CN108793134A - A kind of preparation method of graphene - Google Patents
A kind of preparation method of graphene Download PDFInfo
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- CN108793134A CN108793134A CN201810893388.0A CN201810893388A CN108793134A CN 108793134 A CN108793134 A CN 108793134A CN 201810893388 A CN201810893388 A CN 201810893388A CN 108793134 A CN108793134 A CN 108793134A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of preparation methods of graphene, include the following steps：Step 1, graphite is removed by supercritical carbon dioxide stripping method, in deionized water by the dispersion of obtained graphite powder, is crushed by homogenizer, pressure is controlled in 90~150MPa, is disperseed successively and is dried；Step 2, the desciccate of step 1 impregnated with dilute hydrochloric acid, washed, soaking temperature is -10~15 DEG C, and soaking time is 1~4h, and the mass ratio of the dilute hydrochloric acid and graphite is (1~2.5)：1, the compound of potassium bichromate and hydroperoxides is added, oxidation reaction is carried out under conditions of 10~85 DEG C of reaction temperature, 2.5~6h of reaction time, washed, filtered successively, dried after the completion of reaction, obtaining graphene oxide powder.Amination graphene piece diameter that the preparation method of graphene of the present invention obtains is small, the number of plies is low, and when modified polymer material contributes to the dispersion in basis material, avoids reuniting, while can reach preferable modified effect in the case where additive amount is smaller.
Description
Technical field
The invention belongs to the preparing technical fields of graphene, and in particular to a kind of preparation method of graphene.
Background technology
It is larger to the destruction of graphene sheet layer that existing oxidation-reduction method prepares graphene oxide, to cause graphene
Reduced performance further influences the modification application in high molecular material.Therefore there is an urgent need for a kind of efficient, volume production graphene preparations
Method.
Invention content
One, technical problems to be solved
The technical problem to be solved in the present invention is to provide a kind of preparation methods of graphene, to solve the technical problem.
Two, technical solution
To solve the technical problem, the technical solution adopted in the present invention is：A kind of preparation method of graphene, including
Following steps：
Step 1, graphite is removed by supercritical carbon dioxide stripping method, by obtained graphite powder be dispersed in from
It in sub- water, is crushed by homogenizer, pressure is controlled in 90~150MPa, is disperseed successively and is dried；
Step 2, the desciccate of step 1 impregnated with dilute hydrochloric acid, washed, soaking temperature is -10~15 DEG C, is impregnated
Time is 1~4h, and the mass ratio of the dilute hydrochloric acid and graphite is (1~2.5)：1, add potassium bichromate and hydroperoxides
Compound carries out oxidation reaction, after the completion of reaction successively under conditions of 10~85 DEG C of reaction temperature, 2.5~6h of reaction time
Washed, filtered, dried, obtain graphene oxide powder, the graphite, potassium bichromate, hydroperoxides mass ratio be
1:(0.1~0.9):(0.05~0.1)；
Step 3, in a solvent, chlorine is added at a temperature of -20~15 DEG C in graphene oxide powder dispersion step 2 obtained
Agent, is warming up to 50~120 DEG C after 1~4h after being added dropwise to complete, and after reaction 12~for 24 hours, suitable water is slowly added to, until system
There is no gas generation, filtered, washed, product will be filtered and disperseed again in a solvent, the quality of the chlorinating agent and oxidation
The mass ratio of graphene powder is (0.3~2.8)：1；
Step 4, ethylenediamine is added dropwise in the dispersion liquid obtained in step 3, is 180~220 DEG C in temperature, pressure 0.25
Under conditions of~0.6MPa reaction 10~filtered afterwards for 24 hours, solvent washing, obtained filter cake is finally dispersed in deionized water
In, obtain amination graphene aqueous slurry, the mass ratio of the ethylenediamine and chlorinating agent is (0.5~1.5)：1；
Step 5, the amination graphene aqueous slurry obtained in step 4 is dried, obtains amination graphene powder
Body.
Solvent in the step 3 and step 4 is selected from N, N~dimethylformamide, dichloromethane, toluene, dimethylbenzene, four
It is one or more in chlorination carbon.
Chlorinating agent in the step 3 is in phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, sulfonic acid chloride
It is one or more.
Dispersing mode in step 1~4 is ultrasound, shearing, emulsifies the composite diffusion mode being carried out at the same time.
Drying mode in step 1~5 is pneumatic spray drying, the temperature of pneumatic spray drying is 150~
230℃。
Three, advantageous effect
The present invention is compared to the prior art, has the advantages that：
1, graphite is carried out physical mechanical stripping by the present invention first, then is aoxidized, and the mode first removed reduces
The dosage of oxidant and oxidation promoter, to ensure that the lamellar structure in oxidation process to graphene destroys smaller, oxygen content
It reduces, to which the performance of graphene will not be reduced, the modifying function of graphene can be given full play in application process, reach reason
The modified effect thought；
2, the preparation method for the graphene that the present invention uses, the addition manner of oxidant is using major catalyst, co-catalyst
Compounding mixture be added, it is simple, safe efficient that this way than traditional substep is added oxidant, while can play
Mutual synergistic effect, oxidation efficiency is high, reduces the dosage of oxidant；
3, the preparation method for the graphene that the present invention uses, it is higher using the reactivity of chlorinating agent, it can be simultaneously to oxygen
Hydroxyl and carboxyl on graphite alkene lamella are activated, then are reacted with diamines, form the branch of terminal amino group sealing end, together
When the epoxy group that can not react with chlorinating agent and diamine reactant, also form amino-terminated branch, prepared by this method
Amination graphene amino content is high, nitrogen content is high, amination graphene and basis material during composite modification
It is connected in the form of chemical bond, interface binding power is high, and mechanical property modified effect is more preferable；
4, the preparation method for the graphene that the present invention uses, is reacted, high temperature and pressure item using the condition of high temperature and pressure
Unstable group can be lost under part, by the modification under high temperature and pressure, on the one hand increase group reaction probability, another party
Contribute to the further stripping of graphene under the high temperature and pressure of face, while reaction demonstrates the stabilization of modified group under high temperature and pressure
Property, it was demonstrated that amination graphene group when carrying out the reaction modifying of high temperature and pressure still remains, and realization is connected chemically original position
It is modified；
5, the preparation method of graphene of the present invention utilizes the excessive chlorination of water decomposition after the completion of chlorinating agent participates in reacting
Agent generates gas and passes through vent gas treatment, avoids excess chlorine agent and volatilization occurs during filtering and washing, contacts production with air
Raw a large amount of smog cause the influence to environment, personnel, equipment；
6, the preparation method of graphene of the present invention, by first and chlorination reaction, then and diamine reactant, improve graphite
The stability of alkene surface-modifying groups substantially increases the nitrogen content of amination graphene, in the modifying process of high molecular material
In, the raising of nitrogen content, by the modified adding proportion of adjusting, control carbon, nitrogen ratio contribute to base in reasonable range
The flame retardant property of body material improves；
7, the preparation method of graphene of the present invention, the broken and ultrasound of homogenizer, shearing, emulsification are carried out at the same time compound
Dispersing mode, dispersion effect is more preferable, and the piece diameter of obtained graphene oxide is small, the number of plies is low, greatly strengthens modifying agent and oxidation
The contact area of graphene improves modified effect；
8, the preparation method of graphene of the present invention obtains amination graphene piece diameter is small, the number of plies is low, modified high-molecular material
Contribute to the dispersion in basis material when material, avoid reuniting, while can reach preferable in the case where additive amount is smaller
Modified effect.
Specific implementation mode
With reference to embodiment, the specific implementation mode of the present invention is described in detail.
Embodiment 1
A kind of graphene preparation method of the present invention, using following steps：
Step 1,100kg graphite powders are removed by supercritical carbon dioxide process, 500kg is added in obtained graphite powder
Water, obtained slurry are crushed by homogenizer, and the pressure of homogenizer is 90MPa, after the completion of being crushed by ultrasound, shearing,
The composite diffusion mode of emulsification is handled, and is dried after dispersion, and drying temperature is 150 DEG C.
Step 2, desciccate is added in 100kg dilute hydrochloric acid at -10 DEG C and is impregnated, dichromic acid is added after 4h
The compound of potassium, hydroperoxides, wherein potassium bichromate 10kg, hydroperoxides quality be 10kg, control temperature at 10 DEG C,
400kg deionized waters are added after reacting 2.5h, filters, washing, is finally dried to obtain graphene oxide powder, drying temperature
160℃。
Step 3, the graphene oxide powder that step 2 obtains is disperseed by the composite diffusion mode of ultrasound, shearing, emulsification
In 200kg dichloromethane, it is added thionyl chloride at -20 DEG C, the mass ratio of thionyl chloride and graphene oxide powder is 0.3:
1, it carries out being warming up to 50 DEG C after 1 hour after being added dropwise to complete, condensing reflux and tail gas absorption is carried out at the same time in reaction process, react
It after for 24 hours, is slowly added to there is no gas generation in suitable water to system, then filter, wash, product will be filtered and be dispersed in again
In 200kg dichloromethane.
Step 4, ethylenediamine, the mass ratio of ethylenediamine and thionyl chloride is added dropwise in room temperature in the dispersion liquid obtained in step 3
It is 0.5:1,180 DEG C, react for 24 hours under 0.25MPa, filtered after reaction, solvent (dichloromethane) washing, finally by
Ultrasound, the composite diffusion mode sheared, emulsified disperse in deionized water, to obtain amination graphene aqueous slurry.
Step 5, the amination graphene aqueous slurry obtained in step 4 is dried, 190 DEG C of drying temperature obtains
Amination graphene powder.
The volume that water is added when washing in step 2 is 1~4 times of dilute hydrochloric acid.
The nitrogen, piece diameter size, lamellar spacing of the amination graphene of the present embodiment are tested, acquired results are shown in
Table 1；Carry out composite modified, tensile strength, fracture to composite material to PA6 using the amination graphene of the present embodiment simultaneously
Elongation, maximum deflection intensity, impact strength and oxygen index (OI) are tested, and acquired results are shown in Table 2.
Embodiment 2
2 a kind of graphene preparation method of the present embodiment, using following steps：
Step 1,100kg worm graphite is removed by supercritical carbon dioxide, 500kg is added in obtained graphite powder
Water, obtained slurry are crushed by homogenizer, and the pressure of homogenizer is 150MPa, after the completion of being crushed by ultrasound, shearing,
The composite diffusion mode of emulsification is handled, and dispersion terminates to be dried by pneumatic spray drying, drying temperature 230
DEG C,
Step 2, desciccate is added in 250kg dilute hydrochloric acid at 15 DEG C and is impregnated, dichromic acid is added after 1h
The compounding mixture of potassium, hydroperoxides, wherein potassium bichromate are 90kg, the quality of hydroperoxides is 5kg, and control temperature exists
85 DEG C, 400kg deionized waters are added after reacting 6h, filters, washing, graphene oxide is obtained finally by pneumatic spray drying
Powder, 230 DEG C of drying temperature.
Step 3, the graphene oxide powder that step 2 obtains is disperseed by the composite diffusion mode of ultrasound, shearing, emulsification
In 200kg toluene, it is added dropwise phosphorus trichloride at -20 DEG C, the mass ratio of phosphorus trichloride and graphene oxide powder is 2.8:1, drop
It carries out being warming up to 120 DEG C after 1 hour after the completion of adding, condensing reflux and tail gas absorption is carried out at the same time in reaction process, react 12h
Afterwards, it is slowly added to there is no gas generation in suitable water to system, then filters, washs, product will be filtered and be dispersed in 200kg again
In toluene.
Step 4, ethylenediamine, the mass ratio of ethylenediamine and phosphorus trichloride are added dropwise under the dispersion liquid room temperature obtained in step 3
It is 1.5:1,220 DEG C, react 10h under 0.6MPa, filtered after reaction, solvent (toluene) washing, finally by ultrasound,
Shearing, the composite diffusion mode emulsified disperse in deionized water, to obtain amination graphene aqueous slurry.
Step 5, the amination graphene aqueous slurry obtained in step 4 is dried by pneumatic spray drying,
190 DEG C of drying temperature, obtains amination graphene powder.
The amination graphene nitrogen, piece diameter size, lamellar spacing of the present embodiment are tested, acquired results are shown in Table
1；It is composite modified to PA6 progress using the amination graphene of the present embodiment simultaneously, the tensile strength of composite material, fracture are stretched
Long rate, maximum deflection intensity, impact strength and oxygen index (OI) are tested, and acquired results are shown in Table 2.
Embodiment 3
3 a kind of graphene preparation method of the present embodiment, using following steps：
Step 1,100kg crystalline flake graphites are removed by supercritical carbon dioxide, 500kg is added in obtained graphite powder
Water, obtained slurry are crushed by homogenizer, and the pressure of homogenizer is 110MPa, after the completion of being crushed by ultrasound, shearing,
The composite diffusion mode of emulsification is handled, and dispersion terminates to be dried by pneumatic spray drying, drying temperature 170
DEG C,
Step 2, desciccate is added in 120kg dilute hydrochloric acid at -1 DEG C and is impregnated, added after 2h potassium bichromate,
The compounding mixture of hydroperoxides, potassium bichromate 40kg, hydroperoxides quality be 9kg, control temperature at 55 DEG C, reaction
300kg deionized waters are added after 3.5h, filters, washing, graphene oxide powder is obtained finally by pneumatic spray drying, do
170 DEG C of dry temperature.
Step 3, the graphene oxide powder that step 2 obtains is disperseed by the composite diffusion mode of ultrasound, shearing, emulsification
In 250kg dimethylbenzene, it is added dropwise phosphorus pentachloride at 15 DEG C, the mass ratio of phosphorus pentachloride and graphene oxide powder is 0.5:1, drop
It carries out being warming up to 90 DEG C after 2 hours after the completion of adding, condensing reflux and tail gas absorption is carried out at the same time in reaction process, after reacting 16h,
It is slowly added to there is no gas generation in suitable water to system, then filters, washs, product will be filtered and be dispersed in 200kg bis- again
In toluene.
Step 4, ethylenediamine, the mass ratio of ethylenediamine and phosphorus pentachloride are added dropwise under the dispersion liquid room temperature obtained in step 3
It is 0.7:1,200 DEG C, react 13h under 0.55MPa, filtered, washed after reaction, finally by ultrasound, shearing, emulsification
Composite diffusion mode disperse in deionized water, to obtain amination graphene aqueous slurry.
Step 5, the amination graphene aqueous slurry obtained in step 4 is dried by pneumatic spray drying,
180 DEG C of drying temperature, obtains amination graphene powder.
The amination graphene nitrogen, piece diameter size, lamellar spacing of the present embodiment are tested, acquired results are shown in Table
1；It is composite modified to PA6 progress using the amination graphene of the present embodiment simultaneously, the tensile strength of composite material, fracture are stretched
Long rate, maximum deflection intensity, impact strength and oxygen index (OI) are tested, and acquired results are shown in Table 2.
Comparative example 1
This comparative example substantially with embodiment 1, the difference is that, graphite is directly impregnated with dilute hydrochloric acid, is not carried out
Physics is removed and broken dispersion, tests the amination graphene nitrogen, piece diameter size, lamellar spacing of this comparative example,
Acquired results are shown in Table 1, composite modified to PA6 progress using the amination graphene of this comparative example, strong to the stretching of composite material
Degree, elongation at break, maximum deflection intensity, impact strength and oxygen index (OI) are tested, and acquired results are shown in Table 2.
Comparative example 2
This comparative example substantially with embodiment 1, the difference is that, obtained graphene oxide slurry directly and ethylenediamine into
Row reaction, tests the amination graphene nitrogen, piece diameter size, lamellar spacing of this comparative example, while right using this
The amination graphene of ratio is composite modified to PA6 progress, to the tensile strength of composite material, elongation at break, maximum deflection
Intensity, impact strength and oxygen index (OI) are tested, and acquired results are shown in Tables 1 and 2 respectively.
Comparative example 3
This comparative example substantially with embodiment 1, the difference is that, designed according to the preparation method of conventional graphene oxide
The dosage of the concentrated sulfuric acid, potassium permanganate, hydrogen peroxide, to the amination graphene nitrogen, piece diameter size, lamellar spacing of this comparative example
It is tested, while composite modified to PA6 progress using the amination graphene of this comparative example, it is strong to the stretching of composite material
Degree, elongation at break, maximum deflection intensity, impact strength and oxygen index (OI) are tested, and acquired results are shown in Table 1 and table respectively
2。
Comparative example 4
This comparative example is pure PA6 samples, in order that the PA6 being modified with addition amination graphene is compared, as right
Ratio 4 is tested the tensile strength of material, elongation at break, maximum deflection intensity, impact strength and oxygen index (OI),
Acquired results are shown in Table 2.
Amination graphene test result is made in 1 each embodiment of table and comparative example
| GO pieces diameter (nm) | GO lamellar spacings (nm) | N content (%) | |
| Embodiment 1 | 200 | 1.3 | 18.5 |
| Embodiment 2 | 350 | 1.6 | 19.2 |
| Embodiment 3 | 270 | 1.4 | 18.9 |
| Comparative example 1 | 3500 | 4.0 | 13.2 |
| Comparative example 2 | 620 | 1.7 | 8.0 |
| Comparative example 3 | 380 | 1.5 | 22.1 |
As shown in Table 1, amination graphene piece diameter prepared by the method for the present invention is smaller, and lamellar spacing is small, and nitrogen contains
The amino that amount less carries out the method for physics stripping and broken dispersion and directly prepared with the method that ethylenediamine is modified
Graphite alkene is significantly improved, this is because do not carry out amination graphene piece diameter prepared by physics stripping and broken dispersion compared with
Greatly, lamella is thicker, and surface group is less, and modified small molecule can not come into full contact with graphene sheet layer when modified, modified effect
Fruit is bad, so nitrogen content is relatively low.Regular oxidation legal system obtains the lamellar spacing of amination graphene and the side of piece diameter and the present invention
Amination graphene prepared by method is not much different, while nitrogen content is higher, this is because conventional oxidizing process degree of oxidation is higher,
Surface oxygen-containing groups are more, but the consequence that degree of oxidation height is brought is larger to the lamella destruction of graphene, influence modified effect
Fruit.The method of modifying modified effect of the present invention is good, and Surface oxygen-containing groups are all transformed into amino-terminated branch, so nitrogen content
Become larger.
The test result of composite material obtained by 2 each embodiment of table and comparative example
As can be seen from Table 2, PA6 tensile strengths, the maximum that the graphene prepared using the method for the present invention is modified
Bending strength, impact strength are obviously improved, this is because amination graphene in the base in the form of chemical bond with
Matrix connects, and interface interaction power is larger.The anti-flammability of material also significantly improves, this is because graphite prepared by the method for the present invention
Alkene nitrogen content is higher, and the extent of the destruction of graphene sheet layer is smaller, has preferable coordination fire retarding effect.By comparative example 3 it is found that often
It is larger to piece damage layer that rule oxidizing process prepares graphene oxide, while oxygen content increases and brings influence to flame retardant effect.Simultaneously
It was found that there is lower elongation at break, this feature using the PA6 that amination graphene prepared by the method for the present invention is modified
Meet requirement of the current PA6 industrial yarns requirement elongation at break 15~20%, and routine PA6 products can not accomplish this point.
The specific application example that the above is only the present invention, is not limited in any way protection scope of the present invention.
Claims (5)
1. a kind of preparation method of graphene, which is characterized in that include the following steps：
Step 1, graphite is removed by supercritical carbon dioxide stripping method, obtained graphite powder is dispersed in deionized water
In, it is crushed by homogenizer, pressure is controlled in 90~150MPa, is disperseed successively and is dried；
Step 2, the desciccate of step 1 impregnated with dilute hydrochloric acid, washed, soaking temperature is -10~15 DEG C, soaking time
For 1~4h, the mass ratio of the dilute hydrochloric acid and graphite is (1~2.5)：1, add the compounding of potassium bichromate and hydroperoxides
Object carries out oxidation reaction under conditions of 10~85 DEG C of reaction temperature, 2.5~6h of reaction time, is carried out successively after the completion of reaction
Washing filters, is dry, obtains graphene oxide powder, the graphite, potassium bichromate, hydroperoxides mass ratio be 1:
(0.1~0.9):(0.05~0.1)；
Step 3, in a solvent, chlorination is added at a temperature of -20~15 DEG C in graphene oxide powder dispersion step 2 obtained
Agent, is warming up to 50~120 DEG C after 1~4h after being added dropwise to complete, and after reaction 12~for 24 hours, suitable water is slowly added to, until system does not have
There is gas generation, filtered, washed, product will be filtered and disperseed again in a solvent, quality and the oxidation stone of the chlorinating agent
The mass ratio of black alkene powder is (0.3~2.8)：1；
Step 4, ethylenediamine is added dropwise in the dispersion liquid obtained in step 3, temperature be 180~220 DEG C, pressure be 0.25~
Under conditions of 0.6MPa reaction 10~filtered afterwards for 24 hours, solvent washing, obtained filter cake is finally dispersed in deionized water
In, obtain amination graphene aqueous slurry, the mass ratio of the ethylenediamine and chlorinating agent is (0.5~1.5)：1；
Step 5, the amination graphene aqueous slurry obtained in step 4 is dried, obtains amination graphene powder.
2. graphene according to claim 1, which is characterized in that solvent in the step 3 and step 4 is selected from N, N~
It is one or more in dimethylformamide, dichloromethane, toluene, dimethylbenzene, carbon tetrachloride.
3. the preparation method of graphene according to claim 1, which is characterized in that the chlorinating agent in the step 3 is selected from
It is one or more in phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, sulfonic acid chloride.
4. the preparation method of graphene according to claim 1, which is characterized in that the dispersing mode in step 1~4
It is ultrasound, shearing, emulsifies the composite diffusion mode being carried out at the same time.
5. the preparation method of graphene according to claim 1, which is characterized in that the drying mode in step 1~5
Temperature for pneumatic spray drying, pneumatic spray drying is 150~230 DEG C.
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| CN115261002A (en) * | 2021-04-30 | 2022-11-01 | 中国石油天然气股份有限公司 | Superparamagnetic graphene oxide oil displacement agent and preparation method thereof |
| CN116854549A (en) * | 2023-07-26 | 2023-10-10 | 中国工程物理研究院化工材料研究所 | Method for cooperatively improving mechanical and heat conducting properties of mixed explosive and obtained mixed explosive |
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