Preparation method of wear-resistant modified polyaryletherketone composite material

Abstract

The present invention relates to the technical field of composite materials, and particularly relates to a preparation method of a wear-resistant modified polyaryletherketone composite material, which comprises the following steps: S1. Add a wear-resistant and heat-conducting material and carbon fiber during the synthesis of polyetherimide to obtain a wear-resistant carbon fiber polyetherimide-based in-situ masterbatch; the heat conductivity coefficient of the wear-resistant and heat-conducting material is greater than 30 W / m·K and the Mohs hardness is greater than 2; melt-blend and extrude the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch and polyaryletherketone to obtain the wear-resistant modified polyaryletherketone composite material; the polyaryletherketone composite material prepared by the method of the present invention has good wear resistance, and the heat generated during the friction process can be quickly conducted out in time, which improves the anti-creep performance of the material and at the same time improves the service life of the material.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and particularly relates to a preparation method of a wear-resistant modified polyaryletherketone composite material. Background Art

[0002] Polyetheretherketone is a semi-crystalline, thermoplastic special engineering plastic with ultra-high performance. Its maximum crystallinity is 48%, and the crystallinity of ordinary products can reach 20% - 30%. The melting point is 343°C, and the glass transition temperature is 143°C. At present, polyetheretherketone is gradually applied to many fields such as aerospace, automotive, and energy with its excellent mechanical properties, high temperature resistance, wear resistance, etc., and has become an increasingly eye-catching high-performance material.

[0003] Carbon fiber (CF) has the characteristics of light weight and high strength. Carbon fiber-reinforced polyetheretherketone composite materials have excellent friction resistance and creep resistance. However, the smooth surface of CF and its strong inertness on the surface lead to poor interfacial compatibility with the matrix resin, resulting in lower mechanical properties of the composite material; moreover, the content, length, and orientation of carbon fiber will all affect the wear resistance of the composite material. In the actual application process, the carbon fiber-reinforced resin material has poor thermal conductivity and usually relies on adding a thermal conductive phase to improve it. In addition, compared with other special engineering plastics, the glass transition temperature of PEEK is relatively low, and a large amount of heat is generated during the friction process, which will cause the material strength to decrease.

[0004] Therefore, it is necessary to deeply study the properties of CF / PEEK composite materials in terms of interface strengthening, forming process, and material property optimization. Summary of the Invention

[0005] In order to solve the technical problem of poor wear resistance caused by the interfacial bonding between carbon fiber and matrix resin, a preparation method of a wear-resistant modified polyaryletherketone composite material is provided. The polyaryletherketone composite material prepared by the method of the present invention has good wear resistance, and the heat generated during the friction process can be quickly conducted out in time, improving the creep resistance of the material and at the same time extending the service life of the material.

[0006] In order to achieve the above object, the present invention is realized through the following technical solutions:

[0007] A preparation method of a wear-resistant modified polyaryletherketone composite material, comprising the following steps:

[0008] S1. Add a wear-resistant and heat-conductive material and carbon fiber during the synthesis of polyetherimide to obtain a wear-resistant carbon fiber polyetherimide-based in-situ masterbatch;

[0009] The thermal conductivity coefficient of the wear-resistant and heat-conductive material is greater than 30 W / m·K and the Mohs hardness is greater than 2;

[0010] S2. Carry out melt blending and extrusion of the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch and polyaryletherketone to obtain the wear-resistant modified polyaryletherketone composite material.

[0011] Further, the wear-resistant and heat-conducting material is selected from one or more of metals or their oxides, silicon carbide, aluminum nitride, boron carbide, tungsten carbide, graphene, and steel.

[0012] Preferably, the wear-resistant and heat-conducting material is selected from the combination of metal powder and flaky aluminum nitride and silicon carbide whiskers.

[0013] The metal powder is selected from one or several of copper powder, silver-plated copper powder, silver powder, and nickel powder.

[0014] The mass ratio of the metal powder, the flaky aluminum nitride, and the silicon carbide whiskers is 6 - 10:3 - 5:1.

[0015] The particle size of the metal powder is less than 100 μm; the average particle size of the flaky aluminum nitride is 5 - 30 μm, and the thickness is 0.5 - 3 μm; the diameter of the silicon carbide whiskers is 0.5 - 3 μm, and the length is 10 - 50 μm.

[0016] Further, S1 specifically includes the following steps: Under stirring, dissolve the aromatic dietheramine and the coupling agent in an aprotic solvent. After dissolving and mixing evenly, successively add the wear-resistant and heat-conducting material and carbon fiber. After dispersing evenly, add the aromatic dianhydride for polycondensation reaction. After the polycondensation reaction is completed, carry out thermal imidization to obtain the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch.

[0017] Furthermore, the aromatic dietheramine is diaminodiphenyl ether (ODA); the aromatic dianhydride is 4,4'-(4,4'-isopropyl diphenoxy) diphthalic anhydride (BPADA).

[0018] The coupling agent is a silane coupling agent, specifically preferably one or several of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(β-methoxyethoxy)silane.

[0019] The aprotic solvent is selected from one of DMF, NMP, DMAc, and DMSO.

[0020] Further, the molar volume ratio of the aromatic dietheramine, the aromatic dianhydride, and the aprotic solvent in S1 is 1 mol:1 mol:1.5 - 3.5 L; the dosage of the coupling agent is 1% - 5% of the total weight of the wear-resistant and heat-conducting material and the carbon fiber.

[0021] The mass proportion of the wear-resistant and heat-conductive material in the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch ranges from 10% to 20%, and the mass proportion of the carbon fiber in the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch ranges from 20% to 40%;

[0022] Further, the temperature of the polycondensation reaction is 5 - 35°C and the time is 2 - 5 h; the temperature of the thermal imidization is 140 - 170°C and the time is 3 - 5 h.

[0023] Further, the polyaryletherketone is selected from one or more of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), phenolphthalein polyaryletherketone (PEKC, PAEK-HT), polyetherketone (PEK), polyetheretherketoneketone (PEEKK), and polyetherketoneetherketoneketone (PEKEKK); the melt index of the polyaryletherketone at 400°C and a load of 2.16 kg is 25 - 70 g / 10 min.

[0024] Further, the process of melt blending and extrusion is as follows: the temperatures of each zone of the extruder are set at 250 - 280°C, 320 - 350°C, 350 - 380°C, 350 - 380°C, 350 - 380°C, 350 - 380°C, the temperature of the die head and the die is 350 - 380°C, the rotation speed is set at 50 - 280 rpm, and the residence period of the material is 0.5 - 6 min.

[0025] Further, the dosage of the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch is 1 to 3 times the mass of the polyaryletherketone.

[0026] Beneficial technical effects:

[0027] In the present invention, granular copper powder, flaky aluminum nitride, and fibrous silicon carbide are used to synthesize a wear-resistant in-situ masterbatch by in-situ introduction under the action of a coupling agent, and the masterbatch is blended with PEEK to obtain a composite material. The problem of uneven dispersion of filler particles in the matrix is solved by combining the coupling agent in both in-situ and blending ways; in the present invention, three fillers with different dimensions and both high thermal conductivity and wear resistance are in-situ introduced into polyetherimide together with carbon fiber, which can not only construct an effective heat conduction channel, but also endow the composite material with good wear resistance, improve the mechanical strength and heat resistance of the composite, and extend the service life at high temperatures. Specific embodiments

[0028] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way limits the present invention and its application or use. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0029] Unless otherwise specifically stated, the numerical values set forth in these embodiments do not limit the scope of the present invention. Technologies and methods known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the said technologies and methods should be regarded as part of the specification. In all the examples shown and discussed here, any specific value should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.

[0030] In the following embodiments, the experimental methods without specific conditions are generally determined according to national standards; if there are no corresponding national standards, they are carried out according to general standard requirements or general methods.

[0031] Example 1

[0032] A preparation method of a wear-resistant modified polyaryletherketone composite material includes the following steps:

[0033] S1. Preparation of wear-resistant carbon fiber polyetherimide-based in-situ masterbatch:

[0034] Under stirring, 30L DMAc, 188g vinyltrimethoxysilane coupling agent, and 10 mol of 4,4'-diaminodiphenyl ether (4,4'-ODA) are added to a reaction kettle. After dissolving and mixing evenly, a total of 1.4 kg of wear-resistant and heat-conducting materials are added. The wear-resistant and heat-conducting materials are copper powder, flaky aluminum nitride, and silicon carbide whiskers configured according to a mass ratio of 10:3:1 (where the average particle size of the copper powder is 3 μm, the average particle size of the flaky aluminum nitride is 5 - 30 μm, and the thickness is 0.5 - 3 μm, and the diameter of the silicon carbide whiskers is 0.5 - 3 μm and the length is 10 - 50 μm). After dispersing evenly, 3.3 kg of carbon fiber (short-cut fiber, diameter 8 μm, length 5 mm) is added, and dispersed evenly again. 10 mol of 4,4'-(4,4'-isopropyl diphenoxy) diphthalic anhydride (BPADA) is slowly added and subjected to polycondensation reaction at 30°C for 4 h. After the polycondensation reaction is completed, thermal imidization is carried out at 160°C for 180 min to obtain a wear-resistant carbon fiber polyetherimide-based in-situ masterbatch. In the in-situ masterbatch, the proportion of the wear-resistant and heat-conducting materials is 12.39 wt%, and the proportion of the carbon fiber is 29.2 wt%.

[0035] S2. Melt-blend and extrude 5.14 kg of the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch obtained in the previous step with 2 kg of PEEK. The process parameters are as follows: the temperature settings for each zone of the extruder are 275 ± 5 °C, 345 ± 5 °C, 370 ± 5 °C, 370 ± 5 °C, 370 ± 5 °C, 370 ± 5 °C, the temperature of the die head and die is 375 ± 2 °C, the rotation speed is set at 350 rpm, and the residence time of the material is 2 min, thus obtaining the wear-resistant modified polyaryletherketone composite material.

[0036] Example 2

[0037] A preparation method of a wear-resistant modified polyaryletherketone composite material, comprising the following steps:

[0038] S1. Preparation of the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch:

[0039] Under stirring, add 30 L of DMAc, 288 g of vinyltriethoxysilane coupling agent, and 10 mol of 4,4'-diaminodiphenyl ether (4,4'-ODA) to the reaction kettle. After dissolving and mixing evenly, add a total of 2.2 kg of wear-resistant and heat-conducting materials. The wear-resistant and heat-conducting materials are copper powder, flaky aluminum nitride, and silicon carbide whiskers configured according to a mass ratio of 6:5:1 (where the average particle size of the copper powder is 3 μm, the average particle size of the flaky aluminum nitride is 5 - 30 μm, the thickness is 0.5 - 3 μm, the diameter of the silicon carbide whiskers is 0.5 - 3 μm, and the length is 10 - 50 μm). After dispersing evenly, add 5 kg of carbon fiber, disperse evenly again, slowly add 10 mol of 4,4'-(4,4'-isopropyl diphenoxy) diphthalic anhydride (BPADA), and carry out a polycondensation reaction at 23 °C for 4 h. After the polycondensation reaction is completed, carry out thermal imidization at 140 °C for 220 min to obtain the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch. The proportion of the wear-resistant and heat-conducting materials in the in-situ masterbatch is 15.94 wt%, and the proportion of the carbon fiber is 36.23 wt%.

[0040] S2. Melt-blend and extrude 5.23 kg of the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch obtained in the previous step with 2.5 kg of PEEK. The process parameters are as follows: the temperature settings for each zone of the extruder are 255 ± 5 °C, 325 ± 5 °C, 355 ± 5 °C, 360 ± 5 °C, 365 ± 5 °C, 365 ± 5 °C, the temperature of the die head and die is 370 ± 5 °C, the rotation speed is set at 400 rpm, and the residence time of the material is 1.7 min, thus obtaining the wear-resistant modified polyaryletherketone composite material.

[0041] Example 3

[0042] A preparation method of a wear-resistant modified polyaryletherketone composite material, comprising the following steps:

[0043] S1. Preparation of the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch:

[0044] Under stirring, 30 L of DMAc, 198 g of γ-aminopropyltriethoxysilane coupling agent, and 10 mol of 4,4'-diaminodiphenyl ether (4,4'-ODA) were added to a reaction kettle. After dissolving and mixing evenly, a total of 2.6 kg of wear-resistant and heat-conductive material was added. The wear-resistant and heat-conductive material was configured with copper powder, flaky aluminum nitride, and silicon carbide whiskers in a mass ratio of 8:4:1 (where the average particle size of copper powder was 3 μm, the average particle size of flaky aluminum nitride was 5 - 30 μm, and the thickness was 0.5 - 3 μm, and the diameter of silicon carbide whiskers was 0.5 - 3 μm and the length was 10 - 50 μm). After dispersing evenly, 4 kg of carbon fiber was added, and after dispersing evenly again, 10 mol of 4,4'-(4,4'-isopropyl diphenoxy) diphthalic anhydride (BPADA) was slowly added, and a polycondensation reaction was carried out at 20 °C for 4 h. After the polycondensation reaction was completed, thermal imidization was carried out at 150 °C for 180 min to obtain a wear-resistant carbon fiber polyetherimide-based in-situ masterbatch. In the in-situ masterbatch, the wear-resistant and heat-conductive material accounted for 19.7 wt%, and the carbon fiber accounted for 30.3 wt%.

[0045] S2. 2.5 kg of the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch obtained in the previous step was melt-blended and extruded with 2.5 kg of PEEK. The process parameters were as follows: the temperature of each zone of the extruder was set at 260 ± 5 °C, 335 ± 5 °C, 360 ± 5 °C, 365 ± 5 °C, 365 ± 5 °C, 370 ± 5 °C, the temperature of the die head and die was 375 ± 2 °C, the rotation speed was set at 300 rpm, and the residence time of the material was 2.5 min, thus obtaining a wear-resistant modified polyaryletherketone composite material.

[0046] Comparative Example 1

[0047] The preparation process of the composite material in this example was the same as that in Example 1, except that the wear-resistant and heat-conductive material was not added (i.e., only carbon fiber was contained).

[0048] Comparative Example 2

[0049] The preparation process of the composite material in this example was the same as that in Example 1, except that the wear-resistant and heat-conductive material was only copper powder (thermal conductivity 380 W / m·K, Mohs hardness about 3).

[0050] Comparative Example 3

[0051] The preparation process of the composite material in this example was the same as that in Example 1, except that the wear-resistant and heat-conductive material was only flaky aluminum nitride (thermal conductivity 150 - 320 W / m·K, Mohs hardness about 9 - 10).

[0052] Comparative Example 4

[0053] The preparation process of the composite material in this example is the same as that in Example 1, except that the wear-resistant and heat-conducting material is only silicon carbide whiskers (thermal conductivity 58 - 83 W / m·K, Mohs hardness about 9.5).

[0054] Comparative Example 5

[0055] The preparation process of the composite material in this example is the same as that in Example 1, except that the wear-resistant and heat-conducting material is copper powder and flaky aluminum nitride (keeping the mass percentage of copper unchanged).

[0056] Comparative Example 6

[0057] The preparation process of the composite material in this example is the same as that in Example 1, except that the wear-resistant and heat-conducting material is copper powder and silicon carbide whiskers (keeping the mass percentage of copper unchanged).

[0058] Comparative Example 7

[0059] The preparation process of the composite material in this example is the same as that in Example 1, except that:

[0060] Only polyetherimide was synthesized in S1 (without adding wear-resistant and heat-conducting materials and carbon fiber);

[0061] The preparation of the polyaryl ether ketone composite material in S2 is the blending method. Specifically, polyetherimide, wear-resistant and heat-conducting material, carbon fiber, and PEEK are mixed evenly according to the ratio in Example 1 and then directly melt-blended and extruded. This example is the blending method.

[0062] Perform performance tests on the above materials, as shown in Table 1 specifically.

[0063] Table 1 Material Properties of Each Example

[0064]

[0065] It can be seen from the data in Table 1 that in the present invention, granular copper powder, flaky aluminum nitride, and fibrous silicon carbide are in-situ introduced during the synthesis of polyetherimide to prepare a wear-resistant in-situ masterbatch, which is blended with PEEK to obtain a composite material. The three fillers with high thermal conductivity and wear resistance in different dimensions can not only construct effective heat conduction channels, but also endow the composite material with good wear resistance, and improve the mechanical strength and heat resistance of the composite, as well as its service temperature and service life at high temperatures.

[0066] As mentioned above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

Claims

1. A method for preparing a wear-resistant modified polyaryletherketone composite material, characterized in that: The steps include: S1. Adding wear-resistant heat-conductive material and carbon fiber during the synthesis of polyetherimide to prepare wear-resistant carbon fiber polyetherimide-based in-situ masterbatch; specifically comprising the following steps: Under stirring, the aromatic dietheramine and the coupling agent are dissolved in a non-protonic solvent, and after being dissolved and mixed evenly, the wear-resistant thermal conductive material and the carbon fiber are added in sequence, and after being evenly dispersed, the aromatic dianhydride is added to carry out polycondensation reaction, and after the polycondensation reaction is completed, thermal imidization is carried out to obtain a wear-resistant carbon fiber polyetherimide-based in-situ masterbatch; The wear-resistant heat-conducting material is selected from a combination of metal powder, flaky aluminum nitride, and silicon carbide whiskers; The metal powder is selected from one or more of copper powder, silver-plated copper powder, silver powder and nickel powder; The mass ratio of the metal powder, the flaky aluminum nitride, and the silicon carbide whisker is 6-10:3-5:1; The particle size of the metal powder is less than 100 μm; the average particle size of the flaky aluminum nitride is 5-30 μm and the thickness is 0.5-3 μm; the diameter of the silicon carbide whisker is 0.5-3 μm and the length is 10-50 μm; The mass proportion of the wear-resistant heat-conductive material in the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch is in the range of 10%-20%, and the mass proportion of the carbon fiber in the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch is in the range of 20%-40%; S2, melt-blending and extruding the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch and polyaryletherketone to obtain a wear-resistant modified polyaryletherketone composite material; The polyaryletherketone has a melt index of 25-70 g / 10 min at 400° C. and a load of 2.16 kg; The amount of the wear-resistant carbon fiber polyetherimide-based in-situ masterbatch is 1 to 3 times the mass of the polyaryletherketone.

2. The method for preparing a wear-resistant modified polyaryletherketone composite material according to claim 1, characterized in that: The aromatic dietheramine is diaminodiphenyl ether; the aromatic dianhydride is 4,4'-(4,4'-isopropyldiphenoxy) diphthalic anhydride; The coupling agent is one or more of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltri(β-methoxyethoxy)silane; The aprotic solvent is selected from one of DMF, NMP, DMAc and DMSO.

3. The method for preparing a wear-resistant modified polyaryletherketone composite material according to claim 1, characterized in that: The molar volume ratio of the aromatic dietheramine, the aromatic dianhydride and the aprotic solvent in S1 is 1 mol:1 mol:1.5-3.5 L; the amount of the coupling agent is 1%-5% of the total weight of the wear-resistant heat-conductive material and the carbon fiber.

4. The method for preparing a wear-resistant modified polyaryletherketone composite material according to claim 1, characterized in that: The temperature of the polycondensation reaction is 5-35° C. and the time is 2-5 hours; the temperature of the thermal imidization is 140-170° C. and the time is 3-5 hours.

5. The method for preparing a wear-resistant modified polyaryletherketone composite material according to claim 1, characterized in that: The polyaryletherketone is selected from one or more of polyetheretherketone, polyetherketoneketone, phenolphthalein polyaryletherketone, polyetherketone, polyetheretherketoneketone, and polyetherketoneetherketoneketone.

6. The method for preparing a wear-resistant modified polyaryletherketone composite material according to claim 1, characterized in that: The process of melt blending extrusion is as follows: the temperatures of each zone of the extruder are set at 250-280°C, 320-350°C, 350-380°C, 350-380°C, 350-380°C, 350-380°C, 350-380°C, the temperature of the die head and the die is 350-380°C, the speed is set at 50-280rpm, and the material residence period is 0.5-6min.

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