CN105645388B - Graphene dispersion agent and its application - Google Patents
Graphene dispersion agent and its application Download PDFInfo
- Publication number
- CN105645388B CN105645388B CN201510776825.7A CN201510776825A CN105645388B CN 105645388 B CN105645388 B CN 105645388B CN 201510776825 A CN201510776825 A CN 201510776825A CN 105645388 B CN105645388 B CN 105645388B
- Authority
- CN
- China
- Prior art keywords
- graphene
- oligomer
- phenylamine
- aniline
- decentralized medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of graphene dispersion agent comprising has electroactive oligomer of phenylamine, and the oligomer of phenylamine can form π π compounds with graphene.The invention also discloses the applications of the graphene dispersion agent, such as provide dispersing method, dispersion etc. based on the graphene dispersion agent.The present invention is utilized and is readily synthesized; low-cost conductive-type oligomer of phenylamine and/or its derivative are as graphene dispersion agent; and by the way that the dispersant and graphene or other nano-carbon materials are simply mixed in a dispersion medium; dispersion degree, dispersion stabilization and redispersibility energy of the nano-carbon material in decentralized medium can be substantially improved; also without detriment to the physics of these carbon materials, chemical property; and it is easy to operate, it is conducive to scale and implements.
Description
Technical field
The present invention relates to a kind of graphene dispersion method, more particularly to a kind of graphene dispersion agent and its application.
Background technology
Graphene is the carbon that monoatomic layer thickness bi-dimensional cellular shape lattice structure is interconnected to form by sp2 hydbridized carbon atoms
Material has excellent electricity, mechanics, calorifics and mechanical performance.The preparation method of graphene generally includes mechanical stripping, chemistry
The methods of vapor deposition, oxidationreduction, solution ultrasound glass.The graphene of stripping due to the strong π-π interaction of lamella,
Graphene sheet layer is easy to reunite together, causes the solubility in organic solvent or water limited, this is just largely limited
It is applied.
In view of this, researcher proposes kinds of schemes, to solve these problems.Wherein commonly a kind of mode is
By the way that the auxiliary dispersants such as surfactant are added in a dispersion medium, although graphene can be promoted to a certain extent
Dispersion degree, but effect unobvious, and usually, specific surfactant is only applicable to specific decentralized medium, does not have
Universality.Another mode is by carrying out chemical modification processing to graphene, to promote its dispersion performance, but this side
Formula can cause chemical composition and physical pattern of grapheme material etc. to change.
Therefore, how height of the graphene in decentralized medium is realized on the basis of not destroying graphene uniqueness physicochemical property
Effect, stable dispersion, are always industry problem urgently to be resolved hurrily.
Invention content
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of graphene dispersion agent, the thereby stone
Black alkene dispersant can realize graphene fine dispersion in a dispersion medium in a manner of easy.
Another object of the present invention is to provide a kind of applications of the graphene dispersion agent, such as based on the graphene
The graphene dispersion body of dispersant, high-efficient graphite alkene dispersing method and redisperse method etc..
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of graphene dispersion agent is provided in some embodiments comprising have electroactive oligomer of phenylamine, and
The oligomer of phenylamine can form π-π compounds with graphene.
π-π the compounds of graphene and the graphene dispersion agent are additionally provided in some embodiments.
A kind of graphene dispersion body is additionally provided in some embodiments, it includes：Decentralized medium, and, it is scattered in institute
State π-π compounds in decentralized medium, as described above.
A kind of preparation method of graphene dispersion body is additionally provided in some embodiments comprising：By graphene and institute
The graphene dispersion agent stated is uniformly mixed to form stabilising dispersions in decentralized medium.
A kind of graphene dispersion and redisperse method are additionally provided in some embodiments comprising：
Graphene and the graphene dispersion agent are uniformly mixed to form stabilising dispersions in decentralized medium,
It removes the decentralized medium in the dispersion and obtains the compound of graphene and the graphene dispersion agent,
And be scattered in the compound in decentralized medium again, stabilising dispersions are formed again.
A kind of nano-carbon material dispersant is additionally provided in some embodiments, and it includes 2-8 that active ingredient, which is selected from,
Aromatic rings, and relative molecular weight 10000 hereinafter, simultaneously can with nano-carbon material formed π-π compounds compound.
Wherein, the nano-carbon material is at least selected from graphene, carbon nanotube, carbon nano-fiber, preferably graphene.
Preferably, the nano-carbon material dispersant, which is selected from, has electroactive oligomer of phenylamine.
Compared with the prior art, beneficial effects of the present invention include at least：Using being readily synthesized, low-cost conductive-type benzene
Amine oligomer and/or its derivative are as graphene dispersion agent, and by the way that the dispersant and graphene is simple in a dispersion medium
Single mixing, you can dispersion degree, dispersion stabilization and redispersibility energy of the graphene in decentralized medium is substantially improved, also without detriment to
Unique physical, the chemical property of graphene, and it is easy to operate, it is conducive to scale and implements.
Description of the drawings
Fig. 1 is a kind of system of graphene dispersing solution and redispersible graphene powder among an exemplary embodiments of the invention
Cheng Tu；
Fig. 2 is the UV-visible spectrum of graphene dispersion agent and graphene-dispersant compound in embodiment 1；
Fig. 3 is the Raman spectrogram of graphene in embodiment 1, graphene dispersion agent and graphene-dispersant compound；
Fig. 4 is the XRD spectra of graphene in embodiment 1, graphene dispersion agent and graphene-dispersant compound；
Fig. 5 a- Fig. 5 b are the SEM figures of graphene in embodiment 1-dispersant compound；
Fig. 6 is the AFM figures of graphene in embodiment 1-dispersant compound；
Fig. 7 is the TEM figures of graphene in embodiment 1-dispersant compound；
Fig. 8 a are the SEM shape appearance figures of the solidfied material of carbon nano-fiber and composition epoxy resin；
Fig. 8 b are the solidfied materials of 1 graphene dispersion agent of embodiment-carbon nano-fiber compound and composition epoxy resin
SEM shape appearance figures；
Fig. 9 a are the preservative efficacy testing figures of epoxy zinc-rich anti-corrosion primer；
Fig. 9 b are the preservative efficacy testing figures of 1 graphene of embodiment-dispersant compound/epoxy resin primer；
Figure 10 is the anti-corrosion effect of 1 graphene of embodiment-dispersant compound/epoxy resin primer and other commercially available priming paint
Comparison diagram.
Specific implementation mode
As previously mentioned, in view of graphene in the prior art in common decentralized medium, such as tetrahydrofuran, dimethyl formyl
Amine, the bad deficiency (refering to fig. 1) of dispersion effect in the organic solvents such as dimethyl sulfoxide (DMSO), inventor is through studying for a long period of time and greatly
Amount practice, spy proposes technical scheme of the present invention, and obtains unexpected good technique effect.It as follows will be to the present invention's
Technical solution carries out more detailed explanation.
One aspect of the present invention provides a kind of graphene dispersion agent, and it includes 2~8 fragrance that active ingredient, which is selected from,
Ring, and relative molecular weight 10000 hereinafter, simultaneously can with graphene formed π-π compounds compound.
More preferred, the relative molecular weight of the compound can be 100~1000.
In some embodiments, the compound is selected from oligomer of phenylamine and/or its derivative.Correspondingly, described herein
" π-π compounds " mean and mainly acted on through π-π with graphene by oligomer of phenylamine and/or oligomer of phenylamine derivative, without
It is the compound formed by chemical bonds.
The oligomer of phenylamine is also known as aniline oligomer, it includes aniline conjugation segment be shorter than polyaniline, it is electroactive
It is similar to polyaniline, but defect is not present in molecule, and there is better dissolubility.
For example, the graphene dispersion agent can be mainly by can be combined by π-π interactions with graphene, to
Graphene is set to be stably dispersed in the oligomer of phenylamine composition with aromatic structure in organic solvent.
In some more specifically case, the graphene dispersion agent can be by can be mutual by π-π with graphene
Effect combines, to keep the aniline with aromatic structure that the Maximum single layer distribution threshold value of graphene in organic solvent reaches 5mg/mL low
Polymers forms.It should be noted that " Maximum single layer distribution threshold value " described herein corresponds to the graphene dispersion using minimal effective dose
The case where agent.Wherein, by the graphene dispersion agent, graphene is enable to be stably dispersed in by physical method organic molten
In agent, physical method described herein can be the simple physicals mode such as stirring, ultrasound, but not limited to this.
In some preferred embodiment, the graphene dispersion agent is preferably from aniline tripolymer, Tetraaniline, aniline
Any one in pentamer, six aggressiveness of aniline or two or more combinations.
Be suitable for the invention oligomer of phenylamine can commercially available from approach obtain, can also bibliography (for example,
《CHEM.COMMUN.》, 2003, the 2768-2769 pages；《Synthetic Metals》, 2001, the 237- of volume 122
Page 242；CN101811997A；CN 1369478A, CN 1204655A etc.) self-control.
Another aspect of the present invention additionally provides the π-π compounds of graphene and the graphene dispersion agent.
More preferred, graphene and the molar ratio of graphene dispersion agent are 100 in the π-π compounds:1~1:
100, preferably 10:1~1:10, especially preferably 2:1~1:2.
In fact, π-π the compounds also can be considered a kind of redispersible graphene powder, mainly passing through will be main
The powder obtained after the dispersion being made of graphene and graphene dispersion agent, such as graphene dispersing solution drying, and the powder
Body can be directly scattered in decentralized medium, such as organic solvent again.
Wherein, the mode of the drying includes spray drying, naturally it is also possible to be other suitable drying sides known to industry
Formula, such as freeze-drying, supercritical drying etc..
Another aspect of the present invention additionally provides a kind of dispersion, it includes：Decentralized medium, and, it is scattered in described
In decentralized medium, foregoing π-π compounds.
More preferred, the dispersion is flow-like dispersion, especially preferably liquid dispersion.
More preferred, the dispersion includes the graphene of a concentration of 0.1mg/ml~100mg/ml.
Wherein, the definition of the grapheme material can be found in document " All in the graphene family-A
recommended nomenclature for two-dimensional carbon materials”.It can be from commercially available etc.
Approach obtain, can also make by oneself, for example, by using graphene product well known to those skilled in the art or with routine preparation method system
It is standby, such as can be selected from any one method system in chemical oxidization method such as Brodie methods, Hummers methods or Staudenmaier methods
Standby graphene oxide, through grapheme material made from thermal expansion.Mechanical stripping, liquid phase stripping or electrochemistry stripping can also be selected
Grapheme material from preparation or redox graphene.Its structure is also not limited to graphene nanometer sheet, graphene micron
Piece, graphene nanobelt, few layer graphene (2~5 layers), multi-layer graphene (2~9 layers), graphene quantum dot and these stones
The derivative of black alkenes material.Its thickness is preferably≤20nm, it is highly preferred that thickness≤10nm.
Wherein, the decentralized medium may include in water, organic solvent, high molecular polymer any one or it is two or more
Combination；Such as preferably from organic solvent.
Wherein, the organic solvent can be selected from suitable species known to industry, especially polar organic solvent, such as alcohols
Organic solvent, ether organic solvent, alkyl halide hydrocarbon organic solvent etc., such as may be selected from but not limited to ethyl alcohol (EtOH), tetrahydrochysene
Furans (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) and chloroform etc..
Wherein, the high molecular polymer can be selected from appropriate resin known to industry etc., such as alkyd resin, amino tree
Fat, epoxy resin, polyester resin, acrylic resin, organic siliconresin, furane resins etc., and it is without being limited thereto.
In some embodiments, a kind of graphene dispersing solution may include aforementioned any graphene dispersion agent, graphene with
And organic solvent.Preferably, the graphene dispersing solution is formed by the graphene dispersion agent, graphene and organic solvent
Stabilization graphene dispersion system.In some more specifically case, the content of graphene in the graphene dispersing solution
It is up to 5mg/mL.Likewise, " Maximum single layer distribution threshold value " described herein corresponds to the graphene dispersion agent using minimal effective dose
The case where.
Inventor also found that graphene dispersion agent of the present invention has especially excellent with the π-π compounds that graphene is formed
Different stability, for example, when being scattered in water, organic solvent or high molecular polymer (such as resin), even if in low temperature
Under the extreme temperature conditions for being 80 DEG C for -50 DEG C or high temperature, which can also be stabilized.And very make us pleasantly surprised
Including even if the dispersion of the π-π compounds is also not in bright under the centrifugal condition of 10000r/min in rotating speed
Aobvious sedimentation, therefore conducive to the application under the particular surroundings such as high temperature, low temperature.
In the present invention, the mechanism that graphene dispersion agent forms π-π compounds with graphene may is that：The graphite of the present invention
Aromatic rings is contained in alkene dispersant, especially contains multiple phenyl groups, and to cause it to have special for the benzene ring structure that benzene has
Armaticity.For example, be not to be arranged by singly-bound and double bond between carbon atom on phenyl ring main chain, the key between each two carbon atom
All same is by one neither double bond nor the key connection of singly-bound.Moreover, benzene molecular is planar molecule, 12 atoms are in same
In one plane, 6 p rail interactions form 6 π molecular orbits, and wherein ψ 1, ψ 2, ψ 3 are the lower bonding orbital of energy, ψ
4, ψ 5, ψ 6 are the higher antibonding orbitals of energy.ψ 2, ψ 3 and ψ 4, ψ 5 are two pairs of degeneracy tracks.The Cloud Distribution of benzene is when ground state
The superposition of three bonding orbitals as a result, therefore electron cloud is uniformly distributed in phenyl ring up and down and on annular atom, form the electron cloud of closure.
And in graphene sheet layer include the structure similar to phenyl ring, and therefore, the benzene ring units energy in graphene dispersion agent of the invention
Corresponding units structure in enough and graphene is strong bonded under conditions of not chemically reacting, and then is conducive to grapheme material
Efficient in a dispersion medium, stable dispersion.
An additional aspect of the present invention additionally provides a kind of preparation method of graphene dispersion body comprising：By graphene
And the graphene dispersion agent is uniformly mixed to form stabilising dispersions in decentralized medium.
In some embodiments, a kind of graphene dispersion method may include：Only by the graphene dispersion agent and stone
Black alkene is dissolved in organic solvent jointly, to form stable dispersion liquid.It should be noted that " being dissolved in " described herein is not
The dissolving that those of ordinary skill is understood, and be interpreted as " mixing ", " being dispensed into " or " being mixed into " etc..For example, can will be described
Organic solvent, and stirring or ultrasonic disperse, such as ultrasonic disperse 1h or more is added with graphene in graphene dispersion agent, to be formed
Stable dispersion liquid.
More preferred, the dispersion includes the graphene of a concentration of 1mg/ml~10mg/ml.
In the graphene dispersion method, the molar ratio of graphene and graphene dispersion agent is 100:1~1:100, it is excellent
It is selected as 10:1~1:10, especially preferably 2:1~1:2.
An additional aspect of the present invention additionally provides a kind of graphene dispersion and redisperse method comprising：
Graphene and the graphene dispersion agent are uniformly mixed to form stabilising dispersions in decentralized medium,
It removes the decentralized medium in the dispersion and obtains the compound of graphene and the graphene dispersion agent,
And be scattered in the compound in decentralized medium again, stabilising dispersions are formed again.
For example, in some embodiments, a kind of graphene dispersion and redisperse method based on physical method may include：
By graphene with aromatic structure oligomer of phenylamine by strong π-π interact in conjunction with by be stably dispersed in
In solvent, graphene dispersing solution is formed；
Processing is dried to the graphene dispersing solution and forms powder；
And be scattered in the powder again, it is especially directly scattered in the organic solvent, is formed stablize again
Graphene dispersing solution.
In addition, the discovery that inventor is also pleasantly surprised, the graphene dispersion agent of the invention is for disperseing other receive
Whens rice carbon material, such as carbon nanotube, carbon nano-fiber etc., also there is very excellent performance, therefore can be used as a kind of excellent
Nano-carbon material dispersant.
Correspondingly, an additional aspect of the present invention, which additionally provides the graphene dispersion agent, is preparing nano-carbon material dispersion
Purposes in body.
Wherein, the nano-carbon material at least can be selected from graphene, carbon nanotube, carbon nano-fiber, but not limited to this.
Additionally provide in some embodiments include nano-carbon material and the graphene dispersion agent composition.
π-π the compounds of nano-carbon material and the graphene dispersion agent are additionally provided in some embodiments.
π-π compounds and decentralized medium comprising nano-carbon material Yu the dispersant are additionally provided in some embodiments
Dispersion.
It is described in detail, shows below in conjunction with several embodiments and attached drawing technical solution in the embodiment of the present invention
So, described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, the every other embodiment that those of ordinary skill in the art are obtained without making creative work all belong to
In the scope of protection of the invention.
Please continue to refer to Fig. 1, in the following embodiment (such as embodiment 1- embodiments 2) of the present invention, by base
In the graphene dispersion agent of the oligomer of phenylamine with aromatic structure, it is not required to that any additive and reactant is added, stone can be made
Black alkene stable dispersion in organic solvent (such as EtOH, DMF, THF etc.), and dispersion liquid it is spray-dried after obtain it is redispersible
Graphene powder, the redispersible graphene powder can be stably dispersed in organic solvent again.
The synthesis of 1 aniline tripolymer of embodiment and its dispersion for graphene in oil-based solvent
The HCl solution of 2.96g p-phenylenediamine sulfates, 1.85g aniline and a concentration of 1M of 50mL are added in round-bottomed flask,
Cooling, formation reaction solution A is placed in -5 DEG C of ice salt baths.In addition 4.5g ammonium persulfates are weighed and are dissolved in a concentration of 1M's of 50mL
HCl solution forms reaction solution B, and solution B is slowly dropped in above-mentioned reaction solution A with about 1 drop/sec of speed, waits dripping
After adding, continue to stir 1h.After reaction, product is poured into Buchner funnel and is filtered, be used in combination and be cooled to 0 DEG C in advance in advance
, the HCl solution cleaning of a concentration of 1M, then cleaned with a large amount of deionized waters, acquisition dark green solid product.First with 10%
The ammonia scrubbing of (mass fraction) product, then cleaned with a large amount of deionized waters, finally obtain 3.6g aniline tripolymers.
Obtained aniline tripolymer and graphene slurry are mixed in a certain ratio, and are dissolved in ethyl alcohol, tetrahydrofuran respectively
(THF) in, ultrasonic disperse 1 hour examines its dispersion effect to be in the solution not added with aniline tripolymer as shown in Tables 1 and 2
Graphene slurry cannot disperse in tetrahydrofuran and ethyl alcohol (EtOH), and aniline tripolymer-graphene 1：1 compound is in second
In alcohol, tetrahydrofuran, stable dispersion liquid can be formed in a concentration of 2.5mg/ml or less of graphene.
By the dispersion liquid using can get graphene-dispersant compound after spray dried form drying, at normal temperatures
The graphene-dispersant compound is directly added into the organic solvents such as EtOH, DMF, THF, by stirring or the modes such as ultrasound,
Graphene dispersing solution that is uniform and stablizing can be regained.
Dispersion effect (the aniline tripolymer-graphene mass ratio 1 of 1. aniline tripolymer of table-graphene in ethanol：1)
| 5mg/10ml | 10mg/10ml | 25mg/10ml | 50mg/10ml | 100mg/10ml |
| Well | Well | Well | There is a small amount of precipitation | It is bad |
Dispersion effect (aniline tripolymer-graphene mass ratio 1 of 2. aniline tripolymer of the table-graphene in THF：1)
| 5mg/10ml | 10mg/10ml | 25mg/10ml | 50mg/10ml | 100mg/10ml |
| Well | Well | Well | There is a small amount of precipitation | It is bad |
The synthesis of 2. Tetraaniline of embodiment and its be used for graphene oily dispersion
18.5g aniline dimers are weighed in round-bottomed flask, the HCl of 200ml acetone and a concentration of 1M of 300ml is added,
Agitation and dropping ammonium persulfate containing 45.65g, a concentration of 1M HCl solution in ice bath, after reaction 3 hours, 1M is used in filtering successively
Ammonium hydroxide distills water washing, obtains Tetraaniline.Obtained Tetraaniline and graphene slurry are dissolved in tetrahydrochysene by a certain percentage
In furans, ultrasonic disperse 1 hour examines its dispersion effect in the solution, and as shown in table 3, Tetraaniline and graphene are multiple
Object is closed in a concentration of 2.5mg/ml or less, stable dispersions can be formed in tetrahydrofuran.
By the dispersion liquid using can get graphene-dispersant compound after spray dried form drying, at normal temperatures
The graphene-dispersant compound is directly added into the organic solvents such as EtOH, DMF, THF, by stirring or the modes such as ultrasound,
Graphene dispersing solution that is uniform and stablizing can be regained.
The THF dispersion liquids of 3. Tetraanilines of table-graphene
| 5mg/10ml | 10mg/10ml | 25mg/10ml | 50mg/10ml |
| Well | Well | Well | There is a small amount of precipitation |
Embodiment 3- embodiments 4：With reference to the operation of embodiment 1-2, using six aggressiveness of aniline pentamer or aniline etc. as dividing
Powder, and with ethyl alcohol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide (DMSO) and chloroform etc. are used as solvent, test it for stone
The dispersibility of black alkene, and obtain and test result essentially identical embodiment 1-2.
Comparative example 1：
Directly untreated graphene powder is directly added into ethyl alcohol, tetrahydrofuran (THF) equal solvent, ultrasonic disperse
1h。
Comparative example 2：
First by graphene powder and silane coupling agent, high-speed stirred disperses 20min, and ultrasonic disperse at 1500rad/min
20min obtains mixture.Mixture is dried in vacuo at 60 DEG C and obtains the graphene powder handled through silane coupling agent, then
The powder is directly added into ethyl alcohol, tetrahydrofuran (THF) equal solvent, ultrasonic disperse 1h.
Please refer to shown in Fig. 2 be graphene and graphene-dispersant compound in embodiment 1 UV-visible spectrum,
Wherein a corresponds to graphene dispersion agent (following abbreviation " dispersant "), and b corresponds to graphene-dispersant compound (as follows referred to as
" compound ").It can be seen that the pi-pi bond of dispersant inside itself makes it, there are two apparent suctions at 307nm and 474nm
Peak is received, and in dispersion liquid, the position of absorption peak shifts to 311nm and 468nm, illustrates between dispersant and graphene
There is π-π interactions so that characteristic peak is subjected to displacement.
Please refer to shown in Fig. 3 be graphene in embodiment 1, graphene dispersion agent and graphene-dispersant compound drawing
Graceful spectrogram, wherein a correspond to graphene, and b corresponds to graphene dispersion agent (following abbreviation " dispersant "), and c corresponds to graphite
Alkene-dispersant compound (following abbreviation " compound ").It can be seen that pure graphene is in 1345cm-1Place there are the peaks D,
1582cm-1There are the peaks G at place, in 2711cm-1There are the peaks 2D at place；And in the composite, the corresponding characteristic peak of graphene all has occurred
Displacement illustrates that there are electric charge transfers between dispersant and graphene, it was demonstrated that the π-π of dispersant and graphene interact.
Please refer to shown in Fig. 4 be graphene in embodiment 1, graphene dispersion agent and graphene-dispersant compound XRD
Collection of illustrative plates, the also π-π interactions of susceptible of proof dispersant and graphene.
Please refer to shown in Fig. 5 a- Fig. 5 b be 1 obtained graphene of embodiment-dispersant compound SEM figure, it can be seen that
Graphene system is in good dispersity, and basic soilless sticking.
AFM figures and TEM figures that Fig. 6-Fig. 7 respectively illustrates 1 obtained graphene of embodiment-dispersant compound are please referred to,
It can be seen that, wherein graphene presents the very smooth form unfolded, this phenomenon is very wondrous, may be because
Caused by the plane state molecular structure of graphene dispersion agent of the present invention.
Likewise, for embodiment 2- embodiments 4, similar characterization can also be obtained in the same way by being characterized
As a result.
The graphene dispersing solution that Example 1- embodiments 4 are obtained again in standing 3 months or more under room temperature, with observation
Its stability, it can be seen that without sedimentation phenomenon in these graphene dispersing solutions.And the dispersion of reference examples 1- reference examples 2
In, graphene almost settles.
In addition, substituting graphene with reference to the mode of embodiment 1- embodiments 4, but with carbon nanotube, carbon nano-fiber and carrying out
Experiment, as a result, it was confirmed that the graphene dispersion agent of the present invention is also suitable for assisting such nano-carbon material in dispersions such as organic solvents
Efficient, stable dispersion in medium.
Embodiment 5：The graphene dispersion agent in Example 1-4 is added a variety of commercially available by a certain percentage with graphene respectively
In bisphenol A epoxide resin, ultrasonic disperse 1h or so examines its dispersion effect in bisphenol A epoxide resin, it is found that when
The molar ratio of graphene dispersion agent and graphene is 10:1~1:When in 10 ranges, graphene is in bisphenol A epoxide resin
Homogeneously dispersed state, basic soilless sticking.
Embodiment 6：Commercially available bisphenol-A epoxy is added in the graphene dispersion agent of Example 1 and the compound of carbon nano-fiber
In resin, ultrasonic disperse 1h or so cures under the conditions of ultraviolet lighting or suitable temperature later.Take one such Typical cure
Object is observed, and pattern is as shown in Figure 8 b, it can be seen that carbon nano-fiber is discrete to be distributed in the solidfied material, and soilless sticking is existing
As especially without apparent interface between carbon nano-fiber and epoxy resin cured product, showing its good combination.It is another to take equally
Carbon nano-fiber be added in same epoxy resin, under equal conditions cure, solidfied material pattern is as shown in Figure 8 a, can be with
See, there are clear interfaces between carbon nano-fiber and epoxy resin cured product.
Other types are separately added with the graphene dispersion agent of embodiment 2-4 and carbon nano-fiber or the compound of carbon nanotube
Commercial epoxy resins in, such as novolac epoxy resin, polyfunctional epoxy resin, modified epoxy, with it is similar above
Mode disperseed, cure after, its solidfied material is observed respectively, also can get substantially similar conclusion.
Embodiment 7：The graphene of Example 1-dispersant compound, which is added in epoxy resin E44, forms coating, and will
It is coated in surface of steel plate as priming paint, is formed by curing coating (refering to fig. 10 in " E44+G ").Separately take pure epoxy resin E44
It is coated in identical surface of steel plate as priming paint, is formed by curing coating.In addition, take respectively Commercial epoxy zinc-rich anti-corrosion primer (refering to
" epoxy zinc-rich " in Figure 10), available glass flake paint (refering to fig. 10 in " glass flake ") formed on identical steel plate
Coating.The anti-corrosion effect of these coatings is tested respectively again, result sees Fig. 9 a, Fig. 9 b and Figure 10, it can be seen that
Using anti-corrosion primer made from graphene-dispersant compound than pure epoxy resin E44 and commercially available epoxy zinc-rich anti-corrosion primer,
Glass-flake coating has more excellent corrosion protection effect.
It should be noted that graphene dispersion agent, decentralized medium, all kinds of raw materials and technique item used by embodiment as above
Part is more typical example, but is verified by inventor's a large number of experiments, in the other graphenes of those listed above point
Powder, decentralized medium, raw material and process conditions etc. are also applicable, and also equal attainable cost invents claimed technology effect
Fruit.
Postscript, herein, the terms "include", "comprise" or its any other variant are intended to the packet of nonexcludability
Contain, so that the process, method, article or equipment including a series of elements includes not only those elements, but also includes
Other elements that are not explicitly listed, or further include for elements inherent to such a process, method, article, or device.
It should be appreciated that the above is only the specific implementation mode of the present invention, it is noted that for the general of the art
For logical technical staff, various improvements and modifications may be made without departing from the principle of the present invention, these improve and
Retouching also should be regarded as protection scope of the present invention.
Claims (29)
1. application of the electroactive oligomer of phenylamine of tool in dispersed graphite alkene, the application include：By graphene and institute
It states oligomer of phenylamine only uniformly to mix by physics mode in decentralized medium, makes oligomer of phenylamine with graphene mainly through π-π
It acts on rather than forms π-π compounds by chemical bonds, to obtain stabilising dispersions, the oligomer of phenylamine is selected from benzene
Any one in amine tripolymer, Tetraaniline, aniline pentamer, six aggressiveness of aniline or two or more combinations.
2. application according to claim 1, it is characterised in that：The relative molecular weight of the oligomer of phenylamine be 100~
1000。
3. graphene and the π-π compounds for having electroactive oligomer of phenylamine, the π-π compounds are oligomeric by the aniline
Object mainly acts on through π-π with graphene rather than passes through the compound that chemical bonds are formed, the electroactive aniline of the tool
Oligomer in aniline tripolymer, Tetraaniline, aniline pentamer, six aggressiveness of aniline any one or it is two or more
Combination.
4. π-π compounds according to claim 3, it is characterised in that：The relative molecular weight of the oligomer of phenylamine is 100
~1000.
5. π-π compounds according to claim 3, it is characterised in that：Wherein graphene and the oligomer of phenylamine rubs
You are than being 100:1~1:100.
6. π-π compounds according to claim 5, it is characterised in that：Wherein graphene and the oligomer of phenylamine rubs
You are than being 10:1~1:10.
7. π-π compounds according to claim 6, it is characterised in that：Wherein graphene and the oligomer of phenylamine rubs
You are than being 2:1~1:2.
8. a kind of graphene dispersion body, it is characterised in that include：Decentralized medium；And it is scattered in the decentralized medium, such as
π-π compounds described in any one of claim 3-7.
9. graphene dispersion body according to claim 8, it is characterised in that：The graphene dispersion body disperses for flow-like
Body.
10. graphene dispersion body according to claim 9, it is characterised in that：The graphene dispersion body is liquid dispersed
Body or slurry.
11. graphene dispersion body according to claim 8, it is characterised in that：The decentralized medium includes water, You Jirong
Any one in agent, resin or two or more combinations.
12. graphene dispersion body according to claim 11, it is characterised in that：The decentralized medium is selected from organic solvent.
13. graphene dispersion body according to claim 8, it is characterised in that：The graphene dispersion body includes 0.1mg/
The graphene of ml~100mg/ml.
14. a kind of preparation method of graphene dispersion body, it is characterised in that including：Graphene and the electroactive aniline of tool is low
Polymers is only uniformly mixed to form stabilising dispersions in decentralized medium by physics mode, and the oligomer of phenylamine is selected from aniline three
Any one in aggressiveness, Tetraaniline, aniline pentamer, six aggressiveness of aniline or two or more combinations.
15. preparation method according to claim 14, it is characterised in that：The relative molecular weight of the oligomer of phenylamine is
100~1000.
16. preparation method according to claim 14, it is characterised in that：Wherein graphene and the oligomer of phenylamine rubs
You are than being 100:1~1:100.
17. preparation method according to claim 16, it is characterised in that：Wherein graphene and the oligomer of phenylamine rubs
You are than being 10:1~1:10.
18. preparation method according to claim 17, it is characterised in that：Wherein graphene and the oligomer of phenylamine rubs
You are than being 2:1~1:2.
19. preparation method according to claim 14, it is characterised in that：The decentralized medium is selected from water, organic solvent, height
Any one in Molecularly Imprinted Polymer or two or more combinations.
20. preparation method according to claim 19, it is characterised in that：The decentralized medium is selected from organic solvent.
21. preparation method according to claim 19, it is characterised in that：The high molecular polymer is selected from resin, described
Resin includes in alkyd resin, amino resins, epoxy resin, polyester resin, acrylic resin, organic siliconresin, furane resins
Any one or two or more combinations.
22. preparation method according to claim 14, it is characterised in that：The dispersion includes 0.1mg/ml~100mg/
The graphene of ml.
23. a kind of graphene dispersion and redisperse method, it is characterised in that including：
Graphene and the electroactive oligomer of phenylamine of tool are only uniformly mixed to form surely by physics mode in decentralized medium
Determine dispersion, the oligomer of phenylamine appointing in aniline tripolymer, Tetraaniline, aniline pentamer, six aggressiveness of aniline
Meaning a combination of one or more,
It removes the decentralized medium in the dispersion and obtains the compound of graphene and the oligomer of phenylamine,
And be scattered in the compound in decentralized medium again, stabilising dispersions are formed again.
24. graphene dispersion according to claim 23 and redisperse method, it is characterised in that：The oligomer of phenylamine
Relative molecular weight is 100~1000.
25. graphene dispersion according to claim 23 and redisperse method, it is characterised in that：The decentralized medium is selected from
Any one in water, organic solvent or two or more combinations.
26. graphene dispersion according to claim 25 and redisperse method, it is characterised in that：The decentralized medium is selected from
Organic solvent.
27. graphene dispersion according to claim 23 and redisperse method, it is characterised in that：The stabilising dispersions packet
Graphene containing 0.1mg/ml~100mg/ml.
28. nano-carbon material dispersant is in disperseing the application in nano-carbon material, the nano-carbon material dispersant it is effective at
It includes 2-8 aromatic rings to be selected from, and relative molecular weight 10000 hereinafter, that π-π simultaneously can be formed with nano-carbon material is compound
The compound of object, the compound appointing in aniline tripolymer, Tetraaniline, aniline pentamer, six aggressiveness of aniline
Meaning a combination of one or more, the nano-carbon material are at least selected from carbon nanotube or carbon nano-fiber, the application
Including：Nano-carbon material and the nano-carbon material dispersant are only uniformly mixed by physics mode in decentralized medium, made
The compound mainly through π-π effects rather than forms π-π compounds with nano-carbon material by chemical bonds, to obtain
Obtain stabilising dispersions.
29. application according to claim 28, it is characterised in that：The relative molecular weight of the compound is 100~1000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410722468 | 2014-12-02 | ||
| CN2014107224681 | 2014-12-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105645388A CN105645388A (en) | 2016-06-08 |
| CN105645388B true CN105645388B (en) | 2018-08-28 |
Family
ID=56481821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510776825.7A Active CN105645388B (en) | 2014-12-02 | 2015-11-12 | Graphene dispersion agent and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105645388B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117853A (en) * | 2016-06-21 | 2016-11-16 | 烟台市烯能新材料股份有限公司 | A kind of Graphene Masterbatch |
| CN105948032A (en) * | 2016-07-04 | 2016-09-21 | 烟台市烯能新材料股份有限公司 | Method for etching multilayer graphene |
| CN108299996B (en) * | 2016-08-15 | 2020-01-10 | 中国科学院宁波材料技术与工程研究所 | Modified fiber reinforced anticorrosive paint and preparation method and application thereof |
| CN106751458A (en) * | 2016-11-17 | 2017-05-31 | 中国科学院宁波材料技术与工程研究所 | Epoxy resin carbon nano tube compound material and preparation method thereof |
| CN108002376A (en) * | 2017-11-02 | 2018-05-08 | 广东华材实业股份有限公司 | A kind of high stable graphene dispersion body and preparation method thereof |
| CN110902670B (en) | 2018-09-14 | 2021-07-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented film, preparation method and application thereof |
| CN110922803A (en) * | 2019-12-16 | 2020-03-27 | 水利部交通运输部国家能源局南京水利科学研究院 | Graphene-doped water-based conductive anticorrosive coating composition for surface of steel bar in concrete and preparation method thereof |
| CN112457744A (en) * | 2020-12-01 | 2021-03-09 | 四川科嘉能源科技有限公司 | Graphene modified anticorrosive paint and preparation method thereof |
| CN116355454A (en) * | 2023-02-13 | 2023-06-30 | 杭州烯创科技有限公司 | Graphene resin dispersion, corrosion-resistant graphene electrophoretic paint and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086362A (en) * | 2012-12-11 | 2013-05-08 | 武汉工程大学 | Preparation method for electroactive aniline oligomer-modified graphene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781458B (en) * | 2010-02-04 | 2012-06-27 | 南京理工大学 | Graphene -organic acid doped polyaniline composite material and preparation method thereof |
| CN103449420B (en) * | 2013-08-22 | 2015-03-25 | 中国科学院金属研究所 | High-quality graphene dispersion method and film preparation method |
-
2015
- 2015-11-12 CN CN201510776825.7A patent/CN105645388B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086362A (en) * | 2012-12-11 | 2013-05-08 | 武汉工程大学 | Preparation method for electroactive aniline oligomer-modified graphene |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis of Water Soluble Graphene";Yongchao Si et al.;《NANO LETTERS》;20081231;第8卷(第6期);第1679-1682页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105645388A (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105645388B (en) | Graphene dispersion agent and its application | |
| CN105642184B (en) | Graphene dispersion agent and its application | |
| CN105645387B (en) | Graphene dispersion agent and its application | |
| US11692079B2 (en) | 2-dimensional MXene particle surface-modified with functional group containing saturated or unsaturated hydrocarbon, preparation method thereof and use thereof | |
| El-Shafai et al. | Fabrication and characterization of graphene oxide–titanium dioxide nanocomposite for degradation of some toxic insecticides | |
| Zhou et al. | Modification of montmorillonite surfaces using a novel class of cationic gemini surfactants | |
| CN102807803B (en) | Method for preparing organic and inorganic composite super-hydrophobic coatings | |
| JP5795840B2 (en) | Silica particle material, silica particle material-containing composition, and silica particle surface treatment method | |
| CN107365259A (en) | Molybdenum disulfide dispersant, molybdenum disulfide dispersion, its preparation method and application | |
| CN105778571B (en) | A kind of graphene composite mortar and preparation method thereof | |
| CN108025916A (en) | Polymer-graphite alkene composite material, its preparation method and use its polymer-graphite alkene complex composition | |
| CN109266165A (en) | A kind of epoxy composite coating and preparation method thereof | |
| CN102532896A (en) | Modified graphene/polyimide resin composite material and preparation method thereof | |
| Hu et al. | Synthesis and anticorrosive properties of polymer–clay nanocomposites via chemical grafting of polyaniline onto Zn-Al layered double hydroxides | |
| CN107793823B (en) | Graphene modified heat-conducting coating ink and preparation method thereof | |
| Dinari et al. | Ultrasound-assisted one-pot preparation of organo-modified nano-sized layered double hydroxide and its nanocomposites with polyvinylpyrrolidone | |
| Yeole et al. | The effect of carbon nanotubes loaded with 2-mercaptobenzothiazole in epoxy-based coatings | |
| Lu et al. | Aqueous soluble boron nitride nanosheets via anionic compound-assisted exfoliation | |
| CN107364839A (en) | Nitrogenize borated dispersant, liquid phase peels off the method and its application of two-dimentional boron nitride nanosheet | |
| Wang et al. | Preparation and dielectric properties of copper phthalocyanine/graphene oxide nanohybrids via in situ polymerization | |
| Tomić et al. | Dispersion efficiency of montmorillonites in epoxy nanocomposites using solution intercalation and direct mixing methods | |
| CN110330815A (en) | A kind of nitrogen-doped carbon quantum dot and the preparation method and application thereof | |
| CN107828309B (en) | Dispersion used for graphene anticorrosive paint and preparation method thereof | |
| Raja et al. | Synthesis and characterization of polyaniline-copper (ii) oxide nanocomposite by wet chemical route | |
| CN105273454B (en) | Nano inorganic zinc-rich composite anticorrosion coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211118 Address after: 315200 Zhongguan Road, Jiaochuan Street, Zhenhai District, Ningbo City, Zhejiang Province, 1188 Patentee after: NINGBO ZHONGKE JIANHUA NEW MATERIAL Co.,Ltd. Address before: 315201, No. 519, Zhuang Avenue, Zhenhai District, Zhejiang, Ningbo Patentee before: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |