CN114874529A - Flexible cable and preparation method thereof - Google Patents

Flexible cable and preparation method thereof Download PDF

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CN114874529A
CN114874529A CN202210715001.9A CN202210715001A CN114874529A CN 114874529 A CN114874529 A CN 114874529A CN 202210715001 A CN202210715001 A CN 202210715001A CN 114874529 A CN114874529 A CN 114874529A
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罗祥
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
    • H01B13/24—Sheathing; Armouring; Screening; Applying other protective layers by extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/04—Flexible cables, conductors, or cords, e.g. trailing cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a flexible cable and a preparation method thereof, and relates to the technical field of wires and cables. The preparation method comprises the steps of reacting hyperbranched polyester with thiophenol polyethylene glycol to prepare modified hyperbranched polyester, mixing methyl methacrylate, methyl acrylate, N-heptane, dilauroyl peroxide and the modified hyperbranched polyester to prepare polymer microspheres, spraying the polymer microspheres on a cable core, reacting 4,4' -methylene bis (phenyl isocyanate) with hydroxyl-terminated vinyl polysiloxane, reacting with graphene oxide, reacting with furfuryl alcohol to prepare modified graphene oxide, mixing the modified graphene oxide, N ' - (4,4' -methylene diphenyl) bismaleimide, poly-1, 3-butadiene and polyethylene to prepare a sheath material, wrapping the sheath material on the surface of the cable core irradiated by a high-pressure mercury lamp, and rolling to obtain the flexible cable. The flexible cable prepared by the invention has excellent impact resistance, flame retardance and self-repairing performance.

Description

Flexible cable and preparation method thereof
Technical Field
The invention relates to the technical field of wires and cables, in particular to a flexible cable and a preparation method thereof.
Background
A cable is a power or signal transmission device, and is generally composed of several wires or groups of wires. The derivation/new product of the electric wire and the cable is mainly generated by adopting new materials and special materials, changing the structure of the product, improving the process requirements, or combining different products due to different application occasions and application requirements, convenience of equipment, reduction of equipment cost and the like.
With the rapid development of power cable application, higher requirements are put on cable protection, and common faults of a cable line include mechanical damage, insulation moisture, insulation aging deterioration, overvoltage, cable overheating fault and the like. In specific occasions of high temperature, vibration and impact, the flexible and flame-retardant effect is also needed to achieve better and longer-lasting using effect.
Disclosure of Invention
The invention aims to provide a flexible cable and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the flexible cable is characterized in that the flexible cable is prepared by spraying polymer microspheres on a cable core to obtain a sprayed cable core, mixing modified graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly-1, 3-butadiene and polyethylene to prepare a sheath material, irradiating the surface of the sprayed cable core by using a high-pressure mercury lamp, and wrapping the sheath material on the surface of the irradiated cable core to roll.
Preferably, the polymer microspheres are prepared by mixing methyl methacrylate, methyl acrylate, n-heptane, dilauroyl peroxide and modified hyperbranched polyester into an oil phase and stirring in a water phase.
Preferably, the modified hyperbranched polyester is prepared by reacting 4-chloro-4' -hydroxybenzophenone with trimethylolpropane triglycidyl ether to prepare a prepolymer, reacting the prepolymer with terephthalic acid, trimethylolpropane triglycidyl ether and p-vinylbenzoic acid in sequence to prepare a hyperbranched polyester, reacting polyethylene glycol with succinic anhydride, thionyl chloride and p-aminophenol in sequence to prepare thiophenol-based polyethylene glycol, and reacting the hyperbranched polyester with the thiophenol-based polyethylene glycol.
Preferably, the modified graphene oxide is prepared by reacting 4,4' -methylene bis (phenyl isocyanate) with hydroxyl-terminated vinyl polysiloxane, then reacting with graphene oxide, and then reacting with furfuryl alcohol.
Preferably, the preparation method of the flexible cable comprises the following preparation steps:
(1) preparation of hyperbranched polyester: mixing prepolymer, terephthalic acid, tetrabutylammonium bromide and N, N-dimethylformamide according to the mass ratio of 10: 5: 1: 20-10: 7: 1: 25, uniformly mixing, stirring and reacting at 80-90 ℃ for 2-3 h at 800-1000 r/min in a nitrogen atmosphere, adding trimethylolpropane triglycidyl ether with the mass being 1.4-1.8 times that of the prepolymer, continuously stirring and reacting for 2-3 h, adding p-vinylbenzoic acid with the mass being 0.8-1 time that of the prepolymer, continuously stirring and reacting for 2-3 h, standing at 40-50 ℃ for 8-10 h under 1-2 kPa, adding ethyl acetate with the mass being 3-5 times that of the prepolymer, sequentially washing 3-5 times with a sodium bicarbonate solution with the mass fraction being 5-6%, a sodium chloride solution with the mass fraction being 15-20% and deionized water, drying the washed solution with anhydrous magnesium sulfate, filtering to obtain a filtrate, and standing at 40-50 ℃ for 8-10 h under 1-2 kPa to obtain a hyperbranched polyester;
(2) modification of hyperbranched polyester: hyperbranched polyester, thiophenol polyethylene glycol, potassium hydroxide, toluene and N-methyl pyrrolidone are mixed according to the mass ratio of 6: 1: 2: 50: 20-6: 2: 3: 60: 25, uniformly mixing, stirring at 10-30 ℃ for 20-30 min at 300-500 r/min, heating to 120-130 ℃ and keeping for 3-4 h, continuously heating to 150-160 ℃ and keeping for 3-4 h, cooling to room temperature, filtering to obtain a filtrate, dripping the filtrate into hydrochloric acid with the mass fraction of 36-38% which is 6-8 times of the mass of the filtrate stirred at 0-3 ℃ and 300-500 r/min at the speed of 1-2 mL/min, filtering, washing 3-5 times by using pure water and petroleum ether respectively, immersing in a saturated sodium acetate solution, performing ultrasonic treatment at 30-40 kHz for 20-30 min, filtering, washing 3-5 times by using pure water and petroleum ether respectively, and standing at-10 to-1 ℃ for 6-8 h at-2 kPa to obtain a modified hyperbranched poly-ester;
(3) preparing elastic microspheres: mixing methyl methacrylate, methyl acrylate, n-heptane, dilauroyl peroxide and modified hyperbranched poly-acid ester according to a mass ratio of 40: 14: 30: 2: 25-50: 18: 35: 4: 30 at 0 ℃ to prepare an oil phase, and mixing polyvinyl alcohol and pure water according to a mass ratio of 1: 140-1: 160, uniformly mixing to prepare a water phase, and mixing the oil phase and the water phase according to a mass ratio of 1: 4-1: 6, pouring the mixture into a reaction kettle, sealing and keeping the nitrogen atmosphere, stirring for 20-30 min at 500-700 r/min, reacting for 10-12 h at 90-100 ℃, cooling to room temperature, filtering, and drying for 6-8 h at 20-30 ℃ under 1-2 kPa to obtain elastic microspheres;
(4) spraying the cable core: mixing polymer microspheres and pure water according to a mass ratio of 1: 4-1: 6, mixing uniformly to prepare a spraying liquid, and then mixing at a ratio of 0.06-0.08 g/cm 2 The amount of the composite material is sprayed on the surface of the cable core, and the composite material is dried for 6 to 8 hours at the temperature of between-1 and-10 ℃ and under the pressure of 1 to 10Pa to prepare the sprayed cable core;
(5) modification of graphene oxide: hydroxyl-terminated vinyl polysiloxane and N, N-dimethylformamide are mixed according to the mass ratio of 1: 10-1: 15 mixing uniformly to prepare a titration solution; mixing 4,4' -methylene bis (phenyl isocyanate) and N, N-dimethylformamide according to a mass ratio of 1: 6-1: 8, uniformly mixing, dropwise adding a titration solution with the mass of 0.8-1.2 times of that of 4,4' -methylenebis (phenyl isocyanate) at the speed of 0.1-0.2 mL/s in a nitrogen atmosphere at the temperature of 70-90 ℃ under the stirring condition of 800-1000 r/min, keeping the condition unchanged after dropwise adding, continuously reacting for 2-3 h, adding a graphene oxide dispersion with the mass of 1.2-1.6 times of that of 4,4' -methylenebis (phenyl isocyanate), continuously reacting for 4-6 h in a nitrogen atmosphere, adding furfuryl alcohol with the mass of 0.5-0.7 time of 4,4' -methylenebis (phenyl isocyanate), and continuously reacting for 3-4 h in the nitrogen atmosphere to obtain modified graphene oxide;
(6) rolling and assembling: modified graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly (1, 3-butadiene) and polyethylene are mixed according to a mass ratio of 1: 1: 1: 3-2: 1: 1: 4, uniformly mixing, mixing at 140-160 ℃ for 20-30 min to prepare a sheath material with the thickness of 2-3 mm, irradiating the surface of the sprayed cable core with a 800-1000W high-pressure mercury lamp for 5-7 min, wrapping the sheath material on the surface of the irradiated cable core, raising the temperature to 100-120 ℃, standing for 8-10 min, and rolling for 2-3 times at the pressure of 8-10 MPa and at the speed of 220-240 m/min to prepare the flexible cable.
As optimization, the preparation method of the prepolymer in the step (1) comprises the following steps: 4-chloro-4' -hydroxybenzophenone, trimethylolpropane triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 8: 1: 20-10: 10: 1: 25, uniformly mixing, stirring and reacting for 2-3 h at 80-90 ℃ and 800-1000 r/min in a nitrogen atmosphere, and standing for 8-10 h at 40-50 ℃ and 1-2 kPa to prepare the nano-composite material.
As optimization, the preparation method of the thiophenol polyethylene glycol in the step (2) comprises the following steps: mixing p-aminophenol, triethylamine and dichloromethane in a mass ratio of 3: 1: 30-4: 1: 40, uniformly mixing at 0-5 ℃ to prepare a p-aminophenol solution; mixing succinic anhydride and polyethylene glycol with the molecular weight of 500-600 according to the mass ratio of 1: 3-1: 4, uniformly mixing, stirring at 70-80 ℃ for 3-4 h at 800-1000 r/min, and mixing with thionyl chloride and tetrahydrofuran according to a mass ratio of 15: 100: 1-40: 300: 1, uniformly mixing, stirring and reacting for 2-3 h at 40-50 ℃ at 300-500 r/min, heating to 60-70 ℃, continuing to stir and react for 2-3 h, standing for 30-40 min at 10-30 ℃ under 1-2 kPa, adding a p-aminophenol solution with the mass 2-3 times that of polyethylene glycol, stirring for 2-3 h at 0-5 ℃ at 300-500 r/min, standing for 20-24 h at room temperature, and standing for 6-8 h at-10-1 ℃ under 1-2 kPa.
Preferably, the cable core in the step (4) is formed by bundling and fixing copper wires with the diameter of 0.03-0.05 mm into copper wire bundles with the diameter of 0.8-1.2 mm, wrapping a polyethylene layer with the thickness of 0.8-1 mm on the periphery of the copper wire bundles to form wires, fixing a plurality of wires, and winding a circle of aluminum tape on the periphery to fix the wires, wherein the aluminum tape is 0.3-0.5 mm in thickness, 1-3 cm in width and 1-3 cm in winding gap.
Preferably, the preparation method of the hydroxyl-terminated vinyl polysiloxane in the step (5) comprises the following steps: octamethylcyclotetrasiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane in a mass ratio of 20: 1-30: 1, adding tetramethylammonium hydroxide with the mass of 0.03-0.05 time of that of octamethylcyclotetrasiloxane, uniformly mixing, stirring at 100-120 ℃ and 500-700 r/min for 3-4 h, and standing at 160-180 ℃ and 1-2 kPa for 3-4 h to prepare the octamethylcyclotetrasiloxane.
Preferably, the graphene oxide dispersion liquid in the step (5) is prepared by mixing graphene oxide and N, N-dimethylformamide according to a mass ratio of 1: 10-1: 15, uniformly mixing, and carrying out ultrasonic treatment at the temperature of 20-30 ℃ and the frequency of 30-40 kHz for 10-15 min.
Compared with the prior art, the invention has the following beneficial effects:
when the flexible cable is prepared, methyl methacrylate, methyl acrylate, N-heptane, dilauroyl peroxide and modified hyperbranched polyester are mixed to form an oil phase, the oil phase is stirred in a water phase to prepare polymer microspheres, the polymer microspheres are sprayed on a cable core to obtain a sprayed cable core, modified graphene oxide, N '- (4,4' -methylenediphenyl) bismaleimide, poly-1, 3-butadiene and polyethylene are mixed to prepare a sheath material, the surface of the sprayed cable core is irradiated by a high-pressure mercury lamp, and then the sheath material is wrapped on the surface of the irradiated cable core and is rolled to obtain the flexible cable.
Firstly, 4-chloro-4' -hydroxybenzophenone and trimethylolpropane triglycidyl ether react to prepare a prepolymer, the prepolymer sequentially reacts with terephthalic acid, trimethylolpropane triglycidyl ether and p-vinylbenzoic acid to prepare hyperbranched polyester, polyethylene glycol sequentially reacts with succinic anhydride, thionyl chloride and p-aminophenol to prepare thiophenyl polyethylene glycol, the hyperbranched polyester reacts with the thiophenyl polyethylene glycol to prepare modified hyperbranched polyester, the hyperbranched polyester is modified, substituted sulfur promotes the hydrogen abstraction photoinitiation effect of the benzophenone, a sulfur free radical is formed by a diphenyl sulfide group under the illumination of light to initiate the cross-linking polymerization of carbon-carbon double bonds in a main material to form a cross-linked network structure, a polyethylene glycol branched chain can promote the stable formation of elastic microspheres, and the elastic microspheres have good adhesion effect on cable cores in the spraying process, the elastic microspheres are prevented from falling off, the hyperbranched structure can enable the structure on the surfaces of the elastic microspheres to be more stable, the elastic microspheres are heated to expand into the middle air bag to keep the structure stable, and the middle air bag is not broken and collapsed, so that the impact resistance of the flexible cable is improved.
Secondly, reacting 4,4' -methylene bis (phenyl isocyanate) with hydroxyl-terminated vinyl polysiloxane, then reacting with graphene oxide, and reacting with furfuryl alcohol to prepare modified graphene oxide, wherein the hydroxyl-terminated vinyl polysiloxane is used to ensure that the modified graphene oxide is easy to form silicon dioxide and a carbon layer to be attached to the surface of a main body at high temperature, so that the flame retardant property of the material is improved, and meanwhile, the vinyl on the hydroxyl-terminated vinyl polysiloxane enables the modified graphene oxide to participate in ultraviolet-initiated free radical polymerization reaction in the subsequent process, so that the impact resistance of the flexible cable is improved; the furfuryl alcohol is used for modification, so that the modified graphene can perform a thermal reversible reaction with a maleimide group in the main body, and the self-repairing effect of the flexible cable is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided to illustrate the method for testing each index of the flexible cable manufactured in the following examples as follows:
impact resistance: the flexible cable obtained in each example and the comparative example were weighed to the same size and mass, and the impact strength was measured according to the QJ1632 standard.
Flame retardant property: the flexible cables obtained in the examples and the comparative example material are measured for flame retardancy by measuring the extreme oxygen index according to the GB/T2406 standard method.
Self-repairing performance: the flexible cable obtained in each example and the comparative example material are subjected to the same size and mass, wounds with the same depth, size and density are scratched by a knife, the flexible cable is kept stand at 100 ℃ for the same time, the impact strength is measured again, and the repair rate is calculated as the impact strength after repair/the initial impact strength
Example 1
A preparation method of a flexible cable mainly comprises the following preparation steps:
(1) preparation of hyperbranched polyester: 4-chloro-4' -hydroxybenzophenone, trimethylolpropane triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 8: 1: 20, uniformly mixing, stirring and reacting for 3 hours at 80 ℃ and 800r/min in a nitrogen atmosphere, and standing for 10 hours at 40 ℃ and 1kPa to obtain a prepolymer; the prepolymer, terephthalic acid, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 5: 1: 20, uniformly mixing, stirring and reacting for 3 hours at 80 ℃ at 800r/min in a nitrogen atmosphere, adding trimethylolpropane triglycidyl ether with the mass being 1.4 times that of the prepolymer, continuously stirring and reacting for 3 hours, adding p-vinylbenzoic acid with the mass being 0.8 time that of the prepolymer, continuously stirring and reacting for 2 hours, standing for 10 hours at 40 ℃ under 1kPa, adding ethyl acetate with the mass being 3 times that of the prepolymer, sequentially washing for 5 times by using a sodium bicarbonate solution with the mass fraction of 5%, a sodium chloride solution with the mass fraction of 15% and deionized water respectively, drying the washed solution by using anhydrous magnesium sulfate, filtering to obtain a filtrate, and standing for 10 hours at 40 ℃ under 1kPa to obtain the hyperbranched polyester;
(2) modification of hyperbranched polyester: mixing p-aminophenol, triethylamine and dichloromethane in a mass ratio of 3: 1: 30, mixing uniformly at 0 ℃ to prepare a p-aminophenol solution; mixing succinic anhydride and polyethylene glycol with molecular weight of 500 according to a mass ratio of 1: 3, uniformly mixing, stirring at 70 ℃ for 4h at 800r/min, and mixing with thionyl chloride and tetrahydrofuran according to a mass ratio of 15: 100: 1, uniformly mixing, stirring and reacting for 3h at 40 ℃ and 300r/min, heating to 60 ℃, continuing to stir and react for 3h, standing for 40min at 10 ℃ and 1kPa, adding a p-aminophenol solution with the mass 2 times that of polyethylene glycol, stirring for 3h at 0 ℃ and 300r/min, standing for 20h at room temperature, and standing for 8h at-10 ℃ and 1kPa to prepare thiophenol-based polyethylene glycol; hyperbranched polyester, thiophenol polyethylene glycol, potassium hydroxide, toluene and N-methyl pyrrolidone are mixed according to the mass ratio of 6: 1: 2: 50: 20, uniformly mixing, stirring at 10 ℃, 300r/min for 30min, heating to 120 ℃, keeping for 4h, continuously heating to 150 ℃ and keeping for 4h, cooling to room temperature, filtering to obtain a filtrate, dripping the filtrate into hydrochloric acid with the mass fraction of 38% which is 6 times of that of the filtrate stirred at 0 ℃, 300r/min at the speed of 1mL/min, filtering, washing 3 times respectively by using pure water and petroleum ether, immersing in a saturated sodium acetate solution, performing ultrasonic treatment at 30kHz for 30min, filtering, washing 3 times respectively by using the pure water and the petroleum ether, and standing for 8h at-10 ℃ and 1kPa to obtain the modified hyperbranched polyester;
(3) preparing elastic microspheres: mixing methyl methacrylate, methyl acrylate, n-heptane, dilauroyl peroxide and modified hyperbranched poly-acid ester according to a mass ratio of 40: 14: 30: 2: 25, uniformly mixing at 0 ℃ to prepare an oil phase, and mixing polyvinyl alcohol and pure water according to a mass ratio of 1: 140, uniformly mixing to prepare a water phase, and mixing the oil phase and the water phase according to a mass ratio of 1: 4, pouring the mixture into a reaction kettle, sealing and keeping the nitrogen atmosphere, stirring the mixture for 30min at the speed of 500r/min, reacting the mixture for 12h at the temperature of 90 ℃, cooling the mixture to room temperature, filtering the mixture, and drying the mixture for 8h at the temperature of 20 ℃ under 1kPa to obtain elastic microspheres;
(4) spraying the cable core: bundling and fixing copper wires with the diameter of 0.04mm into copper wire bundles with the diameter of 1mm, wrapping a polyethylene layer with the thickness of 0.9mm on the periphery of the copper wire bundles to obtain wires, fixing a plurality of wires, and winding a circle of aluminum tape on the periphery to fix the wires, wherein the aluminum tape is 0.4mm thick, 2cm wide and 2cm in winding gap to obtain a cable core; mixing polymer microspheres and pure water according to a mass ratio of 1: 4 mixing uniformly to obtain spraying liquid, and then mixing at a ratio of 0.06g/cm 2 The amount of the coating is sprayed on the surface of the cable core, and the cable core is dried for 8 hours at the temperature of minus 1 ℃ under 1Pa to prepare the sprayed cable core;
(5) modification of graphene oxide: octamethylcyclotetrasiloxane and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane are mixed according to the mass ratio of 20: 1, adding tetramethylammonium hydroxide with the mass of 0.03 time of that of octamethylcyclotetrasiloxane, uniformly mixing, stirring at 100 ℃ and 500r/min for 4 hours, standing at 160 ℃ and 1kPa for 4 hours, and obtaining hydroxyl-terminated vinyl polysiloxane; hydroxyl-terminated vinyl polysiloxane and N, N-dimethylformamide are mixed according to the mass ratio of 1: 10 mixing uniformly to prepare a titration solution; mixing graphene oxide and N, N-dimethylformamide according to a mass ratio of 1: 10, uniformly mixing, and carrying out ultrasonic treatment at 20 ℃ and 30kHz for 10min to prepare a graphene oxide dispersion liquid; mixing 4,4' -methylene bis (phenyl isocyanate) and N, N-dimethylformamide according to a mass ratio of 1: 6, uniformly mixing, dropwise adding a titration solution with the mass of 0.8 time that of 4,4' -methylenebis (phenyl isocyanate) at the speed of 0.1mL/s in a nitrogen atmosphere under the stirring condition of 800r/min at 70 ℃, keeping the condition unchanged after dropwise adding, continuously reacting for 2 hours, adding a graphene oxide dispersion liquid with the mass of 1.2 times that of 4,4' -methylenebis (phenyl isocyanate), continuously reacting for 6 hours in a nitrogen atmosphere, adding furfuryl alcohol with the mass of 0.5 time that of 4,4' -methylenebis (phenyl isocyanate), and continuously reacting for 4 hours in the nitrogen atmosphere to obtain modified graphene oxide;
(6) rolling and assembling: modified graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly (1, 3-butadiene) and polyethylene are mixed according to a mass ratio of 1: 1: 1: 3, uniformly mixing, mixing for 30min at 140 ℃, preparing a sheath material with the thickness of 2mm, irradiating the surface of the sprayed cable core for 5min by using a high-pressure mercury lamp of 800W, wrapping the sheath material on the surface of the irradiated cable core, raising the temperature to 100 ℃, standing for 10min, and rolling for 3 times at 220m/min under the pressure of 8MPa to obtain the flexible cable.
Example 2
A preparation method of a flexible cable mainly comprises the following preparation steps:
(1) preparation of hyperbranched polyester: 4-chloro-4' -hydroxybenzophenone, trimethylolpropane triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 9: 1: 22, uniformly mixing, stirring and reacting for 2.5 hours at 85 ℃ and 900r/min in a nitrogen atmosphere, and standing for 9 hours at 45 ℃ and 1.5kPa to obtain a prepolymer; the prepolymer, terephthalic acid, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 6: 1: 22, uniformly mixing, stirring and reacting for 2.5 hours at 85 ℃ and 900r/min in a nitrogen atmosphere, adding trimethylolpropane triglycidyl ether with the mass being 1.6 times that of the prepolymer, continuously stirring and reacting for 2.5 hours, adding p-vinylbenzoic acid with the mass being 0.9 time that of the prepolymer, continuously stirring and reacting for 2.5 hours, standing for 9 hours at 45 ℃ under 1.5kPa, adding ethyl acetate with the mass being 4 times that of the prepolymer, sequentially washing for 4 times by using a sodium bicarbonate solution with the mass fraction being 5.5%, a sodium chloride solution with the mass fraction being 17% and deionized water respectively, drying the washed solution by using anhydrous magnesium sulfate, filtering, taking a filtrate, and standing for 9 hours at 45 ℃ under 1.5kPa to obtain hyperbranched polyester;
(2) modification of hyperbranched polyester: mixing p-aminophenol, triethylamine and dichloromethane in a mass ratio of 3: 1: 35 at 3 ℃ to prepare a p-aminophenol solution; mixing succinic anhydride and polyethylene glycol with molecular weight of 550 according to a mass ratio of 1: 3.5, stirring for 3.5h at 75 ℃ and 900r/min, and mixing with thionyl chloride and tetrahydrofuran according to a mass ratio of 25: 350: 1, uniformly mixing, stirring and reacting for 2.5h at 45 ℃ and 400r/min, heating to 65 ℃, continuing to stir and react for 2.5h, standing for 35min at 20 ℃ and 1.5kPa, adding a p-aminophenol solution with the mass of 2.5 times that of polyethylene glycol, stirring for 2.5h at 3 ℃ and 400r/min, standing for 22h at room temperature, and standing for 7h at-5 ℃ and 1.5kPa to prepare thiophenol-based polyethylene glycol; hyperbranched polyester, thiophenol polyethylene glycol, potassium hydroxide, toluene and N-methyl pyrrolidone are mixed according to the mass ratio of 6: 1: 2.5: 55: 22, uniformly mixing, stirring at 20 ℃, 400r/min for 25min, heating to 125 ℃, keeping for 3.5h, continuously heating to 155 ℃, keeping for 3.5h, cooling to room temperature, filtering to obtain filtrate, dripping the filtrate into hydrochloric acid with mass fraction of 37% which is 7 times of the mass of the filtrate stirred at 2 ℃, 400r/min at the speed of 1.5mL/min, filtering, washing with pure water and petroleum ether for 4 times respectively, immersing in a saturated sodium acetate solution, performing ultrasonic treatment at 35kHz for 25min, filtering, washing with pure water and petroleum ether for 4 times respectively, and standing at-5 ℃ and 1.5kPa for 7h to obtain the modified hyperbranched polyester;
(3) preparing elastic microspheres: methyl methacrylate, methyl acrylate, n-heptane, dilauroyl peroxide and modified hyperbranched polyester polyol are mixed according to the mass ratio of 45: 16: 32: 3: 27 at 0 ℃ to prepare an oil phase, and mixing polyvinyl alcohol and pure water according to a mass ratio of 1: 150 to prepare a water phase, and mixing the oil phase and the water phase according to a mass ratio of 1: 5, pouring the mixture into a reaction kettle, sealing and keeping the nitrogen atmosphere, stirring the mixture for 25min at the speed of 600r/min, reacting the mixture for 11h at the temperature of 95 ℃, cooling the mixture to room temperature, filtering the mixture, and drying the mixture for 7h at the temperature of 25 ℃ under 1.5kPa to obtain elastic microspheres;
(4) spraying the cable core: bundling and fixing copper wires with the diameter of 0.04mm into copper wire bundles with the diameter of 1mm, wrapping a polyethylene layer with the thickness of 0.9mm on the periphery of the copper wire bundles to obtain wires, fixing a plurality of wires, and winding a circle of aluminum tape on the periphery to fix the wires, wherein the aluminum tape is 0.4mm thick, 2cm wide and 2cm in winding gap to obtain a cable core; mixing polymer microspheres and pure water according to a mass ratio of 1: 5 mixing uniformly to obtain spraying liquid, and then mixing at a ratio of 0.07g/cm 2 The amount of the coating is sprayed on the surface of the cable core, and the cable core is dried for 7 hours at the temperature of minus 5 ℃ and under 5Pa to prepare the sprayed cable core;
(5) modification of graphene oxide: octamethylcyclotetrasiloxane and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane are mixed according to the mass ratio of 25: 1, uniformly mixing, adding tetramethylammonium hydroxide with the mass of 0.04 times of that of octamethylcyclotetrasiloxane, uniformly mixing, stirring at 110 ℃ and 600r/min for 3.5h, standing at 170 ℃ and 1.5kPa for 3.5h to obtain hydroxyl-terminated vinyl polysiloxane; hydroxyl-terminated vinyl polysiloxane and N, N-dimethylformamide are mixed according to the mass ratio of 1: 12 mixing uniformly to prepare a titration solution; mixing graphene oxide and N, N-dimethylformamide according to a mass ratio of 1: 12, uniformly mixing, and carrying out ultrasonic treatment at 25 ℃ and 35kHz for 12min to prepare a graphene oxide dispersion liquid; mixing 4,4' -methylene bis (phenyl isocyanate) and N, N-dimethylformamide according to a mass ratio of 1: 7, uniformly mixing, dropwise adding a titration solution with the mass of 1 time that of 4,4' -methylenebis (phenyl isocyanate) at the speed of 0.15mL/s in a nitrogen atmosphere under the stirring condition of 80 ℃ and 900r/min, keeping the condition unchanged after dropwise adding, continuously reacting for 2.5 hours, adding a graphene oxide dispersion liquid with the mass of 1.4 times that of 4,4' -methylenebis (phenyl isocyanate), continuously reacting for 5 hours in a nitrogen atmosphere, then adding furfuryl alcohol with the mass of 0.6 time that of 4,4' -methylenebis (phenyl isocyanate), and continuously reacting for 3.5 hours in the nitrogen atmosphere to obtain modified graphene oxide;
(6) rolling and assembling: modified graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly (1, 3-butadiene) and polyethylene are mixed according to a mass ratio of 1.5: 1: 1: 3.5, uniformly mixing, mixing for 25min at 150 ℃ to prepare a sheath material with the thickness of 2.5mm, irradiating the surface of the sprayed cable core for 6min by using a 900W high-pressure mercury lamp, wrapping the sheath material on the surface of the irradiated cable core, raising the temperature to 110 ℃, standing for 9min, and rolling for 2 times at 230m/min under the pressure of 9MPa to prepare the flexible cable.
Example 3
A preparation method of a flexible cable mainly comprises the following preparation steps:
(1) preparation of hyperbranched polyester: 4-chloro-4' -hydroxybenzophenone, trimethylolpropane triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 10: 1: 25, uniformly mixing, stirring and reacting for 2 hours at 90 ℃ and 1000r/min in a nitrogen atmosphere, and standing for 8 hours at 50 ℃ and 2kPa to obtain a prepolymer; the prepolymer, terephthalic acid, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 7: 1: 25, uniformly mixing, stirring and reacting for 2 hours at 90 ℃ and 1000r/min in a nitrogen atmosphere, adding trimethylolpropane triglycidyl ether with the mass of 1.8 times that of the prepolymer, continuously stirring and reacting for 3 hours, adding p-vinylbenzoic acid with the mass of 1 time that of the prepolymer, continuously stirring and reacting for 2 hours, standing for 8 hours at 50 ℃ and 2kPa, adding ethyl acetate with the mass of 5 times that of the prepolymer, sequentially washing for 3 times by using a sodium bicarbonate solution with the mass fraction of 6%, a sodium chloride solution with the mass fraction of 20% and deionized water, drying the washed solution by using anhydrous magnesium sulfate, filtering to obtain a filtrate, and standing for 8 hours at 50 ℃ and 2kPa to obtain the hyperbranched polyester;
(2) modification of hyperbranched polyester: p-aminophenol, triethylamine and dichloromethane are mixed according to a mass ratio of 4: 1: 40 at 5 ℃ to prepare a p-aminophenol solution; succinic anhydride and polyethylene glycol with the molecular weight of 600 are mixed according to the mass ratio of 1: 4, uniformly mixing, stirring for 3 hours at 80 ℃ at 1000r/min, and mixing with thionyl chloride and tetrahydrofuran according to a mass ratio of 40: 300: 1, uniformly mixing, stirring and reacting for 2h at 50 ℃ and 500r/min, heating to 70 ℃, continuing to stir and react for 2h, standing for 30min at 30 ℃ and 2kPa, adding a p-aminophenol solution with the mass of 3 times that of polyethylene glycol, stirring for 2h at 5 ℃ and 500r/min, standing for 24h at room temperature, and standing for 6h at-1 ℃ and 2kPa to prepare thiophenol-based polyethylene glycol; hyperbranched polyester, thiophenol polyethylene glycol, potassium hydroxide, toluene and N-methyl pyrrolidone are mixed according to the mass ratio of 6: 2: 3: 60: 25, uniformly mixing, stirring at 30 ℃, 500r/min for 20min, heating to 130 ℃ and keeping for 3h, continuously heating to 160 ℃ and keeping for 3h, cooling to room temperature, filtering to obtain a filtrate, dripping the filtrate into hydrochloric acid with the mass fraction of 36 percent 6 times of that of the filtrate stirred at 3 ℃, 500r/min at the speed of 2mL/min, filtering and washing with pure water and petroleum ether for 5 times respectively, immersing in a saturated sodium acetate solution, performing ultrasonic treatment at 40kHz for 20min, filtering and washing with pure water and petroleum ether for 5 times respectively, and standing at-1 ℃ and 2kPa for 6h to obtain the modified hyperbranched polyester;
(3) preparing elastic microspheres: methyl methacrylate, methyl acrylate, n-heptane, dilauroyl peroxide and modified hyperbranched polyester polyol are mixed according to the mass ratio of 50: 18: 35: 4: 30 at 0 ℃ to prepare an oil phase, and mixing polyvinyl alcohol and pure water according to a mass ratio of 1: 160, uniformly mixing to prepare a water phase, and mixing the oil phase and the water phase according to a mass ratio of 1: 6, pouring the mixture into a reaction kettle, sealing and keeping the nitrogen atmosphere, stirring for 20min at 700r/min, reacting for 10h at 100 ℃, cooling to room temperature, filtering, and drying for 6h at 30 ℃ under 2kPa to obtain elastic microspheres;
(4) spraying the cable core: bundling and fixing copper wires with the diameter of 0.04mm into copper wire bundles with the diameter of 1mm, wrapping a polyethylene layer with the thickness of 0.9mm on the periphery of the copper wire bundles to obtain wires, fixing a plurality of wires, and winding a circle of aluminum tape on the periphery to fix the wires, wherein the aluminum tape is 0.4mm thick, 2cm wide and 2cm in winding gap to obtain a cable core; mixing polymer microspheres and pure water according to a mass ratio of 1: 6 mixing uniformly to obtain spraying liquid, and then mixing at a ratio of 0.08g/cm 2 The amount of the coating is sprayed on the surface of the cable core, and the cable core is dried for 6 hours at the temperature of minus 10 ℃ and 10Pa to prepare the sprayed cable core;
(5) modification of graphene oxide: octamethylcyclotetrasiloxane and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane are mixed according to the mass ratio of 30: 1, uniformly mixing, adding tetramethylammonium hydroxide with the mass of 0.05 time of that of octamethylcyclotetrasiloxane, uniformly mixing, stirring at 120 ℃, 700r/min for 3h, standing at 180 ℃, 2kPa for 3h, and obtaining hydroxyl-terminated vinyl polysiloxane; hydroxyl-terminated vinyl polysiloxane and N, N-dimethylformamide are mixed according to the mass ratio of 1: 15 mixing uniformly to prepare a titration solution; mixing graphene oxide and N, N-dimethylformamide according to a mass ratio of 1: 15, uniformly mixing, and carrying out ultrasonic treatment at 30 ℃ and 40kHz for 10min to prepare a graphene oxide dispersion liquid; mixing 4,4' -methylene bis (phenyl isocyanate) and N, N-dimethylformamide according to a mass ratio of 1: 8, uniformly mixing, dropwise adding a titration solution with the mass of 1.2 times that of 4,4' -methylenebis (phenyl isocyanate) at the speed of 0.2mL/s in a nitrogen atmosphere at the temperature of 90 ℃ under the stirring condition of 1000r/min, keeping the conditions unchanged after dropwise adding, continuously reacting for 3 hours, adding a graphene oxide dispersion solution with the mass of 1.6 times that of 4,4' -methylenebis (phenyl isocyanate), continuously reacting for 6 hours in a nitrogen atmosphere, adding furfuryl alcohol with the mass of 0.7 times that of 4,4' -methylenebis (phenyl isocyanate), and continuously reacting for 3 hours in the nitrogen atmosphere to obtain modified graphene oxide;
(6) rolling and assembling: modified graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly (1, 3-butadiene) and polyethylene are mixed according to a mass ratio of 2: 1: 1: 4, uniformly mixing, mixing at 160 ℃ for 20min, preparing a sheath material with the thickness of 3mm, irradiating the surface of the sprayed cable core for 5min by using a 1000W high-pressure mercury lamp, wrapping the sheath material on the surface of the irradiated cable core, raising the temperature to 120 ℃, standing for 8min, and rolling for 2 times at the pressure of 10MPa and at the speed of 240m/min to obtain the flexible cable.
Comparative example 1
The preparation method of the flexible cable of comparative example 1 is different from that of example 2 only in the difference of step (1), and the step (1) is modified as follows: 4-chloro-4' -hydroxybenzophenone, diglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide in a mass ratio of 10: 9: 1: 22, uniformly mixing, stirring and reacting for 2.5 hours at 85 ℃ and 900r/min in a nitrogen atmosphere, and standing for 9 hours at 45 ℃ and 1.5kPa to obtain a prepolymer; the prepolymer, terephthalic acid, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 6: 1: 22, uniformly mixing, stirring and reacting for 2.5 hours at 85 ℃ and 900r/min in a nitrogen atmosphere, adding diglycidyl ether with the mass of 1.6 times of that of the prepolymer, continuously stirring and reacting for 2.5 hours, adding p-vinylbenzoic acid with the mass of 0.9 time of that of the prepolymer, continuously stirring and reacting for 2.5 hours, standing for 9 hours at 45 ℃ and 1.5kPa, adding ethyl acetate with the mass of 4 times of that of the prepolymer, sequentially washing for 4 times by using a sodium bicarbonate solution with the mass fraction of 5.5%, a sodium chloride solution with the mass fraction of 17% and deionized water, drying the washed solution by using anhydrous magnesium sulfate, filtering to obtain a filtrate, and standing for 9 hours at 45 ℃ and 1.5kPa to obtain the linear polyacid ester. And the "hyperbranched polyester" and the "modified hyperbranched polyester" in the subsequent steps were replaced with "linear polyester" and "modified linear polyester", the rest of the steps being simultaneous with example 2.
Comparative example 2
The manufacturing method of the flexible cable of comparative example 2 is different from example 2 only in that step (2) is not performed and step (3) is modified: mixing methyl methacrylate, methyl acrylate, n-heptane, dilauroyl peroxide, hyperbranched polyester and polyethylene glycol laurate according to a mass ratio of 45: 16: 32: 3: 20: 7, uniformly mixing at 0 ℃ to prepare an oil phase, and mixing polyvinyl alcohol and pure water according to a mass ratio of 1: 150 to prepare a water phase, and mixing the oil phase and the water phase according to a mass ratio of 1: 5, pouring the mixture into a reaction kettle, sealing and keeping the nitrogen atmosphere, stirring the mixture for 25min at the speed of 600r/min, reacting the mixture for 11h at the temperature of 95 ℃, cooling the mixture to room temperature, filtering the mixture, and drying the mixture for 7h at the temperature of 25 ℃ under 1.5kPa to obtain the elastic microspheres. The remaining steps were performed in the same manner as in example 2.
Comparative example 3
The preparation method of the flexible cable of comparative example 3 is different from that of example 2 only in the difference of step (5), and the step (5) is modified as follows: polyethylene glycol and N, N-dimethylformamide are mixed according to the mass ratio of 1: 12 mixing uniformly to prepare a titration solution; mixing graphene oxide and N, N-dimethylformamide according to a mass ratio of 1: 12, uniformly mixing, and carrying out ultrasonic treatment at 25 ℃ and 35kHz for 12min to prepare a graphene oxide dispersion liquid; mixing 4,4' -methylene bis (phenyl isocyanate) and N, N-dimethylformamide according to a mass ratio of 1: 7, uniformly mixing, dropwise adding a titration solution with the mass of 1 time that of 4,4' -methylenebis (phenyl isocyanate) at the speed of 0.15mL/s in a nitrogen atmosphere under the stirring condition of 900r/min at 80 ℃, continuously reacting for 2.5h after dropwise adding and keeping the condition unchanged, adding a graphene oxide dispersion liquid with the mass of 1.4 times that of 4,4' -methylenebis (phenyl isocyanate), continuously reacting for 5h in a nitrogen atmosphere, then adding furfuryl alcohol with the mass of 0.6 time that of 4,4' -methylenebis (phenyl isocyanate), and continuously reacting for 3.5h in the nitrogen atmosphere to obtain the modified graphene oxide. The remaining steps were performed in the same manner as in example 2.
Comparative example 4
The preparation method of the flexible cable of comparative example 4 is different from that of example 2 only in the difference of step (5), and the step (5) is modified as follows: octamethylcyclotetrasiloxane and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane are mixed according to the mass ratio of 25: 1, adding tetramethylammonium hydroxide with the mass of 0.04 times of that of octamethylcyclotetrasiloxane, uniformly mixing, stirring at 110 ℃ and 600r/min for 3.5 hours, standing at 170 ℃ and 1.5kPa for 3.5 hours to obtain hydroxyl-terminated vinyl polysiloxane; hydroxyl-terminated vinyl polysiloxane and N, N-dimethylformamide are mixed according to the mass ratio of 1: 12 mixing uniformly to prepare a titration solution; mixing graphene oxide and N, N-dimethylformamide according to a mass ratio of 1: 12, uniformly mixing, and carrying out ultrasonic treatment at 25 ℃ and 35kHz for 12min to prepare a graphene oxide dispersion liquid; mixing 4,4' -methylene bis (phenyl isocyanate) and N, N-dimethylformamide according to a mass ratio of 1: 7, uniformly mixing, dropwise adding a titration solution with the mass of 1 time that of 4,4 '-methylenebis (phenyl isocyanate) at the speed of 0.15mL/s in a nitrogen atmosphere at the temperature of 80 ℃ under the stirring condition of 900r/min, keeping the conditions unchanged after dropwise adding, continuously reacting for 2.5 hours, adding a graphene oxide dispersion liquid with the mass of 1.4 times that of 4,4' -methylenebis (phenyl isocyanate), and continuously reacting for 5 hours in a nitrogen atmosphere to obtain the modified graphene oxide. The remaining steps were performed in the same manner as in example 2.
Comparative example 5
A preparation method of a flexible cable mainly comprises the following preparation steps:
(1) cable core: bundling and fixing copper wires with the diameter of 0.04mm into copper wire bundles with the diameter of 1mm, wrapping a polyethylene layer with the thickness of 0.9mm on the periphery of the copper wire bundles to obtain wires, fixing a plurality of wires, and winding a circle of aluminum tape on the periphery to fix the wires, wherein the aluminum tape is 0.4mm thick, 2cm wide and 2cm in winding gap to obtain a cable core;
(2) modification of graphene oxide: octamethylcyclotetrasiloxane and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane are mixed according to the mass ratio of 25: 1, uniformly mixing, adding tetramethylammonium hydroxide with the mass of 0.04 times of that of octamethylcyclotetrasiloxane, uniformly mixing, stirring at 110 ℃ and 600r/min for 3.5h, standing at 170 ℃ and 1.5kPa for 3.5h to obtain hydroxyl-terminated vinyl polysiloxane; hydroxyl-terminated vinyl polysiloxane and N, N-dimethylformamide are mixed according to the mass ratio of 1: 12 mixing uniformly to prepare a titration solution; mixing graphene oxide and N, N-dimethylformamide according to a mass ratio of 1: 12, uniformly mixing, and carrying out ultrasonic treatment at 25 ℃ and 35kHz for 12min to prepare a graphene oxide dispersion liquid; mixing 4,4' -methylene bis (phenyl isocyanate) and N, N-dimethylformamide according to a mass ratio of 1: 7, uniformly mixing, dropwise adding a titration solution with the mass of 1 time that of 4,4' -methylenebis (phenyl isocyanate) at the speed of 0.15mL/s in a nitrogen atmosphere under the stirring condition of 80 ℃ and 900r/min, keeping the condition unchanged after dropwise adding, continuously reacting for 2.5 hours, adding a graphene oxide dispersion liquid with the mass of 1.4 times that of 4,4' -methylenebis (phenyl isocyanate), continuously reacting for 5 hours in a nitrogen atmosphere, then adding furfuryl alcohol with the mass of 0.6 time that of 4,4' -methylenebis (phenyl isocyanate), and continuously reacting for 3.5 hours in the nitrogen atmosphere to obtain modified graphene oxide;
(3) rolling and assembling: modified graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly (1, 3-butadiene) and polyethylene are mixed according to a mass ratio of 1.5: 1: 1: 3.5, uniformly mixing, mixing for 25min at 150 ℃ to prepare a sheath material with the thickness of 2.5mm, irradiating the surface of the cable core for 6min by using a high-pressure mercury lamp of 900W, wrapping the sheath material on the surface of the irradiated cable core, raising the temperature to 110 ℃, standing for 9min, and rolling for 2 times at the pressure of 230m/min under the pressure of 9MPa to prepare the flexible cable.
Comparative example 6
A preparation method of a flexible cable mainly comprises the following preparation steps:
(1) cable core: bundling and fixing copper wires with the diameter of 0.04mm into copper wire bundles with the diameter of 1mm, wrapping a polyethylene layer with the thickness of 0.9mm on the periphery of the copper wire bundles to obtain wires, fixing a plurality of wires, and winding a circle of aluminum tape on the periphery to fix the wires, wherein the aluminum tape is 0.4mm thick, 2cm wide and 2cm in winding gap to obtain a cable core;
(2) rolling and assembling: graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly-1, 3-butadiene and polyethylene are mixed according to a mass ratio of 1.5: 1: 1: 3.5, uniformly mixing, mixing for 25min at 150 ℃ to prepare a sheath material with the thickness of 2.5mm, irradiating the surface of the cable core for 6min by using a high-pressure mercury lamp of 900W, wrapping the sheath material on the surface of the irradiated cable core, raising the temperature to 110 ℃, standing for 9min, and rolling for 2 times at the pressure of 230m/min under the pressure of 9MPa to prepare the flexible cable.
Examples of effects
The following table 1 shows performance analysis results of the impact resistance, the flame retardancy and the self-repairing performance of the flexible cables of examples 1 to 3 and comparative examples 1 to 6 of the present invention.
TABLE 1
Figure BDA0003708502070000131
As can be seen from comparison of experimental data of examples 1-3 and comparative examples 1-6 in Table 1, the flexible cable prepared by the invention has good impact resistance, flame retardance and self-repairing performance.
The experimental data comparison of examples 1, 2 and 3 and comparative example 1 shows that the impact strength of examples 1, 2 and 3 is higher than that of comparative example 1, which indicates that the modified hyperbranched polyester can stabilize the structure on the surface of the elastic microspheres compared with the linear structure, so that the elastic microspheres expand into medium air cells by heating to keep the structure stable without breaking and collapsing, thereby improving the impact resistance of the flexible cable; compared with the experimental data of the examples 1, 2 and 3 and the comparative example 2, the experimental data shows that the impact strength of the examples 1, 2 and 3 is higher than that of the comparative example 2, which indicates that the hyperbranched polyester is modified, the substituted sulfur promotes the hydrogen abstraction photoinitiation effect of benzophenone, the diphenyl sulfide group forms a sulfur free radical under illumination, the crosslinking polymerization of carbon-carbon double bonds in the main material is initiated to form a crosslinking network structure, the polyethylene glycol branched chain can promote the stable formation of the elastic microspheres, and the elastic microspheres have good adhesion effect on cable cores in the spraying process, so that the falling of the elastic microspheres is avoided, and the impact resistance of the flexible cable is improved; the experimental data comparison of examples 1, 2 and 3 and comparative example 3 shows that the impact strength and the limiting oxygen index of examples 1, 2 and 3 are higher than that of comparative example 3, which indicates that the hydroxyl-terminated vinyl polysiloxane is used in the preparation process of the modified graphene oxide, so that the modified graphene oxide is easy to form silicon dioxide and a carbon layer to be attached to the surface of a main body at high temperature, thereby improving the flame retardant property of the material, and meanwhile, the vinyl group on the hydroxyl-terminated vinyl polysiloxane enables the modified graphene oxide to participate in the ultraviolet light-initiated radical polymerization reaction subsequently, thereby improving the impact resistance of the flexible cable; compared with the experimental data of the examples 1, 2 and 3 and the comparative example 4, the experimental data of the examples 1, 2 and 3 show that the repair rate of the comparative example 4 is high, and the furfuryl alcohol is used for modification, so that the modified graphene can perform a thermal reversible reaction with a maleimide group in a main body, and the self-repairing effect of the flexible cable is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The preparation method of the flexible cable is characterized in that the flexible cable is prepared by spraying polymer microspheres on a cable core to obtain a sprayed cable core, mixing modified graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly-1, 3-butadiene and polyethylene to prepare a sheath material, irradiating the surface of the sprayed cable core by using a high-pressure mercury lamp, and wrapping the sheath material on the surface of the irradiated cable core to roll.
2. The method of claim 1, wherein the polymer microspheres are prepared by mixing methyl methacrylate, methyl acrylate, n-heptane, dilauroyl peroxide, and modified hyperbranched polyester into an oil phase and stirring in an aqueous phase.
3. The method of claim 2, wherein the modified hyperbranched polyester is prepared by reacting 4-chloro-4' -hydroxybenzophenone with trimethylolpropane triglycidyl ether to obtain a prepolymer, reacting the prepolymer with terephthalic acid, trimethylolpropane triglycidyl ether and p-vinylbenzoic acid in sequence to obtain a hyperbranched polyester, reacting polyethylene glycol with succinic anhydride, thionyl chloride and p-aminophenol in sequence to obtain thiophenol-based polyethylene glycol, and reacting the hyperbranched polyester with thiophenol-based polyethylene glycol.
4. The method for preparing a flexible cable according to claim 1, wherein the modified graphene oxide is prepared by reacting 4,4' -methylenebis (phenyl isocyanate) with hydroxyl-terminated vinyl polysiloxane, then reacting with graphene oxide, and further reacting with furfuryl alcohol.
5. The method for preparing a flexible cable according to claim 1, wherein the method for preparing a flexible cable comprises the following steps:
(1) preparation of hyperbranched polyester: the prepolymer, terephthalic acid, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 5: 1: 20-10: 7: 1: 25, uniformly mixing, stirring and reacting at 80-90 ℃ for 2-3 h at 800-1000 r/min in a nitrogen atmosphere, adding trimethylolpropane triglycidyl ether with the mass being 1.4-1.8 times that of the prepolymer, continuously stirring and reacting for 2-3 h, adding p-vinylbenzoic acid with the mass being 0.8-1 time that of the prepolymer, continuously stirring and reacting for 2-3 h, standing at 40-50 ℃ for 8-10 h under 1-2 kPa, adding ethyl acetate with the mass being 3-5 times that of the prepolymer, sequentially washing 3-5 times with a sodium bicarbonate solution with the mass fraction being 5-6%, a sodium chloride solution with the mass fraction being 15-20% and deionized water, drying the washed solution with anhydrous magnesium sulfate, filtering to obtain a filtrate, and standing at 40-50 ℃ for 8-10 h under 1-2 kPa to obtain a hyperbranched polyester;
(2) modification of hyperbranched polyester: hyperbranched polyester, thiophenol polyethylene glycol, potassium hydroxide, toluene and N-methyl pyrrolidone are mixed according to the mass ratio of 6: 1: 2: 50: 20-6: 2: 3: 60: 25, uniformly mixing, stirring at 10-30 ℃ for 20-30 min at 300-500 r/min, heating to 120-130 ℃ and keeping for 3-4 h, continuously heating to 150-160 ℃ and keeping for 3-4 h, cooling to room temperature, filtering to obtain a filtrate, dripping the filtrate into hydrochloric acid with the mass fraction of 36-38% which is 6-8 times of the mass of the filtrate stirred at 0-3 ℃ and 300-500 r/min at the speed of 1-2 mL/min, filtering, washing 3-5 times by using pure water and petroleum ether respectively, immersing in a saturated sodium acetate solution, performing ultrasonic treatment at 30-40 kHz for 20-30 min, filtering, washing 3-5 times by using pure water and petroleum ether respectively, and standing at-10 to-1 ℃ for 6-8 h at-2 kPa to obtain a modified hyperbranched poly-ester;
(3) preparing elastic microspheres: mixing methyl methacrylate, methyl acrylate, n-heptane, dilauroyl peroxide and modified hyperbranched poly-acid ester according to a mass ratio of 40: 14: 30: 2: 25-50: 18: 35: 4: 30 at 0 ℃ to prepare an oil phase, and mixing polyvinyl alcohol and pure water according to a mass ratio of 1: 140-1: 160, uniformly mixing to prepare a water phase, and mixing the oil phase and the water phase according to a mass ratio of 1: 4-1: 6, pouring the mixture into a reaction kettle, sealing and keeping the nitrogen atmosphere, stirring for 20-30 min at 500-700 r/min, reacting for 10-12 h at 90-100 ℃, cooling to room temperature, filtering, and drying for 6-8 h at 20-30 ℃ under 1-2 kPa to obtain elastic microspheres;
(4) spraying the cable core: mixing polymer microspheres and pure water according to a mass ratio of 1: 4-1: 6, mixing uniformly to prepare a spraying liquid, and then mixing at a ratio of 0.06-0.08 g/cm 2 The amount of the composite material is sprayed on the surface of the cable core, and the composite material is dried for 6 to 8 hours at the temperature of between-1 and-10 ℃ and under the pressure of 1 to 10Pa to prepare the sprayed cable core;
(5) modification of graphene oxide: hydroxyl-terminated vinyl polysiloxane and N, N-dimethylformamide are mixed according to the mass ratio of 1: 10-1: 15 mixing uniformly to prepare a titration solution; mixing 4,4' -methylene bis (phenyl isocyanate) and N, N-dimethylformamide according to a mass ratio of 1: 6-1: 8, uniformly mixing, dropwise adding a titration solution with the mass of 0.8-1.2 times of that of 4,4' -methylenebis (phenyl isocyanate) at the speed of 0.1-0.2 mL/s in a nitrogen atmosphere at the temperature of 70-90 ℃ under the stirring condition of 800-1000 r/min, keeping the condition unchanged after dropwise adding, continuously reacting for 2-3 h, adding a graphene oxide dispersion with the mass of 1.2-1.6 times of that of 4,4' -methylenebis (phenyl isocyanate), continuously reacting for 4-6 h in a nitrogen atmosphere, adding furfuryl alcohol with the mass of 0.5-0.7 time of 4,4' -methylenebis (phenyl isocyanate), and continuously reacting for 3-4 h in the nitrogen atmosphere to obtain modified graphene oxide;
(6) rolling and assembling: modified graphene oxide, N '- (4,4' -methylene diphenyl) bismaleimide, poly (1, 3-butadiene) and polyethylene are mixed according to a mass ratio of 1: 1: 1: 3-2: 1: 1: 4, uniformly mixing, mixing at 140-160 ℃ for 20-30 min to prepare a sheath material with the thickness of 2-3 mm, irradiating the surface of the sprayed cable core with a 800-1000W high-pressure mercury lamp for 5-7 min, wrapping the sheath material on the surface of the irradiated cable core, raising the temperature to 100-120 ℃, standing for 8-10 min, and rolling for 2-3 times at the pressure of 8-10 MPa and at the speed of 220-240 m/min to prepare the flexible cable.
6. The method for preparing the flexible cable according to claim 5, wherein the prepolymer prepared in the step (1) is prepared by: 4-chloro-4' -hydroxybenzophenone, trimethylolpropane triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10: 8: 1: 20-10: 10: 1: 25, uniformly mixing, stirring and reacting for 2-3 h at 80-90 ℃ and 800-1000 r/min in a nitrogen atmosphere, and standing for 8-10 h at 40-50 ℃ and 1-2 kPa to prepare the nano-composite material.
7. The method for preparing a flexible cable according to claim 5, wherein the thiophenol-based polyethylene glycol of step (2) is prepared by: mixing p-aminophenol, triethylamine and dichloromethane in a mass ratio of 3: 1: 30-4: 1: 40, uniformly mixing at 0-5 ℃ to prepare a p-aminophenol solution; mixing succinic anhydride and polyethylene glycol with the molecular weight of 500-600 according to the mass ratio of 1: 3-1: 4, uniformly mixing, stirring at 70-80 ℃ for 3-4 h at 800-1000 r/min, and mixing with thionyl chloride and tetrahydrofuran according to a mass ratio of 15: 100: 1-40: 300: 1, uniformly mixing, stirring and reacting for 2-3 h at 40-50 ℃ at 300-500 r/min, heating to 60-70 ℃, continuing to stir and react for 2-3 h, standing for 30-40 min at 10-30 ℃ under 1-2 kPa, adding a p-aminophenol solution with the mass 2-3 times that of polyethylene glycol, stirring for 2-3 h at 0-5 ℃ at 300-500 r/min, standing for 20-24 h at room temperature, and standing for 6-8 h at-10-1 ℃ under 1-2 kPa.
8. The preparation method of the flexible cable according to claim 5, wherein the cable core in the step (4) is prepared by bundling and fixing copper wires with the diameter of 0.03-0.05 mm into a copper wire bundle with the diameter of 0.8-1.2 mm, wrapping a polyethylene layer with the thickness of 0.8-1 mm on the periphery of the copper wire bundle to prepare a lead, fixing a plurality of leads, and winding a circle of aluminum tape on the periphery for fixing, wherein the aluminum tape is 0.3-0.5 mm in thickness, 1-3 cm in width and 1-3 cm in winding gap.
9. The method for preparing a flexible cable according to claim 5, wherein the hydroxyl-terminated vinyl polysiloxane of step (5) is prepared by: octamethylcyclotetrasiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane in a mass ratio of 20: 1-30: 1, adding tetramethylammonium hydroxide with the mass of 0.03-0.05 time of that of octamethylcyclotetrasiloxane, uniformly mixing, stirring at 100-120 ℃ and 500-700 r/min for 3-4 h, and standing at 160-180 ℃ and 1-2 kPa for 3-4 h to prepare the octamethylcyclotetrasiloxane.
10. The method for preparing a flexible cable according to claim 5, wherein the graphene oxide dispersion liquid in the step (5) is prepared by mixing graphene oxide and N, N-dimethylformamide according to a mass ratio of 1: 10-1: 15, uniformly mixing, and carrying out ultrasonic treatment at the temperature of 20-30 ℃ and the frequency of 30-40 kHz for 10-15 min.
CN202210715001.9A 2022-06-22 2022-06-22 Flexible cable and preparation method thereof Pending CN114874529A (en)

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