Anti-aging and anti-interference industrial wire harness and preparation method thereof

Abstract

The invention discloses an anti-aging and anti-interference industrial wire harness and a preparation method thereof, belongs to the technical field of industrial wire harness processing, is used for solving the technical problem that the high temperature resistance, the anti-aging performance and the anti-interference performance of an industrial wire harness in the prior art need to be further improved, and specifically comprises a plurality of wires, an anti-interference layer, a bridle layer and a terminal, the anti-interference layer is obtained by coating the exteriors of the plurality of wires with aluminum foil, and the bridle layer is obtained by uniformly winding a winding adhesive tape on the exterior of the anti-interference layer. According to the invention, a wire harness product is obtained by winding an aluminum foil-coated wire group by using the prepared winding adhesive tape, and the electromagnetic interference suppression, the thermal environment adaptability and the long-term service stability of the wire harness are remarkably improved through the multi-level structural design of combining the outer layer winding adhesive tape and the inner layer aluminum foil layer.

Description

Technical Field

[0001] This invention relates to the field of industrial wire harness processing technology, specifically to an aging-resistant and interference-resistant industrial wire harness and its preparation method. Background Technology

[0002] Industrial wire harnesses are essential key connection components in industrial equipment, electrical equipment, automotive engine compartments, rail transportation, and power systems. They are exposed to complex and ever-changing environments, including external factors such as high temperature, vibration, electromagnetic radiation, humidity, and chemical media. During their service life, wire harnesses not only transmit electrical signals and power, but also need to ensure the mechanical strength, structural stability, and long-term reliability of the outer protective material. Therefore, the aging resistance, high temperature resistance, and electromagnetic interference resistance of the outer winding material of the wire harness have become important factors limiting the overall performance of the wire harness.

[0003] Currently, industrial wire harnesses commonly use polyethylene, polyvinyl chloride, rubber-based tape, or modified polyolefin materials as the winding base tape to achieve wire harness fixation, mechanical protection, and outer layer encapsulation. However, traditional polyethylene materials are prone to chain breakage and oxidative degradation under high temperature conditions, leading to mechanical performance degradation, deformation and cracking, which significantly reduces the long-term service reliability of wire harnesses in high-temperature environments.

[0004] Moreover, the strong chemical inertness of polyethylene molecular chains makes it difficult to fix antioxidant groups in the system for a long time. Conventional small molecule antioxidants are prone to migration, volatilization or failure, making it difficult to meet the requirements of industrial wire harnesses for long-term heat aging resistance. At the same time, polyethylene base tape softens and creeps under high temperature environment, which cannot guarantee the binding effect of the wire harness and affects the service life of the wire harness in engine compartments, electrical heating equipment and other places. With the continuous improvement of the electrification of industrial equipment, the electromagnetic coupling inside the wire harness and between the wire harness and external equipment is strengthened, and the electromagnetic interference problem is becoming increasingly prominent.

[0005] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide an aging-resistant and interference-resistant industrial wire harness and its preparation method, in order to solve the technical problem that the high temperature resistance, aging resistance and interference resistance of industrial wire harnesses in the prior art need to be further improved.

[0007] The objective of this invention can be achieved through the following technical solution: an aging-resistant and interference-resistant industrial wire harness, comprising several conductors, an interference-resistant layer, a cable tie layer, and terminals. The interference-resistant layer is obtained by covering the outside of several conductors with aluminum foil. The cable tie layer is obtained by uniformly wrapping the outside of the interference-resistant layer with adhesive tape. The terminals are installed at both ends of the wire harness.

[0008] The wrapping tape includes an aging-resistant base tape and an adhesive layer. The aging-resistant base tape comprises the following components by weight: 60-70 parts of low-density polyethylene, 25-35 parts of high-density polyethylene, 50-60 parts of anti-aging modified PE, 28-32 parts of epoxy-based reinforcing agent, and 5-6 parts of additives. The epoxy-based reinforcing agent is composed of epoxy-modified dicyanobenzene and bisphenol A type epoxy resin in a weight ratio of 2:3.

[0009] Furthermore, the preparation method of anti-aging modified PE is as follows: anti-aging modified polysiloxane, low-density polyethylene, initiator and auxiliary additives are added to a twin-screw extruder, melt-mixed for 5-6 minutes and then extruded, cooled and cured, pulverized and passed through a 100-mesh sieve to obtain anti-aging modified PE.

[0010] Furthermore, the weight ratio of the anti-aging modified polysiloxane, low-density polyethylene, initiator, and auxiliary additives is 45-55:70-80:2-3:3-5. The initiator is benzoyl peroxide. The auxiliary additives are composed of dispersant, lubricant, and heat stabilizer in a weight ratio of 3:2:1. The dispersant is stearate, the lubricant is ethylene bis-stearamide, and the heat stabilizer is triethyl phosphite. The temperature of the twin-screw extruder is 150-160℃ in zone one, 155-165℃ in zone two, 160-170℃ in zone three, and 160-170℃ in zone four, with a die temperature of 165-175℃.

[0011] Furthermore, the preparation method of anti-aging modified polysiloxane is as follows: octamethylcyclotetrasiloxane, aminopropylmethyldimethoxysilane, 3,5-di-tert-butyl-4-(carbamate-propyldiethoxysilane)methoxybenzene and sulfuric acid are mixed, the reaction system is heated to 85-95℃, and the reaction is maintained at this temperature for 30-50 min. Diallyltetramethyldisiloxane is then added to the reaction system, and the reaction is maintained at this temperature for 60-80 min. After post-treatment, the anti-aging modified polysiloxane is obtained.

[0012] The synthesis reaction formula for anti-aging modified polysiloxane is as follows:

[0013]

[0014] In the formula:

[0015] Furthermore, the ratio of octamethylcyclotetrasiloxane, aminopropylmethyldimethoxysilane, 3,5-di-tert-butyl-4-(carbamate-propyldiethoxysilane)methoxybenzene, sulfuric acid, and diallyltetramethyldisiloxane is 10g:2.8-3.2g:3g:5mL:2g, and the sulfuric acid has a mass fraction of 50%. The post-treatment includes: after the reaction is complete, cooling the reaction system to room temperature, adding 1-3wt% sodium bicarbonate aqueous solution to the reaction system to adjust the pH of the system to 8, allowing it to stand and separate the layers, washing the upper organic matter three times with purified water, and then transferring it to a rotary evaporator with a water bath temperature of 70-80℃, drawing a negative pressure to -0.1MPa, and removing low-boiling substances by vacuum evaporation to obtain anti-aging modified polysiloxane.

[0016] Furthermore, the preparation method of 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene is as follows: under an inert gas atmosphere, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 3-propyl isocyanate methyl diethoxysilane, and tetrahydrofuran are mixed and stirred. The reaction system is heated to 45-50℃ and kept at that temperature for 40-60 min. After post-treatment, 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene is obtained.

[0017] The synthetic reaction formula for 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene is as follows:

[0018]

[0019] The 1H NMR data for 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene are as follows:¹H NMR (400 MHz, CDCl3) δ: 7.07 (s, 2H, Ar-H), 5.50 (brs, 1H, NH), 4.86 (s, 2H, Ar-CH2-O), 3.78–3.72 (m, 4H, -SiOCH2CH3), 3.36 (t, J = 6.4 Hz, 2H, -NHCOO-CH2-), 1.63–1.54 (m, 2H, -NHCOO-CH2-CH2-), 1.32 (s, 18H, C(CH3)3), 1.23 (t, J = 7.0 Hz, 6H, -SiOCH2CH3), 0.61 (t, J = 7.6 Hz, 2H, -Si-CH2-).

[0020] Furthermore, the molar ratio of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and 3-propylisocyanate methyldiethoxysilane is 1:1, and the molar ratio of 3-propylisocyanate methyldiethoxysilane to tetrahydrofuran is 1 g:7 mL. The post-treatment includes: after the reaction is complete, the reaction system is heated to 60°C, the pressure is reduced to -0.1 MPa, and the low-boiling substances are removed by vacuum distillation to obtain 3,5-di-tert-butyl-4-(carbamate propyldiethoxysilane)methoxybenzene.

[0021] Furthermore, the preparation method of epoxy-modified dicyanobenzene is as follows: phenylamine-modified dicyanobenzene and N,N-dimethylformamide are mixed and stirred until the system is dissolved. Sodium hydroxide solution is added to the reaction system, the temperature of the reaction system is raised to 50-60℃, epichlorohydrin is added dropwise to the reaction system, and after the addition is complete, the reaction is kept at the temperature for 5-6 hours. After post-treatment, epoxy-modified dicyanobenzene is obtained.

[0022] The synthesis reaction formula for epoxy-modified dicyanobenzene is as follows:

[0023]

[0024] The carbon spectral analysis data of epoxy-modified dicyanobenzene are as follows: ¹³C NMR (100 MHz, CDCl3) δ (ppm): 159.2 (Ar-O-ipso-C), 148.6, 145.9 (Ar-C-NH, Ar-C-CN), 138.7, 135.4, 132.8 (Ar-C), 128.6, 125.8, 123.9 (Ar-CH), 118.2, 116.9 (sp²-C of ortho-CN of aromatic ring), 114.2, 112.8 (-C≡N), 53.1 (epoxy-CH-O), 46.8, 44.3 (epoxy-CH2), 41.2 (N-CH2-CH(oxirane)).

[0025] Furthermore, the molar ratio of phenylamine-modified dicyanobenzene to epichlorohydrin is 1:3, the volume ratio of phenylamine-modified dicyanobenzene, N,N-dimethylformamide, and sodium hydroxide solution is 1g:8mL:3mL, the mass fraction of the sodium hydroxide solution is 40-50%, and the post-treatment includes: after the reaction is complete, adding 2wt% sodium dodecyl sulfate aqueous solution to the reaction system, stirring at a constant temperature for 20-30 minutes, filtering, washing the filter cake with purified water until neutral, washing it three times with anhydrous ethanol, transferring the filter cake to a drying oven at a temperature of 60-70℃, and drying it to constant weight to obtain epoxy-modified dicyanobenzene.

[0026] Furthermore, the preparation method of phenylamine-modified dicyanobenzene is as follows: under an inert gas atmosphere, 1,4-diamino-2-nitrobenzene and N,N-dimethylformamide are mixed and stirred until the system is dissolved. A catalyst and 3,4-dicyanophenol are added to the reaction system. The temperature of the reaction system is raised to 80-90℃ and the reaction is maintained at this temperature for 6-8 hours. After post-treatment, phenylamine-modified dicyanobenzene is obtained.

[0027] The synthetic reaction formula for phenylamine-modified dicyanobenzene is as follows:

[0028]

[0029] The carbon spectral analysis data of phenylamine-modified dicyanobenzene are as follows: ¹³C NMR (100 MHz, CDCl3) δ (ppm): 159.4 (Ar-O-ipso-C), 149.8, 147.3 (Ar-C-NH, Ar-C-CN), 138.6, 135.4, 133.1 (Ar-C), 129.2, 126.4, 124.1 (Ar-CH), 118.6, 117.1 (ortho-CN aromatic ring sp²-C), 114.5, 113.1 (-C≡N), 109.8 (substituted aromatic ring sp²-C).

[0030] Furthermore, the molar ratio of 1,4-diamino-2-nitrobenzene and 3,4-dicyanophenol is 1:1, and the molar ratio of 1,4-diamino-2-nitrobenzene, N,N-dimethylformamide, and catalyst is 1g:7mL:1.8-2g. The catalyst is potassium carbonate. The post-treatment includes: after the reaction is complete, the reaction system is cooled to room temperature, 2wt% sodium dodecyl sulfate aqueous solution is added to the reaction system, the mixture is kept warm and stirred for 20-30 minutes, filtered, the filter cake is washed with purified water until neutral, dried, and the filter cake is transferred to a drying oven at 60-70℃ and dried to constant weight to obtain phenylamine-modified dicyanophenol.

[0031] This invention also proposes a method for preparing an aging-resistant and interference-resistant industrial wire harness, comprising the following steps:

[0032] S1. Low-density polyethylene, high-density polyethylene, anti-aging modified PE, epoxy-based reinforcing agent and additives are mixed evenly and then added to a twin-screw extruder. After melting and mixing for 3-4 minutes, the mixture is extruded from the die to obtain an aging-resistant base tape with a thickness of 0.4 mm. Adhesive is coated on one side of the aging-resistant base tape to form an adhesive layer with a thickness of 60-70 μm, thus preparing a winding tape.

[0033] S2. Using copper core wires with an insulating layer on the surface as conductors, several groups of conductors are placed in parallel to form a wire group, and then aluminum foil is wrapped around the outside to form an anti-interference layer.

[0034] S3. The wrapping tape prepared in step S1 is evenly wrapped around the outside of the anti-interference layer to form a cable harness layer, and fixed terminals are installed at both ends of the wire group bound by it to obtain the finished wire harness.

[0035] Further, in step S1, the added additives are composed of plasticizer, dispersant, lubricant and antioxidant in a weight ratio of 5:3:1:2. The plasticizer is phthalate, the dispersant is stearate, the lubricant is ethylene bis-stearamide, and the antioxidant is any one of antioxidant 1010, antioxidant 1520 and antioxidant 1024. The temperature of the twin-screw extruder is 150-160℃ in zone one, 155-165℃ in zone two, 160-170℃ in zone three and 160-170℃ in zone four, and the die temperature is 165-175℃.

[0036] The present invention has the following beneficial effects:

[0037] 1. This invention employs a multi-layered structural design combining an outer layer of wrapping tape and an inner layer of aluminum foil, significantly improving the wire harness's electromagnetic interference suppression, thermal environment adaptability, and long-term service stability. The aluminum foil, as a continuous and dense metallic shielding layer, effectively reflects and absorbs external electromagnetic waves, blocking electromagnetic coupling between conductors within the wire harness and between the wire harness and external devices, thereby significantly reducing the risk of signal crosstalk and electromagnetic interference. Furthermore, the aluminum foil has excellent heat-resistant reflective properties, blocking some heat radiation from penetrating the conductors. The outer wrapping tape, with its high heat resistance and dimensional stability, ensures the wire harness maintains its shape stability under high-temperature conditions, preventing softening, cracking, or strength reduction. The synergistic effect of both enhances the overall high-temperature resistance of the wire harness, enabling it to remain stable and reliable in high-temperature environments such as automotive engine compartments and industrial heating environments.

[0038] 2. This invention also provides good flexibility and low-temperature toughness through low-density polyethylene, improves crystallinity and longitudinal tensile strength through high-density polyethylene, and combines the role of matrix and long-term thermo-oxidative stability with anti-aging modified PE. The epoxy-based reinforcing agent introduces a certain proportion of rigid phase, so that the strength of the tape is not easily reduced after high temperature and long-term aging. By controlling the proportion of each component, the system as a whole exhibits a state of "moderate to high strength and still good flexibility", which not only ensures the stretchability and tightness during winding construction, but also improves the mechanical protection capability of the wire harness during service.

[0039] 3. This invention also introduces a hindered phenolic group-siloxane structural anti-aging system into the polyethylene matrix, fixing the antioxidant units to the polymer backbone via chemical bonds, significantly enhancing the long-term stability of the material under thermo-oxidative environments. The anti-aging modified polysiloxane possesses a flexible silicon-oxygen backbone, antioxidant groups, and graftable allyl groups. During processing, it undergoes free radical grafting with polyethylene, allowing the antioxidant structure to function uniformly and persistently within the system. This fundamentally inhibits chain breakage and excessive cross-linking, improving both the material's mechanical strength and its heat aging resistance. Furthermore, by combining epoxy-modified dicyanobenzene containing polynitrile and aromatic groups with bisphenol A type epoxy resin to form epoxy groups... The reinforcing agent, with its polynitrile groups, aromatic rings, and polyepoxy functional groups introduced by epoxy-modified dicyanobenzene, possesses high thermal stability, high rigidity, and high reactivity. This allows the reinforcing agent to form a highly thermally stable, highly polar, and uniformly dispersed reinforcing network in the polyethylene-siloxane system. This not only effectively improves the material's load-bearing capacity, dimensional stability, and anti-aging properties at medium and high temperatures, but also creates interfacial compatibility with amino-containing polysiloxanes, enhancing interphase bonding at the microscopic level, reducing stress concentration and deformation relaxation, and improving the high-temperature resistance of the wrapping tape. This ensures that the wire harness does not deform or crack in high-temperature environments, electrical heating, or engine compartments, providing higher thermal stability protection for the wire harness. Detailed Implementation

[0040] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0041] In this invention, the manufacturer of low-density polyethylene is Sinopec Yanshan, and the grade is LD163;

[0042] In this invention, the high-density polyethylene is manufactured by Sinopec Yanshan, and the model is 3000JE;

[0043] In this invention, the domestically produced type of bisphenol A epoxy resin is E-35;

[0044] In this invention, the environmentally friendly butyl rubber is selected from commercially available products of Dongguan Shenghao Plastic Raw Materials Co., Ltd., with a molecular weight of 100,000 and product number HH1220L5Y16P.

[0045] Example 1

[0046] This embodiment provides a method for preparing anti-aging modified PE, including the following steps:

[0047] Step A1: Preparation of 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene

[0048] Weigh out 23.6 g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 21.7 g of 3-propyl isocyanate methyl diethoxysilane, and 165.2 mL of tetrahydrofuran and add them to a reaction flask under argon protection. Stir the mixture and heat it to 45 °C. Maintain the temperature for 40 min. Then heat the mixture to 60 °C and apply a vacuum of -0.1 MPa to remove low-boiling substances by vacuum distillation to obtain 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane) methoxybenzene.

[0049] In the reaction, argon gas is used to prevent air from entering, which causes the 3-isocyanate methyl diethoxysilane molecule to change. The hydroxyl group on the 3,5-di-tert-butyl-4-hydroxybenzyl alcohol molecule acts as an active reaction site and condenses with the isocyanate group on the 3-isocyanate methyl diethoxysilane molecule to prepare diethoxysilane-modified 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane) methoxybenzene.

[0050] Step A2: Preparation of anti-aging modified polysiloxane

[0051] Weigh out 50g of octamethylcyclotetrasiloxane, 14g of aminopropylmethyldimethoxysilane, 15g of 3,5-di-tert-butyl-4-(carbamate-propyldiethoxysilane)methoxybenzene, and 25mL of 50wt% sulfuric acid and add them to a reaction flask. Stir the mixture and heat it to 85℃. Keep the temperature for 30min. Add 10g of diallyltetramethyldisiloxane to the reaction flask and keep the temperature for 60min. Cool the reaction flask to room temperature and add 1wt% sodium bicarbonate aqueous solution to adjust the pH of the system to 8. Allow the mixture to stand and separate the layers. Wash the upper organic matter three times with purified water and transfer it to a rotary evaporator with a water bath temperature of 70℃. Apply a negative pressure to -0.1MPa and remove low-boiling substances by vacuum evaporation to obtain anti-aging modified polysiloxane.

[0052] In the reaction, octamethylcyclotetrasiloxane undergoes ring-opening under high temperature conditions with sulfuric acid as a catalyst to form a silanol-terminated linear siloxane backbone. Simultaneously, the siloxane bonds on aminopropylmethyldimethoxysilane and 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene molecules hydrolyze to form silanols, which are then inserted into the chain via silicon-oxygen exchange to form long polysiloxane chains modified with BHT and amino groups. Diallyltetramethyldisiloxane is used as a capping agent, and its hydrolysis caps the polysiloxane chains, thus preparing olefin-terminated anti-aging modified polysiloxanes.

[0053] Step A3: Preparation of anti-aging modified PE

[0054] Sodium stearate, ethylene bis-stearamide and triethyl phosphite were mixed evenly in a weight ratio of 3:2:1 to obtain the auxiliary additive.

[0055] Weigh out the following by weight: 45 parts of anti-aging modified polysiloxane, 70 parts of low-density polyethylene, 2 parts of initiator benzoyl peroxide, and 3 parts of auxiliary additives, and add them to a twin-screw extruder. Set the temperature of the twin-screw extruder to 150℃ in zone 1, 155℃ in zone 2, 160℃ in zone 3, and 160℃ in zone 4, and the die temperature to 165℃. After melting and mixing for 5 minutes, extrude the mixture, cool it down to solidify, pulverize it, and pass it through a 100-mesh sieve to obtain anti-aging modified PE.

[0056] In the reaction, under high-temperature twin-screw extrusion conditions, benzoyl peroxide in the system first undergoes homolytic cracking to generate benzoyloxy radicals and phenyl radicals. These radicals catalyze the formation of alkyl radicals from the methylene groups on the low-density polyethylene molecular chain, which then undergo free radical polymerization with the olefin double bonds on the anti-aging modified polysiloxane molecules. This results in a chemical bond between the anti-aging modified polysiloxane and the low-density polyethylene, thus preparing anti-aging modified PE.

[0057] Example 2

[0058] This embodiment provides a method for preparing anti-aging modified PE, including the following steps:

[0059] Step A1: Preparation of 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene

[0060] Weigh out 23.6 g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 21.7 g of 3-propyl isocyanate methyl diethoxysilane, and 165.2 mL of tetrahydrofuran and add them to a reaction flask under argon protection. Stir the mixture and heat it to 47 °C. Maintain the temperature for 50 min. Then heat the mixture to 60 °C and apply a negative pressure of -0.1 MPa to remove low-boiling substances by vacuum distillation to obtain 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane) methoxybenzene.

[0061] Step A2: Preparation of anti-aging modified polysiloxane

[0062] Weigh out 50g of octamethylcyclotetrasiloxane, 15g of aminopropylmethyldimethoxysilane, 15g of 3,5-di-tert-butyl-4-(carbamate-propyldiethoxysilane)methoxybenzene, and 25mL of 50wt% sulfuric acid and add them to a reaction flask. Stir the mixture and heat it to 90℃. Keep the temperature for 40min. Add 10g of diallyltetramethyldisiloxane to the reaction flask and keep the temperature for 70min. Cool the reaction flask to room temperature and add 2wt% sodium bicarbonate aqueous solution to adjust the pH of the system to 8. Allow the mixture to stand and separate the layers. Wash the upper organic matter three times with purified water and transfer it to a rotary evaporator with a water bath temperature of 75℃. Apply a negative pressure to -0.1MPa and remove low-boiling substances by vacuum evaporation to obtain anti-aging modified polysiloxane.

[0063] Step A3: Preparation of anti-aging modified PE

[0064] Calcium stearate, ethylene bis-stearamide and triethyl phosphite were mixed evenly in a weight ratio of 3:2:1 to obtain the auxiliary additive.

[0065] Weigh out the following components by weight: 50 parts of anti-aging modified polysiloxane, 75 parts of low-density polyethylene, 2.5 parts of initiator benzoyl peroxide, and 4 parts of auxiliary additives. Add them to a twin-screw extruder. Set the temperature of the twin-screw extruder to 155℃ in zone 1, 160℃ in zone 2, 165℃ in zone 3, and 165℃ in zone 4, and the die temperature to 170℃. After melting and mixing for 5.5 minutes, extrude the mixture, cool it down to solidify, pulverize it, and pass it through a 100-mesh sieve to obtain anti-aging modified PE.

[0066] Example 3

[0067] This embodiment provides a method for preparing anti-aging modified PE, including the following steps:

[0068] Step A1: Preparation of 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene

[0069] Weigh out 23.6 g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 21.7 g of 3-propyl isocyanate methyl diethoxysilane, and 165.2 mL of tetrahydrofuran and add them to a reaction flask under argon protection. Stir the mixture and heat it to 50 °C. Maintain the temperature for 60 min. Then heat the mixture to 60 °C and apply a vacuum of -0.1 MPa to remove low-boiling substances by vacuum distillation to obtain 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane) methoxybenzene.

[0070] Step A2: Preparation of anti-aging modified polysiloxane

[0071] Weigh out 50g of octamethylcyclotetrasiloxane, 16g of aminopropylmethyldimethoxysilane, 15g of 3,5-di-tert-butyl-4-(carbamate-propyldiethoxysilane)methoxybenzene, and 25mL of 50wt% sulfuric acid and add them to a reaction flask. Stir the mixture and heat it to 95℃. Keep the temperature for 50min. Add 10g of diallyltetramethyldisiloxane to the reaction flask and keep the temperature for 80min. Cool the reaction flask to room temperature and add 3wt% sodium bicarbonate aqueous solution to adjust the pH of the system to 8. Allow the mixture to stand and separate the layers. Wash the upper organic matter three times with purified water and transfer it to a rotary evaporator with a water bath temperature of 80℃. Apply a negative pressure to -0.1MPa and remove low-boiling substances by vacuum evaporation to obtain anti-aging modified polysiloxane.

[0072] Step A3: Preparation of anti-aging modified PE

[0073] Zinc stearate, ethylene bis-stearamide and triethyl phosphite were mixed evenly in a weight ratio of 3:2:1 to obtain the auxiliary additive.

[0074] Weigh out the following by weight: 55 parts of anti-aging modified polysiloxane, 80 parts of low-density polyethylene, 3 parts of initiator benzoyl peroxide, and 5 parts of auxiliary additives, and add them to a twin-screw extruder. Set the temperature of the twin-screw extruder to 160℃ in zone 1, 165℃ in zone 2, 170℃ in zone 3, and 170℃ in zone 4, and the die temperature to 175℃. After melting and mixing for 6 minutes, extrude the mixture, cool it down to solidify, pulverize it, and pass it through a 100-mesh sieve to obtain anti-aging modified PE.

[0075] Example 4

[0076] This embodiment provides a method for preparing an epoxy-based reinforcing agent, including the following steps:

[0077] Step B1: Preparation of phenylamine-modified dicyanobenzene

[0078] Weigh 153g of 1,4-diamino-2-nitrobenzene and 1071mL of N,N-dimethylformamide and add them to an argon-protected reaction flask. Stir until the system dissolves. Add 275g of potassium carbonate and 144g of 3,4-dicyanophenol to the reaction flask. Raise the temperature of the reaction flask to 80℃ and keep it at this temperature for 6 hours. Cool the reaction flask to room temperature and add 5L of 2wt% sodium dodecyl sulfate aqueous solution. Keep it at this temperature and stir for 20 minutes. Filter the mixture. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 60℃ and dry it to constant weight to obtain phenylamine-modified dicyanobenzene.

[0079] In the reaction, under the action of the strong base potassium carbonate, the phenolic hydroxyl group of 3,4-dicyanophenol is first deprotonated to generate a highly nucleophilic phenolate. The phenolate attacks the carbon atom activated by the strong electron-withdrawing effect of the nitro group on the aromatic ring via the SNAr mechanism, promoting the formation of a σ-complex intermediate. Subsequently, through proton migration and leaving group rearrangement, the nitro group leaves and the conjugated structure of the aromatic ring is restored. Finally, a stable aryl ether bond is formed between the aniline structure and dicyanophenol, thus preparing phenylamine-modified dicyanophenol with a diarylamine modification in its structure.

[0080] Step B2: Preparation of epoxy-modified dicyanobenzene

[0081] Weigh 250.3 g of phenylamine-modified dicyanobenzene and 200 2 mL of N,N-dimethylformamide and add them to a reaction flask. Stir until the system is dissolved. Add 751 mL of 40 wt% sodium hydroxide solution to the reaction flask. Raise the temperature of the reaction flask to 50 °C. Add 277.5 g of epichlorohydrin dropwise to the reaction flask. After the addition is complete, keep the reaction at this temperature for 5 h. Allow the reaction system to cool naturally to room temperature. Add 6 L of 2 wt% sodium dodecyl sulfate aqueous solution to the reaction flask. Keep the system at this temperature and stir for 20 min. Filter the mixture. Wash the filter cake with purified water until neutral and then wash it three times with anhydrous ethanol. Transfer the filter cake to a drying oven at 60 °C and dry it to constant weight to obtain epoxy-modified dicyanobenzene.

[0082] In the reaction, the aromatic amino group in the phenylamine-modified dicyanobenzene molecule is partially deprotonated by sodium hydroxide and undergoes a nucleophilic substitution reaction with epichlorohydrin. Subsequently, the amino group attacks the primary carbon atom in the epichlorohydrin molecule that is attached to chlorine via an SN2 mechanism. The chloride ion is released as a leaving group, introducing an epoxy end group onto the aromatic amine nitrogen, resulting in an epoxy-modified dicyanobenzene with multiple active epoxy groups.

[0083] Step B3: Preparation of epoxy group reinforcing agent

[0084] An epoxy-modified dicyanobenzene and bisphenol A type epoxy resin were mixed at a weight ratio of 2:3 to obtain an epoxy-based reinforcing agent.

[0085] Example 5

[0086] This embodiment provides a method for preparing an epoxy-based reinforcing agent, including the following steps:

[0087] Step B1: Preparation of phenylamine-modified dicyanobenzene

[0088] Weigh 153g of 1,4-diamino-2-nitrobenzene and 1071mL of N,N-dimethylformamide into an argon-protected reaction flask and stir until dissolved. Add 291g of potassium carbonate and 144g of 3,4-dicyanophenol to the reaction flask. Raise the temperature of the reaction flask to 85℃ and keep it at this temperature for 7 hours. Cool the reaction flask to room temperature and add 5L of 2wt% sodium dodecyl sulfate aqueous solution. Keep it at this temperature and stir for 25 minutes. Filter the mixture and wash the filter cake with purified water until neutral. Dry the filter cake and transfer it to a drying oven at 65℃. Dry the cake to constant weight to obtain phenylamine-modified dicyanobenzene.

[0089] Step B2: Preparation of epoxy-modified dicyanobenzene

[0090] Weigh 250.3 g of phenylamine-modified dicyanobenzene and 200 2 mL of N,N-dimethylformamide and add them to a reaction flask. Stir until the system is dissolved. Add 751 mL of 45 wt% sodium hydroxide solution to the reaction flask. Raise the temperature of the reaction flask to 55 °C. Add 277.5 g of epichlorohydrin dropwise to the reaction flask. After the addition is complete, keep the reaction at this temperature for 5.5 h. Allow the reaction system to cool naturally to room temperature. Add 6 L of 2 wt% sodium dodecyl sulfate aqueous solution to the reaction flask. Keep the system at this temperature and stir for 25 min. Filter the mixture. Wash the filter cake with purified water until neutral and then wash it three times with anhydrous ethanol. Transfer the filter cake to a drying oven at 65 °C and dry it to constant weight to obtain epoxy-modified dicyanobenzene.

[0091] Step B3: Preparation of epoxy group reinforcing agent

[0092] An epoxy-modified dicyanobenzene and bisphenol A type epoxy resin were mixed at a weight ratio of 2:3 to obtain an epoxy-based reinforcing agent.

[0093] Example 6

[0094] This embodiment provides a method for preparing an epoxy-based reinforcing agent, including the following steps:

[0095] Step B1: Preparation of phenylamine-modified dicyanobenzene

[0096] Weigh 153g of 1,4-diamino-2-nitrobenzene and 1071mL of N,N-dimethylformamide and add them to an argon-protected reaction flask. Stir until the system dissolves. Add 306g of potassium carbonate and 144g of 3,4-dicyanophenol to the reaction flask. Raise the temperature of the reaction flask to 90℃ and keep it at that temperature for 8 hours. Cool the reaction flask to room temperature and add 5L of 2wt% sodium dodecyl sulfate aqueous solution. Keep it at that temperature and stir for 30 minutes. Filter the mixture. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 70℃ and dry it to constant weight to obtain phenylamine-modified dicyanobenzene.

[0097] Step B2: Preparation of epoxy-modified dicyanobenzene

[0098] Weigh 250.3 g of phenylamine-modified dicyanobenzene and 200 2 mL of N,N-dimethylformamide and add them to a reaction flask. Stir until the system is dissolved. Add 751 mL of 50 wt% sodium hydroxide solution to the reaction flask. Raise the temperature of the reaction flask to 60 °C. Add 277.5 g of epichlorohydrin dropwise to the reaction flask. After the addition is complete, keep the reaction at this temperature for 6 h. Allow the reaction system to cool naturally to room temperature. Add 6 L of 2 wt% sodium dodecyl sulfate aqueous solution to the reaction flask. Keep the system at this temperature and stir for 30 min. Filter the mixture. Wash the filter cake with purified water until neutral and then wash it three times with anhydrous ethanol. Transfer the filter cake to a drying oven at 70 °C and dry it to constant weight to obtain epoxy-modified dicyanobenzene.

[0099] Step B3: Preparation of epoxy group reinforcing agent

[0100] An epoxy-modified dicyanobenzene and bisphenol A type epoxy resin were mixed at a weight ratio of 2:3 to obtain an epoxy-based reinforcing agent.

[0101] Example 7

[0102] This embodiment provides a method for preparing an aging-resistant and interference-resistant industrial wire harness, including the following steps:

[0103] Step S1: Prepare the wrapping tape

[0104] Diamyl phthalate, stearate, ethylene bis-stearamide and antioxidant 1010 were mixed evenly in a weight ratio of 5:3:1:2 to obtain the additive.

[0105] Weigh out the following by weight: 60 parts of low-density polyethylene, 25 parts of high-density polyethylene, 50 parts of anti-aging modified PE prepared in Example 1, 28 parts of epoxy-based reinforcing agent prepared in Example 4, and 5 parts of additives. Mix them evenly and add them to a twin-screw extruder. Set the temperature of the twin-screw extruder to 150°C in zone 1, 155°C in zone 2, 160°C in zone 3, and 160°C in zone 4, and the die temperature to 165°C. After melting and mixing for 3 minutes, extrude the mixture from the die. Then, stretch the mixture twice along its length at a temperature of 150°C to obtain an aging-resistant base tape with a thickness of 0.4 mm.

[0106] Environmentally friendly butyl rubber adhesive is coated on one side of the aging-resistant base tape to form an adhesive layer with a thickness of 60 μm, thus preparing the winding tape.

[0107] Step S2, Anti-interference coating

[0108] Using copper core wires with an insulating layer on the surface as conductors, several groups of conductors are placed in parallel to form a wire group, and then aluminum foil is wrapped around the outside to form an anti-interference layer.

[0109] Step S3: Prepare the finished wire harness

[0110] The wrapping tape prepared in step S1 is evenly wrapped around the outside of the anti-interference layer to form a cable harness layer, and fixed terminals are installed at both ends of the wire group bound by it to obtain the finished wire harness.

[0111] Example 8

[0112] This embodiment provides a method for preparing an aging-resistant and interference-resistant industrial wire harness, including the following steps:

[0113] Step S1: Prepare the wrapping tape

[0114] Dioctyl phthalate, stearate, ethylene bis-stearamide and antioxidant 520 were mixed evenly in a weight ratio of 5:3:1:2 to obtain the additive.

[0115] Weigh out the following by weight: 65 parts of low-density polyethylene, 27 parts of high-density polyethylene, 55 parts of anti-aging modified PE prepared in Example 2, 30 parts of epoxy-based reinforcing agent prepared in Example 5, and 5.5 parts of additives. Mix them evenly and add them to a twin-screw extruder. Set the temperature of the twin-screw extruder to 155°C in zone 1, 160°C in zone 2, 165°C in zone 3, and 165°C in zone 4, and the die temperature to 170°C. After melting and mixing for 3.5 minutes, extrude the mixture from the die. Then, stretch the mixture twice along its length at a temperature of 155°C to obtain an aging-resistant base tape with a thickness of 0.4 mm.

[0116] Environmentally friendly butyl rubber adhesive is coated on one side of the aging-resistant base tape to form an adhesive layer with a thickness of 65 μm, thus preparing the winding tape.

[0117] Step S2, Anti-interference coating

[0118] Using copper core wires with an insulating layer on the surface as conductors, several groups of conductors are placed in parallel to form a wire group, and then aluminum foil is wrapped around the outside to form an anti-interference layer.

[0119] Step S3: Prepare the finished wire harness

[0120] The wrapping tape prepared in step S1 is evenly wrapped around the outside of the anti-interference layer to form a cable harness layer, and fixed terminals are installed at both ends of the wire group bound by it to obtain the finished wire harness.

[0121] Example 9

[0122] This embodiment provides a method for preparing an aging-resistant and interference-resistant industrial wire harness, including the following steps:

[0123] Step S1: Prepare the wrapping tape

[0124] Diisobutyl phthalate, stearate, ethylene bis-stearamide and antioxidant 1024 were mixed evenly in a weight ratio of 5:3:1:2 to obtain the additive.

[0125] Weigh out the following by weight: 70 parts of low-density polyethylene, 35 parts of high-density polyethylene, 60 parts of anti-aging modified PE prepared in Example 3, 32 parts of epoxy-based reinforcing agent prepared in Example 6, and 6 parts of additives. Mix them evenly and add them to a twin-screw extruder. Set the temperature of the twin-screw extruder to 160°C in zone 1, 165°C in zone 2, 170°C in zone 3, and 170°C in zone 4, and the die temperature to 175°C. After melting and mixing for 4 minutes, extrude the mixture from the die. Then, stretch the mixture twice along its length at a temperature of 160°C to obtain an aging-resistant base tape with a thickness of 0.4 mm.

[0126] Environmentally friendly butyl rubber adhesive is coated on one side of the aging-resistant base tape to form an adhesive layer with a thickness of 70 μm, thus preparing the winding tape.

[0127] Step S2, Anti-interference coating

[0128] Using copper core wires with an insulating layer on the surface as conductors, several groups of conductors are placed in parallel to form a wire group, and then aluminum foil is wrapped around the outside to form an anti-interference layer.

[0129] Step S3: Prepare the finished wire harness

[0130] The wrapping tape prepared in step S1 is evenly wrapped around the outside of the anti-interference layer to form a cable harness layer, and fixed terminals are installed at both ends of the wire group bound by it to obtain the finished wire harness.

[0131] Comparative Example 1

[0132] The difference between this comparative example and Example 9 is that, in the preparation of the anti-aging modified PE, 3,5-di-tert-butyl-4-(carbamate propyl diethoxysilane)methoxybenzene was not added in step A2.

[0133] Comparative Example 2

[0134] The difference between this comparative example and Example 9 is that, in the preparation of the anti-aging modified PE, aminopropylmethyldimethoxysilane was not added in step A2.

[0135] Comparative Example 3

[0136] The difference between this comparative example and Example 9 is that, in the preparation of the epoxy-based reinforcing agent, 1,4-diamino-2-nitrobenzene is replaced by 4-nitroaniline in equimolar form in step B1.

[0137] Comparative Example 4

[0138] The difference between this comparative example and Example 9 is that, in the preparation of the epoxy-based reinforcing agent, epoxy-modified dicyanobenzene was not added in step B3.

[0139] Performance testing:

[0140] The spiral wrapping tape samples used in Examples 7-9 and Comparative Examples 1-4 were placed in a heat aging test chamber at 100°C and heat-aged for 100 hours. The longitudinal breaking strength and elongation at break of the spiral wrapping tape before and after heat aging were determined in accordance with the standard FZ / T 64071-2019 "Sewn nonwoven base fabric for hand-tearable tape".

[0141] After cutting the wrapping tape samples used in Examples 7-9 and Comparative Examples 1-4 to standard, place them flat on a heating plate. The heating plate is gradually heated at a heating rate of 0.5℃ / min until the surface area changes by 2%. Record the temperature at this time, which is expressed as the high temperature resistance temperature of the tape sample.

[0142] During the performance test, each sample was tested 30 times to obtain 30 sets of data. The five largest and five smallest values ​​were removed, and the average value of the remaining 20 sets of data was calculated to obtain the experimental data. The specific test data is shown in Table 1 below.

[0143] Data Test Record Table 1

[0144]

[0145] Data Analysis:

[0146] Comparative analysis of the data in Table 1 shows that the high-temperature resistance of the spiral wrapping tape prepared by this invention reaches 135.1-136.3℃. Before heat aging, the tensile strength of the spiral wrapping tape reaches 107.3-108.5N and the elongation at break reaches 173.8-175.5%. After heat aging, the tensile strength of the spiral wrapping tape reaches 98.5-99.8N and the elongation at break reaches 140.2-142.3%. The test data of various performance parameters of the sample are better than those of the comparative example. By using the prepared spiral wrapping tape to wrap the aluminum foil-covered wire group, a wire harness product is obtained. The multi-level structure design combining the outer layer of spiral wrapping tape and the inner layer of aluminum foil significantly improves the wire harness in terms of electromagnetic interference suppression, thermal environment adaptability, and long-term service stability.

[0147] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. An aging-resistant and interference-resistant industrial wire harness, comprising a plurality of conductors, an interference-resistant layer, a cable tie layer, and terminals, characterized in that, The anti-interference layer is obtained by covering several wires with aluminum foil, the cable tie layer is obtained by evenly wrapping the anti-interference layer with adhesive tape, and the terminals are installed at both ends of the cable tie. The wrapping tape includes an aging-resistant base tape and an adhesive layer. The aging-resistant base tape comprises the following components by weight: 60-70 parts of low-density polyethylene, 25-35 parts of high-density polyethylene, 50-60 parts of anti-aging modified PE, 28-32 parts of epoxy-based reinforcing agent, and 5-6 parts of additives. The epoxy-based reinforcing agent is composed of epoxy-modified dicyanobenzene and bisphenol A type epoxy resin in a weight ratio of 2:

3.

2. The aging-resistant and interference-resistant industrial wire harness according to claim 1, characterized in that, The preparation method of anti-aging modified PE is as follows: anti-aging modified polysiloxane, low-density polyethylene, initiator and auxiliary additives are added to a twin-screw extruder, melt-mixed for 5-6 minutes and then extruded, cooled and cured, pulverized and passed through a 100-mesh sieve to obtain anti-aging modified PE.

3. The aging-resistant and interference-resistant industrial wire harness according to claim 2, characterized in that, The weight ratio of the anti-aging modified polysiloxane, low-density polyethylene, initiator, and auxiliary additives is 45-55:70-80:2-3:3-5. The initiator is benzoyl peroxide. The auxiliary additives consist of a dispersant, a lubricant, and a heat stabilizer in a weight ratio of 3:2:

1. The dispersant is stearate, the lubricant is ethylene bis-stearamide, and the heat stabilizer is triethyl phosphite. The temperature of the twin-screw extruder is 150-160℃ in zone one, 155-165℃ in zone two, 160-170℃ in zone three, and 160-170℃ in zone four, with a die temperature of 165-175℃.

4. The aging-resistant and interference-resistant industrial wire harness according to claim 2, characterized in that, The method for preparing anti-aging modified polysiloxane is as follows: octamethylcyclotetrasiloxane, aminopropylmethyldimethoxysilane, 3,5-di-tert-butyl-4-(carbamate-propyldiethoxysilane)methoxybenzene and sulfuric acid are mixed, the reaction system is heated to 85-95℃, and the reaction is maintained at this temperature for 30-50 min. Diallyltetramethyldisiloxane is then added to the reaction system, and the reaction is maintained at this temperature for 60-80 min. After post-treatment, the anti-aging modified polysiloxane is obtained.

5. The aging-resistant and interference-resistant industrial wire harness according to claim 4, characterized in that, The ratio of octamethylcyclotetrasiloxane, aminopropylmethyldimethoxysilane, 3,5-di-tert-butyl-4-(carbamate-propyldiethoxysilane)methoxybenzene, sulfuric acid, and diallyltetramethyldisiloxane is 10g:2.8-3.2g:3g:5mL:2g, and the sulfuric acid has a mass fraction of 50%.

6. The aging-resistant and interference-resistant industrial wire harness according to claim 1, characterized in that, The preparation method of epoxy-modified dicyanobenzene is as follows: phenylamine-modified dicyanobenzene and N,N-dimethylformamide are mixed and stirred until the system is dissolved. Sodium hydroxide solution is added to the reaction system, and the temperature of the reaction system is raised to 50-60℃. Epichlorohydrin is added dropwise to the reaction system. After the addition is complete, the reaction is kept at the temperature for 5-6 hours. After post-treatment, epoxy-modified dicyanobenzene is obtained.

7. The aging-resistant and interference-resistant industrial wire harness according to claim 6, characterized in that, The molar ratio of phenylamine-modified dicyanobenzene to epichlorohydrin is 1:3, the volume ratio of phenylamine-modified dicyanobenzene, N,N-dimethylformamide, and sodium hydroxide solution is 1g:8mL:3mL, and the mass fraction of the sodium hydroxide solution is 40-50%.

8. The aging-resistant and interference-resistant industrial wire harness according to claim 6, characterized in that, The preparation method of phenylamine-modified dicyanobenzene is as follows: under an inert gas atmosphere, 1,4-diamino-2-nitrobenzene and N,N-dimethylformamide are mixed and stirred until the system is dissolved. A catalyst and 3,4-dicyanophenol are added to the reaction system. The temperature of the reaction system is raised to 80-90℃ and the reaction is maintained for 6-8 hours. After post-treatment, phenylamine-modified dicyanobenzene is obtained.

9. The aging-resistant and interference-resistant industrial wire harness according to claim 8, characterized in that, The molar ratio of 1,4-diamino-2-nitrobenzene and 3,4-dicyanophenol is 1:1, and the molar ratio of 1,4-diamino-2-nitrobenzene, N,N-dimethylformamide and catalyst is 1g:7mL:1.8-2g. The catalyst is potassium carbonate.

10. A method for preparing an aging-resistant and interference-resistant industrial wire harness according to any one of claims 1-9, characterized in that, Includes the following steps: S1. Low-density polyethylene, high-density polyethylene, anti-aging modified PE, epoxy-based reinforcing agent and additives are mixed evenly and then added to a twin-screw extruder. After melting and mixing for 3-4 minutes, the mixture is extruded from the die to obtain an aging-resistant base tape with a thickness of 0.4 mm. Adhesive is coated on one side of the aging-resistant base tape to form an adhesive layer with a thickness of 60-70 μm, thus preparing a winding tape. S2. Using copper core wires with an insulating layer on the surface as conductors, several groups of conductors are placed in parallel to form a wire group, and then aluminum foil is wrapped around the outside to form an anti-interference layer. S3. The wrapping tape prepared in step S1 is evenly wrapped around the outside of the anti-interference layer to form a cable harness layer, and fixed terminals are installed at both ends of the wire group bound by it to obtain the finished wire harness.

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