A polyetheretherketone (PEEK) cable material and its preparation method

Abstract

This invention provides a polyetheretherketone (PEEK) cable compound and its preparation method. The PEEK cable compound comprises the following components in parts by weight: 60-80 parts of a PEEK composite, 0.5-2 parts of filler, 0.5-3 parts of lubricant, and 10-30 parts of a polyetherimide composite material. The PEEK composite is a mixture of PEEK and a titanium dioxide / PEEK composite material, with a mass ratio of PEEK to the titanium dioxide / PEEK composite material of 1:0.3-0.6. The titanium dioxide / PEEK composite material is prepared from titanium dioxide pretreated material and PEEK. When using the components and contents provided by this invention to prepare the PEEK cable compound, the resulting PEEK cable compound exhibits high tensile strength, elongation at break, and flexural strength, as well as good salt spray resistance and aging resistance. Although the tensile strength decreases somewhat after prolonged exposure to salt spray, the decrease is not significant, thus increasing the service life of the PEEK cable compound.

Description

Technical Field

[0001] This invention belongs to the field of wire and cable materials technology, specifically relating to a polyetheretherketone (PEEK) cable material and its preparation method. Background Technology

[0002] Polyetheretherketone (PEEK) is a polymer composed of repeating units containing one ketone bond and two ether bonds in its main chain structure, belonging to the category of special polymer materials. PEEK is widely used in aerospace, automotive, electrical, marine engineering, and medical fields due to its excellent thermal stability, flame retardancy, hydrolysis resistance, electrical insulation, and ease of processing. However, the use of PEEK in the manufacture of wires and cables is significantly limited by its characteristics such as deterioration of mechanical properties after prolonged exposure to salt spray environments and low flexural strength at high temperatures.

[0003] Patent CN103450631B discloses a polyetheretherketone (PEEK) cable material and its preparation method. The material is prepared by combining PEEK, lubricant, nucleating agent, compatibilizer, and hardness modifier. However, when used in wires and cables, the resulting cable material exhibits characteristics such as deterioration of mechanical properties in long-term salt spray environments and low bending strength in high-temperature environments. This makes it unsuitable for the current development trend of high-end cables. Furthermore, the cable's heat dissipation performance deteriorates, leading to stress concentration during operation and significantly reducing its usability and operational stability. It also struggles to meet the requirements of long-term, complex operating conditions.

[0004] The existing technology for using polyetheretherketone (PEEK) in wires and cables suffers from problems such as deterioration of mechanical properties in long-term salt spray environments and low bending strength in high-temperature environments. How to produce PEEK cable materials that can maintain good mechanical properties in long-term salt spray environments and have high bending strength in high-temperature environments to meet the needs of wire and cable manufacturing is a problem that this invention urgently needs to solve. Summary of the Invention

[0005] The purpose of this invention is to provide a polyetheretherketone (PEEK) cable material and its preparation method to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: On one hand, the present invention provides a polyetheretherketone cable material, which comprises the following components in parts by weight: 60-80 parts of polyetheretherketone composite, 0.5-2 parts of filler, 0.5-3 parts of lubricant, and 10-30 parts of polyetherimide composite material; The polyetheretherketone (PEEK) composite is a mixture of PEEK and titanium dioxide / PEEK composite materials, with a mass ratio of PEEK to titanium dioxide / PEEK composite materials of 1:0.3-0.6. The raw materials for preparing titanium dioxide / polyetheretherketone composite materials include titanium dioxide pretreated material and polyetheretherketone.

[0007] As a further improvement, the preparation method of the titanium dioxide / polyetheretherketone composite material includes the following steps: The titanium dioxide pretreated material was mixed with polyetheretherketone (PEEK) and then transferred to a ball mill jar for ball milling. The milled material was then calcined. After calcination, the titanium dioxide / PEEK composite material was obtained.

[0008] As a further improvement, the raw materials for preparing polyetherimide composite materials include polyetherimide particles and expandable graphite powder.

[0009] As a further improvement, the preparation method of the polyetherimide composite material includes the following steps: (1.1) Add polyetherimide particles and amide organic solvent to the reaction vessel, stir under heating until dissolved, then cool to room temperature, pour the substance in the reaction vessel into deionized water, stir until a white filamentous substance is obtained, soak in deionized water, crush with a pulverizer, ultrasonically disperse, dry, crush and sieve to obtain pretreated material one; (1.2) The expandable graphite powder is placed in a tube furnace and heated, then taken out and cooled to room temperature, and then crushed to obtain pre-treated material II; pre-treated material II and pre-treated material I are simultaneously placed in a pulverizer and crushed and sieved to obtain a mixture; the obtained mixture is placed in a twin-screw extruder for melt blending to obtain polyetherimide composite material.

[0010] As a further improvement, the mass of the titanium dioxide pretreated material is 2wt%-8wt% of the mass of polyetheretherketone.

[0011] As a further improvement, the mass of the titanium dioxide pretreated material is 5wt%-7wt% of the mass of polyetheretherketone.

[0012] As a further improvement, the titanium dioxide pretreatment includes the following steps: Tetrabutyl titanate was placed in an alkane organic solvent, magnetically stirred, and hydrochloric acid solution was added dropwise until complete acid hydrolysis. The acid-hydrolyzed material was then placed in a reaction vessel for hydrothermal reaction. After the reaction was completed, the mixture was cooled to room temperature, centrifuged to obtain the precipitate, ultrasonically dispersed, centrifuged, vacuum dried, and ground to obtain the titanium dioxide pretreated material.

[0013] As a further improvement, the filler also includes at least one of nano-calcium carbonate, nano-barium sulfate, nano-magnesium phosphate, nano-zinc oxide, and nano-silica.

[0014] As a further improvement, the lubricant is at least one of calcium stearate, polyethylene wax, and boron nitride.

[0015] As a further improvement, the alkane organic solvent is at least one of n-hexane, n-pentane, and cyclohexane.

[0016] On the other hand, the present invention also provides a method for preparing polyetheretherketone cable material, comprising the following steps: Polyetheretherketone (PEEK) composite, lubricant, polyetherimide composite, and filler are added to a twin-screw extruder for melt extrusion granulation to obtain PEEK cable material.

[0017] Furthermore, the preparation method of polyetheretherketone cable material includes the following steps: The polyetheretherketone (PEEK) composite was dried at 140-160℃ for 2-4 hours, and the polyetherimide (PEI) composite was dried at 100-140℃ for 4-6 hours. The dried PEEK composite, PEI, filler, and lubricant were then added to a twin-screw extruder for granulation. The extruder temperatures for each zone during granulation were set as follows: Zone 1: 340-350℃; Zone 2: 360-380℃; Zone 3: 360-380℃; Zone 4: 360-380℃; Extruder flange: 340-360℃; Extruder die: 340-355℃. This yielded the PEEK cable material. The twin-screw extruder speed was 200-400 r / min.

[0018] Compared with the prior art, the beneficial effects of the present invention are: when the components and contents provided by the present invention are used to prepare polyetheretherketone cable materials, the resulting polyetheretherketone cable materials have high tensile strength, elongation at break and flexural strength, and good salt spray resistance and aging resistance. Although the tensile strength decreases after being placed in a salt spray environment for a long time, the decrease in tensile strength is not significant, thus increasing the service life of the polyetheretherketone cable materials. Detailed Implementation

[0019] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0020] In the following examples, the monomers and related reagents used were all commercially available. Polyetheretherketone (PEEK) was purchased from Dongguan Jinxiang Plastic New Materials Co., Ltd., product number KT-880NT; commercially available titanium dioxide was purchased from Shanghai Zhenlishi Network Technology Co., Ltd., product number TiO2 P25; polyetherimide granules were purchased from Dongguan Hongjiexing Plastic Co., Ltd., product number 1010-1000; and expandable graphite powder was purchased from Qingdao Haishuo Graphite Co., Ltd., product number HD-SM027.

[0021] The method for preparing titanium dioxide pretreated material includes the following steps: 10 mL of tetrabutyl titanate was placed in 110 mL of n-hexane and magnetically stirred for 5 min at 600 r / min. Then, hydrochloric acid solution (0.9 mol / L, 20 mL) was slowly added dropwise to allow the system to be completely acidified within 10 min. The acidified material was then placed in a reaction vessel for hydrothermal reaction at 180 °C for 30 h. After cooling to room temperature, the precipitate was obtained by centrifugation at 6000 r / min for 5 min. The precipitate was ultrasonically dispersed in 60 mL of anhydrous ethanol. The centrifugation and ultrasonic dispersion were repeated 4 times. The precipitate was then dried under 0.1 bar negative pressure for 20 h (drying temperature was 60 °C), ground, and sieved (pore size 200 μm) to obtain the titanium dioxide pretreated material.

[0022] The preparation method of titanium dioxide / polyetheretherketone composite material A includes the following steps: Titanium dioxide pretreated material and polyetheretherketone (PEEK) were mixed at a mass ratio of 1:15 and then transferred to a ball mill jar for ball milling. The ball milling beads were mixed with 3 mm, 5 mm and 10 mm zirconia ball milling beads at a mass ratio of 2:3:1, and the number of ball milling beads was 5 times that of the titanium dioxide pretreated material and PEEK mixture. The ball milling speed was 200 r / min and the ball milling time was 2 hours. Anhydrous ethanol was used as the medium for ball milling. After the ball milling material was vacuum dried at 80℃ to remove anhydrous ethanol, it was calcined in an inert environment at 400℃ for 4 min to obtain titanium dioxide / PEEK composite material A.

[0023] The preparation method of titanium dioxide / polyetheretherketone composite material B includes the following steps: Commercially available titanium dioxide and polyetheretherketone (PEEK) were mixed at a mass ratio of 1:15 and then transferred to a ball mill jar for ball milling. The grinding balls were mixed with 3 mm, 5 mm and 10 mm zirconia grinding balls at a mass ratio of 2:3:1, with the grinding balls being 5 times the amount of the titanium dioxide pretreated material and the PEEK mixture. The ball milling speed was 200 r / min and the ball milling time was 2 hours. Anhydrous ethanol was used as the medium for ball milling. After the ball-milled material was vacuum dried at 80℃ to remove the anhydrous ethanol, it was calcined in an inert environment at 400℃ for 4 min to obtain titanium dioxide / PEEK composite material A.

[0024] The preparation method of polyetherimide composite material A includes the following steps: (2.1) 100g of polyetherimide particles and 1.1L of N,N-dimethylacetamide were added to the reaction vessel and stirred at a heating temperature of 120℃ until dissolved. Then, the mixture was cooled to room temperature. The contents of the reaction vessel were poured into 4L of deionized water and stirred until a white filamentous substance was obtained. The white filamentous substance was then soaked in deionized water for 12h, pulverized, dispersed in ethanol, sonicated for 4h, dried in an oven at 115℃, pulverized again, and sieved (with a sieve aperture of 200 μm) to obtain pretreated material one. (2.2) The expandable graphite powder was placed in a tube furnace at a temperature of 900℃. After 50s, it was taken out and cooled to room temperature. Then it was crushed by a pulverizer to obtain pretreatment material II. Pretreatment material II and pretreatment material I with a mass ratio of 1:4 were simultaneously placed in a pulverizer for crushing and sieved (the sieve aperture was 200 μm) to obtain a mixture. The obtained mixture was put into a twin-screw extruder for melt blending to obtain polyetherimide composite material A. The temperature of the twin-screw extruder was set to 370℃ and the rotation speed of the twin-screw extruder was 300r / min.

[0025] The preparation method of polyetherimide composite material B is basically the same as that of polyetherimide composite material A, except that step (2.2) is modified to "put expandable graphite powder and pretreatment material in a mass ratio of 1:4 into a pulverizer for crushing, sieve (the sieve aperture is 200 μm) to obtain a mixture, put the obtained mixture into a twin-screw extruder for melt blending to obtain polyetherimide composite material B, wherein the temperature of the twin-screw extruder is set to 370℃ and the rotation speed of the twin-screw extruder is 300r / min".

[0026] Example 1: A polyetheretherketone (PEEK) cable material comprising the following components in parts by weight: 50 parts of polyetheretherketone, 20 parts of titanium dioxide / PEEK composite material A, 1.5 parts of nano-silica, 0.5 parts of nano-zinc oxide, 2 parts of boron nitride, and 15 parts of polyetherimide composite material A.

[0027] Example 2: A polyetheretherketone (PEEK) cable material comprising the following components in parts by weight: 35 parts PEEK, 15 parts titanium dioxide / PEEK composite material A, 2 parts nano-silica, 1.5 parts boron nitride, and 20 parts polyetherimide composite material A.

[0028] Example 3: A polyetheretherketone (PEEK) cable material comprising the following components in parts by weight: 40 parts of polyetheretherketone, 20 parts of titanium dioxide / PEEK composite material A, 1.5 parts of nano zinc oxide, 2 parts of boron nitride, and 12 parts of polyetherimide composite material A.

[0029] Example 4: The composition and content of a polyether ether ketone cable material are basically the same as those in Example 1, except that "15 parts of polyetherimide composite material A" is replaced with "15 parts of polyetherimide composite material B".

[0030] Example 5: The composition and content of a polyether ether ketone cable material are basically the same as those in Example 1, except that "15 parts of polyetherimide composite material A" are replaced with "15 parts of pretreatment material".

[0031] Example 6: The composition and content of a polyetheretherketone cable material are basically the same as those in Example 1, except that "20 parts of titanium dioxide / polyetheretherketone composite material A" are replaced with "20 parts of titanium dioxide / polyetheretherketone composite material B".

[0032] Comparative Example 1: The composition and content of a polyetheretherketone (PEEK) cable material are basically the same as those in Example 1, except that "50 parts of PEEK and 20 parts of titanium dioxide / PEEK composite material A" are replaced with "35 parts of PEEK and 35 parts of titanium dioxide / PEEK composite material A".

[0033] Comparative Example 2: The composition and content of a polyetheretherketone (PEEK) cable material are basically the same as those in Example 1, except that "50 parts of PEEK and 20 parts of titanium dioxide / PEEK composite material A" are replaced with "70 parts of PEEK".

[0034] Comparative Example 3: The composition and content of a polyetheretherketone cable material are basically the same as those in Example 1, except that "50 parts of polyetheretherketone and 20 parts of titanium dioxide / polyetheretherketone composite material A" are replaced with "70 parts of polyetheretherketone", and "15 parts of polyetherimide composite material A" are replaced with "15 parts of polyetherimide".

[0035] The preparation methods of the polyetheretherketone cable materials of Examples 1-6 and Comparative Examples 1-3 include the following steps: The polyetheretherketone (PEEK) composite was dried at 150°C for 4 hours, and the polyetherimide (PEI) composite was dried at 120°C for 6 hours. The dried PEEK composite, PEI, filler, and lubricant were then fed into a twin-screw extruder for granulation. The extruder temperatures were set as follows: Zone 1: 345°C; Zone 2: 360°C; Zone 3: 380°C; Zone 4: 360°C; Extruder flange: 345°C; and Extruder die: 350°C. This yielded PEEK cable material. The twin-screw extruder speed was 250 r / min.

[0036] In the preparation methods of polyetheretherketone (PEEK) cable materials in Examples 1-6 and Comparative Examples 1-3, the PEEK composites involved are PEEK and / or titanium dioxide / PEEK composite material A and / or titanium dioxide / PEEK composite material B; the PEEK composite material is PEEK composite material A and / or PEEK composite material B and / or PEEK and / or pretreatment material one.

[0037] The test methods are as follows. For the bending strength test and aging resistance test, the polyetheretherketone (PEEK) cable material used is 90mm × 10mm × 4mm; for the tensile strength, elongation at break, and salt spray resistance test, the PEEK cable material used is 150mm × 10mm × 4mm. Tensile strength and elongation at break tests: Tested according to GB / T 1040.2-2022 standard, using 1A standard specimen, tensile rate 50 mm / min, test temperature 23℃, and relative humidity 50%; Bending strength test: Tested according to GB / T 9341-2022 standard, with a span-to-thickness ratio of 16:1, a support span of 64mm, and a loading rate of 2mm / min; Salt spray resistance test: The test was conducted using a salt spray test chamber according to the standard GB / T 2423.17-2008. The polyetheretherketone cable materials of Examples 1-6 and Comparative Examples 1-3 were exposed to a 5% NaCl solution at a temperature of 35°C and a spray volume of 1.5 mL / (80 cm²·h) for 30 days and 60 days, respectively. After rinsing with tap water for 10 min and deionized water for 2 min, they were dried at room temperature and allowed to stand for 24 h before the tensile strength was tested and the rate of change of tensile strength was calculated.

[0038] Aging resistance test: According to GB / T 7141-2021 standard, the bending strength is measured after heating at 300℃ for 300h and placing it in an environment with a temperature of 23℃ and a relative humidity of 50% for 24h. According to GB / T 9341-2022 standard, the bending strength is measured.

[0039] The test results are shown in Table 1, and are as follows: Table 1

[0040] As can be seen from the comparison between Examples 1 and Examples 4-5, the polyetherimide composite material prepared by the preparation method provided by the present invention is used to prepare polyetheretherketone cable material. The prepared polyetheretherketone cable material has high tensile strength, elongation at break and bending strength, good salt spray resistance, and the tensile strength does not decrease significantly when placed in a salt spray environment for a long time, and has better aging resistance. As can be seen from the comparison between Example 1 and Example 6, the titanium dioxide / polyetheretherketone composite material prepared by the preparation method provided by the present invention is used to prepare polyetheretherketone cable material. The prepared polyetheretherketone cable material has high tensile strength, elongation at break and bending strength, and good salt spray resistance and aging resistance. Although the tensile strength decreases after being placed in a salt spray environment for a long time, the decrease is not significant. As can be seen from the comparison of Example 1 and Comparative Example 1, when the polyetheretherketone composite material composed of polyetheretherketone and titanium dioxide / polyetheretherketone composite material provided by the present invention is within a suitable range, the polyetheretherketone cable material prepared has higher tensile strength, elongation at break and bending strength, and better salt spray resistance and aging resistance. When placed in a salt spray environment for a long time, the decrease in tensile strength is less obvious. As can be seen from the comparison of Example 1 and Comparative Example 2, when the polyetheretherketone composite is a mixture of polyetheretherketone and titanium dioxide / polyetheretherketone composite material, the polyetheretherketone cable material prepared has high tensile strength, elongation at break and flexural strength, and good salt spray resistance and aging resistance. As can be seen from the comparison of Example 1 and Comparative Example 3, when the polyetheretherketone composite is a mixture of polyetheretherketone and titanium dioxide / polyetheretherketone composite material, and the polyetherimide composite material prepared by the preparation method provided by the present invention is used to prepare polyetheretherketone cable material, the prepared polyetheretherketone cable material has high tensile strength, elongation at break and flexural strength, good salt spray resistance, and the tensile strength does not decrease significantly when placed in a salt spray environment for a long time, and has better aging resistance.

[0041] In summary, when the components and contents provided by this invention are used to prepare polyetheretherketone (PEEK) cable materials, the resulting PEEK cable materials have high tensile strength, elongation at break, and flexural strength, as well as good salt spray resistance and aging resistance. Although the tensile strength decreases somewhat when placed in a salt spray environment for a long time, the decrease is not significant, thus increasing the service life of the PEEK cable materials.

[0042] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A polyetheretherketone (PEEK) cable material, characterized in that: The polyetheretherketone (PEEK) cable material comprises the following components in parts by weight: 60-80 parts of polyetheretherketone composite, 0.5-2 parts of filler, 0.5-3 parts of lubricant, and 10-30 parts of polyetherimide composite material; The polyetheretherketone composite is a mixture of polyetheretherketone and titanium dioxide / polyetheretherketone composite material, wherein the mass ratio of polyetheretherketone to titanium dioxide / polyetheretherketone composite material is 1:0.3-0.6; The raw materials for preparing the titanium dioxide / polyetheretherketone composite material include titanium dioxide pretreated material and polyetheretherketone.

2. The polyetheretherketone cable material according to claim 1, characterized in that: The preparation method of the titanium dioxide / polyetheretherketone composite material includes the following steps: The titanium dioxide pretreated material was mixed with polyetheretherketone (PEEK) and then transferred to a ball mill jar for ball milling. The milled material was then calcined. After calcination, the titanium dioxide / PEEK composite material was obtained.

3. The polyetheretherketone cable material according to claim 2, characterized in that: The raw materials for preparing the polyetherimide composite material include polyetherimide particles and expandable graphite powder.

4. The polyetheretherketone cable material according to claim 3, characterized in that: The preparation method of the polyetherimide composite material includes the following steps: (1.1) Add polyetherimide particles and amide organic solvent to the reaction vessel, stir under heating until dissolved, then cool to room temperature, pour the substance in the reaction vessel into deionized water, stir until a white filamentous substance is obtained, soak in deionized water, crush with a pulverizer, ultrasonically disperse, dry, crush and sieve to obtain pretreated material one; (1.2) The expandable graphite powder is placed in a tube furnace and heated, then taken out and cooled to room temperature, and then crushed to obtain pre-treated material II; pre-treated material II and pre-treated material I are simultaneously placed in a pulverizer and crushed and sieved to obtain a mixture; the obtained mixture is placed in a twin-screw extruder for melt blending to obtain polyetherimide composite material.

5. The polyetheretherketone cable material according to claim 2, characterized in that: The mass of the titanium dioxide pretreated product is 2wt%-8wt% of the mass of polyetheretherketone.

6. The polyetheretherketone cable material according to claim 4, characterized in that: The titanium dioxide pretreated product includes the following steps: Tetrabutyl titanate was placed in an alkane organic solvent, magnetically stirred, and hydrochloric acid solution was added dropwise until complete acid hydrolysis. The acid-hydrolyzed material was then placed in a reaction vessel for hydrothermal reaction. After the reaction was completed, the mixture was cooled to room temperature, centrifuged to obtain the precipitate, ultrasonically dispersed, centrifuged, vacuum dried, and ground to obtain the titanium dioxide pretreated material.

7. The polyetheretherketone cable material according to claim 6, characterized in that: The filler also includes at least one of nano-calcium carbonate, nano-barium sulfate, nano-magnesium phosphate, nano-zinc oxide, and nano-silica.

8. The polyetheretherketone cable material according to claim 3, characterized in that: The lubricant is at least one of calcium stearate, polyethylene wax, and boron nitride.

9. The polyetheretherketone cable material according to claim 1, characterized in that: The alkane organic solvent is at least one of n-hexane, n-pentane, and cyclohexane.

10. A method for preparing a polyetheretherketone cable material according to any one of claims 1-9, characterized in that: Includes the following steps: Polyetheretherketone (PEEK) composite, lubricant, polyetherimide composite, and filler are added to a twin-screw extruder for melt extrusion granulation to obtain PEEK cable material.

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