Corrosion-resistant cable for rail transport

Abstract

The application discloses a kind of corrosion-resistant cable for rail transit, belongs to cable technical field.A kind of corrosion-resistant cable for rail transit, it is characterized in that, including cable core and the sheath layer being covered in the outside of cable core;The sheath layer includes the following components: by weight fraction, 90-100 parts butyl rubber, 10-15 parts polytetrafluoroethylene micro powder, 1-2 parts vulcanizing agent, 10-12 parts plasticizer, 2-3 parts lubricant, 1-2 parts accelerator, 2-3 parts antioxidant, 20-30 parts modified graphene.The corrosion-resistant cable for rail transit provided in the application, the sheath layer is introduced by modified graphene of specific structure, significantly improve the comprehensive performance of material, especially suitable for the harsh requirements under the environment of rail transit.

Description

Technical Field

[0001] This invention belongs to the field of cable technology, and specifically relates to a corrosion-resistant cable for rail transportation. Background Technology

[0002] With the rapid development of rail transit, the performance requirements for cables are becoming increasingly stringent, especially in terms of corrosion resistance, flame retardancy, and mechanical strength. Rail transit cables are exposed to complex environments such as humidity and acids / alkalis for extended periods, making them susceptible to corrosive media, leading to insulation aging and damage, severely impacting cable lifespan and operational safety. Current technologies often employ fillers added to the rubber matrix to improve cable sheath performance, such as carbon black or inorganic fillers. However, this approach often fails to achieve a synergistic improvement in corrosion resistance, flame retardancy, and mechanical properties. For example, ordinary fillers have poor dispersibility in rubber, easily forming agglomerates and failing to create an effective physical barrier layer, allowing corrosive media to still penetrate along the interface. Simultaneously, large amounts of traditional flame retardants can negatively affect the material's mechanical properties, and their flame retardant efficiency is limited. Graphene, due to its excellent barrier and mechanical reinforcing effects, has been explored for use in cable materials; however, unmodified graphene exhibits poor dispersibility in the rubber matrix and weak interfacial bonding with the matrix, hindering the full realization of its performance advantages.

[0003] Therefore, developing a rail transit cable sheath material that combines excellent corrosion resistance, flame retardancy, and mechanical strength has become an urgent technical problem to be solved in this field. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a corrosion-resistant cable for rail transportation.

[0005] The objective of this invention can be achieved through the following technical solutions: A corrosion-resistant cable for rail transit includes a cable core and a sheath covering the outside of the cable core; the sheath comprises the following components: by weight, 90-100 parts butyl rubber, 10-15 parts polytetrafluoroethylene powder, 1-2 parts vulcanizing agent, 10-12 parts plasticizer, 2-3 parts lubricant, 1-2 parts accelerator, 2-3 parts antioxidant, and 20-30 parts modified graphene.

[0006] In a more optimized manner, the preparation process of the modified graphene is as follows: S1: Under a protective atmosphere, 3-aminopyrazole, triethylamine, and tetrahydrofuran were mixed and stirred to dissolve. Then, diphenylphosphonic chloride was slowly added dropwise. After the addition was complete, the mixture was stirred and reacted overnight at room temperature. After filtration, the solvent was removed from the filtrate by rotary evaporation. After recrystallization, intermediate product A was obtained. S2: Allyl glycidyl ether and chloroplatinic acid are added to isopropanol and stirred until homogeneous. Under a protective atmosphere, the resulting mixed solution is slowly added dropwise to a heptamethyltrisiloxane solution. The temperature is raised to 70-80℃ and the reaction is carried out for 4-5 hours. After the reaction is completed, the product is distilled under reduced pressure to obtain intermediate product B. S3: Mix intermediate product A, intermediate product B and isopropanol, raise the temperature to 70-80℃ under a protective atmosphere, and react for 6-7 hours. After the reaction is completed, remove the solvent and impurities by rotary evaporation to obtain the modifier. S4: Under a protective atmosphere, graphene oxide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, and anhydrous N,N-dimethylformamide were mixed and stirred evenly. The mixture was then activated at room temperature for 3-4 hours. Subsequently, a modifier was added, and the mixture was stirred overnight at room temperature. After centrifugation, washing, and drying, modified graphene was obtained.

[0007] The structure of the modifier is shown below: In this scheme, the nitrogen atom on the pyrazole ring of 3-aminopyrazole reacts with diphenylphosphonic chloride to generate intermediate A; simultaneously, allyl glycidyl ether and heptamethyltrisiloxane undergo a hydrosilylation reaction under chloroplatinic acid catalysis, isopropanol system, and 70-80℃ conditions to generate intermediate B; subsequently, the unreacted amino group in intermediate A reacts with intermediate B under a protective atmosphere and 70-80℃ conditions to generate a modifier containing phosphorus, silicon, and pyrazole structures; then, graphene oxide is activated in an anhydrous N,N-dimethylformamide system at room temperature for 3-4 hours under the activation of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide to activate its surface carboxyl groups, and then the above-mentioned modifier is added. Through the reaction of the activated carboxyl groups with the active groups of the modifier, the target groups are grafted onto the surface of graphene oxide. After centrifugation, washing, and drying, modified graphene is obtained.

[0008] In a more optimized manner, the raw materials for preparing intermediate product A include the following components: by weight, 10-12 parts of 3-aminopyrazole, 12-18 parts of triethylamine, 80-100 parts of tetrahydrofuran, and 15-20 parts of diphenylphosphonic chloride.

[0009] In a more optimized manner, the raw materials for preparing the intermediate product B include the following components: by weight, 15-18 parts allyl glycidyl ether, 0.05-0.1 parts chloroplatinic acid, 60-80 parts isopropanol, and 50-70 parts heptamethyltrisiloxane solution; wherein the concentration of the heptamethyltrisiloxane solution is 35 wt%.

[0010] In a more optimized manner, the raw materials for preparing the modifier include the following components: by weight, 10-12 parts of intermediate product A, 12-15 parts of intermediate product B, and 50-80 parts of isopropanol.

[0011] In a more optimized manner, the raw materials for preparing the modified graphene include the following components: by weight, 2-3 parts graphene oxide, 2-5 parts 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-3 parts N-hydroxysuccinimide, 100-120 parts anhydrous N,N-dimethylformamide, and 8-10 parts modifier.

[0012] Ideally, the vulcanizing agent is dicumyl peroxide.

[0013] More preferably, the lubricant is calcium stearate; the plasticizer is DPHP; the accelerator is TTTE; and the antioxidant is MB.

[0014] The beneficial effects of this invention are: This invention provides a corrosion-resistant cable for rail transit, whose sheath layer significantly improves the overall performance of the material by introducing modified graphene with a specific structure, making it particularly suitable for the stringent requirements of rail transit environments. Firstly, regarding corrosion resistance, the modified graphene surface is grafted with organic structures containing pyrazole rings, phosphoryl groups, and siloxane segments. These groups synergistically enhance the corrosion resistance of the sheath layer. On one hand, the polar groups in the grafted material can form a strong interaction with the butyl rubber matrix, allowing the modified graphene to be uniformly dispersed in the rubber and form a dense physical barrier layer, effectively extending the penetration path of corrosive media. On the other hand, the presence of phosphoryl groups and siloxane structures improves the overall chemical inertness and hydrophobicity of the material, further blocking the erosion of acidic media such as hydrochloric acid, thereby significantly extending the service life of the cable in humid and acidic environments.

[0015] Secondly, regarding flame retardant properties, the phosphorus element and siloxane segments introduced by the modified graphene play a synergistic flame-retardant role. The phosphorus-containing groups decompose at high temperatures to generate polyphosphoric acid, which promotes the charring of butyl rubber and forms an expanded char layer to isolate oxygen and heat; while the siloxane structure migrates to the material surface during combustion, generating a heat-resistant silica ceramic layer, which further enhances the density of the char layer, effectively inhibiting flame spread and smoke generation, giving the cable excellent self-extinguishing properties and flame-retardant safety.

[0016] In addition, in terms of mechanical strength, the modified graphene is uniformly dispersed in the butyl rubber matrix, and the organic long chains grafted on its surface cross-link or entangle with the rubber molecular chains to form a physical and chemical dual reinforcement network, which significantly improves the tensile strength of the sheath layer; at the same time, the addition of polytetrafluoroethylene micro powder further reduces the coefficient of friction and improves the material's scratch resistance, ensuring that the cable maintains its structural integrity during laying and use. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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.

[0018] Example 1: A corrosion-resistant cable for rail transit, comprising a cable core and a sheath covering the outside of the cable core; its preparation method is as follows: multiple wire cores are arranged in a ring array to form a cable core, then 90 parts of butyl rubber, 10 parts of polytetrafluoroethylene micro powder, 10 parts of plasticizer (plasticizer DPHP), 2 parts of lubricant (calcium stearate), 1 part of accelerator (accelerator TTTE), 2 parts of antioxidant (anti-aging agent MB), and 20 parts of modified graphene are mixed, and 1 part of vulcanizing agent (diisopropylbenzene peroxide) is added for vulcanization to obtain a compound rubber, which is extruded onto the outside of the cable core through an extruder to obtain a corrosion-resistant cable; The preparation process of modified graphene is as follows: S1: Under a protective atmosphere, 10 parts of 3-aminopyrazole, 12 parts of triethylamine, and 80 parts of tetrahydrofuran were mixed and stirred to dissolve. Then, 15 parts of diphenylphosphonic chloride were slowly added dropwise. After the addition was completed, the mixture was stirred and reacted overnight at room temperature. After filtration, the solvent was removed from the filtrate by rotary evaporator. After recrystallization, intermediate product A was obtained. S2: Add 15 parts allyl glycidyl ether and 0.05 parts chloroplatinic acid to 60 parts isopropanol, stir well, and under a protective atmosphere, slowly add the resulting mixed solution dropwise to 50 parts heptamethyltrisiloxane solution (35 wt%, solvent is isopropanol), heat to 70℃ and react for 4 h, and after the reaction is completed, distill under reduced pressure to obtain intermediate product B. S3: Mix 10 parts of intermediate product A, 12 parts of intermediate product B and 50 parts of isopropanol, raise the temperature to 70°C under a protective atmosphere, and react for 6 hours. After the reaction is completed, remove the solvent and impurities by rotary evaporation to obtain the modifier. S4: Under a protective atmosphere, 2 parts of graphene oxide, 2 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1 part of N-hydroxysuccinimide, and 100 parts of anhydrous N,N-dimethylformamide were mixed and stirred evenly. The mixture was then activated at room temperature for 3 hours. Subsequently, 8 parts of modifier were added, and the mixture was stirred overnight at room temperature. After centrifugation, washing, and drying, modified graphene was obtained.

[0019] Example 2: A corrosion-resistant cable for rail transit, comprising a cable core and a sheath covering the outside of the cable core; its preparation method is as follows: multiple cores are arranged in a ring array to form a cable core, then 100 parts of butyl rubber, 15 parts of polytetrafluoroethylene micro powder, 12 parts of plasticizer (plasticizer DPHP), 3 parts of lubricant (calcium stearate), 2 parts of accelerator (accelerator TTTE), 3 parts of antioxidant (anti-aging agent MB), and 30 parts of modified graphene are mixed, and 2 parts of vulcanizing agent (diisopropylbenzene peroxide) are added for vulcanization to obtain a compound rubber, which is then extruded onto the outside of the cable core to obtain a corrosion-resistant cable; The preparation process of modified graphene is as follows: S1: Under a protective atmosphere, 12 parts of 3-aminopyrazole, 18 parts of triethylamine, and 100 parts of tetrahydrofuran were mixed and stirred to dissolve. Then, 20 parts of diphenylphosphonic chloride were slowly added dropwise. After the addition was completed, the mixture was stirred and reacted overnight at room temperature. After filtration, the solvent was removed from the filtrate by rotary evaporator. After recrystallization, intermediate product A was obtained. S2: Add 18 parts allyl glycidyl ether and 0.1 parts chloroplatinic acid to 80 parts isopropanol, stir well, and under a protective atmosphere, slowly add the resulting mixed solution dropwise to 70 parts heptamethyltrisiloxane solution (35 wt%, solvent is isopropanol), heat to 80℃ and react for 5 h, and after the reaction is completed, distill under reduced pressure to obtain intermediate product B. S3: Mix 12 parts of intermediate product A, 15 parts of intermediate product B and 80 parts of isopropanol, raise the temperature to 80°C under a protective atmosphere, and react for 7 hours. After the reaction is completed, remove the solvent and impurities by rotary evaporation to obtain the modifier. S4: Under a protective atmosphere, 3 parts of graphene oxide, 5 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 3 parts of N-hydroxysuccinimide, and 120 parts of anhydrous N,N-dimethylformamide were mixed and stirred evenly. The mixture was then activated at room temperature for 4 hours. Subsequently, 10 parts of modifier were added, and the mixture was stirred overnight at room temperature. After centrifugation, washing, and drying, modified graphene was obtained.

[0020] Example 3: A corrosion-resistant cable for rail transit, comprising a cable core and a sheath covering the outside of the cable core; its preparation method is as follows: multiple cores are arranged in a ring array to form a cable core, then 95 parts of butyl rubber, 12.5 parts of polytetrafluoroethylene micro powder, 11 parts of plasticizer (plasticizer DPHP), 2.5 parts of lubricant (calcium stearate), 1.5 parts of accelerator (accelerator TTTE), 2.5 parts of antioxidant (anti-aging agent MB), and 25 parts of modified graphene are mixed, and 1.5 parts of vulcanizing agent (diisopropylbenzene peroxide) are added for vulcanization to obtain a compound rubber, which is extruded onto the outside of the cable core through an extruder to obtain a corrosion-resistant cable; The preparation process of modified graphene is as follows: S1: Under a protective atmosphere, 11 parts of 3-aminopyrazole, 15 parts of triethylamine, and 90 parts of tetrahydrofuran were mixed and stirred to dissolve. Then, 17.5 parts of diphenylphosphonic chloride were slowly added dropwise. After the addition was complete, the mixture was stirred and reacted overnight at room temperature. After filtration, the solvent was removed from the filtrate by rotary evaporator. After recrystallization, intermediate product A was obtained. S2: 16.5 parts of allyl glycidyl ether and 0.075 parts of chloroplatinic acid were added to 70 parts of isopropanol and stirred until homogeneous. Under a protective atmosphere, the resulting mixed solution was slowly added dropwise to 60 parts of heptamethyltrisiloxane solution (35 wt%, solvent is isopropanol). The mixture was heated to 75 °C and reacted for 4.5 h. After the reaction was completed, the product was distilled under reduced pressure to obtain intermediate product B. S3: Mix 11 parts of intermediate product A, 13.5 parts of intermediate product B, and 65 parts of isopropanol. Under a protective atmosphere, raise the temperature to 75°C and react for 6.5 hours. After the reaction is complete, remove the solvent and impurities by rotary evaporation to obtain the modifier. S4: Under a protective atmosphere, 2.5 parts of graphene oxide, 3.5 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 2 parts of N-hydroxysuccinimide, and 110 parts of anhydrous N,N-dimethylformamide were mixed and stirred evenly. The mixture was then activated at room temperature for 3.5 h. Subsequently, 9 parts of modifier were added, and the mixture was stirred overnight at room temperature. After centrifugation, washing, and drying, modified graphene was obtained.

[0021] Comparative Example 1: No modification was made to the graphene oxide, as follows: A corrosion-resistant cable for rail transit includes a cable core and a sheath covering the outside of the cable core. The preparation method is as follows: multiple cores are arranged in a ring array to form a cable core. Then, 95 parts of butyl rubber, 12.5 parts of polytetrafluoroethylene micro powder, 11 parts of plasticizer (plasticizer DPHP), 2.5 parts of lubricant (calcium stearate), 1.5 parts of accelerator (accelerator TTTE), 2.5 parts of antioxidant (anti-aging agent MB), and 25 parts of graphene oxide are mixed, and 1.5 parts of vulcanizing agent (diisopropylbenzene peroxide) are added for vulcanization to obtain a compound. This compound is then extruded onto the outside of the cable core using an extruder to obtain a corrosion-resistant cable.

[0022] Testing experiment: (1) The tensile strength of the protective sleeve materials obtained in the examples and comparative examples was tested in accordance with standard GB / T1040-2006; (2) The oxygen index of the protective sleeve materials obtained in the examples and comparative examples was determined according to standard GB / T2406-2022; (3) The protective sleeve materials obtained in the examples and comparative examples were immersed in 20wt% hydrochloric acid for 30 days, and the tensile strength retention rate was measured; The obtained data is shown in the table below: Conclusion: The corrosion-resistant cable for rail transit prepared in this invention significantly improves the overall performance of the sheath layer by introducing modified graphene with a specific structure. The test data shows that the tensile strength of Examples 1 to 3 all reached over 22.5 MPa, far exceeding the 16.5 MPa of Comparative Example 1 (unmodified graphene oxide), indicating that the addition of modified graphene effectively enhanced the mechanical strength of the material. The oxygen index of all examples was above 32%, while that of Comparative Example 1 was only 28.9%, indicating excellent flame retardant properties. After immersion in 20 wt% hydrochloric acid for 30 days, the tensile strength retention rate of the examples all exceeded 95%, while that of Comparative Example 1 was only 80.9%, demonstrating superior corrosion resistance.

[0023] In summary, the cable sheath material of this invention exhibits outstanding performance in terms of mechanical strength, flame retardancy, and corrosion resistance, and can meet the usage requirements of harsh environments such as rail transit.

[0024] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above 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 one or more embodiments or examples.

[0025] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions 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 in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A corrosion-resistant cable for rail transit, characterized in that, It includes a cable core and a sheath layer covering the outside of the cable core; the sheath layer includes the following components by weight: 90-100 parts butyl rubber, 10-15 parts polytetrafluoroethylene powder, 1-2 parts vulcanizing agent, 10-12 parts plasticizer, 2-3 parts lubricant, 1-2 parts accelerator, 2-3 parts antioxidant, and 20-30 parts modified graphene.

2. The corrosion-resistant cable for rail transit according to claim 1, characterized in that, The preparation process of the modified graphene is as follows: S1: Under a protective atmosphere, 3-aminopyrazole, triethylamine, and tetrahydrofuran were mixed and stirred to dissolve. Then, diphenylphosphonic chloride was slowly added dropwise. After the addition was complete, the mixture was stirred and reacted overnight at room temperature. After filtration, the solvent was removed from the filtrate by rotary evaporation. After recrystallization, intermediate product A was obtained. S2: Allyl glycidyl ether and chloroplatinic acid are added to isopropanol and stirred until homogeneous. Under a protective atmosphere, the resulting mixed solution is slowly added dropwise to a heptamethyltrisiloxane solution. The temperature is raised to 70-80℃ and the reaction is carried out for 4-5 hours. After the reaction is completed, the product is distilled under reduced pressure to obtain intermediate product B. S3: Mix intermediate product A, intermediate product B and isopropanol, raise the temperature to 70-80℃ under a protective atmosphere, and react for 6-7 hours. After the reaction is completed, remove the solvent and impurities by rotary evaporation to obtain the modifier. S4: Under a protective atmosphere, graphene oxide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, and anhydrous N,N-dimethylformamide were mixed and stirred evenly. The mixture was then activated at room temperature for 3-4 hours. Subsequently, a modifier was added, and the mixture was stirred overnight at room temperature. After centrifugation, washing, and drying, modified graphene was obtained.

3. A corrosion-resistant cable for rail transit according to claim 2, characterized in that, The raw materials for preparing intermediate product A include the following components: by weight, 10-12 parts of 3-aminopyrazole, 12-18 parts of triethylamine, 80-100 parts of tetrahydrofuran, and 15-20 parts of diphenylphosphonic chloride.

4. A corrosion-resistant cable for rail transit according to claim 2, characterized in that, The raw materials for preparing intermediate product B include the following components: by weight, 15-18 parts allyl glycidyl ether, 0.05-0.1 parts chloroplatinic acid, 60-80 parts isopropanol, and 50-70 parts heptamethyltrisiloxane solution; wherein the concentration of heptamethyltrisiloxane solution is 35 wt%.

5. A corrosion-resistant cable for rail transit according to claim 2, characterized in that, The raw materials for preparing the modifier include the following components: by weight, 10-12 parts intermediate product A, 12-15 parts intermediate product B, and 50-80 parts isopropanol.

6. A corrosion-resistant cable for rail transit according to claim 2, characterized in that, The raw materials for preparing the modified graphene include the following components: by weight, 2-3 parts graphene oxide, 2-5 parts 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-3 parts N-hydroxysuccinimide, 100-120 parts anhydrous N,N-dimethylformamide, and 8-10 parts modifier.

7. A corrosion-resistant cable for rail transit according to claim 1, characterized in that, The vulcanizing agent is dicumyl peroxide.

8. A corrosion-resistant cable for rail transit according to claim 1, characterized in that, The lubricant is calcium stearate; the plasticizer is DPHP; the accelerator is TTTE; and the antioxidant is MB.

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