CN109610049B - Method for regulating and controlling composition and structure of mesophase pitch through co-thermal polymerization - Google Patents
Method for regulating and controlling composition and structure of mesophase pitch through co-thermal polymerization Download PDFInfo
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- CN109610049B CN109610049B CN201811548944.7A CN201811548944A CN109610049B CN 109610049 B CN109610049 B CN 109610049B CN 201811548944 A CN201811548944 A CN 201811548944A CN 109610049 B CN109610049 B CN 109610049B
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- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 90
- 238000012719 thermal polymerization Methods 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 17
- 230000001276 controlling effect Effects 0.000 title claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 38
- 239000004917 carbon fiber Substances 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 238000002074 melt spinning Methods 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 239000010426 asphalt Substances 0.000 claims description 54
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000000295 fuel oil Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000011295 pitch Substances 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000011317 mixed pitch Substances 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011300 coal pitch Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
Classifications
-
- 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
- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
-
- 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
- D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Working-Up Tar And Pitch (AREA)
- Inorganic Fibers (AREA)
Abstract
本发明涉及一种共热聚反应调控中间相沥青组成和结构的方法，包括以下步骤：1)向高芳香度稠环沥青中加入含支链芳烃活性组分，使沥青原料热态混合均匀；2)将混合均匀的沥青原料在密闭容器内自升压进行共热聚反应；3)将共热聚反应得到的中间相沥青进行熔融纺丝、氧化不熔化和高温炭化处理得到中间相沥青基炭纤维。通过中间相沥青原料组成和结构的调控实现降低中间相沥青基炭纤维劈裂程度的目的，从而改善或提高炭纤维的结构和性能。The invention relates to a method for regulating the composition and structure of mesophase pitch by co-thermal polymerization, comprising the following steps: 1) adding active components containing branched aromatic hydrocarbons to the high aromatic condensed-ring pitch, so that the pitch raw materials are uniformly mixed in a hot state; 2) self-boosting the uniformly mixed pitch raw material in a closed container to carry out co-thermal polymerization reaction; 3) subjecting the mesophase pitch obtained by co-thermal polymerization to melt spinning, oxidation infusibilization and high temperature carbonization to obtain mesophase pitch base carbon fiber. The purpose of reducing the splitting degree of mesophase pitch-based carbon fibers is achieved by regulating the composition and structure of the mesophase pitch raw materials, thereby improving or improving the structure and properties of carbon fibers.
Description
Technical Field
The invention belongs to the technical field of mesophase pitch-based carbon fibers, and particularly relates to a method for regulating and controlling the composition and structure of mesophase pitch through a co-thermal polymerization reaction.
Background
The mesophase pitch is a condensed ring aromatic hydrocarbon aggregate with regular and ordered molecular arrangement, has the advantages of high carbon yield, melt-regulated orientation, easy graphitization and the like, and is a high-quality precursor raw material for preparing high-performance and multifunctional carbon materials. A spinnable mesophase pitch feedstock for use as high performance mesophase pitch-based carbon fibers, the essential requirements of which are: the content of hetero atoms and ash is low, the molecular size is moderate, the molecular weight distribution is narrow, the molecular structure composition is uniform, the aromaticity is high, the condensation degree is low, the intermediate phase asphalt melt is rich in alkyl short chains and naphthenic groups and the like, and particularly has proper viscosity, fluidity and thermal stability in the melt spinning process. Usually, mesophase pitch (such as coal pitch-based mesophase pitch) prepared by thermal polymerization at 400-450 ℃ for a long time (5-10H) has a regular condensed ring molecular composition and an ideal preferred orientation texture (namely high-content optical anisotropy), but the pitch with high mesophase content usually has the defects of higher condensation degree, fewer alkyl side chains or branched chains, lower H/C ratio and the like, so that the problems of higher melt spinning temperature, difficult oxidation and stabilization of the spun pitch fiber and the like are caused, and the pitch with high mesophase content is easy to form mesophase pitch-based carbon fiber with a radial cross-section structure.
The section structure of the intermediate phase pitch-based carbon fiber prepared by taking the intermediate phase pitch as a raw material at present presents various textures (disordered structure, radial structure, folded radial structure, concentric circle structure and the like). The fiber with the radial and radial structure has higher molecular orientation degree, perfect crystal growth and development after graphitization treatment and larger crystallite dimension, thereby having excellent axial electric conduction and heat conduction performance, but the wedge-shaped splitting is caused by the stress concentration generated at the circle center because the growth and the orientation direction of the graphite crystallite are inconsistent in the high-temperature heat treatment process, and the fiber structure damage and the performance reduction can not be avoided due to the splitting. The existing research at home and abroad changes the section texture of the mesophase pitch-based carbon fiber by blending the mesophase pitch raw material composition or carrying out macromolecule doping modification on the mesophase pitch raw material (such as blending with a certain amount of isotropic pitch or polyacrylonitrile or polyimide or doping with a second-phase carbon filler, such as a carbon nano-tube, carbon black, graphene and the like), reduces the splitting degree of the mesophase pitch-based carbon fiber or avoids forming a radial structure, thereby regulating or improving the performance of the mesophase pitch-based carbon fiber.
Therefore, it is a research focus in the art how to adjust the structure and properties of the mesophase pitch raw material in order to control the degree of splitting of the mesophase pitch-based carbon fibers. The high-aromaticity condensed ring asphalt modified by the active component containing branched-chain aromatic hydrocarbon is adopted, and the composition and the structure of a mesophase asphalt raw material are regulated and controlled through a co-thermal polymerization reaction, so that the purpose of improving or enhancing the structure and the performance of the mesophase asphalt-based carbon fiber is achieved.
Disclosure of Invention
Aiming at the problems, the invention adopts the active component containing the branched-chain aromatic hydrocarbon to modify the condensed ring asphalt, the formation and the conversion of the asphalt mesophase liquid crystal are accelerated by the co-thermal polymerization reaction, and the composition and the structure of the mesophase asphalt are regulated and controlled. Meanwhile, the aim of reducing the splitting degree of the mesophase pitch-based carbon fibers is fulfilled by regulating and controlling the composition and the structure of the mesophase pitch raw materials, so that the structure and the performance of the mesophase pitch-based carbon fibers are improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for regulating and controlling the composition and structure of mesophase pitch by a co-thermal polymerization reaction comprises the following steps:
1) adding an active component containing branched-chain aromatic hydrocarbon into the high-aromaticity condensed ring asphalt to uniformly mix asphalt raw materials in a hot state;
2) self-boosting the uniformly mixed asphalt raw material in a closed container to carry out co-heating polymerization reaction;
3) and carrying out melt spinning, oxidation non-melting and high-temperature carbonization treatment on the mesophase pitch obtained by the co-thermal polymerization reaction to obtain the mesophase pitch-based carbon fiber.
The pressure of the asphalt raw material is automatically increased in the closed container to form volatile components, the volatile components are changed into gas in the closed container, so that the pressure in the closed container is automatically increased, and the pressure is uncertain due to different raw material components.
Wherein the high-aromaticity condensed ring asphalt is any one of naphthalene asphalt, anthracene asphalt and coal asphalt.
The branched-chain aromatic hydrocarbon-containing active component is a cyclohexane soluble component in petroleum asphalt or heavy oil, and the adding amount of the branched-chain aromatic hydrocarbon-containing active component is 4-15 wt% of high-aromaticity fused ring asphalt. Wherein the cyclohexane-soluble component in the petroleum asphalt or the heavy oil means a component from which cyclohexane has been removed, which is a product well known to those skilled in the art.
Wherein the thermal state mixing process conditions are as follows: in nitrogen atmosphere, the softening temperature of the high-aromaticity condensed ring asphalt is 80 ℃ higher, and the mixture is stirred for 2 hours at the speed of 500 r/min.
Wherein the co-thermal polymerization reaction conditions are as follows: stirring at the temperature of 386-432 ℃ at the speed of 550-1180 r/min for 3-6 h.
Wherein the melt spinning, oxidation non-melting and high-temperature carbonization treatment conditions are respectively as follows: melt spinning at 60 ℃ higher than the softening temperature of the mesophase pitch, oxidation non-melting at 20 ℃ lower than the softening temperature of the mesophase pitch, and carbonization at 1000 ℃ in nitrogen atmosphere. The melt spinning, oxidative infusions and high temperature charring are all carried out by means well known to those skilled in the art.
In addition, the invention also provides the mesophase pitch-based carbon fiber obtained by using the method for regulating and controlling the composition and the structure of the mesophase pitch through the co-thermal polymerization reaction.
Compared with the prior art, the invention has the advantages that:
(1) the high-aromaticity condensed ring asphalt modified by the active component containing the branched-chain aromatic hydrocarbon is adopted, the formation and conversion of the asphalt mesophase liquid crystal are accelerated through the co-thermal polymerization reaction, the formation time of the whole liquid crystal mesophase asphalt is shortened, and the preparation time of the whole mesophase asphalt is shortened by 0.5-2.5 h compared with the condensed ring asphalt raw material without the active component;
(2) the introduction of the active component containing branched chain aromatic hydrocarbon changes the composition and structure of plane macromolecules of the condensed ring asphalt, compared with the original mesophase asphalt without the active component, the branched chain aromatic hydrocarbon component is doped into the condensed ring asphalt molecules, the H/C molar ratio is increased by 0.05-0.2, the softening point of the mesophase asphalt can be reduced by 8-25 ℃, the viscosity and the fluidity of mesophase asphalt melt are adjusted, and the stable spinning fiber forming is facilitated;
(3) the branched aromatic hydrocarbon-containing active component is introduced into the mesophase pitch raw material, so that the oxidation stabilization of mesophase pitch fibers can be accelerated, the non-melting time can be shortened by 1-3 h at the same oxidation temperature, and the production cost of the mesophase pitch-based carbon fibers is reduced;
(4) the aim of reducing the splitting degree of the mesophase pitch-based carbon fiber can be fulfilled by regulating and controlling the composition and the structure of the mesophase pitch raw material, the splitting degree (splitting rate and splitting angle) of the carbon fiber is reduced by 50-95% compared with the mesophase pitch-based carbon fiber prepared from the original mesophase pitch without adding the active component, and the structure and the performance of the mesophase pitch-based carbon fiber are obviously improved or enhanced, so that the wide application of the mesophase pitch-based carbon fiber in a composite material is accelerated.
(5) The mesophase pitch obtained by the co-thermal polymerization reaction is used as a raw material, and the mesophase pitch-based carbon fiber is prepared by melt spinning, oxidation infusibility and high-temperature carbonization treatment, so that the oxidation infusibility time of the mesophase pitch fiber can be shortened, and the splitting degree of the mesophase pitch-based carbon fiber can be reduced.
Detailed Description
The principles and features of the present invention are described below in conjunction with specific examples, which are provided only for illustrating the advantages of the present invention in controlling the composition and structure of mesophase pitch using the co-thermal polymerization, and are not intended to limit the scope of the present invention.
Example 1
A method for regulating and controlling the composition and structure of mesophase pitch by a co-thermal polymerization reaction. The specific process is as follows:
(1) adding 12 wt.% of cyclohexane soluble component in petroleum asphalt into high-aromaticity condensed ring naphthalene asphalt, and stirring for 2 hours at the speed of 500r/min in a nitrogen atmosphere at the temperature which is 80 ℃ higher than the softening temperature of the naphthalene asphalt so as to uniformly mix asphalt raw materials in a hot state;
(2) carrying out co-thermal polymerization reaction on the uniformly mixed asphalt raw materials in a self-boosting closed container, wherein the co-thermal polymerization reaction conditions are as follows: stirring at the temperature of 422 ℃ for 5 hours at the speed of 750 r/min;
(3) the mesophase pitch obtained by the co-thermal polymerization is used as a raw material, and the mesophase pitch-based carbon fiber is prepared by adopting melt spinning at 60 ℃ higher than the softening temperature of the mesophase pitch, oxidation non-melting at 20 ℃ lower than the softening temperature of the mesophase pitch and carbonization at 1000 ℃ in nitrogen atmosphere.
Compared with the naphthalene asphalt raw material without the active component, the preparation time of the integral mesophase asphalt of the embodiment is shortened by 1.5 h; compared with the original mesophase pitch without the active component, the H/C molar ratio of the mesophase pitch prepared by the embodiment is increased by 0.15, the softening point is reduced by 20 ℃, and the non-melting time of the spun mesophase pitch fiber can be shortened by 3 hours; compared with the mesophase pitch-based carbon fiber prepared from the original mesophase pitch without the active component, the degree of splitting of the mesophase pitch-based carbon fiber prepared by the embodiment is reduced by 95%, and the structure and the performance of the mesophase pitch-based carbon fiber are obviously improved or enhanced.
Example 2
A method for regulating and controlling the composition and structure of mesophase pitch by a co-thermal polymerization reaction. The specific process is as follows:
(1) adding 8 wt.% of cyclohexane soluble component in petroleum asphalt into the high-aromaticity condensed ring anthracene asphalt, in a nitrogen atmosphere, the softening temperature of the cyclohexane soluble component is 80 ℃ higher than that of the anthracene asphalt, and stirring the mixture for 2 hours at the speed of 500r/min to ensure that the asphalt raw materials are uniformly mixed in a hot state;
(2) the asphalt raw materials which are uniformly mixed are subjected to self-boosting in a closed container to carry out the co-thermal polymerization reaction, wherein the co-thermal polymerization reaction conditions are as follows: stirring at the temperature of 410 ℃ for 4 hours at the speed of 1100 r/min;
(3) the mesophase pitch obtained by the co-thermal polymerization is used as a raw material, and the mesophase pitch-based carbon fiber is prepared by adopting melt spinning at 60 ℃ higher than the softening temperature of the mesophase pitch, oxidation non-melting at 20 ℃ lower than the softening temperature of the mesophase pitch and carbonization at 1000 ℃ in nitrogen atmosphere.
Compared with anthracene asphalt raw material without active component, the preparation time of the integral mesophase asphalt of the embodiment is shortened by 2 h; compared with the original mesophase pitch without the active component, the H/C molar ratio of the mesophase pitch prepared by the embodiment is increased by 0.1, the softening point is reduced by 15 ℃, and the non-melting time of the spun mesophase pitch fiber can be shortened by 2 hours; compared with the mesophase pitch-based carbon fiber prepared from the original mesophase pitch without the active component, the degree of splitting of the mesophase pitch-based carbon fiber prepared by the embodiment is reduced by 75%, and the structure and the performance of the mesophase pitch-based carbon fiber are obviously improved or enhanced.
Example 3
A method for regulating and controlling the composition and structure of mesophase pitch by a co-thermal polymerization reaction. The specific process is as follows
(1) Adding 5 wt.% of cyclohexane soluble component in heavy oil into the high-aromaticity fused ring coal pitch, and stirring for 2 hours at a speed of 500r/min in a nitrogen atmosphere at a temperature higher than the softening temperature of the coal pitch to uniformly mix the pitch raw materials in a hot state;
(2) the asphalt raw materials which are uniformly mixed are subjected to self-boosting in a closed container to carry out the co-thermal polymerization reaction, wherein the co-thermal polymerization reaction conditions are as follows: stirring at 390 ℃ for 3.5h at the speed of 700 r/min;
(3) the mesophase pitch obtained by the co-thermal polymerization is used as a raw material, and the mesophase pitch-based carbon fiber is prepared by adopting melt spinning at 60 ℃ higher than the softening temperature of the mesophase pitch, oxidation non-melting at 20 ℃ lower than the softening temperature of the mesophase pitch and carbonization at 1000 ℃ in nitrogen atmosphere.
Compared with the coal tar pitch raw material without the added active component, the preparation time of the integral mesophase pitch of the embodiment is shortened by 1 h; compared with the original mesophase pitch without the active component, the H/C molar ratio of the mesophase pitch prepared by the embodiment is increased by 0.08, the softening point is reduced by 10 ℃, and the non-melting time of the spun mesophase pitch fiber can be shortened by 1.5H; compared with the mesophase pitch-based carbon fiber prepared from the original mesophase pitch without the active component, the degree of splitting of the mesophase pitch-based carbon fiber prepared by the embodiment is reduced by 60%, and the structure and the performance of the mesophase pitch-based carbon fiber are obviously improved or enhanced.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (2)
1. A method for regulating and controlling the composition and structure of mesophase pitch through co-thermal polymerization is characterized by comprising the following steps:
1) adding an active component containing branched-chain aromatic hydrocarbon into the high-aromaticity condensed ring asphalt to uniformly mix asphalt raw materials in a hot state;
2) self-boosting the uniformly mixed asphalt raw material in a closed container to carry out co-heating polymerization reaction;
3) carrying out melt spinning, oxidation non-melting and high-temperature carbonization treatment on the mesophase pitch obtained by the co-thermal polymerization reaction to obtain mesophase pitch-based carbon fibers;
the high-aromaticity fused ring asphalt is any one of naphthalene asphalt, anthracene asphalt and coal asphalt, the branched-chain aromatic hydrocarbon-containing active component is a cyclohexane soluble component in petroleum asphalt or heavy oil, the addition amount of the cyclohexane soluble component is 4-15 wt% of the high-aromaticity fused ring asphalt, and the hot-state mixing process conditions are as follows: stirring for 2 hours at the speed of 500r/min at the temperature which is 80 ℃ higher than the softening temperature of the high-aromaticity condensed ring asphalt in a nitrogen atmosphere, wherein the co-thermal polymerization reaction conditions are as follows: stirring at the speed of 550-1180 r/min for 3-6 hours at the temperature of 386-432 ℃, carrying out melt spinning at the temperature 60 ℃ higher than the softening temperature of the mesophase pitch, carrying out oxidation without melting at the temperature 20 ℃ lower than the softening temperature of the mesophase pitch, and carrying out carbonization at the temperature of 1000 ℃ in a nitrogen atmosphere.
2. A mesophase pitch-based carbon fiber prepared by the method for controlling the composition and structure of mesophase pitch using the co-thermal polymerization according to claim 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055024B1 (en) * | 1980-11-19 | 1984-10-03 | Toa Nenryo Kogyo Kabushiki Kaisha | Carbonaceous pitch, production thereof and carbon fibers therefrom |
| CN103305942A (en) * | 2013-06-06 | 2013-09-18 | 天津大学 | Spinneret plate and method for preparing mesophase pitch-based strip carbon fibers |
| CN104610994A (en) * | 2015-01-16 | 2015-05-13 | 中国海洋石油总公司 | Preparation method of mesophase pitch with low softening point and high mesophase content |
| CN106435840A (en) * | 2016-10-21 | 2017-02-22 | 中国石油大学(华东) | Preparation method of asphalt based carbon fiber |
-
2018
- 2018-12-18 CN CN201811548944.7A patent/CN109610049B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055024B1 (en) * | 1980-11-19 | 1984-10-03 | Toa Nenryo Kogyo Kabushiki Kaisha | Carbonaceous pitch, production thereof and carbon fibers therefrom |
| CN103305942A (en) * | 2013-06-06 | 2013-09-18 | 天津大学 | Spinneret plate and method for preparing mesophase pitch-based strip carbon fibers |
| CN104610994A (en) * | 2015-01-16 | 2015-05-13 | 中国海洋石油总公司 | Preparation method of mesophase pitch with low softening point and high mesophase content |
| CN106435840A (en) * | 2016-10-21 | 2017-02-22 | 中国石油大学(华东) | Preparation method of asphalt based carbon fiber |
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