CN113980467A - Conductive composite PPS material and preparation method thereof - Google Patents
Conductive composite PPS material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 175
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 113
- 239000004917 carbon fiber Substances 0.000 claims abstract description 113
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 99
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 98
- 239000004593 Epoxy Substances 0.000 claims abstract description 48
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 12
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- 230000001590 oxidative effect Effects 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
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- YUPLJNGZNHMXGM-UHFFFAOYSA-N 2-(3-bromophenyl)oxirane Chemical compound BrC1=CC=CC(C2OC2)=C1 YUPLJNGZNHMXGM-UHFFFAOYSA-N 0.000 claims description 8
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
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- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 12
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- 239000012286 potassium permanganate Substances 0.000 description 12
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- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 11
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- PGXWDLGWMQIXDT-UHFFFAOYSA-N methylsulfinylmethane;hydrate Chemical compound O.CS(C)=O PGXWDLGWMQIXDT-UHFFFAOYSA-N 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
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- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K7/00—Use of ingredients characterised by shape
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon 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
- D01F9/22—Carbon 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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Abstract
The invention relates to a preparation method of a conductive composite PPS material, which is obtained by melt blending of modified graphene/epoxy phenyl graft/PAN carbon fiber and amino-functionalized polyphenylene sulfide. The regular graphene with the network structure is prepared by the oxidation and re-reduction method and is used for manufacturing the PAN carbon fiber, so that the PAN carbon fiber with fewer defects and smaller preferred orientation angle is prepared. Then, phenyl ethylene oxide is further grafted on the surface of the PAN carbon fiber, and covalent bond grafting of the PAN carbon fiber and polyphenylene sulfide is realized by utilizing epoxy and amino reaction, so that the binding force of the modified graphene/epoxy phenyl graft/PAN carbon fiber and polyphenylene sulfide is greatly enhanced, the phase interfacial force of the modified graphene/epoxy phenyl graft/PAN carbon fiber and polyphenylene sulfide is weakened, the modified graphene/epoxy phenyl graft/PAN carbon fiber is dispersed more uniformly, and the mechanical property and the electrical property of the polyphenylene sulfide are enhanced.
Description
Technical Field
The invention belongs to the field of PPS materials, and particularly relates to a conductive composite PPS material and a preparation method thereof.
Background
Polyphenylene Sulfide (PPS), also called Polyphenylene sulfide or Polyphenylene ether, has a main chain of a large molecule formed by alternating benzene rings and sulfur atoms. PPS has high mechanical property, dimensional stability, heat resistance, chemical corrosion resistance and other excellent comprehensive properties due to the unique structure, is widely applied to high-tech fields such as environmental protection, automobiles, textiles, war industry, electronic and electric appliances, mechanical industry, aerospace and the like, and becomes a first variety in special engineering plastics. In addition, PPS fiber has high insulation and low conductive capability (10)-16s/m), so that static electricity is easily generated when the fiber product is rubbed in the processing and using processes, and serious static discharge can cause ignition and explosion of combustible materials, thereby bringing great hidden danger to industrial production and daily life. These problems faced by PPS fibers have largely limited their use in particular environments.
In recent years, the novel nano particle modified PPS is a new direction for the development of PPS materials, the method is simple in operation process, not only can the cost be reduced, but also the PPS can be endowed with brand new performance, and the method has wide commodity development and application prospects. Researchers at home and abroad add various nano particles (such as TiO) into PPS2、SiO2Carbon black, MWCNTS, graphene, montmorillonite and the like) to make up for the defects of poor oxidation resistance and low conductivity of PPS, but the final PPS fiber modification effect is not ideal due to the problems of easy agglomeration of nano particles and poor compatibility of a PPS matrix.
PAN carbon fiber is a specialty fiber composed of carbon. The graphite fiber has the characteristics of high temperature resistance, friction resistance, electric conduction, heat conduction, corrosion resistance and the like, is fibrous and soft in appearance, can be processed into various fabrics, and has high strength and modulus along the fiber axis direction due to the preferred orientation of the graphite microcrystalline structure along the fiber axis. The PAN carbon fiber has a small density and thus a high specific strength and a high specific modulus. The PAN carbon fiber is mainly used as a reinforcing material to be compounded with resin, metal, ceramic, carbon and the like to manufacture an advanced composite material. The polyacrylonitrile-based carbon fiber (PAN carbon fiber) is formed by spinning polyacrylonitrile, pre-oxidizing and carbonizing. The composite material has the characteristics of high strength, high rigidity, light weight, high temperature resistance, corrosion resistance, excellent electrical property and the like, has very strong compression resistance and bending resistance, and always keeps a leading position in reinforced composite materials.
CN 113045900 a discloses a continuous carbon fiber reinforced polyphenylene sulfide composite material, which adopts an interface modifier to introduce active groups to improve the interface bonding property between continuous carbon fibers and polyphenylene sulfide resin. However, since the bonding force between the active groups is not strong, and the groups are gradually deactivated with the lapse of time, the service life of the composite material is reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a modified graphene/epoxy phenyl grafted/PAN carbon fiber and a preparation method thereof, and the modified graphene/epoxy phenyl grafted/PAN carbon fiber is applied to a PPS material, so that the prepared conductive composite PPS material has excellent conductivity and mechanical properties.
A preparation method of modified graphene/epoxy phenyl grafted/PAN carbon fiber comprises the following steps:
s1, dissolving the modified graphene, acrylonitrile, azodiisobutyronitrile and methyl methacrylate in dimethyl sulfoxide for reaction to obtain a modified graphene/acrylonitrile polymer solution;
s2, filtering and defoaming the modified graphene/acrylonitrile polymer solution to obtain a spinning solution;
s3, extruding the polymer spinning solution through a spinneret plate, and then, allowing the extruded polymer spinning solution to enter a coagulating bath for coagulation forming to obtain modified graphene-polyacrylonitrile composite fibers;
s4, pre-oxidizing and carbonizing the modified graphene-polyacrylonitrile composite fiber to obtain a modified graphene/PAN carbon fiber;
s5, under the atmosphere of nitrogen, mixing and reacting 15 wt% of butyl lithium n-hexane solution, 3-bromophenyl ethylene oxide, PAN carbon fiber and toluene to obtain the modified graphene/epoxy phenyl grafted/PAN carbon fiber.
Further, the preparation method of the modified graphene/epoxy phenyl grafted/PAN carbon fiber comprises the following steps:
s1, dispersing 0.2-0.6 part of modified graphene in 400 parts of dimethyl sulfoxide (200) by mass, carrying out ultrasonic treatment for 1-3h at the power of 300-360W and the frequency of 80-120kHz, then adding 90-100 parts of acrylonitrile, 0.1-0.5 part of azodiisobutyronitrile and 1-2 parts of acrylamide, and heating to 60-70 ℃ in a nitrogen atmosphere to react for 18-24h to obtain a modified graphene/acrylonitrile polymer solution;
s2, filtering the modified graphene/acrylonitrile polymer solution by using a 600-mesh filter membrane, and then performing vacuum defoaming on the filtered modified graphene/acrylonitrile polymer solution at the temperature of 40 ℃, the vacuum degree of-0.06 MPa and the time of 1h to obtain a spinning solution;
s3, heating the spinning solution to 65-75 ℃, extruding the spinning solution by a spinneret plate, and then putting the extruded spinning solution into a coagulating bath for coagulation forming, wherein the spinneret hole diameter of the spinneret plate is 0.06-0.1mm, the spinning speed is 2-3m/min, the drafting ratio is 4.5, and the temperature of the coagulating bath is 35-45 ℃, so that the modified graphene-polyacrylonitrile composite fiber is obtained;
s4, pre-oxidizing the modified graphene-polyacrylonitrile composite fiber at the temperature of 200-300 ℃ for 60-90 min;
s5, raising the temperature from 300 ℃ to 900 ℃ at the speed of 1-5 ℃/min, keeping the temperature constant for 20-40min, then raising the temperature to 1500 ℃ at the speed of 1-5 ℃/min, and keeping the temperature at 1500 ℃ of 1300 ℃ for reaction for 15-30min to obtain the modified graphene/PAN carbon fiber;
s6, mixing 1-5 parts of modified graphene/PAN carbon fiber and 90-100 parts of toluene by mass, carrying out ultrasonic treatment for 1-2 hours under the atmosphere of nitrogen, adding 2-4 parts of 15 wt% butyl lithium n-hexane solution, carrying out ultrasonic treatment for 0.5-2 hours, wherein the ultrasonic power is 300-360W and the ultrasonic frequency is 80-120kHz, adding 0.5-1 part of 3-bromophenyl ethylene oxide, stirring for 30-60min at the rotating speed of 80-120r/min, centrifuging, washing with acetone for precipitation, and drying to obtain the modified graphene/epoxy phenyl grafted/PAN carbon fiber.
The coagulating bath is one of dimethyl sulfoxide aqueous solution with the concentration of 50-60 wt%, dimethyl formamide aqueous solution with the concentration of 50-60 wt% and dimethyl acetamide aqueous solution with the concentration of 50-60 wt%; preferably, the coagulation bath is 50-60 wt% aqueous dimethyl sulfoxide solution.
According to the invention, butyl lithium is adopted for catalysis, the phenyl oxirane is grafted to the surface of the PAN carbon fiber by utilizing the reaction of halogen atoms on the 3-bromophenyl oxirane and hydroxyl groups on the surface of the PAN carbon fiber, the reaction equation is as follows, an oxygen ring on the phenyl oxirane can open a ring at a high temperature and react with amino groups on amino-functionalized polyphenylene sulfide to realize covalent bond linkage, the bonding force of the modified graphene/epoxy phenyl graft/PAN carbon fiber and the polyphenylene sulfide is greatly enhanced, the phase interface force of the modified graphene/epoxy phenyl graft/PAN carbon fiber and the polyphenylene sulfide is weakened, the modified graphene/epoxy phenyl graft/PAN carbon fiber is dispersed more uniformly, and the mechanical property and the electrical property of the polyphenylene sulfide are enhanced.
Furthermore, the performance of the PAN carbon fiber composite PPS material is improved by improving the performance of the PAN carbon fiber. The quality of the PAN carbon fiber is mainly the quality of the PAN precursor, and the PAN precursor effectively controls the axial orientation of PAN molecules in the precursor and reduces defects in the production process, thereby being beneficial to improving a series of performances such as strength, conductivity and the like of the prepared PAN carbon fiber. During the whole spinning process, under the action of uniaxial drawing stress, PAN molecules are preferentially oriented along the axial direction, however, in the pre-oxidation process, due to the fact that molecular thermal motion can generate de-orientation, only after a cross-linking and heat-resisting structure is formed, the oriented structure can be fixed. Therefore, how to reduce the de-orientation in the pre-oxidation process has great significance for improving the performance of the PAN carbon fiber. Rigid graphene oxide molecules are added, so that the limitation of the disorientation of PAN molecules caused by thermal motion is facilitated.
However, the conventional graphene sheet has small size, weak orientation effect, easy agglomeration, poor dispersibility in PAN spinning solution and weak orientation effect on the molecular arrangement of the fixed PAN polymer. On the basis, the invention further modifies the added graphene material, and provides a preparation method of modified graphene, which comprises the following steps:
n1, mixing graphite, sodium nitrate, potassium permanganate and concentrated sulfuric acid for reaction to obtain graphene oxide;
n2, ultrasonically dispersing the graphene oxide and the surfactant in water, and reducing with sodium sulfide to obtain the modified graphene.
Further, a preparation method of the modified graphene comprises the following steps:
n1 is prepared by mixing 4-6 parts of graphite, 2-3 parts of sodium nitrate and 7-8 parts of potassium permanganate by mass, adding 130 parts of 120-one concentrated sulfuric acid, stirring at-1- (-5) DEG C for 1-2H, adding 17-18 parts of potassium permanganate, heating to 30-40 ℃, reacting for 1-2H, raising the temperature to 95-100 ℃, adding 300 parts of 200-one water at the rate of 20-30mL/min, stirring at the rotating speed of 80-120r/min for 40-50min, and adding 18-22 parts of H2O2Continuously stirring for 10min, centrifuging, washing and drying to obtain graphene oxide;
n2, adding 1-2 parts of graphene oxide and 5-7 parts of surfactant into 500 parts of water containing 300-fold impurities by mass, ultrasonically dispersing for 1-2 hours with ultrasonic power of 300-fold impurities of 360W and ultrasonic frequency of 80-120kHz, then adding 4-6 parts of ammonia water, continuing to ultrasonically disperse for 2-3 hours to form a uniform solution, then heating to 95-100 ℃, adding 4-6 parts of anhydrous sodium sulfide, refluxing for 20-26 hours, stopping reaction, filtering, washing and drying to obtain the modified graphene.
The surfactant is prepared by mixing one or two or more of cetyl trimethyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride, diisooctyl succinate sodium sulfonate and sodium dodecyl benzene sulfonate; preferably, the surfactant is prepared from tetradecyl dimethyl benzyl ammonium chloride and diisooctyl succinate sodium sulfonate according to the mass ratio of (7-9): (2-4) mixing.
According to the scheme, potassium permanganate and concentrated sulfuric acid are used as strong oxidants to intercalate graphite, hydroxyl and epoxy are generated on the surface of the graphite to separate graphite sheets, graphene oxide is obtained, anhydrous sodium sulfide is used as a reducing agent to reduce the graphene oxide, the anhydrous sodium sulfide has strong reducibility, the epoxy and hydroxyl generated on the surface of the graphene in an oxidation step can be eliminated, reducing sulfur elements in the anhydrous sodium sulfide have nucleophilicity and can perform nucleophilic substitution reaction with the hydroxyl on the surface of the graphene to form C-S-C bonds, the adjacent graphene sheets are connected to form a larger and more ordered graphene sheet space network, the orderliness of the graphene sheets is increased, and the improvement of the dispersibility of the graphene sheets in a spinning solution and the directional effect in a pre-oxidation process is facilitated. In addition, in order to reduce agglomeration between graphene sheets, the present invention further separates the graphene sheets using a surfactant. According to the invention, a surfactant compounded by tetradecyl dimethyl benzyl ammonium chloride and diisooctyl succinate sodium sulfonate is preferably used as a separant of a graphene lamellar layer, and the tetradecyl dimethyl benzyl ammonium chloride is a cationic surfactant, so that the tetradecyl dimethyl benzyl ammonium chloride can be well adsorbed on the surface of graphene due to negative charge on the surface of the graphene, and the polymerization of the graphene lamellar layer is blocked; in addition, the invention discovers that the aggregated graphene sheet layers are difficult to separate in water, but the anionic surfactant-sodium diisooctyl succinate sulfonate is added into the aggregated graphene sheet layers and mutually repels graphene, so that the graphene sheet layers can be rapidly and effectively separated with the help of ultrasound, and the cationic surfactant is assisted to prevent the aggregation of the graphene sheet layers. At the moment, sodium sulfide is used for reduction, a more regular graphene net structure can be formed through C-S-C bonds, and the PAN carbon fiber with fewer defects and a smaller preferred orientation angle is obtained when the graphene net structure is applied to the manufacturing of the PAN carbon fiber.
Furthermore, the modified graphene/epoxy phenyl grafted/PAN carbon fiber prepared by the special process is applied to the preparation of the PPS material, so that the conductive composite PPS material is obtained.
A preparation method of a conductive composite PPS material comprises the following steps:
(1) mixing 0.6-1.2 parts of polyphenylene sulfide and 8-12 parts of concentrated sulfuric acid by mass, stirring at the rotating speed of 80-120r/min for 1-3min, adding 0.5-1.2 parts of concentrated nitric acid, continuously stirring for 2-5min, heating to 60-70 ℃, reacting for 0.5-2h, centrifuging, washing and drying to obtain a semi-finished product;
(2) mixing 0.5-1 part of the semi-finished product and 15-30 parts of N, N-dimethylformamide according to parts by mass, stirring at the rotating speed of 80-120r/min for 1-3min, then adding 1-2 parts of sodium hydrosulfite, heating to 160-170 ℃ under the protection of nitrogen, carrying out reflux reaction for 3-4h, and carrying out centrifugation, washing and drying to obtain amino-functionalized polyphenylene sulfide;
(3) modified graphene/epoxy phenyl grafted/PAN carbon fiber and amino-functionalized polyphenylene sulfide are mixed according to the mass ratio of (15-30): (95-110), carrying out mechanical premixing, then carrying out melt blending through a double-screw extruder, and carrying out extrusion granulation to obtain the conductive composite PPS material.
The temperature of each zone of the double-screw extruder is respectively as follows: the first zone is 270-280 ℃, the second zone 285-295 ℃, the third zone is 300-310 ℃, the fourth zone is 310-315 ℃, the fifth zone is 315-320 ℃, the sixth zone is 315-320 ℃, the seventh zone is 310-315 ℃, the eighth zone is 305-310 ℃, the ninth zone is 300-305 ℃ and the head 290-300 ℃.
The invention has the beneficial effects that:
1. the modified graphene is prepared, the graphene sheet layers are connected through the C-S-C bonds, a more regular reticular graphene structure is formed, and the dispersibility of the graphene in a spinning solution and the orientation effect of the graphene in a pre-oxidation process are greatly improved.
2. According to the invention, the modified graphene is used for improving the PAN fiber, and the high-strength PAN carbon fiber is prepared through oxidation and carbonization.
3. According to the invention, phenyl ethylene oxide is further grafted on the surface of the obtained high-strength PAN carbon fiber, the polyphenylene sulfide is aminated, and the covalent bond grafting of the PAN carbon fiber and the polyphenylene sulfide is realized by utilizing the epoxy and amino reaction, so that the binding force of the modified graphene/epoxy phenyl graft/PAN carbon fiber and the polyphenylene sulfide is greatly enhanced, the phase interface force of the modified graphene/epoxy phenyl graft/PAN carbon fiber and the polyphenylene sulfide is weakened, the modified graphene/epoxy phenyl graft/PAN carbon fiber is dispersed more uniformly, and the mechanical property and the electrical property of the polyphenylene sulfide are enhanced.
Detailed Description
Acrylonitrile, CAS No.: 107-13-1.
Methyl methacrylate, CAS No.: 80-62-6.
Graphite, good number: s26651, particle size: 8000 mesh, Shanghai Yuan leaf Biotech Co., Ltd.
Polyphenylene sulfide, CAS No.: 25212-74-2, cat number: 1150C, zhejiang new and specialty materials ltd.
Ammonia water used in examples, concentration: 27 wt%.
Concentrated nitric acid used in the examples: the concentration was 60 wt%.
Concentrated sulfuric acid used in the examples: the concentration was 98 wt%.
H used in examples2O2: the concentration was 12 wt%.
Tetradecyldimethylbenzylammonium chloride, CAS number: 139-08-2.
Sodium diisooctyl succinate sulfonate, CAS No.: 577-11-7.
N, N-dimethylformamide, CAS No.: 68-12-2.
Example 1
A preparation method of a conductive composite PPS material comprises the following steps:
(1) mixing 1 part of polyphenylene sulfide and 10 parts of concentrated sulfuric acid in parts by mass, stirring at the rotating speed of 100r/min, adding 1 part of concentrated nitric acid, continuously stirring for 3min, heating to 65 ℃, reacting for 1h, centrifuging, washing and drying to obtain a semi-finished product;
(2) mixing 1 part of the semi-finished product and 20 parts of N, N-dimethylformamide according to parts by mass, stirring at the rotating speed of 100r/min, then adding 1 part of sodium hydrosulfite, heating to 165 ℃ under the protection of nitrogen, carrying out reflux reaction for 3.5 hours, centrifuging, washing and drying to obtain amino-functionalized polyphenylene sulfide;
(3) PAN carbon fiber and amino-functional polyphenylene sulfide are mixed according to the mass ratio of 20: 100, mechanically premixing, then carrying out melt blending through a double-screw extruder, and carrying out extrusion granulation to obtain the conductive composite PPS material.
The temperature of each zone of the double-screw extruder is respectively as follows: 275 ℃ in the first zone, 290 ℃ in the second zone, 305 ℃ in the third zone, 310 ℃ in the fourth zone, 315 ℃ in the fifth zone, 315 ℃ in the sixth zone, 310 ℃ in the seventh zone, 305 ℃ in the eighth zone, 300 ℃ in the ninth zone and 290 ℃ in the head.
The preparation method of the PAN carbon fiber comprises the following steps:
s1, mixing 300 parts of dimethyl sulfoxide, 95 parts of acrylonitrile, 0.3 part of azobisisobutyronitrile and 1.5 parts of acrylamide by mass, heating to 65 ℃ in a nitrogen atmosphere, and reacting for 20 hours to obtain an acrylonitrile polymer solution;
s2, filtering the acrylonitrile polymer solution by using a 600-mesh filter membrane, and then performing vacuum defoaming on the filtered acrylonitrile polymer solution at the temperature of 40 ℃, the vacuum degree of-0.06 MPa and the time of 1h to obtain a spinning solution;
s3, heating the spinning solution to 70 ℃, extruding the spinning solution by a spinneret plate, and then putting the extruded spinning solution into 55 wt% of dimethyl sulfoxide water solution for solidification forming, wherein the spinneret hole diameter of the spinneret plate is 0.08mm, the spinning speed is 3m/min, the drafting ratio is 4.5, and the solidification bath temperature is 40 ℃ to obtain the polyacrylonitrile composite fiber;
s4, pre-oxidizing the polyacrylonitrile composite fiber at 265 ℃ for 75 min;
s5, heating the temperature from 265 ℃ to 835 ℃ at the speed of 5 ℃/min, keeping the temperature constant for 30min, then heating the temperature to 1400 ℃ at the speed of 5 ℃/min, and keeping the temperature constant at 1400 ℃ for reaction for 20min to obtain the PAN carbon fiber.
Example 2
A preparation method of a conductive composite PPS material comprises the following steps:
(1) mixing 1 part of polyphenylene sulfide and 10 parts of concentrated sulfuric acid in parts by mass, stirring at the rotating speed of 100r/min for 2min, adding 1 part of concentrated nitric acid, continuously stirring for 3min, heating to 65 ℃ for reaction for 1h, centrifuging, washing and drying to obtain a semi-finished product;
(2) mixing 1 part of the semi-finished product and 20 parts of N, N-dimethylformamide according to parts by mass, stirring at the rotating speed of 100r/min for 2min, then adding 1 part of sodium hydrosulfite, heating to 165 ℃ under the protection of nitrogen, carrying out reflux reaction for 3.5h, centrifuging, washing and drying to obtain amino-functionalized polyphenylene sulfide;
(3) epoxy phenyl grafted/PAN carbon fiber and amino-functionalized polyphenylene sulfide are mixed according to the mass ratio of 20: 100, mechanically premixing, then carrying out melt blending through a double-screw extruder, and carrying out extrusion granulation to obtain the conductive composite PPS material.
The temperature of each zone of the double-screw extruder is respectively as follows: 275 ℃ in the first zone, 290 ℃ in the second zone, 305 ℃ in the third zone, 310 ℃ in the fourth zone, 315 ℃ in the fifth zone, 315 ℃ in the sixth zone, 310 ℃ in the seventh zone, 305 ℃ in the eighth zone, 300 ℃ in the ninth zone and 290 ℃ in the head.
The preparation method of the epoxy phenyl grafted/PAN carbon fiber comprises the following steps:
s1, mixing 300 parts of dimethyl sulfoxide, 95 parts of acrylonitrile, 0.3 part of azobisisobutyronitrile and 1.5 parts of acrylamide by mass, heating to 65 ℃ in a nitrogen atmosphere, and reacting for 20 hours to obtain an acrylonitrile polymer solution;
s2, filtering the acrylonitrile polymer solution by using a 600-mesh filter membrane, and then performing vacuum defoaming on the filtered acrylonitrile polymer solution at the temperature of 40 ℃, the vacuum degree of-0.06 MPa and the time of 1h to obtain a spinning solution;
s3, heating the spinning solution to 70 ℃, extruding the spinning solution by a spinneret plate, and then putting the extruded spinning solution into 55 wt% of dimethyl sulfoxide water solution for solidification forming, wherein the spinneret hole diameter of the spinneret plate is 0.08mm, the spinning speed is 3m/min, the drafting ratio is 4.5, and the solidification bath temperature is 40 ℃ to obtain the polyacrylonitrile composite fiber;
s4, pre-oxidizing the polyacrylonitrile composite fiber at 265 ℃ for 75 min;
s5, heating the temperature from 265 ℃ to 835 ℃ at the speed of 5 ℃/min, keeping the temperature constant for 30min, then heating the temperature to 1400 ℃ at the speed of 5 ℃/min, and keeping the temperature constant at 1400 ℃ for reacting for 20min to obtain PAN carbon fiber;
s6, mixing 3 parts of PAN carbon fiber and 95 parts of toluene, carrying out ultrasonic treatment for 1 hour under a nitrogen atmosphere, wherein the ultrasonic power is 340W and the ultrasonic frequency is 90kHz, then adding 3 parts of 15 wt% butyl lithium n-hexane solution, continuing the ultrasonic treatment for 1 hour, then adding 0.6 part of 3-bromophenyl ethylene oxide, stirring for 40 minutes at the rotating speed of 100r/min, centrifuging, washing with acetone for precipitation, and drying to obtain the epoxy phenyl graft/PAN carbon fiber.
Example 3
Essentially the same as example 2, except that: graphene oxide/epoxy phenyl graft/PAN carbon fiber is adopted to replace epoxy phenyl graft/PAN carbon fiber.
The preparation method of the graphene oxide/epoxy phenyl grafted/PAN carbon fiber comprises the following steps:
s1, dispersing 0.4 part of graphene oxide in 300 parts of dimethyl sulfoxide by mass, carrying out ultrasonic treatment for 2 hours at the power of 340W and the frequency of 90kHz, then adding 95 parts of acrylonitrile, 0.3 part of azobisisobutyronitrile and 1.5 parts of acrylamide, heating to 65 ℃ in a nitrogen atmosphere, and reacting for 20 hours to obtain a graphene oxide/acrylonitrile polymer solution;
s2, filtering the graphene oxide/acrylonitrile polymer solution by using a 600-mesh filter membrane, and then performing vacuum defoaming on the filtered graphene oxide/acrylonitrile polymer solution at the temperature of 40 ℃, the vacuum degree of-0.06 MPa and the time of 1h to obtain a spinning solution;
s3, heating the spinning solution to 70 ℃, extruding the spinning solution by a spinneret plate, and then putting the extruded spinning solution into 55 wt% of dimethyl sulfoxide water solution for solidification forming, wherein the spinneret hole diameter of the spinneret plate is 0.08mm, the spinning speed is 3m/min, the drafting ratio is 4.5, and the solidification bath temperature is 40 ℃, so that the graphene oxide-polyacrylonitrile composite fiber is obtained;
s4, pre-oxidizing the graphene oxide-polyacrylonitrile composite fiber at 265 ℃ for 75 min;
s5, heating the temperature from 265 ℃ to 835 ℃ at the speed of 5 ℃/min, keeping the temperature constant for 30min, then heating the temperature to 1400 ℃ at the speed of 5 ℃/min, and keeping the temperature constant at 1400 ℃ for reacting for 20min to obtain the graphene oxide/PAN carbon fiber;
s6, mixing 20 parts of modified graphene/PAN carbon fiber and 95 parts of toluene by mass, carrying out ultrasonic treatment for 1 hour under a nitrogen atmosphere, wherein the ultrasonic power is 340W and the ultrasonic frequency is 90kHz, then adding 3 parts of a 15 wt% butyl lithium n-hexane solution, continuing to carry out ultrasonic treatment for 1 hour, then adding 0.6 part of 3-bromophenyl ethylene oxide, stirring for 40 minutes at a rotating speed of 100r/min, centrifuging, washing with acetone for precipitation, and drying to obtain the graphene oxide/epoxyphenyl grafted/PAN carbon fiber.
The preparation method of the graphene oxide comprises the following steps: mixing 5.0 parts of graphite, 2.5 parts of sodium nitrate and 7.5 parts of potassium permanganate according to parts by mass, adding 125 parts of concentrated sulfuric acid, stirring at the temperature of minus 2 ℃ for 1 hour at the rotating speed of 100r/min, adding 17.5 parts of potassium permanganate, heating to 35 ℃ for reaction for 1.5 hours, raising the temperature to 98 ℃, adding 250 parts of water at the speed of 25mL/min, continuously stirring for 45 minutes, and adding 20 parts of H2O2And stirring for 10min, centrifuging, washing and drying to obtain the graphene oxide.
Example 4
Essentially the same as example 3, except that: modified graphene is adopted to replace graphene oxide.
The preparation method of the modified graphene comprises the following steps:
n1 is prepared by mixing 5.0 parts of graphite, 2.5 parts of sodium nitrate and 7.5 parts of potassium permanganate, adding 125 parts of concentrated sulfuric acid, stirring at-2 ℃ for 1H at a rotating speed of 100r/min, adding 17.5 parts of potassium permanganate, heating to 35 ℃ for reaction for 1.5H, raising the temperature to 98 ℃, adding 250 parts of water at a speed of 25mL/min, continuously stirring for 45min, and adding 20 parts of H2O2Stirring for 10min, centrifuging, washing and drying to obtain graphene oxide;
n2, adding 1.5 parts of graphene oxide and 6 parts of surfactant into 400 parts of water by mass, ultrasonically dispersing for 1.5 hours at an ultrasonic power of 340W and an ultrasonic frequency of 90kHz, then adding 5 parts of ammonia water, continuously ultrasonically dispersing for 2 hours to form a uniform solution, heating to 98 ℃, then adding 5 parts of anhydrous sodium sulfide, refluxing for 24 hours, stopping reaction, filtering, washing and drying to obtain the modified graphene.
The surfactant is prepared from tetradecyl dimethyl benzyl ammonium chloride and diisooctyl succinate sodium sulfonate according to a mass ratio of 8: 3, and mixing.
Example 5
Essentially the same as example 4, except that:
the preparation method of the modified graphene comprises the following steps:
n1 is prepared by mixing 5.0 parts of graphite, 2.5 parts of sodium nitrate and 7.5 parts of potassium permanganate by weight, adding 125 parts of concentrated sulfuric acid, stirring at-2 ℃ for 1H at a rotating speed of 100r/min, adding 17.5 parts of potassium permanganate, heating to 35 ℃, reacting for 1.5H, heating to 98 ℃, adding 250 parts of water at a speed of 25mL/min, stirring for 45min, and adding 20 parts of H2O2Stirring for 10min, centrifuging, washing and drying to obtain graphene oxide;
n2, adding 1.5 parts of graphene oxide and 6 parts of surfactant into 400 parts of water by mass, ultrasonically dispersing for 1.5 hours at an ultrasonic power of 340W and an ultrasonic frequency of 90kHz, then adding 5 parts of ammonia water, continuously ultrasonically dispersing for 2 hours to form a uniform solution, then heating to 98 ℃, adding 5 parts of anhydrous sodium sulfide, refluxing for 24 hours, stopping reaction, filtering, washing and drying to obtain the modified graphene.
The surfactant is tetradecyl dimethyl benzyl ammonium chloride.
Example 6
Essentially the same as example 4, except that:
the preparation method of the modified graphene comprises the following steps:
n1 is prepared by mixing 5.0 parts of graphite, 2.5 parts of sodium nitrate and 7.5 parts of potassium permanganate by weight, adding 125 parts of concentrated sulfuric acid, stirring at-2 ℃ for 1H at a rotating speed of 100r/min, adding 17.5 parts of potassium permanganate, heating to 35 ℃, reacting for 1.5H, raising the temperature to 98 ℃, adding 250 parts of water at a speed of 25mL/min, continuously stirring for 45min, and adding 20 parts of H2O2Stirring for 10min, centrifuging, washing and drying to obtain graphene oxide;
n2, adding 1.5 parts of graphene oxide and 6 parts of surfactant into 400 parts of water by mass, ultrasonically dispersing for 1.5 hours at an ultrasonic power of 340W and an ultrasonic frequency of 90kHz, then adding 5 parts of ammonia water, continuously ultrasonically dispersing for 2 hours to form a uniform solution, heating to 98 ℃, adding 5 parts of anhydrous sodium sulfide, refluxing for 24 hours, stopping reaction, filtering, washing and drying to obtain the modified graphene.
The surfactant is sodium diisooctyl succinate sulfonate.
Comparative example
Mixing PAN carbon fiber and polyphenylene sulfide according to a mass ratio of 20: 100, mechanically premixing, then carrying out melt blending through a double-screw extruder, and carrying out extrusion granulation to obtain the conductive composite PPS material.
The temperature of each zone of the double-screw extruder is respectively as follows: 275 ℃ in the first zone, 290 ℃ in the second zone, 305 ℃ in the third zone, 310 ℃ in the fourth zone, 315 ℃ in the fifth zone, 315 ℃ in the sixth zone, 310 ℃ in the seventh zone, 305 ℃ in the eighth zone, 300 ℃ in the ninth zone and 290 ℃ in the head.
The preparation method of the PAN carbon fiber comprises the following steps:
s1, mixing 300 parts of dimethyl sulfoxide, 95 parts of acrylonitrile, 0.3 part of azobisisobutyronitrile and 1.5 parts of acrylamide by mass, heating to 65 ℃ in a nitrogen atmosphere, and reacting for 20 hours to obtain an acrylonitrile polymer solution;
s2, filtering the acrylonitrile polymer solution by using a 600-mesh filter membrane, and then performing vacuum defoaming on the filtered acrylonitrile polymer solution at the temperature of 40 ℃, the vacuum degree of-0.06 MPa and the time of 1h to obtain a spinning solution;
s3, heating the spinning solution to 70 ℃, extruding the spinning solution by a spinneret plate, and then putting the extruded spinning solution into 55 wt% of dimethyl sulfoxide water solution for solidification forming, wherein the spinneret hole diameter of the spinneret plate is 0.08mm, the spinning speed is 3m/min, the drafting ratio is 4.5, and the solidification bath temperature is 40 ℃ to obtain the polyacrylonitrile composite fiber;
s4, pre-oxidizing the polyacrylonitrile composite fiber at 265 ℃ for 75 min;
s5, heating the temperature from 265 ℃ to 835 ℃ at the speed of 5 ℃/min, keeping the temperature constant for 30min, then heating the temperature to 1400 ℃ at the speed of 5 ℃/min, and keeping the temperature constant at 1400 ℃ for reaction for 20min to obtain the PAN carbon fiber.
Test example 1
The resistivity of the conductive composite PPS materials prepared in the examples and the comparative examples is determined by referring to GB/T15738-. Testing an instrument: the north guangjing instrument produced a resistivity tester model number BEST-212. And (3) testing conditions are as follows: room temperature 25 ℃ and relative humidity 50%. Injection molding of the conductive composite PPS materials prepared in examples 1-6 to obtain a sample, wherein the sample size is as follows: 75mm long, 10mm wide and 4mm thick. Each sample was tested 3 times and averaged. The results are shown in Table 1.
Table 1: results of resistivity testing
| Resistivity (omega. m) | |
| Example 1 | 2.1×104 |
| Example 2 | 3.2×103 |
| Example 3 | 1.4×103 |
| Example 4 | 32.9 |
| Example 5 | 59.8 |
| Example 6 | 61.2 |
| Comparative example | 1.6×105 |
As can be seen from table 1, the electrical resistivity of the conductive composite PPS material prepared in example 4 is the lowest, and correspondingly, the conductive effect is the best, because the graphene sheet layers are connected by using the C-S-C bonds, a more regular network graphene structure is formed, and the dispersibility of graphene in the spinning solution and the orientation effect of graphene in the pre-oxidation process are greatly improved. And then, oxidizing and carbonizing the modified graphene-modified PAN fiber to prepare the high-strength PAN carbon fiber, wherein the modified graphene is used as an orientation material to obtain the PAN carbon fiber with fewer defects and a smaller preferred orientation angle. Furthermore, phenyl ethylene oxide is grafted on the surface of the obtained high-strength PAN carbon fiber, polyphenylene sulfide is aminated, and epoxy and amino reactions are utilized to realize covalent bond grafting of the PAN carbon fiber and the polyphenylene sulfide, so that the binding force of the modified graphene/epoxy phenyl grafted/PAN carbon fiber and the polyphenylene sulfide is greatly enhanced, the phase interface force of the modified graphene/epoxy phenyl grafted/PAN carbon fiber and the polyphenylene sulfide is weakened, the modified graphene/epoxy phenyl grafted/PAN carbon fiber is dispersed more uniformly, and the mechanical property and the electrical property of the polyphenylene sulfide are enhanced. The conductivity of example 3 is greater than that of example 4, since example 3 does not reduce graphene with sodium sulfide, the aggregation is extremely severe, and the orientation effect is very weak in the preparation of PAN carbon fibers. The resistivity of example 2 is greater than that of example 3, because no graphene oxide is added in the preparation process of the PAN carbon fiber, the conductivity of the prepared PAN carbon fiber is poor, and the resistivity of the PAN carbon fiber is greater. The resistivity of the embodiment 1 is greater than that of the embodiment 2, because the PAN carbon fiber has no grafted phenyl oxirane on the surface, and cannot open the ring at a high temperature through an oxygen ring on the phenyl oxirane and react with an amino group on the amino-functionalized polyphenylene sulfide to realize covalent bond linkage, the bonding force between the modified graphene/epoxy phenyl graft/PAN carbon fiber and the polyphenylene sulfide is enhanced, the phase interface force between the modified graphene/epoxy phenyl graft/PAN carbon fiber and the polyphenylene sulfide is weakened, the modified graphene/epoxy phenyl graft/PAN carbon fiber is dispersed more uniformly, and the mechanical property and the electrical property of the polyphenylene sulfide are enhanced. The resistivity of the graphene in the embodiments 5 and 6 is slightly larger than that of the graphene in the embodiment 4, because the surfactant compounded by tetradecyl dimethyl benzyl ammonium chloride and diisooctyl succinate sodium sulfonate is used as a separant of the graphene sheet layer, and the tetradecyl dimethyl benzyl ammonium chloride is a cationic surfactant, the graphene can be well adsorbed on the surface of graphene due to negative charge on the surface of the graphene, so that the polymerization of the graphene sheet layer is blocked; in addition, the invention discovers that the aggregated graphene sheet layers are difficult to separate in water, but the anionic surfactant-sodium diisooctyl succinate sulfonate is added into the aggregated graphene sheet layers and mutually exclusive with graphene, so that the graphene sheet layers can be rapidly and effectively separated with the help of ultrasound, the cationic surfactant is assisted to prevent the aggregation of the graphene sheet layers, and the synergistic effect of the anionic surfactant and the cationic surfactant is better. At the moment, sodium sulfide is used for reduction, a more regular graphene net structure can be formed through C-S-C bonds, and the PAN carbon fiber with fewer defects and a smaller preferred orientation angle is obtained when the graphene net structure is applied to the manufacturing of the PAN carbon fiber. It can be seen from the comparative example and the example 1 that amination also improves the conductivity of the enhanced carbon fiber composite PPS material to a certain extent, because amination reduces the resistance of the PPS material, and the aminated PPS material contains amino groups, and the bonding force formed between the amino groups and the hydroxyl groups and epoxy groups on the surface of the PAN carbon fibers is stronger, which is beneficial to the dispersion of the PAN carbon fibers and further reduces the resistivity of the PAN carbon fibers.
Test example 2
Reference is made to GB/T1040.2-2006 section 2 of determination of tensile Properties of plastics: test conditions for molded and extruded plastics the mechanical properties of the conductive composite PPS materials prepared in the examples were measured. Testing an instrument: model number WEW-600C universal tester manufactured by Meits Industrial systems (China) Ltd. And (3) testing conditions are as follows: room temperature 25 ℃ and relative humidity 65%. The test method comprises the following steps: the conductive composite PPS material prepared in the examples and the comparative examples is subjected to a tensile test on a universal testing machine, and injection molding is carried out on the conductive composite PPS material to obtain a sample, wherein the sample size is as follows: 80mm long, 10mm wide and 4mm thick. The grip length was 75mm, the tensile speed was 5mm/min, the tensile strength and elongation at break were measured, and the average value was taken 5 times per sample. The test results are shown in Table 2.
Table 2: test results of breaking Strength
| Tensile strength/MPa | Elongation at break/% | |
| Example 1 | 105 | 1.7 |
| Example 2 | 126 | 2.3 |
| Example 3 | 131 | 3.0 |
| Example 4 | 159 | 3.5 |
| Example 5 | 152 | 3.3 |
| Example 6 | 150 | 3.3 |
| Comparative example | 94 | 1.2 |
As can be seen from Table 2, the change rule of the mechanical property of the conductive composite PPS material prepared by the embodiment is the same as that of the electrical property of the conductive composite PPS material. As can be seen from examples 3 and 4, the mechanical properties of the modified graphene/PAN carbon fiber itself greatly contribute to the improvement of the mechanical properties of the PAN carbon fiber-modified PPS material. It can be seen from the comparison between example 2 and example 1 that the PAN carbon fiber is surface-modified, phenyl ethylene oxide is grafted on the surface of the PAN carbon fiber, and the epoxy ring on the phenyl ethylene oxide opens the ring at a high temperature to react with the amino group on the amino-functionalized polyphenylene sulfide to realize covalent bond linkage, so that the bonding force between the modified graphene/epoxy phenyl graft/PAN carbon fiber and the polyphenylene sulfide can be enhanced, the phase interface force between the modified graphene/epoxy phenyl graft/PAN carbon fiber and the polyphenylene sulfide is weakened, the modified graphene/epoxy phenyl graft/PAN carbon fiber is dispersed more uniformly, and the mechanical property of the polyphenylene sulfide is enhanced. By comparing the embodiment 4, the embodiment 5 and the embodiment 6, it can be seen that the tetradecyl dimethyl benzyl ammonium chloride and the diisooctyl succinate sodium sulfonate act synergistically to improve the dispersibility of the graphene, so that the mechanical property of the PAN carbon fiber is enhanced, and the mechanical property of the prepared conductive composite PPS material is indirectly improved. As can be seen from the comparison of the comparative example and the example 1, the PAN carbon fiber composite aminated PPS material has better mechanical property, the aminated PPS material contains amino, and the bonding force formed between the amino and the hydroxyl and epoxy on the surface of the PAN carbon fiber is stronger, so that the PAN carbon fiber is favorably dispersed, the stress is more uniform, and the mechanical property is improved.
Claims (10)
1. The conductive composite PPS material is characterized by comprising the following raw materials: modified graphene/PAN carbon fiber or modified graphene/epoxy phenyl graft/PAN carbon fiber or polyphenylene sulfide.
2. The conductive composite PPS material as defined in claim 1, wherein the modified graphene/epoxy phenyl grafted/PAN carbon fiber is prepared by the following method: and in the nitrogen atmosphere, mixing and reacting butyl lithium n-hexane solution, 3-bromophenyl ethylene oxide, modified graphene/PAN carbon fiber and toluene to obtain the modified graphene/epoxy phenyl grafted/PAN carbon fiber.
3. The conductive composite PPS material as defined in claim 2, wherein the modified graphene/epoxy phenyl grafted/PAN carbon fiber is prepared by the following method: mixing 1-5 parts of modified graphene/PAN carbon fiber and 90-100 parts of toluene by mass, carrying out ultrasonic treatment for 1-2 hours under the atmosphere of nitrogen, wherein the ultrasonic power is 300-360W, the ultrasonic frequency is 80-120kHz, then adding 2-4 parts of 10-20 wt% butyl lithium n-hexane solution, continuing to carry out ultrasonic treatment for 0.5-2 hours, then adding 0.5-1 part of 3-bromophenyl ethylene oxide, stirring for 30-60 minutes, finally, centrifuging, washing and precipitating with acetone, and drying to obtain the modified graphene/epoxy phenyl grafted PAN carbon fiber.
4. The conductive composite PPS material of any of claims 1-3 wherein the method of preparing the modified graphene/PAN carbon fiber comprises the steps of:
s1, dissolving the modified graphene, acrylonitrile, azodiisobutyronitrile and methyl methacrylate in dimethyl sulfoxide for reaction to obtain a modified graphene/acrylonitrile polymer solution;
s2, filtering and defoaming the modified graphene/acrylonitrile polymer solution by adopting a conventional technical means in the field to obtain a spinning solution;
s3, extruding the polymer spinning solution through a spinneret plate, and then, allowing the extruded polymer spinning solution to enter a coagulating bath for coagulation forming to obtain modified graphene-polyacrylonitrile composite fibers;
s4, pre-oxidizing and carbonizing the modified graphene-polyacrylonitrile composite fiber to obtain the modified graphene/PAN carbon fiber.
5. The conductive composite PPS material of claim 4 wherein the modified graphene/PAN carbon fiber is prepared by a method comprising the steps of:
s1, dispersing 0.2-0.6 part of modified graphene in 400 parts of dimethyl sulfoxide (200) by mass, carrying out ultrasonic treatment for 1-3h at the power of 300-360W and the frequency of 80-120kHz, then adding 90-100 parts of acrylonitrile, 0.1-0.5 part of azodiisobutyronitrile and 1-2 parts of acrylamide, and heating to 60-70 ℃ in a nitrogen atmosphere to react for 18-24h to obtain a modified graphene/acrylonitrile polymer solution;
s2, filtering the modified graphene/acrylonitrile polymer solution by using a 600-mesh filter membrane, and then performing vacuum defoaming on the filtered modified graphene/acrylonitrile polymer solution at the temperature of 40 ℃, the vacuum degree of-0.06 MPa and the time of 1h to obtain a spinning solution;
s3, heating the spinning solution to 65-75 ℃, extruding the spinning solution through a spinneret plate, and then putting the extruded spinning solution into a coagulating bath for coagulation forming, wherein the spinneret hole diameter of the spinneret plate is 0.06-0.1mm, the spinning speed is 2-3m/min, the drafting ratio is 4.5, and the coagulating bath temperature is 35-45 ℃, so that the modified graphene-polyacrylonitrile composite fiber is obtained, and the coagulating bath is one of a dimethyl sulfoxide aqueous solution with the concentration of 50-60 wt%, a dimethylformamide aqueous solution with the concentration of 50-60 wt% and a dimethylacetamide aqueous solution with the concentration of 50-60 wt%;
s4, pre-oxidizing the modified graphene-polyacrylonitrile composite fiber at the temperature of 200-300 ℃ for 60-90 min;
s5, raising the temperature from 300 ℃ to 900 ℃ at the speed of 1-5 ℃/min, keeping the temperature constant for 20-40min, then raising the temperature to 1500 ℃ at the speed of 1-5 ℃/min, and keeping the temperature at 1500 ℃ of 1300 ℃ for reaction for 15-30min, thus obtaining the modified graphene/PAN carbon fiber.
6. The conductive composite PPS material of claim 1 wherein the polyphenylene sulfide is an amino-functionalized polyphenylene sulfide.
7. A method of producing a conductive composite PPS material according to any of claims 1 to 6 comprising the steps of:
(1) mixing 0.6-1.2 parts of polyphenylene sulfide and 8-12 parts of concentrated sulfuric acid by mass, stirring at the rotating speed of 80-120r/min for 1-3min, adding 0.5-1.2 parts of concentrated nitric acid, continuously stirring for 2-5min, heating to 60-70 ℃, reacting for 0.5-2h, centrifuging, washing and drying to obtain a semi-finished product;
(2) mixing 0.5-1 part of the semi-finished product and 15-30 parts of N, N-dimethylformamide according to parts by mass, stirring at the rotating speed of 80-120r/min for 1-3min, then adding 1-2 parts of sodium hydrosulfite, heating to 160-170 ℃ under the protection of nitrogen, carrying out reflux reaction for 3-4h, and carrying out centrifugation, washing and drying to obtain amino-functionalized polyphenylene sulfide;
(3) modified graphene/PAN carbon fiber or modified graphene/epoxy phenyl grafted/PAN carbon fiber and amino-functionalized polyphenylene sulfide are mixed according to the mass ratio of (15-30): (95-110), carrying out mechanical premixing, then carrying out melt blending through a double-screw extruder, and carrying out extrusion granulation to obtain the conductive composite PPS material.
8. The conductive composite PPS material of any of claims 1-6, used in environmental protection, aerospace, electronics and electrical, automobile and machinery industries.
9. A modified graphene/PAN carbon fiber is characterized by comprising the following steps:
s1, dispersing 0.2-0.6 part of modified graphene in 400 parts of dimethyl sulfoxide (200) by mass, carrying out ultrasonic treatment for 1-3h at the power of 300-360W and the frequency of 80-120kHz, then adding 90-100 parts of acrylonitrile, 0.1-0.5 part of azodiisobutyronitrile and 1-2 parts of acrylamide, and heating to 60-70 ℃ in a nitrogen atmosphere to react for 18-24h to obtain a modified graphene/acrylonitrile polymer solution;
s2, filtering the modified graphene/acrylonitrile polymer solution by using a 600-mesh filter membrane, and then performing vacuum defoaming on the filtered modified graphene/acrylonitrile polymer solution at the temperature of 40 ℃, the vacuum degree of-0.06 MPa and the time of 1h to obtain a spinning solution;
s3, heating the spinning solution to 65-75 ℃, extruding the spinning solution through a spinneret plate, and then putting the extruded spinning solution into a coagulating bath for coagulation forming, wherein the spinneret hole diameter of the spinneret plate is 0.06-0.1mm, the spinning speed is 2-3m/min, the drafting ratio is 4.5, and the coagulating bath temperature is 35-45 ℃, so that the modified graphene-polyacrylonitrile composite fiber is obtained, and the coagulating bath is one of a dimethyl sulfoxide aqueous solution with the concentration of 50-60 wt%, a dimethylformamide aqueous solution with the concentration of 50-60 wt% and a dimethylacetamide aqueous solution with the concentration of 50-60 wt%;
s4, pre-oxidizing the modified graphene-polyacrylonitrile composite fiber at the temperature of 200-300 ℃ for 60-90 min;
s5, raising the temperature from 300 ℃ to 900 ℃ at the speed of 1-5 ℃/min, keeping the temperature constant for 20-40min, then raising the temperature to 1500 ℃ at the speed of 1-5 ℃/min, and keeping the temperature at 1500 ℃ of 1300 ℃ for reaction for 15-30min, thus obtaining the modified graphene/PAN carbon fiber.
10. The modified graphene/epoxy phenyl grafted/PAN carbon fiber is characterized by being prepared by the following method:
s1, dissolving the modified graphene, acrylonitrile, azodiisobutyronitrile and methyl methacrylate in dimethyl sulfoxide for reaction to obtain a modified graphene/acrylonitrile polymer solution;
s2, filtering and defoaming the modified graphene/acrylonitrile polymer solution to obtain a spinning solution;
s3, extruding the polymer spinning solution through a spinneret plate, and then, allowing the extruded polymer spinning solution to enter a coagulating bath for coagulation forming to obtain modified graphene-polyacrylonitrile composite fibers;
s4, pre-oxidizing and carbonizing the modified graphene-polyacrylonitrile composite fiber to obtain a modified graphene/PAN carbon fiber;
s5, under the atmosphere of nitrogen, mixing and reacting 15 wt% of butyl lithium n-hexane solution, 3-bromophenyl ethylene oxide, PAN carbon fiber and toluene to obtain the modified graphene/epoxy phenyl grafted/PAN carbon fiber.
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