Graphene high-strength, high-toughness and impact-resistant 3D printing wire rod and preparation method thereof

Abstract

The invention discloses a graphene high-strength, high-toughness and impact-resistant 3D printing wire rod and a preparation method thereof.The graphene high-strength, high-toughness and impact-resistant 3D printing wire rod is prepared from, by weight, 75-90 parts of polyphenylene sulfide resin, 0.5-5 parts of functionalized graphene, 5-12 parts of a toughening agent, 2-6 parts of a compatilizer, 1-4 parts of a dispersing agent, 0.3-1 part of an antioxidant and 0.5-2 parts of a lubricating agent. Through synergistic interface design of functionalized graphene and a PPS matrix, the strength, toughness and impact resistance of the wire are remarkably improved, the material is endowed with good thermal conductivity and dimensional stability, the problems that nanofiller is prone to agglomeration and poor in interface bonding are solved, and the preparation method is suitable for industrial production. Furthermore, the wire prepared by the preparation method is uniform in diameter, free of bubbles, smooth in printing and high in interlayer binding force, and can be widely applied to industrial-grade FDM 3D printing scenes.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, and further to a graphene high-strength, high-toughness, impact-resistant 3D printing filament and its preparation method. Background Technology

[0002] Polyphenylene sulfide (PPS) is a high-performance specialty engineering plastic favored for its excellent high temperature resistance, chemical corrosion resistance and mechanical strength. However, its inherent brittleness and poor impact resistance limit its application in high-end 3D printing, especially in applications that require dynamic loads, impacts or high thermal / electrical conductivity.

[0003] Graphene possesses extremely high specific surface area, excellent mechanical properties, and outstanding thermal and electrical conductivity, making it an ideal polymer reinforcement. However, effectively using graphene to reinforce PPS faces two major technical bottlenecks: First, the strong π-π interactions between graphene sheets make them prone to agglomeration, making it difficult to achieve nanoscale uniform dispersion in the PPS matrix; second, the weak interfacial interactions between graphene and the PPS matrix result in low stress transfer efficiency and unsatisfactory toughening and reinforcement effects. Simple physical blending not only fails to fully realize the reinforcing potential of graphene but may even deteriorate the mechanical properties of the material due to agglomerates acting as stress concentration points.

[0004] Therefore, there is an urgent need to develop a graphene high-strength, high-toughness, and impact-resistant 3D printing filament to solve the technical problems in the existing technology. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide a graphene high-strength, high-toughness, and impact-resistant 3D printing filament, which can solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: This application provides a graphene high-strength, high-toughness, and impact-resistant 3D printing filament, comprising the following components by weight: 75-90 parts of polyphenylene sulfide resin, 0.5-5 parts of functionalized graphene, 5-12 parts of toughening agent, 2-6 parts of compatibilizer, 1-4 parts of dispersant, 0.3-1 part of antioxidant, and 0.5-2 parts of lubricant.

[0007] In some embodiments, the functionalized graphene is hydroxylated graphene or carboxylated graphene.

[0008] In some embodiments, the compatibilizer is an epoxy-functionalized polymer, preferably a polyolefin elastomer grafted with glycidyl methacrylate.

[0009] According to another aspect of the present invention, the present invention further provides a method for preparing graphene high-strength, high-toughness, and impact-resistant 3D printing filament, for preparing the graphene high-strength, high-toughness, and impact-resistant 3D printing filament described in any of the above embodiments, comprising the following steps: Step S1: Prepare polyphenylene sulfide resin, functionalized graphene, toughening agent, compatibilizer, dispersant, antioxidant and lubricant by weight parts; Step S2: Functionalized graphene and dispersant are ultrasonically dispersed in a solvent, then a portion of polyphenylene sulfide resin is added for impregnation, the solvent is removed, and the mixture is melt-blended and granulated to obtain a high-concentration graphene masterbatch. Step S3: The graphene masterbatch obtained in step S2 is dried with the remaining polyphenylene sulfide resin, toughening agent, compatibilizer, antioxidant and lubricant, and then premixed to obtain a premix. Step S4: Melt-blend and granulate the premix obtained in step S3 to obtain the final masterbatch; Step S5: Extrude the final mixed masterbatch into 3D printing filament.

[0010] In some embodiments, the solvent in step S2 is N-methylpyrrolidone, and the ultrasonic dispersion treatment time is 0.5h-2h.

[0011] In some embodiments, the weight of the polyphenylene sulfide resin in step S2 accounts for 15%-30% of the total weight of the polyphenylene sulfide resin.

[0012] In some embodiments, the melt blending in steps S2 and S4 is carried out in a twin-screw extruder with a processing temperature range of 280°C to 310°C.

[0013] In some embodiments, the extrusion molding in step S5 is performed in a single-screw extruder with a processing temperature range of 280°C to 305°C.

[0014] According to another aspect of the present invention, the present invention further provides a flame-retardant component, which is prepared by using graphene high-strength, high-toughness, and impact-resistant 3D printing filament as described in any of the above embodiments. The flame-retardant component is used in any one of the following applications: customized housings for electrical equipment, lightweight flame-retardant brackets for aerospace applications, ventilation duct models for buildings, and components for fire-fighting robots.

[0015] Compared with existing technologies, the graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its preparation method provided by this invention have at least the following beneficial effects: 1. By introducing graphene, this invention not only significantly improves mechanical properties but also endows the filament with good thermal conductivity and certain antistatic capabilities. The printed parts have better thermal management performance and higher dimensional stability. At the same time, the innovative "two-step method" of first preparing high-concentration graphene masterbatch and then diluting and finally mixing effectively overcomes the problem of direct graphene dispersion. Liquid-phase ultrasonic pre-dispersion combined with dispersant ensures that graphene is "pre-exfoliated" in the form of nanosheets. The design of pre-granulating some PPS also "solidifies" the dispersed state in the masterbatch, avoiding secondary agglomeration during the final mixing process. 2. This invention utilizes multiple chemical reactions between functionalized graphene, compatibilizer (GMA), and toughening agent / PPS to construct a robust chemical "interface bridge" between graphene and the matrix, achieving efficient stress transfer from the matrix to the graphene. At the same time, the large specific surface area of ​​graphene effectively induces crazes and shear bands, consuming a large amount of impact energy, thus achieving a perfect unity of reinforcement and toughening. 3. The preparation method provided by this invention is an upgrade of the existing twin-screw extrusion production line. The prepared wire has a uniform diameter, is free of bubbles, prints smoothly, and has strong interlayer bonding, thus it can be widely applied to industrial-grade FDM 3D printing scenarios. Detailed Implementation The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0017] The main raw materials and their component contents used in the examples and comparative examples are shown below: The present application will be further described in detail below with reference to embodiments and comparative examples.

[0018] The toughening agent is mainly styrene-ethylene-butadiene-styrene-grafted maleic anhydride copolymer (SEBS-g-MAH), the compatibilizer is mainly glycidyl methacrylate-grafted polyolefin elastomer (GMA-g-POE), and the solvent is mainly N-methylpyrrolidone (NMP).

[0019] Examples 1-2 and Comparative Examples 1-4 provide a graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its fabrication method.

[0020] Example 1 Example 1 provides a graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its preparation method. The preparation method of the graphene high-strength, high-toughness, and impact-resistant 3D printing filament includes the following steps: Raw materials selected by weight: 85 parts polyphenylene sulfide resin (PPS), 2 parts carboxylated graphene, 8 parts toughening agent (SEBS-g-MAH), 4 parts glycidyl methacrylate grafted polyolefin elastomer (GMA-g-POE), 2 parts dispersant (PVP), 0.5 parts antioxidant, and 1 part lubricant (EBS).

[0021] Preparation steps: Graphene masterbatch preparation: 2 parts of carboxylated graphene and 2 parts of dispersant (PVP) were dispersed in 500 ml of N-methylpyrrolidone (NMP) and ultrasonically dispersed for 1 hour. Then, 15 parts of polyphenylene sulfide resin (PPS) were added and stirred at high speed. Then, N-methylpyrrolidone (NMP) was removed by rotary evaporation to obtain a premixed powder. The premixed powder was then granulated by a twin-screw extruder with a processing temperature range of 300℃-310℃ to obtain graphene masterbatch.

[0022] Final mixing and wire preparation: The above graphene masterbatch, the remaining 70 parts of polyphenylene sulfide resin (PPS), and other additives are dried and then mixed. The mixture is then granulated by a twin-screw extruder with a processing temperature range of 285℃-305℃, and finally formed into wire with a diameter of 1.75mm by a single-screw extruder with a processing temperature range of 290℃-300℃.

[0023] Example 2 Example 2 provides a graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its preparation method. The preparation method of the graphene high-strength, high-toughness, and impact-resistant 3D printing filament includes the following steps: Raw materials selected by weight: 80 parts polyphenylene sulfide resin (PPS), 3.5 parts hydroxylated graphene, 5 parts toughening agent (SEBS-g-MAH), 5 parts glycidyl methacrylate grafted polyolefin elastomer (GMA-g-POE), 3 parts polyether dispersant, 0.7 parts antioxidant 168, and 1.5 parts zinc stearate.

[0024] Preparation steps: Graphene masterbatch preparation: 3.5 parts of hydroxylated graphene and 3 parts of polyether dispersant were dispersed in 500 ml of N-methylpyrrolidone (NMP) and ultrasonically dispersed for 1 hour. Then, 15 parts of polyphenylene sulfide resin (PPS) were added and stirred at high speed. Then, N-methylpyrrolidone (NMP) was removed by rotary evaporation to obtain a premixed powder. The premixed powder was then granulated by a twin-screw extruder with a processing temperature range of 300℃-310℃ to obtain graphene masterbatch.

[0025] Final mixing and wire preparation: The above graphene masterbatch, the remaining 70 parts of polyphenylene sulfide resin (PPS), and other additives are dried and then mixed. The mixture is then granulated by a twin-screw extruder with a processing temperature range of 285℃-305℃, and finally formed into wire with a diameter of 1.75mm by a single-screw extruder with a processing temperature range of 290℃-300℃.

[0026] Comparative Example 1 Comparative Example 1 provides a graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its preparation method. The preparation method of the graphene high-strength, high-toughness, and impact-resistant 3D printing filament includes the following steps: Raw materials selected by weight: 85 parts polyphenylene sulfide resin (PPS), 8 parts toughening agent (SEBS-g-MAH), 4 parts glycidyl methacrylate grafted polyolefin elastomer (GMA-g-POE), 2 parts dispersant (PVP), 0.5 parts antioxidant (1076), and 1 part lubricant (EBS).

[0027] Preparation steps: Graphene masterbatch preparation: 2 parts of dispersant (PVP) were dispersed in 500 ml of N-methylpyrrolidone (NMP) and ultrasonically dispersed for 1 hour. Then, 15 parts of polyphenylene sulfide resin (PPS) were added and stirred at high speed. The N-methylpyrrolidone (NMP) was then removed by rotary evaporation to obtain a premixed powder. The premixed powder was then granulated by a twin-screw extruder with a processing temperature range of 300℃-310℃ to obtain the masterbatch.

[0028] Final mixing and wire preparation: The above masterbatch, the remaining 70 parts of polyphenylene sulfide resin (PPS), and other additives are dried and then mixed. The mixture is then granulated by a twin-screw extruder with a processing temperature range of 285℃-305℃, and finally formed into wire with a diameter of 1.75mm by a single-screw extruder with a processing temperature range of 290℃-300℃.

[0029] Comparative Example 2 Comparative Example 2 provides a graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its preparation method. The preparation method of the graphene high-strength, high-toughness, and impact-resistant 3D printing filament includes the following steps: Raw materials selected by weight: 85 parts polyphenylene sulfide resin (PPS), 2 parts carboxylated graphene, 8 parts toughening agent (SEBS-g-MAH), 4 parts glycidyl methacrylate grafted polyolefin elastomer (GMA-g-POE), 2 parts dispersant (PVP), 0.5 parts antioxidant, and 1 part lubricant (EBS).

[0030] Preparation steps: Graphene masterbatch preparation: 2 parts of carboxylated graphene, 2 parts of dispersant (PVP), 70 parts of polyphenylene sulfide resin (PPS), and other additives are dried and then mixed. The mixture is then granulated by a twin-screw extruder with a processing temperature range of 285℃-305℃, and finally formed into wire with a diameter of 1.75mm by a single-screw extruder with a processing temperature range of 290℃-300℃.

[0031] Comparative Example 3 Comparative Example 3 provides a graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its preparation method. The preparation method of the graphene high-strength, high-toughness, and impact-resistant 3D printing filament includes the following steps: Raw materials selected by weight: 85 parts polyphenylene sulfide resin (PPS), 2 parts carboxylated graphene, 4 parts glycidyl methacrylate-grafted polyolefin elastomer (GMA-g-POE), 2 parts dispersant (PVP), 0.5 parts antioxidant 1076, and 1 part lubricant (EBS).

[0032] Preparation steps: Graphene masterbatch preparation: 2 parts of carboxylated graphene and 2 parts of dispersant (PVP) were dispersed in 500 ml of N-methylpyrrolidone (NMP) and ultrasonically dispersed for 1 hour. Then, 15 parts of polyphenylene sulfide resin (PPS) were added and stirred at high speed. Then, N-methylpyrrolidone (NMP) was removed by rotary evaporation to obtain a premixed powder. The premixed powder was then granulated by a twin-screw extruder with a processing temperature range of 300℃-310℃ to obtain graphene masterbatch.

[0033] Final mixing and wire preparation: The above graphene masterbatch, the remaining 70 parts of polyphenylene sulfide resin (PPS), and other additives are dried and then mixed. The mixture is then granulated by a twin-screw extruder with a processing temperature range of 285℃-305℃, and finally formed into wire with a diameter of 1.75mm by a single-screw extruder with a processing temperature range of 290℃-300℃.

[0034] Comparative Example 4 Comparative Example 4 provides a graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its preparation method. The preparation method of the graphene high-strength, high-toughness, and impact-resistant 3D printing filament includes the following steps: Raw materials selected by weight: 85 parts polyphenylene sulfide resin (PPS), 2 parts carboxylated graphene, 8 parts toughening agent (SEBS-g-MAH), 4 parts glycidyl methacrylate grafted polyolefin elastomer (GMA-g-POE), 2 parts dispersant (PVP), 0.5 parts antioxidant, and 1 part lubricant (EBS).

[0035] Preparation steps: Graphene masterbatch preparation: 2 parts of carboxylated graphene and 2 parts of dispersant (PVP) were dispersed in 500 ml of N-methylpyrrolidone (NMP) and ultrasonically dispersed for 1 hour. Then, 15 parts of polyphenylene sulfide resin (PPS) were added and stirred at high speed. Then, N-methylpyrrolidone (NMP) was removed by rotary evaporation to obtain a premixed powder. The premixed powder was then granulated by a twin-screw extruder with a processing temperature range of 350℃-400℃ to obtain graphene masterbatch.

[0036] Final mixing and wire preparation: The above graphene masterbatch, the remaining 70 parts of polyphenylene sulfide resin (PPS), and other additives are dried and then mixed. The mixture is then granulated by a twin-screw extruder with a processing temperature range of 350℃-400℃, and finally formed into wire with a diameter of 1.75mm by a single-screw extruder with a processing temperature range of 290℃-300℃.

[0037] Comparative Example 5 Comparative Example 5 provides a graphene high-strength, high-toughness, and impact-resistant 3D printing filament and its preparation method. The preparation method of the graphene high-strength, high-toughness, and impact-resistant 3D printing filament includes the following steps: Raw materials selected by weight: 85 parts polyphenylene sulfide resin (PPS), 2 parts carboxylated graphene, 8 parts toughening agent (SEBS-g-MAH), 4 parts glycidyl methacrylate grafted polyolefin elastomer (GMA-g-POE), 2 parts dispersant (PVP), 0.5 parts antioxidant, and 1 part lubricant (EBS).

[0038] Preparation steps: Graphene masterbatch preparation: 2 parts of carboxylated graphene and 2 parts of dispersant (PVP) were dispersed in 500 ml of N-methylpyrrolidone (NMP) and ultrasonically dispersed for 1 hour. Then, 15 parts of polyphenylene sulfide resin (PPS) were added and stirred at high speed. Then, N-methylpyrrolidone (NMP) was removed by rotary evaporation to obtain a premixed powder. The premixed powder was then granulated by a twin-screw extruder with a processing temperature range of 300℃-310℃ to obtain graphene masterbatch.

[0039] Final mixing and wire preparation: The above graphene masterbatch, the remaining 70 parts of polyphenylene sulfide resin (PPS), and other additives are dried and then mixed. The mixture is then granulated by a twin-screw extruder with a processing temperature range of 285℃-305℃, and finally formed into a wire with a diameter of 1.75mm by a single-screw extruder with a processing temperature range of 350℃-370℃.

[0040] Product performance testing: The high-strength, high-toughness, and impact-resistant graphene 3D printing filaments prepared in Examples 1-2 and Comparative Examples 1-5 were printed into corresponding standard strips for testing various properties. The test results are shown in Table 1.

[0041] Table 1

[0042] As shown in Table 1, Examples 1 and 2 exhibit excellent mechanical properties, thermal conductivity, and antistatic properties. Furthermore, a comparison between Examples 1 and Comparative Examples 1-5 reveals that the flame retardancy rating and limiting oxygen index of Comparative Examples 1-4 are significantly worse than those of Examples 1, while the overall performance of Examples 1-4 is superior to that of the Comparative Examples. Therefore, it can be concluded that the addition of graphene and toughening agent combined with the two-step process can not only significantly improve mechanical properties but also endow the wire with good thermal conductivity and a certain degree of antistatic ability, avoiding the problem of direct dispersion of graphene.

[0043] This specific embodiment is merely an explanation of this application and is not intended to limit it. Based on the above description, those skilled in the art can make various changes and modifications without departing from the technical concept of this application. The technical scope of this application is not limited to the contents of the specification but must be determined according to the scope of the claims.

Claims

1. A graphene high-strength, high-toughness, impact-resistant 3D printing filament, characterized in that, By weight, it includes the following components: 75-90 parts of polyphenylene sulfide resin, 0.5-5 parts of functionalized graphene, 5-12 parts of toughening agent, 2-6 parts of compatibilizer, 1-4 parts of dispersant, 0.3-1 part of antioxidant, and 0.5-2 parts of lubricant.

2. The graphene high-strength, high-toughness, impact-resistant 3D printing filament according to claim 1, characterized in that, The functionalized graphene is hydroxylated graphene or carboxylated graphene.

3. The graphene high-strength, high-toughness, impact-resistant 3D printing filament according to claim 1, characterized in that, The compatibilizer is an epoxy-functionalized polymer, preferably a polyolefin elastomer grafted with glycidyl methacrylate.

4. A method for preparing graphene high-strength, high-toughness, and impact-resistant 3D printing filament, used to prepare the graphene high-strength, high-toughness, and impact-resistant 3D printing filament as described in any one of claims 1-3, characterized in that, Includes the following steps: Step S1: Prepare polyphenylene sulfide resin, functionalized graphene, toughening agent, compatibilizer, dispersant, antioxidant and lubricant by weight parts; Step S2: Functionalized graphene and dispersant are ultrasonically dispersed in a solvent, then a portion of polyphenylene sulfide resin is added for impregnation, the solvent is removed, and the mixture is melt-blended and granulated to obtain a high-concentration graphene masterbatch. Step S3: The graphene masterbatch obtained in step S2 is dried with the remaining polyphenylene sulfide resin, toughening agent, compatibilizer, antioxidant and lubricant, and then premixed to obtain a premix. Step S4: Melt-blend and granulate the premix obtained in step S3 to obtain the final masterbatch; Step S5: Extrude the final mixed masterbatch into 3D printing filament.

5. The method for preparing the graphene high-strength, high-toughness, and impact-resistant 3D printing filament according to claim 4, characterized in that, The solvent in step S2 is N-methylpyrrolidone, and the ultrasonic dispersion treatment time is 0.5h-2h.

6. The method for preparing the graphene high-strength, high-toughness, and impact-resistant 3D printing filament according to claim 5, characterized in that, The weight of the polyphenylene sulfide resin in step S2 accounts for 15%-30% of the total weight of the polyphenylene sulfide resin.

7. The method for preparing the graphene high-strength, high-toughness, and impact-resistant 3D printing filament according to claim 4, characterized in that, The melt blending in steps S2 and S4 is carried out in a twin-screw extruder with a processing temperature range of 280℃-310℃.

8. The method for preparing the graphene high-strength, high-toughness, and impact-resistant 3D printing filament according to claim 4, characterized in that, The extrusion molding in step S5 is carried out in a single-screw extruder, and the processing temperature range of the single-screw extruder is 280℃-305℃.

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