Polyether-ether-ketone composite material, preparation method thereof and injection molded part

Abstract

The invention provides a polyether-ether-ketone composite material, a preparation method thereof and an injection molded part, and belongs to the field of composite materials. The invention provides a polyetheretherketone composite material. The polyetheretherketone composite material is prepared from the following raw materials: polyetheretherketone and a modified filler, the modified filler comprises filler and villiaumite located on the surface of the filler; the mass content of the modified filler in the polyether-ether-ketone composite material is 10-40%. According to the invention, by utilizing the aggressiveness of the inorganic salt on the surface of the modified filler on ether bonds in a polyether-ether-ketone chain segment, the cross-linking reaction of the filler and polyether-ether-ketone around the filler is realized, and the interface bonding of the polyether-ether-ketone and the filler is enhanced, so that the transverse and longitudinal shrinkage ratio is reduced.

Description

Technical Field

[0001] The present invention relates to the field of composite materials, and in particular to a polyetheretherketone composite material and a preparation method and an injection molded part thereof. Background Art

[0002] Polyaryletherketone (PAEK) is a class of semi-crystalline specialty polymers. PEEK is currently the most widely used PEEK, boasting exceptional properties such as lightweight, high strength, high-temperature resistance, and chemical corrosion resistance. Composite materials such as glass fiber and carbon fiber made from PEEK are commonly used in high-strength, wear-resistant components in aerospace and high-end equipment. However, PEEK exhibits significant lateral and longitudinal shrinkage after injection molding, which can lead to product warping and shrinkage. Summary of the Invention

[0003] The invention provides a polyetheretherketone composite material, a preparation method thereof, and an injection molded part. The polyetheretherketone composite material has a low transverse and longitudinal shrinkage ratio after injection molding.

[0004] The present invention provides a polyetheretherketone composite material, wherein the raw materials for preparing the polyetheretherketone composite material include polyetheretherketone and modified filler;

[0005] The modified filler includes a filler and a fluoride salt located on the surface of the filler;

[0006] The mass content of the modified filler in the polyetheretherketone composite material is 10-40%.

[0007] Preferably, the modified filler includes modified wollastonite and / or modified glass microspheres.

[0008] Preferably, the fluoride salt comprises sodium fluoride and / or potassium fluoride.

[0009] Preferably, when the modified filler is modified wollastonite and modified glass microspheres, the mass content of the modified wollastonite in the polyetheretherketone composite material is 10-30%, and the mass content of the modified glass microspheres is 5-10%.

[0010] Preferably, the particle size of the glass microspheres in the modified glass microspheres is 5 to 180 μm.

[0011] Preferably, the mesh size of the wollastonite in the modified wollastonite is 200-1250 meshes.

[0012] Preferably, the preparation method of the modified filler preferably comprises the following steps:

[0013] The filler is mixed with a strong alkaline solution for pretreatment, thereby increasing the roughness of the filler surface to obtain a pretreated filler;

[0014] The pretreated filler is mixed with a solution of a fluoride salt and separated, and then the obtained wet solid is dried to obtain the modified filler.

[0015] Preferably, the polyetheretherketone includes one or more of PEEK-012G, PEEK-021G, PEEK-085G and PEEK-090G;

[0016] The particle size of the polyetheretherketone is 10 to 150 μm.

[0017] The present invention also provides a method for preparing the polyetheretherketone composite material described in the above technical solution, comprising the following steps:

[0018] The raw materials for preparing the polyetheretherketone composite material are mixed and then extruded, and the fluoride salt and the polyetheretherketone undergo a cross-linking reaction to obtain the polyetheretherketone composite material.

[0019] The present invention also provides an injection molded part, characterized in that it is obtained by injection molding the polyetheretherketone composite material described in the above technical solution or the polyetheretherketone composite material prepared by the preparation method described in the above technical solution.

[0020] The present invention utilizes the aggressiveness of the fluorine salt on the surface of the modified filler to the ether bond in the polyetheretherketone chain segment to achieve a cross-linking reaction between the filler and the polyetheretherketone surrounding the filler, thereby strengthening the interface bonding between the polyetheretherketone and the filler and reducing the transverse and longitudinal shrinkage ratio.

[0021] Furthermore, the modification method of the modified filler of the present invention is simple and the process is stable, and has good prospects for large-scale application.

[0022] Furthermore, the composite material prepared by the present invention using modified wollastonite and modified glass microspheres as fillers has the same transverse and longitudinal shrinkage ratios, and the composite material has good melt fluidity and can be applied to the field of precision injection molding. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 2 are TGA test curves of the polyetheretherketone composite materials of Example 6 and Comparative Example 2;

[0024] Figure 2 This is the SEM image of the tensile cross-section of Example 6. DETAILED DESCRIPTION

[0025] The present invention provides a polyetheretherketone composite material, wherein the raw materials for preparing the polyetheretherketone composite material include polyetheretherketone and modified filler;

[0026] The modified filler includes a filler and a fluoride salt located on the surface of the filler;

[0027] The mass content of the modified filler in the polyetheretherketone composite material is 10-40%.

[0028] In the present application, the raw material for preparing the polyether ether ketone composite material comprises polyether ether ketone, the type of the polyether ether ketone preferably comprises one or more of PEEK-012G, PEEK-021G, PEEK-085G and PEEK-090G; the particle size of the polyether ether ketone is preferably 10-150 μm, in specific embodiments of the present application, the particle size of the polyether ether ketone can be 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm or 140 μm.

[0029] In the present application, the raw material for preparing the polyether ether ketone composite material comprises modified filler, the mass content of the modified filler in the polyether ether ketone composite material is 10-40%, in the present application, the mass content of the modified filler can be 15%, 20%, 25%, 30% or 35%; the modified filler comprises filler and fluorine salt on the surface of the filler; the fluorine salt preferably comprises sodium fluoride and / or potassium fluoride, when multiple modified fillers are contained, the fluorine salt of different modified fillers can be the same or different.

[0030] In the present application, the modified filler comprises modified wollastonite and / or modified glass microbeads, the particle size of the glass microbeads in the modified glass microbeads is preferably 5-180 μm, in specific embodiments of the present application, the particle size of the glass microbeads can be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm μm, 150 μm, 160 μm or 170 μm; the mesh number of the wollastonite in the modified wollastonite is preferably 200-1250 mesh, in specific embodiments of the present application, the mesh number of the wollastonite can be 400 mesh, 600 mesh or 800 mesh.

[0031] In the present application, when the modified filler is modified wollastonite and modified glass microbeads, the mass content of the modified glass microbeads in the polyether ether ketone composite material is preferably 0-10%, in specific embodiments of the present application, the mass content of the modified glass microbeads can be 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%; the mass content of the modified wollastonite is preferably 10-30%, in specific embodiments of the present application, the mass content of the modified wollastonite can be 12%, 15%, 18%, 20%, 24%, 25% or 28%

[0032] In the present application, the preparation method of the modified filler preferably comprises the following steps:

[0033] The filler is mixed with a strong alkaline solution for pretreatment, thereby increasing the roughness of the filler surface to obtain a pretreated filler;

[0034] The pretreated filler is mixed with a solution of a fluoride salt and separated, and then the obtained wet solid is dried to obtain the modified filler.

[0035] In the present invention, the filler is mixed with a strong alkaline solution for pretreatment, and the roughness of the filler surface is increased to obtain the pretreated filler.

[0036] In the present invention, the usage ratio of the filler to the strong alkali solution is preferably 1 kg:1500 mL; the concentration of the strong alkali solution is preferably 1 mol / L, and the strong alkali in the strong alkali solution preferably includes sodium hydroxide.

[0037] In the present invention, the pretreatment is preferably carried out under stirring conditions, and the stirring speed is preferably 1000-6000 rpm. In specific embodiments of the present invention, the stirring speed can be 2000 rpm, 3000 rpm, 4000 rpm, or 5000 rpm. The pretreatment time is preferably 10-24 hours. In specific embodiments of the present invention, the pretreatment time can be 12 hours, 15 hours, 18 hours, or 20 hours. Pretreatment can increase the roughness of the filler.

[0038] After the pretreatment is completed, the present invention preferably performs solid-liquid separation on the obtained pretreated system, and then washes and dries the obtained wet solid to obtain the pretreated filler.

[0039] In the present invention, the washing preferably comprises repeatedly mixing the obtained wet solid with water and then filtering it with suction.

[0040] In the present invention, the drying temperature is preferably 120° C., and the drying time is preferably 4 to 6 hours.

[0041] After obtaining the pretreated filler, the present invention mixes the pretreated filler with a solution of a fluoride salt and separates the mixture, and then dries the obtained wet solid to obtain the modified filler.

[0042] In the present invention, the usage ratio of the pretreated filler to the fluoride salt solution is preferably 1 kg:1500 mL, and the concentration of the fluoride salt solution is preferably 1 mol / L.

[0043] In the present invention, the drying temperature is preferably 120° C., and the drying time is preferably 4 to 6 hours.

[0044] The present invention also provides a method for preparing the polyetheretherketone composite material described in the above technical solution, comprising the following steps:

[0045] The raw materials for preparing the polyetheretherketone composite material are mixed and then extruded, and the fluoride salt and the polyetheretherketone undergo a cross-linking reaction to obtain the polyetheretherketone composite material.

[0046] In the present invention, the mixing is preferably carried out under stirring conditions, the stirring speed is preferably 1000-6000 rpm, and the time is preferably 1-3 hours. In a specific embodiment of the present invention, the speed can be 2000 rpm, 3000 rpm, 4000 rpm or 5000 rpm, and the time can be 2 hours.

[0047] In the present invention, the temperature of the extruder during extrusion is preferably 360-380°C, and the screw speed is preferably 35-45 rpm. In a specific embodiment of the present invention, the temperature of the extruder can be 365°C, 370°C or 375°C, and the screw speed can be 40 rpm.

[0048] The present invention also provides an injection molded part, which is obtained by injection molding the polyetheretherketone composite material described in the above technical solution or the polyetheretherketone composite material prepared by the preparation method described in the above technical solution.

[0049] In the present invention, the injection molding temperature is preferably 360-385°C, and the temperature of the mold used for injection molding is preferably 210-230°C. In a specific embodiment of the present invention, the injection molding temperature can be 360°C, 370°C, 375°C or 380°C, and the temperature of the mold can be 220°C.

[0050] The polyetheretherketone composite material, its preparation method, and injection molded parts provided by the present invention 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.

[0051] In the embodiments and comparative examples, the particle size of wollastonite is 10-100 μm; the particle size of glass microbeads is 30-50 μm; and the model of the PEEK material is PEEK-021G.

[0052] Example 1

[0053] (1) Treatment of wollastonite and glass microspheres: 1 kg of wollastonite or 1 kg of glass microspheres were pretreated by adding 1500 mL of 1 mol / L sodium hydroxide, stirring at 4000 r / min, and treating for 12 h. After filtration and repeated rinsing, the mixture was dried in a forced air oven at 120°C for 6 h. After drying, 1 kg of wollastonite or 1 kg of glass microspheres were added to 1500 mL of 1 mol / L potassium fluoride aqueous solution and ultrasonically treated for 4 h. After filtration, the mixture was dried in a forced air oven at 120°C for 6 h.

[0054] (2) Premixing: The treated wollastonite and glass microspheres, and PEEK powder were added into a blender in a weight ratio of 85:10:5 of PEEK material, treated wollastonite, and treated glass microspheres, and mixed at a stirring speed of 4000 r / min for 3 h.

[0055] (3) Blend extrusion: The premixed material was extruded by a twin-screw extruder, the temperature of the extruder was set to 380°C, and the screw rotation speed was set to 45 rpm to obtain composite granules.

[0056] (4) The composite granules were injected into a standard sample required for testing by using a high-temperature injection molding machine. The injection temperature was 380°C, and the mold temperature was 220°C.

[0057] Example 2

[0058] The difference from Example 1 is only that the weight ratio of PEEK material, treated wollastonite, and treated glass microspheres in step (2) is 75:20:5.

[0059] Example 3

[0060] The difference from Example 1 is only that the weight ratio of PEEK material, treated wollastonite, and treated glass microspheres in step (2) is 65:30:5.

[0061] Example 4

[0062] The difference from Example 1 is only that the weight ratio of PEEK material and treated wollastonite in step (2) is 90:10, and no treated glass microspheres are added.

[0063] Example 5

[0064] The difference from Example 1 is only that the weight ratio of PEEK material and treated wollastonite in step (2) is 80:20, and no treated glass microspheres are added.

[0065] Example 6

[0066] The difference from Example 1 is only that the weight ratio of PEEK material and treated wollastonite in step (2) is 70:30, and no treated glass microspheres are added.

[0067] Comparative Example 1

[0068] The difference from Example 1 is only that the wollastonite and glass microspheres in step (1) are not treated.

[0069] Comparative Example 2

[0070] The difference from Example 6 is only that the wollastonite in step (1) is not treated.

[0071] Comparative Example 3

[0072] The difference from Example 1 is that wollastonite and glass microbeads are not used for treatment.

[0073] Figure 1 These are the TGA test curves of the polyetheretherketone composite materials of Example 6 and Comparative Example 2.

[0074] Depend on Figure 1 It can be seen that the thermal stability of wollastonite is improved after being treated with sodium hydroxide, which may be due to the removal of impurities in the wollastonite after the sodium hydroxide treatment.

[0075] Figure 2 This is the SEM image of the tensile cross-section of Example 6.

[0076] Depend on Figure 2 It can be seen that the filler has good interfacial bonding with the PEEK material and does not debond from the PEEK material during the stretching process.

[0077] Table 1 Transverse and longitudinal shrinkage of Examples 1 to 6 and Comparative Examples 1 to 3

[0078] sample Transverse shrinkage (%) Longitudinal shrinkage (%) Example 1 0.7 0.7 Example 2 0.6 0.6 Example 3 0.4 0.4 Example 4 0.8 0.8 Example 5 0.7 0.7 Example 6 0.5 0.5 Comparative Example 1 0.7 0.7 Comparative Example 2 0.5 0.5 Comparative Example 3 1 1.1

[0079] Table 2 Tensile modulus, tensile strength and wear rate of Examples 1 to 6 and Comparative Examples 1 to 3

[0080]

[0081] It can be seen from Table 1 that the transverse and longitudinal shrinkage rates of the composite materials prepared with wollastonite and glass microspheres are the same, and with the increase of filler content, the transverse and longitudinal shrinkage rates of the materials tend to decrease.

[0082] As shown in Table 2, the tensile strength and wear resistance of the composites prepared with modified wollastonite and glass microspheres are much higher than those of the unmodified sample and pure PEEK. This is because the modified filler causes the ether bonds in the surrounding PEEK to break, forming a cross-linking reaction. This creates a good interfacial interaction between the filler and the resin, improving the tensile strength, tensile modulus, and wear rate of the composite.

[0083] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A polyetheretherketone composite material, characterized in that The raw materials for preparing the polyetheretherketone composite material include polyetheretherketone and modified filler; The modified filler includes a filler and a fluoride salt located on the surface of the filler; The mass content of the modified filler in the polyetheretherketone composite material is 10-40%.

2. The polyetheretherketone composite material according to claim 1, characterized in that The modified filler includes modified wollastonite and / or modified glass microspheres.

3. The polyetheretherketone composite material according to claim 1, characterized in that The fluoride salt includes sodium fluoride and / or potassium fluoride.

4. The polyetheretherketone composite material according to claim 2, characterized in that When the modified filler is modified wollastonite and modified glass microspheres, the mass content of the modified wollastonite in the polyetheretherketone composite material is 10-30%, and the mass content of the modified glass microspheres is 5-10%.

5. The polyetheretherketone composite material according to claim 2, characterized in that The particle size of the glass microspheres in the modified glass microspheres is 5 to 180 μm.

6. The polyetheretherketone composite material according to claim 2, characterized in that The mesh number of the wollastonite in the modified wollastonite is 200-1250 meshes.

7. The polyetheretherketone composite material according to claim 1, characterized in that The preparation method of the modified filler preferably comprises the following steps: The filler is mixed with a strong alkaline solution for pretreatment, thereby increasing the roughness of the filler surface to obtain a pretreated filler; The pretreated filler is mixed with a solution of a fluoride salt and separated, and then the obtained wet solid is dried to obtain the modified filler.

8. The polyetheretherketone composite material according to claim 1, characterized in that The polyetheretherketone model includes one or more of PEEK-012G, PEEK-021G, PEEK-085G and PEEK-090G; The particle size of the polyetheretherketone is 10 to 150 μm.

9. The method for preparing the polyetheretherketone composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: The raw materials for preparing the polyetheretherketone composite material are mixed and then extruded, and the fluoride salt and the polyetheretherketone undergo a cross-linking reaction to obtain the polyetheretherketone composite material.

10. An injection molded part, characterized in that: The polyetheretherketone composite material is obtained by injection molding from the polyetheretherketone composite material according to any one of claims 1 to 8 or the polyetheretherketone composite material prepared by the preparation method according to claim 9.

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