CN108862268B - A kind of macro preparation device and method of carboxyl-functional graphene - Google Patents
A kind of macro preparation device and method of carboxyl-functional graphene Download PDFInfo
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Abstract
The invention discloses the macro preparation devices and method of a kind of carboxyl-functional graphene, belong to the preparation technical field of graphene.The macro preparation device includes the first Scattered Kettle, activated reactor, the first filtration washing tower, the second Scattered Kettle, reaction kettle, the second filtration washing tower, third Scattered Kettle, drying tower, the first storage tank and the second storage tank, first Scattered Kettle, activated reactor, the first filtration washing tower, the second Scattered Kettle, reaction kettle, the second filtration washing tower, third Scattered Kettle and drying tower are sequentially connected, first filtration washing tower, the first storage tank and the first Scattered Kettle are sequentially connected, and the second filtration washing tower, the second storage tank and the second Scattered Kettle are sequentially connected.The present invention has simple and compact for structure, and rationally, the advantage that serialization degree is high and equipment investment is few can efficiently prepare carboxyl-functional graphene, reduce production cost for design.
Description
Technical field
The invention belongs to the preparation technical fields of graphene, more specifically to a kind of carboxyl-functional graphene
Macro preparation device and method.
Background technique
Graphene is a kind of New Two Dimensional carbon nanomaterial, has unique monoatomic layer two dimensional crystal structure, Gao Bibiao
The special performances such as area, high intensity, conductivity, thermal conductivity are known as " changing the magical material of 21 century ".But pure graphene
Due to the high feature of its large specific surface area, surface energy, it is very easy to reunite in solvent and matrix, causes its intrinsic excellent characteristic
Performance be extremely restricted, and functionalization graphene is while retaining graphene characteristic, loads functionalizing group, assigns it
The performances such as good compatibility and adjustable chemistry, electricity efficiently solve grapheme material and use difficult problem.
Graphene oxide is that removing obtains after being aoxidized graphite, has water solubility well, according to graphite oxide
The Lerf-Klinowski model [Chem.Soc.ReV.2010,39,228.] of alkene: hydroxyl is modified in graphene oxide level
And epoxy group, and carboxyl is mainly in layer edge.Solubility and chemical reactivity based on graphene oxide, graphite oxide
Alkene level and edge can be functionalized.Carboxy-modified graphene oxide occupies in the preparation of functional graphene oxide
Consequence can make various organic small points by amidation or esterification using the active carboxyl of surface of graphene oxide
Son, macromolecule, large biological molecule and the functional material containing reactive group are covalently bound on graphene oxide.
There is document to report for the first time and carboxyl-functional is carried out to graphene oxide using monoxone, with active oxidation graphene
The epoxy group and hydroxyl on surface, make it be transformed into carboxyl, to improve its dissolubility and biology performance (Xiaoming
Sun,Zhuang Liu,Kevin Welsher,Joshua Tucker Robinson,Andrew Goodwin,Sasa
Zaric,Hongjie Dai.Nano-Graphene Oxide for Cellular Imaging and Drug
Delivery.Nano Res.2008,1:203-212.2.).Publication date is the Chinese patent on May 2nd, 2012
201110265734.9 " method of controlledly synthesis carboxylated graphene oxide and nano material obtained " discloses a kind of synthesis
The method of carboxylated graphene oxide, this method act on graphene oxide using azo-initiator, obtain cyanomodified oxygen
Then graphite alkene is dissolved in reacting in alkali alcosol again, obtain carboxylated graphene oxide.Publication date is 2015 3
The Chinese patent 201310425628.1 on the moon 25 discloses a kind of grapheme material and preparation method thereof of carboxyl-functional, should
Method carries out functionalization to graphene using diazo-reaction, obtains the grapheme material of carboxylated.Publication date is in March, 2015
Chinese patent 201410647838.X on the 25th discloses a kind of preparation method of carboxylated graphene, and this method first prepares oxidation
Graphene suspension, then reduction prepares graphene turbid solution, then prepares the presoma turbid solution of carboxylated graphene, finally
Carboxylated graphene is obtained after acidified presoma.
At present carboxylated graphene the problem is that: preparation process is complicated, acquired its carboxylic of carboxylated graphene
Base is in lamella or edge, and reactivity is lower, and steric effect is larger, especially carry out in-situ polymerization it is modified when, only very
Few a part of carboxyl can be scattered in product in the form of chemical bond with basis material bonding, cannot preferably be dispersed, or even meeting
There is polymerization inhibitor phenomenon.Therefore, it is necessary to seek a kind of technique of efficient synthesis carboxylated graphene.
Summary of the invention
For the above-mentioned problems in the prior art, one of the objects of the present invention is to provide a kind of process flow letters
The carboxyl-functional graphene macro preparation device of single, green and pollution-free, high production efficiency, compact layout, it is of the invention
The second purpose is to provide the preparation method using the macro preparation device, the carboxyl-functional graphene carboxyl-content of preparation
High, reactivity height.
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
The present invention relates to a kind of macro preparation devices of carboxyl-functional graphene, including the first Scattered Kettle, priming reaction
Device, the first filtration washing tower, the second Scattered Kettle, reaction kettle, the second filtration washing tower, third Scattered Kettle, drying tower, the first storage tank
With the second storage tank, first Scattered Kettle, activated reactor, the first filtration washing tower, the second Scattered Kettle, reaction kettle, the second mistake
Filter washing tower, third Scattered Kettle and drying tower are sequentially connected, the first filtration washing tower, first storage tank and described first
Scattered Kettle is sequentially connected, and the second filtration washing tower, second storage tank and second Scattered Kettle are sequentially connected, and described
High-shear emulsion machine and ultrasonic dispersers are equipped in one Scattered Kettle, the second Scattered Kettle and third Scattered Kettle simultaneously.
The drying tower is upper-spraying type air-stream spraying drying tower.
The invention further relates to a kind of magnanimity preparation methods of carboxyl-functional graphene using above-mentioned apparatus, pass through first
The method of mechanical dispersion carries out dispersion removing to graphite oxide, is then activated to graphene oxide, is eventually adding carboxylic
Base reagent carries out carboxylation reaction.
The following steps are included:
Step 1, graphite oxide and lye are put into the first Scattered Kettle and carries out mechanical dispersion, obtain the aqueous slurry of graphene oxide
Material；
Step 2, step 1 gained slurry is passed through activated reactor, and activator is added, carry out activated carboxylic reaction；
Step 3, step 2 products therefrom is passed through in the first filtration washing tower and is filtered, is washed, filtered fluid passes through first
Storage tank reuse is into the first Scattered Kettle；
Step 4, the product after step 3 washing is delivered to the second Scattered Kettle, carries out mechanical dispersion after adding water, is activated
Graphene oxide aqueous slurry；
Step 5, step 4 gained slurry is passed through in reaction kettle, is slowly added to carboxylated reagent and dehydrating condensation agent carries out
Reaction；
Step 6, step 5 products therefrom is passed through in the second filtration washing tower and is filtered, is washed, filtered fluid passes through second
Storage tank reuse is into the second Scattered Kettle；
Step 7, the product after step 6 washing is delivered to third Scattered Kettle, carries out mechanical dispersion after adding water, obtains carboxyl
Functionalization graphene aqueous slurry；
Step 8, step 7 gained slurry is delivered in drying tower and is dried to get carboxyl-functional graphene powder.
The method of the mechanical dispersion are as follows: the mechanical dispersion side run simultaneously using high-shear emulsion machine and ultrasonic dispersers
Formula, 5~40 DEG C of dispersion temperature, the revolving speed of high-shear emulsion machine is 500~3000r/min, and ultrasonic power is 1~20kW, ultrasound
Time is 1~10h.
The graphite oxide used in the step 1 is by one of graphite powder, worm graphite, crystalline flake graphite, expanded graphite
Or it is a variety of it is oxidation-treated form, lye be selected from one of potassium hydroxide, sodium hydroxide, ammonium hydroxide or a variety of, gained aoxidize stone
The pH value of black alkene aqueous slurry is 8~10.
In the step 2, activator is monoxone or sodium chloroacetate, and the mass ratio of graphene oxide and activator is 1:
(0.1~1), the condition of priming reaction are as follows: 10~90 DEG C of reaction temperature, 2~6h of reaction time.
In the step 5, carboxylated reagent is amion acetic acid, 3- alanine, 4-Aminobutanoicacid, 5- aminovaleric acid, 6-
Aminocaproic acid or p-aminobenzoic acid, dehydrating condensation agent N, N'- Dicyclohexylcarbodiimide, 1- (3- dimethylamino-propyl)-
3- ethyl carbodiimide, 4- (4,6- dimethoxy-triazine) -4- methyl morpholine hydrochloride, 2- (7- aoxidizes benzotriazole)-N,
N, N', N'- tetramethylurea hexafluorophosphoric acid ester or 2- (2- pyridone -1- base) -1,1,3,3- tetramethylurea tetrafluoroborate, it is described
The mass ratio of carboxylated reagent and active oxidation graphene is (0.3~3): 1, the dosage of the dehydrating condensation agent is active oxidation
The 5~100% of graphene quality, reaction condition are as follows: nitrogen protection, 2~48h of back flow reaction at 40~100 DEG C.
In the step 1,4 and 7, the concentration of aqueous slurry is 0.1~10.0g/mL.
Drying mode in the step 8 is dry for upper-spraying type air-stream spraying, and drying temperature is 105~180 DEG C.
Compared with the prior art, the invention has the benefit that
(1) macro preparation device for the carboxyl-functional graphene that the present invention uses, simple and compact for structure, design is reasonable,
Serialization degree is high and equipment investment is few, can efficiently prepare carboxyl-functional graphene, reduces production cost.
(2) preparation method of carboxyl-functional graphene of the invention can be simultaneously using the high reaction activity of activator
To in graphene oxide layer hydroxyl and epoxy group activate, then reacted with carboxylated reagent, form terminal carboxyl group
The branch of sealing end, this preparation method make full use of the oxygen-containing functional group in graphene oxide layer, the carboxyl-functional of preparation
Graphene carboxyl-content is high, reactivity is high.The carboxyl-functional graphene passes through carboxyl during composite modification
Amidation, esterification etc. can occur with basis material, be grafted in basis material in the form of chemical bond, interface binding power
Height, dispersion performance improve, and mechanical property modified effect is more preferable.
(3) carboxyl-functional graphene its carboxyl that the present invention is prepared is located at branch terminals, and branched structure is adjustable,
In in-situ polymerization modified matrix material, reactivity is high, and steric hindrance is small, can more disperse, and can fully demonstrate graphene advantage.
(4) preparation method of carboxyl-functional graphene of the invention, using answering for ultrasound, shearing, emulsification while progress
Dispersing mode is closed, and is repeatedly dispersed in preparation process, dispersion effect is more preferable, the piece diameter of obtained carboxyl-functional graphene
It is small, the number of plies is low, when be used for modified polymer material when, be conducive to the dispersion in basis material, avoid reuniting, while adding
Preferable modified effect can be reached by measuring in lesser situation.
(5) preparation method of carboxyl-functional graphene of the invention, recycles filtered wash solution in technical process
It recycles, increases raw material availability, it is environmentally protective, reduce production cost.
(6) preparation method of carboxyl-functional graphene of the invention, without using any organic solvent in technique, with
Water is reaction medium, and is recycled to devil liquor recovery in the process, the green safe environmental protection of technical process.
Detailed description of the invention
Fig. 1 is the macro preparation device schematic diagram of carboxyl-functional graphene of the invention；
In Fig. 1: 1, the first Scattered Kettle；2, activated reactor；3, the first filtration washing tower；4, the second Scattered Kettle；5, it reacts
Kettle；6, the second filtration washing tower；7, third Scattered Kettle；8, drying tower；9, the first storage tank；10, the second storage tank；
Fig. 2 is the magnanimity preparation flow schematic diagram of carboxyl-functional graphene of the invention.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
The macro preparation device of a kind of carboxyl-functional graphene of the present embodiment, as shown in Figure 1, including the first Scattered Kettle
1, activated reactor 2, the first filtration washing tower 3, the second Scattered Kettle 4, reaction kettle 5, the second filtration washing tower 6, third Scattered Kettle
7, drying tower 8, the first storage tank 9 and the second storage tank 10, the first Scattered Kettle 1, activated reactor 2, the first filtration washing tower 3, second
Scattered Kettle 4, reaction kettle 5, the second filtration washing tower 6, third Scattered Kettle 7 and drying tower 8 are sequentially connected, the first filtration washing tower 3,
First storage tank 9 and the first Scattered Kettle 1 are sequentially connected, and the second filtration washing tower 6, the second storage tank 10 and the second Scattered Kettle 4 successively connect
It connects.
Wherein: the first Scattered Kettle 1 is the place that raw material graphite oxide carries out dispersion removing in lye system, is equipped with height
Emulsification pretreatment machine and ultrasonic disperse device can disperse to remove to raw material graphite oxide, at the same it is internal be equipped with cooling coil, can be with
Material temperature in kettle when effectively control dispersion is removed ensures effective dispersion removing；It is equipped with and takes out at the top of the first filtration washing tower 3
Vacuum port, cleaning solution feed inlet and filtered fluid discharge port, filtered fluid is delivered in the first storage tank 9 through discharge port pipeline, through pipeline
Conveying and valve control, circulation are used for the first Scattered Kettle 1, and the dispersion for graphite oxide is removed, and adds lye as needed；
High-shear emulsion machine and ultrasonic disperse device also are provided in second Scattered Kettle 4；The top of reaction kettle 5 be equipped with simultaneously carboxylated reagent and
Dehydrating agent feeding line；High-shear emulsion machine and ultrasonic disperse device also are provided in third Scattered Kettle 7；In the second filtration washing tower
6 tops are equipped with vacuum orifice, cleaning solution feed inlet and filtered fluid discharge port, and filtered wash solution is through 6 top of the second filtration washing tower
Filtered fluid discharge port conveys the second storage tank 10, controls through pipeline and valve, and circulation is used for the second Scattered Kettle 4；Drying tower 8 is
Upper-spraying type air-stream spraying drying tower.
The magnanimity preparation of carboxyl-functional graphene is carried out using above-mentioned apparatus, as shown in Figure 2, comprising the following steps:
Step 1, graphite oxide and sodium hydroxide solution are put into the first Scattered Kettle 1, passes through high-shear emulsion machine and ultrasound
The mode that dispersal device is run simultaneously carries out dispersion removing, by adjusting sodium hydroxide solution dosage and concentration, makes system pH
To 9.0, by the cooling coil being arranged in kettle, controls dispersion temperature and be lower than 40 DEG C, the revolving speed of high-shear emulsion machine is 600r/
Min, ultrasonic power 10kW, ultrasonic time 60min obtain graphene oxide aqueous slurry.
Step 2, it is conveyed through pipeline and step 1 gained slurry is passed through activated reactor 2, and monoxone is added, be sufficiently stirred
Afterwards, 80 DEG C of reaction temperature are controlled, carries out activated carboxylic reaction under conditions of reaction time 4h；Wherein graphene oxide, monoxone
Mass ratio be 1:0.5.
Step 3, step 2 products therefrom is delivered in the first filtration washing tower 3 through pipeline and is successively filtered, is washed,
Filtered fluid is delivered in the first storage tank 9 through discharge port pipeline, is controlled through pipeline and valve, and circulation is used for the first Scattered Kettle 1,
Dispersion for graphene oxide is removed, and adds lye as needed.
Step 4, the product after step 3 washing is delivered to the second Scattered Kettle 4 through pipeline, passes through high-shear emulsifying after adding water
The mode that machine and ultrasonic disperse device are run simultaneously carries out dispersion removing, passes through the cooling coil being arranged in kettle, control dispersion temperature
Degree is 30 DEG C, and the revolving speed of high-shear emulsion machine is 600r/min, and ultrasonic power 10kW, ultrasonic time 120min are lived
Change graphene oxide aqueous slurry, the concentration of gained slurry is 5g/mL.
Step 5, step 4 gained slurry is delivered in reaction kettle 5 through pipeline, starting stirring is controlled using valve, by one
Determine the aminocaproic acid and N of quality, N'- Dicyclohexylcarbodiimide is added slowly in reaction kettle 5, nitrogen protection, next time in 80 DEG C
Stream reaction 18h；Wherein, the mass ratio of the quality of aminocaproic acid and active oxidation graphene is 1.2:1, N, N'- dicyclohexyl carbon
The de- dosage of acid imide be account for activation graphene oxide quality 80%.
Step 6, step 5 products therefrom is passed through in the second filtration washing tower 6 and is filtered, is washed, filtered fluid is through discharging
Mouth pipeline is delivered in the second storage tank 10, is controlled through pipeline and valve, and circulation is used for the second Scattered Kettle 4.
Step 7, the product after step 6 washing is delivered to third Scattered Kettle 7, passes through high-shear emulsion machine after adding water and surpassed
The mode that sound dispersal device is run simultaneously carries out dispersion removing, and by the cooling coil being arranged in kettle, controlling dispersion temperature is 30
DEG C, the revolving speed of high-shear emulsion machine is 600r/min, and ultrasonic power 10kW, ultrasonic time 120min obtain carboxyl function
Graphite alkene aqueous slurry, the concentration of gained slurry are 1g/mL.
Step 8, step 7 gained slurry is delivered in drying tower 8 through pipeline, using upper-spraying type air-stream spraying drying mode
It is dried, is arranged 130 DEG C of drying temperature, collection obtains carboxyl-functional graphene powder.
Embodiment 2
It is prepared by the magnanimity that the present embodiment equally uses 1 described device of embodiment to carry out carboxyl-functional graphene, including with
Lower step:
Step 1, graphite oxide and sodium hydroxide solution are put into the first Scattered Kettle 1, passes through high-shear emulsion machine and ultrasound
The mode that dispersal device is run simultaneously carries out dispersion removing, by adjusting sodium hydroxide solution dosage and concentration, makes system pH
To 8.5, by the cooling coil being arranged in kettle, controls dispersion temperature and be lower than 40 DEG C, the revolving speed of high-shear emulsion machine is 600r/
Min, ultrasonic power 10kW, ultrasonic time 60min obtain graphene oxide aqueous slurry.
Step 2, it is conveyed through pipeline and step 1 gained slurry is passed through activated reactor 2, and sodium chloroacetate is added, sufficiently stirred
After mixing, 75 DEG C of reaction temperature are controlled, carries out activated carboxylic reaction under conditions of reaction time 4h；Wherein graphene oxide, chloroethene
The mass ratio of acid is 1:0.7.
Step 3, step 2 products therefrom is delivered in the first filtration washing tower 3 through pipeline and is successively filtered, is washed,
Filtered fluid is delivered in the first storage tank 9 through discharge port pipeline, is controlled through pipeline and valve, and circulation is used for the first Scattered Kettle 1,
Dispersion for graphite oxide is removed, and adds lye as needed.
Step 4, the product after step 3 washing is delivered to the second Scattered Kettle 4 through pipeline, passes through high-shear emulsifying after adding water
The mode that machine and ultrasonic disperse device are run simultaneously carries out dispersion removing, passes through the cooling coil being arranged in kettle, control dispersion temperature
Degree is 30 DEG C, and the revolving speed of high-shear emulsion machine is 600r/min, and ultrasonic power 10kW, ultrasonic time 120min are lived
Change graphene oxide aqueous slurry, the concentration of gained slurry is 0.1g/mL.
Step 5, step 4 gained slurry is delivered in reaction kettle 5 through pipeline, starting stirring is controlled using valve, by one
Determine the amion acetic acid and N of quality, N'- Dicyclohexylcarbodiimide is added slowly in reaction kettle 5, nitrogen protection, next time in 80 DEG C
Stream reaction 20h；Wherein, the mass ratio of the quality of amion acetic acid and active oxidation graphene is 1:1, N, N'- dicyclohexyl phosphinylidyne
The de- dosage of imines be account for activation graphene oxide quality 40%.
Step 6, step 5 products therefrom is passed through in the second filtration washing tower 6 and is filtered, is washed, filtered fluid is through discharging
Mouth pipeline is delivered in the second storage tank 10, is controlled through pipeline and valve, and circulation is used for the second Scattered Kettle 4.
Step 7, the product after step 6 washing is delivered to third Scattered Kettle 7, passes through high-shear emulsion machine after adding water and surpassed
The mode that sound dispersal device is run simultaneously carries out dispersion removing, and by the cooling coil being arranged in kettle, controlling dispersion temperature is 30
DEG C, the revolving speed of high-shear emulsion machine is 600r/min, and ultrasonic power 10kW, ultrasonic time 120min obtain carboxyl function
Graphite alkene aqueous slurry, the concentration of gained slurry are 10g/mL.
Step 8, step 7 gained slurry is delivered in drying tower 8 through pipeline, using upper-spraying type air-stream spraying drying mode
It is dried, is arranged 130 DEG C of drying temperature, collection obtains carboxyl-functional graphene powder.
Comparative example 1
Using the macro preparation device of carboxyl-functional graphene provided by embodiment 1, preparation method and 1 base of embodiment
This is identical, and difference from Example 1 is only that, does not enable activated reactor 2, the first filtration washing tower 3 and the second Scattered Kettle
4, i.e. comparative example 1 carry out activation modification without hydroxyl and epoxy group to graphene oxide slurry, directly progress carboxylated
It is modified.
Comparative example 2
Using the macro preparation device of carboxyl-functional graphene provided by embodiment 1, preparation method and 1 base of embodiment
This identical difference from Example 1 is, does not enable reaction kettle 5, the second filtration washing tower 6 and third Scattered Kettle 7, that is, compares
Embodiment 1 only carries out hydroxyl to graphene oxide slurry and epoxy group carries out activation modification, obtains carboxyl graphene.
Graphene in-situ polymerization modified Pa 6, the polymerization side of use are carried out to PA6 using the carboxyl-functional graphene of acquisition
Method is the embodiment 1 of Chinese patent 201711056093.X.Wherein, using the preparation-obtained carboxyl function fossil of embodiment 1
Black alkene powder in-situ polymerization modified polyamide 6 is as test sample A, using the preparation-obtained carboxyl function fossil of embodiment 2
Black alkene powder in-situ polymerization modified polyamide 6 is as test sample B, using the preparation-obtained carboxyl function fossil of comparative example 1
Black alkene powder in-situ polymerization modified polyamide 6 is as test sample C, using the preparation-obtained carboxyl function fossil of comparative example 2
Black alkene powder in-situ polymerization modified polyamide 6 is as test sample D.
Piece diameter size, lamellar spacing, carboxyl-content to the carboxyl-functional graphene of embodiment 1,2 and comparative example 1,2
It is tested, acquired results are shown in Table 1.
Carboxyl-functional graphene test result is made in each embodiment of table 1 and comparative example
| Piece diameter (nm) | Lamellar spacing (nm) | Carboxyl-content (mol/g) | |
| Embodiment 1 | 300 | 1.5 | 56.62 |
| Embodiment 2 | 250 | 1.3 | 62.78 |
| Comparative example 1 | 600 | 2.3 | 25.15 |
| Comparative example 2 | 3500 | 3.8 | 48.10 |
As shown in Table 1, carboxyl-functional graphene film diameter prepared by the method for the present invention is smaller, and lamellar spacing is small,
The carboxyl-functional graphene that carboxyl-content less carries out the method preparation of hydroxyl and epoxy group progress activation modification has obviously
Improve, this is because do not carry out hydroxyl and epoxy-activated, surface of graphene oxide can reaction active groups it is less, carrying out
Group reactivity is low when carboxy-modified, and modified effect is bad, so carboxyl-content is lower, and anti-due to not carrying out activating
It answers, few primary dispersion removing in technical process, so the carboxyl-functional graphene film diameter of preparation is relatively large, lamellar spacing
It is relatively large.
And the carboxyl-content and this hair of the carboxyl graphene of the method preparation of activation modification are only carried out to hydroxyl and epoxy group
The carboxyl-functional graphene of bright method preparation is not much different, this is because carrying out activation modification to graphene oxide, mainly
It is its hydroxyl and epoxy group to be carried out to activation modification into carboxyl, but the carboxylated graphene of such method preparation its carboxyl is in lamella
In or edge, reactivity is lower, and steric effect is larger, especially carry out in-situ polymerization it is modified when, only a small part
Carboxyl can participate in home position polymerization reaction, cannot preferably disperse, and gained graphene film diameter is larger, and lamellar spacing is big, to material
Material performance has large effect.
The tensile strength of test sample A, B, C, D, elongation at break, maximum deflection intensity, impact strength performance are carried out
Test, acquired results are shown in Table 2.
The test result of composite material obtained by each test example of table 2
| Tensile strength/MPa | Elongation at break/% | Maximum deflection intensity/MPa | Impact strength kJ/m2 | |
| Conventional PA6 | 65 | 140 | 92 | 210 |
| Sample A | 78 | 121 | 102 | 274 |
| Sample B | 85 | 130 | 110 | 280 |
| Sample C | 58 | 20 | 69 | 51 |
| Sample D | 43 | 21 | 48 | 38 |
Note: carboxyl function graphene additive amount is 0.3% in test sample A, B, C, D.
As can be seen from Table 2, it is carried out using carboxyl-functional graphene (test sample A, B) prepared by method of the invention
Modified PA6 tensile strength, maximum deflection intensity, impact strength are obviously improved, this is because carboxyl function graphite
Alkene is connect in the form of chemical bond with matrix in the base, and interface interaction power is larger, and is uniformly dispersed, and can largely be mentioned
Rise the mechanical property of composite material.By test sample C it is found that carboxyl function graphene relatively provided by the invention, gathers identical
In the case where closing technique and additive amount, the quality of carboxyl graphene is affected to the performance of modified material.It can by 1 result of table
Know, carboxyl graphene film diameter prepared by comparative example 1 is relatively large, and lamellar spacing is relatively large, and carboxyl-content is low, therefore is polymerizeing
In, graphene cannot preferably disperse in basis material PA6, to finally influence the mechanical property of material.Similar experiment is existing
As being equally present in test sample D, since graphene film diameter used is relatively large, lamellar spacing is relatively large, although carboxyl
Content is higher, but its carboxyl, in lamella or edge, reactivity is lower, and steric effect is larger, therefore in polymerization, graphene
Cannot preferably it disperse in basis material PA6, to finally influence the mechanical property of material.
Claims (10)
1. a kind of macro preparation device of carboxyl-functional graphene, which is characterized in that anti-including the first Scattered Kettle (1), activation
Answer device (2), the first filtration washing tower (3), the second Scattered Kettle (4), reaction kettle (5), the second filtration washing tower (6), third dispersion
Kettle (7), drying tower (8), the first storage tank (9) and the second storage tank (10), first Scattered Kettle (1), activated reactor (2),
One filtration washing tower (3), the second Scattered Kettle (4), reaction kettle (5), the second filtration washing tower (6), third Scattered Kettle (7) and drying
Tower (8) is sequentially connected, and the first filtration washing tower (3), first storage tank (9) and first Scattered Kettle (1) successively connect
It connecing, the second filtration washing tower (6), second storage tank (10) and second Scattered Kettle (4) are sequentially connected, and described first
High-shear emulsion machine and ultrasonic dispersers are equipped in Scattered Kettle (1), the second Scattered Kettle (4) and third Scattered Kettle (7) simultaneously.
2. the apparatus according to claim 1, which is characterized in that the drying tower (8) is upper-spraying type air-stream spraying drying tower.
3. a kind of magnanimity preparation method of the carboxyl-functional graphene using device as claimed in claim 1 or 2, feature exist
In, dispersion removing is carried out to graphite oxide by the method for mechanical dispersion first, then graphene oxide is activated,
It is eventually adding carboxylated reagent and carries out carboxylation reaction.
4. preparation method according to claim 3, which comprises the following steps:
Step 1, graphite oxide and lye investment the first Scattered Kettle (1) are subjected to mechanical dispersion, obtain the aqueous slurry of graphene oxide
Material；
Step 2, step 1 gained slurry is passed through activated reactor (2), and activator is added, carry out activated carboxylic reaction；
Step 3, step 2 products therefrom is passed through in the first filtration washing tower (3) and is filtered, is washed, filtered fluid passes through first
Storage tank (9) reuse is into the first Scattered Kettle (1)；
Step 4, the product after step 3 washing is delivered to the second Scattered Kettle (4), carries out mechanical dispersion after adding water, is activated
Graphene oxide aqueous slurry；
Step 5, step 4 gained slurry is passed through in reaction kettle (5), is slowly added to carboxylated reagent and dehydrating condensation agent carries out instead
It answers；
Step 6, step 5 products therefrom is passed through in the second filtration washing tower (6) and is filtered, is washed, filtered fluid passes through second
Storage tank (10) reuse is into the second Scattered Kettle (4)；
Step 7, the product after step 6 washing is delivered to third Scattered Kettle (7), carries out mechanical dispersion after adding water, obtains carboxyl
Functionalization graphene aqueous slurry；
Step 8, step 7 gained slurry is delivered in drying tower (8) and is dried to get carboxyl-functional graphene powder.
5. preparation method according to claim 3 or 4, which is characterized in that the method for the mechanical dispersion are as follows: cut using height
The mechanical dispersion mode cutting mulser and ultrasonic dispersers while running, 5~40 DEG C of dispersion temperature, the revolving speed of high-shear emulsion machine
For 500~3000r/min, ultrasonic power is 1~20kW, and ultrasonic time is 1~10h.
6. the preparation method according to claim 4, which is characterized in that the graphite oxide used in the step 1 is by graphite
One of powder, worm graphite, crystalline flake graphite or it is a variety of it is oxidation-treated form, lye be selected from potassium hydroxide, sodium hydroxide, ammonia
One of water is a variety of, and the pH value of gained graphene oxide aqueous slurry is 8~10.
7. the preparation method according to claim 4, which is characterized in that in the step 2, activator is monoxone or chloroethene
The mass ratio of sour sodium, graphene oxide and activator is 1:(0.1~1), the condition of priming reaction are as follows: reaction temperature 10~90
DEG C, 2~6h of reaction time.
8. the preparation method according to claim 4, which is characterized in that in the step 5, carboxylated reagent is amino second
Acid, 3- alanine, 4-Aminobutanoicacid, 5- aminovaleric acid, 6-aminocaprolc acid or p-aminobenzoic acid, dehydrating condensation agent N,
N'- Dicyclohexylcarbodiimide, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide, 4- (4,6- dimethoxy-triazine) -4-
Methyl morpholine hydrochloride, 2- (7- aoxidizes benzotriazole)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid ester or 2- (2- pyridine
Ketone -1- base) -1,1,3,3- tetramethylurea tetrafluoroborate, the mass ratio of the carboxylated reagent and active oxidation graphene is
(0.3~3): 1, the dosage of the dehydrating condensation agent is the 5~100% of active oxidation graphene quality, reaction condition are as follows: nitrogen
It protects, 2~48h of back flow reaction at 40~100 DEG C.
9. the preparation method according to claim 4, which is characterized in that in the step 1,4 and 7, the concentration of aqueous slurry
For 0.1~10.0g/mL.
10. the preparation method according to claim 4, which is characterized in that the drying mode in the step 8 is upper-spraying type gas
Stream spray drying, drying temperature are 105~180 DEG C.
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