Polyether-ether-ketone composite material as well as preparation method and application thereof

Abstract

The invention relates to a polyether-ether-ketone composite material as well as a preparation method and application thereof. The polyether-ether-ketone composite material is prepared from the following components in parts by weight: 15 to 45 parts of polyether-ether-ketone A, 20 to 40 parts of polyether-ether-ketone B, 20 to 40 parts of polyether-ether-ketone C, 1 to 20 parts of heat-conducting material and 1 to 10 parts of toughening agent, the intrinsic viscosity of the polyether-ether-ketone A is 0.38 to 0.59 dL / g; the intrinsic viscosity of the polyether-ether-ketone B is 0.7 to 0.88 dL / g; the intrinsic viscosity of the polyether-ether-ketone C is 0.95 to 1.3 dL / g. The polyether-ether-ketone composite material is subjected to formula design, polyether-ether-ketone with different intrinsic viscosities is adopted and matched with the heat conduction material, the flexibilizer and the like, so that the heat deformation temperature of the polyether-ether-ketone composite material is increased while the balance of rigidity and toughness of the polyether-ether-ketone composite material is kept; and the high-heat-resistance polyether-ether-ketone composite material is developed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a polyether ether ketone composite material and a preparation method and application thereof. BACKGROUND

[0002] Polyether ether ketone (PEEK) is a kind of semi-crystalline special polymer material, which contains a ketone bond and two ether bonds in the main chain structure, is generally obtained by condensation with aromatic dihydric phenol, and has high mechanical strength, high temperature resistance, impact resistance, flame resistance, acid and alkali resistance, hydrolysis resistance, wear resistance, fatigue resistance, radiation resistance and good electrical properties, and can be used as high temperature resistant structural material and electrical insulating material. Compared with other high temperature resistant plastics, polyether ether ketone is the resin with the highest heat resistance grade and the best comprehensive performance among the special engineering plastics at present, has excellent self-lubricating property, flame resistance and chemical resistance, and has a large number of applications in the fields of aerospace, medical devices (as artificial bone for repairing bone defects) and industry.

[0003] With the rapid development of manufacturing industry, the requirements for the speed and load of power machinery are increasingly improved. Although the heat resistance grade of polyether ether ketone itself is very high, there are higher requirements for the heat distortion temperature in some special scenarios, and the mechanical properties of pure polyether ether ketone material are insufficient to meet different use requirements.

[0004] Therefore, how to provide a polyether ether ketone composite material with excellent mechanical properties and high heat resistance has become a problem to be solved at present. SUMMARY

[0005] To solve the above technical problems, the present application provides a polyether ether ketone composite material and a preparation method and application thereof, and a polyether ether ketone material with high heat resistance and excellent mechanical properties is developed by formulating the polyether ether ketone composite material.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a polyether ether ketone composite material, which comprises the following raw material components in parts by weight: 15-45 parts of polyether ether ketone A, 20-40 parts of polyether ether ketone B, 20-40 parts of polyether ether ketone C, 1-20 parts of a heat conducting material and 1-10 parts of a toughening agent;

[0008] The intrinsic viscosity of the polyether ether ketone A is 0.38-0.59 dL / g;

[0009] The intrinsic viscosity of the polyether ether ketone B is 0.7-0.88 dL / g;

[0010] The intrinsic viscosity of the polyether ether ketone C is 0.95-1.3 dL / g.

[0011] wherein 15-45 parts may be, for example, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or 45 parts, etc.; 20-40 parts may be, for example, 20 parts, 25 parts, 30 parts, 35 parts, or 40 parts, etc.; 1-20 parts may be, for example, 1 part, 5 parts, 10 parts, 15 parts, or 20 parts, etc.; 1-10 parts may be, for example, 1 part, 2 parts, 4 parts, 5 parts, 6 parts, 8 parts, or 10 parts, etc.

[0012] 0.38-0.59 dL / g, for example, 0.38 dL / g, 0.4 dL / g, 0.42 dL / g, 0.44 dL / g, 0.45 dL / g, 0.46 dL / g, 0.48 dL / g, 0.50 dL / g, 0.52 dL / g, 0.54 dL / g, 0.55 dL / g, 0.56 dL / g, 0.58 dL / g, or 0.59 dL / g, etc.

[0013] 0.7-0.88 dL / g, for example, 0.7 dL / g, 0.72 dL / g, 0.74 dL / g, 0.75 dL / g, 0.76 dL / g, 0.78 dL / g, 0.80 dL / g, 0.82 dL / g, 0.84 dL / g, 0.85 dL / g, 0.86 dL / g, or 0.88 dL / g, etc.

[0014] 0.95-1.3 dL / g, for example, 0.95 dL / g, 1 dL / g, 1.05 dL / g, 1.1 dL / g, 1.15 dL / g, 1.2 dL / g, 1.25 dL / g, or 1.3 dL / g, etc.

[0015] The intrinsic viscosity is tested according to the test method provided in GB / T 1632.1-2024 using a Ubbelohde viscometer.

[0016] The heat distortion temperature of the polyether ether ketone composite is mainly determined by the crystallinity, and the crystalline region can effectively limit the thermal motion of the molecular chain, and the crystallinity is significantly affected by the intrinsic viscosity and the processing conditions of the material. With the increase of the intrinsic viscosity of the polyether ether ketone, the movement ability of the polyether ether ketone molecular chain decreases, resulting in the decrease of the wafer thickness and the spherulite radius in the crystallization process, and the degree of crystallization perfection shows a downward trend.

[0017] The present application can realize the synergistic control of crystallinity by formulating polyether ether ketone composite material, by using polyether ether ketone with different intrinsic viscosity, improve the crystallinity while improving the perfection of crystal structure. The crystallization perfection of polyether ether ketone with low intrinsic viscosity (0.38-0.59 dL / g) is relatively low, but its molecular chain movement ability is stronger, which can play the role of "lubricant" in the crystallization process, promote the crystallization process of the whole system. The crystallization ability of polyether ether ketone with high intrinsic viscosity (0.95-1.3 dL / g) is poor, but its high entangled molecular chain structure can form a three-dimensional network structure in the amorphous region, which can limit the movement of molecular chains in the amorphous region, thereby improving the overall heat resistance of the material. The polyether ether ketone with medium intrinsic viscosity (0.7-0.88 dL / g) has better crystallization kinetics conditions, and the structure of the crystal region is easy to form during processing, which can effectively limit the thermal motion of molecular chains and improve the heat deformation temperature of the material.

[0018] In addition, by introducing polyether ether ketone with medium intrinsic viscosity, although it has better crystallization kinetics conditions and can form more perfect crystal structure during processing, the melting point of the polyether ether ketone composite material increases with the increase of the intrinsic viscosity, and by compounding a certain amount of polyether ether ketone with low intrinsic viscosity, the trend of the melting point increasing with the increase of the intrinsic viscosity can be limited, and after exceeding a certain threshold, the melting point decreases due to the decrease of the crystallization perfection.

[0019] Preferably, the thermally conductive material comprises a nitride ceramic material and / or a carbon-based thermally conductive material.

[0020] Preferably, the thermally conductive material comprises a combination of a nitride ceramic material and a carbon-based thermally conductive material.

[0021] The ceramic-carbon composite material created by combining nitride ceramics with carbon-based thermally conductive materials has the core advantage of realizing the synergy and complementarity of "structural strength" and "thermal conduction flood discharge" in improving the heat distortion temperature, overcoming the inherent defects of single material, achieving the effect of 1+1>2, which is specifically reflected in the following aspects:

[0022] (1) Synergistic enhancement and complementary advantages: nitride ceramics provide a rigid skeleton that is strong, high-temperature resistant, oxidation resistant and high-strength. This is the "load-bearing wall" that does not deform at high temperatures. The carbon-based thermally conductive material is filled between the nitride ceramic skeleton to form a high-efficiency three-dimensional thermal conduction network, which is the "highway" for quickly discharging heat.

[0023] (2) The combination of thermal conductivity and strength: The thermal conductivity of single nitride ceramics is usually limited, and heat is easy to accumulate. Single carbon-based thermal conductive materials have excellent thermal conductivity, but low high-temperature strength and are easy to oxidize. The combined composite material can not only use the carbon network to rapidly disperse the heat of hot spots, but also rely on the ceramic skeleton to maintain shape and strength at high temperatures.

[0024] (3) Achieving isotropic thermal conductivity: The thermal conductivity of highly oriented carbon-based thermal conductive materials has strong directionality (high in-plane thermal conductivity, low between planes), which may form a thermal barrier in practical applications. By embedding it in an isotropic ceramic matrix, the overall direction of heat flow can be effectively controlled, achieving more uniform and controllable heat dissipation.

[0025] (4) Significantly improving thermal shock resistance: Nitride ceramics have high strength, but low thermal expansion coefficient and are sensitive to thermal shock. The thermal expansion coefficient of carbon-based thermal conductive materials is usually lower, and the high thermal conductivity can quickly homogenize the temperature difference. The combined thermal conductive network quickly balances the temperature and reduces internal thermal stress; at the same time, the appropriate combination of two-phase interfaces can deflect and bridge cracks, consume their energy, and greatly improve the material's ability to resist rapid cooling and heating without breaking (i.e. thermal shock resistance). This is a key factor in indirectly but extremely important to improve the upper limit of "thermal deformation temperature" for use.

[0026] Preferably, the nitride ceramic material comprises silicon nitride and / or aluminum nitride.

[0027] Preferably, the carbon-based thermal conductive material comprises any one or a combination of at least two of silicon carbide, graphite or graphene.

[0028] Preferably, the toughening agent comprises any one or a combination of at least two of styrene-acrylonitrile copolymer, epoxy group-containing polymer or polymethyl methacrylate.

[0029] Preferably, the polyether ether ketone composite material further comprises 0.1-1 parts by weight of an antioxidant and / or 0.1-1 parts by weight of a lubricant.

[0030] For example, 0.1-1 parts can be 0.1 parts, 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts or 1 part, etc.

[0031] Preferably, the antioxidant comprises any one or a combination of at least two of hindered phenolic antioxidants, phosphite antioxidants or thioester antioxidants.

[0032] Preferably, the lubricant comprises any one or a combination of at least two of pentaerythritol stearate, polydimethylsiloxane or ethylene bis-stearamide.

[0033] In a second aspect, the present application provides a method for preparing the polyether ether ketone composite material according to the first aspect, the method comprising the following steps:

[0034] After mixing the components of the polyether ether ketone composite material in proportion, melt granulation is performed to obtain the polyether ether ketone composite material.

[0035] Preferably, the mixing time is 5-20 min, for example, it can be 5 min, 10 min, 15 min or 20 min.

[0036] Preferably, the melt granulation is to put the mixture obtained by mixing into a twin-screw extruder, and after extrusion, drying and granulation, the polyether ether ketone composite material is obtained.

[0037] Preferably, the temperature of each zone of the twin-screw extruder is as follows: the temperature of the first zone is 50-100℃, the temperature of the second zone is 50-100℃, the temperature of the third zone is 300-400℃, the temperature of the fourth zone is 300-400℃, the temperature of the fifth zone is 300-400℃, the temperature of the sixth zone is 300-400℃, the temperature of the seventh zone is 300-400℃, the temperature of the eighth zone is 300-400℃, the temperature of the ninth zone is 300-400℃, the temperature of the tenth zone is 300-400℃, and the temperature of the eleventh zone is 300-400℃.

[0038] Preferably, the temperature of each zone of the twin-screw extruder is as follows: the temperature of the first zone is 50-100℃, the temperature of the second zone is 50-100℃, the temperature of the third zone is 300-400℃, the temperature of the fourth zone is 300-400℃, the temperature of the fifth zone is 300-400℃, the temperature of the sixth zone is 300-400℃, the temperature of the seventh zone is 300-400℃, the temperature of the eighth zone is 300-400℃, the temperature of the ninth zone is 300-400℃, the temperature of the tenth zone is 300-400℃, and the temperature of the eleventh zone is 300-400℃.

[0039] Preferably, the screw rotation speed of the twin-screw extruder is 500-600 r / min, for example, it can be 500 r / min, 520 r / min, 540 r / min, 560 r / min, 580 r / min or 600 r / min.

[0040] Preferably, the residence time of the mixture in the twin-screw extruder is 1-5 min, for example, it can be 1 min, 2 min, 3 min, 4 min or 5 min.

[0041] In a third aspect, the present application provides the use of the polyether ether ketone composite material according to the first aspect in aviation parts, automobile parts, robot spinal fusion cages or artificial joints.

[0042] Compared with the prior art, the present application has at least the following beneficial effects:

[0043] (1) The polyether ether ketone composite material provided by the application has high heat resistance, and the heat distortion temperature of the polyether ether ketone composite material is improved while the rigidity and toughness balance of the polyether ether ketone composite material is maintained.

[0044] (2) The polyether ether ketone composite material provided by the application has the characteristics of rigidity and toughness balance and excellent heat resistance, and the bending modulus of the polyether ether ketone composite material can reach 3150-3450 MPa, the bending strength can reach 132-148 MPa, and the heat distortion temperature can reach 143-149℃. DETAILED DESCRIPTION

[0045] To facilitate understanding of the present application, the present application is illustrated as follows. It should be understood by those skilled in the art that the examples are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0046] In the following specific embodiments of the present application, the specific information of the materials used is as follows:

[0047] Polyether ether ketone A, KetaSpire® KT-880, purchased from Syensqo, with an intrinsic viscosity of 0.42 dL / g;

[0048] Polyether ether ketone B, VESTAKEEP® 2000P, purchased from Evonik, with an intrinsic viscosity of 0.8 dL / g;

[0049] Polyether ether ketone C, Zhejiang Pengfulong 8100, purchased from Zhejiang Pengfulong, with an intrinsic viscosity of 1.13 dL / g;

[0050] Styrene-acrylonitrile copolymer, BMAT, purchased from Shanghai Haisenweiyuan Chemical Co., Ltd.;

[0051] Silicon nitride, purchased from Jiangxi Silicon Nitride New Material Co., Ltd.;

[0052] Aluminum nitride, purchased from Liaoning Desheng Ceramics;

[0053] Silicon carbide, purchased from Tianyue Advanced;

[0054] Graphene, purchased from Nanjing Jicang Nanometer Technology Co., Ltd.;

[0055] Antioxidant 168, purchased from BASF.

[0056] Examples 1-5 and Comparative Examples 1-5

[0057] Example 1-5 and Comparative Example 1-5 respectively provide a polyether ether ketone composite material and a preparation method thereof, components of the polyether ether ketone composite material are shown in Table 1-2 (amounts of each component in Table 1-2 are all weight parts), wherein “--” represents that the component is not added.

[0058] The preparation method of the polyether ether ketone composite material is as follows:

[0059] The components of the polyether ether ketone composite material are mixed, stirred for 15 min, and the mixed mixture is added to a double screw extruder for melt co-extrusion, the extruder temperature: the temperature of the first zone is 50°C, the temperature of the second zone is 70°C, the temperature of the third zone is 380°C, the temperature of the fourth zone is 380°C, the temperature of the fifth zone is 380°C, the temperature of the sixth zone is 380°C, the temperature of the seventh zone is 370°C, the temperature of the eighth zone is 370°C, the temperature of the ninth zone is 370°C, the temperature of the tenth zone is 370°C, the temperature of the eleventh zone is 375°C, the screw rotation speed of the extruder is 550 r / min, the residence time is 3 min, and after extrusion by the screw, cooling, blowing dry and granulation are performed to obtain the polyether ether ketone composite material.

[0060] Table 1

[0061]

[0062] Table 2

[0063]

[0064] Test method

[0065] The properties of the polyether ether ketone composite material provided by the above examples and comparative examples are characterized, and the specific test method is as follows:

[0066] Flexural modulus (MPa), flexural strength: tested according to the test method of “ISO-178-2010”, the test span is 64 mm, and the experimental rate is 2 mm / min.

[0067] Heat distortion temperature: tested according to the test method of “ISO75Af”, and the test pressure is 1.80 MPa.

[0068] The test data is shown in Table 3:

[0069] Table 3

[0070]

[0071] From the test results, it can be seen that:

[0072] (1) As can be seen from Examples 1 to 5, the bending modulus of the composite material can reach 3150-3450 MPa, the bending strength can reach 132-148 MPa, and the heat distortion temperature can reach 143-149℃ by formulating the polyether ether ketone composite material, and the composite material has the characteristics of rigidity and toughness balance, excellent heat resistance.

[0073] (2) As can be seen from Examples 1 and 4-5, by further compounding nitride ceramic material and carbon-based thermal conductive material, the addition of nitride ceramic material makes up for the mechanical performance deficiency of carbon material itself, and the technical effects of high temperature resistance and excellent mechanical performance are achieved.

[0074] (3) As can be seen from Examples 1 and Comparative Examples 1-5, by compounding polyether ether ketone with different intrinsic viscosity, the crystallinity of the polyether ether ketone composite material is synergistically controlled, and the technical effects of synergistically improving the heat distortion temperature and mechanical properties of the composite material are achieved.

[0075] The applicant declares that the above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and those skilled in the art should understand that any changes or replacements within the technical scope disclosed by the present application can be easily thought of by any person skilled in the art, and all fall within the protection scope and disclosure scope of the present application.

Claims

1. A polyetheretherketone composite material, characterized in that, The polyetheretherketone composite material comprises the following components by weight: 15-45 parts of polyetheretherketone A, 20-40 parts of polyetheretherketone B, 20-40 parts of polyetheretherketone C, 1-20 parts of thermally conductive material, and 1-10 parts of toughening agent; The intrinsic viscosity of the polyetheretherketone A is 0.38-0.59 dL / g; The intrinsic viscosity of the polyetheretherketone B is 0.7-0.88 dL / g; The intrinsic viscosity of the polyetheretherketone C is 0.95-1.3 dL / g.

2. The polyetheretherketone composite material according to claim 1, characterized in that, The thermally conductive material includes nitride ceramic materials and / or carbon-based thermally conductive materials; Preferably, the thermally conductive material comprises a combination of nitride ceramic material and carbon-based thermally conductive material.

3. The polyetheretherketone composite material according to claim 2, characterized in that, The nitride ceramic material includes silicon nitride and / or aluminum nitride; Preferably, the carbon-based thermally conductive material includes any one or a combination of at least two of silicon carbide, graphite, or graphene.

4. The polyetheretherketone composite material according to any one of claims 1-3, characterized in that, The toughening agent includes any one or a combination of at least two of the following: styrene-acrylonitrile copolymer, polymer containing epoxy groups, or polymethyl methacrylate.

5. The polyetheretherketone composite material according to any one of claims 1-4, characterized in that, The polyetheretherketone composite material further includes 0.1-1 parts antioxidant and / or 0.1-1 parts lubricant by weight.

6. The polyetheretherketone composite material according to claim 5, characterized in that, The antioxidants include any one or a combination of at least two of hindered phenolic antioxidants, phosphite antioxidants, or thioester antioxidants; Preferably, the lubricant comprises any one or a combination of at least two of pentaerythritol stearate, polydimethylsiloxane, or ethylene bis-stearamide.

7. A method for preparing the polyetheretherketone composite material according to any one of claims 1-6, characterized in that, The preparation method includes the following steps: The components of the polyether ether ketone composite material are mixed in proportion and then melt-granulated to obtain the polyether ether ketone composite material.

8. The preparation method according to claim 7, characterized in that, The mixing time is 5-20 min; Preferably, the melt granulation involves feeding the mixed material into a twin-screw extruder, and after extrusion, drying, and pelletizing, obtaining the polyether ether ketone composite material.

9. The preparation method according to claim 8, characterized in that, The temperatures of each zone of the twin-screw extruder are as follows: Zone 1: 50-100℃; Zone 2: 50-100℃; Zone 3: 300-400℃; Zone 4: 300-400℃; Zone 5: 300-400℃; Zone 6: 300-400℃; Zone 7: 300-400℃; Zone 8: 300-400℃; Zone 9: 300-400℃; Zone 10: 300-400℃; Zone 11: 300-400℃. Preferably, the screw speed of the twin-screw extruder is 500-600 r / min; Preferably, the residence time of the mixture in the twin-screw extruder is 1-5 min.

10. The application of a polyetheretherketone composite material as described in any one of claims 1-6 in aerospace parts, automotive parts, robotic spinal fusion devices, or artificial joints.

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