High-strength coal mining machine optical fiber flexible cable and preparation method thereof

Abstract

The application belongs to the technical field of cable preparation, and relates to a high-strength coal mining machine optical fiber soft cable and a preparation method thereof. The high-strength coal mining machine optical fiber soft cable comprises, from outside to inside, an outer sheath, a middle layer, a shielding layer, an insulating layer and a cable core. The outer sheath comprises the following important raw materials: 90-100 parts of modified polyurethane, 10-15 parts of polyvinyl chloride, 18-25 parts of modified filler, 0.3-0.5 parts of antioxidant and 0.3-0.5 parts of lubricant. The modified polyurethane is prepared by ring siloxane ring-opening polymerization to generate a hydroxyl-terminated polysiloxane monomer, and then dehydrated polycondensation reaction with a multiple hydrogen bond-containing monomer. The modified filler is prepared by a heterogeneous precipitation-thermal reduction method to prepare nickel-coated zirconia particles, and then a sol-gel silica coating layer is prepared. The high-strength coal mining machine optical fiber soft cable prepared by the application has excellent wear resistance and toughness.

Description

A high-strength fiber optic flexible cable for coal mining machines and its preparation method Technical Field

[0001] This invention relates to the field of cable manufacturing technology, specifically to a high-strength optical fiber flexible cable for coal mining machines and its manufacturing method. Background Technology

[0002] In intelligent fully mechanized mining faces, high-strength fiber optic cables for coal mining machines are the core link for achieving high-speed and stable data transmission between the coal mining machine and the central control system. They operate for extended periods in extremely harsh environments characterized by confined spaces, pervasive coal dust, high humidity, and constant mechanical impact, requiring high-intensity, high-frequency reciprocating movement and bending along with the equipment. However, existing products face significant challenges in key performance aspects. Firstly, regarding abrasion resistance, ordinary sheaths are prone to rapid wear and cracking due to continuous scraping against coal seams, gangue, and metal structures, leading to exposure of the internal structure and signal transmission failures. Secondly, they exhibit significant shortcomings in toughness. The cable's tensile strength is insufficient, making it susceptible to permanent deformation or even breakage during equipment tension; its resistance to flattening is weak, potentially damaging the optical fiber under roadway compression; simultaneously, its resistance to bending fatigue is limited, making it difficult to withstand tens of thousands of repeated bends during dynamic operation of the coal mining machine, easily leading to a surge in fiber micro-bending loss or breakage due to material fatigue. Therefore, developing a new type of flexible optical fiber cable that can simultaneously overcome the bottlenecks of wear resistance and toughness is of vital importance to ensuring continuous, safe, and efficient production in coal mines. Summary of the Invention

[0003] The purpose of this invention is to provide a high-strength fiber optic flexible cable for coal mining machines to solve the problems of wear resistance and toughness in existing products.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A method for preparing a high-strength fiber optic flexible cable for a coal mining machine, specifically including the following steps:

[0006] Step S1: Place the modified polyurethane, polyvinyl chloride, modified filler, antioxidant and lubricant in a mixer and melt-blend for 10-15 minutes at a temperature of 190-200℃. Pour into a mold and mold to obtain the cable outer sheath.

[0007] Step S2: The cable core is sequentially fitted with an insulation layer, a shielding layer, a middle sheath, and an outer sheath from the inside out to obtain a high-strength coal mining machine fiber optic flexible cable.

[0008] Furthermore, the weight ratio of the modified polyurethane, polyvinyl chloride, modified filler, antioxidant, and lubricant in step S1 is 90-100:10-15:18-25:0.3-0.5:0.3-0.5, the antioxidant is one or two of antioxidant 168 and antioxidant 2246 in any proportion, and the lubricant is one or two of stearic acid and polyethylene wax in any proportion.

[0009] Furthermore, the cable core mentioned in step S2 includes three power cores, one control core, two communication cores, and one optical cable unit. The insulation layer is made of nylon 66 material, the shielding layer is made of steel wire armor, and the middle sheath is made of olefin thermoplastic elastomer insulation material.

[0010] Furthermore, the modified polyurethane is prepared by the following steps:

[0011] Step A1: Mix 2,4,6,8-tetramethylcyclotetrasiloxane, chloroplatinic acid, and isopropanol evenly. Under conditions of 140-150 r / min and 60-70℃, stir and add 2-(1-propen-2-yl)furan and glacial acetic acid. Heat to 100℃ and react for 8-10 h to obtain intermediate 1. Mix intermediate 1 and tetrahydrofuran evenly. Under conditions of 160-180℃, 80-100℃, and nitrogen purging, stir and add tetramethylammonium hydroxide. React for 2-4 h. Add 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane and react for 30-50 min to obtain intermediate 2.

[0012] Step A2: Mix 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine evenly, and react for 10-12 h at a speed of 160-170 r / min and a temperature of 80-85℃ to obtain intermediate 3. Mix intermediate 3 and dichloromethane evenly, and add potassium carbonate and allyl chloroformate at a speed of 150-160 r / min and a temperature of 0-5℃. Stir for 30-50 min, raise the temperature to 20-30℃, and react for 6-8 h to obtain intermediate 4.

[0013] Step A3: Mix malonic acid, 1-hydroxybenzotriazole and dichloromethane evenly. Under conditions of 120-140 r / min and 0-5℃, stir and add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and react for 20-30 min. Raise the temperature to 20-25℃, stir and add intermediate 4, and react for 2-3 h to obtain intermediate 5. Mix intermediate 5, tetrahydrofuran and tetra(triphenylphosphine)palladium evenly. Under conditions of 170-200 r / min, 25-35℃ and nitrogen gas, stir and add triethylsilane, and react for 3-5 h to obtain intermediate 6.

[0014] Step A4: Polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, and N,N-dimethylformamide are mixed evenly and reacted at 140-180 r / min and 60-70℃ for 4-6 h. Ethanol is added and the reaction is carried out for 30-50 min to obtain pretreated polyurethane. The pretreated polyurethane is mixed evenly with tetrahydrofuran and stirred at 140-150 r / min, 30-40℃, and pH 7.4-8.5. A deionized aqueous solution of 1,4-phenylenediboric acid is added and the reaction is carried out for 1-2 h to obtain modified polyurethane.

[0015] Further, in step A1, the ratio of 2,4,6,8-tetramethylcyclotetrasiloxane, chloroplatinic acid, isopropanol, 2-(1-propen-2-yl)furan, and glacial acetic acid is 1 mmol:40 μg:5-10 mL:4.2 mmol:2-3 mL, and the molar ratio of intermediate 1, tetramethylammonium hydroxide, and 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane is 1-1.2 mmol:0.01-0.03 mmol:0.1-0.2 mmol.

[0016] Furthermore, the ratio of 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine in step A2 is 8 mmol:4 mmol:40 mL:15 mL, and the ratio of intermediate 3, dichloromethane, potassium carbonate and allyl chloroformate is 1 mmol:10-12 mL:2-3 mL:1.2 mmol.

[0017] Furthermore, in step A3, the ratio of malonic acid, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, intermediate 4, and triethylamine is 2.4 mmol:1.3 mmol:5-8 mL:1.3 mmol:1 mmol:3.2 mmol, and the ratio of intermediate 5, tetrahydrofuran, tetra(triphenylphosphine)palladium, and triethylsilane is 1 mmol:15 mL:0.01-0.05 mmol:2-3 mmol.

[0018] Furthermore, in step A4, the ratio of polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, N,N-dimethylformamide, and ethanol is 0.5 mmol:0.7 mmol:0.7 mmol:2 mmol:80 mg:40 mL:0.2 mmol, the molecular weight of polyethylene glycol is 1000, the ratio of pretreated polyurethane, tetrahydrofuran, and the deionized aqueous solution of 1,4-phenylenediobionic acid is 5 mmol:20 mL:25 mL, and the molar concentration of the deionized aqueous solution of 1,4-phenylenediobionic acid is 2 mol / L.

[0019] Furthermore, the modified filler is prepared by the following steps:

[0020] Step B1: Disperse basic zirconium carbonate and polyvinylpyrrolidone in deionized water. Stir and add nickel sulfate solution and ammonium bicarbonate solution at a speed of 300-400 r / min, a temperature of 20-30℃, and a pH of 8. React for 6-8 hours to obtain pretreated packing. Place the pretreated packing in a programmable tube furnace and react for 2-4 hours at a temperature of 500-700℃ with mixed gas introduced to obtain pretreated packing.

[0021] Step B2: Mix the pretreated filler, tetraethyl orthosilicate and dichloromethane evenly. Stir and add aminopropyltriethoxysilane at a speed of 200-250 r / min, pH 7-8, and temperature of 60-70℃, and react for 10-12 h. Add maleic anhydride, raise the temperature to 100-110℃, and react for 2-3 h to obtain the modified filler.

[0022] Furthermore, in step B1, the ratio of the amounts of basic zirconium carbonate, polyvinylpyrrolidone, deionized water, nickel sulfate solution, and ammonium bicarbonate solution is 50 mg: 0.5-1 mg: 5 ml: 0.9-1.2 ml: 0.9-1.2 ml, the molar concentration of the nickel sulfate solution is 0.5 mol / L, the molar concentration of the ammonium bicarbonate solution is 1 mol / L, the volume ratio of nitrogen to hydrogen in the mixed gas is 10:1, and the flow rate of hydrogen is 80 mL / min.

[0023] Furthermore, the ratio of the pretreatment filler, tetraethyl orthosilicate, aminopropyltriethoxysilane, and maleic anhydride used in step B2 is 320 mg: 4 mmol: 1 mmol: 1 mmol.

[0024] The beneficial effects of this invention are as follows: When the raw materials are melt-blended in an internal mixer, the maleic anhydride groups introduced on the modified filler and the furan groups introduced on the side chains of the modified polyurethane molecules undergo significant Diels-Alder addition reactions to form chemical crosslinking sites. After molding, the cable outer sheath material is obtained.

[0025] Modified polyurethane: Chloroplatinic acid is reduced in isopropanol to form a highly active zero-valent platinum complex, which promotes the reaction between the carbon-carbon double bond on 2-(1-propen-2-yl)furan and the silane-hydrogen bond on 2,4,6,8-tetramethylcyclotetrasiloxane, introducing a furan ring structure to obtain intermediate 1. Tetramethylammonium hydroxide acts as a base catalyst and initiator, with its hydroxyl group attacking the silicon atom on the cyclosiloxane to generate a silanol anion. This silanol anion then attacks the silicon atom on another cyclosiloxane monomer, causing it to open the ring and attach to the chain, initiating an anionic ring-opening polymerization reaction to synthesize a polysiloxane with hydroxyl end groups, i.e., intermediate 2. Under alkaline conditions, guanidine carbonate releases a guanidine group, and the two guanidine amino groups attack the acetyl carbonyl and lactone carbonyl groups of 2-acetylbutyrolactone, respectively, to generate a pyrimidine ring structure containing amino and hydroxyl structures, to obtain intermediate 3. Allyl chloroformate, acting as an Alloc reagent, specifically protects the amino group to prepare intermediate 4. The carboxyl group on malonic acid is activated and reacts with the hydroxyl group on intermediate 4 to prepare intermediate 5. Tetra(triphenylphosphine)palladium, acting as a palladium catalyst, converts the protecting group back to an amino group to prepare intermediate 6. The isocyanate group on isoflurane diisocyanate reacts with the hydroxyl group on polyethylene glycol and intermediate 2, and then with the amino group on intermediate 6. Finally, the reaction is capped with ethanol to prepare pretreated polyurethane. The β-diketone structure on the pretreated polyurethane readily undergoes enolization, forming a cyclic borate ester with the boric acid structure on 1,4-phenylenediboronic acid to prepare modified polyurethane.

[0026] Modified filler: Polyvinylpyrrolidone (PVP) is used as a dispersant to effectively prevent the agglomeration of basic zirconium carbonate particles. Nickel sulfate and ammonium bicarbonate solutions are then slowly added to the system. In an environment with pH 8, nickel ions and bicarbonate ions converge on the surface of the basic zirconium carbonate particles, undergoing a heterogeneous precipitation reaction to generate basic nickel carbonate-coated basic zirconium carbonate composite particles, i.e., the pretreated filler. The pretreated filler is then heat-treated in a reducing atmosphere of nitrogen and hydrogen to promote the decomposition and reduction of basic nickel carbonate to metallic nickel and basic zirconium carbonate to zirconium oxide, thus obtaining the pretreated filler. Tetraethyl orthosilicate hydrolyzes in a solvent to generate Si(OH)₄, which is then deposited on the surface of the pretreated filler as a SiO₂ layer. Added aminopropyltriethoxysilane simultaneously participates in the hydrolysis and condensation, with its amino group anchored on the SiO₂ layer surface. Subsequently, maleic anhydride is added, which undergoes a ring-opening amidation reaction with the amino group to generate an intermediate. This intermediate is then dehydrated and cyclized under heating conditions to generate a maleimide structure, thus obtaining the pretreated filler.

[0027] Nickel-coated zirconia particles were prepared using a heterogeneous precipitation-thermal reduction method, followed by the fabrication of a silica-nickel-coated zirconia composite material via a sol-gel method. Surface modification was then performed to obtain a modified filler. This core-shell composite material exhibits multi-layer synergistic effects: a robust zirconia core provides wear-resistant support, the intermediate nickel layer effectively toughens the material through plastic deformation and prevents crack propagation, and silica, with its high specific surface area and excellent mechanical properties, serves as the outer layer of the modified filler, enhancing the strength of the matrix resin. The maleic anhydride groups introduced onto the modified filler undergo a Diels-Alder addition reaction with the furan groups introduced onto the side chains of the modified polyurethane molecule, forming a thermally reversible cross-linked network. This network inhibits relative slippage between molecular chains, endowing the cable outer sheath material with excellent self-healing properties and impact toughness. The modified polyurethane molecular chain contains dynamic covalent boron ester bonds and intramolecular quadruple hydrogen bonds. The boron ester bonds dissipate energy and achieve self-healing through reversible fracture and recombination, while the quadruple hydrogen bonds efficiently absorb impact energy through stepwise fracture. The synergistic effect of these two factors enhances the fracture toughness of the material. Detailed Implementation

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Example 1: A method for preparing a high-strength fiber optic flexible cable for a coal mining machine, specifically including the following steps:

[0030] Step S1: Place the modified polyurethane, polyvinyl chloride, modified filler, antioxidant and lubricant in a mixer, melt-blend for 10 minutes at a temperature of 190℃, pour into a mold, and mold to obtain the cable outer sheath.

[0031] Step S2: The cable core is sequentially fitted with an insulation layer, a shielding layer, a middle sheath, and an outer sheath from the inside out to obtain a high-strength coal mining machine fiber optic flexible cable.

[0032] The weight ratio of the modified polyurethane, polyvinyl chloride, modified filler, antioxidant and lubricant mentioned in step S1 is 90:10:18:0.3:0.3, the antioxidant is antioxidant 168 and the lubricant is stearic acid.

[0033] The cable core described in step S2 includes three power cores, one control core, two communication cores, and one optical fiber unit. The insulation layer is made of nylon 66 material, the shielding layer is steel wire armor, and the middle sheath is made of polyethylene thermoplastic elastomer insulation material.

[0034] The modified polyurethane is prepared by the following steps:

[0035] Step A1: 2,4,6,8-Tetramethylcyclotetrasiloxane, chloroplatinic acid, and isopropanol were mixed evenly. Under conditions of 140 r / min and 60°C, 2-(1-propen-2-yl)furan and glacial acetic acid were added with stirring. The mixture was heated to 100°C and reacted for 8 hours to obtain intermediate 1. Intermediate 1 was then mixed evenly with tetrahydrofuran. Under conditions of 160°C, 80°C, and nitrogen purging, tetramethylammonium hydroxide was added with stirring and reacted for 2 hours. 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane was then added and reacted for 30 minutes to obtain intermediate 2.

[0036] Step A2: Mix 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine evenly, and react for 10 h at 160 r / min and 80 °C to obtain intermediate 3. Mix intermediate 3 and dichloromethane evenly, and add potassium carbonate and allyl chloroformate at 150 r / min and 0 °C. Stir for 30 min, raise the temperature to 20 °C and react for 6 h to obtain intermediate 4.

[0037] Step A3: Mix malonic acid, 1-hydroxybenzotriazole and dichloromethane evenly. Stir and add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide at 120 r / min and 0 °C, and react for 20 min. Raise the temperature to 20 °C, stir and add intermediate 4, and react for 2 h to obtain intermediate 5. Mix intermediate 5, tetrahydrofuran and tetra(triphenylphosphine)palladium evenly. Stir and add triethylsilane at 170 r / min and 25 °C under nitrogen atmosphere, and react for 3 h to obtain intermediate 6.

[0038] Step A4: Polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, and N,N-dimethylformamide are mixed evenly and reacted at 140 r / min and 60°C for 4 h. Ethanol is added and the reaction is carried out for 30 min to obtain pretreated polyurethane. The pretreated polyurethane is mixed evenly with tetrahydrofuran and stirred at 140 r / min, 30°C, and pH 7.4. A deionized aqueous solution of 1,4-phenylenediboric acid is added and the reaction is carried out for 1 h to obtain modified polyurethane.

[0039] The ratio of 2,4,6,8-tetramethylcyclotetrasiloxane, chloroplatinic acid, isopropanol, 2-(1-propen-2-yl)furan, and glacial acetic acid in step A1 is as follows:

[0040] The molar ratio of intermediate 1, tetramethylammonium hydroxide, and 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane was 1 mmol: 0.01 mmol: 0.1 mmol, and the amount of intermediate 1 was 1 mmol.

[0041] The ratio of 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine in step A2 is 8 mmol:4 mmol:40 mL:15 mL, and the ratio of intermediate 3, dichloromethane, potassium carbonate and allyl chloroformate is 1 mmol:10 mL:2 mL:1.2 mmol.

[0042] The ratio of malonic acid, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, intermediate 4, and triethylamine in step A3 is 2.4 mmol:1.3 mmol:5 mL:1.3 mmol:1 mmol:3.2 mmol, and the ratio of intermediate 5, tetrahydrofuran, tetra(triphenylphosphine)palladium, and triethylsilane is 1 mmol:15 mL:0.01 mmol:2 mmol.

[0043] In step A4, the ratio of polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, N,N-dimethylformamide, and ethanol is 0.5 mmol:0.7 mmol:0.7 mmol:2 mmol:80 mg:40 mL:0.2 mmol, the amount of polyethylene glycol is 1 mmol, the molecular weight of polyethylene glycol is 1000, the ratio of the pretreated polyurethane, tetrahydrofuran, and the deionized aqueous solution of 1,4-phenylenediobionic acid is 5 mmol:20 mL:25 mL, and the molar concentration of the deionized aqueous solution of 1,4-phenylenediobionic acid is 2 mol / L.

[0044] The modified filler is prepared by the following steps:

[0045] Step B1: Basic zirconium carbonate and polyvinylpyrrolidone are dispersed in deionized water. Under the conditions of 300 r / min, 20℃ and pH 8, nickel sulfate solution and ammonium bicarbonate solution are added and the reaction is carried out for 6 h to obtain pretreated packing. The pretreated packing is placed in a programmable tube furnace and reacted for 2 h at 500℃ with mixed gas introduced to obtain pretreated packing.

[0046] Step B2: Mix the pretreated filler, tetraethyl orthosilicate and dichloromethane evenly. Stir and add aminopropyltriethoxysilane at a speed of 200 r / min, pH 7 and temperature of 60℃, and react for 10 h. Add maleic anhydride, heat to 100℃ and react for 2 h to obtain the modified filler.

[0047] In step B1, the ratio of basic zirconium carbonate, polyvinylpyrrolidone, deionized water, nickel sulfate solution, and ammonium bicarbonate solution is 50 mg: 0.5 mg: 5 ml: 0.9 ml: 0.9 ml. The molar concentration of the nickel sulfate solution is 0.5 mol / L, the molar concentration of the ammonium bicarbonate solution is 1 mol / L, the volume ratio of nitrogen to hydrogen in the mixed gas is 10:1, and the flow rate of hydrogen is 80 mL / min.

[0048] The ratio of the pretreatment filler, tetraethyl orthosilicate, aminopropyltriethoxysilane and maleic anhydride used in step B2 is 320 mg: 4 mmol: 1 mmol: 1 mmol.

[0049] Example 2: A method for preparing a high-strength fiber optic flexible cable for a coal mining machine, specifically including the following steps:

[0050] Step S1: Place the modified polyurethane, polyvinyl chloride, modified filler, antioxidant and lubricant in a mixer, melt-blend for 12 minutes at a temperature of 195℃, pour into a mold, and mold to obtain the cable outer sheath.

[0051] Step S2: The cable core is sequentially fitted with an insulation layer, a shielding layer, a middle sheath, and an outer sheath from the inside out to obtain a high-strength coal mining machine fiber optic flexible cable.

[0052] The weight ratio of the modified polyurethane, polyvinyl chloride, modified filler, antioxidant and lubricant mentioned in step S1 is 95:10:20:0.3:0.3, the antioxidant is an antioxidant, and the lubricant is stearic acid.

[0053] The cable core described in step S2 includes three power cores, one control core, two communication cores, and one optical fiber unit. The insulation layer is made of nylon 66 material, the shielding layer is steel wire armor, and the middle sheath is made of polyethylene thermoplastic elastomer insulation material.

[0054] The modified polyurethane is prepared by the following steps:

[0055] Step A1: 2,4,6,8-Tetramethylcyclotetrasiloxane, chloroplatinic acid, and isopropanol were mixed evenly. Under conditions of 145 r / min and 65°C, 2-(1-propen-2-yl)furan and glacial acetic acid were added with stirring. The mixture was heated to 100°C and reacted for 9 h to obtain intermediate 1. Intermediate 1 was mixed evenly with tetrahydrofuran. Under conditions of 170°C, 90°C, and nitrogen purging, tetramethylammonium hydroxide was added with stirring and reacted for 3 h. Then, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane was added and reacted for 40 min to obtain intermediate 2.

[0056] Step A2: Mix 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine evenly, and react for 11 h at 165 r / min and 80 °C to obtain intermediate 3. Mix intermediate 3 and dichloromethane evenly, and add potassium carbonate and allyl chloroformate at 155 r / min and 2 °C. Stir for 40 min, raise the temperature to 25 °C and react for 7 h to obtain intermediate 4.

[0057] Step A3: Mix malonic acid, 1-hydroxybenzotriazole and dichloromethane evenly. Stir and add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide at 130 r / min and 2 °C, and react for 25 min. Raise the temperature to 22 °C, stir and add intermediate 4, and react for 2 h to obtain intermediate 5. Mix intermediate 5, tetrahydrofuran and tetra(triphenylphosphine)palladium evenly. Stir and add triethylsilane at 180 r / min and 30 °C under nitrogen gas, and react for 4 h to obtain intermediate 6.

[0058] Step A4: Polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, and N,N-dimethylformamide are mixed evenly and reacted at 150 r / min and 65°C for 5 h. Ethanol is added and the reaction is carried out for 40 min to obtain pretreated polyurethane. The pretreated polyurethane is mixed evenly with tetrahydrofuran and stirred at 145 r / min, 5°C, and pH 8. A deionized aqueous solution of 1,4-phenylenediboric acid is added and the reaction is carried out for 1 h to obtain modified polyurethane.

[0059] The ratio of 2,4,6,8-tetramethylcyclotetrasiloxane, chloroplatinic acid, isopropanol, 2-(1-propen-2-yl)furan, and glacial acetic acid in step A1 is 1 mmol:40 μg:8 mL:4.2 mmol:2 mL. The molar ratio of intermediate 1, tetramethylammonium hydroxide, and 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane is 1 mmol:0.01 mmol:0.1 mmol. The amount of intermediate 1 is 2 mmol.

[0060] The ratio of 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine in step A2 is 8 mmol:4 mmol:40 mL:15 mL, and the ratio of intermediate 3, dichloromethane, potassium carbonate and allyl chloroformate is 1 mmol:11 mL:2 mL:1.2 mmol.

[0061] The ratio of malonic acid, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, intermediate 4, and triethylamine in step A3 is 2.4 mmol:1.3 mmol:6 mL:1.3 mmol:1 mmol:3.2 mmol, and the ratio of intermediate 5, tetrahydrofuran, tetra(triphenylphosphine)palladium, and triethylsilane is 1 mmol:15 mL:0.02 mmol:2 mmol.

[0062] In step A4, the ratio of polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, N,N-dimethylformamide, and ethanol is 0.5 mmol:0.7 mmol:0.7 mmol:2 mmol:80 mg:40 mL:0.2 mmol, the amount of polyethylene glycol is 2 mmol, the molecular weight of polyethylene glycol is 1000, the ratio of pretreated polyurethane, tetrahydrofuran, and the deionized aqueous solution of 1,4-phenylenediobionic acid is 5 mmol:20 mL:25 mL, and the molar concentration of the deionized aqueous solution of 1,4-phenylenediobionic acid is 2 mol / L.

[0063] The modified filler is prepared by the following steps:

[0064] Step B1: Basic zirconium carbonate and polyvinylpyrrolidone are dispersed in deionized water. Under the conditions of 350 r / min, 25℃ and pH 8, nickel sulfate solution and ammonium bicarbonate solution are added and the reaction is carried out for 7 h to obtain pretreated packing. The pretreated packing is placed in a programmable tube furnace and reacted for 3 h at 600℃ with mixed gas introduced to obtain pretreated packing.

[0065] Step B2: Mix the pretreated filler, tetraethyl orthosilicate and dichloromethane evenly. Stir and add aminopropyltriethoxysilane at a speed of 230 r / min, pH 7 and temperature of 65℃, and react for 11 h. Add maleic anhydride, raise the temperature to 105℃ and react for 2 h to obtain the modified filler.

[0066] In step B1, the ratio of basic zirconium carbonate, polyvinylpyrrolidone, deionized water, nickel sulfate solution, and ammonium bicarbonate solution is 50 mg: 0.5 mg: 5 ml: 0.9 ml: 0.9 ml. The molar concentration of the nickel sulfate solution is 0.5 mol / L, the molar concentration of the ammonium bicarbonate solution is 1 mol / L, the volume ratio of nitrogen to hydrogen in the mixed gas is 10:1, and the flow rate of hydrogen is 80 mL / min.

[0067] The ratio of the pretreatment filler, tetraethyl orthosilicate, aminopropyltriethoxysilane and maleic anhydride used in step B2 is 320 mg: 4 mmol: 1 mmol: 1 mmol.

[0068] Example 3: A method for preparing a high-strength optical fiber flexible cable for a coal mining machine, specifically including the following steps:

[0069] Step S1: Place the modified polyurethane, polyvinyl chloride, modified filler, antioxidant and lubricant in a mixer, melt-blend for 15 minutes at a temperature of 200℃, pour into a mold, and mold to obtain the cable outer sheath.

[0070] Step S2: The cable core is sequentially fitted with an insulation layer, a shielding layer, a middle sheath, and an outer sheath from the inside out to obtain a high-strength coal mining machine fiber optic flexible cable.

[0071] The weight ratio of the modified polyurethane, polyvinyl chloride, modified filler, antioxidant and lubricant mentioned in step S1 is 100:10:22:0.3:0.3, the antioxidant is antioxidant 168 and the lubricant is stearic acid.

[0072] The cable core described in step S2 includes three power cores, one control core, two communication cores, and one optical fiber unit. The insulation layer is made of nylon 66 material, the shielding layer is steel wire armor, and the middle sheath is made of polyethylene thermoplastic elastomer insulation material.

[0073] The modified polyurethane is prepared by the following steps:

[0074] Step A1: 2,4,6,8-Tetramethylcyclotetrasiloxane, chloroplatinic acid, and isopropanol were mixed evenly. Under conditions of 150 r / min and 70°C, 2-(1-propen-2-yl)furan and glacial acetic acid were added with stirring. The mixture was heated to 100°C and reacted for 10 h to obtain intermediate 1. Intermediate 1 was then mixed evenly with tetrahydrofuran. Under conditions of 180°C, 100°C, and nitrogen purging, tetramethylammonium hydroxide was added with stirring and reacted for 4 h. 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane was then added and reacted for 50 min to obtain intermediate 2.

[0075] Step A2: Mix 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine evenly, and react for 12 h at a speed of 170 r / min and a temperature of 85 °C to obtain intermediate 3. Mix intermediate 3 and dichloromethane evenly, and add potassium carbonate and allyl chloroformate at a speed of 160 r / min and a temperature of 5 °C. Stir for 50 min, raise the temperature to 30 °C and react for 8 h to obtain intermediate 4.

[0076] Step A3: Mix malonic acid, 1-hydroxybenzotriazole and dichloromethane evenly. Stir and add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide at 140 r / min and 5 °C, and react for 30 min. Raise the temperature to 25 °C, stir and add intermediate 4, and react for 3 h to obtain intermediate 5. Mix intermediate 5, tetrahydrofuran and tetra(triphenylphosphine)palladium evenly. Stir and add triethylsilane at 200 r / min and 35 °C under nitrogen atmosphere, and react for 5 h to obtain intermediate 6.

[0077] Step A4: Polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, and N,N-dimethylformamide are mixed evenly and reacted at 180 r / min and 70°C for 6 h. Ethanol is added and the reaction is carried out for 50 min to obtain pretreated polyurethane. The pretreated polyurethane is mixed evenly with tetrahydrofuran and stirred at 150 r / min, 40°C, and pH 8.5. A deionized aqueous solution of 1,4-phenylenediboric acid is added and the reaction is carried out for 2 h to obtain modified polyurethane.

[0078] The ratio of 2,4,6,8-tetramethylcyclotetrasiloxane, chloroplatinic acid, isopropanol, 2-(1-propen-2-yl)furan, and glacial acetic acid in step A1 is 1 mmol:40 μg:10 mL:4.2 mmol:3 mL. The molar ratio of intermediate 1, tetramethylammonium hydroxide, and 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane is 1.2 mmol:0.03 mmol:0.2 mmol. The amount of intermediate 1 is 3 mmol.

[0079] The ratio of 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine in step A2 is 8 mmol:4 mmol:40 mL:15 mL, and the ratio of intermediate 3, dichloromethane, potassium carbonate and allyl chloroformate is 1 mmol:12 mL:3 mL:1.2 mmol.

[0080] The ratio of malonic acid, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, intermediate 4, and triethylamine in step A3 is 2.4 mmol:1.3 mmol:8 mL:1.3 mmol:1 mmol:3.2 mmol, and the ratio of intermediate 5, tetrahydrofuran, tetra(triphenylphosphine)palladium, and triethylsilane is 1 mmol:15 mL:0.05 mmol:3 mmol.

[0081] In step A4, the ratio of polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, N,N-dimethylformamide, and ethanol is 0.5 mmol:0.7 mmol:0.7 mmol:2 mmol:80 mg:40 mL:0.2 mmol, the amount of polyethylene glycol is 3 mmol, the molecular weight of polyethylene glycol is 1000, the ratio of pretreated polyurethane, tetrahydrofuran, and the deionized aqueous solution of 1,4-phenylenediobionic acid is 5 mmol:20 mL:25 mL, and the molar concentration of the deionized aqueous solution of 1,4-phenylenediobionic acid is 2 mol / L.

[0082] The modified filler is prepared by the following steps:

[0083] Step B1: Basic zirconium carbonate and polyvinylpyrrolidone are dispersed in deionized water. Under the conditions of 400 r / min, 20-30℃ and pH 8, nickel sulfate solution and ammonium bicarbonate solution are added and the reaction is carried out for 8 hours to obtain pretreated packing. The pretreated packing is placed in a programmable tube furnace and reacted for 4 hours under the conditions of 700℃ and mixed gas flow to obtain pretreated packing.

[0084] Step B2: Mix the pretreated filler, tetraethyl orthosilicate and dichloromethane evenly. Stir and add aminopropyltriethoxysilane at a speed of 250 r / min, pH 8 and temperature of 70℃, and react for 12 h. Add maleic anhydride, raise the temperature to 110℃ and react for 3 h to obtain the modified filler.

[0085] In step B1, the ratio of the amounts of basic zirconium carbonate, polyvinylpyrrolidone, deionized water, nickel sulfate solution, and ammonium bicarbonate solution is 50 mg: 1 mg: 5 ml: 0.9 ml: 0.9 ml. The molar concentration of the nickel sulfate solution is 0.5 mol / L, the molar concentration of the ammonium bicarbonate solution is 1 mol / L, the volume ratio of nitrogen to hydrogen in the mixed gas is 10:1, and the flow rate of hydrogen is 80 mL / min.

[0086] The ratio of the pretreatment filler, tetraethyl orthosilicate, aminopropyltriethoxysilane and maleic anhydride used in step B2 is 320 mg: 4 mmol: 1 mmol: 1 mmol.

[0087] Comparative Example 1: Compared with Example 1, this comparative example uses 2,4,6,8-tetramethylcyclotetrasiloxane instead of intermediate 1, while the other steps are the same.

[0088] Comparative Example 2: Compared with Example 1, intermediate 6 is replaced by intermediate 3, and the other steps are the same.

[0089] Comparative Example 3: Compared with Example 1, this comparative example uses hydroxylamine instead of intermediate 3, and the other steps are the same.

[0090] Comparative Example 4: Compared with Example 1, this comparative example uses zirconium oxide instead of pretreatment filler, while the other steps are the same.

[0091] The cable outer sheaths prepared in Examples 1-3 and Comparative Examples 1-3 were tested for tensile strength and elongation at break according to GB / T2951.11-2008 "General Test Methods for Cables and Cable Insulation and Sheath Materials - Part 11". The test results are shown in Table 1. The samples were cut into dumbbell shapes with a length of 100 mm.

[0092] The abrasion resistance of the high-strength coal mining machine fiber optic flexible cables prepared in Examples 1-3 and Comparative Examples 1-3 was tested using a friction and wear testing machine. The test results are shown in Table 1. The sample size was 3cm × 2cm × 0.5cm, the rotation speed was 400r / min, the load was 100N, and the test time was 1h. The abrasion amount was measured by weighing method.

[0093] Table 1

[0094]

[0095] Table 1 shows that the high-strength fiber optic flexible cables for coal mining machines prepared in Examples 1-3 exhibited abrasion amounts of 87-94 mg in the abrasion resistance test. The outer sheath of the prepared cables showed tensile strengths ranging from 34.5-38.8 MPa and elongation at break ranging from 378-412%. This indicates that the high-strength fiber optic flexible cables for coal mining machines prepared according to this invention possess excellent abrasion resistance and toughness.

[0096] The above description is merely an example and illustration of the concept 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 concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a high-strength optical fiber flexible cable for a coal mining machine, characterized in that: Specifically, the process includes the following steps: Step S1: Modified polyurethane, polyvinyl chloride, modified filler, antioxidant, and lubricant are placed in a mixer, melt-blended, poured into a mold, and molded to obtain the cable outer sheath; Step S2: The cable core is sequentially fitted with an insulation layer, a shielding layer, a middle sheath, and an outer sheath from the inside out to obtain a high-strength coal mining machine fiber optic flexible cable; The modified polyurethane is prepared by the following steps: Step A1: 2,4,6,8-Tetramethylcyclotetrasiloxane, chloroplatinic acid, and isopropanol are mixed and stirred, and 2-(1-propen-2-yl)furan and glacial acetic acid are added, and the mixture is heated to carry out the reaction. Intermediate 1 was prepared. Intermediate 1 was mixed and stirred with tetrahydrofuran, and tetramethylammonium hydroxide was added to react. 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane was added to react, and intermediate 2 was prepared. Step A2: 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine were mixed evenly and reacted to prepare intermediate 3. Intermediate 3 was mixed evenly with dichloromethane, potassium carbonate and allyl chloroformate were added, stirred and heated to react, and intermediate 4 was prepared. Step A3: malonic acid, 1-hydroxybenzotriazole and dichloromethane were mixed and stirred, and 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane was added to react, and intermediate 4 was prepared. -Ethyl-3-(3-dimethylaminopropyl)carbodiimide was reacted, heated, stirred, and intermediate 4 was added to react and obtain intermediate 5. Intermediate 5, tetrahydrofuran, and tetra(triphenylphosphine)palladium were mixed and stirred, and triethylsilane was added to react and obtain intermediate 6. Step A4: Polyethylene glycol, intermediate 6, intermediate 2, isoflurone diisocyanate, dibutyltin dilaurate, and N,N-dimethylformamide were mixed evenly and reacted. Ethanol was added to react and obtain pretreated polyurethane. The pretreated polyurethane and tetrahydrofuran were mixed and stirred, and 1, A modified polyurethane is prepared by reacting a deionized aqueous solution of 4-phenylenediboric acid. The modified filler is prepared by the following steps: Step B1: Basic zirconium carbonate and polyvinylpyrrolidone are dispersed in deionized water, stirred, and nickel sulfate solution and ammonium bicarbonate solution are added to react and obtain a pretreated filler. The pretreated filler is placed in a programmable tube furnace to react and obtain a pretreated filler. Step B2: The pretreated filler, tetraethyl orthosilicate and dichloromethane are mixed and stirred, and aminopropyltriethoxysilane is added to react. Maleic anhydride is added, and the mixture is heated to react and obtain a modified filler.

2. The method for preparing a high-strength optical fiber flexible cable for a coal mining machine according to claim 1, characterized in that: The weight ratio of the modified polyurethane, polyvinyl chloride, modified filler, antioxidant and lubricant mentioned in step S1 is 90-100:10-15:18-25:0.3-0.5:0.3-0.

5.

3. The method for preparing a high-strength optical fiber flexible cable for a coal mining machine according to claim 1, characterized in that: The ratio of 2,4,6,8-tetramethylcyclotetrasiloxane, chloroplatinic acid, isopropanol, 2-(1-propen-2-yl)furan, and glacial acetic acid in step A1 is 1 mmol: 40 μg: 5-10 mL: 4.2 mmol: 2-3 mL, and the molar ratio of intermediate 1, tetramethylammonium hydroxide, and 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane is 1-1.2 mmol: 0.01-0.03 mmol: 0.1-0.2 mmol.

4. The method for preparing a high-strength optical fiber flexible cable for a coal mining machine according to claim 1, characterized in that: The ratio of 2-acetylbutyrolactone, guanidine carbonate, anhydrous ethanol and triethylamine in step A2 is 8 mmol:4 mmol:40 mL:15 mL, and the ratio of intermediate 3, dichloromethane, potassium carbonate and allyl chloroformate is 1 mmol:10-12 mL:2-3 mL:1.2 mmol.

5. The method for preparing a high-strength optical fiber flexible cable for a coal mining machine according to claim 1, characterized in that: The ratio of malonic acid, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, intermediate 4, and triethylamine in step A3 is 2.4 mmol:1.3 mmol:5-8 mL:1.3 mmol:1 mmol:3.2 mmol, and the ratio of intermediate 5, tetrahydrofuran, tetra(triphenylphosphine)palladium, and triethylsilane is 1 mmol:15 mL:0.01-0.05 mmol:2-3 mmol.

6. The method for preparing a high-strength optical fiber flexible cable for a coal mining machine according to claim 1, characterized in that: In step A4, the ratio of polyethylene glycol, intermediate 6, intermediate 2, isoflurane diisocyanate, dibutyltin dilaurate, N,N-dimethylformamide, and ethanol is 0.5 mmol:0.7 mmol:0.7 mmol:2 mmol:80 mg:40 mL:0.2 mmol, and the ratio of the pretreated polyurethane, tetrahydrofuran, and 1,4-phenylenediboronic acid deionized water solution is 5 mmol:20 mL:25 mL.

7. The method for preparing a high-strength optical fiber flexible cable for a coal mining machine according to claim 1, characterized in that: The ratio of the amounts of basic zirconium carbonate, polyvinylpyrrolidone, deionized water, nickel sulfate solution, and ammonium bicarbonate solution used in step B1 is 50 mg: 0.5-1 mg: 5 mL: 0.9-1.2 mL: 0.9-1.2 mL.

8. The method for preparing a high-strength optical fiber flexible cable for a coal mining machine according to claim 1, characterized in that: The ratio of the pretreatment filler, tetraethyl orthosilicate, aminopropyltriethoxysilane and maleic anhydride used in step B2 is 320 mg: 4 mmol: 1 mmol: 1 mmol.

9. A high-strength fiber optic flexible cable for coal mining machines, characterized in that: Prepared according to any one of the preparation methods described in claims 1-8.

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