Flat cable for high strength wear resistant reel

Abstract

The application discloses a kind of flat cables for high-strength wear-resistant reel, belong to cable technical field.The preparation raw material of outer sheath includes the following components: by weight fraction, 50-60 parts of linear low density polyethylene, 20-35 parts of ethylene-vinyl acetate copolymer, 1-2 parts of antioxidant, 1-2 parts of lubricant, 1-2 parts of heat stabilizer, 10-12 parts of modified nano-silica.The application is modified by nano-silica, and the modified nano-silica is uniformly dispersed in the matrix, and the interface is firmly combined, which significantly improves the tensile strength, wear resistance and flame retardant performance of the cable sheath, and is suitable for frequent winding and unwinding of the reel.

Description

Technical Field

[0001] This invention belongs to the field of cable technology, specifically relating to a high-strength, wear-resistant flat cable for reels. Background Technology

[0002] Flat cables in reels are widely used in port machinery, lifting equipment, mining machinery and other applications. During use, they need to be frequently wound up and unwound, bent and subjected to friction and compression. Therefore, there are high requirements for the mechanical strength, wear resistance and flame retardancy of the cable sheath.

[0003] Currently, cable outer sheaths often use polyolefin materials such as linear low-density polyethylene and ethylene-vinyl acetate copolymer as the matrix, and add inorganic fillers such as nano-silica to improve the material's stiffness and wear resistance. However, in existing technologies, nano-silica has high surface energy and is prone to agglomeration, making it difficult to achieve uniform dispersion in the matrix resin. Direct blending often leads to stress concentration points inside the material, which deteriorates its tensile strength and tear resistance. To solve the dispersion problem, silane coupling agents are commonly used in industry to modify the surface of nano-silica. However, conventional coupling agent modification can only introduce a small number of organic functional groups on the particle surface. Although it improves the dispersibility to some extent, it cannot establish sufficiently strong chemical bonds or physical entanglements between the nanoparticles and the polymer matrix. The interfacial bonding is weak, and the interface is prone to debonding under external force, resulting in low stress transfer efficiency. Therefore, the improvement in the material's mechanical properties and wear resistance is limited. Meanwhile, the flame-retardant properties of existing cable sheath materials typically rely on the addition of halogenated flame retardants or large amounts of inorganic metal hydroxides. The former releases toxic fumes during combustion, failing to meet environmental protection requirements, while the latter requires high filler content, severely impairing the material's processing flowability and mechanical properties. Furthermore, some technologies attempt to introduce flame-retardant elements into modifiers, but often focus only on a single flame-retardant function, neglecting the synergistic improvement of nanofiller dispersibility and interfacial compatibility, resulting in incomplete modification effects.

[0004] Therefore, there is an urgent need to develop a modification technology that can simultaneously improve the dispersibility of nano-silica, enhance the bonding force of the organic-inorganic interface, and impart excellent flame retardant properties to the cable outer sheath, so as to overcome the defects of existing cables in terms of insufficient strength, poor wear resistance, and low flame retardant rating under frequent drum operation conditions. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a high-strength, wear-resistant flat cable for reels.

[0006] The objective of this invention can be achieved through the following technical solutions: A high-strength, wear-resistant flat cable for reels includes a conductor and an outer sheath. The raw materials for preparing the outer sheath include the following components: by weight, 50-60 parts linear low-density polyethylene, 20-35 parts ethylene-vinyl acetate copolymer, 1-2 parts antioxidant, 1-2 parts lubricant, 1-2 parts heat stabilizer, and 10-12 parts modified nano-silica.

[0007] In a more optimized manner, the preparation process of the modified nano-silica is as follows: S1: Triglycidyl isocyanurate was added to N,N-dimethylacetamide, the temperature was raised to 170°C, and the mixture was stirred until completely dissolved. Then, while maintaining the temperature at 170°C, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added in batches and slowly. After the addition was complete, the temperature was maintained at 170°C and the mixture was stirred continuously for 3 hours. After the reaction was completed, the solvent was removed by rotary evaporation to obtain intermediate A. S2: Intermediate A was added to N,N-dimethylacetamide and magnetically stirred in an oil bath at 50°C until completely dissolved, yielding a solution of intermediate A. 3-Aminopropyltriethoxysilane was added to N,N-dimethylacetamide and stirred until homogeneous, yielding a solution of 3-aminopropyltriethoxysilane. Under a protective atmosphere, the 3-aminopropyltriethoxysilane solution was slowly added dropwise to the intermediate A solution at 50°C. After the addition was complete, the temperature was maintained at 50°C, and the reaction was continued with stirring for 6 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was dried under vacuum to obtain the modifier. S3: Disperse nano-silica in N,N-dimethylformamide, add a modifier, raise the temperature to 80℃ under a protective atmosphere, react for 3-4 hours, filter, wash, and vacuum dry to obtain modified nano-silica.

[0008] In this scheme, triglycidyl isocyanurate (TGIC) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) are reacted at a molar ratio of 1:2. At high temperature, the PH bond in DOPO nucleophilically attacks two epoxy groups in the TGIC molecule, generating an intermediate A containing a double DOPO structure and retaining one unreacted epoxy group. Subsequently, this intermediate reacts with an equimolar amount of 3-aminopropyltriethoxysilane (APTES) at 50°C. The primary amino group of APTES undergoes nucleophilic ring-opening addition to the residual epoxy group, forming a carbon-nitrogen bond and introducing the triethoxysilane side chain into the molecule, yielding a modifier containing phosphorus, silicon, and a hydrolyzable ethoxy group. Finally, the ethoxy group on the modifier is hydrolyzed under heating conditions to generate silanol, which undergoes dehydration condensation with the silanol on the surface of nano-silica, thereby achieving a firm grafting of the modifier onto the surface of nanoparticles.

[0009] The structure of the modified nano-silica is shown below:

[0010] In a more optimized manner, in step S1, the ratio of triglycidyl isocyanurate to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 29.73 g: 43.23 g.

[0011] In a more optimized manner, in step S2, the ratio of intermediate A to 3-aminopropyltriethoxysilane is 72.96 g: 22.14 g.

[0012] In a more optimized manner, in step S3, the ratio of nano-silica to modifier is 10g:1.4g.

[0013] Ideally, the lubricant is polyethylene wax.

[0014] More preferably, the antioxidant is antioxidant 1010.

[0015] Ideally, the heat stabilizer is a calcium-zinc stabilizer.

[0016] The beneficial effects of this invention are: This invention significantly improves the dispersibility and interfacial bonding of nano-silica in the cable outer sheath matrix resin by modifying nano-silica. Specifically, the modifier used contains phosphorus, nitrogen, and silicon in its molecular structure. Among them, the phosphorus-phenanthroline structural units and isocyanurate structural units work synergistically to exert a flame-retardant effect, promoting the formation of a dense char layer during combustion and effectively inhibiting the transfer of heat and oxygen, thereby giving the cable outer sheath excellent flame-retardant properties. Meanwhile, the triethoxysilyl groups retained in the modifier molecule form strong chemical bonds with the silanol groups on the surface of nano-silica through hydrolysis and condensation reactions. This not only achieves stable grafting of the modifier onto the nanoparticle surface, preventing migration or detachment during processing and use, but also significantly reduces the surface energy of the nano-silica through the grafted organic long chains, effectively preventing nanoparticle aggregation and ensuring uniform dispersion in the low-density polyethylene and ethylene-vinyl acetate copolymer matrix. More importantly, the active functional groups such as hydroxyl groups introduced after ring-opening addition can interact with the matrix resin during the melt processing of the cable outer sheath, thereby greatly enhancing the interfacial compatibility and bonding strength between the nano-inorganic particles and the organic polymer matrix. This strong interfacial bond can effectively transfer and disperse stress under external force, while the uniformly dispersed modified nano-silica particles, acting as physical crosslinking points, can significantly improve the mechanical properties and wear resistance of the material. 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 manufacturing process for a high-strength, wear-resistant flat cable for reels includes the following steps: 50 parts of linear low-density polyethylene, 20 parts of ethylene-vinyl acetate copolymer, 1 part of antioxidant (antioxidant 1010), 1 part of lubricant (polyethylene wax), 1 part of heat stabilizer (calcium-zinc stabilizer), and 10 parts of modified nano-silica are mixed evenly, extruded onto the surface of the conductor using an extruder, and after cooling, a sheath layer is formed to obtain the cable; The preparation process of modified nano-silica is as follows: S1: 29.73g of triglycidyl isocyanurate was added to 150mL of N,N-dimethylacetamide, the temperature was raised to 170℃, and the mixture was stirred until completely dissolved. Then, while maintaining the temperature at 170℃, 43.23g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added in batches and slowly. After the addition was complete, the temperature was maintained at 170℃ and the mixture was stirred continuously for 3 hours. After the reaction was completed, the solvent was removed by rotary evaporation to obtain intermediate A. S2: 72.96g of intermediate A was added to 150mL of N,N-dimethylacetamide and magnetically stirred in an oil bath at 50℃ until completely dissolved to obtain intermediate A solution; 22.14g of 3-aminopropyltriethoxysilane was added to 100mL of N,N-dimethylacetamide and stirred until homogeneous to obtain 3-aminopropyltriethoxysilane solution; under a protective atmosphere, at 50℃, the 3-aminopropyltriethoxysilane solution was slowly added dropwise to intermediate A solution. After the addition was complete, the temperature was maintained at 50℃ and the reaction was continued with stirring for 6h. After the reaction was completed, the solvent was removed by rotary evaporation and the mixture was dried under vacuum to obtain the modifier; S3: Disperse 10g of nano-silica in 150mL of N,N-dimethylformamide, add 1.4g of modifier, raise the temperature to 80℃ under a protective atmosphere, react for 3-4h, filter, wash, and vacuum dry to obtain modified nano-silica.

[0019] Example 2: A manufacturing process for a high-strength, wear-resistant flat cable for reels includes the following steps: 60 parts of linear low-density polyethylene, 35 parts of ethylene-vinyl acetate copolymer, 2 parts of antioxidant (antioxidant 1010), 2 parts of lubricant (polyethylene wax), 2 parts of heat stabilizer (calcium-zinc stabilizer), and 12 parts of modified nano-silica are mixed evenly, extruded onto the conductor surface using an extruder, and after cooling, a sheath layer is formed to obtain the cable; The preparation process of modified nano-silica is as follows: S1: 29.73g of triglycidyl isocyanurate was added to 150mL of N,N-dimethylacetamide, the temperature was raised to 170℃, and the mixture was stirred until completely dissolved. Then, while maintaining the temperature at 170℃, 43.23g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added in batches and slowly. After the addition was complete, the temperature was maintained at 170℃ and the mixture was stirred continuously for 3 hours. After the reaction was completed, the solvent was removed by rotary evaporation to obtain intermediate A. S2: 72.96g of intermediate A was added to 150mL of N,N-dimethylacetamide and magnetically stirred in an oil bath at 50℃ until completely dissolved to obtain intermediate A solution; 22.14g of 3-aminopropyltriethoxysilane was added to 100mL of N,N-dimethylacetamide and stirred until homogeneous to obtain 3-aminopropyltriethoxysilane solution; under a protective atmosphere, at 50℃, the 3-aminopropyltriethoxysilane solution was slowly added dropwise to intermediate A solution. After the addition was complete, the temperature was maintained at 50℃ and the reaction was continued with stirring for 6h. After the reaction was completed, the solvent was removed by rotary evaporation and the mixture was dried under vacuum to obtain the modifier; S3: Disperse 10g of nano-silica in 150mL of N,N-dimethylformamide, add 1.4g of modifier, raise the temperature to 80℃ under a protective atmosphere, react for 3-4h, filter, wash, and vacuum dry to obtain modified nano-silica.

[0020] Example 3: A manufacturing process for a high-strength, wear-resistant flat cable for reels includes the following steps: 55 parts of linear low-density polyethylene, 30 parts of ethylene-vinyl acetate copolymer, 1.5 parts of antioxidant (antioxidant 1010), 1.5 parts of lubricant (polyethylene wax), 1.5 parts of heat stabilizer (calcium-zinc stabilizer), and 11 parts of modified nano-silica are mixed evenly, extruded onto the conductor surface using an extruder, and cooled to form a sheath layer, thus obtaining the cable; The preparation process of modified nano-silica is as follows: S1: 29.73g of triglycidyl isocyanurate was added to 150mL of N,N-dimethylacetamide, the temperature was raised to 170℃, and the mixture was stirred until completely dissolved. Then, while maintaining the temperature at 170℃, 43.23g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added in batches and slowly. After the addition was complete, the temperature was maintained at 170℃ and the mixture was stirred continuously for 3 hours. After the reaction was completed, the solvent was removed by rotary evaporation to obtain intermediate A. S2: 72.96g of intermediate A was added to 150mL of N,N-dimethylacetamide and magnetically stirred in an oil bath at 50℃ until completely dissolved to obtain intermediate A solution; 22.14g of 3-aminopropyltriethoxysilane was added to 100mL of N,N-dimethylacetamide and stirred until homogeneous to obtain 3-aminopropyltriethoxysilane solution; under a protective atmosphere, at 50℃, the 3-aminopropyltriethoxysilane solution was slowly added dropwise to intermediate A solution. After the addition was complete, the temperature was maintained at 50℃ and the reaction was continued with stirring for 6h. After the reaction was completed, the solvent was removed by rotary evaporation and the mixture was dried under vacuum to obtain the modifier; S3: Disperse 10g of nano-silica in 150mL of N,N-dimethylformamide, add 1.4g of modifier, raise the temperature to 80℃ under a protective atmosphere, react for 3-4h, filter, wash, and vacuum dry to obtain modified nano-silica.

[0021] Comparative Example 1: Modification of nano-silica using a silane coupling agent, as detailed below: A manufacturing process for a high-strength, wear-resistant flat cable for reels includes the following steps: mixing 55 parts of linear low-density polyethylene, 30 parts of ethylene-vinyl acetate copolymer, 1.5 parts of antioxidant (antioxidant 1010), 1.5 parts of lubricant (polyethylene wax), 1.5 parts of heat stabilizer (calcium-zinc stabilizer), and 11 parts of modified nano-silica evenly, extruding the mixture onto the conductor surface using an extruder, and cooling it to form a sheath layer, thus obtaining the cable; The preparation process of modified nano-silica is as follows: 10g of nano-silica was dispersed in 150mL of N,N-dimethylformamide, and 1.4g of 3-aminopropyltriethoxysilane was added. Under a protective atmosphere, the temperature was raised to 80℃ and the reaction was carried out for 3-4 hours. The mixture was then filtered, washed, and vacuum dried to obtain modified nano-silica.

[0022] Testing experiment: (1) The tensile strength of the cable sheath of the embodiments and comparative examples was tested in accordance with standard GB / T 1040.1-2025; (2) According to standard GB / T 9867-2008, the relative volumetric wear of the cable sheath in the embodiment and the comparative example were tested respectively; (3) The oxygen index of the cable sheaths of the examples and comparative examples was determined by high temperature test according to standard GB / T 2406.3-2022; The obtained data is shown in the table below:

[0023] Conclusion: Based on the test results of the above embodiments and comparative examples, it can be concluded that the high-strength wear-resistant flat cable for reels provided by the present invention has significantly better outer sheath material than the comparative example using traditional silane coupling agent modified nano-silica in terms of mechanical properties, wear resistance, and flame retardant properties. Specifically, the tensile strengths of Examples 1 to 3 reached 22.5 MPa, 24.1 MPa, and 24.8 MPa, respectively, all higher than the 19.2 MPa of Comparative Example 1. This indicates that the surface grafting of nano-silica with the unique phosphorus, nitrogen, and silicon ternary synergistic modifier of the present invention can effectively enhance the interfacial bonding force between inorganic particles and the organic matrix, thereby improving the load-bearing capacity of the material. In terms of wear resistance, the relative volumetric wear of Examples 1 to 3 was only 0.22 mm. 3 0.18mm 3 and 0.17mm 3 This is far lower than the 0.38mm of Comparative Example 1. 3 The results confirmed that the uniform dispersion of modified nano-silica and its strong interaction with the matrix resin can significantly reduce the mass loss of the material during friction, giving the cable sheath excellent wear resistance. Meanwhile, the limiting oxygen indices of Examples 1 to 3 were 28.3%, 28.8% and 29.1% respectively, all higher than the 25.1% of Comparative Example 1, indicating that the phosphoranone structure and the isocyanurate structure in the modifier molecule work together to exert flame retardant effect, effectively promoting the formation of a dense char layer during combustion and inhibiting flame spread.

[0024] Considering all three performance indicators, Example 3 exhibits the best overall performance due to its most balanced component ratio. Furthermore, the performance of all examples is significantly better than that of the comparative example, which fully demonstrates that the modified nano-silica and its preparation process used in this invention have a significant effect on improving the overall performance of the outer sheath of flat cables for reels, and can meet the usage requirements under harsh working conditions such as high strength, high wear resistance and flame retardancy.

[0025] 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.

[0026] 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 high-strength, wear-resistant flat cable for reels, comprising a conductor and an outer sheath, characterized in that, The raw materials for preparing the outer sheath include the following components: by weight, 50-60 parts linear low-density polyethylene, 20-35 parts ethylene-vinyl acetate copolymer, 1-2 parts antioxidant, 1-2 parts lubricant, 1-2 parts heat stabilizer, and 10-12 parts modified nano-silica.

2. The high-strength wear-resistant flat cable for reels according to claim 1, characterized in that, The preparation process of the modified nano-silica is as follows: S1: Triglycidyl isocyanurate was added to N,N-dimethylacetamide, the temperature was raised to 170°C, and the mixture was stirred until completely dissolved. Then, while maintaining the temperature at 170°C, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added in batches and slowly. After the addition was complete, the temperature was maintained at 170°C and the mixture was stirred continuously for 3 hours. After the reaction was completed, the solvent was removed by rotary evaporation to obtain intermediate A. S2: Add intermediate A to N,N-dimethylacetamide, place in an oil bath at 50°C and stir magnetically until completely dissolved to obtain intermediate A solution; add 3-aminopropyltriethoxysilane to N,N-dimethylacetamide, stir evenly to obtain 3-aminopropyltriethoxysilane solution; Under a protective atmosphere, at 50°C, a solution of 3-aminopropyltriethoxysilane was slowly added dropwise to intermediate A solution. After the addition was complete, the temperature was maintained at 50°C and the reaction was stirred for 6 hours. After the reaction was completed, the solvent was removed by rotary evaporation and the product was dried under vacuum to obtain the modifier. S3: Disperse nano-silica in N,N-dimethylformamide, add a modifier, raise the temperature to 80℃ under a protective atmosphere, react for 3-4 hours, filter, wash, and vacuum dry to obtain modified nano-silica.

3. A high-strength, wear-resistant flat cable for reels according to claim 2, characterized in that, In step S1, the ratio of triglycidyl isocyanurate to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 29.73 g: 43.23 g.

4. A high-strength, wear-resistant flat cable for reels according to claim 2, characterized in that, In step S2, the ratio of intermediate A to 3-aminopropyltriethoxysilane is 72.96g:22.14g.

5. A high-strength, wear-resistant flat cable for reels according to claim 2, characterized in that, In step S3, the ratio of nano-silica to modifier is 10g:1.4g.

6. A high-strength, wear-resistant flat cable for reels according to claim 1, characterized in that, The lubricant is polyethylene wax.

7. A high-strength, wear-resistant flat cable for reels according to claim 1, characterized in that, The antioxidant is antioxidant 1010.

8. A high-strength, wear-resistant flat cable for reels according to claim 1, characterized in that, The heat stabilizer is a calcium-zinc stabilizer.

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