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CN113201201A - Flame-retardant high-toughness carbon fiber composite material for overhead transmission conductor - Google Patents

Flame-retardant high-toughness carbon fiber composite material for overhead transmission conductor Download PDF

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CN113201201A
CN113201201A CN202110475962.2A CN202110475962A CN113201201A CN 113201201 A CN113201201 A CN 113201201A CN 202110475962 A CN202110475962 A CN 202110475962A CN 113201201 A CN113201201 A CN 113201201A
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carbon fiber
fiber composite
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carrying
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姜鹏博
魏小宁
徐嘉明
贵童
徐华
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Zhoukou Power Supply Co of State Grid Henan Electric Power Co Ltd
State Grid Corp of China SGCC
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Zhoukou Power Supply Co of State Grid Henan Electric Power Co Ltd
State Grid Corp of China SGCC
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
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Abstract

The invention relates to a flame-retardant high-toughness carbon fiber composite material for an overhead power transmission conductor, and belongs to the technical field of carbon fiber composite materials. The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 50-60 parts of polyacrylonitrile, 20-30 parts of single-layer graphene powder, 8-15 parts of bacterial cellulose, 5-10 parts of methyl methacrylate, 5-10 parts of 1, 6-dibromohexane, 30-40 parts of thermosetting resin, 1-5 parts of nano magnesium hydroxide and 3-6 parts of nano aerogel. The carbon fiber composite material has high toughness and good flame retardant property.

Description

Flame-retardant high-toughness carbon fiber composite material for overhead transmission conductor
Technical Field
The invention belongs to the technical field of carbon fiber composite materials, and particularly relates to a flame-retardant high-toughness carbon fiber composite material for an overhead transmission conductor.
Background
The carbon fiber is a special fiber with carbon content more than 90% prepared by taking Polyacrylonitrile (PAN), asphalt, viscose fiber and the like as raw materials through pre-oxidation, carbonization and graphitization processes, is an indispensable engineering material for aerospace, national defense and military industries, and is widely applied to civil fields such as sports goods, transportation, medical appliances, civil engineering and construction and the like. The PAN-based carbon fiber has simple production process and good product comprehensive performance, so the PAN-based carbon fiber is developed quickly, and the yield accounts for more than 90 percent, thereby becoming the most important variety.
The publication number CN102560746A discloses a preparation method of polyacrylonitrile/graphene composite-based carbon fiber, which comprises the steps of firstly preparing a polyacrylonitrile mixed solution in which graphene is uniformly dispersed by an in-situ polymerization method, then using the mixed solution as a spinning solution, obtaining polyacrylonitrile/graphene composite precursor by wet spinning or dry-jet wet spinning, and finally performing pre-oxidation and carbonization treatment on the precursor to obtain the polyacrylonitrile/graphene composite-based carbon fiber. Publication No. CN102586952A discloses a preparation method of graphene reinforced polyacrylonitrile carbon fibers, which comprises the following steps: (1) preparing graphene or graphene oxide; (2) preparing a graphene/polyacrylonitrile spinning solution; (3) preparing graphene/polyacrylonitrile-based composite fibers; (4) preparing graphene/polyacrylonitrile-based carbon. The method effectively improves the dispersion and interface bonding force of the graphene oxide in the polymer matrix, further improves the comprehensive performance of the carbon fiber, obviously improves the mechanical property of the prepared carbon fiber, can be used in multiple fields of material reinforcement, electric conduction, static resistance, heat conduction and the like, and has the advantages of simple preparation process, easy control and low cost. The above mentioned PAN-based carbon fiber composite materials all improve some properties of carbon fibers to some extent, but the improvement of toughness of the carbon fiber composite materials is limited, and further improvement is still needed.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a flame retardant high toughness carbon fiber composite material for overhead power transmission conductors.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 50-60 parts of polyacrylonitrile, 20-30 parts of single-layer graphene powder, 8-15 parts of bacterial cellulose, 5-10 parts of methyl methacrylate, 5-10 parts of 1, 6-dibromohexane, 30-40 parts of thermosetting resin, 1-5 parts of nano magnesium hydroxide and 3-6 parts of nano aerogel.
Preferably, the flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 55 parts of polyacrylonitrile, 23 parts of single-layer graphene powder, 10 parts of bacterial cellulose, 6 parts of methyl methacrylate, 8 parts of 1, 6-dibromohexane, 35 parts of thermosetting resin, 3 parts of nano magnesium hydroxide and 5 parts of nano aerogel.
Preferably, the thermosetting resin is a phenolic resin or an epoxy resin.
Preferably, the curing agent is polyether amine D230 or hexamethylenetetramine.
Preferably, the flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is obtained by the following preparation method:
1) preparing carbon fibers, comprising the steps of:
1.1) carrying out superfine grinding on bacterial cellulose, adding distilled water, fully stirring, then mixing with a single-layer graphene powder solution, continuously stirring for 10-12 hours, carrying out ultrasonic treatment for 30-60 minutes, carrying out sample application on a copper mesh, drying at the temperature lower than 40 ℃, and carrying out film coating by using a vacuum film coating system to obtain a bacterial cellulose-graphene composite material;
1.2) dispersing the bacterial cellulose-graphene composite material in methyl methacrylate, mixing the methyl methacrylate with polyacrylonitrile powder and 1, 6-dibromohexane, isolating air at the temperature of 20-25 ℃, standing for swelling, and heating and dissolving under a stirring state to obtain a spinning solution;
1.3) filtering the spinning solution, extruding out of a spinneret plate in a metering manner, performing primary fiber formation in a solution containing ethanol, and then performing drafting, water washing, oiling, drying and winding to obtain protofilaments;
1.4) carrying out preoxidation and carbonization treatment on the precursor to obtain carbon fiber;
2) mixing thermosetting resin, nano magnesium hydroxide and nano aerogel under the action of high-speed stirring for 40-80 minutes, adding carbon fiber to obtain a preformed material, and carrying out stranding, coating, stranding and heat treatment to obtain the carbon fiber composite material.
Preferably, the power of the ultrasonic treatment is 250-300W, and the frequency is 40-50 kHz.
Preferably, the vacuum coating system has the coating parameters that the vacuum degree is 1 multiplied by 10-4Pa, and the standing time is 72-84 h.
The application research of the carbon fiber prepared by carbonizing the bacterial cellulose is relatively extensive, but the application mainly focuses on the aspects of using the mechanical property of the carbon fiber as a polymer reinforcing material and using the high specific surface area of the carbon fiber in catalyst carriers such as fuel cells, heterogeneous catalysis and the like, biomedicine, sensors, wave-absorbing materials and the like, but the flame-retardant high-toughness carbon fiber composite material for overhead power transmission conductors is rarely involved. The known carbon fiber composite material is formed by compounding carbon fibers with resin, metal and ceramic lamp material matrixes, has improved strength, elastic modulus and the like compared with the common carbon fibers, but has the defects of very large size and poor toughness. Therefore, scientists have also made many studies in this respect, and have achieved certain results. There are two general approaches to solve this problem, one is to use carbon fiber bundles, but practical application is difficult; and secondly, the bonding force between interfaces is reduced, and a layer of oil is coated on the surface of the fiber, so that although the shear stress of the section is greatly reduced, the shear strength is greatly reduced, and the fiber is not practical. The bacterial cellulose is the nano-fiber, so that the high transparency of the resin matrix can be maintained, the mechanical property of the resin matrix can be improved, and the excellent flexibility and toughness of the resin matrix can be endowed.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the bacterial cellulose and the single-layer graphene powder into the composite material, then compounds the composite material with the polyacrylonitrile to prepare the carbon fiber, and finally compounds the carbon fiber with the thermosetting resin to prepare the composite material, compared with the composite material of the polyacrylonitrile and the thermosetting resin or the composite material of the polyacrylonitrile, the graphene and the thermosetting resin, the obtained composite material has outstanding mechanical properties, which is expressed in that the tensile strength can reach more than 6.0GPa, the bending strength reaches more than 8.0GPa, and simultaneously, the compression strength of the composite material after impact is obviously improved. Research shows that (see Zhangbayan, Chenxiangbao, Limin, et. research on the compression strength of a carbon fiber reinforced bismaleimide resin matrix composite system after impact [ J ]. academic report on aeronautical materials, 2002,22(001): 36-40.), the compression strength after impact is more and more apt to be used as a decisive index for representing the toughness of the resin matrix composite in the world at present, and the combination of the performance index obtained by the invention can show that the toughness of the composite material is outstanding, is insensitive to the impact action and is not easy to damage after being impacted by foreign matters.
In addition, according to the invention, a proper amount of nano magnesium hydroxide and nano aerogel are added into the composite material, and the stability of the mixture of the nano magnesium hydroxide and the nano aerogel with thermosetting resin is good.
Detailed Description
The present invention will be further described with reference to the following examples.
Polyacrylonitrile, shanghai maireil chemical technology ltd;
single-layer graphene powder, purity: 99.8 percent; thickness: 0.8-1.2 nm; diameter: 0.5-5 μm; single layer rate: 80 percent;
bacterial cellulose, Hainan Yide food Co.
The composite material performance detection method comprises the following steps:
the tensile strength is tested on a universal mechanical testing machine according to GB/T33501-2017 standard, and the tensile speed is set to be 5 mm/min; the test piece is a standard dumbbell-shaped test piece, the length of the test piece is 165mm, the width of two ends of the test piece is 19mm, the width of a middle test part is 13mm, the gauge length is 50mm, the arc radius is 76mm, and each group of 8 test pieces are arranged.
The bending strength is tested on a universal mechanical testing machine according to the GB/T1449-2005 standard, the length of a test piece is 80mm, the width is 15mm, the thickness is 4mm, the span of a fulcrum is 64mm, the pressurizing speed is set to be 10mm/min, and each group comprises 8 test pieces.
The compression strength after impact (CAI) is tested on a combined impact tester according to GB/T21239-2007 standard, the length of a test piece is 80mm, the width is 10mm, the thickness is 5mm, the span is 60mm, the impact speed is 2.9m/s, the pendulum energy is 2J, and 10 test pieces are tested in each group.
Flame retardant property: according to the GB/T2408-2008 standard, a vertical combustion method is adopted for testing; sample size: length 130.0mm, width 13.0mm, thickness 3.0 mm; each set tested 5 specimens.
Example 1
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 55 parts of polyacrylonitrile, 23 parts of single-layer graphene powder, 10 parts of bacterial cellulose, 6 parts of methyl methacrylate, 8 parts of 1, 6-dibromohexane, 35 parts of thermosetting resin, 3 parts of nano magnesium hydroxide and 5 parts of nano aerogel.
The thermosetting resin is epoxy resin, F46, Shanghai resin factory Co.
The curing agent is hexamethylenetetramine.
Example 2
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 50 parts of polyacrylonitrile, 20 parts of single-layer graphene powder, 8 parts of bacterial cellulose, 5 parts of methyl methacrylate, 5 parts of 1, 6-dibromohexane, 30 parts of thermosetting resin, 1 part of nano magnesium hydroxide and 3 parts of nano aerogel.
The thermosetting resin is phenolic resin.
The curing agent is hexamethylenetetramine.
Example 3
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 60 parts of polyacrylonitrile, 30 parts of single-layer graphene powder, 15 parts of bacterial cellulose, 10 parts of methyl methacrylate, 10 parts of 1, 6-dibromohexane, 40 parts of thermosetting resin, 5 parts of nano magnesium hydroxide and 6 parts of nano aerogel.
The thermosetting resin is epoxy resin.
The curing agent is polyether amine D230.
Example 4
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 52 parts of polyacrylonitrile, 23 parts of single-layer graphene powder, 9 parts of bacterial cellulose, 7 parts of methyl methacrylate, 6 parts of 1, 6-dibromohexane, 32 parts of thermosetting resin, 2 parts of nano magnesium hydroxide and 4 parts of nano aerogel.
The thermosetting resin is epoxy resin.
The curing agent is polyether amine D230.
Example 5
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 50-60 parts of polyacrylonitrile, 20-30 parts of single-layer graphene powder, 8-15 parts of bacterial cellulose, 8 parts of methyl methacrylate, 9 parts of 1, 6-dibromohexane, 38 parts of thermosetting resin, 4 parts of nano magnesium hydroxide and 5 parts of nano aerogel.
The thermosetting resin is epoxy resin.
The curing agent is polyether amine D230.
Example 6
The flame-retardant high-toughness carbon fiber composite material for overhead power transmission conductors exemplified in examples 1 to 5 was obtained by the following preparation method:
1) preparing carbon fibers, comprising the steps of:
1.1) carrying out superfine grinding on bacterial cellulose, adding distilled water, fully stirring, then mixing with a single-layer graphene powder solution, continuously stirring for 10 hours, carrying out ultrasonic treatment for 30 minutes, carrying out sample application on a copper mesh, drying at the temperature lower than 40 ℃, and carrying out film coating by using a vacuum film coating system to obtain a bacterial cellulose-graphene composite material;
1.2) dispersing the bacterial cellulose-graphene composite material in methyl methacrylate, mixing the methyl methacrylate with polyacrylonitrile powder and 1, 6-dibromohexane, isolating air at the temperature of 20-25 ℃, standing for swelling, and heating and dissolving under a stirring state to obtain a spinning solution;
1.3) filtering the spinning solution, extruding out of a spinneret plate in a metering manner, performing primary fiber formation in a solution containing ethanol, and then performing drafting, water washing, oiling, drying and winding to obtain protofilaments;
1.4) carrying out preoxidation and carbonization treatment on the precursor to obtain carbon fiber;
2) mixing thermosetting resin, nano magnesium hydroxide and nano aerogel under the action of high-speed stirring for 60 minutes, adding carbon fiber to obtain a preformed material, and carrying out stranding, coating, stranding and heat treatment to obtain the carbon fiber composite material.
The power of the ultrasonic treatment was 280W and the frequency was 45 kHz.
The vacuum coating system has the coating parameters that the vacuum degree is 1 multiplied by 10-4Pa, and the standing time is 72 h.
"drawing, washing, oiling, drying and winding" in step 1.3) of the above preparation method; and the pre-oxidation and carbonization treatment in the step 1.4) refers to the production process of PAN-based carbon fiber protofilament and oxidation carbonization of petrochemical company Limited, and is a mature technology; the "twisting, coating, stranding and heat treatment" in the step 2) refers to a production process of a carbon fiber composite wire, and is a mature technology (reference: in Guanghui, Deng Yunkun carbon fiber composite wire development reviews [ J ] thermal processing technology, 2019, v.48, No.522(20):8-12+16 ].
Example 7
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared by the following preparation method:
1) preparing carbon fibers, comprising the steps of:
1.1) carrying out superfine grinding on bacterial cellulose, adding distilled water, fully stirring, then mixing with a single-layer graphene powder solution, continuously stirring for 12 hours, carrying out ultrasonic treatment for 60 minutes, carrying out sample application on a copper mesh, drying at the temperature lower than 40 ℃, and carrying out film coating by using a vacuum film coating system to obtain a bacterial cellulose-graphene composite material;
1.2) dispersing the bacterial cellulose-graphene composite material in methyl methacrylate, mixing the methyl methacrylate with polyacrylonitrile powder and 1, 6-dibromohexane, isolating air at the temperature of 20-25 ℃, standing for swelling, and heating and dissolving under a stirring state to obtain a spinning solution;
1.3) filtering the spinning solution, extruding out of a spinneret plate in a metering manner, performing primary fiber formation in a solution containing ethanol, and then performing drafting, water washing, oiling, drying and winding to obtain protofilaments;
1.4) carrying out preoxidation and carbonization treatment on the precursor to obtain carbon fiber;
2) mixing thermosetting resin, nano magnesium hydroxide and nano aerogel under the action of high-speed stirring for 80 minutes, adding carbon fiber to obtain a preformed material, and carrying out stranding, coating, stranding and heat treatment to obtain the carbon fiber composite material.
The power of the ultrasonic treatment is 300W, and the frequency is 40 kHz.
The vacuum coating system has the coating parameters that the vacuum degree is 1 multiplied by 10-4Pa, standing for 84 h.
Example 8
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared by the following preparation method:
1) preparing carbon fibers, comprising the steps of:
1.1) carrying out superfine grinding on bacterial cellulose, adding distilled water, fully stirring, then mixing with a single-layer graphene powder solution, continuously stirring for 11 hours, carrying out ultrasonic treatment for 45 minutes, carrying out sample application on a copper mesh, drying at the temperature lower than 40 ℃, and carrying out film coating by using a vacuum film coating system to obtain a bacterial cellulose-graphene composite material;
1.2) dispersing the bacterial cellulose-graphene composite material in methyl methacrylate, mixing the methyl methacrylate with polyacrylonitrile powder and 1, 6-dibromohexane, isolating air at the temperature of 20-25 ℃, standing for swelling, and heating and dissolving under a stirring state to obtain a spinning solution;
1.3) filtering the spinning solution, extruding out of a spinneret plate in a metering manner, performing primary fiber formation in a solution containing ethanol, and then performing drafting, water washing, oiling, drying and winding to obtain protofilaments;
1.4) carrying out preoxidation and carbonization treatment on the precursor to obtain carbon fiber;
2) mixing thermosetting resin, nano magnesium hydroxide and nano aerogel under the action of high-speed stirring for 40-80 minutes, adding carbon fiber to obtain a preformed material, and carrying out stranding, coating, stranding and heat treatment to obtain the carbon fiber composite material.
The power of the ultrasonic treatment is 250W, and the frequency is 50 kHz.
The vacuum coating system has the coating parameters that the vacuum degree is 1 multiplied by 10-4Pa, and the standing time is 78 h.
The results of the performance test of the composite materials obtained in examples 1 to 5 above by referring to any one of the production methods of examples 6 to 8 are shown in the following table:
examples Tensile strength/GPa Bending strength/GPa Post impact compressive strength/MPa
1 6.63 8.74 271
2 6.42 8.59 258
3 6.51 8.42 263
4 6.30 8.45 250
5 6.25 8.37 254
Comparative example 1
The preparation method of the polyacrylonitrile/graphene carbon fiber composite material comprises the following steps:
(1) adding 1g of graphene powder into 400g of dimethyl sulfoxide (DMSO) solvent, and ultrasonically dispersing by adopting an ultrasonic cell crusher to obtain graphene/DMSO dispersion liquid;
weighing two parts of 100g of graphene/DMSO dispersion liquid, and reserving the rest graphene/DMSO dispersion liquid for later use;
adding 2g of Itaconic Acid (IA) into one 100g of graphene/DMSO dispersion, and stirring for 10min to completely dissolve the Itaconic Acid (IA), wherein the solution is called solution A; adding 1g of Azobisisobutyronitrile (AIBN) into another 100g of graphene/DMSO dispersion liquid, and stirring for 10min to completely dissolve the Azodiisobutyronitrile (AIBN), so as to obtain a solution B;
adding 100g of acrylonitrile into a mixing container, then sequentially adding the solution A and the solution B, then adding the rest graphene/DMSO dispersion, introducing nitrogen and stirring to obtain a mixed solution in which graphene, an acrylonitrile monomer, an IA monomer and an AIBN initiator are uniformly dispersed;
(2) carrying out in-situ polymerization reaction on the mixed solution obtained in the step (1) at the temperature of 60 ℃ under nitrogen atmosphere, and carrying out mechanical stirring for 20 hours to obtain an intermediate solution;
cooling the obtained intermediate solution to 55 ℃, performing demonomerization treatment for 8 hours under the vacuum of 200Pa, removing unreacted residual monomers, then heating to 60 ℃, and performing defoaming treatment for 10 hours to obtain a polyacrylonitrile stock solution dispersed with graphene;
(3) taking the polyacrylonitrile stock solution dispersed with the graphene obtained in the step (2) as a spinning stock solution, and preparing polyacrylonitrile/graphene composite precursor by a wet spinning process; wherein the aperture of the spinneret plate is 0.07mm, the temperature of the coagulating bath is 45 ℃, and the drafting multiple is 8 times, so as to obtain the polyacrylonitrile/graphene composite precursor;
(4) carrying out multi-temperature-zone pre-oxidation on the polyacrylonitrile/graphene composite precursor obtained in the step (3) at the temperature of 240-290 ℃, carrying out multi-temperature-zone low-temperature carbonization at the temperature of 450-600 ℃, and carrying out multi-temperature-zone high-temperature carbonization at the temperature of 1000-500 ℃ to prepare polyacrylonitrile/graphene composite-based carbon fiber;
the mechanical property test is carried out on the polyacrylonitrile/graphene composite-based carbon fiber obtained by the preparation method, the tensile strength is 5.02GPa, the bending strength is 7.08GPa, and the compression strength after impact is 203 MPa.
Comparative example 2
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 55 parts of polyacrylonitrile, 33 parts of bacterial cellulose, 6 parts of methyl methacrylate, 8 parts of 1, 6-dibromohexane, 35 parts of thermosetting resin, 3 parts of nano magnesium hydroxide and 5 parts of nano aerogel. The preparation method comprises the following steps:
1) preparing carbon fibers, comprising the steps of:
1.1) carrying out superfine grinding on bacterial cellulose, dispersing the bacterial cellulose in methyl methacrylate, mixing the bacterial cellulose with polyacrylonitrile powder and 1, 6-dibromohexane, insulating air at the temperature of 20-25 ℃, standing for swelling, and heating and dissolving under the stirring state to obtain a spinning solution;
1.2) filtering the spinning solution, extruding out of a spinneret plate in a metering manner, performing primary fiber formation in a solution containing ethanol, and then performing drafting, water washing, oiling, drying and winding to obtain protofilaments;
1.3) carrying out preoxidation and carbonization treatment on the precursor to obtain carbon fiber;
2) mixing thermosetting resin, nano magnesium hydroxide and nano aerogel under the action of high-speed stirring for 60 minutes, adding carbon fiber to obtain a preformed material, and carrying out stranding, coating, stranding and heat treatment to obtain the carbon fiber composite material.
Other parameters of this comparative example were the same as in example 1.
The mechanical property test is carried out on the polyacrylonitrile/bacterial cellulose compound-based carbon fiber obtained by the preparation method, the tensile strength is 3.22GPa, the bending strength is 4.15GPa, and the compression strength after impact is 152 MPa.
Comparative example 3
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 55 parts of polyacrylonitrile, 23 parts of single-layer graphene powder, 10 parts of bacterial cellulose, 6 parts of methyl methacrylate, 8 parts of 1, 6-dibromohexane, 35 parts of thermosetting resin and 8 parts of nano magnesium hydroxide.
The thermosetting resin is epoxy resin, F46, Shanghai resin factory Co.
The curing agent is hexamethylenetetramine.
The mechanical property test of the composite-based carbon fiber prepared by the method has the advantages that the tensile strength is 6.01GPa, the bending strength is 8.13GPa, and the compression strength after impact is 228 MPa.
Comparative example 4
The flame-retardant high-toughness carbon fiber composite material for the overhead transmission conductor is prepared from the following components in parts by weight: 55 parts of polyacrylonitrile, 23 parts of single-layer graphene powder, 10 parts of bacterial cellulose, 6 parts of methyl methacrylate, 8 parts of 1, 6-dibromohexane, 35 parts of thermosetting resin and 8 parts of nano aerogel.
The thermosetting resin is epoxy resin, F46, Shanghai resin factory Co.
The curing agent is hexamethylenetetramine.
The mechanical property test of the composite-based carbon fiber prepared by the method has the advantages that the tensile strength is 5.83GPa, the bending strength is 7.82GPa, and the compression strength after impact is 220 MPa.
Comparative examples 3-4 were prepared according to the method described in example 6.
The results of the flame retardant property tests of the composites of examples 1-3 and comparative examples 1-4 are shown in the following table:
Figure 964916DEST_PATH_IMAGE002
the test results in the table show that the flame retardant property of the composite material reaches the optimal standard V-0 grade, and the flame retardant property is obvious.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.

Claims (7)

1. A fire-retardant high tenacity carbon fiber composite for overhead transmission conductor which characterized in that: the composition is prepared from the following components in parts by weight: 50-60 parts of polyacrylonitrile, 20-30 parts of single-layer graphene powder, 8-15 parts of bacterial cellulose, 5-10 parts of methyl methacrylate, 5-10 parts of 1, 6-dibromohexane, 30-40 parts of thermosetting resin, 1-5 parts of nano magnesium hydroxide and 3-6 parts of nano aerogel.
2. The flame retardant, high tenacity carbon fiber composite for overhead power transmission conductors of claim 1, wherein: the composition is prepared from the following components in parts by weight: 55 parts of polyacrylonitrile, 23 parts of single-layer graphene powder, 10 parts of bacterial cellulose, 6 parts of methyl methacrylate, 8 parts of 1, 6-dibromohexane, 35 parts of thermosetting resin, 3 parts of nano magnesium hydroxide and 5 parts of nano aerogel.
3. The flame retardant, high tenacity carbon fiber composite for overhead power transmission conductors according to claim 1 or 2, wherein: the thermosetting resin is phenolic resin or epoxy resin.
4. The flame retardant, high tenacity carbon fiber composite for overhead power transmission conductors according to claim 1 or 2, wherein: the curing agent is polyether amine D230 or hexamethylene tetramine.
5. The flame retardant, high tenacity carbon fiber composite for overhead power transmission conductors according to claim 1 or 2, wherein: is obtained by the following preparation method:
1) preparing carbon fibers, comprising the steps of:
1.1) carrying out superfine grinding on bacterial cellulose, adding distilled water, fully stirring, then mixing with a single-layer graphene powder solution, continuously stirring for 10-12 hours, carrying out ultrasonic treatment for 30-60 minutes, carrying out sample application on a copper mesh, drying at the temperature lower than 40 ℃, and carrying out film coating by using a vacuum film coating system to obtain a bacterial cellulose-graphene composite material;
1.2) dispersing the bacterial cellulose-graphene composite material in methyl methacrylate, mixing the methyl methacrylate with polyacrylonitrile powder and 1, 6-dibromohexane, isolating air at the temperature of 20-25 ℃, standing for swelling, and heating and dissolving under a stirring state to obtain a spinning solution;
1.3) filtering the spinning solution, extruding out of a spinneret plate in a metering manner, performing primary fiber formation in a solution containing ethanol, and then performing drafting, water washing, oiling, drying and winding to obtain protofilaments;
1.4) carrying out preoxidation and carbonization treatment on the precursor to obtain carbon fiber;
2) mixing thermosetting resin, nano magnesium hydroxide and nano aerogel under the action of high-speed stirring for 40-80 minutes, adding carbon fiber to obtain a preformed material, and carrying out stranding, coating, stranding and heat treatment to obtain the carbon fiber composite material.
6. The flame retardant, high tenacity carbon fiber composite for an overhead power transmission conductor of claim 5, wherein: the power of the ultrasonic treatment is 250-300W, and the frequency is 40-50 kHz.
7. The flame retardant, high tenacity carbon fiber composite for an overhead power transmission conductor of claim 6, wherein: the vacuum coating system has the coating parameters that the vacuum degree is 1 multiplied by 10-4Pa, and the standing time is 72-84 h.
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