics industry continues to demand higher performance from materials, the development of PA56 / PPO alloys that combine high strength, toughness, antistatic properties, and dimensional stability has become a research priority. Consequently, there is an urgent need to optimize the interfacial compatibility of PA56 / PPO alloys through modification methods such as volume expansion, toughening, and reinforcement, thereby overcoming the inherent flaws of single materials and producing composite materials with superior overall performance to meet the demands of high-end applications. Summary of the Invention

[0005] The object of the present invention is to provide a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material and a preparation method thereof, so as to solve at least one of the above-mentioned technical problems.

[0006] To achieve the above objectives, the first aspect of the present invention provides a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material, which comprises the following components by mass fraction: 20%-40% PA56 resin, 20%-30% PPO resin, 20%-40% modified carbon fiber, 10%-20% silane-modified glass microspheres, 0.5%-5% toughening agent and 0.5%-5% compatibilizer.

[0007] In the first aspect, the method for preparing the modified carbon fiber comprises: adding continuous carbon fiber to a 90% formic acid solution, soaking the solution at room temperature for 24 hours, filtering, and vacuum drying the filter cake at 80-100° C. to obtain the modified carbon fiber.

[0008] In the first aspect, the preparation method of the silane-modified glass microspheres includes: dissolving a silane coupling agent and glass microspheres in anhydrous ethanol at a mass ratio of 1:100-2:100, ultrasonically dispersing, and heating to 80°C, adjusting the pH value to 8-10 with ammonia water, and then stirring at 80°C for 0.5-1h, filtering, and vacuum drying the filter cake at 80-100°C to obtain silane-modified glass microspheres.

[0009] In the first aspect, the toughening agent is silane-modified nano-titanium dioxide.

[0010] In the first aspect, the preparation method of the toughening agent includes: dissolving a silane coupling agent and nano-titanium dioxide in anhydrous ethanol at a mass ratio of 1:100-2:100, ultrasonically dispersing, stirring at 80°C for 2-4h, filtering, and vacuum drying the filter cake at 80-100°C to obtain a toughening agent.

[0011] In the first aspect, the compatibilizer is a PPO-g-MAH series compatibilizer.

[0012] The second aspect of the present invention provides a method for preparing a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material, the preparation method comprising: preparing modified carbon fibers; preparing silane-modified glass microspheres; preparing a toughening agent; weighing the components of the composite material raw materials, the components of the raw materials comprising: 20%-40% PA56 resin, 20%-30% PPO resin, 20%-40% modified carbon fibers, 10%-20% silane-modified glass microspheres, 0.5%-5% toughening agent and 0.5%-5% compatibilizer; pre-mixing the PA56 resin, the PPO resin, the toughening agent and the compatibilizer to obtain an initial mixture; adding the initial mixture from a main feeding hopper and conveying it into the screw cavity of a twin-screw extruder, adding the modified carbon fibers and the silane-modified glass microspheres from a side feeding hopper and conveying them into the screw cavity of the twin-screw extruder, heating and melting, and extruding and granulating to obtain a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material.

[0013] In the second aspect, the preparation of modified carbon fiber specifically includes: adding continuous carbon fiber to 90% formic acid solution, soaking at room temperature for 24 hours, filtering to obtain a filter cake; placing the filter cake in a vacuum drying oven at 80-100°C for drying to obtain modified carbon fiber.

[0014] In the second aspect, the preparation of silane-modified glass microspheres specifically includes: placing a silane coupling agent and glass microspheres in anhydrous ethanol at a mass ratio of 1:100-2:100, ultrasonically dispersing, and obtaining a mixed solution; heating the mixed solution to 80°C, and adjusting the pH value to 8-10 with ammonia water to obtain a reaction solution; stirring the reaction solution at 80°C for 0.5-1h, and filtering to obtain a filter cake; and drying the filter cake in a vacuum drying oven at 80-100°C to obtain silane-modified glass microspheres.

[0015] In the second aspect, the preparation of the toughening agent specifically includes: dissolving a silane coupling agent and nano-titanium dioxide in anhydrous ethanol in a mass ratio of 1:100-2:100, ultrasonically dispersing, and obtaining a mixed solution; heating the mixed solution to 80°C, stirring and reacting for 2-4 hours, filtering, and obtaining a filter cake; and placing the filter cake in a vacuum drying oven at 80-100°C for drying to obtain a toughening agent.

[0016] Beneficial effects: The present invention provides a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material, which includes the following components by mass fraction: 20%-40% PA56 resin, 20%-30% PPO resin, 20%-40% modified carbon fiber, 10%-20% silane-modified glass microspheres, 0.5%-5% toughening agent, and 0.5%-5% compatibilizer; modified carbon fiber and silane-modified glass microspheres are obtained by surface modification of carbon fiber and glass microspheres, and the two are compounded for use to improve the antistatic properties of the composite material. The modified carbon fiber can be evenly dispersed in the resin, showing a typical percolation phenomenon, thereby forming a conductive path and reducing the surface resistivity of the composite material; the silane-modified glass microspheres have good interfacial compatibility with the resin, and play a supporting role similar to a "skeleton" with the modified carbon fiber in the resin matrix, producing a synergistic reinforcement effect and improving the rigidity of the composite material. By compounding the modified carbon fiber and silane-modified glass microspheres, the amount of single carbon fiber material added can be reduced, achieving lightweighting while reducing costs. The toughening agent has good compatibility with the matrix resin and can produce better toughness modification effect when added to the PA56 / PPO system. At the same time, the added compatibilizer can enhance the interface effect between the components to effectively improve the mechanical properties and antistatic properties of the composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of this specification or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0018] Figure 1 A schematic flow chart of a method for preparing a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material provided by the present invention. DETAILED DESCRIPTION

[0019] The present invention will be described in detail below in conjunction with specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific embodiments and examples are for illustrating the present invention, rather than for limiting the present invention.

[0020] Throughout this specification, unless otherwise specified, the terms used herein should be understood as having the same meaning as commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event of any conflict, the present specification shall take precedence.

[0021] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or obtained through existing methods.

[0022] The present invention provides a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material. The composite material comprises the following components, measured by mass fraction: 20%-40% PA56 resin, 20%-30% PPO resin, 20%-40% modified carbon fiber, 10%-20% silane-modified glass microspheres, 0.5%-5% toughening agent, and 0.5%-5% compatibilizer.

[0023] In some possible embodiments, the modified carbon fiber is a surface-treated continuous carbon fiber, and its specific preparation method includes: adding the continuous carbon fiber to a 90% formic acid solution, soaking it at room temperature for 24 hours, filtering it, and vacuum drying the filter cake at 80-100°C to obtain the modified carbon fiber.

[0024] In some possible embodiments, the preparation method of silane-modified glass microspheres includes: dissolving a silane coupling agent and glass microspheres in anhydrous ethanol at a mass ratio of 1:100-2:100, ultrasonically dispersing, and heating to 80°C, adjusting the pH value to 8-10 with ammonia water, and then stirring at 80°C for 0.5-1h, filtering, and vacuum drying the filter cake at 80-100°C to obtain silane-modified glass microspheres.

[0025] In some possible embodiments, the toughening agent is silane-modified nano-titanium dioxide; its specific preparation method includes: dissolving the silane coupling agent and nano-titanium dioxide in anhydrous ethanol at a mass ratio of 1:100-2:100, ultrasonically dispersing, stirring at 80°C for 2-4 hours, filtering, and vacuum drying the filter cake at 80-100°C to obtain the toughening agent.

[0026] In some possible embodiments, the compatibilizer is a PPO-g-MAH series compatibilizer. Based on a general inventive concept, such as Figure 1 As shown, the second aspect of the present invention provides a method for preparing a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material, the preparation method comprising: S1. preparing modified carbon fiber; S2, preparing silane-modified glass microspheres; S3, preparing a toughening agent; S4. Weighing the components of the composite material raw material, wherein the raw material components include: PA56 resin 20%-40%, PPO resin 20%-30%, modified carbon fiber 20%-40%, silane-modified glass microspheres 10%-20%, toughening agent 0.5%-5% and compatibilizer 0.5%-5%; S5, pre-mixing the PA56 resin, the PPO resin, the toughening agent and the compatibilizer to obtain an initial mixture; S6. Add the initial mixture from the main feeding hopper and convey it into the screw cavity of a twin-screw extruder. Add the modified carbon fiber and the silane-modified glass microbeads from the side feeding hopper and convey them into the screw cavity of the twin-screw extruder. After heating, melting, extrusion and granulation, a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material is obtained; wherein the processing temperature of the twin-screw extruder is controlled at 230-260°C and the main engine speed is 370-430rpm.

[0027] The present application will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present application only and are not intended to limit the scope of the present application. The experimental methods in the following examples where specific conditions are not specified are usually measured in accordance with national standards. If there are no corresponding national standards, then the methods are carried out in accordance with general international standards, conventional conditions, or according to the conditions recommended by the manufacturer.

[0028] The raw materials used in the examples and comparative examples are as follows: PA56 resin: Shanghai Kaiser Biotechnology Co., Ltd., 6300; PPO resin: SABIC, N190; Carbon fiber: Teijin, HT C413 6MM; Modified carbon fiber: Add continuous carbon fiber to 90% formic acid solution, soak at room temperature for 24 hours, filter, and vacuum dry the filter cake at 80°C to obtain modified carbon fiber.

[0029] Glass microspheres: 3M Company, S15; Silane-modified glass microspheres: KH550 silane coupling agent and glass microspheres were dissolved in anhydrous ethanol at a mass ratio of 1:100, and ultrasonically dispersed for 30 min. When heated to 80°C with stirring, ammonia water was added to adjust the pH to 9. The mixture was magnetically stirred at 80°C for 0.5 h, filtered, and dried in a vacuum oven at 80°C to obtain silane-modified glass microspheres.

[0030] Nano titanium dioxide: Toughening agent: KH550 silane coupling agent and nano-titanium dioxide were dissolved in anhydrous ethanol at a mass ratio of 1:100, ultrasonically dispersed for 30 minutes, stirred at 80°C for 2 hours, filtered, and washed with anhydrous ethanol to obtain a filter cake; the filter cake was placed in a vacuum dryer at 80°C to obtain a nano-titanium dioxide toughening agent.

[0031] Compatibilizer: Jiayirong Polymer (Shanghai) Co., Ltd., FB820.

[0032] The raw material components in Examples 1-3 and Comparative Examples 1-5 of the present invention are shown in Table 1 below in terms of mass percentage: Table 1 Distribution ratio of each group of raw materials The formulation ratios provided in Examples 1-3 and Comparative Examples 1-5 were used to prepare PA56 / PPO composite materials according to the following experimental steps: (1) Weigh the raw material components according to the respective formula ratios of the examples and comparative examples. Among them, PA56 resin and PPO resin need to be dried at 100°C for 4 hours before weighing; (2) Pre-mixing the weighed PA56 resin, PPO resin, toughening agent and compatibilizer to obtain an initial mixture; (3) The initial mixed material is fed into the main feeding hopper of the twin-screw extruder and transported by its own gravity and the screw of the first feeding zone of the extruder. At the same time, the modified carbon fiber and silane-modified glass microbeads are added to the hopper of the side feeder and transported to the screw cavity of the extruder through the screw of the side feeder. After heating, melting and extrusion granulation by the heating barrel and screw shearing, the processing temperature of the twin-screw extruder is controlled at 230-260°C and the main engine speed is 370-430rpm, and finally the PA56 / PPO composite material is obtained.

[0033] The PA56 / PPO composite materials prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to performance testing. The test results are shown in Table 2 below: Table 2 Test results It can be seen from the above experimental data that in Examples 1-3 of the present invention, carbon fiber-glass beads synergistically reinforced PA56 / PPO composite materials are developed by using different proportions of PA56 resin, PPO resin, modified carbon fiber, silane-modified glass microspheres, toughening agent, and compatibilizer. Carbon fiber is a high-strength, high-modulus fiber mainly composed of carbon elements. It has good electrical conductivity and also has properties such as high temperature resistance, wear resistance, and corrosion resistance. After surface modification of carbon fiber, the surface structure of carbon fiber can be effectively improved. The surface of modified carbon fiber is connected with lipophilic groups, which improves its compatibility with PA56 / PPO polymer, thereby playing a reinforcing and antistatic role. Glass microspheres are commonly used spherical silicate particles with the advantages of low porosity, high filling amount, and good fluidity. After silane modification of glass microspheres, their compatibility with PA56 / PPO polymer is improved, thereby playing a reinforcing role. The compounding of modified carbon fiber and silane-modified glass microspheres can effectively improve the strength, stiffness, and antistatic properties of the composite material. Nano-titanium dioxide is modified with silane. The reactive amino groups on the surface of the modified nano-titanium dioxide can react with the amide groups of the PA56 molecular chain to form a strong interface structure between hydrogen bonds and covalent bonds, causing it to undergo plastic deformation and absorb a large amount of impact energy, achieving a significant toughening effect. The maleic anhydride groups in the compatibilizer PPO-g-MAH can chemically react with the amino groups and carboxyl groups in the PA56 molecular structure, and the main chain in PPO-g-MAH is completely compatible with the PPO matrix, thereby improving the interfacial compatibility between the two phases. The carbon fiber-glass beads synergistically enhance the rigidity, toughness, and antistatic properties of the PA56 / PPO composite material of the present invention, and can be used in automotive electronic and electrical product series that require high strength, high toughness, and antistatic properties.

[0034] Finally, it should be noted that the terms "comprises," "includes," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements, but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0035] Although the preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0036] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.

Claims

1. A carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material, characterized in that: The composite material includes the following components by mass fraction: 20%-40% PA56 resin, 20%-30% PPO resin, 20%-40% modified carbon fiber, 10%-20% silane-modified glass microspheres, 0.5%-5% toughening agent and 0.5%-5% compatibilizer.

2. The carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material according to claim 1, characterized in that: The preparation method of the modified carbon fiber comprises: adding continuous carbon fiber into a 90% formic acid solution, soaking the solution at room temperature for 24 hours, filtering, and vacuum drying the filter cake at 80-100° C. to obtain the modified carbon fiber.

3. The carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material according to claim 1, characterized in that: The preparation method of the silane-modified glass microspheres comprises: dissolving a silane coupling agent and glass microspheres in anhydrous ethanol at a mass ratio of 1:100-2:100, ultrasonically dispersing, heating to 80°C, adjusting the pH value to 8-10 with aqueous ammonia, stirring at 80°C for 0.5-1h, filtering, and vacuum drying the filter cake at 80-100°C to obtain the silane-modified glass microspheres.

4. The carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material according to claim 1, characterized in that: The toughening agent is silane-modified nano titanium dioxide.

5. The carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material according to claim 1, characterized in that: The preparation method of the toughening agent comprises: dissolving a silane coupling agent and nano-titanium dioxide in anhydrous ethanol at a mass ratio of 1:100-2:100, ultrasonically dispersing, stirring at 80°C for 2-4 hours, filtering, and vacuum drying the filter cake at 80-100°C to obtain the toughening agent.

6. The carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material according to claim 1, characterized in that: The compatibilizer is a PPO-g-MAH series compatibilizer.

7. A method for preparing a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material, characterized in that: The preparation method comprises: preparing modified carbon fibers; Preparation of silane-modified glass microspheres; preparing a toughening agent; Weighing the components of the composite material raw material, the raw material components include: PA56 resin 20%-40%, PPO resin 20%-30%, modified carbon fiber 20%-40%, silane modified glass microspheres 10%-20%, toughening agent 0.5%-5% and compatibilizer 0.5%-5%; Premixing the PA56 resin, the PPO resin, the toughening agent, and the compatibilizer to obtain an initial mixture; The initial mixture is added from the main feeding hopper and conveyed into the screw cavity of the twin-screw extruder. The modified carbon fiber and the silane-modified glass microbeads are added from the side feeding hopper and conveyed into the screw cavity of the twin-screw extruder. After heating, melting, extrusion and granulation, a carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material is obtained.

8. The method for preparing the carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material according to claim 7, characterized in that: The preparation of the modified carbon fiber specifically includes: adding continuous carbon fiber to a 90% formic acid solution, soaking at room temperature for 24 hours, filtering to obtain a filter cake; and placing the filter cake in a vacuum drying oven at 80-100° C. for drying to obtain the modified carbon fiber.

9. The method for preparing the carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material according to claim 7, characterized in that: The preparation of silane-modified glass microspheres specifically includes: The silane coupling agent and glass microbeads are placed in anhydrous ethanol at a mass ratio of 1:100-2:100, and ultrasonically dispersed to obtain a mixed solution; The mixed solution was heated to 80° C., and the pH value was adjusted to 8-10 by adding aqueous ammonia to obtain a reaction solution; The reaction solution was stirred at 80° C. for 0.5-1 h, and then filtered to obtain a filter cake; The filter cake is placed in a vacuum drying oven at 80-100° C. for drying to obtain silane-modified glass microbeads.

10. The method for preparing the carbon fiber-glass bead synergistically reinforced PA56 / PPO composite material according to claim 7, characterized in that: The preparation of the toughening agent specifically comprises: Dissolve the silane coupling agent and nano-titanium dioxide in anhydrous ethanol at a mass ratio of 1:100-2:100, and ultrasonically disperse to obtain a mixed solution; The mixed solution was heated to 80° C., stirred and reacted for 2-4 hours, and filtered to obtain a filter cake; The filter cake is placed in a vacuum drying oven at 80-100° C. for drying to obtain a toughening agent.

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