PEEK composite material as well as preparation method and application thereof

Abstract

The invention provides a PEEK composite material as well as a preparation method and application thereof, and belongs to the field of high polymer material manufacturing. The strength of the PEEK composite material is improved due to the high strength of the carbon fibers, and the compatibility of the carbon fibers and the copolymerized polyether-ether-ketone resin is improved due to the fact that the amorphous polyaryletherketone coats the surfaces of the carbon fibers, so that the strength of the PEEK composite material is further improved; the high-strength PEEK composite material is prepared. The copolymerized polyether-ether-ketone resin is low in melting point and melt viscosity, so that the welding performance of the PEEK composite material is improved, good welding strength of the flange and the antistatic PEEK pipe is facilitated, and welding of the PEEK flange and the pipe is facilitated.

Description

Technical Field

[0001] The present invention relates to the field of polymer material manufacturing, and in particular to a PEEK composite material and a preparation method and application thereof. Background Art

[0002] Polyetheretherketone (PEEK) is a semi-crystalline, ultra-high-performance specialty engineering plastic. Its excellent mechanical properties, high-temperature resistance, and chemical resistance have led to its widespread application in films, pipes, and components in aerospace, electronics, medical equipment, and other fields. However, in some applications requiring extremely high strength, the mechanical properties of pure PEEK remain insufficient.

[0003] PEEK plastic flanges are a type of liquid pipeline connection fitting with a wide range of uses, multiple options, and ease of use. However, existing PEEK plastic flanges have low strength and poor welding performance. Summary of the Invention

[0004] The present invention provides a PEEK composite material, a preparation method and an application thereof. The flange prepared from the PEEK composite material of the present invention has high strength and good welding performance.

[0005] The present invention provides a PEEK composite material, comprising a copolymerized polyetheretherketone resin and composite carbon fibers dispersed in the copolymerized polyetheretherketone resin;

[0006] The composite carbon fiber comprises carbon fiber and amorphous polyaryletherketone coating the carbon fiber;

[0007] The copolymerized polyetheretherketone resin has the structural formula shown in Formula I:

[0008]

[0009] At 400° C. and 500N, the melt index of the copolymerized polyetheretherketone resin is 23 to 80 g / 10 min.

[0010] Preferably, the mass fraction of the copolymerized polyetheretherketone resin in the PEEK composite material is 60 to 90%.

[0011] Preferably, the carbon fiber model includes one or more of T700, T800 and T1000.

[0012] Preferably, the method for preparing the composite carbon fiber comprises the following steps:

[0013] After removing the sizing agent from the surface of the carbon fiber, the obtained carbon fiber without the sizing agent on the surface is immersed in a solution of amorphous polyaryletherketone to obtain a wet composite carbon fiber;

[0014] Dry the wet composite carbon fiber to obtain the composite carbon fiber.

[0015] Preferably, the amorphous polyaryletherketone has a melt index of 23-80 g / 10 min at 400 DEG C and 500 N.

[0016] Preferably, the temperature for removing the sizing agent on the surface of the carbon fiber is 380-400 DEG C, the time is 1-4 h, and the vacuum degree is 0.1-0.2 Pa.

[0017] The application further provides a preparation method of the PEEK composite material, comprising the following steps:

[0018] The copolymerized polyether ether ketone resin and the composite carbon fiber are mixed, melt-extruded and granulated to obtain the PEEK composite material.

[0019] Preferably, before the mixing, the method further comprises: washing the copolymerized polyether ether ketone resin, wherein the washing comprises washing with an organic solvent and water in sequence; and the organic solvent comprises acetone and / or ethyl acetate.

[0020] Preferably, the melt-extrusion is performed in a double-screw extruder.

[0021] The rotation speed of the double-screw extruder is 200-300 r / min, the feeding temperature is 220-240 DEG C, the extrusion section temperature is 320-350 DEG C, and the temperature at the extrusion die is 300-330 DEG C.

[0022] The application further provides an application of the PEEK composite material or the PEEK composite material prepared by the preparation method in the preparation of a plastic part.

[0023] The high strength of the carbon fiber improves the strength of the PEEK composite material, the amorphous polyaryletherketone coated on the surface of the carbon fiber improves the compatibility of the carbon fiber and the copolymerized polyether ether ketone resin, thereby further improving the strength of the PEEK composite material, and a high-strength PEEK composite material is prepared. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 a stress-strain curve of the composite material of Example 3;

[0025] Figure 2 a DSC test curve of the composite material of Example 3;

[0026] Figure 3This is a photo of the welding of the PEEK tube and flange prepared from the composite material of Example 3. DETAILED DESCRIPTION

[0027] The present invention provides a PEEK composite material, comprising a copolymerized polyetheretherketone resin and composite carbon fibers dispersed in the copolymerized polyetheretherketone resin;

[0028] The composite carbon fiber comprises carbon fiber and amorphous polyaryletherketone coating the carbon fiber;

[0029] The copolymerized polyetheretherketone resin has the structural formula shown in Formula I:

[0030]

[0031] At 400° C. and 500N, the melt index of the copolymerized polyetheretherketone resin is 23 to 80 g / 10 min.

[0032] In the present invention, the PEEK composite material provided by the present invention includes a copolymerized polyetheretherketone resin; at 400°C and 500N, the melt index of the copolymerized polyetheretherketone resin is 23 to 80 g / 10min. In a specific embodiment of the present invention, the melt index of the copolymerized polyetheretherketone resin can be 30 g / 10min, 40 g / 10min, 50 g / 10min, 60 g / 10min or 70 g / 10min; in terms of mass fraction, the mass fraction of the copolymerized polyetheretherketone resin in the PEEK composite material is preferably 60 to 90%. In a specific embodiment of the present invention, the mass fraction of the copolymerized polyetheretherketone resin in the PEEK composite material can be 65%, 70%, 75%, 80% or 85%.

[0033] In the present invention, the PEEK composite material provided by the present invention includes composite carbon fibers dispersed in the copolymerized polyetheretherketone resin; the composite carbon fibers include carbon fibers and amorphous polyaryletherketone coating the carbon fibers; the carbon fibers preferably have one or more models selected from T700, T800, and T1000.

[0034] In the present invention, the method for preparing the composite carbon fiber preferably comprises the following steps:

[0035] After removing the sizing agent from the surface of the carbon fiber, the obtained carbon fiber without the sizing agent on the surface is immersed in a solution of amorphous polyaryletherketone to obtain a wet composite carbon fiber;

[0036] The wet composite carbon fiber is dried to obtain the composite carbon fiber.

[0037] In the present invention, the concentration of the solution of the amorphous polyaryletherketone is preferably 0.1 mol / L. At 400°C and 500N, the melt index of the amorphous polyaryletherketone is 23 to 80 g / 10min. In a specific embodiment of the present invention, the melt index of the amorphous polyaryletherketone can be 30 g / 10min, 40 g / 10min, 50 g / 10min, 60 g / 10min or 70 g / 10min.

[0038] In the present invention, the removal temperature is preferably 380-400° C., the removal time is preferably 1-4 hours, and the vacuum degree is preferably 0.1-0.2 Pa.

[0039] The present invention also provides a method for preparing the PEEK composite material described in the above technical solution, comprising the following steps:

[0040] The copolymerized polyetheretherketone resin and the composite carbon fiber are mixed, melt-extruded, and granulated to obtain the PEEK composite material.

[0041] Before the mixing, the present invention preferably further comprises: washing the copolymerized polyetheretherketone resin.

[0042] In the present invention, the washing preferably includes washing with an organic solvent and then water; the organic solvent preferably includes acetone and / or ethyl acetate, and the number of washings is preferably 3 to 6. Washing can remove the effects of residual solvent and catalyst on the surface of the thin-walled tube.

[0043] In the present invention, the content of diphenyl sulfone as a solvent in the washed copolymerized polyetheretherketone resin is preferably less than 200 ppm, and the content of inorganic salt is preferably less than 200 ppm.

[0044] In the present invention, the melt extrusion is preferably carried out in a twin-screw extruder; the speed of the twin-screw extruder is preferably 200-300 r / min, the feeding temperature is preferably 220-240°C, the extrusion section temperature is preferably 320-350°C, and the temperature at the extrusion die is preferably 300-330°C.

[0045] The present invention also provides the use of the PEEK composite material described in the above technical solution or the PEEK composite material prepared by the preparation method described in the above technical solution in the preparation of injection molded parts.

[0046] In the present invention, the injection molded part preferably includes a flange.

[0047] The PEEK composite material provided by the present invention, its preparation method and application are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0048] Example 1

[0049] (1) The carbon fiber (T800) was treated by vacuum treatment at 400°C for 4 h to remove the sizing agent on the surface of the carbon fiber. The carbon fiber was then immersed in an amorphous polyaryletherketone solution with a concentration of 0.1 mol / L (the amorphous polyaryletherketone was a copolymerized polyetheretherketone as a 3D printed polyetheretherketone interlayer reinforcement material prepared in Example 1 of CN114805789A, and the solvent was DMF) for sizing. The sizing carbon fiber was dried to obtain a composite carbon fiber.

[0050] (2) Copolymer PEEK resin purification: The 3D printed polyetheretherketone interlayer reinforcement material prepared in Example 1 of CN114805789A was further purified using acetone and deionized water, and washed 4 times (acetone and deionized water washing was one time).

[0051] (3) Using a twin-screw extruder with side feeding, the copolymerized PEEK resin of step (2) and the composite carbon fiber of step (1) are mixed: the weight ratio of the copolymerized PEEK material and the composite carbon fiber is 90:10, the copolymerized PEEK resin is located at the main feeding port, and the composite carbon fiber is located at the side feeding port.

[0052] The twin-screw extruder speed is 300 r / min, the feeding temperature is 240°C, the extrusion section temperature is 350°C, the extrusion die temperature is 330°C, and after pelletizing, antistatic and high-toughness composite material pellets-1 are prepared.

[0053] High-temperature injection molding machines are used to mold tensile and volume resistivity test specimens. The tensile specimen dimensions and test methods are in accordance with GB / T 1040.2-2022; the volume resistivity specimen dimensions and test methods are in accordance with GB / T 31838.2-2019. The composite material has a tensile strength of 190 MPa and a volume resistivity of 10 11 Ω.

[0054] Example 2

[0055] The only difference from Example 1 is that in step (3), the weight ratio of the copolymerized PEEK material and the composite carbon fiber is 80:20. The composite material has a tensile strength of 240 MPa and a volume resistivity of 10 8 Ω.

[0056] Example 3

[0057] The only difference from Example 1 is that in step (3), the weight ratio of the copolymerized PEEK material and the composite carbon fiber is 70:30. The composite material has a tensile strength of 282 MPa and a volume resistivity of 10 6 Ω.

[0058] Example 4

[0059] The only difference from Example 1 is that in step (3), the weight ratio of the copolymerized PEEK material and the composite carbon fiber is 75:25. The composite material has a tensile strength of 275 MPa and a volume resistivity of 10 7 Ω.

[0060] Example 5

[0061] The only difference from Example 3 is that the acetone in step (2) is replaced by ethyl acetate. The composite material has a tensile strength of 289 MPa and a volume resistivity of 10 6 Ω.

[0062] Example 6

[0063] The only difference from Example 1 is that in step (3), the weight ratio of the copolymerized PEEK material and the composite carbon fiber is 60:40. The composite material has a tensile strength of 298 MPa and a volume resistivity of 10 4 Ω.

[0064] Comparative Example 1

[0065] The only difference from Example 3 is that the carbon fibers are not treated in step (1). The composite material has a tensile strength of 240 MPa and a volume resistivity of 10 7 Ω.

[0066] Figure 1 is the stress-strain curve of the composite material of Example 3;

[0067] from Figure 1 It can be found that the tensile strength of the composite material prepared with T800 carbon fiber reaches 282MPa.

[0068] Figure 2 This is the DSC test curve of the composite material of Example 3;

[0069] from Figure 2 It can be found that the glass transition temperature of the composite material is 152°C and the melting point is 298°C, which is more than 7°C higher than the glass transition temperature of PEEK and its composite material (146°C) and the melting point (340°C) is 40°C lower. At the same time, the cold crystallization peak temperature of the material is 200°C, which is higher than the cold crystallization peak of PEEK material (176°C), indicating a decrease in the material's crystallization rate. The reduction in melting point and crystallization rate is beneficial to the welding of the composite material, ensuring the strength of the composite material after welding.

[0070] The flange is prepared by the injection molding method of the composite material prepared in Example 3, and the anti-static pipe and the flange are welded by using a high-temperature welding machine. During welding, multi-mode melting welding is used, and precise melting of the welding interface is realized by local precise temperature control, so that the strength of the flange during processing is maintained, and the precise melting of the welding interface of the welded pipe is also achieved, avoiding thermal deformation during welding. The welding conditions are as follows: heating at 320 DEG C for 10 s, welding rate 1 m / min, and solidification rate 1 m / min.

[0071] The preparation method of the anti-static pipe is as follows:

[0072] (1) Pretreatment of array carbon nanotubes (GT210): vacuum treatment at 400 DEG C for 4 h, vacuum degree 0.1 Pa.

[0073] (2) Purification of copolymer PEEK resin: the 3D printing polyether ether ketone interlayer reinforcing material prepared in Example 1 of CN114805789A is washed with acetone and deionized water in sequence, and the washing times are 4 times (one time for acetone and deionized water washing).

[0074] (3) The copolymer PEEK resin of step (2) and the array carbon nanotubes of step (1) are mixed by using a double-screw extruder with side feeding. The weight ratio of copolymer PEEK resin and array carbon nanotubes is 98:2, the copolymer PEEK resin is located in the main feeding port, and the array carbon nanotubes are located in the side feeding port. The double-screw extruder rotates at 300 r / min, the feeding temperature is 240 DEG C, the extrusion section temperature is 350 DEG C, the temperature at the extrusion die is 330 DEG C, and after granulation, anti-static high-toughness composite material granules-1 are prepared.

[0075] The anti-static pipe with an outer diameter of 40 mm and a wall thickness of 1.5 mm is extruded by using a high-temperature pipe extruder. The extruder rotates at 50 r / min, the feeding temperature is 240 DEG C, the extrusion section temperature is 350 DEG C, and the temperature at the extrusion die is 320 DEG C. After the pipe passes through the vacuum sizing, water cooling box, and air cooling box, the anti-static pipe with the required length is cut.

[0076] After welding, the flange and the anti-static pipe are subjected to tensile test, and the tensile strength is 34 MPa.

[0077] Figure 3 The physical picture of the PEEK pipe and the flange welded by the composite material prepared in Example 3.

[0078] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A PEEK composite material, characterized in that: The invention comprises a copolymerized polyetheretherketone resin and composite carbon fibers dispersed in the copolymerized polyetheretherketone resin; The composite carbon fiber comprises carbon fiber and amorphous polyaryletherketone coating the carbon fiber; The copolymerized polyetheretherketone resin has the structural formula shown in Formula I: At 400° C. and 500N, the melt index of the copolymerized polyetheretherketone resin is 23 to 80 g / 10 min.

2. The PEEK composite material according to claim 1, characterized in that Calculated by mass fraction, the mass fraction of the copolymerized polyetheretherketone resin in the PEEK composite material is 60-90%.

3. The PEEK composite material according to claim 1, characterized in that At 400° C. and 500N, the amorphous polyaryletherketone has a melt index of 23 to 80 g / 10 min.

4. The PEEK composite material according to claim 1, characterized in that The preparation method of the composite carbon fiber comprises the following steps: After removing the sizing agent from the surface of the carbon fiber, the obtained carbon fiber without the sizing agent on the surface is immersed in a solution of amorphous polyaryletherketone to obtain a wet composite carbon fiber; The wet composite carbon fiber is dried to obtain the composite carbon fiber.

5. The PEEK composite material according to claim 1 or 4, characterized in that: The carbon fiber types include one or more of T700, T800 and T1000.

6. The PEEK composite material according to claim 4, characterized in that The temperature for removing the sizing agent from the surface of the carbon fiber is 380-400° C., the time is 1-4 hours, and the vacuum degree is 0.1-0.2 Pa.

7. The method for preparing the PEEK composite material according to any one of claims 1 to 6, characterized in that: The following steps are involved: The copolymerized polyetheretherketone resin and the composite carbon fiber are mixed, melt-extruded, and granulated to obtain the PEEK composite material.

8. The preparation method according to claim 7, characterized in that Before the mixing, the method further comprises: washing the copolymerized polyetheretherketone resin, wherein the washing comprises washing with an organic solvent and then with water in sequence; the organic solvent comprises acetone and / or ethyl acetate.

9. The preparation method according to claim 7, characterized in that The melt extrusion is carried out in a twin-screw extruder; The speed of the twin-screw extruder is 200-300 r / min, the feeding temperature is 220-240° C., the temperature of the extrusion section is 320-350° C., and the temperature at the extrusion die is 300-330° C.

10. Use of the PEEK composite material according to any one of claims 1 to 6 or the PEEK composite material prepared by the preparation method according to any one of claims 7 to 9 in the preparation of injection molded parts.

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