CN105645387B - Graphene dispersion agent and its application - Google Patents
Graphene dispersion agent and its application Download PDFInfo
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- CN105645387B CN105645387B CN201510771523.0A CN201510771523A CN105645387B CN 105645387 B CN105645387 B CN 105645387B CN 201510771523 A CN201510771523 A CN 201510771523A CN 105645387 B CN105645387 B CN 105645387B
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Abstract
The invention discloses a kind of graphene dispersion agent comprising has electroactive oligomer of phenylamine derivative, and the oligomer of phenylamine derivative can form π-π compound 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 derivative is as graphene dispersion agent; and by the way that the dispersing agent 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 nano-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, in particular to a kind of graphene dispersion agent and its application.
Background technique
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.π-π the interaction strong due to lamella of the graphene of removing,
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 a kind of common 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 is unobvious, and usually, and 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 will lead to chemical composition and physical pattern of grapheme material etc. and 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.
Summary of the invention
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 stone whereby
Black alkene dispersing agent 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 graphene dispersion agent, such as based on the graphene
The graphene dispersion body of dispersing agent, 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 it is derivative to have electroactive oligomer of phenylamine
Object, and the oligomer of phenylamine derivative can form π-π compound with graphene.
Further, the relative molecular weight of the oligomer of phenylamine derivative is 10000 hereinafter, preferably 100~1000.
π-π the compound of graphene Yu the graphene dispersion agent is 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 compound 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 Yu the graphene dispersion agent,
And disperse the compound in decentralized medium again, stabilising dispersions are formed again.
A kind of nano-carbon material dispersing agent is additionally provided in some embodiments, and it includes 2-8 that effective component, which is selected from,
Aromatic rings, and relative molecular weight 10000 hereinafter, simultaneously can with nano-carbon material formed π-π compound compound, describedization
It closes object and is selected from and have electroactive oligomer of phenylamine derivative.
Wherein, the nano-carbon material is at least selected from graphene, carbon nanotube, carbon nano-fiber, preferably graphene.
Compared with the prior art, beneficial effects of the present invention are included at least: using being readily synthesized, low-cost conductive-type benzene
Amine oligomer derivative passes through and the dispersing agent is simply mixed in a dispersion medium with graphene as graphene dispersion agent,
Dispersion degree, dispersion stabilization and redispersibility energy of the graphene in decentralized medium can be substantially improved, also without detriment to graphene
Unique physical, chemical property, and it is easy to operate, be conducive to scale and implement.
Detailed description of the invention
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 graphene in embodiment 1, graphene dispersion agent and graphene-dispersing agent compound XRD spectra；
Fig. 3 is graphene in embodiment 1-dispersing agent compound SEM figure；
Fig. 4 is graphene in embodiment 1-dispersing agent compound AFM figure；
Fig. 5 is graphene in embodiment 1-dispersing agent compound TEM figure；
Fig. 6 is 1 graphene dispersion agent of embodiment-carbon nano-fiber compound and composition epoxy resin solidfied material
SEM shape appearance figure；
Fig. 7 is 1 graphene of embodiment-dispersing agent compound/epoxy resin primer preservative efficacy testing figure；
Fig. 8 is 1 graphene of embodiment-dispersing agent compound/epoxy resin primer and other commercially available priming paint anti-corrosion effect
Comparison diagram.
Specific embodiment
In view of graphene in the prior art in common decentralized medium, such as tetrahydrofuran, dimethylformamide, dimethyl is sub-
The bad deficiency of dispersion effect (refering to fig. 1) in the organic solvents such as sulfone, inventor are studied for a long period of time and are largely practiced, and spy mentions
Technical solution of the present invention out, and obtain unexpected good technique effect.As follows will to technical solution of the present invention into
The more detailed explanation of row.
One aspect of the present invention provides a kind of graphene dispersion agent, and it includes 2~8 fragrance that effective component, which is selected from,
Ring, and relative molecular weight 10000 hereinafter, simultaneously can with graphene formed π-π compound 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 compound " mean and mainly acted on through π-π by oligomer of phenylamine and/or oligomer of phenylamine derivative and graphene, 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 that can be combined with graphene by π-π interaction, thus
Graphene is set to be stably dispersed in the oligomer of phenylamine derivative composition with aromatic structure in organic solvent.
In some more specifically cases, the graphene dispersion agent can be mutual by that can pass through π-π with graphene
Effect combines, so that the aniline with aromatic structure for making the Maximum single layer distribution threshold value of graphene in organic solvent reach 5mg/mL is low
Polymers derivative composition.It should be noted that " Maximum single layer distribution threshold value " described herein corresponds to the graphite using minimal effective dose
The case where alkene dispersing agent.Wherein, by the graphene dispersion agent, graphene is enable to be stably dispersed in by physical method
In organic solvent, physical method described herein can be the simple physicals mode such as stirring, ultrasound, but not limited to this.
In some preferred embodiment, the oligomer of phenylamine derivative includes that aniline trimer derivatives, aniline four are poly-
Syntaxy object, any one in six mer derivatives of aniline pentamer derivative and aniline or two or more combinations.
Further, the oligomer of phenylamine derivative can be selected from carboxyl, hydroxyl, carbonyl, ester group, amino, hydrocarbon
In the functionalization groups such as base, alkyl, sulfonic group, phosphate, epoxy group, polyethylene group, polyvinyl alcohol group at least
A kind of oligomer of phenylamine derivative, and it is without being limited thereto.
Further, the oligomer of phenylamine derivative, which is selected from end, has the oligomer of phenylamine of aforementioned functional group derivative
Object.
Wherein, the alkyl includes one of straight chained alkyl or branched alkyl or combination.
In one embodiment, the oligomer of phenylamine derivative is selected from Oligoanilines and is grafted vegetable oil.
Further, the oligomer of phenylamine derivative can also selected from by oligomer of phenylamine and protonic acid doping dosage form at
Aqueous or oiliness oligomer of phenylamine derivative.
Wherein, the protonic acid doping agent can be selected from any application type known to industry, such as phosphoric acid, camphor can be selected
At least one of sulfonic acid and phytic acid.
In some more typical embodiments, be suitable for the invention typical oligomer of phenylamine derivative can have it is as follows
Structure:
(M is mainly sodium ion, potassium ion, quaternary ammonium salt etc.).
Be suitable for the invention oligomer of phenylamine derivative can commercially available from approach obtain, can also with bibliography (for example,
J.Amer.Chem.Soc.,1986,108,8311；Macromol.Rapid Commun.,2011,32,35；CN
104016876A；CN1887854A etc.) self-control.
Another aspect of the present invention additionally provides the π-π compound of graphene Yu the graphene dispersion agent.
More preferred, graphene and the molar ratio of graphene dispersion agent are 100:1~1 in the π-π compound:
100, preferably 10:1~1:10, especially preferably 2:1~1:2.
In fact, π-π the compound 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 compound.
More preferred, the dispersion is flow-like dispersion, especially preferably liquid dispersion.
More preferred, the dispersion includes the graphene that concentration is 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 method, Hummers method or Staudenmaier method
Standby graphene oxide is thermally expanded grapheme material obtained.Mechanical stripping, liquid phase removing or electrochemistry stripping can also be selected
Grapheme material or redox graphene from preparation.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 water, organic solvent, in 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), tetrahydro
Furans (THF), dimethylformamide (DMF), dimethyl sulfoxide (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
Rouge, 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 cases, 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 compound 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 be also stabilized.And very make us pleasantly surprised
It is also not in bright even if the dispersion comprising the π-π compound is in the case where revolving speed is the centrifugal condition of 10000r/min
Aobvious sedimentation, therefore it is conducive to the application under the particular surroundings such as high temperature, low temperature.
In the present invention, the mechanism of graphene dispersion agent and graphene formation π-π compound may is that graphite of the invention
Aromatic rings is contained in alkene dispersing agent, 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 every two carbon atom
It is all the same, it is by one neither the key connection of double bond nor 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
It is enough to be firmly combined under conditions of not chemically reacting with the corresponding units structure in graphene, and then it 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 dissolution 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 in graphene dispersion agent and graphene, to be formed
Stable dispersion liquid.
More preferred, the dispersion includes the graphene that concentration is 1mg/ml~10mg/ml.
In the graphene dispersion method, the molar ratio of graphene and graphene dispersion agent is 100:1~1:100, 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 Yu the graphene dispersion agent,
And disperse 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:
Graphene is combined to stablize with the oligomer of phenylamine derivative with aromatic structure by strong π-π interaction and is divided
It dissipates in organic solvent, forms graphene dispersing solution；
The graphene dispersing solution is dried and forms powder；
And disperse the powder in 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 dispersing 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 dispersing agent.
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 Yu the graphene dispersion agent composition.
π-π the compound of nano-carbon material Yu the graphene dispersion agent is additionally provided in some embodiments.
π-π compound and decentralized medium comprising nano-carbon material Yu the dispersing agent are additionally provided in some embodiments
Dispersion.
Below in conjunction with several embodiments, a detailed description of the technical solution in the embodiment of the present invention is provided, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
Field those of ordinary skill every other embodiment obtained without making creative work, belongs to this hair
The range of bright protection.
In the following embodiment (such as embodiment 1- embodiment 3) of the invention, by based on aromatic structure
Oligomer of phenylamine derivative graphene dispersion agent, be not required to that any additive and reactant is added, graphene can be made to have
Stable dispersion in solvent (such as EtOH, DMF, THF etc.), and dispersion liquid it is spray-dried after obtain redispersible Graphene powder
Body, the redispersible graphene powder can be stably dispersed in organic solvent again.
The synthesis of 1 aniline tripolymer carboxy derivatives of embodiment and its graphene aqueous liquid dispersion
Aniline tripolymer 1.24g is dissolved in 50ml THF, adds 1.04g succinic anhydride, is reacted 3 hours, is used petroleum ether
Precipitating, obtains aniline tripolymer carboxy derivatives.Weigh the NaOH of obtained aniline tripolymer carboxy derivatives and 2 times of molar equivalents
And the aqueous solution with graphene slurry (graphene content 4.5%) configuration various concentration, ultrasonic disperse 1 hour, effect such as table 1
Stable dispersion liquid can be formed when graphene concentration is 3mg/ml or less.
1 aniline tripolymer carboxy derivatives of table-graphene aqueous liquid dispersion
| 5mg/10ml | 10mg/10ml | 20mg/10ml | 30mg/10ml | 50mg/10ml |
| Well | Well | Well | Well | There is precipitating |
The synthesis of 2 Tetraaniline carboxy derivatives of embodiment and its graphene aqueous liquid dispersion
Tetraaniline 2.0g is added in 50ml THF, and 0.67g succinic anhydride is added, and reacts 3 hours at 40 DEG C, uses stone
Oily ether precipitating, obtains Tetraaniline carboxy derivatives.By obtained Tetraaniline carboxy derivatives and 2 times of molar equivalents
NaOH and graphene are configured to certain density aqueous solution, and ultrasonic half an hour, dispersion effect is as shown in table 2, in graphene concentration
To be capable of forming uniform dispersion when 2.5mg/ml or less.
2 Tetraaniline carboxy derivatives of table-graphene aqueous dispersion effect
| 5mg/10ml | 10mg/10ml | 25mg/10ml | 50mg/10ml |
| Well | Well | Well | There is a small amount of precipitating |
The synthesis of 3 Tetraaniline grafted castor oil of embodiment and its graphene oily dispersion
Castor oil 4.66g and Tetraaniline carboxy derivatives 2.3g are dissolved in 100ml THF, 2.3g is then added
EDC and 1.3g NHS is reacted at room temperature 12 hours, and reaction product largely precipitates in water, and Tetraaniline grafting is obtained after dry
Castor oil.Tetraaniline grafted castor oil and graphene are configured into certain density tetrahydrofuran dispersion liquid by phase homogenous quantities,
Its dispersion effect is examined, stable dispersions (table 3) can be formed when graphene concentration is 2.5mg/ml or less.
3 Tetraaniline of table is grafted vegetable oil-graphene dispersion effect
| 5mg/10ml | 10mg/10ml | 25mg/10ml | 50mg/10ml |
| Well | Well | Well | There is a small amount of precipitating |
Embodiment 4- embodiment 5:
Inventor is also with the operation referring to embodiment 1- embodiment 3, with aniline pentamer derivative, six aggressiveness of aniline
Derivative, including contain alkyl, carboxyl, sulfonic group, a variety of oligomer of phenylamine derivatives and benzene of the functionalization group such as vegetable oil
Amine oligomer and phosphoric acid, camphorsulfonic acid, oligomer of phenylamine derivative of the formation such as phytic acid etc. be used as dispersing agent, and with water, ethyl alcohol,
Tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and chloroform etc. are used as solvent, test it for the dispersion energy of graphene
Power, and obtain and embodiment 1-3 essentially identical test result.
Comparative example 1:
Untreated graphene powder is directly directly added into ethyl alcohol, in 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 to the graphene powder for obtaining handling through silane coupling agent at 60 DEG C, then
The powder is directly added into ethyl alcohol, in tetrahydrofuran (THF) equal solvent, ultrasonic disperse 1h.
With ultraviolet-visible spectrometer (UV-Vis) to the graphene and graphene-dispersing agent compound point in embodiment 1-5
It is not tested, it is found that the internal pi-pi bond of these graphene dispersion agent itself makes it, and there are two at 307nm and 474nm
A apparent absorption peak, and in dispersion liquid, the position of absorption peak shifts to 311nm and 468nm, illustrate dispersing agent with
There is π-π interactions between graphene, so that characteristic peak is subjected to displacement.
With Raman spectrometer (Raman) in embodiment 1-5 graphene and graphene-dispersing agent compound carry out respectively
Test, it can be seen that pure graphene is in 1345cm-1There are the peaks D at place, in 1582cm-1There are the peaks G at place, in 2711cm-1It deposits at place
At the peak 2D；And in the composite, the corresponding characteristic peak of graphene is all displaced, and is illustrated between these dispersing agents and graphene
There are electric charge transfers, it was demonstrated that the π-π of dispersing agent and graphene interaction.
With XRD in embodiment 1-5 graphene and graphene-dispersing agent compound test respectively, result is also
π-the π of these dispersing agents of susceptible of proof and graphene interacts (such as can refer to Fig. 2).
It is observed again with the graphene-dispersing agent compound obtained to embodiment 1-5 such as SEM, AFM, TEM, it can be seen that
Graphene system is in good dispersity, and basic soilless sticking (such as can refer to Fig. 3).And make us very surprisingly,
The obtained graphene of embodiment 1-5-dispersing agent compound AFM, TEM are tested in map (refering to Fig. 4 and Fig. 5), it can be seen that stone
Black alkene presents the very smooth form unfolded, this phenomenon is very wondrous, may be because of graphene of the present invention point
Caused by the plane state molecular structure of powder.
The graphene dispersing solution that Example 1- embodiment 5 is obtained again was 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, being carried out referring to the mode of embodiment 1- embodiment 5, but with carbon nanotube, carbon nano-fiber substitution graphene
Test, as a result, it was confirmed that graphene dispersion agent of the invention is also suitable for that such nano-carbon material is assisted to disperse in organic solvent etc.
Efficient, stable dispersion in medium.
Application examples 1: 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
When the molar ratio of graphene dispersion agent and graphene is within the scope of 10:1~1:10, graphene is in bisphenol A epoxide resin
Homogeneously dispersed state, basic soilless sticking.
The compound of the graphene dispersion agent of Example 1 and carbon nano-fiber is added in commercially available bisphenol A epoxide resin again,
Ultrasonic disperse 1h or so solidifies under the conditions of ultraviolet lighting or suitable temperature later.Take one such Typical cure object with SEM
It is observed, pattern is as shown in Figure 6, it can be seen that carbon nano-fiber is discrete to be distributed in the solidfied material, and soilless sticking phenomenon,
Especially without apparent interface between carbon nano-fiber and epoxy resin cured product, show its good combination.It separately takes same
Carbon nano-fiber is directly added into same epoxy resin, is under equal conditions solidified, but in its solidfied material, carbon nano-fiber
There are clear interfaces between epoxy resin cured product.
Other types are separately added with the graphene dispersion agent of embodiment 2-5 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
After mode is dispersed, solidified, its solidfied material is observed respectively, also can get substantially similar conclusion.
Application examples 2: the graphene of Example 1-dispersing agent 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 " E44+G " in Fig. 8).Pure epoxy resin E44 is separately taken to make
It is coated in identical surface of steel plate for priming paint, is formed by curing coating.In addition, taking Commercial epoxy zinc-rich anti-corrosion primer (refering to Fig. 8 respectively
In " epoxy zinc-rich "), available glass flake paint (refering to " glass flake " in Fig. 8) is in forming coating on identical steel plate.
The anti-corrosion effect of these coatings is tested respectively again, result sees Fig. 7 and Fig. 8, these results indicate that described in
Anti-corrosion primer made from graphene-dispersing agent compound is than pure epoxy resin E44 and commercially available epoxy zinc-rich anti-corrosion primer, glass
Flake paint 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.
It is attached and, 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 for including a series of elements not only includes those elements, but also including
Other elements that are not explicitly listed, or further include for elements inherent to such a process, method, article, or device.
In the absence of more restrictions, the element limited by sentence "including a ..." or " at least one ... " etc., not
There is also other identical elements in the process, method, article or apparatus that includes the element for exclusion.
The above is only a specific embodiment of the invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (48)
1. having application of the electroactive oligomer of phenylamine derivative in dispersed graphite alkene, the application includes: by graphite
Alkene and the oligomer of phenylamine derivative are only uniformly mixed by physics mode in decentralized medium, make oligomer of phenylamine derivative
It is mainly acted on through π-π with graphene rather than forms π-π compound by chemical bonds, so that stabilising dispersions are obtained, institute
It states oligomer of phenylamine derivative and is selected from aniline trimer derivatives, Tetraaniline derivative, aniline pentamer derivative and benzene
Any one in six mer derivatives of amine or two or more combinations, and the average molecular of the oligomer of phenylamine derivative
Amount is below 10000.
2. application according to claim 1, it is characterised in that: the relative molecular weight of the oligomer of phenylamine derivative is
100~1000.
3. application described in any one of -2 according to claim 1, it is characterised in that: contained by the oligomer of phenylamine derivative
Functionalization group is selected from carboxyl, hydroxyl, carbonyl, ester group, amino, alkyl, alkyl, sulfonic group, phosphate, epoxy group, poly- second
Any one in glycol group, polyvinyl alcohol group or two or more combinations.
4. application according to claim 3, it is characterised in that: the functionalization group is distributed in the oligomer of phenylamine and spreads out
Biological end.
5. application described in any one of -2 according to claim 1, it is characterised in that: the oligomer of phenylamine derivative be selected from by
Oligomer of phenylamine and protonic acid doping dosage form at aqueous or oiliness oligomer of phenylamine derivative.
6. application according to claim 5, it is characterised in that: the protonic acid doping agent be selected from phosphoric acid, camphorsulfonic acid and
At least one of phytic acid.
7. graphene and the π-π compound for having electroactive oligomer of phenylamine derivative, the π-π compound is by the benzene
Amine oligomer derivative and graphene are mainly acted on through π-π rather than by the compound of chemical bonds formation, the aniline
It is poly- that oligomer derivative is selected from aniline trimer derivatives, Tetraaniline derivative, aniline pentamer derivative and aniline six
Any one in syntaxy object or two or more combinations, and the relative molecular weight of the oligomer of phenylamine derivative exists
10000 or less.
8. π-π compound according to claim 7, it is characterised in that: the average molecular of the oligomer of phenylamine derivative
Amount is 100~1000.
9. π-π the compound according to any one of claim 7-8, it is characterised in that: the oligomer of phenylamine derivative
Contained functionalization group is selected from carboxyl, hydroxyl, carbonyl, ester group, amino, alkyl, alkyl, sulfonic group, phosphate, epoxy group
Group, polyethylene group, any one or two or more combinations in polyvinyl alcohol group.
10. π-π compound according to claim 9, it is characterised in that: it is low that the functionalization group is distributed in the aniline
Polymers derivative end.
11. π-π the compound according to any one of claim 7-8, it is characterised in that: the oligomer of phenylamine derivative
Selected from by oligomer of phenylamine and protonic acid doping dosage form at aqueous or oiliness oligomer of phenylamine derivative.
12. π-π compound according to claim 11, it is characterised in that: the protonic acid doping agent is selected from phosphoric acid, camphor
At least one of sulfonic acid and phytic acid.
13. π-π compound according to claim 7, it is characterised in that: wherein mole of graphene and graphene dispersion agent
Than for 100:1~1:100.
14. π-π compound according to claim 13, it is characterised in that: wherein graphene and graphene dispersion agent rubs
You are than being 10:1~1:10.
15. π-π compound according to claim 14, it is characterised in that: wherein graphene and graphene dispersion agent rubs
You are than being 2:1~1:2.
16. a kind of graphene dispersion body, it is characterised in that include: decentralized medium；And be scattered in it is in the decentralized medium,
π-π compound as described in any one of claim 7-15.
17. graphene dispersion body according to claim 16, it is characterised in that: the graphene dispersion body is flow-like point
Granular media.
18. graphene dispersion body according to claim 17, it is characterised in that: the graphene dispersion body is liquid dispersed
Body or slurry.
19. graphene dispersion body according to claim 16, it is characterised in that: the decentralized medium is selected from water, You Jirong
Any one in agent, resin or two or more combinations.
20. graphene dispersion body according to claim 19, it is characterised in that: the decentralized medium is selected from organic solvent.
21. graphene dispersion body described in any one of 6-20 according to claim 1, it is characterised in that: the graphene dispersion
Body includes the graphene of 0.1mg/ml~100mg/ml.
22. a kind of preparation method of graphene dispersion body, characterized by comprising: graphene and the electroactive aniline of tool is low
Polymers derivative is only uniformly mixed to form stabilising dispersions by physics mode in decentralized medium, and the oligomer of phenylamine is derivative
Object is in aniline trimer derivatives, six mer derivatives of Tetraaniline derivative, aniline pentamer derivative and aniline
Any one or two or more combinations, and the relative molecular weight of the oligomer of phenylamine derivative is below 10000.
23. preparation method according to claim 22, it is characterised in that: the average molecular of the oligomer of phenylamine derivative
Amount is 100~1000.
24. the preparation method according to any one of claim 22-23, it is characterised in that: the oligomer of phenylamine is derivative
Functionalization group contained by object is selected from carboxyl, hydroxyl, carbonyl, ester group, amino, alkyl, alkyl, sulfonic group, phosphate, epoxy group
Group, polyethylene group, any one or two or more combinations in polyvinyl alcohol group.
25. preparation method according to claim 24, it is characterised in that: it is low that the functionalization group is distributed in the aniline
Polymers derivative end.
26. the preparation method according to any one of claim 22-23, it is characterised in that: the oligomer of phenylamine is derivative
Object be selected from by oligomer of phenylamine and protonic acid doping dosage form at aqueous or oiliness oligomer of phenylamine derivative.
27. preparation method according to claim 26, it is characterised in that: the protonic acid doping agent is selected from phosphoric acid, camphor
At least one of sulfonic acid and phytic acid.
28. preparation method according to claim 22, it is characterised in that: wherein mole of graphene and graphene dispersion agent
Than for 100:1~1:100.
29. preparation method according to claim 28, it is characterised in that: wherein mole of graphene and graphene dispersion agent
Than for 10:1~1:10.
30. preparation method according to claim 29, it is characterised in that: wherein mole of graphene and graphene dispersion agent
Than for 2:1~1:2.
31. preparation method according to claim 22, 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.
32. preparation method according to claim 31, it is characterised in that: the decentralized medium is selected from organic solvent.
33. preparation method according to claim 31, it is characterised in that: the high molecular polymer is selected from resin, described
Resin is in alkyd resin, amino resins, epoxy resin, polyester resin, acrylic resin, organic siliconresin, furane resins
Any one or two or more combinations.
34. preparation method according to claim 22, it is characterised in that: the dispersion includes 0.1mg/ml~100mg/
The graphene of ml.
35. a kind of graphene dispersion and redisperse method, characterized by comprising:
Graphene and the electroactive oligomer of phenylamine derivative of tool are only uniformly mixed by physics mode in decentralized medium
Stabilising dispersions are formed, the oligomer of phenylamine derivative is selected from aniline trimer derivatives, Tetraaniline derivative, aniline
Any one in six mer derivatives of pentamer derivative and aniline or two or more combinations, and the oligomer of phenylamine
The relative molecular weight of derivative 10000 hereinafter,
It removes the decentralized medium in the dispersion and obtains the compound of graphene Yu the graphene dispersion agent,
And disperse the compound in decentralized medium again, stabilising dispersions are formed again.
36. graphene dispersion according to claim 35 and redisperse method, it is characterised in that: the oligomer of phenylamine spreads out
The relative molecular weight of biology is 100~1000.
37. the graphene dispersion according to any one of claim 35-36 and redisperse method, it is characterised in that: described
Functionalization group contained by oligomer of phenylamine derivative is selected from carboxyl, hydroxyl, carbonyl, ester group, amino, alkyl, alkyl, sulfonic acid
Base, phosphate, epoxy group, polyethylene group, any one or two or more combinations in polyvinyl alcohol group.
38. the graphene dispersion according to claim 37 and redisperse method, it is characterised in that: the functionalization group point
It is distributed in oligomer of phenylamine derivative end.
39. the graphene dispersion according to any one of claim 35-36 and redisperse method, it is characterised in that: described
Oligomer of phenylamine derivative be selected from by oligomer of phenylamine and protonic acid doping dosage form at aqueous or oiliness oligomer of phenylamine it is derivative
Object.
40. graphene dispersion according to claim 39 and redisperse method, it is characterised in that: the protonic acid doping agent
Selected from phosphoric acid, at least one of camphorsulfonic acid and phytic acid.
41. graphene dispersion according to claim 35 and redisperse method, it is characterised in that: the decentralized medium is selected from
Water, organic solvent, any one or two or more combinations in resin.
42. graphene dispersion according to claim 41 and redisperse method, it is characterised in that: the decentralized medium is selected from
Organic solvent.
43. graphene dispersion according to claim 35 and redisperse method, it is characterised in that: the stabilising dispersions packet
Graphene containing 0.1mg/ml~100mg/ml.
44. nano-carbon material dispersing agent in dispersion nano-carbon material in application, the nano-carbon material dispersing agent it is effective at
Being selected from includes 2-8 aromatic rings, and relative molecular weight 10000 hereinafter, simultaneously can with nano-carbon material formed π-π it is compound
The electroactive oligomer of phenylamine derivative of the tool of object, the oligomer of phenylamine derivative are selected from aniline trimer derivatives, benzene
Any one in six mer derivatives of amine tetramer derivative, aniline pentamer derivative and aniline or two or more groups
It closes, the application includes: that nano-carbon material and the nano-carbon material dispersing agent are only passed through to physics side in decentralized medium
Formula uniformly mixes, and acts on the oligomer of phenylamine derivative and nano-carbon material mainly through π-π rather than passes through chemical bonded refractory
Conjunction forms π-π compound, to obtain stabilising dispersions.
45. application according to claim 44, it is characterised in that: the relative molecular weight of the oligomer of phenylamine derivative is
100~1000.
46. the application according to any one of claim 44-45, it is characterised in that: the oligomer of phenylamine derivative choosing
From with carboxyl, hydroxyl, carbonyl, ester group, amino, alkyl, alkyl, sulfonic group, phosphate, epoxy group, polyethylene group,
The oligomer of phenylamine derivative of at least one of polyvinyl alcohol group.
47. the application according to any one of claim 44-45, it is characterised in that: the oligomer of phenylamine derivative choosing
Free oligomer of phenylamine and protonic acid doping dosage form at aqueous or oiliness oligomer of phenylamine derivative.
48. application according to claim 47, it is characterised in that: the protonic acid doping agent is selected from phosphoric acid, camphorsulfonic acid
At least one of with phytic acid.
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| 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 |
| CN107663672A (en) * | 2017-06-13 | 2018-02-06 | 绍兴标点纺织科技有限公司 | A kind of compound PAN fiber of graphene and preparation method |
| CN109205603A (en) * | 2017-06-30 | 2019-01-15 | 中国科学院宁波材料技术与工程研究所 | The dispersing method of graphene |
| JP2019125481A (en) * | 2018-01-16 | 2019-07-25 | トヨタ自動車株式会社 | Negative electrode mixture for all-solid lithium ion secondary battery and manufacturing 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 |
| CN110128890B (en) * | 2019-06-04 | 2021-04-02 | 江南大学 | Hybrid acrylic acid electrophoretic coating and preparation method thereof |
| KR20220143001A (en) * | 2019-11-29 | 2022-10-24 | 로얄 멜버른 인스티튜트 오브 테크놀로지 | Water-Redispersible Graphene Powder |
| CN113717632A (en) * | 2021-08-07 | 2021-11-30 | 南京中车浦镇城轨车辆有限责任公司 | Polyaniline micelle graphene composite material, electrode coating, working electrode and preparation method thereof |
| CN115572518A (en) * | 2022-09-26 | 2023-01-06 | 厦门大学 | Water-based concrete protective coating composition and preparation method thereof |
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