CN106986740A - A kind of method that methylene halide prepares fullerene derivate - Google Patents
A kind of method that methylene halide prepares fullerene derivate Download PDFInfo
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- CN106986740A CN106986740A CN201710311072.1A CN201710311072A CN106986740A CN 106986740 A CN106986740 A CN 106986740A CN 201710311072 A CN201710311072 A CN 201710311072A CN 106986740 A CN106986740 A CN 106986740A
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- methylene halide
- methylene
- ionization
- halide
- fullerene derivate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that methylene halide prepares fullerene derivate, comprise the following steps：Magnetic stir bar is put into round-bottomed flask, and adds the methylene halide of 1/2 volume, after the assembling for completing ionization reaction device, it is placed into oil bath pan, is passed through inert gas, excludes air, agitating and heating, makes methylene halide flow back, while spherical condensating tube water flowing is cooled down；High voltage power supply generator is opened when methylene halide steam reaches ionization reaction chamber, the strength electric arc of generation is incorporated into ionization reaction chamber, part methylene halide steam is ionized, the gas of generation is discharged by anti-suck bubbler, the cigarette ash that washing reaction is generated after the methylene halide cooling not being ionized, undissolved accessory substance is removed by filtration by core, product is dissolved in methylene halide, is enriched in flask.The ionization material that the present invention is used is methylene halide, cheap and be easy to get；Ionization methylene halide can directly obtain fullerene derivate, and more efficient, cheap, energy consumption is smaller.
Description
Technical field
The present invention relates to field of chemical preparation, and in particular to a kind of method that methylene halide prepares fullerene derivate.
Background technology
In past more than 20 years, particularly nineteen ninety Kratschmer arc process maroscopic quantity fullerene synthesis successes
Afterwards, strangle alkene alkene and its research of derivative is developed rapidly, correlative study turns into a new branch of science.Current fullerene and its spread out
Biology is widely used in the fields such as cosmetics, lubricant, bioactive materials, solar cell, field-effect transistor, fowler
Alkene and its derivative have boundless application prospect, and synthesis turns into grinding for current most active with property fullerene
Study carefully one of field.
Patent CN200510115405.0 reports one kind under inert gas shielding, using solid state laser, bombards quilt
What is continuously flowed contains aromatic hydrocarbons, terpenes liquid phase, the method for preparing fullerene.This method can obtain higher fullerene, but use
Costly, and terpenes cost of material is also higher for equipment laser.
Patent CN201110138848.7 reports a kind of sky of the mixture filling of use graphite and mixing condensed-nuclei aromatics
Cardiolith inker is electrode, and the method for preparing fullerene under He gas shieldeds by arc discharge, the method can obtain a variety of big fowlers
Alkene C76、C78、C84、C86Deng, but its electrode preparation cost is higher, and yield is relatively low.
Patent CN201010592225.2 reports the huge energy that a kind of utilization explosive charge produces and HTHP
The method that environment prepares fullerene, this method is although simple to operate, energy consumption is low, but it has potential safety hazard, is difficult to big
Amount prepares fullerene.
Patent CN 201410495019.8 reports a kind of preparation method of amino fullerene derivate, with halo fowler
Alkene be raw material in organic solvent with amination reagent reacting, then through operations such as precipitation, separation obtain amidized fullerene and spread out
It is biological.It is the potential solid propellant propulsion agent material of a class after this analog derivative nitration, although its synthesis technique is simple, but it is with halogen
It is that Material synthesis cost is higher for fullerene.
Patent CN 201110142776.3 reports a kind of preparation method of fullerene dipolymer derivative, with 1,2-
HRC60Fullerene dipolymer derivative is obtained in oxidizing process for raw material, this analog derivative is that the potential fullerene of a class gathers
Polymer precursor, and with unique electronics and optical property, but its synthetic method still haves the shortcomings that cost is higher.
The preparation method of above fullerene and its derivative all has that cost of material is higher, and the low shortcoming of efficiency is limited
The large-scale application of fullerene and its derivative.
The content of the invention
To solve the above problems, the invention provides a kind of method that methylene halide prepares fullerene derivate, by inciting somebody to action
Methylene halide methane gasifies and ionized, then can directly obtain the fullerene derivate of halo through separation, with simple, efficient, honest and clean
The advantage of valency, it is easier to realize the large-scale production of fullerene derivate.
To achieve the above object, the technical scheme taken of the present invention is：
A kind of method that methylene halide prepares fullerene derivate, comprises the following steps：
S1, it is put into magnetic stir bar in round-bottomed flask, and adds the methylene halide of 1/2 volume, then completes on request
The assembling of ionization reaction device；Round-bottomed flask, ionization reaction chamber, the ball-type that the ionization reaction device includes being sequentially connected are condensed
Pipe and antitheft suction drum bubbler, the ionization reaction chamber include tungsten filament electrode, reative cell, steam lead and core, tungsten filament electrode one
The side wall through reative cell is held, is integrated with reative cell sintering, the other end is connected with high voltage power supply generator, for strength is electric
Arc is incorporated into reative cell, and a steam lead is provided with the right side of the reative cell lower end, and steam lead one end is connected with reative cell,
The other end is connected with round-bottomed flask, described anti-for the methylene halide produced in round-bottomed flask steam to be imported into reative cell
Room lower end is answered to be provided with core, core is located at the top of steam lead inlet end；
S2, ionization reaction device is placed into oil bath pan, led to from the left side bottle neck of round-bottomed flask into reaction system
Enter inert gas, exclude the air in reaction system, be then turned on oil bath pan agitating and heating, methylene halide is flowed back, simultaneously will
Spherical condensating tube water flowing is cooled down；
S3, the opening high voltage power supply generator when methylene halide steam reaches ionization reaction chamber, by the strength electric arc of generation
It is incorporated into by tungsten filament electrode in ionization reaction chamber, part methylene halide steam is ionized, produces a large amount of cigarette ashes and a large amount of chlorinations
Hydrogen and a small amount of chlorine；
S4, a large amount of hydrogen chloride gas and a small amount of chlorine are discharged by anti-suck bubbler, and the methylene halide not being ionized leads to
The cigarette ash that washing reaction is generated after spherical condensating tube cooling is crossed, undissolved accessory substance is removed by filtration by core, product is dissolved in
Methylene halide, is enriched in flask；
S5, when thering is solid to separate out in round-bottomed flask or methylene halide backflow slows down, stop ionization and heat, terminate anti-
Should；
S6, by the reaction solution pillar layer separation in above-mentioned flask, obtain the fullerene derivate of halo.
Wherein, the round-bottomed flask is double-neck flask, and volume is 100-500mL, and methylene halide is difluoromethane, dichloromethane
Alkane, methylene bromide, diiodomethane, preferably dichloromethane, methylene bromide.Wherein, in the step S2 inert gas to be high-purity
One kind in nitrogen, high-purity argon gas；The heating-up temperature of oil bath pan is high compared with methylene halide boiling point 10-20 DEG C..
Wherein, the high voltage power supply generator in the step S3 can produce more than 100KV strength electric spark, from electric fire
Flower vacuum detector, electric spark vacuum detector can produce 180-210KV strength voltage, and its high voltage low current is used
Safety, is entirely capable of meeting the requirement of experiment of ionization reaction.
Wherein, the filler that chromatographic column is used in the step S6 is alundum (Al2O3), and eluent is petroleum ether: toluene is by body
Product is than 7-10: 1 mixing gained.
Wherein, the silica gel or alundum (Al2O3) particle of the thick 100-400 mesh of one layer of 3-5mm are equipped with the core.
The invention has the advantages that：
The ionization material used be methylene halide relative to high purity graphite, aromatic hydrocarbons that general arc process is used etc., it is cheap and
It is easy to get；Ionization methylene halide can directly obtain halogenated fullerenes relative to the method that halogenated fullerenes are prepared in document, more efficient,
Inexpensively, a kind of more practical scheme is provided further to expand the production scale of fullerene derivate；Need not in preparation process
The system such as the aspiration pump of conventional arc method and the water-cooled vacuum room of high-seal, eliminates the expense of complex and expensive, energy consumption is smaller.
Brief description of the drawings
Fig. 1 is the structural representation of the ionization reaction device used in the embodiment of the present invention.
Fig. 2 is the structural representation of ionization reaction chamber in Fig. 1.
Fig. 3 is the structural representation of round-bottomed flask in Fig. 1.
Fig. 4 is the structural representation of spherical condensating tube in Fig. 1.
Fig. 5 is the structural representation of antitheft suction drum bubbler in Fig. 1.
Embodiment
In order that objects and advantages of the present invention are more clearly understood, the present invention is carried out with reference to embodiments further
Describe in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit this hair
It is bright.
The embodiments of the invention provide a kind of method that methylene halide prepares fullerene derivate, comprise the following steps：
S1, it is put into magnetic stir bar in round-bottomed flask, and adds the methylene halide of 1/2 volume, then as shown in Fig. 1-5
Structure complete ionization reaction device assembling；Specifically, the ionization reaction device include be sequentially connected round-bottomed flask 1,
Ionization reaction chamber 2, spherical condensating tube 3 and antitheft suction drum bubbler 4, the ionization reaction chamber 2 include tungsten filament electrode 5, reative cell 6,
Steam lead 7 and core 8, one end of tungsten filament electrode 5 pass through the side wall of reative cell 6, are integrated with the sintering of reative cell 6, the other end connects
High voltage power supply generator is connected to, for strength electric arc to be incorporated into reative cell 6, is steamed on the right side of the lower end of reative cell 6 provided with one
Vapour conduit 7, one end of steam lead 7 is connected with reative cell 6, and the other end is connected with round-bottomed flask 1, for by round-bottomed flask 1
The methylene halide steam of middle generation imported into reative cell, and the lower end of reative cell 6 is provided with core 8, and core 8 is located at steam lead 7
The top of inlet end；
S2, ionization reaction device is placed into oil bath pan, led to from the left side bottle neck of round-bottomed flask into reaction system
Enter inert gas, exclude the air in reaction system, be then turned on oil bath pan agitating and heating, methylene halide is flowed back, simultaneously will
Spherical condensating tube water flowing is cooled down；
S3, the opening high voltage power supply generator when methylene halide steam reaches ionization reaction chamber, by the strength electric arc of generation
It is incorporated into by tungsten filament electrode in ionization reaction chamber, part methylene halide steam is ionized, produces a large amount of cigarette ashes and a large amount of chlorinations
Hydrogen and a small amount of chlorine；
S4, a large amount of hydrogen chloride gas and a small amount of chlorine are discharged by anti-suck bubbler, and the methylene halide not being ionized leads to
The cigarette ash that washing reaction is generated after spherical condensating tube cooling is crossed, undissolved accessory substance is removed by filtration by core, product is dissolved in
Methylene halide, is enriched in flask；
S5, when thering is solid to separate out in round-bottomed flask or methylene halide backflow slows down, stop ionization and heat, terminate anti-
Should；
S6, by the reaction solution pillar layer separation in above-mentioned flask, obtain the fullerene derivate of halo.
The round-bottomed flask is double-neck flask, and volume is 100-500mL, and methylene halide is difluoromethane, dichloromethane, two
Bromomethane, diiodomethane, preferably dichloromethane, methylene bromide.Inert gas for high pure nitrogen, high-purity argon in the step S2
One kind in gas；The heating-up temperature of oil bath pan is high compared with methylene halide boiling point 10-20 DEG C,.High voltage power supply hair in the step S3
Raw device can produce more than 100KV strength electric spark, and from electric spark vacuum detector, electric spark vacuum detector can be produced
180-210KV strength voltage, and its high voltage low current is entirely capable of meeting the requirement of experiment of ionization reaction using safety.
The filler that chromatographic column is used in the step S6 is alundum (Al2O3), and eluent is petroleum ether: toluene 7-10: 1 is mixed by volume
Close gained.The silica gel or alundum (Al2O3) particle of the thick 100-400 mesh of one layer of 3-5mm are equipped with the core 8.The tungsten filament
Electrode material is tungsten filament, is spread out for high-voltage arc to be incorporated into reaction vessel to ionize methylene halide steam and generate containing fullerene
Biological cigarette ash, with tungsten filament as electrode material because being difficult to be oxidized under its high temperature, it is easy to and glass container sintering is integrated,
In ionization reaction, tungsten filament is also more stable is difficult to react with ionization material.
Embodiment 1
Dichloromethane ionization prepares fullerene derivate
S1, magnetic stir bar is put into 100mL round-bottomed flasks, and adds 50mL dichloromethane, then as shown in Figure 1
Connect ionization reaction device；
S2, reaction unit is placed into oil bath pan, high pure nitrogen is passed through into reaction system, is excluded in reaction system
Air, leads to condensed water, opens oil bath pan and is heated with stirring to 55 DEG C, makes methylene chloride reflux；
S3, when dichloromethane steam reach ionization reaction chamber when open electro spark detector (ESD), the strength electric arc of generation is led to
Cross tungsten filament electrode to be incorporated into ionization reaction chamber, part methylene chloride steam is ionized, produce a large amount of cigarette ashes；
The cigarette ash that washing reaction is generated after S4, the dichloromethane not being ionized cooling, undissolved accessory substance, by reative cell
In core be removed by filtration, and the product such as fullerene derivate is dissolved in dichloromethane, is enriched in flask；
S5, when methylene chloride reflux slows down in round-bottomed flask, stop ionization and heat, terminating reaction.
S6, by the alundum (Al2O3) chromatogram post separation of the reaction solution in above-mentioned flask, with petroleum ether: toluene=8: 1 washes
De- liquid elution, isolated fullerene derivate.
Embodiment 2
Methylene bromide ionization prepares fullerene derivate
S1, magnetic stir bar is put into 100mL round-bottomed flasks, and adds 40mL methylene bromide, connected as shown in Figure 1
Good ionization reaction device；
S2, reaction unit is placed into oil bath pan, high pure nitrogen is passed through into reaction system, is excluded in reaction system
Air, leads to condensed water, opens oil bath pan and is heated with stirring to 110 DEG C, methylene bromide is flowed back.
S3, when methylene bromide steam reach ionization reaction chamber when open electro spark detector (ESD), the strength electric arc of generation is led to
Cross tungsten filament electrode to be incorporated into ionization reaction chamber, part methylene bromide steam is ionized, produce a large amount of cigarette ashes.
The cigarette ash that washing reaction is generated after S4, the methylene halide not being ionized cooling, undissolved accessory substance, by reative cell
In core be removed by filtration, and the product such as fullerene derivate is dissolved in methylene bromide, is enriched in flask.
S5, when in round-bottomed flask methylene bromide backflow slow down when, stop ionization and heat, terminating reaction.
S6, by the alundum (Al2O3) chromatogram post separation of the reaction solution in above-mentioned flask, with petroleum ether: toluene=10: 1 washes
De- liquid elution, isolated fullerene derivate.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of method that methylene halide prepares fullerene derivate, it is characterised in that comprise the following steps：
S1, it is put into magnetic stir bar in round-bottomed flask, and adds the methylene halide of 1/2 volume, ionization is then completed on request
The assembling of reaction unit；Round-bottomed flask (1), ionization reaction chamber (2), the ball-type that the ionization reaction device includes being sequentially connected are cold
Solidifying pipe (3) and antitheft suction drum bubbler (4), the ionization reaction chamber (2) include tungsten filament electrode (5), reative cell (6), steam lead
(7) and core (8), tungsten filament electrode (5) one end passes through the side wall of reative cell (6), is integrated with reative cell (6) sintering, the other end
High voltage power supply generator is connected with, for strength electric arc to be incorporated into reative cell (6), is set on the right side of reative cell (6) lower end
There is a steam lead (7), steam lead (7) one end is connected with reative cell (6), and the other end is connected with round-bottomed flask (1), use
In the methylene halide steam produced in round-bottomed flask (1) is imported into reative cell, reative cell (6) lower end is provided with core (8),
Core (8) is located at the top of steam lead (7) inlet end；
S2, ionization reaction device is placed into oil bath pan, is passed through from the left side bottle neck of round-bottomed flask into reaction system lazy
Property gas, exclude the air in reaction system, be then turned on oil bath pan agitating and heating, methylene halide is flowed back, while by ball-type
Condenser pipe water flowing is cooled down；
S3, the opening high voltage power supply generator when methylene halide steam reaches ionization reaction chamber, the strength electric arc of generation is passed through
Tungsten filament electrode is incorporated into ionization reaction chamber, and part methylene halide steam is ionized, and produces a large amount of cigarette ashes and a large amount of hydrogen chloride gas
Body and a small amount of chlorine；
S4, a large amount of hydrogen chloride gas and a small amount of chlorine are discharged by anti-suck bubbler, and the methylene halide not being ionized passes through ball
The cigarette ash that washing reaction is generated after the cooling of type condenser pipe, is removed by filtration undissolved accessory substance, product is dissolved in dihalo- by core
Methane, is enriched in flask；
S5, when have in round-bottomed flask solid separate out or methylene halide backflow slow down when, stop ionization and heat, terminating reaction；
S6, by the reaction solution pillar layer separation in above-mentioned flask, obtain fullerene derivate.
2. the method that a kind of methylene halide as claimed in claim 1 prepares fullerene derivate, it is characterised in that the dihalo-
Methane is difluoromethane, dichloromethane, methylene bromide, diiodomethane, preferably dichloromethane, methylene bromide.
3. the method that methylene halide as claimed in claim 1 prepares fullerene derivate, it is characterised in that in the step S2
Inert gas for one kind in high pure nitrogen, high-purity argon gas；The heating-up temperature of oil bath pan 10-20 high compared with methylene halide boiling point
℃。
4. the method that a kind of methylene halide as claimed in claim 1 prepares fullerene derivate, it is characterised in that the step
High voltage power supply generator in S3 can produce more than 100KV strength electric spark, from electric spark vacuum detector.
5. the method that a kind of methylene halide as claimed in claim 1 prepares fullerene derivate, it is characterised in that the step
The filler that chromatographic column is used in S6 is alundum (Al2O3), and eluent is petroleum ether: toluene is by volume obtained by 7-10: 1 mixing.
6. the method that a kind of methylene halide as claimed in claim 1 prepares fullerene derivate, it is characterised in that the core
(8) silica gel or alundum (Al2O3) particle of the thick 100-400 mesh of one layer of 3-5mm are equipped with.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111579718A (en) * | 2020-05-07 | 2020-08-25 | 西安电子科技大学 | Automatic dynamic testing device for gas sensitivity characteristics |
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| CN1366508A (en) * | 2000-04-18 | 2002-08-28 | 索尼公司 | Method and system for producing fullerene |
| CN102231925A (en) * | 2011-05-20 | 2011-11-02 | 中国科学院化学研究所 | Method for improving yield of C60/C70 fullerene prepared by arc discharge method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1366508A (en) * | 2000-04-18 | 2002-08-28 | 索尼公司 | Method and system for producing fullerene |
| CN102231925A (en) * | 2011-05-20 | 2011-11-02 | 中国科学院化学研究所 | Method for improving yield of C60/C70 fullerene prepared by arc discharge method |
Non-Patent Citations (2)
| Title |
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| THEODORA ALEXAKIS 等: "Synthesis of fullerenes via the thermal plasma dissociation of hydrocarbons", 《APPLIED PHYSICS LETTERS》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111579718A (en) * | 2020-05-07 | 2020-08-25 | 西安电子科技大学 | Automatic dynamic testing device for gas sensitivity characteristics |
| CN111579718B (en) * | 2020-05-07 | 2022-04-29 | 西安电子科技大学 | Automatic dynamic testing device for gas sensitivity characteristics |
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Application publication date: 20170728 |