CN113621130A - Preparation method of high-quality spinning asphalt, product and application thereof - Google Patents
Preparation method of high-quality spinning asphalt, product and application thereof Download PDFInfo
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- CN113621130A CN113621130A CN202110879219.3A CN202110879219A CN113621130A CN 113621130 A CN113621130 A CN 113621130A CN 202110879219 A CN202110879219 A CN 202110879219A CN 113621130 A CN113621130 A CN 113621130A
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- methylnaphthalene
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- asphalt
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- 239000010426 asphalt Substances 0.000 title claims abstract description 38
- 238000009987 spinning Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 12
- 239000004917 carbon fiber Substances 0.000 claims abstract description 12
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000012298 atmosphere Substances 0.000 claims description 21
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 11
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- ARAHGQLNFAGCFZ-UHFFFAOYSA-N 2-bromo-1-(bromomethyl)naphthalene Chemical compound C1=CC=C2C(CBr)=C(Br)C=CC2=C1 ARAHGQLNFAGCFZ-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 21
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 84
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 239000000463 material Substances 0.000 description 40
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 239000000047 product Substances 0.000 description 26
- 238000001816 cooling Methods 0.000 description 23
- RZJGKPNCYQZFGR-UHFFFAOYSA-N 1-(bromomethyl)naphthalene Chemical compound C1=CC=C2C(CBr)=CC=CC2=C1 RZJGKPNCYQZFGR-UHFFFAOYSA-N 0.000 description 15
- 230000001681 protective effect Effects 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000011302 mesophase pitch Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- RUHJZSZTSCSTCC-UHFFFAOYSA-N 2-(bromomethyl)naphthalene Chemical compound C1=CC=CC2=CC(CBr)=CC=C21 RUHJZSZTSCSTCC-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000001307 helium Substances 0.000 description 9
- 229910052734 helium Inorganic materials 0.000 description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011295 pitch Substances 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000011294 coal tar pitch Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011301 petroleum pitch Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007256 debromination reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003562 lightweight material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3326—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkane-based
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/93—Applications in textiles, fabrics and yarns
Abstract
The invention discloses a preparation method of high-quality spinning asphalt, a product and application thereof, and belongs to the field of high-quality synthetic asphalt. The method comprises the following steps: under the protection of nitrogen atmosphere, adding a brominating agent, methylnaphthalene and a solvent in sequence, mixing, carrying out photocatalytic reaction at the temperature of 40-70 ℃, carrying out suction filtration, washing, carrying out reduced pressure distillation and drying to obtain brominated methylnaphthalene; under the protection of nitrogen atmosphere, the obtained brominated methylnaphthalene is subjected to heat treatment for 6-12h at the temperature of 200-350 ℃, then the brominated methylnaphthalene is compensated, and then the heat treatment is carried out for 3-6h under the same conditions, and extraction is carried out, so that the high-quality spinning asphalt is obtained. Compared with the prior art, the raw materials for preparing the pitch precursor are cheap and easy to obtain, the conditions are mild, the product is single, the pitch prepared by the precursor has the advantages of excellent spinnability, narrow molecular weight distribution, good melt fluidity and the like, and the preparation of the pitch-based carbon fiber with high performance is facilitated.
Description
Technical Field
The invention relates to the technical field of high-quality synthetic asphalt, in particular to a preparation method of high-quality spinning asphalt, and a product and application thereof.
Background
In recent years, the increasing production and retention of automobiles has intensified the problems of energy, environment, safety, and the like. Energy conservation and environmental protection are the primary problems facing the global automobile industry. Under the current situation, sustainable development of the automobile industry is realized, and new energy-saving and emission-reduction technologies must be developed to reduce energy consumption of automobiles and generated environmental pollution. Research shows that the light weight of the automobile is one of the most effective measures for reducing energy consumption and emission. The light weight of the automobile can be realized by light weight materials, light weight structures and light weight manufacturing technologies. Among numerous lightweight materials, the carbon fiber composite material has excellent mechanical properties, and has high specific strength, specific modulus and specific energy absorption, and under the design principle of equal rigidity or equal strength, the carbon fiber composite material structure reduces weight by more than 50% compared with a low-carbon steel structure, and reduces weight by 30% compared with a magnesium/aluminum alloy structure. However, the high cost of carbon fibers and the complex manufacturing process greatly limit the application of carbon fiber composites to automobiles. Therefore, it is urgent to reduce the cost of carbon fiber.
The preparation of the carbon fiber mainly comprises the technological processes of precursor synthesis and spinning, fiber oxidation stabilization, carbonization, surface treatment and the like. In all the processes, the synthesis production cost of the precursor is the highest, and accounts for more than 50% of the total cost of the carbon fiber. Therefore, to achieve low cost production of carbon fibers, the development of inexpensive, alternative raw materials and precursors is considered to be one of the most effective approaches. Asphalt is an important raw material for producing carbon fibers, is rich in source and low in price, and is a main byproduct in the petrochemical industry and the coal chemical industry.
The mesophase pitch is a nematic liquid crystal substance formed by disc-shaped or rod-shaped molecules generated in the heat treatment process of heavy aromatic hydrocarbon substances, and the raw materials of the mesophase pitch can be pure aromatic hydrocarbon substances, coal tar pitch and petroleum pitch. The high-quality mesophase pitch has excellent performance and processability, and the carbon fiber prepared by the high-quality mesophase pitch is widely applied to the advanced fields of aerospace, military and national defense, nuclear industry and the like.
The main routes for preparing mesophase pitches at present are:
1) taking coal tar pitch as a raw material: the coal tar has high aromaticity and complex components, and mainly comprises polycyclic aromatic hydrocarbon, alkylated polycyclic aromatic hydrocarbon and partially hydrogenated polycyclic aromatic hydrocarbon. The direct thermal polycondensation reaction of the coal pitch is violent, the viscosity of the system can be sharply increased, the growth and fusion of mesophase globules are seriously influenced, a mosaic mesophase is generally formed, and a wide-area fused body with developed anisotropy is difficult to obtain, so that the pretreatment of the raw material pitch is required, and the method comprises hydrogenation, raw material purification and addition of a co-carbonization substance. The research on the conditions for mesophase formation in the thermal conversion process, which was carried out using purified coal-tar pitch as a raw material, revealed that polycondensation was carried out at 420 ℃ for 5 hours to obtain a streamlined mesophase pitch having a yield of 79.1% and a softening point of 312 ℃, and that high-quality, wide-area spinnable mesophase pitch (huashuin, zhanbo, songhe, oudong, judao red) having a softening point of 305 ℃ and a yield of 81.4% was obtained by reaction at a relatively low temperature (400 ℃) for 10 hours (study on the preparation of coal pitch-based mesophase pitch [ J ] carbon technology, 2009,28(06): 6-10.).
2) Petroleum asphalt is used as a raw material: petroleum asphalt is the residue obtained by fractional distillation of natural crude oil. The molecular structure contains a large amount of alkyl substituents and a partially hydrogenated aromatic hydrocarbon structure, so the aromaticity of the molecular structure is generally lower than that of coal tar pitch. Compared with coal tar pitch, the petroleum pitch has wider molecular weight distribution, higher average molecular weight and less heterocyclic ring components. Park et al prepared a high-solubility, low-softening-point, 100% anisotropic mesophase pitch from petroleum pitch at 450 ℃ under reduced pressure for 3 hours, with 55% quinoline soluble, and better solubility than that obtained by the atmospheric bubbling method (Yang Duk Park, Yozo Korai, Isao Mochida. preparation of anaerobic slurry polymerization by carbon synthesis in open vacuum [ J ]. Journal of Materials Science,1986,21 (2)).
3) Taking a model aromatic compound as a raw material: compared with coal tar pitch and petroleum pitch, the aromatic compound model has the advantages of good aromaticity, single component, no ash content, simple preparation process and the like, and is the best raw material for preparing mesophase pitch. The Song Huaihe and so on use durene as raw materials, firstly obtain low molecular oligomers through formaldehyde/p-toluenesulfonic acid cross-linking reaction, then prepare the intermediate phase asphalt with abundant side chains and low softening point (260 ℃) with molecular structure showing attuned condensation configuration through further heat treatment (research on the non-melting behavior of the intermediate phase asphalt fiber of the Song Huaihe, Liulang, Zhang river Du-durene group [ J ] novel carbon material, 1999(01): 16-21.).
From the above analysis, the methods for preparing mesophase pitch in the prior art have the problems of high raw material cost, severe reaction conditions, low yield, low product purity and the like, so that the prepared pitch has poor spinning performance and cannot achieve good effect in specific application. Therefore, how to prepare a high-quality mesophase pitch with excellent performance is a technical problem that researchers in the field need to solve urgently.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of high-quality spinning asphalt, a product and application thereof, and solves the problem of preparing high-quality mesophase asphalt at low cost in a simple and safe manner.
In order to achieve the technical purpose, the invention provides the following technical scheme:
a preparation method of high-quality spinning asphalt comprises the following steps:
the method comprises the following steps: under the protection of inert gas atmosphere, adding a brominating agent, methylnaphthalene and a solvent in sequence (the adding amount of the solvent at least ensures that 30% of the brominating agent can be dissolved), mixing, carrying out photocatalytic reaction at the temperature of 50-90 ℃, carrying out suction filtration, washing, carrying out reduced pressure distillation, and drying to obtain monobromo bromomethylnaphthalene;
step two: under the protection of inert gas atmosphere, the obtained monobromo bromomethylnaphthalene is subjected to heat treatment for 6-12h under the condition of 200-350 ℃, then the monobromo bromomethylnaphthalene is compensated, and then the heat treatment is carried out for 3-6h under the same condition for extraction, so that the high-quality spinning asphalt is obtained.
Further, the inert gas includes one of argon, nitrogen and helium, preferably nitrogen.
Further, the photocatalysis device is a xenon lamp.
Further, the brominating agent is one of N-bromosuccinimide (NBS), liquid bromine and boron tribromide.
Further, the methylnaphthalene is one of 1-methylnaphthalene, 2-methylnaphthalene and industrial methylnaphthalene.
Further, the solvent is one of N-heptane, benzene, toluene, chloroform, carbon tetrachloride and N, N-dimethylformamide.
Further, the molar ratio of the brominating agent to the methylnaphthalene is 1: (0.1-3).
The molar ratio of the methylnaphthalene to the NBS is (0.5-1): 1.
the molar ratio of the methylnaphthalene to the liquid bromine is (1-2): 1.
the molar ratio of the methylnaphthalene to the boron tribromide is (1.5-3): 1.
further, the flow rate of the inert gas is 50-100 mL/min.
Further, the mass of the offset brominated methylnaphthalene is 10-50% of the mass of the initially brominated methylnaphthalene.
Further, the solvent used for extraction is n-hexane or cyclohexane.
The heat treatment is carried out in a corrosion-resistant apparatus with a stirring device.
The invention also provides high-quality spinning asphalt.
The invention also provides application of the high-quality spinning asphalt in carbon fibers.
Compared with the prior art, the invention has the beneficial effects that:
in order to realize high added value utilization of methylnaphthalene, the invention takes methylnaphthalene as a raw material, performs a photocatalytic reaction under mild conditions, controls the flow of protective gas, and prevents air from entering to generate a polybrominated product, thereby obtaining high-purity monobromomethylnaphthalene and developing a new path for application of methylnaphthalene. The obtained brominated methylnaphthalene is subjected to debromination polymerization after heat treatment, the debrominated molecules are in a linear structure, and then compensation polymerization of the brominated methylnaphthalene is carried out to accelerate the growth of molecular chains and obtain a linear molecular structure product with higher polymerization degree, so that spinning of mesophase pitch is facilitated.
The brominating agent is used in the invention, and compared with a fluorinating agent and a chlorinating agent, the reaction activity is higher.
The invention has the following advantages:
(1) according to the invention, more than 90% of the brominated products of the methylnaphthalene are methyl monobrominated products by adjusting the addition amount of the brominating agent.
(2) The first step of the method adopts photocatalysis, and has the advantages of low cost, no pollution and mild reaction conditions.
(3) The reaction kettle is a conventional reaction kettle and is made of special materials.
(4) The reaction of the invention is normal pressure reaction, and the safety coefficient is high.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
300mL of toluene, 14.38g of liquid bromine and 21.33g of 1-methylnaphthalene (the molar ratio of 1-methylnaphthalene to brominating agent is 1.7: 1) are sequentially added into a 500mL three-neck flask, nitrogen is introduced into a reaction system as soon as possible after the addition is finished as a protective atmosphere, the nitrogen flow is 50mL/min, and reactants are placed in a constant-temperature water bath kettle at 50 ℃ to be preheated and are magnetically stirred to ensure that the reaction materials are uniformly mixed. When the temperature of the reaction materials rises to 50 ℃, the magnetic stirring state is continuously maintained, and a xenon lamp (300w) is turned on to carry out the photocatalytic reaction for 6 hours. And after the reaction is finished, carrying out suction filtration, washing, reduced pressure distillation and drying on the product to obtain the 1-bromomethylnaphthalene. The GC-MS is adopted to determine the yield and the selectivity of the 1-bromomethylnaphthalene, and the result shows that the yield of the 1-bromomethylnaphthalene can reach 94 percent, and the selectivity can reach 98 percent.
200g of prepared 1-bromomethylnaphthalene is put into a reaction kettle, nitrogen is introduced into the reaction system as soon as possible after the charging is finished as protective atmosphere, the nitrogen flow is 50mL/min, reacting for 6 hours at the reaction temperature of 270 ℃ under the nitrogen atmosphere, then compensating 50g (the compensation amount is 25 percent of the raw material) of the prepared 1-bromomethylnaphthalene in the reaction system, continuing to react for 3 hours at the reaction temperature of 270 ℃ under the nitrogen atmosphere, cooling the materials by adopting a natural cooling mode after the reaction is finished, keeping the nitrogen atmosphere in the material cooling process, and cooling the materials to room temperature, stopping nitrogen protection, extracting the product by using 200mL of normal hexane each time for 3 times, the method is used for removing small molecular substances to obtain high-quality spinning asphalt, the softening point of the spinning asphalt is 225 ℃, the residual carbon rate is 67 percent, and the spinning asphalt has the property of being completely soluble in toluene.
Example 2
300mL of benzene, 14.38g of liquid bromine and 21.33g of 1-methylnaphthalene (the molar ratio of 1-methylnaphthalene to brominating agent is 1.7: 1) are sequentially added into a 500mL three-neck flask, nitrogen is introduced into a reaction system as soon as possible after the addition is finished as a protective atmosphere, the nitrogen flow is 50mL/min, and reactants are placed in a constant-temperature water bath kettle at 50 ℃ to be preheated and are magnetically stirred to ensure that the reaction materials are uniformly mixed. When the temperature of the reaction materials rises to 50 ℃, the magnetic stirring state is continuously maintained, and a xenon lamp (300w) is turned on to carry out the photocatalytic reaction for 5 hours. And after the reaction is finished, carrying out suction filtration, washing, reduced pressure distillation and drying on the product to obtain the 1-bromomethylnaphthalene. The GC-MS is adopted to determine the yield and the selectivity of the 1-bromomethylnaphthalene, and the result shows that the yield of the 1-bromomethylnaphthalene can reach 96 percent, and the selectivity can reach 99 percent.
200g of prepared 1-bromomethylnaphthalene is put into a reaction kettle, nitrogen is introduced into the reaction system as soon as possible after the charging is finished as protective atmosphere, the nitrogen flow is 50mL/min, reacting for 9 hours at the reaction temperature of 270 ℃ under the nitrogen atmosphere, then compensating 50g (the compensation amount is 25 percent of the raw material) of the prepared 1-bromomethylnaphthalene in the reaction system, continuing to react for 3 hours at the reaction temperature of 270 ℃ under the nitrogen atmosphere, cooling the materials by adopting a natural cooling mode after the reaction is finished, keeping the nitrogen atmosphere in the material cooling process, and after the temperature of the materials is reduced to the room temperature, stopping nitrogen protection, extracting the product by using 200mL of normal hexane each time for 3 times, used for removing small molecular substances to obtain high-quality spinning asphalt, the softening point of which is 228 ℃, the residual carbon rate of which is 68 percent and the property of being soluble in toluene.
Example 3
300mL of carbon tetrachloride, 12.53g of boron tribromide and 21.33g of 2-methylnaphthalene (the molar ratio of the 2-methylnaphthalene to the brominating agent is 3: 1) are sequentially added into a 500mL three-neck flask, nitrogen is introduced into a reaction system as soon as possible as a protective atmosphere after the addition is finished, the nitrogen flow is 75mL/min, and reactants are placed in a constant-temperature water bath kettle at 60 ℃ to be preheated and are magnetically stirred to ensure that the reaction materials are uniformly mixed. When the temperature of the reaction materials rises to 60 ℃, the magnetic stirring state is continuously maintained, and a xenon lamp (300w) is turned on to carry out the photocatalytic reaction for 4 hours. And after the reaction is finished, carrying out suction filtration, washing, reduced pressure distillation and drying on the product to obtain the 2-bromomethylnaphthalene. The GC-MS is adopted to determine the yield and the selectivity of the 2-bromomethylnaphthalene, and the result shows that the yield of the 2-bromomethylnaphthalene can reach 94 percent, and the selectivity reaches 98 percent.
200g of prepared 2-bromomethylnaphthalene is put into a reaction kettle, nitrogen is introduced into the reaction system as soon as possible after the charging is finished as protective atmosphere, the nitrogen flow is 75mL/min, reacting for 12 hours at the reaction temperature of 270 ℃ under the nitrogen atmosphere, then compensating 20g (the compensation amount is 10 percent of the raw material) of the prepared 2-bromomethylnaphthalene in the reaction system, continuing to react for 3 hours at the reaction temperature of 270 ℃ under the nitrogen atmosphere, cooling the materials by adopting a natural cooling mode after the reaction is finished, keeping the nitrogen atmosphere in the material cooling process, and after the temperature of the materials is reduced to the room temperature, stopping nitrogen protection, extracting the product by using 200mL of normal hexane each time for 3 times, the method is used for removing small molecular substances to obtain high-quality spinning asphalt, the softening point of the spinning asphalt is 236 ℃, the carbon residue rate is 65 percent, and the spinning asphalt has the property of being completely soluble in toluene.
Example 4
300mL of n-heptane, 18.79g of boron tribromide and 21.33g of 2-methylnaphthalene (the molar ratio of the 2-methylnaphthalene to the brominating agent is 2: 1) are sequentially added into a 500mL three-neck flask, nitrogen is introduced into a reaction system as soon as possible as a protective atmosphere after the addition is finished, the nitrogen flow is 75mL/min, and reactants are placed into a constant-temperature water bath kettle at 70 ℃ to be preheated and are magnetically stirred to ensure that the reaction materials are uniformly mixed. When the temperature of the reaction materials rises to 70 ℃, the magnetic stirring state is continuously maintained, and a xenon lamp (300w) is turned on to carry out the photocatalytic reaction for 3 hours. And after the reaction is finished, carrying out suction filtration, washing, reduced pressure distillation and drying on the product to obtain the 2-bromomethylnaphthalene. The GC-MS is adopted to determine the yield and the selectivity of the 2-bromomethylnaphthalene, and the result shows that the yield of the 2-bromomethylnaphthalene can reach 95 percent, and the selectivity can reach 98 percent.
200g of prepared 2-bromomethylnaphthalene is put into a reaction kettle, nitrogen is introduced into the reaction system as soon as possible after the charging is finished as protective atmosphere, the nitrogen flow is 75mL/min, reacting for 9 hours at the reaction temperature of 200 ℃ under the nitrogen atmosphere, then compensating 20g (the compensation amount is 10 percent of the raw material) of the prepared 2-bromomethylnaphthalene in the reaction system, continuing to react for 3 hours at the reaction temperature of 200 ℃ under the nitrogen atmosphere, cooling the materials by adopting a natural cooling mode after the reaction is finished, keeping the nitrogen atmosphere in the material cooling process, and after the temperature of the materials is reduced to the room temperature, stopping nitrogen protection, extracting the product by using 200mL of cyclohexane each time for 3 times, the method is used for removing small molecular substances to obtain high-quality spinning asphalt, the softening point of which is 186 ℃, the residual carbon rate of which is 61 percent, and the high-quality spinning asphalt has the property of being completely soluble in toluene.
Example 5
300mL of chloroform, 26.70g of NBS and 21.33g of industrial methylnaphthalene (the molar ratio of the industrial methylnaphthalene to the brominating agent is 1: 1) are sequentially added into a 500mL three-neck flask, helium is introduced into a reaction system as soon as possible after the addition is finished as a protective atmosphere, the flow rate of the helium is 100mL/min, and reactants are placed in a constant-temperature water bath kettle at 60 ℃ to be preheated and are magnetically stirred to ensure that the reaction materials are uniformly mixed. When the temperature of the reaction materials rises to 60 ℃, the magnetic stirring state is continuously maintained, and a xenon lamp (300w) is turned on to carry out the photocatalytic reaction for 2 hours. And after the reaction is finished, carrying out suction filtration, washing, reduced pressure distillation and drying on the product to obtain the monobromo industrial methylnaphthalene. The yield and the selectivity of the monobromo industrial methylnaphthalene are determined by GC-MS, and the result shows that the yield of the monobromo industrial methylnaphthalene can reach 95 percent, and the selectivity is as high as 98 percent.
200g of prepared monobromo industrial methylnaphthalene is put into a reaction kettle, helium is introduced into the reaction system as soon as possible as protective atmosphere after the feeding is finished, the flow rate of the helium is 100mL/min, reacting for 9h under the conditions that the reaction temperature is 300 ℃ and the helium atmosphere, then compensating 60g (the compensation amount is 30 percent of the raw material%) of the prepared monobrominated industrial methylnaphthalene in the reaction system, continuing to react for 6h under the conditions that the reaction temperature is 300 ℃ and the helium atmosphere, cooling the materials by adopting a natural cooling mode after the reaction is finished, keeping the helium atmosphere in the materials during the cooling process, cooling the materials to room temperature, stopping helium protection, extracting the product by using 200mL of cyclohexane each time for 3 times, the method is used for removing small molecular substances to obtain high-quality spinning asphalt, the softening point of which is 256 ℃, the residual carbon rate of which is 69 percent and the high-quality spinning asphalt has the property of being completely soluble in toluene.
Example 6
300mLN, N-dimethylformamide, 53.40g NBS and 21.33g industrial methylnaphthalene (the molar ratio of the industrial methylnaphthalene to the brominating agent is 0.5: 1) are sequentially added into a 500mL three-neck flask, nitrogen is introduced into a reaction system as a protective atmosphere as soon as possible after the addition is finished, the nitrogen flow is 100mL/min, and reactants are placed in a constant-temperature water bath kettle at the temperature of 40 ℃ to be preheated and are magnetically stirred to ensure that the reaction materials are uniformly mixed. When the temperature of the reaction materials rises to 40 ℃, the magnetic stirring state is continuously maintained, and a xenon lamp (300w) is turned on to carry out the photocatalytic reaction for 1 h. And after the reaction is finished, carrying out suction filtration, washing, reduced pressure distillation and drying on the product to obtain the monobromo industrial methylnaphthalene. The yield and the selectivity of the monobromo industrial methylnaphthalene are determined by GC-MS, and the result shows that the yield of the monobromo industrial methylnaphthalene can reach 97 percent, and the selectivity reaches 98 percent.
200g of prepared monobromo industrial methylnaphthalene is put into a reaction kettle, nitrogen is introduced into the reaction system as soon as possible after the charging is finished as protective atmosphere, the nitrogen flow is 100mL/min, reacting for 9 hours at the reaction temperature of 350 ℃ under the nitrogen atmosphere, then compensating 80g (the compensation amount is 40 percent of the raw material%) of the prepared monobrominated industrial methylnaphthalene in the reaction system, continuing to react for 3 hours at the reaction temperature of 350 ℃ under the nitrogen atmosphere, cooling the materials by adopting a natural cooling mode after the reaction is finished, keeping the nitrogen atmosphere in the material cooling process, and after the temperature of the materials is reduced to the room temperature, stopping nitrogen protection, extracting the product by using 200mL of cyclohexane each time for 3 times, the method is used for removing small molecular substances to obtain high-quality spinning asphalt, the softening point of the spinning asphalt is 287 ℃, the carbon residue rate is 72 percent, and the spinning asphalt has the property of being completely soluble in toluene.
Example 7
300mLN, N-dimethylformamide, 35.60g NBS and 21.33g industrial methylnaphthalene (the molar ratio of the industrial methylnaphthalene to the brominating agent is 0.75: 1) are sequentially added into a 500mL three-neck flask, argon is introduced into a reaction system as a protective atmosphere as soon as possible after the addition is finished, the flow of the argon is 100mL/min, and reactants are placed into a constant-temperature water bath kettle at 70 ℃ to be preheated and are magnetically stirred to ensure that the reaction materials are uniformly mixed. When the temperature of the reaction materials rises to 70 ℃, the magnetic stirring state is continuously maintained, and a xenon lamp (300w) is turned on to carry out the photocatalytic reaction for 1 h. And after the reaction is finished, carrying out suction filtration, washing, reduced pressure distillation and drying on the product to obtain the monobromo industrial methylnaphthalene. The yield and the selectivity of the monobromo industrial methylnaphthalene are determined by GC-MS, and the result shows that the yield of the monobromo industrial methylnaphthalene can reach 98 percent, and the selectivity is as high as 99 percent.
200g of prepared monobromo industrial methylnaphthalene is put into a reaction kettle, argon is introduced into the reaction system as soon as possible as protective atmosphere after the feeding is finished, the flow of the argon is 100mL/min, reacting for 9 hours at the reaction temperature of 310 ℃ in an argon atmosphere, then compensating 100g (the compensation amount is 50 percent of the raw material) of the prepared monobrominated industrial methylnaphthalene in a reaction system, continuing to react for 3 hours at the reaction temperature of 310 ℃ in the argon atmosphere, cooling the materials by adopting a natural cooling mode after the reaction is finished, keeping the argon atmosphere in the material cooling process, and after the temperature of the materials is reduced to the room temperature, stopping argon protection, extracting the product by using 200mL of cyclohexane each time for 3 times, the method is used for removing small molecular substances to obtain high-quality spinning asphalt, the softening point of which is 262 ℃, the residual carbon rate of which is 70 percent and the property of toluene being totally soluble.
Comparative example 1
The difference from example 1 is that no photocatalysis was carried out.
As a result, it was found that 1-bromomethylnaphthalene could not be obtained.
Comparative example 2
The difference from example 1 is that the photocatalytic temperature is 20 ℃.
As a result, it was found that the yield of 1-bromomethylnaphthalene was low, only 45.6%.
Comparative example 3
The difference from example 2 is that 5% of 1-bromomethylnaphthalene is compensated.
As a result, it was found that the obtained pitch had a softening point of 172 ℃ and a residual carbon content of 48%, indicating that the amount of the 1-bromomethylnaphthalene was insufficient for compensation, the molecular weight of the resulting product was low, the softening point and the residual carbon content were low, and the pitch thus obtained was not suitable for spinning.
Comparative example 4
The difference from example 4 is that 60% of the brominated 1-methylnaphthalene is compensated.
As a result, it was found that the molecular weight of the resulting product was low, the softening point and the carbon residue were low, and the pitch produced was not suitable for spinning.
Comparative example 5
The difference from example 6 is that the nitrogen flow rate was 40 mL/min.
As a result, it was found that the gas product generated by the reaction could not be discharged from the reaction system in time due to the small gas flow, and the polymerization degree of the asphalt was reduced, which affected the quality of the asphalt.
Comparative example 6
The difference from example 6 is that the reaction temperature is 400 ℃.
As a result, it was found that the reaction temperature was too high, resulting in partial coking of the resulting pitch and failure to successfully spin.
Comparative example 7
The same as example 6, except that the molar ratio of the industrial methylnaphthalene to the brominating agent was 0.25: 1.
as a result, the product contains a large amount of polybrominated industrial methylnaphthalene which can not form linear molecules in the debromination polymerization process, thereby influencing the quality of asphalt.
Comparative example 8
The difference from example 7 is that the reaction time was 13 hours under nitrogen atmosphere.
As a result, it was found that the resulting pitch was partially coked and could not be successfully spun.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the high-quality spinning asphalt is characterized by comprising the following steps of:
the method comprises the following steps: under the protection of inert gas atmosphere, adding a brominating agent, methylnaphthalene and a solvent in sequence, mixing, carrying out photocatalytic reaction at the temperature of 40-70 ℃, carrying out suction filtration, washing, carrying out reduced pressure distillation, and drying to obtain monobromo bromomethylnaphthalene;
step two: under the protection of inert gas atmosphere, the obtained monobromo bromomethylnaphthalene is subjected to heat treatment for 6-12h under the condition of 200-350 ℃, then the monobromo bromomethylnaphthalene is compensated, and then the heat treatment is carried out for 3-6h under the same condition for extraction, so that the high-quality spinning asphalt is obtained.
2. The method of claim 1, wherein the brominating agent is one of N-bromosuccinimide, liquid bromine, and boron tribromide.
3. The method of claim 1, wherein the methylnaphthalene is one of 1-methylnaphthalene, 2-methylnaphthalene, and industrial methylnaphthalene.
4. The method of claim 1, wherein the solvent is one of N-heptane, benzene, toluene, chloroform, carbon tetrachloride, and N, N-dimethylformamide.
5. The method according to claim 1, wherein the molar ratio of the brominating agent to the methylnaphthalene is 1: (0.1-3).
6. The method of claim 1, wherein the inert gas flow rate is 50-100 mL/min.
7. The method of claim 1, wherein the mass of the offset brominated methylnaphthalenes is 10-50% of the mass of the initial brominated methylnaphthalene.
8. The method of claim 1, wherein the solvent used for the extraction is n-hexane or cyclohexane.
9. A high quality spinning pitch produced according to the production method of any one of claims 1 to 8.
10. Use of the high quality spinning pitch according to claim 9 in carbon fibers.
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Cited By (4)
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| CN114481369A (en) * | 2022-02-16 | 2022-05-13 | 浙江大学 | Preparation method of graphene fiber with high graphite crystallinity |
| CN115197732A (en) * | 2022-06-07 | 2022-10-18 | 中国矿业大学(北京) | Preparation method of high-quality synthetic spinnable asphalt and carbon fiber |
| CN115353903A (en) * | 2022-09-22 | 2022-11-18 | 武汉科技大学 | Method for preparing spinnable asphalt with high softening point by coal asphalt halogenation dehalogenation, product and application thereof |
| CN115466626A (en) * | 2022-09-21 | 2022-12-13 | 武汉科技大学 | Preparation method of high-quality isotropic asphalt |
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| CN114481369A (en) * | 2022-02-16 | 2022-05-13 | 浙江大学 | Preparation method of graphene fiber with high graphite crystallinity |
| CN114481369B (en) * | 2022-02-16 | 2022-12-06 | 浙江大学 | Preparation method of graphene fiber with high graphite crystallinity |
| CN115197732A (en) * | 2022-06-07 | 2022-10-18 | 中国矿业大学(北京) | Preparation method of high-quality synthetic spinnable asphalt and carbon fiber |
| CN115197732B (en) * | 2022-06-07 | 2023-12-22 | 中国矿业大学(北京) | Preparation method of high-quality synthetic spinnable asphalt and carbon fiber |
| CN115466626A (en) * | 2022-09-21 | 2022-12-13 | 武汉科技大学 | Preparation method of high-quality isotropic asphalt |
| CN115466626B (en) * | 2022-09-21 | 2024-01-12 | 武汉科技大学 | Preparation method of high-quality isotropic asphalt |
| CN115353903A (en) * | 2022-09-22 | 2022-11-18 | 武汉科技大学 | Method for preparing spinnable asphalt with high softening point by coal asphalt halogenation dehalogenation, product and application thereof |
| CN115353903B (en) * | 2022-09-22 | 2023-10-20 | 武汉科技大学 | Method for preparing high softening point spinnable asphalt by halogenating and dehalogenating coal asphalt, product and application thereof |
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