Method for producing CF-PPS wire rod with high heat resistance and high dimensional stability

Abstract

The invention is suitable for the technical field of 3D printing, and particularly relates to a method for producing a CF-PPS wire rod with high heat resistance and high dimensional stability, and the method comprises the following steps: carrying out surface modification treatment on carbon fibers to obtain pretreated carbon fibers; the preparation method comprises the following steps: uniformly mixing polyphenylene sulfide, a glycidyl methacrylate grafted modified ethylene-octylene copolymer flexibilizer and glass beads, and putting the mixture into mixing equipment; putting the pretreated carbon fibers into the mixing equipment; feeding plastic is regulated and controlled to control the content of the carbon fibers, extrusion molding is carried out, granulation treatment is carried out, and the carbon fiber reinforced polyphenylene sulfide composite granules are obtained; and extruding and drawing the carbon fiber reinforced polyphenylene sulfide composite granules by a single screw to obtain the CF-PPS wire. The brittleness of polyphenylene sulfide can be improved, the interlayer bonding force of a printed piece can be improved, the prepared wire rod has the characteristics of being tough and not prone to brittle fracture, and the printed piece is low in shrinkage rate, not prone to warping and good in interlayer bonding performance.

Description

Technical Field

[0001] The invention belongs to the technical field of 3D printing, and in particular relates to a method for producing a CF-PPS wire with high heat resistance and high dimensional stability. Background Art

[0002] Polyphenylene sulfide (PPS) has high heat resistance and can be used for a long time below 220°C. It has good chemical resistance, high strength, and natural flame retardancy. Compared with similar special engineering plastics such as polyetheretherketone (PEEK), it has a high cost performance and is widely used in the fields of automobiles, electronics, water treatment, plastic steel, etc.

[0003] At present, the application fields of 3D printing are becoming more and more extensive, and higher requirements are also put forward for the high temperature resistance and durability of materials. The widely used polylactic acid (PLA) and acrylonitrile-butadiene-styrene copolymer (ABS) have a relatively low operating temperature of less than 100°C. The high-performance special plastic polyetheretherketone, which has attracted widespread attention recently, has good heat resistance (can be used for a long time above 260°C), self-lubrication, wear resistance and fatigue resistance, but it is difficult to process and shape, has high requirements for the nozzle temperature and insulation temperature of the equipment, and the material cost is high, which has been subject to certain restrictions in the civilian field. Summary of the invention

[0004] The purpose of the present invention is to provide a method for producing high heat-resistant and high dimensional stability CF-PPS wire, aiming to solve the problem that high-performance special plastic polyetheretherketone is difficult to process and form, has high requirements on equipment nozzle temperature and insulation temperature, and has high material cost, which has limited its use in the civilian field.

[0005] The present invention is achieved by a method for producing a CF-PPS wire with high heat resistance and high dimensional stability, the method comprising:

[0006] Performing surface modification treatment on carbon fiber to obtain pretreated carbon fiber;

[0007] The polyphenylene sulfide, the glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent and the glass microspheres are uniformly mixed and put into a mixing device;

[0008] feeding pre-treated carbon fibers into a mixing device;

[0009] The carbon fiber content is controlled by adjusting the feed plastic, extruding and granulating, and obtaining carbon fiber reinforced polyphenylene sulfide composite granules;

[0010] The carbon fiber reinforced polyphenylene sulfide composite particles are extruded and drawn into CF-PPS wires through a single screw extruder.

[0011] Preferably, in the step of performing surface modification treatment on the carbon fiber to obtain pretreated carbon fiber, 0.1-0.5% of a thermosetting surface sizing agent, bisphenol A epoxy resin and a silane coupling agent are compounded to perform surface modification on the carbon fiber to obtain pretreated carbon fiber.

[0012] Preferably, in the step of uniformly mixing polyphenylene sulfide, glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent and glass microspheres and adding them into a mixing device, the amount of polyphenylene sulfide is 65-90 parts, the amount of glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent is 3-10 parts, and the amount of glass microspheres is 1-5 parts.

[0013] Preferably, in the steps of extrusion molding and granulation treatment, twin-screw extrusion and ten-stage heating are adopted.

[0014] Preferably, in the step of adding pretreated carbon fibers to the mixing device, the amount of pretreated carbon fibers added is 10-25 parts.

[0015] Preferably, polyphenylene sulfide, glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent and glass microbeads are fed from the main feeding port of the mixing device, and the pretreated carbon fiber is fed from the side feeding port.

[0016] Preferably, in the ten-stage heating step, the processing temperature is 290-330°C.

[0017] The present invention provides a method for producing a CF-PPS wire with high heat resistance and high dimensional stability. Carbon fiber can be uniformly dispersed in polyphenylene sulfide, which can greatly improve the rigidity and strength of the composite material. Adding a glycidyl methacrylate graft-modified ethylene octene copolymer toughening agent can improve the brittleness of polyphenylene sulfide and enhance the interlayer bonding strength of printed parts. Adding glass microbeads can reduce the warping rate of printed parts. The prepared wire has the characteristics of being strong and tough and not prone to brittle fracture, and the printed parts have low shrinkage, are not prone to warping, and have good interlayer bonding performance. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0019] A method for producing a CF-PPS wire with high heat resistance and high dimensional stability, the method comprising:

[0020] Performing surface modification treatment on carbon fiber to obtain pretreated carbon fiber;

[0021] The polyphenylene sulfide, the glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent and the glass microspheres are uniformly mixed and put into a mixing device;

[0022] feeding pre-treated carbon fibers into a mixing device;

[0023] The carbon fiber content is controlled by adjusting the feed plastic, extruding and granulating, and obtaining carbon fiber reinforced polyphenylene sulfide composite granules;

[0024] The carbon fiber reinforced polyphenylene sulfide composite particles are extruded and drawn into CF-PPS wires through a single screw extruder.

[0025] In this embodiment, the pretreated carbon fiber is prepared by compounding the surface-modified carbon fiber with a thermosetting surface sizing agent, 0.1 to 0.5% bisphenol A epoxy resin and a silane coupling agent;

[0026] 65-90 parts of polyphenylene sulfide, 3-10 parts of glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent and 1-5 parts of glass microspheres are uniformly mixed and added from the main feeding port;

[0027] Add 10-25 parts of pretreated carbon fiber from the side feeding port;

[0028] The carbon fiber content is controlled by adjusting the feed plastic, using twin-screw extrusion, ten-stage heating, processing temperature 290-330°C, and granulation treatment to obtain carbon fiber reinforced polyphenylene sulfide composite granules;

[0029] CF-PPS wire with stable wire diameter and easy winding is obtained by single-screw extrusion drawing.

[0030] Comparative Example

[0031] Processing temperature 290-330-330-320-320-310-300-300-300-300℃, 85 parts of polyphenylene sulfide, 15 parts of unmodified carbon fiber, X-axis tensile strength of printed parts 55MPa, modulus 3.5GPa, notched impact strength 7kJ / m 2 , Z-axis tensile strength is 13MPa, and the warpage rate is 4.5%.

[0032] Example 1

[0033] Processing temperature 290-330-330-320-320-310-300-300-300-300℃, polyphenylene sulfide 80 parts, toughening agent 5 parts, surface modified carbon fiber 15 parts, printed part X-axis tensile strength 95MPa, modulus 3.3GPa, notched impact strength 13kJ / m 2 , Z-axis tensile strength 41MPa, warpage 1.0%.

[0034] Example 2

[0035] Processing temperature 290-330-330-320-320-310-300-300-300-300℃, polyphenylene sulfide 78 parts, toughening agent 5 parts, glass microbeads 2 parts, surface modified carbon fiber 15 parts, printed part X-axis tensile strength 91MPa, modulus 3.5GPa, notched impact strength 11kJ / m 2 , Z-direction tensile strength is 37MPa, and warpage is 0.9%.

[0036] 1) The present invention adopts a thermosetting surface sizing agent, 0.1-0.5% bisphenol A epoxy resin and a silane coupling agent to compound the surface modified carbon fiber. The hydroxyl group and ether bond contained in the molecular structure of the additive can interact with the PPS matrix to improve the interface bonding between the fiber and the PPS matrix, thereby obtaining a composite material with no bubbles and good interface wetting.

[0037] 2) High-content carbon fiber filling will increase the viscosity of the polymer and reduce its processing fluidity, resulting in more pores between the layers of the printed parts. The introduction of toughening agents and the adjustment of the printing process can enhance the interlayer bonding and improve the anisotropy of the printed parts.

[0038] 3) In order to obtain printed products with low shrinkage, low linear expansion coefficient and high dimensional stability, inorganic fillers such as glass beads are added to cooperate with carbon fiber compounding to improve the shrinkage rate of the material, and the process parameters are controlled (printing speed, printing line width, printing temperature, insulation chamber temperature, etc.) to obtain printed products with high dimensional stability.

[0039] The produced CF-PPS wire has the advantages of high temperature resistance (can be used for a long time at 220 degrees), high strength, low warping and high dimensional stability. It can be used to directly prepare heat-resistant parts or replace some metal molds for hot pressing or vacuum bag molding molds that are highly flexible, require personalized customization and are used in high-temperature environments. The warping rate of the printed parts is low during the molding process, and the dimensional stability is high in high and low temperature changes.

[0040] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for producing high heat-resistant and high dimensional stability CF-PPS wire, characterized in that: The method comprises: Performing surface modification treatment on carbon fiber to obtain pretreated carbon fiber; The polyphenylene sulfide, the glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent and the glass microspheres are uniformly mixed and put into a mixing device; feeding pre-treated carbon fibers into a mixing device; The carbon fiber content is controlled by adjusting the feed plastic, extruding and granulating, and obtaining carbon fiber reinforced polyphenylene sulfide composite granules; The carbon fiber reinforced polyphenylene sulfide composite particles are extruded and drawn into CF-PPS wires through a single screw extruder.

2. The method for producing high heat-resistant and high dimensional stability CF-PPS wire according to claim 1, characterized in that: In the step of performing surface modification on the carbon fiber to obtain pretreated carbon fiber, 0.1-0.5% of a thermosetting surface sizing agent, bisphenol A epoxy resin and a silane coupling agent are compounded to perform surface modification on the carbon fiber to obtain the pretreated carbon fiber.

3. The method for producing high heat-resistant and high dimensional stability CF-PPS wire according to claim 1, characterized in that: In the step of uniformly mixing polyphenylene sulfide, glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent and glass microspheres and adding them into a mixing device, the amount of polyphenylene sulfide is 65-90 parts, the amount of glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent is 3-10 parts, and the amount of glass microspheres is 1-5 parts.

4. The method for producing high heat-resistant and high dimensional stability CF-PPS wire according to claim 1, characterized in that: In the steps of extrusion molding and granulation treatment, twin-screw extrusion and ten-stage heating are adopted.

5. The method for producing high heat-resistant and high dimensional stability CF-PPS wire according to claim 1, characterized in that: In the step of adding the pretreated carbon fiber to the mixing device, the amount of the pretreated carbon fiber added is 10-25 parts.

6. The method for producing high heat-resistant and high dimensional stability CF-PPS wire according to claim 1, characterized in that: Polyphenylene sulfide, glycidyl methacrylate grafted modified ethylene octene copolymer toughening agent and glass microbeads are fed from the main feeding port of the mixing device, and pretreated carbon fiber is fed from the side feeding port.

7. The method for producing high heat-resistant and high dimensional stability CF-PPS wire according to claim 1, characterized in that: In the ten-stage heating step, the processing temperature is 290-330°C.