CN104388109B - The preparation method of a kind of solvable mesophase pitch - Google Patents
The preparation method of a kind of solvable mesophase pitch Download PDFInfo
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- CN104388109B CN104388109B CN201410761063.9A CN201410761063A CN104388109B CN 104388109 B CN104388109 B CN 104388109B CN 201410761063 A CN201410761063 A CN 201410761063A CN 104388109 B CN104388109 B CN 104388109B
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- mesophase pitch
- solvable
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- pitch
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
- C10C3/04—Working-up pitch, asphalt, bitumen by chemical means reaction by blowing or oxidising, e.g. air, ozone
Abstract
The preparation method of a kind of solvable mesophase pitch, it relates to mesophase pitch. 1) under hot water bath, deionized water makees solvent, it may also be useful to potassium permanganate oxidation mesophase pitch; 2) by step 1) gained oxidation mesophase pitch and alkylate or the polymkeric substance of band amino or hydroxy functional group carry out condensation reaction, obtains solvable mesophase pitch. First with chemical method can functionalization carboxyl introduce mesophase pitch. Avoid tradition in the process of synthetic mesophase asphalt phase, hydrogenant agent is used to reduce softening temperature and improve solvability, open new chemical reaction method, multiple group can be introduced mesophase pitch by design cleverly, such that it is able to utilize self-assembly, be separated, revolve painting, be stained with the methods such as painting and prepare many yardsticks carbon material. By controlling the amount of potassium permanganate, thus the big condensed ring structure realizing mesophase pitch is not destroyed, and keeps mesophase pitch excellent properties inherently.
Description
Technical field
The present invention relates to mesophase pitch, especially relate to the preparation method of a kind of solvable mesophase pitch.
Background technology
Mesophase pitch is before the organism such as pitch are solid-state charcoal by isotropic transition in liquid phase carbonation process, there is the intermediate product of anisotropy optics characteristic, it has easy greying and the high advantage of carbonization product rate, is produce the outstanding precursor of high performance carbon material. Mesophase pitch is the [BrooksJ.D. found in the coking of Study on Coal by Brooks and Taylor in the sixties in last century the earliest, TaylorG.H., ChemistryandphysicsofCarbon [M] .NewYork:MarcelDekker, 1968:243-244; BrooksJ.D., TaylorG.H.Carbon, 1965,3 (2): 185-186], the preparation of mesophase pitch has been reacted mainly through thermal polycondensation, after raw material is carried out pre-treatment, being incubated for some time at 350��500 DEG C, product carries out being isolated mesophase spherule [MoriyamaR., HayashiJ., etal.Carbon, 2002,40 (1): 53-64]. Experienced by the development of half a century, form the subject fields such as chemistry, hydrocarbon class carbonization chemistry, mesophase spherule optics structure, mesophase spherule formation chemical kinetics at mesophase spherule and achieve significant progress. And achieve in high-performance asphalt base carbon fiber, needle coke, secondary lithium battery negative material, high-specific surface area activated carbon, high heat conduction mesophase pitch based foam carbon etc. and use widely.
But, the molecule agent structure of mesophase pitch is condensed-nuclei aromatics, strong ��-�� Intermolecular Forces, causing its softening temperature higher, solvability is poor, even if also major part can not be dissolved in strong solubility solvent is such as N-Methyl pyrrolidone, if softening temperature is the naphthalene mesophase pitch of 270 DEG C, in its N-Methyl pyrrolidone, insoluble point reaches 62.1% [YaoY, ChenJ, LiuL, DongY, LiuAJMaterSci, 2012,47:5509]. Because softening temperature height, the solvability of mesophase pitch are poor, limit and using the method for " from bottom to top " to prepare the application in many yardsticks carbon material.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of solvable mesophase pitch.
The preparation method of described a kind of solvable mesophase pitch, comprises the following steps:
1) under hot water bath, deionized water makees solvent, it may also be useful to potassium permanganate oxidation mesophase pitch;
2) by step 1) gained oxidation mesophase pitch and alkylate or the polymkeric substance of band amino or hydroxy functional group carry out condensation reaction, obtains solvable mesophase pitch;
In step 1) in, the temperature of described hot water bath can be 40��100 DEG C; Described mesophase pitch comprises coal measures, petroleum and naphthalene system mesophase pitch; The mass ratio of mesophase pitch and potassium permanganate can be 1: (0.5��10).
In step 2) in, described alkylate can comprise CnH2n+1NH2Or CnH2n+1OH, wherein n=6��20; Described polymkeric substance can comprise be with single-ended base polyethylene oxide, polystyrene, polymethylmethacrylate, one in poly(lactic acid) etc.; Described single-ended base can be amino or hydroxyl etc.; It is acyl chlorides and alkylate or polymer reaction that described condensation reaction can be selected the converting carboxylate groups of oxidized bitumen; Or use dewatering agent directly to be prepared by oxidized bitumen and alkylate or polymer reaction solvable mesophase pitch; The one that described dewatering agent can be selected from Carbodiimides, carbonyl dimidazoles, the vitriol oil, anhydrous sodium sulphate, anhydrous magnesium sulfate, trichlorine oxygen phosphine etc., the one that described Carbodiimides can be selected from dicyclohexylcarbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride etc.
The present invention adopts neutral potassium permanganate as oxygenant, is obtained by reacting the oxidized bitumen of band function base carboxyl with coal measures, petroleum and naphthalene system mesophase pitch, then oxidized bitumen and alkylate is reacted, and prepares solvable mesophase pitch. In obtained solvable mesophase pitch, owing to the oxidizing condition selected is gentleer, therefore the big condensed ring structure of mesophase pitch can more completely keep. The condensed ring structure of mesophase pitch is that it has the key structure factor of high carbonization product rate and easy greying, therefore, selects gentle effective oxidizing condition to be again the key of the present invention. The invention solves existing mesophase pitch softening temperature height, the problems such as solvability difference, and can have the introducing polymer chain etc. of object, it is possible to use self-assembly, be separated, revolve painting, be stained with the methods such as painting and prepare many yardsticks, have the carbon material of Graphitic carbon structure.
The present invention first can functionalization group introduce mesophase pitch, select suitable oxidizing condition, the functional groups such as carboxyl are introduced mesophase pitch, subsequently, the polymkeric substance of long alkyl chain, different polymerization degree etc. is reacted with the mesophase pitch after oxidation, prepares solvable mesophase pitch. Polymkeric substance containing alkyl chain is the excellent raw material preparing various material surface carbon coating; Solvable mesophase pitch containing polymer segment, it is possible to use self-assembly, the method such as be separated are prepared many yardsticks, had the carbon material of Graphitic carbon structure.
Compared with prior art, the advantage of the present invention is as follows:
1) first with chemical method can functionalization carboxyl introduce mesophase pitch.
2) tradition is avoided in the process of synthetic mesophase asphalt phase, hydrogenant agent is used to reduce softening temperature and improve solvability, open new chemical reaction method, multiple group can be introduced mesophase pitch by design cleverly, such that it is able to utilize self-assembly, be separated, revolve painting, be stained with the methods such as painting and prepare many yardsticks carbon material.
3) by the amount of control potassium permanganate, thus the big condensed ring structure realizing mesophase pitch is not destroyed, and keeps mesophase pitch excellent properties inherently.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of MP-COOH pyrolysis carbonization at different temperatures. In FIG, (a) 900 DEG C; (b) 1200 DEG C; X-coordinate is 2 times of diffraction angle (��), and ordinate zou is relative diffracted intensity.
Fig. 2 is the solvable mesophase pitch tetrahydrofuran solution of different concns. In fig. 2, (a) 3mg/mL; (b) 2mg/mL; (c) 1mg/mL.
Fig. 3 is the solvable mesophase pitch solution of different concns, it may also be useful to be stained with the SEM figure of the carbon coating on ceramic fiber surface prepared by painting method. In figure 3, (a, d and g) surface, (b, e and h) cross section and (c, f and i) mass of fibers, solvents tetrahydrofurane, strength of solution 3mg/mL (a, b and c), 2mg/mL (d, e and f) and1mg/mL (g, h and i).
Embodiment
Embodiment 1
1) mass ratio that naphthalene system mesophase pitch and potassium permanganate close stirring, mesophase pitch and potassium permanganate and water in water is 1: 8: 40 very much;
2) by step 1) mixture of gained is at 50 DEG C, continue stirring reaction 24h, question response terminates, it is cooled to room temperature, adds hcl acidifying, keeping dripping under acidic conditions adding hydrogen peroxide, until bubble-free produces, to remove the by product Manganse Dioxide that oxidation generates, then filter, wash and obtain oxidation mesophase pitch for three times. Oxidation mesophase pitch is 900 DEG C of pyrolysis, its carbonization product rate 75%, XRD figure spectrum (Fig. 1) after carbonization illustrate oxidized bitumen can crystallization, retain the essence of easy greying of mesophase pitch, illustrating in oxidising process, the big condensed ring structure of mesophase pitch is not destroyed;
3) by step 2) 5.0g of gained is oxidized mesophase pitch and 6.0g carbonyl dimidazoles anhydrous tetrahydro furan (100ml) is middle and mixes, under room temperature after ultrasonic activation 12h, room temperature drips tetrahydrofuran (THF) (40ml) solution adding 6.0g amino dodecane, continues room temperature ultrasonic concussion 12h after being added dropwise to complete. Reaction is spin-dried for solvent after terminating, and adds deionized water, filters, after washing three times, gained solid is at use dissolve with ethanol, filters, washing with alcohol three times, then namely 50 DEG C of dry 24h of vacuum drying oven obtain solvable mesophase pitch, can dissolve completely (Fig. 2) in THF;
4) step 3) the solvable mesophase pitch of gained adds the THF solution that tetrahydrofuran (THF) is made into 3mg/mL2mg/mL, 1mg/mL. Silicon carbide fiber bundle (about 500) is immersed in MP-CONH (C12H25)/THF solution, ultrasonic, slowly take out. Hanging under dry room temperature environment and stretch, after solvent volatilizees, by pre-soaking fiber bundle at 210 DEG C of baking oven internal oxidition 1min, steeping process repeats 1��10 time, it may be achieved the continuous covering of fiber surface, and coat-thickness on demand controls impregnating speed and number of times simultaneously. Finally, pyrolysis under high temperature (700��1100 DEG C) under an inert atmosphere, precursor generation removing impurities matter, dehydrogenation and carbonization, be converted into the carbon coating being attached to fiber surface. By scanning electronic microscope, fiber and coating are characterized, without bonding phenomenon (Fig. 3) after this art breading between fibrous bundle, fiber surface coating dense uniform (Fig. 3), top coat can controlled in tens nanometer range (Fig. 3).
Embodiment 2
1) mass ratio that naphthalene system mesophase pitch and potassium permanganate close stirring, mesophase pitch and potassium permanganate and water in water is 1: 3: 40 very much;
2) by step 1) mixture of gained is at 70 DEG C, continuing stirring reaction 24h, question response terminates, and is cooled to room temperature, add hcl acidifying, keeping dripping under acidic conditions adding hydrogen peroxide, until bubble-free produces, to remove the by product Manganse Dioxide that oxidation generates, then filter, wash and obtain oxidation mesophase pitch for three times, oxidation mesophase pitch 900 DEG C of pyrolysis, its carbonization product rate 76%;
3) by step 2) 5.0g of gained is oxidized mesophase pitch and 4.0g dicyclohexylcarbodiimide anhydrous tetrahydro furan (100ml) is middle and mixes, under ultrasonic disperse, room temperature drips tetrahydrofuran (THF) (40ml) solution adding 4.0g amino dodecane, continues room temperature ultrasonic concussion 12h after being added dropwise to complete. Reaction is spin-dried for solvent after terminating, and adds deionized water, filters, and after washing three times, gained solid is at use dissolve with ethanol, filters, washing with alcohol three times, and then namely 50 DEG C of dry 24h of vacuum drying oven obtain solvable mesophase pitch, can dissolve completely in THF.
Embodiment 3
1) mass ratio that coal measures mesophase pitch and potassium permanganate close stirring, mesophase pitch and potassium permanganate and water in water is 1: 1: 40 very much;
2) by step 1) mixture of gained is at 90 DEG C, continuing stirring reaction 24h, question response terminates, and is cooled to room temperature, add hcl acidifying, keeping dripping under acidic conditions adding hydrogen peroxide, until bubble-free produces, to remove the by product Manganse Dioxide that oxidation generates, then filter, wash and obtain oxidation mesophase pitch for three times, oxidation mesophase pitch 900 DEG C of pyrolysis, its carbonization product rate 78%;
3) by step 2) 5.0g of gained is oxidized mesophase pitch and 10.0g anhydrous sodium sulphate anhydrous tetrahydro furan (100ml) is middle and mixes, under ultrasonic disperse, room temperature drips tetrahydrofuran (THF) (40ml) solution of the monohydroxy oxyethane adding 10.0g molecular weight 550, continues room temperature ultrasonic concussion 12h after being added dropwise to complete. Reaction is spin-dried for solvent after terminating, and adds deionized water, filters, and after washing three times, gained solid is at use dissolve with ethanol, filters, washing with alcohol three times, and then namely 50 DEG C of dry 24h of vacuum drying oven obtain solvable mesophase pitch, can dissolve completely in THF.
Embodiment 4
1) mass ratio that petroleum mesophase pitch and potassium permanganate close stirring, mesophase pitch and potassium permanganate and water in water is 1: 6: 40 very much;
2) by step 1) mixture of gained is at 80 DEG C, continuing stirring reaction 24h, question response terminates, and is cooled to room temperature, add hcl acidifying, keeping dripping under acidic conditions adding hydrogen peroxide, until bubble-free produces, to remove the by product Manganse Dioxide that oxidation generates, then filter, wash and obtain oxidation mesophase pitch for three times, oxidation mesophase pitch 900 DEG C of pyrolysis, its carbonization product rate 77%;
3) by step 2) 5.0g of gained is oxidized mesophase pitch and 12.0g trichlorine oxygen phosphine anhydrous tetrahydro furan (100ml) is middle and mixes, ultrasonic disperse under room temperature, drip and add tetrahydrofuran (THF) (40ml) solution that 8.0g molecular weight is the monohydroxy oxyethane of 550, after being added dropwise to complete, continue room temperature ultrasonic concussion 12h. Reaction is spin-dried for solvent after terminating, and adds deionized water, filters, and after washing three times, gained solid is at use dissolve with ethanol, filters, washing with alcohol three times, and then namely 50 DEG C of dry 24h of vacuum drying oven obtain solvable mesophase pitch, can dissolve completely in THF.
Claims (10)
1. the preparation method of a solvable mesophase pitch, it is characterised in that comprise the following steps:
1) under hot water bath, deionized water makees solvent, it may also be useful to potassium permanganate oxidation mesophase pitch;
2) by step 1) gained oxidation mesophase pitch and the alkylate of band amino or hydroxy functional group or the polymkeric substance of band amino or hydroxy functional group carry out condensation reaction, obtains solvable mesophase pitch.
2. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, it is characterised in that in step 1) in, the temperature of described hot water bath is 40��100 DEG C.
3. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, it is characterised in that in step 1) in, described mesophase pitch is coal measures mesophase pitch, petroleum mesophase pitch or naphthalene system mesophase pitch.
4. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, it is characterised in that in step 1) in, the mass ratio of described mesophase pitch and potassium permanganate is 1: (0.5��10).
5. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, it is characterised in that in step 2) in, described alkylate comprises CnH2n+1NH2Or CnH2n+1OH, wherein n=6��20.
6. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, it is characterized in that in step 2) in, described polymkeric substance comprise be with single-ended base polyethylene oxide, the polystyrene with single-ended base, the polymethylmethacrylate with single-ended base, one in poly(lactic acid) with single-ended base.
7. the preparation method of a kind of solvable mesophase pitch as claimed in claim 6, it is characterised in that described single-ended base is amino or hydroxyl.
8. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, it is characterised in that in step 2) in, described condensation reaction is that selecting the converting carboxylate groups of oxidized bitumen is acyl chlorides and alkylate or polymer reaction; Or use dewatering agent directly to be prepared by oxidized bitumen and alkylate or polymer reaction solvable mesophase pitch.
9. the preparation method of a kind of solvable mesophase pitch as claimed in claim 8, it is characterised in that the one that described dewatering agent is selected from Carbodiimides, carbonyl dimidazoles, the vitriol oil, anhydrous sodium sulphate, anhydrous magnesium sulfate, trichlorine oxygen phosphine.
10. the preparation method of a kind of solvable mesophase pitch as claimed in claim 9, it is characterised in that the one that described Carbodiimides is selected from dicyclohexylcarbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride.
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| CN108219814B (en) * | 2018-01-16 | 2020-08-04 | 中钢集团鞍山热能研究院有限公司 | Carboxyl asphalt and preparation process and application thereof |
| CN110540853B (en) * | 2019-08-12 | 2021-03-26 | 中国科学院山西煤炭化学研究所 | Method for preparing spinnable asphalt from pyromellitic dianhydride and polystyrene modified coal pitch |
| CN114437398B (en) * | 2020-11-02 | 2023-04-11 | 中国石油化工股份有限公司 | Amino-enriched asphalt hollow pellet and preparation method and application thereof |
| CN114437749B (en) * | 2020-11-02 | 2023-04-11 | 中国石油化工股份有限公司 | Amino-enriched asphalt and preparation method of microspheres thereof |
| CN114959949B (en) * | 2022-04-27 | 2023-06-13 | 北京化工大学 | Condensed ring aromatic hydrocarbon carbon fiber and preparation method thereof |
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| JPH01249887A (en) * | 1988-03-31 | 1989-10-05 | Tonen Corp | Production of mesophase pitch |
| WO1993024590A1 (en) * | 1992-06-04 | 1993-12-09 | Conoco Inc. | Process for producing solvated mesophase pitch and carbon artifacts therefrom |
| JP2002075359A (en) * | 2000-08-25 | 2002-03-15 | Mitsubishi Gas Chem Co Inc | Carbon material for nonaqueous solvent secondary battery, manufacturing method for the material, and secondary battery using the carbon material |
| CN102942945B (en) * | 2012-11-15 | 2014-05-28 | 四川创越炭材料有限公司 | Preparation method of soluble mesophase pitch |
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