CN103342904A - Method for preparing water-soluble graphene by titanate coupling agent modification process - Google Patents
Method for preparing water-soluble graphene by titanate coupling agent modification process Download PDFInfo
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Abstract
The invention relates to a method for preparing water-soluble graphene by a titanate coupling agent modification process, which comprises the following steps: heating expandable graphite at the high temperature of 1100 DEG C to obtain vermicular expanded graphite, oxidating the expanded graphite to obtain graphite oxide, dispersing the graphite oxide in a hydrosolvent, and stripping by magnetically stirring or the like to obtain graphene oxide; sequentially adding a titanate coupling agent and hydrazine hydrate into the graphene oxide dispersion solution to obtain a mixed solution; reacting the mixed solution by a water bath heating process to reduce the graphene oxide and graft the titanate coupling agent molecules; and filtering and cleaning the obtained mixed solution repeatedly to remove the excessive hydrazine hydrate and titanate coupling agent, and carrying out vacuum drying to obtain the powdery modified graphene. The invention has the advantages of simple technique, high production efficiency and environment-friendly production process and product, and the prepared graphene has high dispersion stability in water and can be stored for a long time; and thus, the invention is suitable for preparing composite materials and coating materials.
Description
Technical field
The present invention relates to the method that a kind of titanate coupling agent modification method prepares water-soluble Graphene, belong to Graphene and preparing technical field thereof.
Background technology
Graphene: Graphene only has a carbon atom thick, is present the thinnest known material.It is not only in the known materials the thinnest a kind of, also very firmly and soft.It has high physical strength, good thermal conductivity and carrier mobility fast, for transistor, the contour performance preparation of devices of sensor provide raw material.In addition, Graphene has high specific surface area, can be used for preparing nano composite material.Along with making known of Nobel Prize in physics winner in 2010, scientific circles have begun one again and have taken turns the new discussion about the Nobel prize, and graphite (Graphene) also becomes the focus that everybody discusses simultaneously.
In recent years, people constantly explore novel method to improve the output of Graphene, wherein the chemistry redox method is widely adopted (Songfeng Pei owing to preparing Graphene in a large number, Hui-Ming Cheng.The reduction of graphene oxide.Carbon.2012,50 (9): 1972 – 2012.).This method at first prepares graphite oxide, earlier Graphite Powder 99 is dispersed in the strong oxidizing property mixing acid, for example concentrated nitric acid and the vitriol oil add strong oxidizers such as potassium permanganate or Potcrate then and obtain graphite oxide, obtain graphene oxide through ultrasonic peeling off again, obtain Graphene finally by reduction reaction.Adopt its surface of Graphene of this method preparation that a small amount of oxygen-containing functional group is only arranged, so the surface is hydrophobicity, makes it in water and common organic solvent, very easily reunite and precipitate.Therefore, need effectively modify and functionalization it, to improve its dispersiveness in water.The method that bibliographical information is used for the Graphene surface chemical modification mainly contains amino modified method, surfactant method, silane coupling agent method, (Yan Wang such as polymer grafting, ZiXing Shi ', Jie Yin.Kevlar oligomer functionalized graphene for polymer composites.2011,52 (16): 3661 – 3670.).The range of application of different method of modifying is different, disclosed titanic acid ester method of modifying in this patent, the Graphene that is particluarly suitable for disperseing in the water-based system comprises the aqueous solution for preparing Graphene, the aqueous high molecular matrix material that the preparation Graphene strengthens, the water-borne coatings that the preparation Graphene strengthens etc.
Summary of the invention the present invention proposes the method that a kind of titanate coupling agent modification method prepares water-soluble Graphene at the widespread use problem of Graphene in water-based system that prior art exists.Titanate coupling agent is a kind of novel coupling agent, and it can play the effect of molecule bridge between inorganics and matrix, and it is few to have a consumption, characteristics such as dispersion effect is good, and price is low, and is applied widely.Graphene after the modification is individual layer still, grafting titanium ester acid coupling agent on it; The preparation method is simply effective; The modified graphene that obtains anti-effect of settling in water is good.
Technical problem of the present invention is solved by following technical scheme:
A kind of titanate coupling agent modification method prepares the method for water-soluble Graphene, obtain graphene oxide by oxidation style, reduction connects titanate coupling agent when obtaining Graphene, the modified graphene that obtains can be stable be dispersed in the water, and the bridging effect by titanate coupling agent, can combine with different types of aqueous high molecular material or water-borne coatings, obtain various matrix materials or composite coating that finely dispersed modified graphene strengthens, mainly may further comprise the steps:
A) expansible black lead is reacted 15s under 1100 ℃ of high temperature and obtain vermiform expanded graphite, expanded graphite obtains graphite oxide by oxidation style (hummers) method then, graphite oxide is distributed in the water solvent, and it is 0.2～4mg/ml that graphite oxide disperses concentration; Peel off by magnetic agitation, mechanical vibration or ultrasonic method, obtain graphene oxide;
B) in steps A) the graphene oxide dispersion liquid in successively add titanate coupling agent and hydrazine hydrate, obtain mixed solution; Described titanate coupling agent add-on is 1%～500% of graphene oxide quality; The hydrazine hydrate add-on is 10～500 times of graphene oxide quality;
C) with step B) mixed solution that makes reacts under heating in water bath method, hydro-thermal reaction method or microwave assisting method, makes graphene oxide reduction and the titanate coupling agent of grafting simultaneously molecule;
D) to step C) mixed solution that obtains filters repeatedly and cleans, and removes excessive hydrazine hydrate and titanate coupling agent 60 ℃ of dryings of vacuum then, obtains Powdered modified graphene.
Step B) described titanate coupling agent kind is a kind of among commercially available TM-200S, LD-125, KR-238S or the TM-138S.
Preferably, step C) heating in water bath for reaction temperature is 50 ℃～90 ℃, and the heating in water bath for reaction time is 10h～48h.
The temperature of reaction of hydro-thermal reaction preferably, step C) is 100 ℃～180 ℃, and the reaction times of hydro-thermal reaction is 8h～24h.
Preferably, step C) the microwave reaction temperature is 80 ℃～120 ℃, and the microwave reaction time is 5min～1h.
A kind of have the titanate coupling agent on the chemical graft by above any modified graphene that described method obtains on the Graphene lamella, the anti-sedimentation in water is all above one month.
Compared with prior art, the modified graphene of the present invention's preparation has following advantage:
1. the water-soluble modified Graphene of titanate coupling agent of the present invention has good performance, and the value of surface resistivity is 26～780k Ω/sq, therefore adds the electroconductibility that will improve matrix material in the matrix material to.
2. the modified graphene of the inventive method preparation, there is the titanate coupling agent on the chemical graft on the surface, and the therefore dispersion stabilization height in water can be long time stored, do not change its dispersion state.
3. the titanate coupling agent that uses of the present invention is because the special construction of titanium, thereby the function of multiple uniqueness is arranged, and wide at matrix material and coated material field range of application, effect is remarkable; Therefore the Graphene of titanic acid ester modification is fit to be applied to the preparation of matrix material and coated material.
4. the present invention is water-soluble modified, therefore has more environment protection significance, is applicable to environment friendly composite material and coated material.
5. the present invention adopts heating in water bath for reaction, hydro-thermal reaction or microwave-assisted reaction, and any reaction all can obtain the Graphene of modification, illustrates that Reaction conditions range is big, can obtain target product by multiple path.
6. technology of the present invention is simple, the production efficiency height, and the equal environmental protection of production process and product, production cost is low, and different batches product favorable reproducibility is fit to large-scale production.
Embodiment
The present invention is described in detail below in conjunction with embodiment, but present embodiment can not be used for restriction the present invention, and every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
The numerical value of employing Zeta potential quantizes the stability of modified graphene aqueous dispersions among the embodiment.Zeta potential is to repelling or attract the tolerance of intensity of force between the particle mutually.Zeta potential (plus or minus) is more high, and system is more stable, namely disperses to resist gathering.Otherwise Zeta potential (plus or minus) is more low, more tends to condense or condense, and namely magnetism has surpassed repulsive force, disperses destroyed and generation reunion and precipitation.
Following examples all are expansible black lead to be reacted 15s obtain vermiform expanded graphite under 1100 ℃ of high temperature, and expanded graphite obtains graphite oxide by the oxidation of hummers method then.
[embodiment 1]
With graphite oxide with concentration 0.2mg/ml ultra-sonic dispersion in water; Earlier titanate coupling agent LD-125 is added in the graphene oxide dispersion liquid, add-on is 100% of graphene oxide quality; Add hydrazine hydrate again, add-on is 500 times of graphene oxide quality; Then under heating in water bath 60 ℃ the reaction 10h; Reaction back with washed with de-ionized water to pH=7; Obtain the modified graphene powder after 60 ℃ of dryings of vacuum; The modified graphene powder is dispersed in the deionized water with 1mg/ml.
Anti-sedimentation result: in water, can stable dispersion surpass a week.
Surface resistivity: 321k Ω/sq;
Zeta potential :-32mV.
[embodiment 2]
With graphene oxide with concentration 2mg/ml ultra-sonic dispersion in water; Titanate coupling agent LD-125 is joined in the graphene oxide dispersion liquid, and add-on is 400% of graphene oxide quality; Add hydrazine hydrate, add-on is 500 times of graphene oxide quality; And then the following 80 ℃ of reaction 30min of microwave-assisted;
Anti-sedimentation result: the energy stable dispersion was above one month in water;
Sheet resistance value: 513k Ω/sq;
Zeta potential :-41mV.
[embodiment 3]
Graphite oxide is distributed in the water with concentration 4mg/ml magnetic agitation; Titanate coupling agent TM-200S is joined in the graphene oxide dispersion liquid, and add-on is 200% of graphene oxide quality; Add hydrazine hydrate, add-on is 10 times of graphene oxide quality; Then in water heating kettle 180 ℃ the reaction 24h;
Anti-sedimentation result: the energy stable dispersion was above one month in water;
Sheet resistance value: 712k Ω/sq;
Zeta potential :-42mV.
[embodiment 4]
With graphite oxide with concentration 2mg/ml ultra-sonic dispersion in water; Titanate coupling agent TM-138S is joined in the graphene oxide dispersion liquid, and add-on is 1% of graphene oxide quality; Add hydrazine hydrate, add-on is 300 times of graphene oxide quality; And then the following 120 ℃ of reaction 1h of microwave-assisted;
Anti-sedimentation result: in water, can stable dispersion surpass a week;
Sheet resistance value: 26k Ω/sq;
Zeta potential :-31mV.
[embodiment 5]
Graphite oxide is distributed in the water with concentration 1mg/ml mechanical vibration; Titanate coupling agent TM-200S is joined in the graphene oxide dispersion liquid, and add-on is 500% of graphene oxide quality; Add hydrazine hydrate, add-on is 300 times of graphene oxide quality; Then under heating in water bath 70 ℃ the reaction 40min;
Anti-sedimentation result: the energy stable dispersion was above one month in water;
Sheet resistance value: 103k Ω/sq;
Zeta potential :-37mV.
[embodiment 6]
With graphite oxide with concentration 2mg/ml ultra-sonic dispersion in water; Titanate coupling agent TM-138S is joined in the graphene oxide dispersion liquid, and add-on is 100% of graphene oxide quality; Add hydrazine hydrate, add-on is 500 times of graphene oxide quality; Then in water heating kettle 180 ℃ the reaction 8h;
Anti-sedimentation result: in water, can stable dispersion surpass a week;
Sheet resistance value: 42k Ω/sq;
Zeta potential :-32mV.
[embodiment 7]
Graphite oxide is distributed in the water with concentration 1mg/ml mechanical vibration; Titanate coupling agent LD-125 is joined in the graphene oxide dispersion liquid, and add-on is 500% of graphene oxide quality; Add hydrazine hydrate, add-on is 500 times of graphene oxide quality; Then under microwave-assisted 120 ℃ the reaction 50min;
Anti-sedimentation result: the energy stable dispersion was above one month in water;
Sheet resistance value: 529k Ω/sq;
Zeta potential :-43mV.
[embodiment 8]
Graphite oxide is distributed in the water with concentration 1mg/ml magnetic agitation; Titanate coupling agent KR-238S is joined in the graphene oxide dispersion liquid, and add-on is 200% of graphene oxide quality; Add hydrazine hydrate, add-on is 300 times of graphene oxide quality; Then under microwave-assisted 120 ℃ the reaction 40min;
Anti-sedimentation result: in water, can stable dispersion surpass a week;
Sheet resistance value: 519k Ω/sq;
Zeta potential :-38mV.
[embodiment 9]
With graphite oxide with concentration 0.2mg/ml ultra-sonic dispersion in water; Earlier titanate coupling agent TM-138S is added in the graphene oxide dispersion liquid, add-on is 100% of graphene oxide quality; Add hydrazine hydrate again, add-on is 500 times of graphene oxide quality; Then under heating in water bath 50 ℃ the reaction 48h;
Anti-sedimentation result: in water, can stable dispersion surpass a week.
Surface resistivity: 326k Ω/sq;
Zeta potential :-35mV.
[embodiment 10]
With graphite oxide with concentration 3mg/ml ultra-sonic dispersion in water; Earlier titanate coupling agent KR-238S is added in the graphene oxide dispersion liquid, add-on is 10% of graphene oxide quality; Add hydrazine hydrate again, add-on is 500 times of graphene oxide quality; Then under heating in water bath 90 ℃ the reaction 10h; Reaction back with washed with de-ionized water to pH=7; Obtain the modified graphene powder after 60 ℃ of dryings of vacuum; The modified graphene powder is dispersed in the deionized water with 1mg/ml.
Anti-sedimentation result: in water, can stable dispersion surpass a week.
Surface resistivity: 331k Ω/sq;
Zeta potential :-39mV.
[embodiment 11]
With graphite oxide with concentration 2mg/ml ultra-sonic dispersion in water; Earlier titanate coupling agent LD-125 is added in the graphene oxide dispersion liquid, add-on is 200% of graphene oxide quality; Add hydrazine hydrate again, add-on is 500 times of graphene oxide quality; Then in water heating kettle 100 ℃ the reaction 16h.
Anti-sedimentation result: the energy stable dispersion was above one month in water.
Surface resistivity: 327k Ω/sq;
Zeta potential :-41mV.
Claims (5)
1. a titanate coupling agent modification method prepares the method for water-soluble Graphene, it is characterized in that: obtain graphene oxide by oxidation style, reduction connects titanate coupling agent when obtaining Graphene, the modified graphene that obtains can be stable be dispersed in the water, and the bridging effect by titanate coupling agent, combine with aqueous high molecular material or water-borne coatings, obtain various matrix materials or composite coating that finely dispersed modified graphene strengthens; Specifically may further comprise the steps:
A) expansible black lead is heated 15s under 1100 ℃ of high temperature and obtain vermiform expanded graphite, expanded graphite obtains graphite oxide by oxidation style then, and graphite oxide is distributed in the water solvent, and it is 0.2～4mg/ml that graphite oxide disperses concentration; Peel off by magnetic agitation, mechanical vibration or ultrasonic method, obtain graphene oxide;
B) in steps A) the graphene oxide dispersion liquid in successively add titanate coupling agent and hydrazine hydrate, obtain mixed solution; Described titanate coupling agent add-on is 1%～500% of graphene oxide quality; The hydrazine hydrate add-on is 10～500 times of graphene oxide quality;
C) with step B) mixed solution that makes reacts under heating in water bath method, hydro-thermal reaction method or microwave assisting method, makes graphene oxide reduction and the titanate coupling agent of grafting simultaneously molecule;
D) to step C) mixed solution that obtains filters repeatedly and cleans, and removes excessive hydrazine hydrate and titanate coupling agent 60 ℃ of dryings of vacuum then, obtains Powdered modified graphene.
2. a kind of titanate coupling agent modification method according to claim 1 prepares the method for water-soluble Graphene, it is characterized in that: step B) described titanate coupling agent kind is a kind of among commercially available TM-200S, LD-125, KR-238S or the TM-138S.
3. a kind of titanate coupling agent modification method according to claim 1 prepares the method for water-soluble Graphene, it is characterized in that: step C) described heating in water bath for reaction temperature is 50 ℃～90 ℃, and the heating in water bath for reaction time is 10h～48h.
4. a kind of titanate coupling agent modification method according to claim 1 prepares the method for water-soluble Graphene, it is characterized in that: step C) temperature of reaction of described hydro-thermal reaction is 100 ℃～180 ℃, and the reaction times of hydro-thermal reaction is 8h～24h.
5. a kind of titanate coupling agent modification method according to claim 1 prepares the method for water-soluble Graphene, it is characterized in that: step C) described microwave reaction temperature is 80 ℃～120 ℃, and the microwave reaction time is 5min～1h.
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-
2013
- 2013-07-29 CN CN2013103231605A patent/CN103342904A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| JING LI ET.AL,: "Microwave-assisted simultaneous reduction and titanate treatment of graphene oxide", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
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Application publication date: 20131009 |