A high temperature resistant composite multi-core cable

Abstract

The present invention relates to a high-temperature resistant composite multi-core cable, belonging to the technical field of special cables. The cable comprises a composite core and a modified PEEK sheath, wherein the modified PEEK sheath comprises: 8.5-12wt% of a heat-resistant toughening agent, 3.5-5wt% of aluminum nitride powder, 2-3wt% of a thermal stabilizer, 1.5-2.2wt% of a lubricant, and 3.2-4.5wt% of a friction reducer, with the remainder being PEEK resin; the hydroxyl and secondary amine groups in the modified monomer block segments interact as hydrogen donors with the ketone groups in the molecular chain of PEEK, and simultaneously chelate and bind with the aluminum nitride particles to form a dual anchoring, having a stable high-temperature toughening effect, and maintaining the high strength performance of the PEEK material while effectively toughening to meet the requirements of cable protection.

Description

Technical Field

[0001] The present invention belongs to the technical field of special cables, and in particular relates to a high-temperature resistant composite multi-core cable. Background Art

[0002] High-temperature resistant cables are key materials in the fields of power transmission, aerospace, metallurgy, petrochemicals, etc. They need to maintain insulation performance, mechanical strength and long-term stability at high temperatures. Traditional polyolefin sheathing materials such as PVC and PE are prone to softening and deformation at high temperatures, resulting in protection failure. Moreover, with the upgrading of the demand for high-temperature resistance of cables in the fields of aerospace, new energy, etc., the performance of existing high-temperature resistant materials such as phenolic materials and silicone rubber materials has gradually become difficult to meet. Although inorganic sheathing materials are resistant to high temperatures, they have poor flexibility and a large bending radius, which makes cable laying difficult and has a high density, which does not meet the lightweight requirements, especially in the aerospace field.

[0003] Polyetheretherketone (PEEK) is a polymer composed of repeating units containing one ketone bond and two ether bonds in its main chain structure. It has excellent heat resistance (long-term operating temperature of 260°C), chemical stability and mechanical strength, making it an ideal material for high-end cable sheaths.

[0004] However, the inherent high rigidity and low toughness of PEEK materials limit their application in complex working conditions. In the existing technology, PEEK is toughened and modified to meet the protection needs of cables. Since the processing temperature of PEEK materials reaches above 350°C, conventional toughening agents have problems such as degradation and volatilization during high-temperature processing. Existing toughening materials are still mainly high-temperature resistant silicone preparations, such as high-molecular-weight silicone materials, which can effectively improve the toughness of PEEK materials to adapt to cable protection; however, they have poor compatibility with the PEEK matrix, are prone to phase separation, and thermal migration during high-temperature service leads to deterioration of the performance of the PEEK material, limiting the high-performance utilization of PEEK materials. Summary of the Invention

[0005] In order to solve the technical problems mentioned in the background technology, the purpose of the present invention is to provide a high-temperature resistant composite multi-core cable.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A high-temperature resistant composite multi-core cable comprising a composite core and a modified PEEK sheath;

[0008] The modified PEEK sheath comprises the following components: 8.5-12wt% heat-resistant toughening agent, 3.5-5wt% aluminum nitride powder, 2-3wt% heat stabilizer, 1.5-2.2wt% lubricant, 3.2-4.5wt% friction reducer, and the balance is PEEK resin.

[0009] Wherein, the heat-resistant toughening agent is prepared by the following method:

[0010] Step A1: Premix tetraethylenepentamine and anhydrous tetrahydrofuran, introduce dry nitrogen protection, add ZIF-8 (dissolved in DMF), mix, control the temperature in a water bath at 55-65°C, slowly add allyl glycidyl ether, and stir to react for 2.5-3.2 hours. After the reaction is complete, remove tetrahydrofuran by rotary evaporation to obtain a modified monomer;

[0011] In the reaction of step A1 above, the ratio of tetraethylenepentamine, allyl glycidyl ether, ZIF-8 and anhydrous tetrahydrofuran is 0.1 mol: 0.2 mol: 25-30 mg: 150-200 mL. Under the catalysis of ZIF-8, tetraethylenepentamine and allyl glycidyl ether are effectively ring-opened at low temperature. The specific reaction route is as follows:

[0012]

[0013] Step A2: Take the modified monomer, mercapto-terminated silicone oil and acetone and pre-mix them, then add the photosensitizer and mix them evenly. Use a UV mercury lamp to apply 65-80mw / cm 2 UV irradiation and stirring reaction for 5.5-7h, after the reaction is completed, acetone is removed by rotary evaporation to obtain a heat-resistant toughening agent;

[0014] In the reaction of step A2 above, the ratio of the modified monomer, the thiol content of the terminal thiol silicone oil, the photosensitizer and acetone is 10 mmol: 25-30 mmol: 1.6-2.1 g: 300-350 mL. Under light initiation, the modified monomer and the terminal thiol silicone oil undergo click addition to form a macromolecular compound containing an organosilicon segment.

[0015] Preferably, the aluminum nitride powder is a submicron-sized powder, which contains a large number of chelating active sites on the surface and can maintain a certain degree of dispersibility at this particle size.

[0016] Preferably, the thermal stabilizer is potassium titanate whiskers, which improve the tear resistance and thermal shock resistance of the matrix and enhance the stability under instantaneous high temperatures.

[0017] Preferably, the lubricant is octaphenyl-POSS, which has good thermal stability and is compatible with the processing temperature of PEEK. As a high-temperature internal lubricating material, it is beneficial to the molding of the sheath.

[0018] Preferably, the friction reducer is a compound of polytetrafluoroethylene and molybdenum disulfide to reduce the friction of the sheath and improve the anti-wear performance of the sheath.

[0019] A high-temperature resistant composite multi-core cable is prepared by the following method: uniformly mixing the raw materials of various components, using an extruder to melt extrude the raw materials at 380-390°C to prepare a sleeve, cooling the sleeve to 260-280°C, inserting a composite core into the sleeve for roller-compression compounding, and forming a modified PEEK sheath on the surface of the composite core after cooling to obtain a high-temperature resistant composite multi-core cable.

[0020] Beneficial effects of the present invention:

[0021] The present invention introduces submicron aluminum nitride powder and independently developed heat-resistant toughening agent into the PEEK matrix for synergistic toughening modification, maintaining the high strength performance of the PEEK material under the premise of effective toughening to meet the requirements of cable protection; the heat-resistant toughening agent is prepared by the ring-opening reaction of allyl glycidyl ether and diethylenetriamine, introducing terminal allyl groups to form a modified monomer, and then the modified monomer is photo-initiated and polymerized with terminal mercapto silicone oil to form a macromolecular compound, thus obtaining the heat-resistant toughening agent; compared with the existing organosilicon toughening system, the advantages of the present invention are that the hydroxyl and secondary amine groups in the block chain of the modified monomer act as hydrogen donors to form interactions with the ketone groups in the molecular chain of PEEK The silicone chain is coiled around the outside of the PPEK molecular chain, which toughens the PEEK matrix and improves its protective performance in the sheath material. The heat-resistant toughening agent with a large molecular structure and silicone chains as the main body has good heat resistance. The modified monomer block segments form a chelation effect and combine with aluminum nitride particles. The high thermal conductivity of aluminum nitride compensates for the lack of heat resistance at the block position, thereby improving the overall thermal stability of the heat-resistant toughening agent molecule. In addition, the modified monomer blocks form a double anchoring through the interaction with the PEEK molecular chain and aluminum nitride particles, effectively reducing its migration at high temperatures, thereby exerting a stable and long-lasting toughening effect. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0023] Example 1: Preparation of a high-temperature resistant composite multi-core cable. The specific implementation process is as follows:

[0024] (1) Preparation of heat-resistant toughening agent

[0025] Step A1: 0.1 mol of tetraethylenepentamine and 200 mL of anhydrous tetrahydrofuran were premixed, and dry nitrogen was introduced until a stable airflow escaped. 30 mg of ZIF-8 was dissolved in DMF and then added to the mixture. The temperature of the water bath was controlled at 65°C. 0.2 mol of allyl glycidyl ether was slowly added and stirred for 2.5 hours. After the reaction was completed, the tetrahydrofuran was removed by rotary evaporation to obtain a modified monomer.

[0026] Step A2: Take the modified monomer and X-22-167B type mercapto-terminated silicone oil, and pre-mix them with 350 mL of acetone according to the molar ratio of the mercapto content of the modified monomer and the mercapto-terminated silicone oil being 10 mmol:30 mmol. Then add 2.1 g of the photosensitizer DMPA (benzoin dimethyl ether) and mix well. Apply 80 mW / cm2 of ultraviolet light with a 365 nm mercury lamp. 2 The mixture was irradiated with ultraviolet light and stirred for reaction for 5.5 hours. After the reaction was completed, the acetone was removed by rotary evaporation to obtain a heat-resistant toughening agent.

[0027] (2) Preparation of high temperature resistant composite multi-core cables

[0028] The materials are prepared according to the following components: 8.5wt% heat-resistant toughening agent, which is homemade in this embodiment; 3.5wt% aluminum nitride powder, which is GK-AlN-002 submicron powder with an average particle size of 500nm; 3wt% heat stabilizer, which is commercially available potassium titanate whiskers; 2.2wt% lubricant, which is industrial-grade octaphenyl-POSS; 4.5wt% friction reducer, which is a mixture of polytetrafluoroethylene and molybdenum disulfide powders in a weight ratio of 2:1; the remainder is PEEK-3600G resin raw material.

[0029] The above raw materials are mixed evenly in a high-speed mixer, and the mixture is fed into a twin-screw extruder. The temperature of the plasticizing zone is controlled at 380°C for melt extrusion to prepare a sleeve. After the sleeve is cooled to 260°C, it is inserted into the composite wire core and roller-compounded. After cooling, a modified PEEK sheath is formed on the surface of the composite wire core to obtain a high-temperature resistant composite multi-core cable.

[0030] Example 2: Preparation of a high-temperature resistant composite multi-core cable. The specific implementation process is as follows:

[0031] (1) Preparation of heat-resistant toughening agent

[0032] Step A1: 0.1 mol of tetraethylenepentamine and 150 mL of anhydrous tetrahydrofuran were premixed, and dry nitrogen was introduced until a stable airflow escaped. 25 mg of ZIF-8 was dissolved in DMF and then added to the mixture. The temperature of the water bath was controlled at 55°C. 0.2 mol of allyl glycidyl ether was slowly added and stirred for 3.2 hours. After the reaction was completed, tetrahydrofuran was removed by rotary evaporation to obtain a modified monomer.

[0033] Step A2: Take the modified monomer and X-22-167B type mercapto-terminated silicone oil, and pre-mix them with 300 mL of acetone according to the molar ratio of the mercapto content of the modified monomer and the mercapto-terminated silicone oil being 10 mmol:25 mmol. Then add 1.6 g of the photosensitizer DMPA (benzoin dimethyl ether) and mix well. Apply 65 mW / cm2 of ultraviolet light using a 365 nm mercury lamp. 2 The mixture was irradiated with ultraviolet light and stirred for reaction for 7 hours. After the reaction was completed, the acetone was removed by rotary evaporation to obtain a heat-resistant toughening agent.

[0034] (2) Preparation of high temperature resistant composite multi-core cables

[0035] The materials are prepared according to the following components: 10.5wt% heat-resistant toughening agent, which is homemade in this embodiment; 4wt% aluminum nitride powder, which is GK-AlN-002 submicron powder with an average particle size of 500nm; 2.5wt% heat stabilizer, which is commercially available potassium titanate whiskers; 1.8wt% lubricant, which is industrial-grade octaphenyl-POSS; 4wt% friction reducer, which is a mixture of polytetrafluoroethylene and molybdenum disulfide powders in a weight ratio of 2:1; the remainder is PEEK-3600G resin raw material.

[0036] The above raw materials are mixed evenly in a high-speed mixer, and the mixture is fed into a twin-screw extruder. The temperature of the plasticizing zone is controlled at 380°C for melt extrusion to prepare a sleeve. After the sleeve is cooled to 270°C, it is inserted into the composite wire core and roller-compounded. After cooling, a modified PEEK sheath is formed on the surface of the composite wire core to obtain a high-temperature resistant composite multi-core cable.

[0037] Example 3, preparing a high-temperature resistant composite multi-core cable, the specific implementation process is as follows:

[0038] (1) Preparation of heat-resistant toughening agent

[0039] Step A1: 0.1 mol of tetraethylenepentamine and 180 mL of anhydrous tetrahydrofuran were premixed, and dry nitrogen was introduced until a stable airflow escaped. 27 mg of ZIF-8 was dissolved in DMF and then added to the mixture. The temperature of the water bath was controlled at 60°C. 0.2 mol of allyl glycidyl ether was slowly added and stirred for 3 hours. After the reaction was completed, tetrahydrofuran was removed by rotary evaporation to obtain a modified monomer.

[0040] Step A2: Take the modified monomer and X-22-167B type mercapto-terminated silicone oil, and pre-mix them with 320 mL of acetone according to the molar ratio of the mercapto content of the modified monomer and the mercapto-terminated silicone oil being 10 mmol:28 mmol. Then add 1.9 g of the photosensitizer DMPA (benzoin dimethyl ether) and mix well. Apply 70 mW / cm2 of ultraviolet light with a 365 nm mercury lamp. 2 The mixture was irradiated with ultraviolet light and stirred for reaction for 6.5 hours. After the reaction was completed, acetone was removed by rotary evaporation to obtain a heat-resistant toughening agent.

[0041] (2) Preparation of high temperature resistant composite multi-core cables

[0042] The materials are prepared according to the following components: 12 wt % heat-resistant toughening agent, which is homemade in this embodiment; 5 wt % aluminum nitride powder, which is GK-AlN-002 submicron powder with an average particle size of 500 nm; 2 wt % heat stabilizer, which is commercially available potassium titanate whiskers; 1.5 wt % lubricant, which is industrial-grade octaphenyl-POSS; 3.2 wt % friction reducer, which is a mixture of polytetrafluoroethylene and molybdenum disulfide powders in a weight ratio of 2:1; the remainder is PEEK-3600G resin raw material.

[0043] The above raw materials are mixed evenly in a high-speed mixer, and the mixture is fed into a twin-screw extruder. The temperature of the plasticizing zone is controlled at 390°C for melt extrusion to prepare a sleeve. After the sleeve is cooled to 280°C, it is inserted into the composite wire core and roller-compounded. After cooling, a modified PEEK sheath is formed on the surface of the composite wire core to obtain a high-temperature resistant composite multi-core cable.

[0044] Example 4: Preparation of a high-temperature resistant composite multi-core cable. The specific implementation process is as follows:

[0045] (1) Preparation of heat-resistant toughening agent

[0046] Step A1: 0.1 mol of tetraethylenepentamine and 170 mL of anhydrous tetrahydrofuran were premixed, and dry nitrogen was introduced until a stable airflow escaped. 30 mg of ZIF-8 was dissolved in DMF and then added to the mixture. The temperature of the water bath was controlled at 60°C. 0.2 mol of allyl glycidyl ether was slowly added and stirred for 2.8 hours. After the reaction was completed, the tetrahydrofuran was removed by rotary evaporation to obtain a modified monomer.

[0047] Step A2: Take the modified monomer and X-22-167B type mercapto-terminated silicone oil, and pre-mix them with 300 mL of acetone according to the molar ratio of the mercapto content of the modified monomer and the mercapto-terminated silicone oil being 10 mmol:25 mmol. Then add 2 g of the photosensitizer DMPA (benzoin dimethyl ether) and mix them evenly. Apply 75 mW / cm2 of ultraviolet light with a 365 nm mercury lamp. 2 The mixture was irradiated with ultraviolet light and stirred for reaction for 6 hours. After the reaction was completed, the acetone was removed by rotary evaporation to obtain a heat-resistant toughening agent.

[0048] (2) Preparation of high temperature resistant composite multi-core cables

[0049] The materials are prepared according to the following components: 11.2 wt % heat-resistant toughening agent, which is homemade in this embodiment; 4.5 wt % aluminum nitride powder, which is GK-AlN-002 submicron powder with an average particle size of 500 nm; 2.5 wt % heat stabilizer, which is commercially available potassium titanate whiskers; 1.7 wt % lubricant, which is industrial-grade octaphenyl-POSS; 3.8 wt % friction reducer, which is a mixture of polytetrafluoroethylene and molybdenum disulfide powders in a weight ratio of 2:1; the remainder is PEEK-3600G resin raw material.

[0050] The above raw materials were mixed evenly in a high-speed mixer, and the mixture was fed into a twin-screw extruder. The temperature of the plasticizing zone was controlled at 390°C for melt extrusion to prepare a sleeve. After the sleeve was cooled to 270°C, it was inserted into the composite wire core and roller-compounded. After cooling, a modified PEEK sheath was formed on the surface of the composite wire core to obtain a high-temperature resistant composite multi-core cable.

[0051] In a comparative example, referring to the implementation process of Example 4, the heat-resistant toughening agent and aluminum nitride powder were replaced with HY-6000S silicone powder in equal amounts.

[0052] The sheath melt obtained in the above cable preparation process was extruded into a mold and molded into a sheet specimen with a thickness of 5 mm at 20 MPa. The specimens were subjected to a tensile test according to ISO 527-2-2012, a notched impact test according to ISO 180-2023, and an abrasion test according to ASTM D4060-14. The specific test results are shown in Table 1.

[0053] Table 1

[0054] Tensile strength / MPa Elongation / % <![CDATA[Impact strength / kJ·m -2 > Wear / mg Example 1 91.53 24.17 8.62 19.40 Example 2 88.27 28.60 9.19 21.60 Example 3 86.44 31.59 9.46 25.10 Example 4 90.01 29.32 9.88 23.30 Comparative Example 85.25 20.55 6.39 21.50

[0055] Combined with the test data in Table 1, it can be seen that the sheath of the cable prepared in the embodiment has more excellent strength and toughness, and has excellent protection capability for the composite core.

[0056] Cyclic thermal shock test: Place the sample in an oven, heat it to 280°C at a rate of 5°C / min, hold it for 1 hour, air-cool it to 100°C, cycle it for 100 cycles, take out the sample and let it stand for 24 hours, and then perform tensile, impact and wear resistance tests on the sample again. The specific test results are shown in Table 2:

[0057] Table 2

[0058] Tensile strength / MPa Elongation / % <![CDATA[Impact strength / kJ·m -2 > Wear / mg Example 1 84.57 21.32 7.37 22.68 Example 2 81.12 25.83 8.20 26.24 Example 3 78.23 26.76 8.26 34.46 Example 4 83.80 26.21 9.08 28.94 Comparative Example 62.40 14.04 4.90 41.43

[0059] Combining the test data in Table 1 and Table 2, it can be seen that after high-temperature impact cycles, the toughness retention rate of the sheath of the embodiment is significantly higher than that of the comparative example, wherein the elongation and impact strength of the comparative example are significantly deteriorated, and the wear increases sharply.

[0060] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0061] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A high temperature resistant composite multi-core cable, comprising a composite core and a modified PEEK sheath, characterized in that: The modified PEEK sheath comprises: 8.5-12 wt% of a heat-resistant toughening agent, 3.5-5 wt% of aluminum nitride powder, 2-3 wt% of a heat stabilizer, 1.5-2.2 wt% of a lubricant, and 3.2-4.5 wt% of a friction reducer, with the remainder being PEEK resin. The heat-resistant toughening agent is prepared by the following method: Step A1: Tetraethylenepentamine and anhydrous tetrahydrofuran were premixed, and dry nitrogen was introduced into the mixture. ZIF-8 was added and mixed. The temperature of the water bath was controlled at 55-65°C. Allyl glycidyl ether was slowly added and stirred for 2.5-3.2 hours to prepare a modified monomer. Step A2: Take the modified monomer, mercapto-terminated silicone oil and acetone and pre-mix them, then add the photosensitizer and mix them evenly. Use a UV mercury lamp to apply 65-80mw / cm 2 UV irradiation and stirring reaction for 5.5-7 hours to prepare a heat-resistant toughening agent; Aluminum nitride powder is submicron powder.

2. A high temperature resistant composite multi-core cable according to claim 1, characterized in that: The usage ratio of tetraethylenepentamine, allyl glycidyl ether, ZIF-8 and anhydrous tetrahydrofuran is 0.1 mol: 0.2 mol: 25-30 mg: 150-200 mL.

3. A high temperature resistant composite multi-core cable according to claim 2, characterized in that: The usage ratio of the modified monomer, the mercapto content of the terminal mercapto silicone oil, the photosensitizer and acetone is 10 mmol: 25-30 mmol: 1.6-2.1 g: 300-350 mL.

4. The high temperature resistant composite multi-core cable according to claim 1, characterized in that: The thermal stabilizer is potassium titanate whisker.

5. The high temperature resistant composite multi-core cable according to claim 1, characterized in that: The lubricant is octaphenyl-POSS.

6. The high temperature resistant composite multi-core cable according to claim 1, characterized in that: The friction reducer is a compound of polytetrafluoroethylene and molybdenum disulfide.

7. The high temperature resistant composite multi-core cable according to claim 1, characterized in that: The specific preparation method is as follows: the raw materials of each component are mixed evenly, and the sleeve is prepared by melt extrusion at 380-390℃ using an extruder. After the sleeve is cooled to 260-280℃, a composite wire core is inserted into the sleeve for roller compression and compounding. After cooling, a modified PEEK sheath is formed on the surface of the composite wire core to obtain a high-temperature resistant composite multi-core cable.