CN108373149A - The preparation method of industrial amination graphene - Google Patents
The preparation method of industrial amination graphene Download PDFInfo
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- CN108373149A CN108373149A CN201810212266.0A CN201810212266A CN108373149A CN 108373149 A CN108373149 A CN 108373149A CN 201810212266 A CN201810212266 A CN 201810212266A CN 108373149 A CN108373149 A CN 108373149A
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Abstract
The invention discloses a kind of preparation methods of industrial amination graphene, belong to the preparing technical field of graphene.The method that the present invention is by mechanically pulling off first removes graphite, the proportioning by adjusting primary oxidant and pro-oxidant is aoxidized again, then the hydroxyl and carboxyl of surface of graphene oxide are activated by chlorinating agent, suitable diamines is finally selected to carry out ammoxidation.The mode first removed can reduce the dosage of oxidant, reach ideal modified effect simultaneously, the mode that the present invention first removes can reduce the dosage of oxidant, reach ideal effect simultaneously, avoid oxidizer it is big caused by high oxygen content, it is big to the destructiveness of graphene sheet layer caused by modified effect difference problem.
Description
Technical field
The invention belongs to the preparing technical fields of graphene, more specifically to a kind of industrial amination graphene
Preparation method.
Background technology
Graphene be one kind by carbon atom with sp2Hybridized orbit row is thick at the flat film that hexangle type is in honeycomb lattice
Degree is the thickness (0.35nm) of a carbon atomic layer, is presently found most thin material.Graphene has unique physico
Property is learned, is the highest substance of hardness being currently known, Young's modulus is more than 1000GPa, while having preferable toughness；Thermal conductivity
Rate 3000W/mK；Charge migration speed is 2 × 105cm2/Vs；Specific surface area is up to 2600m2/g。
Graphene oxide (GO) is that functional group is introduced on graphene sheet layer, makes it have the one of certain new features
The graphene of kind functionalization, functional group include the hydroxyl being located on the basal plane of graphene oxide and epoxy group and edge
The carboxyl and hydroxyl at place can carry out recombination reaction using surface of graphene oxide group with other materials, but due to aoxidizing stone
Black alkene surface group has carboxyl, epoxy group, hydroxyl, with other materials carry out compound reaction time, often only a kind of group into
Row reaction, simultaneously because graphene oxide degree of oxidation prepared by various methods is different, the quantity and type of surface group are all
It can not judge, this results in not preparing to determine graphene oxide additive amount with other materials progress compound reaction time, such as
Condensation polymerization reaction is more demanding to the molar ratio for participating in the group of reaction, if so do not known during carrying out in-situ polymerization
Surface of graphene oxide each group content in road can not just determine each group molar ratio, it is possible to the situation that the degree of polymerization can be caused low.
Meanwhile to prepare graphene oxide larger to the destruction of graphene sheet layer for oxidation-reduction method, to cause graphene reduced performance.
How efficiently, volume production amination graphene relationship application of the amination graphene in high molecular material is wide,
Industrial applications can be realized to graphene.The preparation of amination graphene is it has been reported that publication date is in November, 2014 at present
Chinese patent 201410339486.1 on the 12nd is reported is grafted to surface of graphene oxide by the third dicyan, restores to obtain amination
Graphene；Publication date is that the Chinese patent 201210569837.9 on July 2nd, 2014 uses electrolysis, passes through graphene oxide
Amination graphene is made with ammonium hydroxide；Publication date is the Chinese patent 201410124106.2 on June 18th, 2014 by by oxygen
After graphite alkene, organic amine and Dicyclohexylcarbodiimide, n,N-Dimethylformamide mixing, it is prepared by being ultrasonically treated
The amino modified compound forward osmosis membrane of graphene oxide；Publication date is that the Chinese patent 201610012813.1 on June 8th, 2016 will
Graphene oxide powder is dissolved in dimethyl formamide solution, is separately added into ethylenediamine and N, and the four of N '-dicyclohexylcarbodiimides
Hydrogen tetrahydrofuran solution obtains amination graphene, however the nitrogen content of amination graphene that these methods obtain is relatively low, can not
Surface of graphene oxide group is fully utilized, further influences the modification application in high molecular material.Publication date is 2017 7
The Chinese patent 201710286166.8 on the moon 14 reports one kind by the way that graphene oxide is first transformed into cyano graphene again
It carries out catalytic hydrogenation reaction and obtains amination graphene, this method preparation process is complicated, and reaction is more demanding.Publication date is
The Chinese patent on the 4th of September in 2013 201310152941.2 and the Chinese patent that publication date is on July 24th, 2013
201310168803.3 report it is a kind of graphene oxide being prepared by traditional graphene oxide preparation method first, recycle
The method that thionyl chloride and ethylenediamine prepare amination graphene, graphene oxide used in this method use conventional oxidation graphite
Prepared by the preparation method of alkene, larger to the destruction of graphene sheet layer, influences the performance of graphene.
Invention content
In view of the above-mentioned problems existing in the prior art, the present invention is intended to provide a kind of industrialized production amination graphene
Preparation method, solves in current graphene oxide preparation process that oxidizer is big, causes graphene oxide high oxygen content, can not
It determines the amount of the various groups in surface, surface group and can not be fully utilized, conventional oxidation reduction method damages journey to graphene sheet layer
Degree causes graphene reduced performance itself greatly, the problem of to which modified effect be not achieved.
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows：
The method being by mechanically pulling off first removes graphite, then matching by adjusting primary oxidant and pro-oxidant
Than being aoxidized, the mode first removed can reduce the dosage of oxidant, while reach ideal effect, and avoiding problems oxidations
High oxygen content caused by agent dosage is big, it is big to the destructiveness of graphene sheet layer caused by modified effect difference problem；Then pass through
Chlorinating agent activates the hydroxyl and carboxyl of surface of graphene oxide；Suitable diamines is finally selected to carry out ammoxidation,
The reaction of high temperature and pressure has carried out secondary stripping to graphene oxide while improving reaction probability, while also having demonstrated amino
The stability of graphite alkene surface group.
In particular, the preparation method of the industrial amination graphene of the present invention, includes the following steps：
Step 1, graphite is removed by supercritical carbon dioxide stripping method, by obtained graphite powder be dispersed in from
In sub- water, it is crushed, is disperseed and is dried successively；
Step 2, the desciccate of step 1 impregnated with acid solution, washed, add appropriate primary oxidant and help oxidation
The compound of agent carries out oxidation reaction under conditions of 10~90 DEG C of reaction temperature, 2~6h of reaction time, after the completion of reaction according to
It is secondary to be washed, filtered, dried, obtain graphene oxide powder, the graphite, primary oxidant, pro-oxidant mass ratio be
1:(0.1~1):(0.01~0.1)；
Step 3, in a solvent, chlorine is added at a temperature of -20~20 DEG C in graphene oxide powder dispersion step 2 obtained
Agent, is warming up to 50~130 DEG C after 0.5~4h after being added dropwise to complete, and after reaction 10~for 24 hours, suitable water is slowly added to, until body
It is that no gas generates, is filtered, washed, product will be filtered and disperseed again in a solvent, the quality and oxygen of the chlorinating agent
The mass ratio of graphite alkene powder is 0.3~3；
Step 4, diamines is added dropwise in the dispersion liquid obtained in step 3, temperature be 160~220 DEG C, pressure be 0.25~
Under conditions of 0.7MPa reaction 8~filtered afterwards for 24 hours, solvent washing, finally by obtained filter cake dispersion in deionized water,
Obtain amination graphene aqueous slurry, the mass ratio of the diamines and chlorinating agent is 0.5~1.5；
Step 5, the amination graphene aqueous slurry obtained in step 4 is dried, obtains amination graphene powder
Body.
Further, the graphite in the step 1 is selected from graphite powder, worm graphite, crystalline flake graphite, expanded graphite.
Further, broken by homogenizer progress in the step 1, pressure is controlled in 80~150MPa.
Further, the acid solution in the step 2 is in dilute hydrochloric acid, dilute sulfuric acid, dust technology, phosphoric acid,diluted, oxalic acid, formic acid
It is one or more, the mass ratio of the acid solution and graphite is 1:(1~3).
Further, the temperature of the graphite acid soak in the step 2 be 0~20 DEG C, soaking time be 0.5~
4h。
Further, the primary oxidant in the step 2 is potassium bichromate, potassium hyperchlorate, postassium hypochlorite, permanganic acid
It is one or more in potassium, molybdenum dioxide, pro-oxidant be hydroperoxides, dialkyl peroxide, diacyl peroxide,
It is one or more in peroxy esters, peroxycarbonates and ketone peroxide.
Further, the dispersing mode in step 1~3 is ultrasound, shearing, emulsifies compound point be carried out at the same time
The mode of dissipating.
Further, the solvent in the step 3 and step 4 is selected from n,N-Dimethylformamide, dichloromethane, first
Benzene, dimethylbenzene, carbon tetrachloride.
Further, it is sub- to be selected from phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, dichloro for the chlorinating agent in the step 3
Sulfone, sulfonic acid chloride.
Further, the diamines in the step 4 is selected from ethylenediamine, butanediamine, pentanediamine, hexamethylene diamine, heptamethylene diamine, pungent
Diamines, nonamethylene diamine, decamethylene diamine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine.
Compared with the prior art, beneficial effects of the present invention are：
(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) addition manner of the preparation method for the industrial amination graphene that the present invention uses, oxidant uses main catalytic
Agent, co-catalyst compounding mixture be added, it is simple, safe efficient that this way than traditional substep is added oxidant, together
When can play mutual synergistic effect, oxidation efficiency is high, reduces the dosage of oxidant；
(3) preparation method for the industrial amination graphene that the present invention uses, energy higher using the reactivity of chlorinating agent
It is enough simultaneously in graphene oxide layer hydroxyl and carboxyl activate, then reacted with diamines, form terminal amino group envelope
The branch at end, while the epoxy group and diamine reactant that can not be reacted with chlorinating agent, also form amino-terminated branch, this
Amination graphene amino content height, nitrogen content prepared by method is high, amination graphene during composite modification
It is connect in the form of chemical bond with basis material, interface binding power is high, and mechanical property modified effect is more preferable；
(4) preparation method for the industrial amination graphene that the present invention uses, is reacted using the condition of high temperature and pressure,
Unstable group can be lost under high-temperature and high-pressure conditions, by the modification under high temperature and pressure, on the one hand increase group reaction
Probability contributes to the further stripping of graphene under another aspect high temperature and pressure, while reaction demonstrates modification under high temperature and pressure
The stability of group, it was demonstrated that amination graphene group when carrying out the reaction modifying of high temperature and pressure still remains, realizationization
It is in-situ modified to learn connection；
(5) preparation method of industrial amination graphene of the invention utilizes moisture after the completion of chlorinating agent participates in reacting
Solve excessive chlorinating agent, generate gas and pass through vent gas treatment, avoid excess chlorine agent occurs to volatilize during filtering and washing,
It is contacted with air and generates a large amount of smog and cause influence to environment, personnel, equipment；
(6) preparation method of industrial amination graphene of the invention, by first and chlorination reaction, then it is anti-with diamines
It answers, improves the stability of graphene surface modified group, substantially increase the nitrogen content of amination graphene, in macromolecule material
In the modifying process of material, the raising of nitrogen content, (by the modified adding proportion of adjusting, control carbon, nitrogen ratio are in rational model
In enclosing) contribute to the flame retardant property of basis material to improve；
(7) preparation method of industrial amination graphene of the invention, the broken and ultrasound of homogenizer, shearing, emulsification
The composite diffusion mode being carried out at the same time, dispersion effect is more preferable, and the piece diameter of obtained graphene oxide is small, the number of plies is low, greatly enhances
The contact area of modifying agent and graphene oxide improves modified effect；
(8) preparation method of industrial amination graphene of the invention obtains amination graphene piece diameter is small, the number of plies is low,
Contribute to the dispersion in basis material when modified polymer material, avoids reuniting, while just in the case where additive amount is smaller
Preferable modified effect can be reached.
Description of the drawings
Fig. 1 is the preparation method flow chart of the industrial amination graphene of the present invention.
Specific implementation mode
The present invention is further described below with reference to specific embodiment.
Embodiment 1
The method of the industrial amination graphene of preparation of the present invention as shown in Figure 1, 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 80MPa, 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 to be produced dry at 150 DEG C, -10 DEG C
Object, which is added in 100kg dilute hydrochloric acid, to be impregnated, and the compound of potassium permanganate, hydrogen peroxide, wherein potassium permanganate are added after 4h
10kg, hydrogen peroxide quality be 10kg, control temperature at 10 DEG C, react 2h after be added 400kg deionized waters, filter, washing, most
After carry out being dried to obtain graphene oxide powder, 160 DEG C of drying temperature.
Step 2, the graphene oxide powder that step 1 obtains is disperseed by the composite diffusion mode of ultrasound, shearing, emulsification
In 200kg DMF, it is added thionyl chloride at 0 DEG C, the mass ratio of thionyl chloride and graphene oxide powder is 0.3:1, it is added dropwise
It carries out being warming up to 50 DEG C after 2 hours after the completion, condensing reflux and tail gas absorption is carried out at the same time in reaction process, after reaction for 24 hours, delay
Slowly being added in suitable water to system does not have gas generation, then filters, washs, and will filter product and is dispersed in 200kg DMF again
In.
Step 3, ethylenediamine, the mass ratio of ethylenediamine and thionyl chloride is added dropwise in room temperature in the dispersion liquid obtained in step 2
It is 0.5:1,160 DEG C, react for 24 hours under 0.25MPa, filtered after reaction, solvent (DMF) washing, finally by ultrasound,
Shearing, the composite diffusion mode emulsified disperse in deionized water, to obtain amination graphene aqueous slurry.
Step 4, the amination graphene aqueous slurry obtained in step 3 is dried, 190 DEG C of drying temperature obtains
Amination graphene powder.
Pneumatic spray drying or freeze-drying, air-flowing type spray may be selected in drying mode in above-mentioned steps 1,2 and step 4
The temperature of mist drying is 150~230 DEG C.
The volume that water is added when washing in step 1 is 1~4 times of acid solution.
The nitrogen, piece diameter size, lamellar spacing of the amination graphene of the present embodiment are tested, acquired results are shown in
Table 1；Carrying out graphene in-situ polymerization modified Pa 6 to PA6 using the amination graphene of the present embodiment, (polymerization of use is shown in
The embodiment 1 of Chinese patent 201711056093.X), it is strong to the tensile strength of composite material, elongation at break, maximum deflection
Degree, impact strength and oxygen index (OI) are tested, and acquired results are shown in Table 2.
Embodiment 2
The method of the industrial amination graphene of preparation of the present embodiment 2, 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, desciccate is added in 300kg dilute sulfuric acids at 20 DEG C and is impregnated, potassium hyperchlorate, benzoyl peroxide are added after 0.5h
The compounding mixture of formyl, wherein potassium hyperchlorate are 100kg, the quality of benzoyl peroxide is 1kg, control temperature at 90 DEG C,
400kg deionized waters are added after reacting 6h, filters, washing, graphene oxide powder is obtained finally by pneumatic spray drying,
230 DEG C of drying temperature.
Step 2, the graphene oxide powder that step 1 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 3:1, it is added dropwise
It carries out being warming up to 130 DEG C after 0.5 hour after the completion, condensing reflux and tail gas absorption is carried out at the same time in reaction process, react 10h
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 3, decamethylene diamine, the mass ratio of decamethylene diamine and phosphorus trichloride are added dropwise under the dispersion liquid room temperature obtained in step 2
It is 1.5:1,220 DEG C, react 8h under 0.7MPa, 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 4, the amination graphene aqueous slurry obtained in step 3 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
The method of the industrial amination graphene of preparation of the present embodiment 3, 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, it desciccate is added in 120kg dust technologies at -1 DEG C impregnates, potassium bichromate, hydrogen peroxide are added after 1.5h
Compound mixture, potassium bichromate 40kg, hydrogen peroxide quality be 9kg, control temperature at 55 DEG C, react 3h after be added 300kg go
Ionized water filters, washing, graphene oxide powder, 170 DEG C of drying temperature is obtained finally by pneumatic spray drying.
Step 2, the graphene oxide powder that step 1 obtains is disperseed by the composite diffusion mode of ultrasound, shearing, emulsification
In 250kg CCl4In, it is added dropwise phosphorus pentachloride at 20 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 1.5 hours after the completion of adding, condensing reflux and tail gas absorption is carried out at the same time in reaction process, react 16h
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
CCl4In.
Step 3, o-phenylenediamine, the matter of o-phenylenediamine and phosphorus pentachloride are added dropwise under the dispersion liquid room temperature obtained in step 2
Amount is than being 0.7:1,180 DEG C, react 12h under 0.55MPa, filtered, washed after reaction, finally by ultrasound, shearing,
The composite diffusion mode of emulsification disperses in deionized water, to obtain amination graphene aqueous slurry.
Step 4, the amination graphene aqueous slurry obtained in step 3 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.
Embodiment 4
The method of the industrial amination graphene of preparation of the present embodiment 4, using following steps：
Step 1,100kg expanded 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 125MPa, 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 180
DEG C, desciccate is added in 150kg dilute hydrochloric acid at -3 DEG C and is impregnated, postassium hypochlorite, t-butyl peroxy are added after 1h
Change pivalate compounding mixture, postassium hypochlorite 50kg, t-butylperoxy pivarate quality be 10kg, control temperature
At 45 DEG C, 270kg deionized waters are added after reacting 3.5h, filter, washing, oxidation stone is obtained finally by pneumatic spray drying
Black alkene powder, 180 DEG C of drying temperature.
Step 2, the graphene oxide powder that step 1 obtains is disperseed by the composite diffusion mode of ultrasound, shearing, emulsification
In 200kg dimethylbenzene, it is added dropwise thionyl chloride at -6 DEG C, the mass ratio of thionyl chloride and graphene oxide powder is 0.9:1, drop
It carries out being warming up to 90 DEG C after 4 hours after the completion of adding, condensing reflux and tail gas absorption is carried out at the same time in reaction process, after reacting 20h,
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 3, hexamethylene diamine, the mass ratio of hexamethylene diamine and thionyl chloride are added dropwise under the dispersion liquid room temperature obtained in step 2
It is 0.6:1,160 DEG C, react 16h under 0.45MPa, filtered, washed after reaction, finally by ultrasound, shearing, emulsification
Composite diffusion mode disperse in deionized water, to obtain amination graphene aqueous slurry.
Step 4, the amination graphene aqueous slurry obtained in step 3 is dried by pneumatic spray drying,
160 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 diamines 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
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 amination that amount less carries out the method for physics stripping and broken dispersion and directly prepared with the method that diamines is modified
Graphene 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, the PA6 that the amination graphene prepared using the method for the present invention is modified stretches strong
Degree, maximum deflection intensity, impact strength are obviously improved, this is because amination graphene is in the base with chemical bond
Form is connect with matrix, and interface interaction power is larger.The anti-flammability of material also significantly improves, this is because prepared by the method for the present invention
Graphene nitrogen content it is higher, the extent of the destruction of graphene sheet layer is smaller, has and preferable coordinates fire retarding effect.By comparative example 3
It is found that prepare graphene oxide larger to piece damage layer for regular oxidation method, while oxygen content increases and brings shadow to flame retardant effect
It rings.Find that the PA6 that amination graphene prepared by the method using the present invention is modified has lower elongation at break simultaneously, this
One feature meets requirement of the current PA6 industrial yarns requirement elongation at break 15~20%, and routine PA6 products can not accomplish this
A bit.
Claims (10)
1. a kind of preparation method of industry amination 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, disperseed and dried successively；
Step 2, the desciccate of step 1 impregnated with acid solution, washed, add appropriate primary oxidant and pro-oxidant
Compound carries out oxidation reaction under conditions of 10 ~ 90 DEG C of reaction temperature, 2 ~ 6h of reaction time, is carried out successively after the completion of reaction
Washing filters, is dry, obtains graphene oxide powder, the graphite, primary oxidant, pro-oxidant mass ratio be 1:（0.1~
1）:（0.01~0.1）；
Step 3, in a solvent, chlorinating agent is added at a temperature of -20 ~ 20 DEG C in graphene oxide powder dispersion step 2 obtained,
It is warming up to 50 ~ 130 DEG C after 0.5 ~ 4h after being added dropwise to complete, after reaction 10 ~ for 24 hours, suitable water is slowly added to, until system does not have gas
Body generates, and is filtered, is washed, and will filter product and disperses again in a solvent, the quality and graphene oxide of the chlorinating agent
The mass ratio of powder is（0.3~3）：1；
Step 4, diamines is added dropwise in the dispersion liquid obtained in step 3, is 160 ~ 220 DEG C in temperature, pressure is 0.25 ~ 0.7MPa
Under conditions of reaction 8 ~ filtered afterwards for 24 hours, solvent washing, finally by obtained filter cake dispersion in deionized water, obtain ammonia
The mass ratio of base graphite alkene aqueous slurry, the diamines 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. the preparation method of industry amination graphene according to claim 1, which is characterized in that in the step 1
Graphite is selected from graphite powder, worm graphite, crystalline flake graphite or expanded graphite.
3. the preparation method of industry amination graphene according to claim 1 or 2, which is characterized in that in the step 1
It is broken carried out by homogenizer, pressure control is in 80 ~ 150MPa.
4. the preparation method of industry amination graphene according to claim 1, which is characterized in that in the step 2
Acid solution is one or more, the matter of the acid solution and graphite in dilute hydrochloric acid, dilute sulfuric acid, dust technology, phosphoric acid,diluted, oxalic acid, formic acid
Amount is than being 1:（1~3）.
5. the preparation method of industry amination graphene according to claim 1 or 4, which is characterized in that in the step 2
Graphite acid soak temperature be -10 ~ 20 DEG C, soaking time be 0.5 ~ 4h.
6. the preparation method of industry amination graphene according to claim 5, which is characterized in that in the step 2
Primary oxidant is one or more, the pro-oxidant in potassium bichromate, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, molybdenum dioxide
For in hydroperoxides, dialkyl peroxide, diacyl peroxide, peroxy esters, peroxycarbonates and ketone peroxide
It is one or more.
7. the preparation method of industry amination graphene according to claim 1, which is characterized in that in step 1 ~ 3
Dispersing mode be ultrasound, shearing, the composite diffusion mode that is carried out at the same time of emulsification.
8. the preparation method of industry amination graphene according to claim 1, which is characterized in that the step 3 and step
Solvent in rapid 4 is selected from N,N-dimethylformamide, dichloromethane, toluene, dimethylbenzene, carbon tetrachloride.
9. the preparation method of industry amination graphene according to claim 1, which is characterized in that in the step 3
Chlorinating agent is selected from phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, sulfonic acid chloride.
10. the preparation method of industry amination graphene according to claim 1, which is characterized in that in the step 4
Diamines is selected from ethylenediamine, butanediamine, pentanediamine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, o-phenylenediamine, isophthalic
Diamines, p-phenylenediamine.
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