Extrusion type 3D printing polyphenylene sulfide composite material as well as preparation method and application thereof

Abstract

The invention discloses an extrusion type 3D printing polyphenylene sulfide composite material and a preparation method and application thereof, and belongs to the technical field of special engineering plastic composites.The extrusion type 3D printing polyphenylene sulfide composite material is prepared from, by weight, 60-70 parts of polyphenylene sulfide, 10-20 parts of glass fibers, 10-20 parts of glass fiber powder, 0.5-1 part of a coupling agent, 0.5-1 part of a deacidification agent, 0.5-1 part of a release agent and 0.5-3 parts of an antioxidant. According to the extrusion type 3D printing polyphenylene sulfide composite material as well as the preparation method and the application thereof, the glass fiber powder is added, so that the strength and the rigidity of the composite material can be improved, and shrinkage and cracking are effectively reduced; by adding the glass fibers, the strength and rigidity of the material can be improved, the heat resistance is improved, the heat deformation temperature is increased, and the glass fiber powder can reduce buckling deformation and creep deformation; glass fibers and glass fiber powder are mixed for use, so that the surface glossiness of the material can be effectively improved, and the problem of floating fibers is solved; the pre-dried polyphenylene sulfide can reduce precipitation of components such as moisture and impurities in the processing process.

Description

Technical Field

[0001] This invention relates to the field of special engineering plastic composite materials technology, and in particular to extrusion 3D printing of polyphenylene sulfide composite materials, their preparation methods and applications. Background Technology

[0002] After 30 years of development, 3D printing technology has formed a complete industrial chain applicable to industrial fields. With the popularization of the technology, many industries, such as automotive manufacturing, aerospace, and healthcare, have begun to widely use 3D printing. Especially in areas such as automotive chassis, interiors, and exterior body panels, ABS plastics and carbon fiber materials have been successfully used, providing a solid foundation for 3D printing production.

[0003] Polyphenylene sulfide (PPS) is a high-performance thermoplastic material with excellent heat resistance, chemical resistance, flame retardancy, and electrical properties. Furthermore, its heat distortion temperature exceeds 260℃, and its long-term service temperature can reach over 200℃. Its chemical resistance is second only to fluoropolymers, and it also possesses excellent V-0 flame retardancy. PPS is widely used in automotive parts such as electric drive system components, engine parts, braking systems, and thermal management systems. However, due to its high melting point, poor flowability, and high toughness, PPS's application in 3D printing technology is somewhat limited, necessitating modification to improve its suitability for 3D printing.

[0004] In the extrusion printing process, material properties such as thermal history, viscoelasticity, phase change behavior and microstructure of different polymers are coupled with each other. This may make it difficult to predict the internal stress and interfacial (interlayer) fusion of the printed parts, thus causing process problems such as warping, interlayer cracking and appearance defects. Summary of the Invention

[0005] The purpose of this invention is to provide extrusion-type 3D printing of polyphenylene sulfide (PPS) composite materials, their preparation methods, and applications. By adding glass fiber powder, the strength and rigidity of the composite material can be improved, effectively reducing shrinkage and cracking. Furthermore, the addition of glass fiber powder can improve the properties of plastic products, such as creep behavior and coefficient of thermal expansion, thereby extending their service life. The increase in glass fiber can improve the strength and rigidity of the material, increase heat resistance and heat distortion temperature, and reduce warping and creep. The mixed use of glass fiber and glass fiber powder can effectively improve the surface gloss of the material and solve the problem of fiber floating. Pre-drying and preheating the PPS raw powder with low gas release reduces the release of moisture, impurities, and other components during processing. Moreover, the preparation method is simple to operate and has a short production cycle.

[0006] To achieve the above objectives, the present invention provides an extrusion-type 3D printing polyphenylene sulfide composite material, comprising the following raw materials by weight: 60-70 parts polyphenylene sulfide, 10-20 parts glass fiber, 10-20 parts glass fiber powder, 0.5-1 part coupling agent, 0.5-1 part acid remover, 0.5-1 part release agent, and 0.5-3 parts antioxidant.

[0007] Preferably, the polyphenylene sulfide is a thermoplastic polyphenylene sulfide resin with a molecular weight of 6,000-120,000; the acid remover is one or more of hydrotalcite, calcium stearate, magnesium oxide, and zinc carbonate; the mold release agent is one or more of pentaerythritol stearate, glyceryl monostearate, and ethylene bis-stearamide; the antioxidant is one of hydroxyphenyl acrylate and hydroxyphenyl methyl acrylate; and the coupling agent is one or more of γ-aminopropyltriethoxysilane coupling agent, epoxy silane coupling agent, methacryloyloxysilane coupling agent, and bisaminosilane coupling agent.

[0008] Preferably, the fiber diameter of the glass fiber is 10-15μm, and the particle size of the glass fiber powder is 100-1000 mesh.

[0009] This invention also provides a method for preparing extruded 3D printed polyphenylene sulfide composite materials, comprising the following steps: Step 1: Raw material pretreatment: Pre-dry the polyphenylene sulfide; Step 2: Add the glass fiber powder, coupling agent, acid remover, mold release agent, antioxidant, and pre-dried polyphenylene sulfide into a high-speed mixer and mix. Step 3: The mixed raw materials are fed into a twin-screw extruder, and glass fiber is added during the extrusion process. The mixture is then stretched, cooled, pelletized, and dried to obtain the extruded 3D printed polyphenylene sulfide composite material.

[0010] Preferably, in step one, the drying temperature is 110-130℃ and the drying time is 3-5 hours.

[0011] Preferably, in step two, the mixing time is 20-30 minutes.

[0012] Preferably, in step three, the temperature in the twin-screw extruder is 180-320℃, and the screw speed is 200-300rpm.

[0013] Preferably, in step three, the glass fiber is added through the side feed port of the twin-screw extruder.

[0014] This invention also provides the application of extrusion-type 3D printing of polyphenylene sulfide composite materials, applying the above-described extrusion-type 3D printing of polyphenylene sulfide composite materials in 3D printing.

[0015] Therefore, the present invention, employing the above-mentioned extrusion-type 3D printing of polyphenylene sulfide composite materials, its preparation method, and its application, has the following beneficial effects: (1) By adding glass fiber powder, the strength and rigidity of composite materials can be improved, and shrinkage and cracking can be effectively reduced. In addition, the addition of glass fiber powder can also improve the properties of plastic products, such as creep behavior and coefficient of thermal expansion, thereby extending their service life; (2) The addition of glass fiber can improve the strength and rigidity of the material, improve the heat resistance and heat distortion temperature, and reduce warping deformation and creep. (3) The use of glass fiber and glass fiber powder in combination can effectively improve the surface gloss of the material and solve the problem of fiber floating; (4) Dry and preheat the polyphenylene sulfide raw powder with low gas release in advance to reduce the release of moisture, impurities and other components during the processing; (5) The preparation method is simple to operate and has a short production cycle.

[0016] The technical solution of the present invention will be further described in detail below through embodiments. Detailed Implementation

[0017] This invention provides an extrusion-type 3D printing polyphenylene sulfide composite material, which, by weight, comprises the following raw materials: 60-70 parts polyphenylene sulfide, 10-20 parts glass fiber, 10-20 parts glass fiber powder, 0.5-1 part coupling agent, 0.5-1 part acid remover, 0.5-1 part release agent, and 0.5-3 parts antioxidant.

[0018] In this invention, the polyphenylene sulfide is a thermoplastic polyphenylene sulfide resin with a molecular weight of 6,000-120,000; the acid remover is one or more of hydrotalcite, calcium stearate, magnesium oxide, and zinc carbonate; the mold release agent is one or more of pentaerythritol stearate, glyceryl monostearate, and ethylene bis-stearamide; the antioxidant is one of hydroxyphenyl acrylate and hydroxyphenylmethyl acrylate; and the coupling agent is one or more of γ-aminopropyltriethoxysilane coupling agent, epoxy silane coupling agent, methacryloyloxysilane coupling agent, and bisaminosilane coupling agent.

[0019] In this invention, the fiber diameter of the glass fiber is 10-15 μm, and the particle size of the glass fiber powder is 100-1000 mesh.

[0020] This invention also provides a method for preparing extruded 3D printed polyphenylene sulfide composite materials, comprising the following steps: Step 1: Raw material pretreatment: Pre-dry the polyphenylene sulfide; Step 2: Add the glass fiber powder, coupling agent, acid remover, mold release agent, antioxidant, and pre-dried polyphenylene sulfide into a high-speed mixer and mix. Step 3: The mixed raw materials are fed into a twin-screw extruder, and glass fiber is added during the extrusion process. The mixture is then stretched, cooled, pelletized, and dried to obtain the extruded 3D printed polyphenylene sulfide composite material.

[0021] In this invention, in step one, the drying temperature is 110-130℃ and the drying time is 3-5h.

[0022] In this invention, the mixing time in step two is 20-30 minutes.

[0023] In this invention, in step three, the temperature in the twin-screw extruder is 180-320℃, and the screw speed is 200-300rpm.

[0024] In this invention, in step three, glass fiber is added through the side feed port of the twin-screw extruder.

[0025] This invention also provides the application of extrusion-type 3D printing of polyphenylene sulfide composite materials, applying the above-described extrusion-type 3D printing of polyphenylene sulfide composite materials in 3D printing.

[0026] The technical solution of the present invention will be further illustrated by the following embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention should be considered equivalent substitutions and are included within the protection scope of the present invention. Furthermore, it should be understood that after reading the contents of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims and are all within the protection scope of the present invention.

[0027] In this document, the term "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The term "embodiment" appearing in various places throughout the specification does not necessarily refer to the same embodiment, nor does it specifically limit its independence or connection with other embodiments. In principle, in this application, as long as there are no technical contradictions or conflicts, the technical features mentioned in each embodiment can be combined in any way to form corresponding implementable technical solutions.

[0028] Unless otherwise defined, the technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the use of related terms herein is merely for the purpose of describing particular embodiments and is not intended to limit this application.

[0029] In this invention, unless otherwise specified, all other test materials and instruments are conventional test materials in the field and can be purchased through commercial channels.

[0030] Example 1 The extrusion-type 3D printing polyphenylene sulfide (PPS) composite material, by weight, includes the following raw materials: 67 parts polyphenylene sulfide, 20 parts glass fiber, 10 parts glass fiber powder, 0.5 parts coupling agent, 0.5 parts acid remover, 0.5 parts release agent, and 1.5 parts antioxidant.

[0031] The coupling agent is KH560, the acid remover is zinc carbonate, the mold release agent is pentaerythritol stearate, and the antioxidant is antioxidant 1010.

[0032] The preparation method of extrusion-type 3D printing polyphenylene sulfide composite material is as follows: 3000g of polyphenylene sulfide raw powder is dried in an oven at 120℃ for 4 hours. The dried polyphenylene sulfide and 22g of coupling agent are added to a high-speed mixer and stirred for 10 minutes. Then, 448g of glass fiber powder, 22g of acid remover, 22g of release agent, and 67g of antioxidant are added and mixed in the high-speed mixer for 20 minutes to obtain a mixture. The mixture is then extruded in a twin-screw extruder. The barrel and die head temperatures of the twin-screw extruder are 150℃, 250℃, 300℃, 320℃, 320℃, 320℃, 320℃, 320℃, 310℃, and 310℃, respectively. The screw speed is 250r / min. At the same time, 896g of glass fiber is added from the side feed port. The extruded material undergoes stranding, cooling, pelletizing, and drying processes in sequence to produce granules.

[0033] Example 2 The extrusion-type 3D printed polyphenylene sulfide composite material, by weight, includes the following raw materials: 64 parts polyphenylene sulfide, 15 parts glass fiber, 15 parts glass fiber powder, 1 part coupling agent, 1 part acid remover, 1 part release agent, and 3 parts antioxidant.

[0034] The coupling agent is KH560, the acid remover is zinc carbonate, the mold release agent is pentaerythritol stearate, and the antioxidant is antioxidant 1010.

[0035] The preparation method of extrusion-type 3D printing polyphenylene sulfide composite material is as follows: 3000g of polyphenylene sulfide raw powder is dried in an oven at 120℃ for 4 hours. The dried polyphenylene sulfide and 47g of coupling agent are added to a high-speed mixer and stirred for 10 minutes. Then, 703g of glass fiber powder, 47g of acid remover, 47g of release agent, and 47g of antioxidant are added and mixed in the high-speed mixer for 20 minutes to obtain a mixture. The mixture is then extruded in a twin-screw extruder. The barrel and die head temperatures of the twin-screw extruder are 150℃, 250℃, 300℃, 320℃, 320℃, 320℃, 320℃, 320℃, 310℃, and 310℃, respectively, and the screw speed is 250r / min. At the same time, 703g of glass fiber is added from the side feed port. The extruded material undergoes stranding, cooling, pelletizing, and drying processes in sequence to produce granules.

[0036] Example 3 The extrusion-type 3D printed polyphenylene sulfide composite material, by weight, includes the following raw materials: 68 parts polyphenylene sulfide, 10 parts glass fiber, 15 parts glass fiber powder, 0.5 parts coupling agent, 0.5 parts acid remover, 0.5 parts release agent, and 0.5 parts antioxidant.

[0037] The coupling agent is KH560, the acid remover is zinc carbonate, the mold release agent is pentaerythritol stearate, and the antioxidant is antioxidant 1010.

[0038] The preparation method of extrusion-type 3D printing polyphenylene sulfide composite material is as follows: 3000g of polyphenylene sulfide raw powder is dried in an oven at 120℃ for 4 hours. The dried polyphenylene sulfide and 22g of coupling agent are added to a high-speed mixer and stirred for 10 minutes. Then, 662g of glass fiber powder, 22g of acid remover, 22g of release agent, and 22g of antioxidant are added and mixed in the high-speed mixer for 20 minutes to obtain a mixture. The mixture is then extruded in a twin-screw extruder. The barrel and die temperatures of the twin-screw extruder are 150℃, 250℃, 300℃, 320℃, 320℃, 320℃, 320℃, 320℃, 310℃, and 310℃, respectively. The screw speed is 250r / min. At the same time, 441g of glass fiber is added from the side feed port. The extruded material undergoes stranding, cooling, pelletizing, and drying processes in sequence to produce granules.

[0039] Comparative Example 1 The extrusion-type 3D printed polyphenylene sulfide composite material, by weight, includes the following raw materials: 68 parts polyphenylene sulfide, 10 parts glass fiber, 15 parts glass fiber powder, 0.5 parts coupling agent, 0.5 parts acid remover, 0.5 parts release agent, and 0.5 parts antioxidant.

[0040] The coupling agent is KH560, the acid remover is zinc carbonate, the mold release agent is pentaerythritol stearate, and the antioxidant is antioxidant 1010.

[0041] The preparation method of extrusion-type 3D printing polyphenylene sulfide composite material is as follows: 3000g of polyphenylene sulfide raw powder and 22g of coupling agent are added to a high-speed mixer and stirred for 10min. Then, 662g of glass fiber powder, 22g of acid remover, 22g of release agent, and 22g of antioxidant are added and mixed in the high-speed mixer for 20min to obtain a mixture. The mixture is then extruded in a twin-screw extruder. The barrel and die temperatures of the twin-screw extruder are 150℃, 250℃, 300℃, 320℃, 320℃, 320℃, 320℃, 320℃, 310℃, and 310℃, respectively. The screw speed is 250r / min. Simultaneously, 441g of glass fiber is added from the side feed port. The extruded material undergoes stranding, cooling, pelletizing, and drying processes to produce granules.

[0042] Comparative Example 2 The extrusion-type 3D printed polyphenylene sulfide composite material, by weight, includes the following raw materials: 67 parts polyphenylene sulfide, 30 parts glass fiber, 0.5 parts coupling agent, 0.5 parts acid remover, 0.5 parts release agent, and 1.5 parts antioxidant.

[0043] The coupling agent is KH560, the acid remover is zinc carbonate, the mold release agent is pentaerythritol stearate, and the antioxidant is antioxidant 1010.

[0044] The preparation method of extrusion-type 3D printing polyphenylene sulfide composite material is as follows: 3000g of polyphenylene sulfide raw powder is dried in an oven at 120℃ for 4 hours. The dried polyphenylene sulfide and 22g of coupling agent are added to a high-speed mixer and stirred for 10 minutes. Then, 22g of deacidifying agent, 22g of release agent, and 67g of antioxidant are added and mixed in the high-speed mixer for 20 minutes to obtain a mixture. The mixture is then extruded in a twin-screw extruder. The barrel and die head temperatures of the twin-screw extruder are 150℃, 250℃, 300℃, 320℃, 320℃, 320℃, 320℃, 320℃, 310℃, and 310℃, respectively. The screw speed is 250r / min. At the same time, 1343g of glass fiber is added from the side feed port. The extruded material undergoes stranding, cooling, pelletizing, and drying processes in sequence to produce granules.

[0045] The granules prepared in Examples 1-3 and Comparative Examples 1-2 were used to print samples using an extrusion 3D printer. The cantilever beam notched impact strength (ISO 180 standard) of the samples was tested, and the porosity and fiber floating of the printed parts were observed. The test results are shown in Table 1.

[0046] Table 1 Test Results

[0047] Table 1 shows that the PPS composite material prepared by the method provided by this invention, suitable for extrusion 3D printing, exhibits a significant decrease in impact strength compared to Comparative Example 2. However, the porosity and fiber floating conditions are improved. This indicates that using low-gas-emission polyphenylene sulfide powder, as shown in the comparison between Example 3 and Comparative Example 1, can improve porosity through pretreatment. Furthermore, glass fiber powder improves fiber floating conditions, but excessive addition leads to a decrease in toughness.

[0048] Therefore, this invention utilizes the aforementioned extrusion-based 3D printing of polyphenylene sulfide composite materials, their preparation method, and applications. By adding glass fiber powder, the strength and rigidity of the composite material can be improved, effectively reducing shrinkage and cracking. Furthermore, the addition of glass fiber powder can improve the performance of plastic products, such as creep behavior and coefficient of thermal expansion, thereby extending their service life. The increase in glass fiber can improve the material's strength and rigidity, increase heat resistance and heat distortion temperature, and reduce warping and creep. The mixed use of glass fiber and glass fiber powder can effectively improve the surface gloss of the material and solve the problem of loose fibers. Pre-drying and preheating the polyphenylene sulfide raw powder with low gas release reduces the release of moisture, impurities, and other components during processing. Moreover, the preparation method is simple to operate and has a short production cycle.

[0049] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. 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 still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. Extruded 3D printed polyphenylene sulfide composite material, characterized in that: By weight, it includes the following raw materials: 60-70 parts polyphenylene sulfide, 10-20 parts glass fiber, 10-20 parts glass fiber powder, 0.5-1 part coupling agent, 0.5-1 part acid remover, 0.5-1 part mold release agent, and 0.5-3 parts antioxidant.

2. The extruded 3D printed polyphenylene sulfide composite material of claim 1, wherein: Polyphenylene sulfide is a thermoplastic polyphenylene sulfide resin with a molecular weight of 6,000-120,000. The acid remover is one or more of hydrotalcite, calcium stearate, magnesium oxide, and zinc carbonate. The mold release agent is one or more of pentaerythritol stearate, glyceryl monostearate, and ethylene bis-stearamide. The antioxidant is one of hydroxyphenyl acrylate and hydroxyphenyl methyl acrylate. The coupling agent is one or more of γ-aminopropyltriethoxysilane coupling agent, epoxy silane coupling agent, methacryloyloxysilane coupling agent, and bisaminosilane coupling agent.

3. The extrusion-type 3D printed polyphenylene sulfide composite material according to claim 1, characterized in that: The fiber diameter of glass fiber is 10-15μm, and the particle size of glass fiber powder is 100-1000 mesh.

4. The method for preparing extrusion-type 3D printed polyphenylene sulfide composite material according to any one of claims 1-3, characterized in that: Includes the following steps: Step 1: Raw material pretreatment: Pre-dry the polyphenylene sulfide; Step 2: Add the glass fiber powder, coupling agent, acid remover, mold release agent, antioxidant, and pre-dried polyphenylene sulfide into a high-speed mixer and mix. Step 3: The mixed raw materials are fed into a twin-screw extruder, and glass fiber is added during the extrusion process. The mixture is then stretched, cooled, pelletized, and dried to obtain the extruded 3D printed polyphenylene sulfide composite material.

5. The method for preparing extruded 3D printed polyphenylene sulfide composite material according to claim 4, characterized in that: In step one, the drying temperature is 110-130℃ and the drying time is 3-5 hours.

6. The method for preparing extruded 3D printed polyphenylene sulfide composite material according to claim 4, characterized in that: In step two, the mixing time is 20-30 minutes.

7. The method for preparing extruded 3D printed polyphenylene sulfide composite material according to claim 4, characterized in that: In step three, the temperature in the twin-screw extruder is 180-320℃, and the screw speed is 200-300rpm.

8. The method for preparing extruded 3D printed polyphenylene sulfide composite material according to claim 4, characterized in that: In step three, the glass fiber is added through the side feed port of the twin-screw extruder.

9. The application of extrusion-based 3D printing of polyphenylene sulfide composite materials, characterized by: The extrusion-type 3D printing polyphenylene sulfide composite material according to any one of claims 1-3 is applied to 3D printing.

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