A high elastic optical cable and its preparation method

Abstract

The present invention discloses a high-elasticity optical cable and a preparation method thereof, and relates to the technical field of sheath materials. In the preparation of the high-elasticity optical cable, the present invention comprises the following steps: first, subjecting a carbon source gas to vapor deposition to produce helical carbon nanotubes; then, treating the helical carbon nanotubes with nitric acid and reacting them with thionyl chloride and aminopropyltrimethoxysilane to produce modified helical carbon nanotubes; then, reacting 3-furoic acid, 2-mercaptobenzimidazole, and neodymium chloride in an ethanol solution to produce a fluorescent complex solution; then, reacting a styrene-butadiene-styrene block copolymer with ethyl diallylsilane, diethoxysilane, and p-aminostyrene to produce a pre-modified styrene-butadiene-styrene block copolymer; then, reacting the pre-modified styrene-butadiene-styrene block copolymer with the fluorescent complex solution to produce a modified styrene-butadiene-styrene block copolymer; then, reacting the modified helical carbon nanotubes, the modified styrene-butadiene-styrene block copolymer, and polyethylene to produce a sheath material; and finally, wrapping the sheath material around an optical cable core material and rolling it to produce the high-elasticity optical cable. The high-elasticity optical cable prepared by the invention has excellent tensile fracture resistance and anti-aging performance.

Description

Technical Field

[0001] The present invention relates to the technical field of sheath materials, in particular to a high-elasticity optical cable and a preparation method thereof. Background Art

[0002] An optical cable is a communication line made of a single optical fiber, multiple optical fibers, or a fiber bundle, plus an outer sheath. It meets the required optical, mechanical, and environmental performance requirements and is used to transmit optical signals. The general structure of an optical cable can be divided into a fiber buffer layer, a core, a tension-resistant layer, a sheath, and a waterproof layer. Based on their construction, they can be broadly categorized as ribbon cables, all-dielectric self-supporting cables, ground-wire composite cables, and submarine cables.

[0003] With the development of society and the construction of global integration, optical cables have begun to be laid in various regions, such as the seabed, mountains, forests, deserts and other special environments. Due to the constant maintenance, the requirements for the sheath materials of optical cables are getting higher and higher. The market demand for optical cables with corrosion resistance, shock resistance, anti-aging and other properties is growing. However, there are still many areas that need improvement in performance on the market. Most of the aging optical cables on the market are anti-ultraviolet aging. The high-elasticity optical cable made by the present invention has anti-aging properties in a variety of environments. Summary of the Invention

[0004] The object of the present invention is to provide a highly elastic optical cable and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A method for preparing a high-elasticity optical cable is characterized in that the high-elasticity optical cable is made of a sheath material made of modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer and polyethylene, and the sheath material is wrapped around an optical cable core material and rolled.

[0007] As an optimization, the modified helical carbon nanotubes are prepared by vapor-depositing carbon source gas under the catalysis of nano-iron oxide to obtain helical carbon nanotubes, and then treating the helical carbon nanotubes with nitric acid and reacting with thionyl chloride and aminopropyltrimethoxysilane to obtain the helical carbon nanotubes.

[0008] As an optimization, the modified styrene-butadiene-styrene block copolymer is prepared by reacting a styrene-butadiene-styrene block copolymer with ethyl diallylsilane, diethoxysilane, and p-aminostyrene to obtain a pre-modified styrene-butadiene-styrene block copolymer, which is then reacted with a fluorescent complex solution to obtain the pre-modified styrene-butadiene-styrene block copolymer.

[0009] As an optimization, the fluorescent complex solution is prepared by reacting 3-furoic acid, 2-mercaptobenzimidazole and neodymium chloride in an ethanol solution.

[0010] As an optimization, the preparation method of the highly elastic optical cable includes the following preparation steps:

[0011] (1) The helical carbon nanotubes were treated with acid, and the acid-treated helical carbon nanotubes, thionyl chloride, and tetrahydrofuran were mixed in a mass ratio of 1:4:4 to 1:6:6, stirred at 40 to 50 ° C and 400 to 500 r / min for 2 to 3 hours, heated to 60 to 70 ° C and continued to stir for 2 to 3 hours, filtered, and allowed to stand at 10 to 30 ° C and 1 to 2 kPa for 4 to 6 hours, and then mixed with aminopropyltrimethoxysilane, triethylamine, and dichloromethane in a mass ratio of 3:2:0.5:20 to 3:3:1:25, stirred at 0 to 5 ° C and 300 to 500 r / min for 50 to 60 minutes, allowed to stand at room temperature for 20 to 24 hours, filtered, washed with anhydrous ethanol for 3 to 5 times, and dried at -10 to -1 ° C and 1 to 10 Pa for 6 to 8 hours to obtain modified helical carbon nanotubes;

[0012] (2) The pre-modified styrene-butadiene-styrene block copolymer, the fluorescent complex solution and n-hexane are mixed uniformly in a mass ratio of 1:5:3 to 1:7:5, and then 0.01 to 0.03 times the mass of the pre-modified styrene-butadiene-styrene block copolymer is added with carbodiimide, and the mixture is stirred at 20 to 30°C and 800 to 1000 r / min for 2 to 3 hours, and then allowed to stand at 30 to 40°C and 1 to 2 kPa for 8 to 10 hours, filtered and washed with pure water for 3 to 5 times, and dried at -10 to -1°C and 1 to 10 Pa for 6 to 8 hours to obtain a modified styrene-butadiene-styrene block copolymer;

[0013] (3) The modified helical carbon nanotubes are placed in pure water and allowed to stand for 2 to 3 minutes, and dried at -10 to -1°C and 1 to 10 Pa for 6 to 8 hours to obtain pretreated modified helical carbon nanotubes; the pretreated modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer, and polyethylene are uniformly mixed in a mass ratio of 1:1:2 to 1:2:3, and kneaded at 120 to 140°C for 20 to 30 minutes to prepare a sheath material with a thickness of 3 to 5 mm, and the sheath material is wrapped on the optical cable core material, and rolled at 120 to 130°C and 8 to 10 MPa for 2 to 3 times at 220 to 240 m / min to obtain a high elastic optical cable.

[0014] As an optimization, the preparation method of the spiral carbon nanotubes in step (1) is as follows: acetone, pyridine and acetylene are uniformly mixed in a mass ratio of 1:1:1 to 1:2:3 as a carbon source gas, a glass plate carrier uniformly distributed with nano-iron oxide is placed in a reaction chamber in a nitrogen atmosphere, and a carbon source gas 1000 to 1200 times the mass of the nano-iron oxide is introduced at a flow rate of 800 to 1000 sscm at 700 to 800° C., and then aeration is stopped for 5 to 10 minutes, and then nitrogen is introduced at the same flow rate for 10 to 20 minutes, cooled to 10 to 30° C., and the product on the glass plate carrier is placed in a hydrochloric acid solution with a mass fraction of 10 to 15%, ultrasonicated at 30 to 40 kHz for 15 to 20 minutes, filtered and washed with anhydrous ethanol and pure water 3 to 5 times each, and dried at -10 to -1° C. and 1 to 10 Pa for 6 to 8 hours to prepare the product.

[0015] As an optimization, the acid treatment method in step (1) is: the spiral carbon nanotubes and nitric acid with a mass fraction of 40 to 50% are mixed uniformly in a mass ratio of 1:8 to 1:10, stirred at 80 to 90°C and 800 to 1000 r / min for 20 to 30 minutes, cooled to room temperature and then filtered, washed with pure water 3 to 5 times, and dried at -10 to -1°C and 1 to 10 Pa for 6 to 8 hours.

[0016] As an optimization, the preparation method of the pre-modified styrene-butadiene-styrene block copolymer in step (2) is as follows: styrene-butadiene-styrene block copolymer, ethyl diallylsilane and n-hexane are uniformly mixed in a mass ratio of 1:1:8 to 1:1:10, and then 0.03 to 0.05 of the mass of styrene-butadiene-styrene block copolymer of divinyltetramethyldisiloxane platinum salt is added, and the mixture is stirred and refluxed at 70 to 80°C and 500 to 800 r / min for 3 to 4 minutes. 5h, add diethoxysilane in an amount of 1.3 to 1.5 times the mass of styrene-butadiene-styrene block copolymer, continue stirring and refluxing for 3 to 5h, add p-aminostyrene in an amount of 1.3 to 1.5 times the mass of styrene-butadiene-styrene block copolymer, continue stirring and refluxing for 3 to 5h, let stand at 20 to 30°C, 1 to 2kPa for 3 to 4h, filter and wash with pure water 3 to 5 times, and dry at -10 to -1°C, 1 to 10Pa for 6 to 8h to prepare.

[0017] As an optimization, the preparation method of the fluorescent complex solution in step (2) is: 3-furoic acid, 2-mercaptobenzimidazole, anhydrous ethanol and pure water are mixed uniformly in a mass ratio of 1:1:4:4 to 1:1:6:6, and then 0.3 to 0.5 times the mass of neodymium chloride of 3-furoic acid is added, and stirred at 30 to 40°C and 800 to 1000 r / min for 4 to 5 hours to prepare the solution.

[0018] As an optimization, the optical cable core material in step (3) is a central tube optical cable, model GYXTS.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] When preparing the high elastic optical cable, the present invention prepares a sheath material by using modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer and polyethylene, and wraps the sheath material on the optical cable core material and rolls it to obtain the high elastic optical cable.

[0021] First, carbon source gas is vapor-deposited under the catalysis of nano-iron oxide to produce helical carbon nanotubes, which are then treated with nitric acid and reacted with thionyl chloride and aminopropyltrimethoxysilane to produce modified helical carbon nanotubes. The helical structure allows the helical carbon nanotubes to have more contact with the remaining components of the overall material, has a greater conduction effect on the thermal motion of molecules, and improves the overall heat dissipation effect of the material, thereby improving the anti-aging performance of the high-elasticity optical cable under wet heat and temperature-changing conditions; aminopropyltrimethoxysilane forms an amide bond connection with the helical carbon nanotubes, and the trimethoxysilane on the modified helical carbon nanotubes can be decomposed into silanol groups, which are cross-linked with each other through the silanol groups to form a helical carbon nanotube heat-conducting network, thereby improving the overall cross-linking degree while improving the thermal conductivity and thermal stability, thereby improving the anti-aging performance and tensile fracture resistance of the high-elasticity optical cable under wet heat and temperature-changing conditions.

[0022] Secondly, 3-furoic acid, 2-mercaptobenzimidazole and neodymium chloride are reacted in an ethanol solution to obtain a fluorescent complex solution, styrene-butadiene-styrene block copolymer is reacted with ethyl diallylsilane, diethoxysilane and p-aminostyrene to obtain a pre-modified styrene-butadiene-styrene block copolymer, and the pre-modified styrene-butadiene-styrene block copolymer is reacted with the fluorescent complex solution to obtain a modified styrene-butadiene-styrene block copolymer. The fluorescent complex can absorb strong light and ultraviolet rays and convert them into weak light and heat, reducing the damage of strong light and ultraviolet rays to the material. In an ozone environment, when the overall system contains oxidizing substances, the benzimidazole on the fluorescent complex can respond in time, and the metal-sulfur coordination bond is broken to form a benzimidazole containing sulfur free, which reacts with the oxidizing substances. The combination of the fluorescent complex and the pre-modified styrene-butadiene-styrene block copolymer reduces the oxidative decomposition of the main material, thereby improving the anti-aging performance of the high-elasticity optical cable under ultraviolet and ozone conditions; the fluorescent complex and the pre-modified styrene-butadiene-styrene block copolymer form amide bonds that can form hydrogen bonds with the amide bonds on the modified helical carbon nanotubes, so that the fluorescent complex is close to the modified helical carbon nanotubes, and the heat converted by ultraviolet absorption is transferred in time, and the fluorescent complex is protected to avoid loss, further improving the anti-aging performance of the high-elasticity optical cable under ultraviolet and ozone conditions. At the same time, the silicone chain segments generated during the pre-modification of the styrene-butadiene-styrene block copolymer increase the stability of the styrene-butadiene-styrene block copolymer, reducing the impact of temperature changes on the overall performance, and improving the anti-aging performance of the high-elasticity optical cable under temperature changes. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0024] In order to more clearly illustrate the method provided by the present invention, the following examples are provided in detail. The test methods for various indicators of the high elasticity optical cable prepared in the following examples are as follows:

[0025] Tensile fracture resistance: The high elasticity optical cables obtained in each embodiment and the comparative example materials were taken with the same mass, and the tensile strength was tested and recorded according to the GB / T528 standard.

[0026] Anti-aging performance: The high-elasticity optical cables obtained in each example and the comparative example materials were taken with the same mass and placed in the same constant temperature aging chamber. Under the same conditions, aging tests were carried out in different environments such as humidity and heat, temperature fluctuation, ultraviolet light, and ozone. The tensile strength was measured again after the same period of time. The performance retention rate was recorded as tensile strength after aging test / initial tensile strength.

[0027] Example 1

[0028] A method for preparing a highly elastic optical cable, the method mainly comprising the following preparation steps:

[0029] (1) Acetone, pyridine and acetylene were mixed in a mass ratio of 1:1:1 as a carbon source gas. A glass plate carrier uniformly distributed with nano-iron oxide was placed in a reaction chamber in a nitrogen atmosphere. A carbon source gas 1000 times the mass of nano-iron oxide was introduced at a flow rate of 800 sscm at 700°C, and then ventilation was stopped for 5 minutes. Nitrogen was then introduced at the same flow rate for 10 minutes, and the mixture was cooled to 10°C. The product on the glass plate carrier was placed in a 10% hydrochloric acid solution by mass, ultrasonicated at 30kHz for 15 minutes, filtered and washed with anhydrous ethanol and pure water for 3 times each, and dried at -10°C, 1Pa for 8 hours to obtain helical carbon nanotubes. The helical carbon nanotubes and 40% nitric acid by mass were mixed in a mass ratio of 1:8, and heated at 80°C, 800r / m in stirring and reacting for 30 minutes, cooling to room temperature and filtering, washing with pure water 3 times, and drying at -10°C and 1Pa for 8 hours to obtain acid-treated spiral carbon nanotubes; the acid-treated spiral carbon nanotubes, thionyl chloride, and tetrahydrofuran are mixed uniformly in a mass ratio of 1:4:4, stirred and reacted at 40°C and 400r / min for 3 hours, heated to 60°C and continued to stir and react for 3 hours, filtered, and allowed to stand at 10°C and 1kPa for 6 hours, and then mixed uniformly with aminopropyltrimethoxysilane, triethylamine, and dichloromethane in a mass ratio of 3:2:0.5:20, stirred at 0°C and 300r / min for 60 minutes, allowed to stand at room temperature for 20 hours, filtered and washed with anhydrous ethanol 5 times, and dried at -10°C and 1Pa for 8 hours to obtain modified spiral carbon nanotubes;

[0030] (2) 3-furoic acid, 2-mercaptobenzimidazole, anhydrous ethanol and pure water were mixed in a mass ratio of 1:1:4:4, and then 0.3 times the mass of neodymium chloride of 3-furoic acid was added, and the mixture was stirred at 30°C and 800 r / min for 5 hours to obtain a fluorescent complex solution; styrene-butadiene-styrene block copolymer, ethyl diallylsilane and n-hexane were mixed in a mass ratio of 1:1:8, and then 0.03 times the mass of divinyltetramethyldisiloxane platinum salt of styrene-butadiene-styrene block copolymer was added, and the mixture was stirred and refluxed at 70°C and 500 r / min for 5 hours, and 1.3 times the mass of diethoxysilane of styrene-butadiene-styrene block copolymer was added, and the stirring and reflux was continued for 3 hours, and styrene-butadiene-styrene block copolymer was added. The reaction mixture was stirred at 1.3 times the mass of p-aminostyrene, and refluxed under stirring for 5 hours. The mixture was allowed to stand at 20°C and 1 kPa for 4 hours, filtered, washed with pure water for 3 times, and dried at -10°C and 1 Pa for 8 hours to obtain a pre-modified styrene-butadiene-styrene block copolymer. The pre-modified styrene-butadiene-styrene block copolymer, the fluorescent complex solution, and n-hexane were mixed uniformly in a mass ratio of 1:5:3, and then 0.01 times the mass of the pre-modified styrene-butadiene-styrene block copolymer was added with carbodiimide. The mixture was stirred at 20°C and 800 r / min for 2 hours, and allowed to stand at 30°C and 1 kPa for 10 hours. The mixture was filtered, washed with pure water for 3 times, and dried at -10°C and 1 Pa for 8 hours to obtain a modified styrene-butadiene-styrene block copolymer.

[0031] (3) The modified helical carbon nanotubes were placed in pure water and allowed to stand for 2 minutes, and dried at -10°C and 1Pa for 8 hours to obtain pretreated modified helical carbon nanotubes; the pretreated modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer, and polyethylene were uniformly mixed in a mass ratio of 1:1:2, and kneaded at 120°C for 20 minutes to prepare a sheath material with a thickness of 4 mm. The sheath material was wrapped on the optical cable core material, and rolled twice at 120°C and 8MPa at 220m / min to obtain a high elastic optical cable.

[0032] Example 2

[0033] A method for preparing a highly elastic optical cable, the method mainly comprising the following preparation steps:

[0034] (1) Acetone, pyridine and acetylene were mixed in a mass ratio of 1:1:2 as a carbon source gas. A glass plate carrier uniformly distributed with nano-iron oxide was placed in a reaction chamber in a nitrogen atmosphere. A carbon source gas 1100 times the mass of nano-iron oxide was introduced at a flow rate of 900 sscm at 750°C, and then ventilation was stopped for 7 minutes. Nitrogen was then introduced at the same flow rate for 15 minutes, and cooled to 20°C. The product on the glass plate carrier was placed in a 12% hydrochloric acid solution by mass, ultrasonicated at 35kHz for 18 minutes, filtered and washed with anhydrous ethanol and pure water for 4 times each, and dried at -5°C, 5Pa for 7 hours to obtain helical carbon nanotubes; the helical carbon nanotubes and 45% nitric acid by mass were mixed in a mass ratio of 1:9, and heated at 85°C, 900 r / mi The acid-treated spiral carbon nanotubes were uniformly mixed with thionyl chloride and tetrahydrofuran in a mass ratio of 1:5:5, stirred and reacted at 45°C for 450min for 2.5h, heated to 65°C and continued to stir and react for 2.5h, filtered, and allowed to stand at 20°C and 1.5kPa for 5h, and then uniformly mixed with aminopropyltrimethoxysilane, triethylamine and dichloromethane in a mass ratio of 3:2:0.8:22, stirred at 3°C and 400r / min for 55min, allowed to stand at room temperature for 22h, filtered and washed with anhydrous ethanol 4 times, and dried at -5°C and 5Pa for 7h to obtain modified spiral carbon nanotubes;

[0035] (2) 3-furoic acid, 2-mercaptobenzimidazole, anhydrous ethanol and pure water were mixed in a mass ratio of 1:1:5:5, and then 0.4 times the mass of neodymium chloride of 3-furoic acid was added, and the mixture was stirred at 35°C and 900 r / min for 4.5 hours to obtain a fluorescent complex solution; styrene-butadiene-styrene block copolymer, ethyl diallylsilane and n-hexane were mixed in a mass ratio of 1:1:9, and then 0.04 times the mass of divinyltetramethyldisiloxane platinum salt of styrene-butadiene-styrene block copolymer was added, and the mixture was stirred and refluxed at 75°C and 650 r / min for 4 hours, and 1.4 times the mass of diethoxysilane of styrene-butadiene-styrene block copolymer was added, and the mixture was stirred and refluxed for 4 hours, and styrene-butadiene-styrene block copolymer was added. 1.4 times the amount of p-aminostyrene was added, and the mixture was stirred and refluxed for 4 hours. The mixture was allowed to stand at 25°C and 1.5 kPa for 3.5 hours, filtered, washed with pure water for 4 times, and dried at -5°C and 5 Pa for 7 hours to obtain a pre-modified styrene-butadiene-styrene block copolymer; the pre-modified styrene-butadiene-styrene block copolymer, the fluorescent complex solution, and n-hexane were mixed uniformly in a mass ratio of 1:6:4, and then 0.02 times the mass of the pre-modified styrene-butadiene-styrene block copolymer was added with carbodiimide, and the mixture was stirred and reacted at 25°C and 900 r / min for 2.5 hours. The mixture was allowed to stand at 35°C and 1.5 kPa for 9 hours, filtered, washed with pure water for 4 times, and dried at -5°C and 5 Pa for 7 hours to obtain a modified styrene-butadiene-styrene block copolymer;

[0036] (3) The modified helical carbon nanotubes were placed in pure water and allowed to stand for 2.5 minutes, and dried at -5°C and 5 Pa for 6 to 8 hours to obtain pretreated modified helical carbon nanotubes; the pretreated modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer, and polyethylene were uniformly mixed in a mass ratio of 1:1.5:2.5, and kneaded at 130°C for 25 minutes to prepare a sheath material with a thickness of 4 mm. The sheath material was wrapped on the optical cable core material, and rolled twice at 125°C and 9 MPa at 230 m / min to obtain a high-elasticity optical cable.

[0037] Example 3

[0038] A method for preparing a highly elastic optical cable, the method mainly comprising the following preparation steps:

[0039] (1) Acetone, pyridine and acetylene were mixed in a mass ratio of 1:2:3 as a carbon source gas. A glass plate carrier uniformly distributed with nano-iron oxide was placed in a reaction chamber in a nitrogen atmosphere. A carbon source gas 1200 times the mass of nano-iron oxide was introduced at a flow rate of 1000 sscm at 800°C, and then ventilation was stopped for 10 minutes. Nitrogen was then introduced at the same flow rate for 20 minutes, and cooled to 30°C. The product on the glass plate carrier was placed in a 15% mass fraction hydrochloric acid solution, ultrasonicated at 40kHz for 20 minutes, filtered and washed with anhydrous ethanol and pure water for 5 times each, and dried at -1°C, 10Pa for 8 hours to obtain helical carbon nanotubes; the helical carbon nanotubes and 50% mass fraction nitric acid were mixed in a mass ratio of 1:10, and heated at 90°C, 1000 sscm. r / min and stirred for 20 minutes, cooled to room temperature and filtered, washed with pure water 5 times, and dried at -1°C and 10Pa for 8 hours to obtain acid-treated spiral carbon nanotubes; the acid-treated spiral carbon nanotubes, thionyl chloride, and tetrahydrofuran were mixed uniformly in a mass ratio of 1:6:6, stirred at 50°C and 500r / min for 2 hours, heated to 670°C and continued to stir for 3 hours, filtered, and allowed to stand at 30°C and 2kPa for 6 hours, and then mixed uniformly with aminopropyltrimethoxysilane, triethylamine, and dichloromethane in a mass ratio of 3:3:1:25, stirred at 5°C and 500r / min for 50 minutes, allowed to stand at room temperature for 24 hours, filtered and washed with anhydrous ethanol 5 times, and dried at -1°C and 10Pa for 6 hours to obtain modified spiral carbon nanotubes;

[0040] (2) 3-furoic acid, 2-mercaptobenzimidazole, anhydrous ethanol and pure water were mixed in a mass ratio of 1:1:6:6, and then 0.5 times the mass of neodymium chloride of 3-furoic acid was added, and the mixture was stirred at 40°C and 1000 r / min for 4 hours to obtain a fluorescent complex solution; styrene-butadiene-styrene block copolymer, ethyl diallylsilane and n-hexane were mixed in a mass ratio of 1:1:10, and then 0.05 times the mass of divinyltetramethyldisiloxane platinum salt of styrene-butadiene-styrene block copolymer was added, and the mixture was stirred and refluxed at 80°C and 800 r / min for 5 hours, and 1.5 times the mass of diethoxysilane of styrene-butadiene-styrene block copolymer was added, and the mixture was stirred and refluxed for 5 hours, and styrene-butadiene-styrene block copolymer was added. 1.5 times the mass of p-aminostyrene was continued, and stirring and refluxing were continued for 5 hours. The mixture was allowed to stand at 30°C and 2kPa for 4 hours, filtered and washed with pure water for 5 times, and dried at -1°C and 10Pa for 6 hours to obtain a pre-modified styrene-butadiene-styrene block copolymer; the pre-modified styrene-butadiene-styrene block copolymer, the fluorescent complex solution, and n-hexane were mixed in a mass ratio of 1:7:5, and then 0.03 times the mass of the pre-modified styrene-butadiene-styrene block copolymer was added with carbodiimide. The mixture was stirred at 30°C and 1000 r / min for 2 hours, and allowed to stand at 40°C and 2kPa for 8 hours. The mixture was filtered and washed with pure water for 5 times, and dried at -1°C and 10Pa for 6 hours to obtain a modified styrene-butadiene-styrene block copolymer.

[0041] (3) The modified helical carbon nanotubes were placed in pure water and allowed to stand for 3 minutes, and dried at -1°C and 10 Pa for 6 hours to obtain pretreated modified helical carbon nanotubes; the pretreated modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer, and polyethylene were uniformly mixed in a mass ratio of 1:2:3, and kneaded at 140°C for 20 minutes to prepare a sheath material with a thickness of 4 mm. The sheath material was wrapped on the optical cable core material, and rolled twice at 130°C and 8 MPa at 240 m / min to obtain a high-elasticity optical cable.

[0042] Comparative Example 1

[0043] The preparation method of the high elastic optical cable of Comparative Example 1 is different from that of Example 2 only in step (1). Step (1) is modified as follows: the carbon nanotubes and nitric acid with a mass fraction of 45% are mixed uniformly in a mass ratio of 1:9, stirred at 85°C and 900r / min for 25min, cooled to room temperature and filtered, washed with pure water 4 times, and dried at -5°C and 5Pa for 7h to obtain acid-treated carbon nanotubes; the acid-treated carbon nanotubes, thionyl chloride and tetrahydrofuran are mixed uniformly in a mass ratio of 1:5:5, and stirred at 4 The mixture was stirred at 5°C for 450 min and reacted for 2.5 h. The mixture was heated to 65°C and stirred for 2.5 h before filtering. The mixture was allowed to stand at 20°C and 1.5 kPa for 5 h to obtain pre-modified carbon nanotubes. The pre-modified carbon nanotubes, aminopropyltrimethoxysilane, triethylamine, and dichloromethane were mixed uniformly in a mass ratio of 3:2:0.8:22, stirred at 3°C and 400 rpm for 55 min, allowed to stand at room temperature for 22 h, filtered, washed four times with anhydrous ethanol, and dried at -5°C and 5 Pa for 7 h to obtain modified carbon nanotubes. The remaining steps were the same as in Example 2.

[0044] Comparative Example 2

[0045] The preparation method of the high elastic optical cable of Comparative Example 2 is different from that of Example 2 only in step (1). Step (1) is modified as follows: acetone, pyridine and acetylene are mixed uniformly in a mass ratio of 1:1:2 as a carbon source gas, a glass plate carrier uniformly distributed with nano-iron oxide is placed in a reaction chamber in a nitrogen atmosphere, and a carbon source gas 1100 times the mass of nano-iron oxide is introduced at a flow rate of 900 sscm at 750°C, and then the ventilation is stopped for 7 minutes, and then nitrogen is introduced at the same flow rate for 15 minutes, cooled to 20°C, and the reaction mixture is heated to 400 ℃. The product on the glass plate carrier was placed in a 12% hydrochloric acid solution, sonicated at 35 kHz for 18 minutes, filtered, washed four times with anhydrous ethanol and four times with pure water, and dried at -5°C, 5 Pa for 7 hours to produce helical carbon nanotubes. The helical carbon nanotubes were then mixed with 45% nitric acid at a mass ratio of 1:9, stirred at 85°C, 900 rpm for 25 minutes, cooled to room temperature, filtered, washed four times with pure water, and dried at -5°C, 5 Pa for 7 hours to produce modified helical carbon nanotubes. The remaining steps were the same as in Example 2.

[0046] Comparative Example 3

[0047] The preparation method of the high elastic optical cable of Comparative Example 3 differs from that of Example 2 only in step (2). Step (2) is modified as follows: 3-furoic acid, 2-mercaptobenzimidazole, anhydrous ethanol, and pure water are mixed uniformly in a mass ratio of 1:1:5:5, and then 0.4 times the mass of neodymium chloride of 3-furoic acid is added, and stirred at 35°C, 900 r / min for 4.5 hours to obtain a fluorescent complex solution; pre-modified styrene-butadiene-styrene block copolymer, fluorescent complex solution, and n-hexane are mixed uniformly in a mass ratio of 1:6:4, and then 0.02 times the mass of carbodiimide of pre-modified styrene-butadiene-styrene block copolymer is added, and the mixture is stirred at 25°C, 900 r / min for 2.5 hours, and then allowed to stand at 35°C, 1.5 kPa for 9 hours, filtered, washed with pure water 4 times, and dried at -5°C, 5 Pa for 7 hours to obtain a modified styrene-butadiene-styrene block copolymer. The remaining steps are the same as those of Example 2.

[0048] Comparative Example 4

[0049] The preparation method of the high elastic optical cable of Comparative Example 4 differs from that of Example 2 only in step (2). Step (2) is modified as follows: styrene-butadiene-styrene block copolymer, ethyl diallylsilane and n-hexane are uniformly mixed in a mass ratio of 1:1:9, and then 0.04 times the mass of the styrene-butadiene-styrene block copolymer of divinyltetramethyldisiloxane platinum salt is added, and the mixture is stirred and refluxed at 75°C and 650 r / min for 4 hours. Diethoxysilane is added at 1.4 times the mass of the styrene-butadiene-styrene block copolymer, and the mixture is stirred and refluxed for another 4 hours. Para-aminostyrene is added at 1.4 times the mass of the styrene-butadiene-styrene block copolymer, and the mixture is stirred and refluxed for another 4 hours. The mixture is allowed to stand at 25°C and 1.5 kPa for 3.5 hours, filtered and washed with pure water four times, and dried at -5°C and 5 Pa for 7 hours to obtain a modified styrene-butadiene-styrene block copolymer. The remaining steps are the same as those of Example 2.

[0050] Comparative Example 5

[0051] A method for preparing a highly elastic optical cable, the method mainly comprising the following preparation steps:

[0052] (1) Acetone, pyridine and acetylene were mixed in a mass ratio of 1:1:2 as a carbon source gas. A glass plate carrier uniformly distributed with nano-iron oxide was placed in a reaction chamber in a nitrogen atmosphere. A carbon source gas 1100 times the mass of nano-iron oxide was introduced at a flow rate of 900 sscm at 750°C, and then ventilation was stopped for 7 minutes. Nitrogen was then introduced at the same flow rate for 15 minutes, and cooled to 20°C. The product on the glass plate carrier was placed in a 12% hydrochloric acid solution by mass, ultrasonicated at 35kHz for 18 minutes, filtered and washed with anhydrous ethanol and pure water for 4 times each, and dried at -5°C, 5Pa for 7 hours to obtain helical carbon nanotubes; the helical carbon nanotubes and 45% nitric acid by mass were mixed in a mass ratio of 1:9, and heated at 85°C, 900 r / mi The acid-treated spiral carbon nanotubes were uniformly mixed with thionyl chloride and tetrahydrofuran in a mass ratio of 1:5:5, stirred and reacted at 45°C for 450min for 2.5h, heated to 65°C and continued to stir and react for 2.5h, filtered, and allowed to stand at 20°C and 1.5kPa for 5h, and then uniformly mixed with aminopropyltrimethoxysilane, triethylamine and dichloromethane in a mass ratio of 3:2:0.8:22, stirred at 3°C and 400r / min for 55min, allowed to stand at room temperature for 22h, filtered and washed with anhydrous ethanol 4 times, and dried at -5°C and 5Pa for 7h to obtain modified spiral carbon nanotubes;

[0053] (2) Styrene-butadiene-styrene block copolymer, ethyl diallylsilane and n-hexane were mixed in a mass ratio of 1:1:9, and then 0.04 times the mass of styrene-butadiene-styrene block copolymer of divinyltetramethyldisiloxane platinum salt was added, and the mixture was stirred and refluxed at 75 ° C, 650 r / min for 4 hours, and 1.4 times the mass of styrene-butadiene-styrene block copolymer of diethoxysilane was added, and the mixture was stirred and refluxed for 4 hours. 1.4 times the mass of styrene-butadiene-styrene block copolymer of p-aminostyrene was added, and the mixture was stirred and refluxed for 4 hours. The mixture was allowed to stand at 25 ° C, 1.5 kPa for 3.5 hours. The mixture was filtered and washed with pure water for 4 times, and dried at -5°C and 5Pa for 7h to obtain a pre-modified styrene-butadiene-styrene block copolymer; the pre-modified styrene-butadiene-styrene block copolymer, the fluorescent complex solution, and n-hexane were mixed uniformly in a mass ratio of 1:6:4, and then 0.02 times the mass of the pre-modified styrene-butadiene-styrene block copolymer was added with carbodiimide, and the mixture was stirred at 25°C and 900r / min for 2.5h, and allowed to stand at 35°C and 1.5kPa for 9h, filtered and washed with pure water for 4 times, and dried at -5°C and 5Pa for 7h to obtain a modified styrene-butadiene-styrene block copolymer;

[0054] (3) 3-furoic acid, 2-mercaptobenzimidazole, anhydrous ethanol and pure water were mixed in a mass ratio of 1:1:5:5, and then 0.4 times the mass of neodymium chloride of 3-furoic acid was added, and the mixture was stirred at 35°C and 900 r / min for 4.5 hours, and dried at -5°C and 5Pa for 7 hours to obtain a fluorescent complex; the modified helical carbon nanotubes were placed in pure water and allowed to stand for 2.5 minutes, and dried at -5°C and 5Pa for 6 to 8 hours to obtain pretreated modified helical carbon nanotubes; the pretreated modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer, fluorescent complex and polyethylene were mixed in a mass ratio of 1:1.5:0.5:2.5, and kneaded at 130°C for 25 minutes to prepare a sheath material with a thickness of 4 mm. The sheath material was wrapped on the optical cable core material, and rolled twice at 125°C and 9MPa at 230m / min to obtain a high elastic optical cable.

[0055] Effect Examples

[0056] Table 1 below shows the performance analysis results of the tensile fracture resistance and anti-aging performance of the high elasticity optical cables of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0057] Table 1

[0058]

[0059] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 1, it can be found that the high elasticity optical cable prepared in the present invention has good tensile fracture resistance and anti-aging performance.

[0060] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1, it can be found that the performance retention rate of Examples 1, 2, 3 is higher than that of Comparative Example 1 under wet heat and temperature change conditions, which shows that the use of helical carbon nanotubes is compared with the direct use of carbon nanotubes. The helical structure makes the helical carbon nanotubes have more contact with the other components of the overall material, and has a greater conduction effect on the thermal motion of molecules, thereby improving the anti-aging performance of the high elastic optical cable under wet heat and temperature change conditions; From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2, it can be found that the performance retention rate of Examples 1, 2, 3 is higher than that of Comparative Example 2 under wet heat and temperature change conditions. The high rate and high tensile strength indicate that the acid-treated helical carbon nanotubes are modified to form amide bonds with aminopropyltrimethoxysilane and the helical carbon nanotubes, and the trimethoxysilane on the modified helical carbon nanotubes can be decomposed into silanol groups, which are cross-linked with each other to form a helical carbon nanotube heat-conducting network, thereby improving the overall cross-linking degree and the thermal conductivity and thermal stability, thereby improving the anti-aging performance and tensile fracture resistance of the high elastic optical cable under wet heat and temperature change conditions; from the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3, it can be found that Examples 1, 2, 3 have better anti-aging performance and tensile fracture resistance than Comparative Example 3 under temperature change and ultraviolet The performance retention rate under external conditions is high, which shows that after the styrene-butadiene-styrene block copolymer is pre-modified, the styrene-butadiene-styrene block copolymer has a longer silicone segment. The silicone segment increases the stability of the styrene-butadiene-styrene block copolymer, reduces the impact of temperature changes on the overall performance, and cannot react with the subsequent fluorescent complex solution, thereby improving the anti-aging performance of the high-elasticity optical cable under temperature changes and ultraviolet conditions; Comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4 shows that the performance of Examples 1, 2, 3 compared with Comparative Example 4 under ultraviolet and ozone conditions is better. The high retention rate indicates that after the pre-modified styrene-butadiene-styrene block copolymer is modified with a fluorescent complex solution, the fluorescent complex on the modified styrene-butadiene-styrene block copolymer can absorb strong light and ultraviolet rays and convert them into weak light and heat, reducing the damage to the material caused by strong light and ultraviolet rays. In an ozone environment, when the overall composition contains oxidizing substances, the benzimidazole on the fluorescent complex can respond promptly, breaking the metal-sulfur coordination bond to form a benzimidazole containing free sulfur. This combines with the oxidizing substance to reduce the oxidative decomposition of the main material, thereby improving the anti-aging performance of the high-elasticity optical cable under UV and ozone conditions.Comparison of the experimental data from Examples 1, 2, and 3 with Comparative Example 5 reveals that Examples 1, 2, and 3 exhibit higher performance retention rates than Comparative Example 5 under UV and ozone conditions. This demonstrates that grafting the fluorescent complex onto the styrene-butadiene-styrene block copolymer, compared to mixing and kneading, allows the amide bonds on the modified styrene-butadiene-styrene block copolymer to form hydrogen bonds with the amide bonds on the modified helical carbon nanotubes, allowing the fluorescent complex to be closely attached to the modified helical carbon nanotubes. This allows for the timely transfer of heat converted from UV absorption and protects the fluorescent complex from loss, thereby improving the anti-aging performance of the highly elastic optical cable under UV and ozone conditions.

[0061] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A method for preparing a highly elastic optical cable, characterized in that: The high elastic optical cable is made of a sheath material made of modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer and polyethylene, and the sheath material is wrapped around the optical cable core material and rolled. The method for preparing the highly elastic optical cable comprises the following steps: (1) The helical carbon nanotubes and nitric acid (40-50% by mass) were mixed in a mass ratio of 1:8-1:10, stirred at 80-90°C and 800-1000 r / min for 20-30 min, cooled to room temperature and filtered, washed with pure water for 3-5 times, and dried at -10--1°C and 1-10 Pa for 6-8 h; the acid-treated helical carbon nanotubes, thionyl chloride, and tetrahydrofuran were mixed in a mass ratio of 1:4:4-1:6:

6. Stir the reaction at 40-50°C and 400-500 r / min for 2-3 hours, heat to 60-70°C and continue stirring for 2-3 hours, filter, and stand at 10-30°C and 1-2 kPa for 4-6 hours. Then mix evenly with aminopropyltrimethoxysilane, triethylamine, and dichloromethane in a mass ratio of 3:2:0.5:20-3:3:1:25, stir at 0-5°C and 300-500 r / min for 50-60 minutes, and stand at room temperature for 20-2 4h, filtered and washed with anhydrous ethanol 3~5 times, and dried at -10~-1℃, 1~10Pa for 6~8h to obtain modified helical carbon nanotubes; the preparation method of the helical carbon nanotubes is as follows: acetone, pyridine and acetylene are mixed uniformly in a mass ratio of 1:1:1~1:2:3 as a carbon source gas, a glass plate carrier uniformly distributed with nano-iron oxide is placed in a reaction chamber in a nitrogen atmosphere, and heated at 700~800℃ at a flow rate of 800~1000sscm. After introducing carbon source gas at a mass of 1000 to 1200 times that of nano-iron oxide, the aeration is stopped for 5 to 10 minutes, and then nitrogen is introduced at the same flow rate for 10 to 20 minutes, and the mixture is cooled to 10 to 30° C., and the product on the glass plate carrier is placed in a 10 to 15% by mass hydrochloric acid solution, ultrasonicated at 30 to 40 kHz for 15 to 20 minutes, filtered, and washed with anhydrous ethanol and pure water 3 to 5 times each, and dried at -10 to -1° C. and 1 to 10 Pa for 6 to 8 hours to prepare the product; (2) The pre-modified styrene-butadiene-styrene block copolymer, fluorescent complex solution and n-hexane were mixed in a mass ratio of 1:5:3~1:7:5, and then 0.01~0.03 times the mass of the pre-modified styrene-butadiene-styrene block copolymer of carbodiimide was added. The mixture was stirred at 20~30℃ and 800~1000r / min for 2~3h, and then allowed to stand at 30~40℃ and 1~2kPa for 8~10h. The mixture was filtered and washed with pure water for 3 hours. The pre-modified styrene-butadiene-styrene block copolymer is prepared by mixing the styrene-butadiene-styrene block copolymer, ethyl diallylsilane and n-hexane in a mass ratio of 1:1:8 to 1:1:10, and then adding 0.03 to 0.05 of the mass of the styrene-butadiene-styrene block copolymer to obtain the modified styrene-butadiene-styrene block copolymer. Ethylene tetramethyl disiloxane platinum salt, stir and reflux at 70~80℃, 500~800r / min for 3~5h, add diethoxysilane (1.3~1.5 times the mass of styrene-butadiene-styrene block copolymer), continue stirring and reflux for 3~5h, add p-aminostyrene (1.3~1.5 times the mass of styrene-butadiene-styrene block copolymer), continue stirring and reflux for 3~5h, and let it stand at 20~30℃, 1~2kPa for 3~4h , filtering and washing with pure water for 3 to 5 times, and drying at -10 to -1°C and 1 to 10 Pa for 6 to 8 hours to prepare the fluorescent complex solution; the preparation method of the fluorescent complex solution is: 3-furoic acid, 2-mercaptobenzimidazole, anhydrous ethanol and pure water are uniformly mixed in a mass ratio of 1:1:4:4 to 1:1:6:6, and then 0.3 to 0.5 times the mass of neodymium chloride of 3-furoic acid is added, and the mixture is stirred at 30 to 40°C and 800 to 1000 r / min for 4 to 5 hours to prepare the fluorescent complex solution; (3) placing the modified helical carbon nanotubes in pure water for 2-3 minutes, and drying them at -10--1°C and 1-10 Pa for 6-8 hours to obtain pretreated modified helical carbon nanotubes; The pretreated modified helical carbon nanotubes, modified styrene-butadiene-styrene block copolymer, and polyethylene are uniformly mixed in a mass ratio of 1:1:2 to 1:2:3, and kneaded at 120-140°C for 20-30 minutes to prepare a sheath material with a thickness of 3-5 mm. The sheath material is wrapped around the optical cable core material, and rolled 2-3 times at 120-130°C and 8-10 MPa at a speed of 220-240 m / min to prepare a high-elasticity optical cable.

2. The method for preparing a highly elastic optical cable according to claim 1, wherein: The core material in step (3) is a central tube optical cable, model GYXTS.

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