High-temperature-resistant composite multi-core cable

Abstract

The invention relates to a high-temperature-resistant composite multi-core cable, and belongs to the technical field of special cables. The cable comprises a composite wire core and a modified PEEK sheath, and the modified PEEK sheath comprises the following components: 8.5-12 wt% of a heat-resistant toughening agent, 3.5-5 wt% of aluminum nitride micro powder, 2-3 wt% of a heat stabilizer, 1.5-2.2 wt% of a lubricant, 3.2-4.5 wt% of an antifriction agent, and the balance of PEEK resin; hydroxyl and secondary amine groups in a block chain segment of the modified monomer serve as hydrogen donors to interact with ketone groups in a molecular chain of PEEK and are chelated and combined with aluminum nitride particles at the same time, double anchoring is formed, a stable high-temperature toughening effect is achieved, and the high-strength performance of the PEEK material is maintained on the premise that cable protection is met through effective toughening.

Description

Technical Field

[0001] The present invention belongs to the technical field of special cables, and specifically, 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, petrochemical, etc. They need to maintain insulation performance, mechanical strength, and long-term stability at high temperatures. Traditional polyolefin sheath 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 the high-temperature resistance performance 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 sheath materials are high-temperature resistant, they have poor flexibility, large bending radii, resulting in difficult cable laying, and 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 a ketone bond and two ether bonds in the main chain structure. It has excellent heat resistance (long-term use temperature of 260 °C), chemical stability, and mechanical strength, and has become the preferred 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 prior art, the PEEK is toughened and modified to meet the protection requirements 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. The existing toughening materials are 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 have thermal migration during high-temperature service, resulting in the deterioration of the performance of PEEK materials and limiting the high-performance utilization of PEEK materials. Summary of the Invention

[0005] In order to solve the technical problems mentioned in the background art, 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 by the following technical solutions: A high-temperature resistant composite multi-core cable includes a composite core and a modified PEEK sheath; Among them, the components of the modified PEEK sheath are: 8.5 - 12 wt% of a heat-resistant toughening agent, 3.5 - 5 wt% of aluminum nitride micropowder, 2 - 3 wt% of a heat stabilizer, 1.5 - 2.2 wt% of a lubricant, and 3.2 - 4.5 wt% of an antifriction agent, and the balance is PEEK resin.

[0007] Among them, the heat-resistant toughening agent is prepared by the following method: Step A1: Take tetraethylenepentamine and anhydrous tetrahydrofuran, premix them, introduce dry nitrogen for protection, add ZIF-8 (dissolved in DMF) and mix, control the temperature in a water bath at 55 - 65°C, slowly add allyl glycidyl ether and stir for reaction for 2.5 - 3.2 h. After the reaction ends, rotary evaporate to remove tetrahydrofuran to obtain a modified monomer; In the reaction of Step A1 above, the dosage 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 effectively ring-open at low temperature, and the specific reaction route is as follows:

[0008] Step A2: Take the modified monomer, terminal mercapto silicone oil and acetone, premix them, then add a photosensitizer and mix evenly. Apply ultraviolet mercury lamp with 65 - 80 mw / cm 2 Ultraviolet irradiation and stir for reaction for 5.5 - 7 h. After the reaction ends, rotary evaporate to remove acetone to obtain a heat-resistant toughening agent; In the reaction of Step A2 above, the dosage ratio of the modified monomer, the mercapto content of terminal mercapto silicone oil, the photosensitizer and acetone is 10 mmol : 25 - 30 mmol : 1.6 - 2.1 g : 300 - 350 mL. Under photoinitiation, the modified monomer and terminal mercapto silicone oil undergo click addition to form a macromolecular compound containing organosilicon segments.

[0009] Preferably, the aluminum nitride micropowder is submicron micropowder, and the surface contains more chelating active sites. At this particle size, a certain dispersibility can be maintained.

[0010] Preferably, the heat stabilizer is potassium titanate whiskers, which can improve the tear resistance and heat shock resistance of the matrix and enhance the stability at instantaneous high temperatures.

[0011] 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 forming of the sheath.

[0012] Preferably, the friction reducer is a compound of polytetrafluoroethylene and molybdenum disulfide, which can reduce the friction of the sheath and improve the anti-wear performance of the sheath.

[0013] A high-temperature resistant composite multi-core cable, and its preparation method is: Mix the raw material components of each component, use an extruder to melt and extrude at 380 - 390°C to prepare a sleeve. Wait for the sleeve to cool to 260 - 280°C, insert the composite wire core and roll and compound. 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.

[0014] The beneficial effects of the present invention: The present invention introduces submicron aluminum nitride micropowder and a self-developed heat-resistant toughening agent into the PEEK matrix for synergistic toughening modification, maintaining the high-strength performance of the PEEK material while effectively toughening it 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 to introduce terminal allyl groups to form a modified monomer, and then the modified monomer and terminal mercapto silicone oil are photoinitiated and polymerized to form a macromolecular compound, thus obtaining the heat-resistant toughening agent; compared with the existing silicone toughening system, the advantages of the present invention are as follows: the hydroxyl groups and secondary amine groups in the block segments of the modified monomer act as hydrogen donors to form interactions with the keto groups in the molecular chain of PEEK, enabling the silicone chain to coil outside the PEEK molecular chain to toughen the PEEK matrix and improve its protective performance in the sheath material. The heat-resistant toughening agent with a macromolecular structure and a silicone chain as the main body has good heat resistance itself. The block segments of its modified monomer form a chelating effect with aluminum nitride particles, and the high thermal conductivity of aluminum nitride is used to make up for the deficiency of heat resistance at the block position, improving the overall thermal stability of the heat-resistant toughening agent molecule; in addition, the interaction between the block segments of the modified monomer and the PEEK molecular chain and aluminum nitride particles forms a double anchoring effect, effectively reducing its migration at high temperatures, and then playing a stable and long-lasting toughening role. Detailed implementation mode

[0015] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0016] Example 1, preparation of a high-temperature resistant composite multi-core cable, and the specific implementation process is as follows: (1) Preparation of the heat-resistant toughening agent Step A1: Weigh 0.1 mol of tetraethylenepentamine and 200 mL of anhydrous tetrahydrofuran, mix them in advance, introduce dry nitrogen until a stable gas flow escapes, take 30 mg of ZIF-8, dissolve it in DMF and add it to the mixture, control the temperature of the water bath at 65 °C, weigh 0.2 mol of allyl glycidyl ether, slowly add it and stir for reaction for 2.5 h. After the reaction is completed, rotary evaporate to remove tetrahydrofuran to obtain the modified monomer.

[0017] Step A2: Take the modified monomer and X-22-167B type terminal mercapto silicone oil. According to the molar ratio of the mercapto content of the modified monomer and terminal mercapto silicone oil being 10 mmol:30 mmol, premix the two with 350 mL of acetone, then add 2.1 g of photosensitizer DMPA (benzoin dimethyl ether) and mix well. Apply an 80 mw / cm 2Under ultraviolet irradiation, stir and react for 5.5 h. After the reaction is completed, rotary evaporate to remove acetone to obtain the heat-resistant toughening agent.

[0018] (2)Preparation of high-temperature resistant composite multi-core cable Weigh the raw materials according to the following ratio: 8.5 wt% of heat-resistant toughening agent, self-made in this example; 3.5 wt% of aluminum nitride micropowder, select GK-AlN-002 type submicron micropowder with an average particle size of 500 nm; 3 wt% of heat stabilizer, select commercially available potassium titanate whiskers; 2.2 wt% of lubricant, select industrial-grade octaphenyl-POSS; 4.5 wt% of antifriction agent, select the powder of polytetrafluoroethylene and molybdenum disulfide compounded in a weight ratio of 2:1; the balance is PEEK-3600G type resin raw material.

[0019] Mix the above raw materials evenly by a high-speed mixer, and feed the mixture into a twin-screw extruder. Control the temperature of the plasticizing zone at 380 °C to melt and extrude to prepare the casing. Wait for the casing to cool down to 260 °C, insert the composite wire core and roll and compound it. 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.

[0020] Example 2, preparation of high-temperature resistant composite multi-core cable, the specific implementation process is as follows: (1)Preparation of heat-resistant toughening agent Step A1: Measure 0.1 mol of tetraethylenepentamine and 150 mL of anhydrous tetrahydrofuran, feed and premix them, pass dry nitrogen until a stable gas flow escapes, take 25 mg of ZIF-8, dissolve it in DMF and add it to the mixture. Control the temperature of the water bath at 55 °C, measure 0.2 mol of allyl glycidyl ether and slowly add it and stir and react for 3.2 h. After the reaction is completed, rotary evaporate to remove tetrahydrofuran to obtain the modified monomer.

[0021] Step A2: Take the modified monomer and X-22-167B type terminal mercapto silicone oil. According to the molar ratio of the mercapto content of the modified monomer and the terminal mercapto silicone oil of 10 mmol:25 mmol, premix the two with 300 mL of acetone, then add 1.6 g of photosensitizer DMPA (benzoin dimethyl ether) and mix well. Apply 65 mw / cm with a 365 nm ultraviolet mercury lamp 2 Under ultraviolet irradiation, stir and react for 7 h. After the reaction is completed, rotary evaporate to remove acetone to obtain the heat-resistant toughening agent.

[0022] (2)Preparation of high-temperature resistant composite multi-core cable 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 compound of polytetrafluoroethylene and molybdenum disulfide powders in a weight ratio of 2:1; the remainder is PEEK-3600G resin raw material.

[0023] The above raw materials are mixed evenly with a high-speed mixer, and the mixture is sent to a twin-screw extruder. The temperature of the plasticizing zone is controlled to be 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 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.

[0024] Example 3, preparing a high temperature resistant composite multi-core cable, the specific implementation process is as follows: (1) Preparation of heat-resistant toughening agent Step A1: 0.1 mol of tetraethylenepentamine and 180 mL of anhydrous tetrahydrofuran were premixed, dry nitrogen was introduced until a stable gas flow 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 reaction for 3 h, and after the reaction was completed, tetrahydrofuran was removed by rotary evaporation to obtain a modified monomer.

[0025] Step A2: Take the modified monomer and X-22-167B type terminal mercapto silicone oil, and premix them with 320mL acetone according to the molar ratio of the mercapto content of the modified monomer and the terminal mercapto silicone oil of 10mmol:28mmol, then add 1.9g of photosensitizer DMPA (benzoin dimethyl ether) and mix well, and apply 70mw / cm2 of ultraviolet mercury lamp with 365nm 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.

[0026] (2) Preparation of high temperature resistant composite multi-core cables The materials are prepared according to the following components: 12wt% heat-resistant toughening agent, which is homemade in this embodiment; 5wt% aluminum nitride powder, which is GK-AlN-002 submicron powder with an average particle size of 500nm; 2wt% heat stabilizer, which is commercially available potassium titanate whiskers; 1.5wt% lubricant, which is industrial-grade octaphenyl-POSS; 3.2wt% friction reducer, which is a compound of polytetrafluoroethylene and molybdenum disulfide powders in a weight ratio of 2:1; the remainder is PEEK-3600G resin raw material.

[0027] Mix the above raw materials evenly with a high-speed mixer, feed the mixed materials into a twin-screw extruder, control the temperature of the plasticizing zone at 390 °C for melt extrusion to prepare the sleeve. Wait for the sleeve to cool down to 280 °C, thread in the composite wire core and roll press for 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.

[0028] Example 4: Prepare a high-temperature resistant composite multi-core cable. The specific implementation process is as follows: (1)Preparation of heat-resistant toughening agent Step A1: Weigh 0.1 mol of tetraethylenepentamine and 170 mL of anhydrous tetrahydrofuran, feed and premix them, introduce dry nitrogen until a stable gas flow escapes. Take 30 mg of ZIF-8, dissolve it in DMF and add it to the mixture. Control the temperature of the water bath at 60 °C. Weigh 0.2 mol of allyl glycidyl ether and slowly add it while stirring and reacting for 2.8 h. After the reaction ends, rotary evaporate to remove tetrahydrofuran to obtain a modified monomer.

[0029] Step A2: Take the modified monomer and X-22-167B type terminal mercapto silicone oil. According to the molar ratio of the mercapto content of the modified monomer to the terminal mercapto silicone oil of 10 mmol:25 mmol, premix the two with 300 mL of acetone, then add 2 g of photosensitizer DMPA (benzoin dimethyl ether) and mix evenly. Apply ultraviolet irradiation with a 365 nm ultraviolet mercury lamp at 75 mw / cm 2 Ultraviolet irradiation, stir and react for 6 h. After the reaction ends, rotary evaporate to remove acetone to obtain a heat-resistant toughening agent.

[0030] (2)Preparation of high-temperature resistant composite multi-core cable Weigh the raw materials as follows: 11.2 wt% of heat-resistant toughening agent, self-made in this example; 4.5 wt% of aluminum nitride micropowder, select GK-AlN-002 type submicron micropowder with an average particle size of 500 nm; 2.5 wt% of heat stabilizer, select commercially available potassium titanate whiskers; 1.7 wt% of lubricant, select industrial grade octaphenyl-POSS; 3.8 wt% of antifriction agent, select a powder of polytetrafluoroethylene and molybdenum disulfide compounded in a weight ratio of 2:1; the balance is PEEK-3600G type resin raw material.

[0031] Mix the above raw materials evenly with a high-speed mixer, feed the mixed materials into a twin-screw extruder, control the temperature of the plasticizing zone at 390 °C for melt extrusion to prepare the sleeve. Wait for the sleeve to cool down to 270 °C, thread in the composite wire core and roll press for 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.

[0032] Comparative example: Refer to the implementation process of Example 4, and replace the heat-resistant toughening agent and aluminum nitride micropowder with HY-6000S type silicone powder in equal amounts.

[0033] Extrude the sheath melt during the cable preparation process as described above into a mold, and press-mold it into a sheet sample with a thickness of 5 mm under 20 MPa. Conduct a tensile test according to the ISO527-2-2012 standard; conduct a notched impact test according to the ISO 180-2023 standard; conduct a wear resistance test according to the ASTM D4060-14 standard. The specific test results are shown in Table 1: Table 1 Tensile strength / MPa Elongation at break / % <![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 Combined with the test data in Table 1, it can be seen that the sheath of the cable prepared in the example has more excellent strength and toughness, and has excellent protection ability for the composite core.

[0034] Cyclic thermal shock test: Place the sample in an oven, heat it up to 280°C at a rate of 5°C / min and hold for 1 h, then air-cool it to 100°C, cycle 100 times, take out the sample and let it stand for 24 h, and conduct tensile, impact and wear resistance tests on the sample again. The specific test results are shown in Table 2: Table 2 Tensile strength / MPa Elongation at break / % <![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 Combined with the test data in Table 1 and Table 2, it can be seen that after high-temperature shock cycling, the retention rate of the strength and toughness of the sheath in the example is significantly higher than that of the comparative example. Among them, the elongation rate and impact strength of the comparative example deteriorate significantly, and the abrasion increases sharply.

[0035] In the description of the specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0036] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described, or use similar methods to replace them. As long as they do not deviate from the invention or exceed the scope defined by the claims of this patent, they should all fall within the protection scope of the present invention.

Claims

1. A high-temperature resistant composite multi-core cable, comprising a composite wire core and a modified PEEK sheath, characterized in that, The components of the modified PEEK sheath are as follows: 8.5-12 wt% of heat-resistant toughening agent, 3.5-5 wt% of aluminum nitride micropowder, 2-3 wt% of heat stabilizer, 1.5-2.2 wt% of lubricant, and 3.2-4.5 wt% of antifriction agent, with the balance being PEEK resin; The heat-resistant toughening agent is prepared by the following method: Step A1: Premix tetraethylenepentamine and anhydrous tetrahydrofuran, introduce dry nitrogen for protection, add ZIF-8 and mix, control the temperature in a water bath at 55-65 °C, slowly add allyl glycidyl ether and stir for reaction for 2.5-3.2 h to prepare a modified monomer; Step A2: Premix the modified monomer, terminal mercapto silicone oil and acetone, then add the photosensitizer and mix well. Apply ultraviolet mercury lamp with 65 - 80 mw / cm 2 for ultraviolet irradiation and stir the reaction for 5.5 - 7 h to prepare the heat-resistant toughening agent.

2. The high-temperature resistant composite multi-core cable according to claim 1, wherein, The dosage 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. The high-temperature resistant composite multi-core cable according to claim 2, characterized in that, The dosage ratio of the modified monomer, the mercapto content of terminal mercapto silicone oil, photosensitizer and acetone is 10 mmol: 25-30 mmol: 1.6-2.1 g: 300-350 mL.

4. A high-temperature resistant composite multi-core cable according to claim 1, characterized in that, The aluminum nitride micropowder is a submicron-level micropowder.

5. A high-temperature resistant composite multi-core cable according to claim 1, characterized in that, The heat stabilizer is potassium titanate whiskers.

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

7. The high-temperature resistant composite multi-core cable according to claim 1, characterized in that, The antifriction agent is prepared by compounding polytetrafluoroethylene and molybdenum disulfide.

8. The high-temperature resistant composite multicore cable according to claim 1, wherein, The specific preparation method is as follows: Mix the raw materials of each component, and use an extruder to melt and extrude at 380-390 °C to prepare a sleeve. Wait for the sleeve to cool to 260-280 °C, thread it through a composite wire core and roll and compound it. 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.

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