CN113527639A - Method for preparing spinnable asphalt with high softening point from naphthalene and product thereof - Google Patents
Method for preparing spinnable asphalt with high softening point from naphthalene and product thereof Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
- C08G2261/352—Macromonomers, i.e. comprising more than 10 repeat units containing only carbon atoms
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- 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
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Abstract
The invention discloses a method for preparing spinnable asphalt with high softening point from naphthalene and a product thereof, belonging to the technical field of coal chemical industry and spinnable asphalt materials. Naphthalene, a bromomethylation reagent, a catalyst and an organic solvent are added into a reaction system, and a hydrogen bromide gas supplementary reagent is dropwise added into the reaction system for reaction; layering the products after the reaction is finished, and washing the upper layer substances to obtain a naphthalene bromomethylation product; then carrying out polycondensation and extraction reaction to obtain the spinnable asphalt with high softening point. The method has simple process, takes the naphthalene which is a byproduct in the coal chemical industry as a raw material, thereby reducing the cost for preparing the asphalt, improving the additional value of the coal tar, and the prepared asphalt with the high softening point can be used for preparing excellent carbon fiber materials by spinning.
Description
Technical Field
The invention relates to the technical field of coal chemical industry and spinnable asphalt materials, in particular to a method for preparing spinnable asphalt with high softening point from naphthalene and a product thereof.
Background
China is a big coal country in the world and is also the largest coke producing country in the world, the industrial application of the coal-based carbon material is increasingly wide, and the utilization of the coal-based carbon material in China has a history of many years. Naphthalene is a fused ring aromatic organic compound, which is produced in large quantities from coal tar and petroleum distillation, which are by-products of coking. Therefore, the preparation of the pitch-based carbon fiber by using the naphthalene can reduce the cost and generate a coal chemical industry byproduct with higher added value. Compared with coal tar pitch and petroleum pitch, the pitch prepared from naphthalene has the advantages of good aromaticity, single component, no ash content, simple preparation process and the like.
The high-quality asphalt has wide reworkability in the research field of carbon materials, and can be used for producing carbon fibers, graphite, C/C composite materials and the like. The polycyclic aromatic hydrocarbon is formed by polymerizing polycyclic aromatic hydrocarbon, and has the characteristics of higher molecular weight, adjustable softening point, good high-temperature rheological property, low ash content and the like. The preparation of the carbon fiber with excellent performance mainly depends on the performance of the asphalt, so that the excellent asphalt has higher application value.
The traditional modified asphalt method mainly comprises a thermal polycondensation method and a catalytic method, wherein the thermal polycondensation method and the catalytic method belong to high-temperature free radical polycondensation reaction under certain temperature and pressure, the reaction is uncontrollable, and the prepared asphalt has over-high softening point and poor fluidity. The latter adopts the early addition of anhydrous AlCl3The catalyst is used as a catalyst, but the catalyst residue is distributed in the asphalt after the reaction is finished, so that the asphalt performance is influenced due to the fact that the catalyst residue cannot be separated completely, and the cleaning cost is increased. The later stage of the process using superacid (HF/BF)3) The corrosivity is high, and the cost of equipment maintenance and safety guarantee in the production process is increased.
Mochida et al prepared mesophase pitch by a two-step reaction process using naphthalene as a raw material and a superacid HF/BF as a catalyst. First, the naphthalene is treated with HF/BF at 80 DEG C3Catalyzing to generate low-polymerization-degree naphthyl polymerized asphalt, and then performing high-temperature heat treatment to obtain mesophase asphalt (Mochida Isao, Shimizu Kiyoyuki, Korai Yozo, Otsuka Hi)royuki,Sakai Yukio,Fujiyama Susumu.Preparation of mesophase pitch from aromatic hydrocarbons by the aid of HF/BF3[J]Pergamon,1990,28(2-3). Korai et al use naphthalene and methylnaphthalene as copolymerization raw materials (adding ratio 7:3) to prepare mesophase pitch by super acid catalysis. The mesophase pitch obtained by copolymerization is similar in molecular structure to a pure naphthyl mesophase pitch, but superior in molecular orientation to the naphthyl mesophase pitch (Yozo Korai, Seong-Ho Yoon, Hidetoshi Oka, Isao Mochida, Tsutomu Nakamura, Isamu Kato, Yukio Sakai. the properties of Co-oligomeric mesophase from methyl naphthalene and naphthalene catalyzed by HF/BF3[J]Carbon,1998,36(4). The above prior arts all use super acidic catalyst, super acid (HF/BF)3) The corrosivity is high, and the cost of equipment maintenance and safety guarantee in the production process is increased.
Gekko Swinhonis et al synthesized high-softening-point polymerized pitch from 1-methylnaphthalene by visible light irradiation assisted radical bromination, which produced pitch with highly adjustable softening point and polymerization degree (Ge C, Yang H, Miyawaki J, et al, Synthesis and catalysis-of high-softening-point synthesized pitch by visualized polymerization [ J ] Carbon 2015,95: 780-788.). And ethylene residue vacuum distillation heavy component (ET-HR) is used as a raw material, and a bromination/debromination polymerization two-step method is adopted to prepare the novel high-softening-point isotropic asphalt (Gezhuang Chang, Sunzhonglong, Yanhai, Longdonghui, Qiaociviling, Lingzhiing). The brominated product is prepared from 1-methylnaphthalene, illumination is needed, a byproduct is bromine introduced on an aromatic ring, and a chain-shaped but net-woven structure cannot be formed in the subsequent asphalt preparation process. The byproduct of the method is 2, 6-bis-bromomethylnaphthalene, still is bromine introduced on a side chain, does not have bromine on an aromatic ring, does not have the problems, and the method directly prepares bromomethylation from naphthalene, has wide raw material sources and does not need illumination, so the preparation process is simpler.
Disclosure of Invention
The invention aims to provide a method for preparing spinnable asphalt with high softening point from naphthalene and a product thereof, so as to solve the problems of uncontrollable reaction, poor fluidity of the prepared asphalt, high cost and the like. The method has simple flow, prepares the spinnable asphalt with high softening point by taking the 1-bromomethylnaphthalene as a monomer through condensation debromination after preparing the 1-bromomethylnaphthalene from the naphthalene, has more adjustable and controllable reaction, and is simple, safe and efficient.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for preparing spinnable asphalt with high softening point from naphthalene, which comprises the following steps:
(1) adding naphthalene, a bromomethylation reagent, a catalyst and an organic solvent into a reaction system, and dropwise adding a hydrogen bromide gas supplementary reagent into the reaction system for reaction;
(2) layering the products after the reaction is finished, and washing the upper layer substances to obtain a naphthalene bromomethylation product;
(3) and carrying out polycondensation and extraction reaction on the obtained naphthalene bromomethylation product to obtain the spinnable asphalt with the high softening point.
Furthermore, the mol ratio of the naphthalene, the bromomethylation reagent, the catalyst, the organic solvent and the hydrogen bromide gas replenishing reagent in the step (1) is 1 (2-5): 1-5): 0-3): 1-2.
Further, the bromomethylation reagent is one group of formaldehyde/hydrobromic acid, polyformaldehyde/hydrobromic acid, trioxymethylene/hydrobromic acid, formaldehyde dimethyl acetal/hydrobromic acid and bromomethyl ether, and the molar ratio of solid to hydrobromic acid in the bromomethylation reagent is (1-2) to (1-3);
the catalyst is one or more of acetic acid, phosphoric acid, sulfuric acid, aluminum tribromide, zinc bromide and stannous bromide;
the organic solvent is one of cyclohexane, dichloromethane and n-heptane;
the hydrogen bromide gas supplementing reagent is phosphorus tribromide.
Further, the dropping speed of the hydrogen bromide gas supplementary reagent in the step (1) is 0.3-0.6 mL/min, the reaction temperature is 30-100 ℃, and the reaction time is 4-8 h.
Further, the upper layer substance in the step (2) is separated by a separating funnel, and the washing is to carry out alkali washing and water washing on the upper layer substance respectively.
Further, the alkali washing is performed by potassium carbonate, and the water washing is performed by deionized water.
Further, the polycondensation reaction in the step (3) is carried out after inert gas is introduced.
Further, the inert gas is nitrogen, the temperature of the polycondensation reaction is 200-330 ℃, and the time is 2-6 h.
Further, the solvent for the extraction reaction in the step (3) is n-hexane.
The invention also provides the spinnable asphalt with high softening point prepared by the method.
The invention discloses the following technical effects:
1. the method has a simple production mode, takes the naphthalene which is a byproduct in the coal chemical industry as a raw material, thereby reducing the cost for preparing the asphalt and improving the additional value of the coal tar. The prepared high-softening-point asphalt can be used for preparing excellent carbon fiber materials by spinning. Compared with the traditional method, the softening point of the prepared asphalt is relatively adjustable and controllable, the softening point of the prepared asphalt is increased along with the increase of the reaction temperature during the preparation of the asphalt, the softening point is also increased along with the increase of the reaction time, and the control of the softening point can be realized by controlling the conditions. Compared with the traditional method, the method of the invention is relatively simple, safe and efficient.
2. The polyformaldehyde reacts with hydrogen bromide acetic acid to generate electrophilic species, then the electrophilic species and aromatic compounds generate aromatic electrophilic substitution reaction to generate hydroxymethylation intermediates, and benzyl alcohol is further brominated to obtain bromomethylation products. The invention directly starts from naphthalene, and directly adopts a mode of combining bromomethylation and debromination polymerization to form a methylene bridging structure, thereby being beneficial to obtaining carbon fibers with better performance by directional arrangement under the action of shearing force in the subsequent spinning process.
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 description and examples are intended to be illustrative 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
Step 1: weighing 128g of naphthalene, 35g of polyformaldehyde, 300mL of 40% hydrobromic acid solution, 130mL of 99.5% acetic acid, 80mL of 85% phosphoric acid solution and 120mL of 99.7% cyclohexane solution, and placing the weighed materials in a 1000mL three-neck flask; weighing 85mL of 99% phosphorus tribromide solution in a dropping funnel, heating and stirring by using a heat collection type constant temperature heating magnetic stirrer, adjusting the temperature to 50 ℃, controlling the phosphorus tribromide to be dropped at the speed of 0.3mL/min, stirring vigorously at the speed of 300rpm, and reacting for 6 h.
Step 2: after the reaction is finished, the product is layered, the upper layer is an organic layer, and the lower layer is a mixed acid layer. Separating out mixed acid layer with separating funnel, adding 10% potassium carbonate solution into organic layer, repeatedly washing with alkali until it is not acidic, and washing with deionized water for three times. Then, vacuum-filtering by using a vacuum pump, vacuum-drying to remove water, slowly condensing the organic layer into a solid at low temperature to obtain the 1-bromomethylnaphthalene, wherein the yield is 90%, the naphthalene conversion rate is 97.9%, and the byproduct is 2, 6-bis-bromomethylnaphthalene.
And step 3: placing 1-bromomethylnaphthalene in a flask, introducing nitrogen at the speed of 80mL/min for atmosphere protection, heating by a heating jacket under normal pressure, stirring by magnetons at the speed of 700rpm, heating to 290 ℃, and keeping the temperature at 290 ℃ for 5 hours; finally, the asphalt with the softening point of 266.2 ℃ is obtained and extracted by normal hexane, and the yield is 57.95%.
Example 2
Step 1: 3.2g of naphthalene, 1.6g of polyoxymethylene, 10mL of 40% hydrobromic acid solution, 0.7g of zinc bromide and 30mL of 99.7% cyclohexane solution were weighed into a 250mL three-necked flask; weighing 20mL of 99% phosphorus tribromide solution in a dropping funnel, heating and stirring by using a heat collection type constant temperature heating magnetic stirrer, adjusting the temperature to 50 ℃, controlling the phosphorus tribromide to be dropped at the speed of 0.3mL/min, stirring violently at the speed of 300rpm, and reacting for 6 h.
Step 2: after the reaction is finished, the product is layered, the upper layer is an organic layer, and the lower layer is a mixed acid layer. Separating out mixed acid layer with separating funnel, adding 10% potassium carbonate solution into organic layer, repeatedly washing with alkali until it is not acidic, and washing with deionized water for three times. Then, vacuum-filtering by using a vacuum pump, vacuum-drying to remove water, slowly condensing the organic layer into a solid at low temperature to obtain the 1-bromomethylnaphthalene, wherein the yield is 92%, the naphthalene conversion rate is 98%, and the byproduct is 2, 6-double bromomethylnaphthalene.
And step 3: placing a mixture of 1-bromomethylnaphthalene and 2, 6-bisbromomethylnaphthalene in a flask, introducing nitrogen at a speed of 80mL/min for atmosphere protection, heating at normal pressure by a heating jacket, stirring by magnetons at a speed of 700rpm, heating to 270 ℃, and keeping the temperature at 270 ℃ for 5 hours; part of the product is not reacted completely, and is extracted by normal hexane to obtain the asphalt with the softening point of 259.2 ℃, and the yield is 60.5%.
Example 3
Step 1: weighing 128g of naphthalene, 40g of polyoxymethylene, 300mL of 40% hydrobromic acid solution, 130mL of 99.5% acetic acid, 80mL of 85% phosphoric acid solution and 200mL of 99.7% cyclohexane in a 1000mL three-necked flask; weighing 100mL of 99% phosphorus tribromide solution in a dropping funnel, heating and stirring by using a heat collection type constant temperature heating magnetic stirrer, adjusting the temperature to 40 ℃, controlling the phosphorus tribromide to be dropped at the speed of 0.3mL/min, stirring vigorously at the speed of 300rpm, and reacting for 7 hours.
Step 2: after the reaction is finished, the product is layered, the upper layer is an organic layer, and the lower layer is a mixed acid layer. Separating out mixed acid layer with separating funnel, adding 10% potassium carbonate solution into organic layer, repeatedly washing with alkali until it is not acidic, and washing with deionized water for three times. Then, vacuum-filtering by using a vacuum pump, vacuum-drying to remove water, slowly condensing the organic layer into a solid at low temperature to obtain the 1-bromomethylnaphthalene, wherein the yield is 90%, the naphthalene conversion rate is close to 100%, and the byproduct is 2, 6-double bromomethylnaphthalene.
And step 3: placing 1-bromomethylnaphthalene in a flask, introducing nitrogen at the speed of 80mL/min for atmosphere protection, heating by a heating jacket under normal pressure, stirring by magnetons at the speed of 700rpm, heating to 250 ℃, and keeping the temperature at 250 ℃ for 5 hours; finally, the asphalt with the softening point of 246.3 ℃ is obtained, and is extracted by n-hexane, and the yield is 62.2%.
Example 4
Step 1: weighing 128g of naphthalene, 35g of polyformaldehyde, 300mL of 40% hydrobromic acid solution, 130mL of 99.5% acetic acid and 80mL of 85% phosphoric acid, placing in a 1000mL three-neck flask, and adding no solvent; weighing 85mL of 99% phosphorus tribromide solution in a dropping funnel, heating and stirring by using a heat collection type constant temperature heating magnetic stirrer, adjusting the temperature to 50 ℃, controlling the phosphorus tribromide to be dropped at the speed of 0.3mL/min, stirring vigorously at the speed of 300rpm, and reacting for 6 h.
Step 2: after the reaction is finished, the product is layered, the upper layer is an organic layer, and the lower layer is a mixed acid layer. Separating out mixed acid layer with separating funnel, adding 10% potassium carbonate solution into organic layer, repeatedly washing with alkali until it is not acidic, and washing with deionized water for three times. Then, vacuum-filtering by using a vacuum pump, vacuum-drying to remove water, slowly condensing the organic layer into a solid at low temperature to obtain the 1-bromomethylnaphthalene, wherein the yield is 94%, the naphthalene conversion rate is close to 100%, and the byproduct is 2, 6-double bromomethylnaphthalene.
And step 3: placing 1-bromomethylnaphthalene in a flask, introducing nitrogen at the speed of 80mL/min for atmosphere protection, heating by a heating jacket under normal pressure, stirring by magnetons at the speed of 700rpm, heating to 230 ℃, and keeping the temperature at 230 ℃ for 5 hours; finally, the asphalt with the softening point of 220.9 ℃ is obtained and extracted by normal hexane, and the yield is 66.4%.
Performance test of the asphalt obtained in examples 1 to 4 was carried out, and the test results are shown in Table 1.
TABLE 1 Properties of the bitumens
| Examples | Yield/% | Softening point/. degree.C | TS/％ | TI-PS/％ | PS/％ |
| Example 1 | 57.95 | 266.2 | 75.02 | 8.49 | 83.52 |
| Example 2 | 60.50 | 259.2 | 82.64 | 14.90 | 97.54 |
| Example 3 | 62.20 | 246.3 | 91.23 | 6.64 | 97.87 |
| Example 4 | 66.40 | 220.9 | 98.29 | 2.23 | 100 |
Wherein TS is the content of toluene soluble matter, TI-PS is the content of toluene insoluble pyridine soluble matter, and PS is the content of pyridine soluble matter.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A method for preparing high softening point spinnable pitch from naphthalene, which is characterized by comprising the following steps:
(1) adding naphthalene, a bromomethylation reagent, a catalyst and an organic solvent into a reaction system, and dropwise adding a hydrogen bromide gas supplementary reagent into the reaction system for reaction;
(2) layering the products after the reaction is finished, and washing the upper layer substances to obtain a naphthalene bromomethylation product;
(3) and carrying out polycondensation and extraction reaction on the obtained naphthalene bromomethylation product to obtain the spinnable asphalt with the high softening point.
2. The method of claim 1, wherein the naphthalene, the bromomethylation reagent, the catalyst, the organic solvent, and the hydrogen bromide gas supplementing reagent in the step (1) are present in a molar ratio of 1 (2-5) to (1-5) to (0-3) to (1-2).
3. The method for preparing spinnable asphalt from naphthalene as claimed in claim 1 or 2, wherein the bromomethylation reagent is one group of formaldehyde/hydrobromic acid, polyformaldehyde/hydrobromic acid, trioxymethylene/hydrobromic acid, formaldehyde dimethyl acetal/hydrobromic acid and bromomethyl ether, and the molar ratio of solid to hydrobromic acid in the bromomethylation reagent is (1-2): (1-3);
the catalyst is one or more of acetic acid, phosphoric acid, sulfuric acid, aluminum tribromide, zinc bromide and stannous bromide;
the organic solvent is one of cyclohexane, dichloromethane and n-heptane;
the hydrogen bromide gas supplementing reagent is phosphorus tribromide.
4. The method for preparing high-softening-point spinnable asphalt from naphthalene according to claim 1, wherein the hydrogen bromide gas supplementary reagent in the step (1) is added at a dropping rate of 0.3-0.6 mL/min, the reaction temperature is 30-100 ℃, and the reaction time is 4-8 h.
5. The method for preparing high-softening-point spinnable asphalt from naphthalene according to claim 1, wherein the upper substance in step (2) is separated by using a separating funnel, and the washing is alkali washing and water washing respectively.
6. The method for preparing high-softening-point spinnable asphalt from naphthalene as claimed in claim 5, wherein the alkali washing is performed with potassium carbonate, and the water washing is performed with deionized water.
7. The method for preparing spinnable asphalt with high softening point from naphthalene according to claim 1, wherein the polycondensation reaction in step (3) is carried out after inert gas is introduced.
8. The method for preparing spinnable asphalt with high softening point from naphthalene as claimed in claim 7, wherein the inert gas is nitrogen, and the temperature of the polycondensation reaction is 200-330 ℃ for 2-6 h.
9. The method for preparing high-softening-point spinnable asphalt from naphthalene according to claim 1, wherein the solvent for the extraction reaction in step (3) is n-hexane.
10. A high softening point spinnable pitch obtainable by the process of any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| CN113527639B (en) | 2022-08-02 |
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