CN105036121A - Preparation method for reinforced graphene surfactant - Google Patents
Preparation method for reinforced graphene surfactant Download PDFInfo
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- CN105036121A CN105036121A CN201510394309.8A CN201510394309A CN105036121A CN 105036121 A CN105036121 A CN 105036121A CN 201510394309 A CN201510394309 A CN 201510394309A CN 105036121 A CN105036121 A CN 105036121A
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Abstract
The invention relates to a preparation method for a reinforced graphene surfactant. The objective of the invention is to overcome the technical problem of poor compatibility between graphene oxide and organic solvents in the prior art while maintain carboxyl groups at the edge of graphene oxide and guarantee hydrophilicity of graphene oxide. The method comprises the following steps: 1, preparation of graphene oxide; 2, preparation of brominated graphene; 3, preparation of sodium ethoxide; and 4, grafting of a -OCH2CH3 group on the surface of graphene: a step of adding the brominated graphene powder prepared in the step 2 into 10 mL of tetrahydrofuran, carrying out ultrasonic treatment, then adding sodium ethoxide prepared in the step 3, continuing ultrasonic treatment, then carrying out reflux, subjecting the obtained solution to centrifugation with ethanol at first and then successively carrying out cleaning and then drying in a vacuum drying box so as to obtain a solid which is the reinforced graphene surfactant. The method has the advantages of simplicity, low cost, good repeatability, a short production period, etc. The preparation method is applied to the field of preparation of graphene surfactants.
Description
Technical field
The present invention relates to a kind of preparation method of graphenic surface promoting agent.
Background technology
Graphene is a kind of material with premium properties grown up in recent years, by carbon atom with sp
2the monoatomic layer that hydridization connects is formed, and is the thinnest two-dimensional material found at present.This special structure many peculiar physicochemical property that made it contain, as high specific surface area and excellent heat conductivility, mechanical property and electron transmission ability.Graphene oxide is generally oxidized through strong acid by graphite and obtains.Mainly contain the method that three kinds are prepared graphite oxide: Brodie method, Staudenmaier method and Hummers method.Wherein Hummers method preparation process ageing relatively better and safety, be one the most frequently used at present.The main raw material of Hummers method is the vitriol oil, potassium permanganate, hydrogen peroxide and natural graphite, oxidizing reaction is there is in lepidiod graphite under the effect of the vitriol oil and potassium permanganate, obtain the brown graphite flake having derivative carboxylic acid group at edge and be mainly phenolic hydroxyl group and epoxide group in the plane, add in hydrogen peroxide subsequently and remaining sulfuric acid and potassium permanganate, form stable, flavous suspension, after ultrasonic or high-shear vigorous stirring are peeled off, obtain graphene oxide.
The functional group contained due to graphene oxide is hydrophilic group, thus makes graphene oxide can have good dispersiveness in water.Meanwhile, the graphene functionalized that exists for of surface of graphene oxide functional group provides a good platform, and by the reaction with surface functional group, past graphenic surface that can be autonomous introduces multiple group, thus realizes the doping of Graphene and corresponding functionalization.The oxygen-containing functional group on surface makes graphene oxide be wetting ability, and it is incompatible with most of organic solvent.Therefore, researcher have employed many methods and modifies graphene oxide, improves its dispersiveness in organic solvent.Wherein carboxyl can react with functional group widely, such as amino, hydroxyl, and both are by forming amido linkage with carboxyl reaction and ester bond is adsorbed on surface of graphene oxide.
Main containing epoxy group(ing), hydroxyl and carboxyl in graphene oxide.Wherein, epoxy group(ing) and hydroxyl multidigit are in the molecule face of graphene oxide, and with molecular layer vertical distribution, and carboxyl is positioned at molecular layer edge.In redox graphene process, what different oxygen-containing functional groups was left away is difficult to degree varies sample.Fan Xiaobin etc. find in redox graphene that under highly basic heating condition epoxy group(ing) and hydroxyl more easily remove, and carboxyl relative difficult.In the research of the at high temperature redox graphene such as Ren little Meng, by under contrast differing temps, the speed that oxygen-containing functional group content declines, show that the decomposition complexity of surface of graphene oxide functional group is: epoxy group(ing) > hydroxyl > carboxyl.
Utilize reinforced graphite alkene tensio-active agent obtained by this invention can in the design of resin base microstructure ordered composite material and preparation, the aspects such as the preparation of the surface structure ordered and barrier properties for gases pressurized vessel of composite propeller obtain application.
Summary of the invention
The present invention is the poor compatibility that will solve existing graphene oxide and organic solvent, and retains the carboxyl of graphene oxide edge simultaneously, ensures its hydrophilic technical problem, thus provides a kind of preparation method of reinforced graphite alkene tensio-active agent.
The preparation method of a kind of reinforced graphite alkene tensio-active agent of the present invention carries out according to the following steps:
One, the preparation of graphene oxide: by the mass concentration of 23mL be 98% the vitriol oil join in the large beaker of 250mL, ice bath, then add the natural graphite of 1g, under rotating speed is 300 ~ 400r/min, stir 10 ~ 40min, at temperature is 0 ~ 5 DEG C, average mark adds the KMnO of 6g for 6 times
4, then under rotating speed is 300 ~ 400r/min, 2 ~ 2.5h is stirred, change ice bath, be placed in 30 ~ 40 DEG C of waters bath with thermostatic control, stir 30 ~ 60min under the rotating speed of 300 ~ 400r/min after, solution becomes sticky thick, last water temperature stability is at 40 ~ 50 DEG C, forward to again in 80 DEG C of thermostat water baths and stir under 300 ~ 400r/min, wait to be warmed up to 80 DEG C, average mark adds the distilled water of 80mL for 4 times, stir 15 ~ 20min under 300 ~ 400r/min after, add the distilled water diluting of 60mL, add the mixing solutions of the hydrogen peroxide of 30% of 10.81mL and the distilled water composition of 60mL again, after ultrasonic 1 ~ 2h, centrifugal 10min under 8000r/min, washing to pH value is 5 ~ 6, in vacuum chamber at temperature is 60 DEG C dry 7 ~ 8h, obtain graphene oxide powder,
Two, the preparation of bromination Graphene: graphene oxide powder step one prepared is dissolved in the tetrahydrofuran (THF) of 20mL, 48% Hydrogen bromide of 0.8mL is added after ultrasonic 1 ~ 2h, stir under 400 ~ 500r/min, temperature is the 30 ~ 60min that refluxes at 40 ~ 60 DEG C, obtains khaki color solution, with analytical pure tetrahydrofuran (THF) centrifugal 10min under 7000r/min, wash three times, then dry 3 ~ 4h at 40 ~ 50 DEG C in vacuum chamber, obtains bromination graphene powder, by powder-tight, deposit as dry place;
Three, the preparation of sodium ethylate: by the sodium Metal 99.5 of 12.0mg, join in the dehydrated alcohol of 10mL and react 2 ~ 3h, obtain the ethanolic soln of oyster white sodium ethylate, be transferred in Florence flask, 90 DEG C of distillation 1 ~ 2h steam residue ethanol, after not having liquid to steam, obtain sodium ethylate solid, hermetically drying is preserved;
Four, graphenic surface grafting-OCH
2cH
3group: bromination graphene powder prepared by step 2, join in the tetrahydrofuran (THF) of 10mL, ultrasonic 30 ~ 60min, add sodium ethylate prepared by step 3 subsequently, continue ultrasonic 30 ~ 40min, reflux 1 ~ 1.5h at temperature is 60 ~ 80 DEG C, then solution first used ethanol centrifugal 10min under 7000r/min, clean 3 times, being washed to pH value is subsequently 6 ~ 7, dry 6 ~ 8h at 60 DEG C in vacuum drying oven, obtain solid, gained solid is reinforced graphite alkene tensio-active agent.
Principle of the present invention is:
Prepare graphene oxide.Adopt and improve Hummers legal system for graphene oxide.Hummers legal system will successively through peroxidation and reduction two processes for graphene oxide, and the principle of oxidising process is that natural graphite is oxidized by employing strong oxidizer, makes its surface produce oxygen-containing functional group, and then produces stripping of expanding; Then add hydrogen peroxide to reduce to the Graphene peeled off.
Preparation bromination Graphene.Hydrogen bromide has very strong acidity, can with epoxy group(ing) generation addition reaction.The epoxide group of surface of graphene oxide mostly is three-membered ring structures, make the track of each atom can not front fully overlapping, but to be interconnected with Bending Bond, thus make in molecule, to there is a kind of tension force, very easily react with plurality of reagents, ring is opened, especially in acid condition, open loop is easy to.Take Hydrogen bromide as Ring Opening Reagent, effective open loop can be realized.Simultaneously Hydrogen bromide is as nucleophilic reagent, can also with hydroxyl generation nucleophilic substitution.The hydroxyl of surface of graphene oxide can see tertiary alcohol as, and because carbon-oxygen bond is polar covalent bond, and the electronegativity of oxygen is greater than carbon, so share electron pair is partial to oxygen, the carbon atom participating in into key becomes positivity carbon.When bromine negative ion attack positivity carbon as nucleophilic reagent, C―O bond cleavage, hydroxyl is replaced by bromide anion.Just energy and Hydrogen bromide react at a lower temperature for tertiary alcohol and epoxy group(ing).
Graphenic surface grafted hydrophobic group-OCH
2cH
3.Utilize the reaction of sodium ethylate and halohydrocarbon, in anhydrous conditions, make the C-Br key in bromination Graphene atomic plane be converted into C-OCH
2cH
3.Because C-O key bond energy is comparatively large, stable reinforced graphite alkene tensio-active agent can be obtained.
The present invention includes following beneficial effect:
1, the present invention changes the functional group of graphene oxide, the modified graphene tensio-active agent of the type that is enhanced by organic chemical reactions.Owing to there is hydrophobic functional group and hydrophilic functional groups in this graphene-structured simultaneously, make ideally, in the mixing solutions of water and low-pole during violent stirring, Graphene serves as tensio-active agent can form emulsion, become a microreactor, thus provide a new method for other particles graphene-supported.
2, when the concentration of graphene aqueous solution of the present invention is less, the Graphene in solution can preferentially be sprawled at the interface of water oil, can be used for preparing graphene film.
The advantages such as 3, present method has easy, low cost, favorable repeatability, with short production cycle.
Accompanying drawing explanation
Fig. 1 is the preparation feedback schematic diagram of reinforced graphite alkene tensio-active agent of the present invention;
Fig. 2 be the graphene oxide of 0.5mg/mL and reinforced graphite alkene tensio-active agent of the present invention ultrasonic in water and cyclohexane solution before deployment conditions; Wherein, a be the graphene oxide of 0.5mg/mL ultrasonic in water and cyclohexane solution before deployment conditions, b be the reinforced graphite alkene tensio-active agent of the present invention of 0.5mg/mL ultrasonic in water and cyclohexane solution before deployment conditions;
Fig. 3 is the graphene oxide of 0.5mg/mL and the ultrasonic 10min of reinforced graphite alkene tensio-active agent of the present invention of 0.5mg/mL, the deployment conditions after static 5min in water and cyclohexane solution; Wherein, a is the ultrasonic 10min of graphene oxide of 0.5mg/mL, deployment conditions after static 5min in water and cyclohexane solution, b is the ultrasonic 10min of reinforced graphite alkene tensio-active agent of the present invention of 0.5mg/mL, the deployment conditions after static 5min in water and cyclohexane solution;
Fig. 4 is the infrared sight spectrogram of graphene oxide and reinforced graphite alkene tensio-active agent of the present invention; Wherein, 1 is the infrared sight spectrogram of graphene oxide, and 2 is the infrared sight spectrogram of reinforced graphite alkene tensio-active agent of the present invention.
Embodiment
Embodiment one: the preparation method of a kind of reinforced graphite alkene tensio-active agent of present embodiment carries out according to the following steps:
One, the preparation of graphene oxide: by the mass concentration of 23mL be 98% the vitriol oil join in the large beaker of 250mL, ice bath, then add the natural graphite of 1g, under rotating speed is 300 ~ 400r/min, stir 10 ~ 40min, at temperature is 0 ~ 5 DEG C, average mark adds the KMnO of 6g for 6 times
4, then under rotating speed is 300 ~ 400r/min, 2 ~ 2.5h is stirred, change ice bath, be placed in 30 ~ 40 DEG C of waters bath with thermostatic control, stir 30 ~ 60min under the rotating speed of 300 ~ 400r/min after, solution becomes sticky thick, last water temperature stability is at 40 ~ 50 DEG C, forward to again in 80 DEG C of thermostat water baths and stir under 300 ~ 400r/min, wait to be warmed up to 80 DEG C, average mark adds the distilled water of 80mL for 4 times, stir 15 ~ 20min under 300 ~ 400r/min after, add the distilled water diluting of 60mL, add the mixing solutions of the hydrogen peroxide of 30% of 10.81mL and the distilled water composition of 60mL again, after ultrasonic 1 ~ 2h, centrifugal 10min under 8000r/min, washing to pH value is 5 ~ 6, in vacuum chamber at temperature is 60 DEG C dry 7 ~ 8h, obtain graphene oxide powder,
Two, the preparation of bromination Graphene: graphene oxide powder step one prepared is dissolved in the tetrahydrofuran (THF) of 20mL, 48% Hydrogen bromide of 0.8mL is added after ultrasonic 1 ~ 2h, stir under 400 ~ 500r/min, temperature is the 30 ~ 60min that refluxes at 40 ~ 60 DEG C, obtains khaki color solution, with analytical pure tetrahydrofuran (THF) centrifugal 10min under 7000r/min, wash three times, then dry 3 ~ 4h at 40 ~ 50 DEG C in vacuum chamber, obtains bromination graphene powder, by powder-tight, deposit as dry place;
Three, the preparation of sodium ethylate: by the sodium Metal 99.5 of 12.0mg, join in the dehydrated alcohol of 10mL and react 2 ~ 3h, obtain the ethanolic soln of oyster white sodium ethylate, be transferred in Florence flask, 90 DEG C of distillation 1 ~ 2h steam residue ethanol, after not having liquid to steam, obtain sodium ethylate solid, hermetically drying is preserved;
Four, graphenic surface grafting-OC
2h
7group: bromination graphene powder prepared by step 2, join in the tetrahydrofuran (THF) of 10mL, ultrasonic 30 ~ 60min, add sodium ethylate prepared by step 3 subsequently, continue ultrasonic 30 ~ 40min, reflux 1 ~ 1.5h at temperature is 60 ~ 80 DEG C, then solution first used ethanol centrifugal 10min under 7000r/min, clean 3 times, being washed to pH value is subsequently 6 ~ 7, dry 6 ~ 8h at 60 DEG C in vacuum drying oven, obtain solid, gained solid is reinforced graphite alkene tensio-active agent.
The principle of present embodiment is:
Prepare graphene oxide.Adopt and improve Hummers legal system for graphene oxide.Hummers legal system will successively through peroxidation and reduction two processes for graphene oxide, and the principle of oxidising process is that natural graphite is oxidized by employing strong oxidizer, makes its surface produce oxygen-containing functional group, and then produces stripping of expanding; Then add hydrogen peroxide to reduce to the Graphene peeled off.
Preparation bromination Graphene.Hydrogen bromide has very strong acidity, can with epoxy group(ing) generation addition reaction.The epoxide group of surface of graphene oxide mostly is three-membered ring structures, make the track of each atom can not front fully overlapping, but to be interconnected with Bending Bond, thus make in molecule, to there is a kind of tension force, very easily react with plurality of reagents, ring is opened, especially in acid condition, open loop is easy to.Take Hydrogen bromide as Ring Opening Reagent, effective open loop can be realized.Simultaneously Hydrogen bromide is as nucleophilic reagent, can also with hydroxyl generation nucleophilic substitution.The hydroxyl of surface of graphene oxide can see tertiary alcohol as, and because carbon-oxygen bond is polar covalent bond, and the electronegativity of oxygen is greater than carbon, so share electron pair is partial to oxygen, the carbon atom participating in into key becomes positivity carbon.When bromine negative ion attack positivity carbon as nucleophilic reagent, C―O bond cleavage, hydroxyl is replaced by bromide anion.Just energy and Hydrogen bromide react at a lower temperature for tertiary alcohol and epoxy group(ing).
Graphenic surface grafted hydrophobic group-OCH
2cH
3.Utilize the reaction of sodium ethylate and halohydrocarbon, in anhydrous conditions, make the C-Br key in bromination Graphene atomic plane be converted into C-OCH
2cH
3.Because C-O key bond energy is comparatively large, stable reinforced graphite alkene tensio-active agent can be obtained.
Present embodiment comprises following beneficial effect:
1, present embodiment changes the functional group of graphene oxide by organic chemical reactions, the modified graphene tensio-active agent of the type that is enhanced.Owing to there is hydrophobic functional group and hydrophilic functional groups in this graphene-structured simultaneously, make ideally, in the mixing solutions of water and low-pole during violent stirring, Graphene serves as tensio-active agent can form emulsion, become a microreactor, thus provide a new method for other particles graphene-supported.
2, when the concentration of the graphene aqueous solution of present embodiment is less, the Graphene in solution can preferentially be sprawled at the interface of water oil, can be used for preparing graphene film.
The advantages such as 3, present method has easy, low cost, repeatable, with short production cycle.
Embodiment two: present embodiment and embodiment one, unlike the natural graphite adding 1g in step one, stir 30min under rotating speed is 400r/min.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: be placed in 30 DEG C of waters bath with thermostatic control in step one, under 300r/min, stir 40min.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: stir under 500r/min in step 2, temperature is the 60min that refluxes at 60 DEG C.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: in step 2 in vacuum chamber dry 3h at 40 DEG C.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: reflux in step 4 1h at temperature is 70 DEG C.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: in step 4 in vacuum drying oven dry 8h at 60 DEG C.Other is identical with one of embodiment one to six.
Test one: the preparation method of a kind of reinforced graphite alkene tensio-active agent of this test realizes according to the following steps:
One, the preparation of graphene oxide: by the mass concentration of 23mL be 98% the vitriol oil join in the large beaker of 250mL, ice bath, then add the natural graphite of 1g, under rotating speed is 400r/min, stirs 30min, at temperature is 4 DEG C, average mark adds the KMnO of 6g for 6 times
4, then under rotating speed is 400r/min, 2h is stirred, change ice bath, be placed in 30 DEG C of waters bath with thermostatic control, stir 40min under the rotating speed of 400r/min after, solution becomes sticky thick, last water temperature stability is at 45 DEG C, forward to again in 80 DEG C of thermostat water baths and stir under 400r/min, wait to be warmed up to 80 DEG C, average mark adds the distilled water of 80mL for 4 times, stir 20min under 400r/min after, add 60mL distilled water diluting, add the mixing solutions of the hydrogen peroxide of 30% of 10.81mL and the distilled water composition of 60mL again, after ultrasonic 1.5h, centrifugal 10min under 8000r/min, washing to pH value is 6, in vacuum chamber at temperature is 60 DEG C dry 8h, obtain graphene oxide powder,
Two, the preparation of bromination Graphene: graphene oxide powder 96.0mg step one prepared is dissolved in the tetrahydrofuran (THF) of 20mL, 48% Hydrogen bromide of 0.8mL is added after ultrasonic 1h, stir under 500r/min, temperature is the 1h that refluxes at 60 DEG C, obtains khaki color solution, with analytical pure tetrahydrofuran (THF) centrifugal 10min under 7000r/min, wash three times, then dry 3h at 40 DEG C in vacuum chamber, obtains bromination graphene powder, by powder-tight, deposit as dry place;
Three, the preparation of sodium ethylate: by the sodium Metal 99.5 of 12.0mg, joins in the dehydrated alcohol of 10mL and reacts 3h, obtains the ethanolic soln of oyster white sodium ethylate, be transferred in Florence flask, 90 DEG C steam residue ethanol, after not having liquid to steam, obtain sodium ethylate solid, hermetically drying is preserved;
Four, graphenic surface grafting-OCH
2cH
3group: get bromination graphene powder 23.8mg prepared by step 2, join in the tetrahydrofuran (THF) of 10mL, ultrasonic 30min, add sodium ethylate prepared by step 3 subsequently, continue ultrasonic 30min, reflux 1h at temperature is 70 DEG C, centrifugal 10min under solution first carries 7000r/min with ethanol, cleans 3 times, being washed to pH value is subsequently 6, in vacuum drying oven, dry 8h at 60 DEG C, obtains solid, and gained solid is reinforced graphite alkene tensio-active agent.
Fig. 1 is the preparation feedback schematic diagram of reinforced graphite alkene tensio-active agent of the present invention.
Fig. 2 be the graphene oxide of 0.5mg/mL and reinforced graphite alkene tensio-active agent of the present invention ultrasonic in water and cyclohexane solution before deployment conditions; Wherein, a be the graphene oxide of 0.5mg/mL ultrasonic in water and cyclohexane solution before deployment conditions, b be the reinforced graphite alkene tensio-active agent of the present invention of 0.5mg/mL ultrasonic in water and cyclohexane solution before deployment conditions; As can be seen from Figure 2, graphene oxide and reinforced graphite alkene tensio-active agent of the present invention can well disperse in water, illustrate that reinforced graphite alkene tensio-active agent of the present invention has wetting ability.
Fig. 3 is the graphene oxide of 0.5mg/mL and the ultrasonic 10min of reinforced graphite alkene tensio-active agent of the present invention of 0.5mg/mL, the deployment conditions after static 5min in water and cyclohexane solution; Wherein, a is the ultrasonic 10min of graphene oxide of 0.5mg/mL, deployment conditions after static 5min in water and cyclohexane solution, b is the ultrasonic 10min of reinforced graphite alkene tensio-active agent of the present invention of 0.5mg/mL, the deployment conditions after static 5min in water and cyclohexane solution; As can be seen from Figure 3, the very fast interface at water and hexanaphthene of reinforced graphite alkene tensio-active agent of the present invention is assembled, and illustrates that reinforced graphite alkene tensio-active agent of the present invention has stronger hydrophobicity than graphene oxide.
Fig. 4 is the infrared sight spectrogram of graphene oxide and reinforced graphite alkene tensio-active agent of the present invention; Wherein, 1 is the infrared sight spectrogram of graphene oxide, and 2 is the infrared sight spectrogram of reinforced graphite alkene tensio-active agent of the present invention; As can be seen from Figure 4, compared with graphene oxide, reinforced graphite alkene tensio-active agent of the present invention is at 1227cm
-1place does not have the stretching vibration peak of C-OH, and is belonging to the antisymmetric stretching vibration 2920cm of alkyl C-H
-1place and belong to the in-plane bending vibration 1453cm of alkyl C-H
-1place has strong absorption peak, shows that-the OH of surface of graphene oxide is effectively by-OCH
2cH
3replace, thus make reinforced graphite alkene tensio-active agent of the present invention have good hydrophobicity.Meanwhile, at 3400cm
-1near-OH stretching vibration absorption peak, reinforced graphite alkene tensio-active agent of the present invention and graphene oxide all have a strong and wide absorption peak, show still to retain this carboxyl in reinforced graphite alkene tensio-active agent of the present invention, ensure that its wetting ability.
Claims (7)
1. a preparation method for reinforced graphite alkene tensio-active agent, is characterized in that the preparation method of reinforced graphite alkene tensio-active agent carries out according to the following steps:
One, the preparation of graphene oxide: by the mass concentration of 23mL be 98% the vitriol oil join in the large beaker of 250mL, ice bath, then add the natural graphite of 1g, under rotating speed is 300 ~ 400r/min, stir 10 ~ 40min, at temperature is 0 ~ 5 DEG C, average mark adds the KMnO of 6g for 6 times
4, then under rotating speed is 300 ~ 400r/min, 2 ~ 2.5h is stirred, change ice bath, be placed in 30 ~ 40 DEG C of waters bath with thermostatic control, stir 30 ~ 60min under the rotating speed of 300 ~ 400r/min after, solution becomes sticky thick, last water temperature stability is at 40 ~ 50 DEG C, forward to again in 80 DEG C of thermostat water baths and stir under 300 ~ 400r/min, wait to be warmed up to 80 DEG C, average mark adds the distilled water of 80mL for 4 times, stir 15 ~ 20min under 300 ~ 400r/min after, add the distilled water diluting of 60mL, add the mixing solutions of the hydrogen peroxide of 30% of 10.81mL and the distilled water composition of 60mL again, after ultrasonic 1 ~ 2h, centrifugal 10min under 8000r/min, washing to pH value is 5 ~ 6, in vacuum chamber at temperature is 60 DEG C dry 7 ~ 8h, obtain graphene oxide powder,
Two, the preparation of bromination Graphene: graphene oxide powder step one prepared is dissolved in the tetrahydrofuran (THF) of 20mL, 48% Hydrogen bromide of 0.8mL is added after ultrasonic 1 ~ 2h, stir under 400 ~ 500r/min, temperature is the 30 ~ 60min that refluxes at 40 ~ 60 DEG C, obtains khaki color solution, with analytical pure tetrahydrofuran (THF) centrifugal 10min under 7000r/min, wash three times, then dry 3 ~ 4h at 40 ~ 50 DEG C in vacuum chamber, obtains bromination graphene powder, by powder-tight, deposit as dry place;
Three, the preparation of sodium ethylate: by the sodium Metal 99.5 of 12.0mg, join in the dehydrated alcohol of 10mL and react 2 ~ 3h, obtain the ethanolic soln of oyster white sodium ethylate, be transferred in Florence flask, 90 DEG C of distillation 1 ~ 2h steam residue ethanol, after not having liquid to steam, obtain sodium ethylate solid, hermetically drying is preserved;
Four, graphenic surface grafting-OCH
2cH
3group: bromination graphene powder prepared by step 2, join in the tetrahydrofuran (THF) of 10mL, ultrasonic 30 ~ 60min, add sodium ethylate prepared by step 3 subsequently, continue ultrasonic 30 ~ 40min, reflux 1 ~ 1.5h at temperature is 60 ~ 80 DEG C, then solution first used ethanol centrifugal 10min under 7000r/min, clean 3 times, being washed to pH value is subsequently 6 ~ 7, dry 6 ~ 8h at 60 DEG C in vacuum drying oven, obtain solid, gained solid is reinforced graphite alkene tensio-active agent.
2. the preparation method of a kind of reinforced graphite alkene tensio-active agent according to claim 1, is characterized in that the natural graphite adding 1g in step one, under rotating speed is 400r/min, stirs 30min.
3. the preparation method of a kind of reinforced graphite alkene tensio-active agent according to claim 1, is characterized in that being placed in 30 DEG C of waters bath with thermostatic control in step one, under the rotating speed of 300r/min, stirs 40min.
4. the preparation method of a kind of reinforced graphite alkene tensio-active agent according to claim 1, is characterized in that stirring under 500r/min in step 2, and temperature is the 60min that refluxes at 60 DEG C.
5. the preparation method of a kind of reinforced graphite alkene tensio-active agent according to claim 1, to is characterized in that in step 2 in vacuum chamber dry 3h at 40 DEG C.
6. the preparation method of a kind of reinforced graphite alkene tensio-active agent according to claim 1, is characterized in that refluxing at temperature is 70 DEG C in step 4 1h.
7. the preparation method of a kind of reinforced graphite alkene tensio-active agent according to claim 1, to is characterized in that in step 4 in vacuum drying oven dry 8h at 60 DEG C.
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| CN105503581A (en) * | 2015-12-31 | 2016-04-20 | 陕西师范大学 | Water-soluble nano graphene surfactant, and synthesis method and application thereof |
| CN108314032A (en) * | 2018-04-18 | 2018-07-24 | 哈尔滨工业大学 | It is a kind of that there is anti-icing and deicing function the graphene-based material of 3 D stereo reticular structure and preparation method thereof |
| CN110562970A (en) * | 2019-06-20 | 2019-12-13 | 昆明物理研究所 | Preparation method of bromine-doped graphene oxide |
| CN111693578A (en) * | 2020-06-11 | 2020-09-22 | 中国农业科学院农业信息研究所 | Crop growth information monitoring method and device and manufacturing method thereof |
| CN111908847A (en) * | 2020-08-18 | 2020-11-10 | 蔡燕嫦 | Anti-freezing and anti-cracking concrete and preparation method thereof |
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| CN105503581A (en) * | 2015-12-31 | 2016-04-20 | 陕西师范大学 | Water-soluble nano graphene surfactant, and synthesis method and application thereof |
| CN108314032A (en) * | 2018-04-18 | 2018-07-24 | 哈尔滨工业大学 | It is a kind of that there is anti-icing and deicing function the graphene-based material of 3 D stereo reticular structure and preparation method thereof |
| CN110562970A (en) * | 2019-06-20 | 2019-12-13 | 昆明物理研究所 | Preparation method of bromine-doped graphene oxide |
| CN113025188A (en) * | 2020-06-08 | 2021-06-25 | 深圳市烯世传奇科技有限公司 | Antifogging coating and preparation method thereof |
| CN111693578A (en) * | 2020-06-11 | 2020-09-22 | 中国农业科学院农业信息研究所 | Crop growth information monitoring method and device and manufacturing method thereof |
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