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CN108559092B - Carbon material dispersant, method for producing the same, and stable aqueous dispersion of carbon material containing the dispersant - Google Patents

Carbon material dispersant, method for producing the same, and stable aqueous dispersion of carbon material containing the dispersant Download PDF

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CN108559092B
CN108559092B CN201810209767.3A CN201810209767A CN108559092B CN 108559092 B CN108559092 B CN 108559092B CN 201810209767 A CN201810209767 A CN 201810209767A CN 108559092 B CN108559092 B CN 108559092B
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姜学松
李瑾
苏志龙
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Shanghai Jiaotong University
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Abstract

The present invention relates to a carbon material dispersant, a method for producing the same, and a stable aqueous dispersion of a carbon material containing the dispersant. In particular, the dispersant is suitable for dispersing carbon materials having a graphene structure, comprising an amphiphilic hyperbranched polymer having a backbone structure comprising amine groups and a monocyclic, polycyclic, fused or heterocyclic aryl group covalently bonded to the backbone structure that is non-covalently associated with the graphene structure. The carbon material dispersant is prepared by the following steps: i) reacting a polyglycidyl compound with a polyfunctional amine, thereby forming a hyperbranched polymer having a secondary amine group at a terminal, wherein the amino hydrogen of the polyfunctional amine is in molar excess relative to the glycidyl groups of the polyglycidyl compound; and ii) introducing a monocyclic, polycyclic, fused ring, or heterocyclic aromatic group non-covalently associated with the graphene structure into the hyperbranched polymer via reaction with a secondary amine group, thereby forming a dispersant comprising an amphiphilic hyperbranched polymer.

Description

Carbon material dispersant, method for producing the same, and stable aqueous dispersion of carbon material containing the dispersant
Technical Field
The invention relates to a carbon material dispersant and a preparation method thereof. The invention also relates to a stable aqueous dispersion of carbon material containing the carbon material dispersant and its use in various fields. The invention additionally relates to an amphiphilic hyperbranched polymer.
Background
The carbon material, especially the carbon material with a graphene structure, has extremely high application value due to the specific structure. As a typical representative of such carbon materials, graphene is a material consisting of carbon atoms in sp form2The two-dimensional crystal material of the regular hexagonal honeycomb lattice structure formed by the hybridization mode has the thickness of only one or a few carbon atoms. The ordered and ultrathin two-dimensional structure endows the graphene with the following excellent physical and chemical properties: light weight, low density, high chemical stability and high specific surface area, so that the material is an ideal hydrogen storage material; high conductivity, high strength, ultra-light and thin, etc., so thatThe material has great application prospect in the fields of ultralight airplanes, ultralight body armor and aerospace; the material has excellent mechanical property, superstrong high toughness, high optical transparency and high electric and thermal conductivity, so that the material has wide application prospect in the fields of flexible devices, photosensitive elements, sensors, liquid crystal displays, transparent conductive electrodes and the like. Thus, graphene is also known as the "king of new materials". In order to obtain various excellent performances of graphene, the preparation of high-quality graphene two-dimensional nanosheets is a crucial part.
Currently, methods for preparing graphene developed mainly include epitaxial growth methods, chemical vapor deposition methods, redox methods, chemical synthesis methods, physical exfoliation methods, and the like. However, these methods have some drawbacks, and are not suitable for industrial scale production. For example, epitaxial growth and vapor deposition have high requirements on temperature and equipment, which limits the application range. Although the redox method has the advantages of simple operation, high yield and the like, the prepared graphene inevitably has structural defects, so that the product quality is low, and the use of strong acids such as sulfuric acid and nitric acid has great danger and pollution. Moreover, due to the particularities of the redox process, the oxygen content of the resulting product is difficult to control, so that there is a possibility of further reduction during subsequent storage and transportation, and thus the product quality is difficult to guarantee. The chemical synthesis method has high cost, cannot realize large-scale quantitative production, and has uncontrollable product performance (chem. -Eur.J.2002,8,1424.).
Compared with the foregoing methods, the physical stripping method is the most concerned method due to its advantages of relatively simple process, controllable product quality, etc. Physical exfoliation methods include solid phase exfoliation (i.e., mechanical exfoliation) and liquid phase exfoliation. Mechanical exfoliation refers to the direct cutting of graphene sheets from larger crystals. Although single-layer graphene can be obtained by the method, the size of the obtained graphene sheet layer is difficult to control, the production efficiency is extremely low, and large-scale preparation is difficult to realize. Liquid phase stripping refers to stripping a powder material into a two-dimensional nanosheet layer by means of ultrasonic, shearing and the like of each system formed by bulk phase powder and an organic solvent (such as N-methylpyrrolidone (NMP)), a surfactant (such as sodium cholate, sodium dodecyl sulfate and the like) aqueous solution or an ionic liquid. Although the method is simple and convenient to operate and low in cost, the stripping system has respective defects, such as high toxicity of the used organic solvent, low stripping efficiency of the surfactant and danger of the ionic liquid. Moreover, liquid phase stripping usually requires complicated steps such as pretreatment, high temperature reduction and the like (as disclosed in CN 104692363B), and the use of ultrasonic method results in poor structural integrity of the product and is difficult to realize industrial production.
Accordingly, there remains a need in the industry for improved methods for preparing aqueous dispersions of carbon materials.
Disclosure of Invention
One object of the present invention is: an aqueous dispersion of carbon material is provided that is suitable for scale-up processes to produce carbon materials without the aforementioned deficiencies.
The inventors of the present invention have surprisingly found that amphiphilic hyperbranched polymers having specific functional groups, i.e. monocyclic, polycyclic, fused ring or heterocyclic aromatic groups capable of non-covalently associating with graphene structures, can undergo non-covalent association with carbon materials when milled therewith, thereby successfully achieving separation of the carbon materials and obtaining stable aqueous dispersions of carbon materials. Furthermore, the use of such amphiphilic hyperbranched polymer as a carbon material dispersant enables the preparation of an aqueous dispersion of a carbon material on an industrial scale, and the prepared aqueous dispersion of a carbon material has desirable material properties, such as desirable sheet size, number of sheets, and the like.
Accordingly, in one aspect, the present invention provides a carbon material dispersant comprising an amphiphilic hyperbranched polymer having a backbone structure comprising amine groups and a single, multi, fused or heterocyclic aromatic group covalently bonded to the backbone structure in non-covalent association with a graphene structure, and the carbon material having a graphene structure. Preferably, the backbone structure of the amphiphilic hyperbranched polymer is formed by an addition reaction of a polyglycidyl compound and a polyfunctional amine. Optionally, the amphiphilic hyperbranched polymer further comprises hydrophilic polyether segments and/or hydrophobic organic segments, wherein the molar ratio of the hydrophilic polyether segments to the hydrophobic organic segments is in the range of 10:0 to 0: 10.
Another aspect of the present invention provides a method for preparing a carbon material dispersant, comprising i) reacting a polyglycidyl compound with a polyfunctional amine, thereby forming a hyperbranched polymer having a secondary amine group at the end, wherein the amino hydrogen of the polyfunctional amine is in molar excess relative to the glycidyl groups of the polyglycidyl compound; and ii) introducing a monocyclic, polycyclic, fused ring, or heterocyclic aromatic group non-covalently associated with a graphene structure into the hyperbranched polymer via reaction with a secondary amine group, thereby forming a dispersant comprising an amphiphilic hyperbranched polymer, wherein the carbon material has a graphene structure.
Yet another aspect of the invention provides a stable aqueous dispersion of a carbon material comprising a carbon material dispersant non-covalently associated with the carbon material, wherein the carbon material dispersant is as defined above or prepared according to the method of the invention, and wherein the carbon material has a graphene structure. Preferably, the aqueous dispersion in which the carbon material is graphene is formed by milling a mixture of graphite and the carbon material dispersant according to the present invention in the presence of an aqueous solvent.
Yet another aspect of the present invention provides the use of an aqueous dispersion of a carbon material according to the present invention in hydrogen storage materials, ultra light aircraft, ultra light body armor, aerospace materials, flexible devices, light sensitive elements, sensors, liquid crystal display materials, transparent electrically conductive electrodes.
As is well known, water is a polar solvent, and a carbon material having a graphene structure is difficult to disperse in water and is very easy to agglomerate, so that it is a great challenge to prepare an aqueous dispersion of the carbon material having a graphene structure. The inventors of the present invention have surprisingly found that amphiphilic hyperbranched polymers having specific functional groups, i.e. monocyclic, polycyclic, fused ring or heterocyclic aromatic groups capable of non-covalent association with graphene structures, can be non-covalently associated with carbon materials when milled therewith, thereby successfully achieving exfoliation of the carbon materials. The inventors of the present invention have also surprisingly found that stable aqueous dispersions of carbon materials can be prepared even under long-term storage using the carbon material dispersant of the present invention, and that aqueous dispersions of carbon materials prepared with the carbon material dispersant of the present invention at high concentrations (for example, concentrations of 10mg/ml or more, preferably 11mg/ml or more, more preferably 12 mg/ml or more, and even more preferably 15mg/ml or more) are stable under long-term storage. The obtained aqueous dispersion of carbon material, wherein the carbon material having a graphene structure has a two-dimensional size with an average side length of 0.5 to 20 μm and/or the number of layers thereof is not more than 10, is suitable for various applications such as hydrogen storage materials, ultra-light aircraft, ultra-light body armor, aerospace materials, flexible devices, photosensitive elements, sensors, liquid crystal display materials, and transparent conductive electrodes.
Furthermore, the use of the above amphiphilic hyperbranched polymer having a specific structure as a carbon material dispersant may additionally bring about the following advantages.
First, the carbon material dispersants of the present invention can incorporate tailored properties in the carbon materials prepared therefrom. As described above, the carbon material dispersant according to the present invention is prepared by an addition reaction of an industrial raw material including a polyglycidyl compound and a polyfunctional amine. In view of the structural diversity of the polyglycidyl compounds and polyfunctional amine materials, the structure of the carbon material dispersant can be customized according to requirements, and further functionalization is carried out, so that the carbon material prepared from the carbon material dispersant has customized properties, such as optical properties, electrical properties and the like.
Secondly, the carbon material dispersant of the present invention can simplify the preparation process of the aqueous dispersant of a carbon material. Specifically, the carbon material dispersant according to the present invention may be directly mixed with a carbon material having a graphene structure, such as bulk graphite, in water, and an aqueous dispersion of the carbon material is obtained by simple grinding without any complicated steps of pretreatment, post-reduction, and the like. Moreover, the grinding equipment is common equipment in industry, and can be used for large-scale industrial production.
Thirdly, the carbon material dispersing agent disclosed by the invention contains amphiphilic hyperbranched polymer, so that a dispersion of the carbon material taking an aqueous medium as a solvent can be prepared, and the safety and no toxicity in a stripping process are realized, and the carbon material dispersing agent is green, energy-saving, environment-friendly and low in cost.
Fourth, since the carbon material dispersant of the present invention contains a polymer having a hyperbranched structure, its addition does not significantly increase the viscosity of the dispersion system, and a small amount of dispersant can achieve significant exfoliation.
In addition, the invention also provides a novel amphiphilic hyperbranched polymer, which has a framework structure containing amine groups and a monocyclic, polycyclic, fused or heterocyclic aryl group which is covalently bonded to the framework structure and is non-covalently associated with the graphene structure. Optionally, the backbone structure of the amphiphilic hyperbranched polymer is formed by an addition reaction of a polyglycidyl compound and a polyfunctional amine. The novel amphiphilic hyperbranched polymer can be used as a dispersant for carbon materials and can also be used for dispersing inorganic particles such as pigments, fillers and the like.
The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.
Definition of
As used herein, the terms "a," "an," and "one or more" are not used interchangeably.
Where a composition is described as including or comprising a particular component, optional components not contemplated by the present invention are not contemplated as being excluded from the composition and it is contemplated that the composition may consist of or consist of the recited component or where a method is described as including or comprising a particular process step, optional process steps not contemplated by the present invention are not contemplated as being excluded from the method and it is contemplated that the method may consist of or consist of the recited process step.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
The term "hyperbranched polymer" refers herein to a macromolecule, defined as a dendrimer with a random branch-branch topology prepared by a one-step condensation of monomers of the a2 and B3 types.
When used with respect to a "monocyclic, polycyclic, fused ring, or heterocyclic aryl group," the phrase "non-covalently associated with a graphene structure in a sp state refers to the ability of the monocyclic, polycyclic, fused ring, or heterocyclic aryl group to non-covalently associate with a graphene structure in a manner including, but not limited to, hydrophobic bonds, van der waals forces, wherein the graphene structure refers to a structure formed from carbon atoms in an sp state2The hexagonal shape of the hybrid orbit is a honeycomb lattice structure, such as the structure shown in the following formula:
Figure DEST_PATH_IMAGE001
the term "organic moiety", when used in reference to an "amphiphilic hyperbranched polymer", is defined as a moiety from an organic compound comprising carbon, hydrogen, and optionally elements such as oxygen, nitrogen, sulfur, phosphorus, and the like. In some embodiments of the present invention, the organic segment may be derived from polyglycidyl compounds including, but not limited to, C having a molecular weight in the range of 382-6000g/mol3-C10Alkoxy polyethers or structures based on bisphenol A, bisphenol F, bisphenol S and derivatives thereof, C1-C20Alkyl groups and derivatives thereof.
The term "stable" when used in reference to an "aqueous dispersion of carbon material" means that the aqueous dispersion is left at ambient temperature for a period of time, for example 1 week, 1 month, 3 months or six months, with less than 0.1% post-precipitation, or even no precipitation.
The terms "comprise" and "comprise," and variations thereof, when appearing in the specification and claims, have no limiting meaning.
The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of dispersant 1 according to example 1.
Fig. 2 is an infrared spectrum of the dispersant 1 according to example 1.
Fig. 3 is a TEM and electron diffraction photograph of an aqueous dispersion of graphene according to example 1.
Fig. 4 is an AFM profile of an aqueous dispersion of graphene according to example 1, and corresponding phase diagram and height profile, wherein (a) is a nanoplatelet layer height profile of graphene; (b) a phase diagram corresponding to the topography; (c) is a height profile.
Fig. 5 is a photograph showing the stability of an aqueous dispersion of graphene prepared using the carbon material dispersant of the present invention, in which the left figure is an aqueous dispersion of newly prepared graphene and the right figure is an aqueous dispersion of graphene after being left for 150 days. In fig. 5, the concentration of the aqueous dispersion of graphene is illustrative, and the aqueous dispersion of graphene at a high concentration may have a concentration of 11.3mg/ml, but is not limited thereto, and the concentration may be higher; the aqueous dispersion of low concentration graphene may have a concentration of 0.514 mg/ml.
Fig. 6 is a TEM photograph of an aqueous dispersion of carbon nanotubes according to example 7.
Fig. 7 is a photograph showing the stability of the aqueous dispersion of carbon nanotubes according to example 7, in which the left is an aqueous dispersion of newly prepared carbon nanotubes and the right is an aqueous dispersion of carbon nanotubes after being left for 150 days.
Fig. 8 is a TEM photograph of an aqueous dispersion of carbon nanotubes according to example 8.
Fig. 9 is a photograph showing the stability of the aqueous dispersion of carbon nanotubes according to example 8, in which the left is an aqueous dispersion of newly prepared carbon nanotubes and the right is an aqueous dispersion of carbon nanotubes after being left for 150 days.
Detailed Description
According to a first aspect of the present invention, there is provided a carbon material dispersant comprising an amphiphilic hyperbranched polymer having a backbone structure comprising amine groups and single-, multiple-and fused-ring or heterocyclic aromatic groups covalently bonded to the backbone structure in non-covalent association with graphene structures, and the carbon material having graphene structures.
The carbon material dispersant according to the present invention comprises an amphiphilic hyperbranched polymer. In the context of the present invention, the phrase "carbon material dispersant comprises an amphiphilic hyperbranched polymer" means that the dispersant according to the present invention may contain, in addition to the amphiphilic hyperbranched polymer (i.e. an amphiphilic hyperbranched polymer bearing single-ring, multi-ring, fused-ring or heterocyclic aromatic groups non-covalently associated with the graphene structure), other components that do not adversely affect the performance of the carbon material dispersant, including but not limited to organic solvents, raw materials for preparing the amphiphilic hyperbranched polymer, etc. According to the invention, the amphiphilic hyperbranched polymer refers to a hyperbranched polymer having both hydrophilicity and hydrophobicity, wherein the hyperbranched polymer comprises single-ring, multi-ring or condensed ring aromatic rings which are non-covalently associated with a graphene structure, so that certain hydrophobicity can be given to the hyperbranched polymer, and amino groups present in the skeleton of the hyperbranched polymer can give certain hydrophilicity to the hyperbranched polymer. Thus, the carbon material dispersant according to the present invention can achieve dispersion of the carbon material in water or an organic solvent without an additional surfactant.
As mentioned above, the amphiphilic hyperbranched polymer according to the invention comprises single, multi, fused or heterocyclic aromatic groups non-covalently associated with graphene structures. Besides providing certain hydrophobicity, the monocyclic, polycyclic, fused ring or heterocyclic aryl group can interact with the surface of the carbon material with a graphene structure to realize the separation of the carbon material. In embodiments of the present invention, the carbon material having a graphene structure includes, but is not limited to, graphene, carbon nanotubes, or other carbon materials having a graphene structure. In one embodiment of the present invention, in which graphite is used as a raw material to prepare graphene, a single-ring, multi-ring, condensed-ring, or heterocyclic aryl group carried by the amphiphilic hyperbranched polymer may interact with the surface of graphene to realize exfoliation of graphite, thereby forming a graphene dispersion. By way of example, the monocyclic, polycyclic, fused ring, or heterocyclic aryl group includes substituted or unsubstituted groups derived from: benzene, naphthalene, pyrene, anthracene, pentacene, benzo [ a ]]Pyrene, benzophenone, thioxanthone, pyridine, coronene, caryophyllene, tetracene, phenanthrene and benzo [9,10]]Phenanthrene, oomycete, triphenylene, perylene, benzo [ ghi ]]Perylene, anthanthrone, pentabenzene, picene, dibenzo [3, 4; 9,10]Pyrene, benzo [3,4]]Pyrene, dibenzo [3, 4; 8,9]Pyrene, dibenzo [3, 4; 6,7]Pyrene, dibenzo [1, 2; 3,4]Pyrene, naphtho [2, 3; 3,4]Pyrene, porphyrin derivative or any combination thereof. Alternatively, the monocyclic, polycyclic, fused ring or heterocyclic aryl group is substituted with a substituent selected from the group consisting of: c1-C20Alkyl, halo C1-C20Alkyl radical, C1-C20Alkoxy, carboxyl, carbonyl, hydroxyl, halogen, amino, C2-C20Alkynyl, C2-C20Alkenyl, aldehyde, anhydride, cyano.
As described above, the amphiphilic hyperbranched polymer according to the present invention has a backbone structure containing amine groups including, but not limited to, tertiary amine groups and secondary amine groups. The presence of such amine groups leads to a certain hydrophilicity of the hyperbranched polymer according to the invention. In addition to this, the amphiphilic hyperbranched polymer may also comprise a backbone having any suitable compositional structure. The backbone can have different compositional structures depending on various factors, such as the materials used to form the backbone, cost, and the desired properties of the polymer. The backbone optionally comprises one or more other step-growth linkages, such as amide linkages, ester linkages, carbonate linkages, ether linkages, amide linkages, imine linkages, urethane linkages, or combinations thereof.
As one presently preferred embodiment, the backbone structure of the amphiphilic hyperbranched polymer is formed via an addition reaction of a polyglycidyl compound and a polyfunctional amine. Preferably, the amino hydrogens of the polyfunctional amine are in molar excess with respect to the glycidyl groups of the polyglycidyl compounds, preferably the molar ratio of the amino hydrogens of the polyfunctional amine with respect to the glycidyl groups of the polyglycidyl compounds is 3: 2.
According to the invention, polyglycidyl compounds are monomers, oligomers or polymers having two or more glycidyl groups in the molecule. Preferably, the polyglycidyl compounds are selected from the group consisting of polyglycidyl esters, polyglycidyl ethers, or combinations thereof. In an embodiment according to the invention, the polyglycidyl compound is a polyglycidyl ether. As examples of polyglycidyl ethers, diglycidyl ethers of polyhydric phenols, diglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of phenolic resins, or combinations thereof can be used. Suitable polyglycidyl ethers include, for example, diglycidyl ethers of polyhydric phenols such as diglycidyl ether of resorcinol, diglycidyl ether of catechol, diglycidyl ether of hydroquinone, diglycidyl ether of bisphenol a, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of tetramethylbiphenol; diglycidyl ethers of aliphatic and polyether diols, such as C2-24A diglycidyl ether of an alkylene glycol, a diglycidyl ether of a poly (ethylene oxide) glycol, or a diglycidyl ether of a poly (propylene oxide) glycol; polyglycidyl ethers of phenolic resins, such as polyglycidyl ethers of phenol-formaldehyde resins, polyglycidyl ethers of alkyl-substituted phenol-formaldehyde resins, phenol-hydroxybenzenesPolyglycidyl ethers of aldehyde resins or polyglycidyl ethers of cresol-hydroxybenzaldehyde resins; or a combination thereof.
According to the invention, multifunctional amines are amines having two or more amino groups in the molecule, wherein the presence of trifunctional amines can provide branching points during the reaction and the presence of difunctional amines can be used to adjust the branching of the hyperbranched polymer. The degree of branching of the hyperbranched polymers decreases with increasing amounts of difunctional amines.
Preferably, the multifunctional amine comprises an aliphatic trifunctional amine, an aromatic trifunctional amine, an alicyclic trifunctional amine, a heterocyclic trifunctional amine, or a combination thereof, and optionally further comprises an aliphatic difunctional amine, an aromatic difunctional amine, an alicyclic difunctional amine, a heterocyclic difunctional amine, or a combination thereof. In some embodiments of the invention, N-ethylethylenediamine, N- (2-hydroxyethyl) ethylenediamine, may be used as the polyfunctional amine. In these embodiments, the multifunctional amine may further comprise difunctional amines such as N, N' -diethylethylenediamine, butylamine, piperazine, and the like to adjust the degree of branching of the hyperbranched polymer.
According to the present invention, the amphiphilic hyperbranched polymer may further comprise hydrophilic polyether segments to impart further hydrophilicity to the amphiphilic hyperbranched polymer and/or may further comprise hydrophobic organic segments to impart further hydrophobicity to the amphiphilic hyperbranched polymer. The presence of the above hydrophilic polyether segment and/or hydrophobic organic segment in a molar ratio of the hydrophilic polyether segment to the hydrophobic organic segment in the range of 10:0 to 0:10, preferably in the range of 10:1 to 1:10, more preferably in the range of 8:1 to 1:8, still more preferably in the range of 4:1 to 1:4, even still more preferably in the range of 2:1 to 1:2, and particularly still more preferably 1:1 results in achieving a better dispersing effect.
In some embodiments according to the invention, the hydrophilic polyether segment is derived from polyoxyethylene having a molecular weight in the range of 174-6000 g/mol.
In some embodiments according to the invention, the hydrophobic organic segment is derived from a moleculeC in an amount in the range 382-6000g/mol3-C10Alkoxy polyethers or structures based on bisphenol A, bisphenol F or bisphenol S and derivatives thereof, C1-C20Alkyl groups and derivatives thereof or combinations thereof. Preferably, the hydrophobic organic segment is derived from C having a molecular weight in the range of 382-6000g/mol3- C10An alkoxy polyether. In one embodiment of the present invention, the hydrophobic organic segment is derived from polyoxypropylene having a molecular weight in the range of 382-6000 g/mol.
According to the invention, the amphiphilic hyperbranched polymer has a structure represented by the following formula I:
Figure BDA0001596853480000101
in the above formula, the first and second carbon atoms are,
x represents a divalent organic fragment derived from a polyglycidyl compound;
y represents substituted or unsubstituted C2-C10Alkyl, substituted or unsubstituted C2-C10Alkoxy, substituted or unsubstituted C3-C10A cycloalkyl group;
r represents said monocyclic, polycyclic, fused or heterocyclic aryl group; and
r' represents substituted or unsubstituted C1-C10Alkyl radical, C1-C10Alkoxy, cycloalkyl, aryl, heteroaryl.
Preferably, X represents a polyether segment having the structure shown in formula II below:
Figure BDA0001596853480000111
wherein R is1Represents substituted or unsubstituted C1-C20Alkyl radical, C1-C10Alkoxy radical, C1-C10Acyloxy, C3-C10Cycloalkyl radical, C6-C14Aryl radicals, silane radicals, or thereofIn combination, optionally the substituents are selected from the group consisting of1-C20Alkyl, hydroxy, halogen.
More preferably, X represents-O- (CH)2CH(CH3)-O)n-CH2-、-O-(CH2CH2-O)n-CH2-or a combination thereof, wherein n represents a positive integer from 1 to 150, preferably from 1 to 20.
According to the present invention, the amphiphilic hyperbranched polymer may have a broad molecular weight distribution. Preferably, the amphiphilic hyperbranched polymers disclosed herein may have a number average molecular weight in the range of 2000 to 30,000g/mol, preferably in the range of 2000 to 20,000g/mol, more preferably in the range of 2500 to 20,000g/mol, still more preferably in the range of 3000 to 18,000 g/mol. The number average molecular weight can be measured using GPC.
According to the present invention, the amphiphilic hyperbranched polymer may have a suitable degree of branching, thus being suitable for providing a suitable viscosity and functionality. Preferably, the amphiphilic hyperbranched polymers disclosed herein may have a degree of branching in the range of 0.21 to 062, preferably in the range of 0.39 to 0.62, more preferably in the range of 0.44 to 0.62, still more preferably in the range of 0.52 to 0.62. The degree of branching can be calculated according to the method described in "highly branched Polymers Synthesis, Properties and Applications" of Deyue Yan et al, Chapter 81-84.
The carbon material dispersant according to the present invention can be prepared by: i) reacting a polyglycidyl compound with a polyfunctional amine, thereby forming a hyperbranched polymer having a secondary amine group at a terminal, wherein the amino hydrogen of the polyfunctional amine is in molar excess relative to the glycidyl groups of the polyglycidyl compound; and ii) introducing a monocyclic, polycyclic, fused ring, or heterocyclic aromatic group non-covalently associated with a graphene structure into the hyperbranched polymer via reaction with a secondary amine group, thereby forming a dispersant comprising an amphiphilic hyperbranched polymer, wherein the carbon material has a graphene structure.
Thus, according to another aspect of the present invention, there is provided a method for preparing a carbon material dispersant, comprising i) reacting a polyglycidyl compound with a polyfunctional amine, thereby forming a hyperbranched polymer having terminal secondary amine groups, wherein the amino hydrogen of the polyfunctional amine is in molar excess relative to the glycidyl groups of the polyglycidyl compound; and ii) introducing a monocyclic, polycyclic, fused ring, or heterocyclic aromatic group non-covalently associated with a graphene structure into the hyperbranched polymer via reaction with a secondary amine group, thereby forming a dispersant comprising an amphiphilic hyperbranched polymer, wherein the carbon material has a graphene structure.
In the method for preparing a carbon material dispersant according to the present invention, step i) comprises reacting a polyglycidyl compound with a polyfunctional amine, wherein the amino hydrogens of the polyfunctional amine are in molar excess relative to the glycidyl groups of the polyglycidyl compound, preferably the molar ratio of the amino hydrogens of the polyfunctional amine relative to the glycidyl groups of the polyglycidyl compound is 3: 2.
As mentioned above, polyglycidyl compounds refer to monomers, oligomers or polymers having two or more glycidyl groups in the molecule. Preferably, the polyglycidyl compounds are selected from the group consisting of polyglycidyl esters, polyglycidyl ethers, or combinations thereof. In an embodiment according to the invention, the polyglycidyl compound is a polyglycidyl ether. As examples of polyglycidyl ethers, diglycidyl ethers of polyhydric phenols, diglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of phenolic resins, or combinations thereof can be used. Suitable polyglycidyl ethers include, for example, diglycidyl ethers of polyhydric phenols such as diglycidyl ether of resorcinol, diglycidyl ether of catechol, diglycidyl ether of hydroquinone, diglycidyl ether of bisphenol a, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of tetramethylbiphenol; diglycidyl ethers of aliphatic and polyether diols, such as C2-24A diglycidyl ether of an alkylene glycol, a diglycidyl ether of a poly (ethylene oxide) glycol, or a diglycidyl ether of a poly (propylene oxide) glycol; polyglycidyl ethers of phenolic resins, such as phenol-formaldehyde resinsA polyglycidyl ether of a lipid, a polyglycidyl ether of an alkyl-substituted phenol-formaldehyde resin, a polyglycidyl ether of a phenol-hydroxybenzaldehyde resin, or a polyglycidyl ether of a cresol-hydroxybenzaldehyde resin; or a combination thereof.
As mentioned above, multifunctional amines refer to amines having two or more amino groups in the molecule, wherein the presence of trifunctional amines can provide branching points during the reaction, and the presence of difunctional amines can be used to adjust the degree of branching of the hyperbranched polymer. The degree of branching of the hyperbranched polymers decreases with increasing amounts of difunctional amines.
Preferably, the multifunctional amine comprises an aliphatic trifunctional amine, an aromatic trifunctional amine, an alicyclic trifunctional amine, a heterocyclic trifunctional amine, or a combination thereof. Optionally, the multifunctional amine further comprises an aliphatic difunctional amine, an aromatic difunctional amine, a cycloaliphatic difunctional amine, a heterocyclic difunctional amine, or a combination thereof. In some embodiments of the invention, N-ethylethylenediamine, N- (2-hydroxyethyl) ethylenediamine, may be used as examples of polyfunctional amines. In these embodiments, the multifunctional amine may further comprise difunctional amines such as N, N' -diethylethylenediamine, butylamine, piperazine, and the like to adjust the degree of branching of the hyperbranched polymer. In the above step i), the appropriate conditions for the reaction to be carried out depend on various factors including the type of polyglycidyl compound or polyfunctional amine used, the presence or absence of a catalyst, the type of catalyst if present, and the like, which can be determined empirically by those skilled in the art.
In one embodiment of the invention, the polyglycidyl compound comprises ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, or a combination thereof, and the polyfunctional amine comprises N-ethyl ethylenediamine or N- (2-hydroxyethyl) ethylenediamine. Preferably, in this embodiment, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, or a combination thereof is reacted with N-ethyl ethylenediamine or N- (2-hydroxyethyl) ethylenediamine at a temperature of 60-100 ℃ in the absence of a catalyst, wherein the amino hydrogens of the polyfunctional amine are in molar excess relative to the glycidyl groups of the polyglycidyl compounds, to give a hyperbranched polymer with terminal secondary amine groups.
In the method for preparing a carbon material dispersant according to the present invention, step ii) comprises introducing a monocyclic, polycyclic, fused ring or heterocyclic aromatic group non-covalently associated with a graphene structure into the hyperbranched polymer via reaction with a secondary amine group.
According to the present invention, a mono-, multi-, fused-or heterocyclic aryl compound bearing an amino-reactive functional group selected from the group consisting of a carboxyl group, an epoxy group, an ester group, an acid chloride group, or a combination thereof is used to introduce a mono-, multi-, fused-or heterocyclic aryl group non-covalently associated with a graphene structure into a hyperbranched polymer.
In embodiments according to the present invention, the monocyclic, polycyclic, fused ring, or heterocyclic aryl compound bearing an amino-reactive functional group can be commercially available, for example, 9-anthracenecarboxylic acid, or can be synthetic. In one embodiment according to the present invention, the monocyclic, polycyclic, fused ring or heterocyclic aryl compound having an amino-reactive functional group is synthesized by: reacting the monocyclic, polycyclic or condensed ring compound having a hydroxyl group with epichlorohydrin to form a monocyclic, polycyclic, condensed ring or heterocyclic aryl compound having a glycidyl group.
In the above step ii), the appropriate conditions for the reaction to be carried out depend on various factors including the type of the monocyclic, polycyclic, fused-ring or heterocyclic aryl compound having an amino-reactive functional group used, the presence or absence of a catalyst, the type of catalyst, if present, and the like, which can be determined empirically by those skilled in the art.
In one embodiment of the present invention, the monocyclic, polycyclic, fused ring, or heterocyclic aryl compound having an amino-reactive functional group comprises 9-anthracenecarboxylic acid. Preferably, in this embodiment, the product of step i) is refluxed with 9-anthracenecarboxylic acid under an inert atmosphere for 24 hours, thereby forming a dispersant comprising an amphiphilic hyperbranched polymer.
In another embodiment of the present invention, the mono-, poly-, fused-, or heterocyclic aryl compound having an amino-reactive functional group is obtained by reacting 9-anthracenemthanol with epichlorohydrin. Preferably, in this embodiment, the product of step i) is refluxed with epoxy-functionalized anthracene under an inert atmosphere for 24 hours, thereby forming a dispersant comprising an amphiphilic hyperbranched polymer.
In some embodiments of the invention, both step i) and step ii) are performed under the protection of an inert gas, wherein the inert gas is selected from the group consisting of nitrogen, argon or a combination thereof.
In some embodiments of the invention, both step i) and step ii) are carried out in an organic solvent, wherein the organic solvent is selected from the group consisting of alcohols, ethers, ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, 1, 4-dioxane, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
The inventors of the present invention have surprisingly found that the carbon material dispersant according to the present invention prepared by the above method has excellent dispersing performance, and is suitable for stripping graphene from graphite to form a stable aqueous dispersion of graphene.
Accordingly, another aspect of the present invention provides a stable aqueous dispersion of a carbon material comprising a carbon material dispersant as disclosed above non-covalently associated with the carbon material, wherein the carbon material has a graphene structure. Preferably, the carbon material having a graphene structure includes, but is not limited to, graphene, carbon nanotubes, or other carbon materials having a graphene structure.
The graphene aqueous dispersion prepared by the carbon material dispersant has excellent material properties. In one embodiment according to the present invention, the resulting aqueous dispersion comprises graphene having an average side length of 0.5 to 20 microns. In another embodiment according to the present invention, the resulting aqueous dispersion comprises no more than 10 layers of graphene. In another embodiment according to the present invention, the resulting aqueous dispersion comprises graphene having an average side length of 0.5 to 20 microns, and the number of layers of graphene does not exceed 10.
In an embodiment according to the invention, the aqueous dispersion of graphene is formed by milling a mixture of graphite and the dispersant for the carbon material of the invention in the presence of an aqueous solvent. Preferably, the grinding is performed using a grinding device selected from the group consisting of a grinder, a horizontal sand mill, a vertical sand mill, a multi-functional disperser, and an oscillating disperser. In the above embodiments, the milling is performed at a temperature of 3-95 ℃ and/or the weight ratio of the graphite to the amphiphilic hyperbranched dispersant is in the range of 1:10 to 40: 1. As a raw material for preparing graphene, graphite selected from natural graphite, foamed graphite, highly oriented cracked graphite, flake graphite, or a mixture thereof may be used.
In one embodiment according to the present invention, a method for preparing a stable aqueous dispersion of graphene comprises the steps of:
step 1, mixing graphite and a graphene dispersing agent in water to obtain a mixed solution, wherein the weight ratio of the graphite to the graphene dispersing agent is 1:10-40: 1;
step 2, circularly grinding and stripping the mixed solution through a grinding device to obtain a suspension;
step 3, standing or filtering the suspension to obtain supernatant and grinding beads;
and 4, carrying out centrifugal separation on the supernatant by a centrifugal separation technology to obtain a two-dimensional graphene aqueous solution and the nano graphite sheets used as precipitates.
According to the invention, the nano graphite sheet as the precipitate can be circularly stripped as the graphite to be stripped or used as a lubricant for downstream products of graphene.
The aqueous dispersion of carbon material according to the present invention has a wide range of applications, and can be used in hydrogen storage materials, ultra-light aircraft, ultra-light body armor, aerospace materials, flexible devices, light-sensitive elements, sensors, liquid crystal display materials, transparent computer electrodes.
The inventors of the present invention have also surprisingly found that the amphiphilic hyperbranched polymer in the carbon material dispersant according to the present invention is novel per se, and can be used not only for dispersing carbon materials but also for dispersing inorganic particles such as pigments, fillers, and the like.
Accordingly, in yet another aspect of the present invention, there is provided an amphiphilic hyperbranched polymer. To further illustrate this aspect of the invention, some non-limiting embodiments are specifically provided below:
1. an amphiphilic hyperbranched polymer having a backbone structure comprising amine groups and a monocyclic, polycyclic, fused or heterocyclic aryl group covalently bonded to the backbone structure that is non-covalently associated with a graphene structure.
2. The amphiphilic hyperbranched polymer according to embodiment 1, wherein the weight average molecular weight of the amphiphilic hyperbranched polymer is in the range of 2000-30000 g/mol.
3. The amphiphilic hyperbranched polymer according to embodiment 1, wherein the degree of branching of the amphiphilic hyperbranched polymer is in the range of 0.21-0.62.
4. The amphiphilic hyperbranched polymer according to embodiment 1, wherein the monocyclic, polycyclic, fused ring or heterocyclic aryl group comprises a substituted or unsubstituted group derived from: benzene, naphthalene, pyrene, anthracene, pentacene, benzo [ a ] pyrene, benzophenone, thioxanthone, pyridine, coronene, caryophyllene, tetracene, phenanthrene, benzo [9,10] phenanthrene, ovalene, triphenylene, perylene, benzo [ ghi ] perylene, anthanthrone, pentacene, picene, dibenzo [3, 4; 9,10] pyrene, benzo [3,4] pyrene, dibenzo [3, 4; 8,9] pyrene, dibenzo [3, 4; 6,7] pyrene, dibenzo [1, 2; 3,4] pyrene, naphtho [2, 3; 3,4] pyrene, a porphyrin derivative or any combination thereof.
5. The amphiphilic hyperbranched polymer according to embodiment 4, wherein the monocyclic, polycyclic, fused ring or heterocyclic aryl groups are substituted with substituents selected from the group consisting of: c1-C20Alkyl, halo C1-C20Alkyl radical, C1-C20Alkoxy, carboxyl, carbonyl, hydroxyl, halogen, amino, C2-C20Alkynyl, C2-C20Alkenyl, aldehyde, anhydride, cyano.
6. The amphiphilic hyperbranched polymer according to embodiment 1, wherein the amphiphilic hyperbranched polymer further comprises hydrophilic polyether segments and/or hydrophobic organic segments, wherein the molar ratio of the hydrophilic polyether segments to the hydrophobic organic segments is in the range of 10:0 to 0: 10.
7. The amphiphilic hyperbranched polymer according to embodiment 6, wherein the hydrophilic polyether segment is derived from polyoxyethylene having a molecular weight in the range of 174-6000 g/mol.
8. The amphiphilic hyperbranched polymer according to embodiment 6, wherein the hydrophobic organic segment is derived from C having a molecular weight in the range of 382-6000g/mol3-C10Alkoxy polyethers or structures based on bisphenol A, bisphenol F or bisphenol S and derivatives thereof, C1-C20Alkyl groups and derivatives thereof or combinations thereof.
9. The amphiphilic hyperbranched polymer according to embodiment 1, wherein the backbone structure of the amphiphilic hyperbranched polymer is formed by an addition reaction of a polyglycidyl compound and a polyfunctional amine.
10. The amphiphilic hyperbranched polymer according to embodiment 9, wherein the polyglycidyl compounds are selected from the group consisting of polyglycidyl esters, polyglycidyl ethers or combinations thereof, preferably polyglycidyl ethers.
11. The amphiphilic hyperbranched polymer according to embodiment 10, wherein the polyglycidyl ethers are selected from the group consisting of diglycidyl ethers of polyhydric phenols, diglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of phenolic resins, and combinations thereof.
12. The amphiphilic hyperbranched polymer according to embodiment 9, wherein the multifunctional amine is selected from the group consisting of aliphatic trifunctional amines, aromatic trifunctional amines, alicyclic trifunctional amines, heterocyclic trifunctional amines, or combinations thereof, and optionally further comprises aliphatic difunctional amines, aromatic difunctional amines, alicyclic difunctional amines, heterocyclic difunctional amines, or combinations thereof.
13. The amphiphilic hyperbranched polymer according to embodiment 9, wherein the amino hydrogen of the polyfunctional amine is in molar excess relative to the glycidyl groups of the polyglycidyl compounds.
14. The amphiphilic hyperbranched polymer according to embodiment 9, wherein the amphiphilic hyperbranched polymer has a structure represented by the following formula I:
Figure BDA0001596853480000171
in the above formula, the first and second carbon atoms are,
x represents a divalent organic fragment derived from a polyglycidyl compound;
y represents substituted or unsubstituted C2-C10Alkyl, substituted or unsubstituted C2-C10Alkoxy, substituted or unsubstituted C3-C10A cycloalkyl group;
r represents said monocyclic, polycyclic, fused or heterocyclic aryl group; and
r' represents substituted or unsubstituted C1-C10Alkyl radical, C1-C10Alkoxy, cycloalkyl, aryl, heteroaryl.
15. The amphiphilic hyperbranched polymer according to embodiment 14, wherein X represents a polyether segment having a structure represented by formula II below:
Figure BDA0001596853480000181
wherein R is1Represents substituted or unsubstituted C1-C20Alkyl radical, C1-C10Alkoxy radical, C1-C10Acyloxy, C3-C10Cycloalkyl radical, C6-C14An aromatic group, a silane group, or a combination thereof, optionally a substituent selected from the group consisting of C1-C20Alkyl, hydroxy, halogen.
16. The amphiphilic hyperbranched polymer according to embodiment 15, wherein X represents-O- (CH)2CH(CH3)-O)n-CH2-、-O-(CH2CH2-O)n-CH2-or a combination thereof, wherein n represents a positive integer from 1 to 150, preferably from 1 to 20.
The present disclosure is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available and can be used directly without further treatment.
Examples
Synthesis example 1: synthesis of hyperbranched polymers
Polyethylene glycol diglycidyl ether (PEG-DE, Mn ═ 500 g/mol), polypropylene glycol diglycidyl ether (PPG-DE, Mn ═ 640g/mol), and N-ethyl ethylenediamine (NEED) and N, N' -diethyl ethylenediamine in the amounts indicated in table 1 below were dissolved in ethanol, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃ and refluxed for 24 h. After completion of the reaction, it was cooled to room temperature, and ethanol was removed by distillation under reduced pressure to obtain a pale yellow viscous solid product, i.e., Polymer 1-5, with a yield of about 90%.
TABLE 1
Figure BDA0001596853480000191
As can be seen from the results in table 1, the ring-opening reaction of polyglycidyl ethers and polyfunctional amines, such as trifunctional amines, can form hyperbranched polymers, where the presence of difunctional amines can be used to adjust the degree of branching of the polymer. The hyperbranched polymers 1 to 4 obtained above can be further modified by monocyclic, polycyclic, fused or heterocyclic polymers containing functional groups, thereby forming amphiphilic hyperbranched polymers suitable for dispersing carbon materials, i.e., carbon material dispersants.
Example 1: synthesis of a dispersant with 9-anthracenemethanol as a component non-covalently bonded to graphene, and use of the component Powder preparation of graphene aqueous dispersion
(1) And (3) preparing a hyperbranched polymer framework. Polyethylene glycol diglycidyl ether (PEG-DE, Mn ═ 500g/mol,10.52g), polypropylene glycol diglycidyl ether (PPG-DE, Mn ═ 640g/mol,12.8g), and N-ethyl ethylenediamine (NEED, 3.52g) were dissolved in ethanol, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃, and refluxed for 24 h. After the reaction is finished, the reaction product is cooled to room temperature, and ethanol is removed by reduced pressure distillation to obtain a light yellow viscous solid product, namely the hyperbranched polymer-1, wherein the yield is about 90%.
(2) And (3) synthesizing a functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound. 9-Anthracene methanol (4.17g,0.02mol) and epichlorohydrin (9.25g,0.1mol) were dissolved in 80ml of butanone, 5g of potassium carbonate was added as a catalyst, and the mixture was refluxed for 12 hours under nitrogen protection. After the reaction is finished, the catalyst and the solvent are removed, and the functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-1 is obtained with the yield of about 90 percent.
(3) And (3) synthesis of an amphiphilic hyperbranched polymer. The functional group-containing monocyclic, polycyclic or fused ring compound-1 (E-AN, 0.01mol) and the hyperbranched polymer-1 (0.01mol, calculated by the amount of secondary amine groups) are dissolved in 20ml of ethanol and refluxed for 20h under the protection of nitrogen. After the reaction is finished, precipitating the obtained mixture in n-hexane, and drying in vacuum to obtain the amphiphilic hyperbranched polymer-1 serving as the dispersing agent-1 for dispersing the graphene.
Fig. 1 shows a structural diagram and a nuclear magnetic hydrogen spectrum diagram of the amphiphilic hyperbranched polymer, and fig. 2 shows an infrared spectrum diagram of the amphiphilic hyperbranched polymer.
1H NMR(CDCl3,ppm):δ=1.0-0.9(m,3H,-CH3),3.87(m,2H,- CHCH2-O),5.66-5.53(m,2H,ArCH2O-),7.58-7.46(m,4H, aryl), 8.02(d,2H, aryl), 8.41(d,2H, aryl).
FT-IR(KBr,cm-1): 3200-.
(4) 1.0g of dispersant-1, 2.0g of graphite was weighed, mixed in 200mL of water, and ground by a sand mill at room temperature for 3 hours to obtain a black suspension-1.
(5) Filtering the black suspension-1 obtained in the step (4) to obtain a supernatant-1 and grinding beads.
(6) And (3) centrifuging the supernatant-1 obtained in the step (5) for 30min under the condition of 7000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-1, and a lower precipitate which is a nano graphite sheet.
(7) The grinding beads obtained in the step (5) can be recycled, and the graphite nanoplatelets obtained in the step (6) can be used as a downstream product of graphene as a lubricant or used as graphite to be stripped for recycling.
TEM and AFM photographs of the aqueous dispersion of graphene are shown in fig. 3 and 4, respectively. As can be seen from the results of the attached drawings, the length side of the obtained graphene is 8-15 mu m, and the number of layers is less than 10.
Example 2: synthesis of a dispersant with 9-anthracenecarboxylic acid as a component non-covalently bonded to graphene, and use of the component Powder preparation of graphene aqueous dispersion
(1) And (3) preparing a hyperbranched polymer framework. Polypropylene glycol diglycidyl ether (PPG-DE, Mn 640g/mol,12.8g) and N-ethyl ethylenediamine (NEED, 1.76g) were dissolved in ethanol, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃, and refluxed for 24 h. After the reaction is finished, the reaction product is cooled to room temperature, and ethanol is removed by reduced pressure distillation to obtain a light yellow viscous solid product, namely the hyperbranched polymer-2, wherein the yield is about 95%.
(2) And (3) synthesis of an amphiphilic hyperbranched polymer. 9-anthracene formic acid (0.01mol) and hyperbranched polymer-2 (0.01mol, calculated by the total amount of amino and hydroxyl) are dissolved in chloroform and refluxed for 24 hours under the protection of nitrogen. And after the reaction is finished, removing the solvent, and performing vacuum drying to obtain the amphiphilic hyperbranched polymer-2 serving as the dispersing agent-2 for dispersing the graphene.
(3) 0.4g of dispersant-2, 4.0g of graphite was weighed, mixed in 200mL of water, and ground by a sand mill at 65 ℃ for 1 hour to obtain a black suspension-2.
(4) Filtering the black suspension-2 obtained in the step (3) to obtain supernatant-2 and grinding beads.
(5) And (3) centrifuging the supernatant-2 obtained in the step (4) for 30min under the condition of 10000 r/min by using a centrifugal separation technology to obtain an upper black clear liquid which is a two-dimensional graphene aqueous solution-2, and a lower precipitate which is a nano graphite sheet.
(6) The grinding beads obtained in the step (4) can be recycled, and the graphite nanoplatelets obtained in the step (5) can be used as downstream products of graphene as a lubricant or used as graphite to be stripped for recycling.
Example 3: synthesis of a dispersant with 9-anthracenemethanol as a component non-covalently bonded to graphene, and use of the component Powder preparation of graphene aqueous dispersion
(1) And (3) preparing a hyperbranched polymer framework. Polyethylene glycol diglycidyl ether (PEG-DE, Mn 500g/mol,10.52g) and N-ethyl ethylenediamine (NEED, 1.76g) were dissolved in ethanol, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃, and refluxed for 24 h. After the reaction is finished, the reaction product is cooled to room temperature, and ethanol is removed by reduced pressure distillation to obtain a light yellow viscous solid product, namely the hyperbranched polymer-3, wherein the yield is about 95%.
(2) And (3) synthesizing a functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound. 9-Anthracene methanol (4.17g,0.02mol) and epichlorohydrin (9.25g,0.1mol) were dissolved in 100ml of tetrahydrofuran, and 5g of potassium hydroxide was added as a catalyst, and the mixture was refluxed for 12 hours under nitrogen protection. After the reaction is finished, the catalyst and the solvent are removed, and the functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-1 is obtained with the yield of about 90 percent.
(3) And (3) synthesis of an amphiphilic hyperbranched polymer. The preparation method comprises the steps of dissolving a functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-1 (E-AN, 0.01mol) and AN amphiphilic hyperbranched polymer-3 (0.01mol, calculated by the amount of secondary amine groups) in 20ml of ethanol, and refluxing for 20h under the protection of nitrogen. After the reaction is finished, precipitating the obtained mixture in n-hexane, and drying in vacuum to obtain the amphiphilic hyperbranched polymer-3 serving as the dispersing agent-3 for dispersing the graphene.
(4) 0.1g of dispersant-3, 4.0g of graphite was weighed, mixed in 200mL of water, and ground at 85 ℃ for 1 hour by a sand mill to obtain a black suspension-3.
(5) And (5) standing the black suspension-3 obtained in the step (4) for 12h to obtain a supernatant-3.
(6) And (3) centrifuging the supernatant-3 obtained in the step (5) for 60min under the condition of 12000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-3, and a lower precipitate which is a nano graphite sheet.
(7) And (4) the graphite nanoplatelets in the step (6) can be used as a downstream product of graphene as a lubricant or can be recycled as graphite to be stripped.
Example 4: synthesis of a dispersant with 9-anthracenemethanol as a component non-covalently bonded to graphene, and use of the component Powder preparation of graphene aqueous dispersion
(1) And (3) preparing a hyperbranched polymer framework. Ethylene glycol diglycidyl ether (PEG-DE, Mn ═ 174g/mol,3.48g), polypropylene glycol diglycidyl ether (PPG-DE, Mn ═ 6000g/mol,12.0g), and N-ethyl ethylenediamine (NEED, 1.94g) were dissolved in tetrahydrofuran, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃, and refluxed for 12 h. After the reaction is finished, the reaction product is cooled to room temperature, and ethanol is removed by reduced pressure distillation to obtain a light yellow viscous solid product, namely the hyperbranched polymer-4, wherein the yield is about 88 percent.
(2) And (3) synthesizing a functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound. 9-Anthracene methanol (4.17g,0.02mol) and epichlorohydrin (9.25g,0.1mol) were dissolved in 80ml of butanone, 5g of potassium carbonate was added as a catalyst, and the mixture was refluxed for 12 hours under nitrogen protection. After the reaction is finished, the catalyst and the solvent are removed, and the functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-1 is obtained with the yield of about 90 percent.
(3) And (3) synthesis of an amphiphilic hyperbranched polymer. The functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-1 (E-AN, 0.01mol) and the hyperbranched polymer-4 (0.01mol, calculated by the amount of secondary amine groups) are dissolved in ethanol and refluxed for 20 hours under the protection of nitrogen. After the reaction is finished, precipitating the obtained mixture in n-hexane, and drying in vacuum to obtain the water-based amphiphilic high molecular polymer-4 serving as the dispersing agent-4 for dispersing the graphene.
(4) 5.0g of dispersant-4 and 0.5g of graphite were weighed, mixed in 200mL of water, and ground at 3 ℃ for 5 hours by a sand mill to obtain a black suspension-4.
(5) And (4) filtering the black suspension-4 obtained in the step (4) to obtain supernatant-4 and grinding beads.
(6) And (3) centrifuging the supernatant-4 obtained in the step (5) for 30min under the condition of 7000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-4, and a lower precipitate which is a nano graphite sheet.
(7) The grinding beads obtained in the step (5) can be recycled, and the graphite nanoplatelets obtained in the step (6) can be used as a downstream product of graphene as a lubricant or used as graphite to be stripped for recycling.
Example 5: synthesis of a dispersant with 9-anthracenecarboxylic acid as a component non-covalently bonded to graphene, and use of the component Powder preparation of graphene aqueous dispersion
(1) And (3) preparing a hyperbranched polymer framework. Polyethylene glycol diglycidyl ether (PEG-DE, Mn ═ 6000g/mol,12.0g), polypropylene glycol diglycidyl ether (PPG-DE, Mn ═ 382g/mol,3.82g), and N- (2-hydroxyethyl) ethylenediamine (AEEA, 1.25g) were dissolved in tetrahydrofuran and refluxed at 80 ℃ for 24h under nitrogen. After the reaction is finished, the reaction product is cooled to room temperature, and the solvent is removed to obtain a light yellow viscous solid product, namely the hyperbranched polymer-5, wherein the yield is about 92%.
(2) And (3) synthesis of an amphiphilic hyperbranched polymer. 9-anthracene formic acid (0.01mol) and hyperbranched polymer-5 (0.01mol, calculated by the total amount of amino and hydroxyl) are dissolved in butanone and refluxed for 24 hours under the protection of nitrogen. And after the reaction is finished, removing the solvent, and performing vacuum drying to obtain the amphiphilic hyperbranched polymer-5 serving as the dispersing agent-5 for dispersing the graphene.
(3) 0.3g of dispersant-5 and 2.0g of graphite were weighed, mixed in 200mL of water, and ground at 95 ℃ for 1 hour by a sand mill to obtain a black suspension-5.
(4) And (4) standing the black suspension liquid-5 obtained in the step (3) for 24 hours to obtain supernatant liquid-5 and nano graphite sheet precipitates.
(5) And (3) centrifuging the supernatant-5 obtained in the step (4) for 20min at 6000 r/min by utilizing a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-5, and a lower precipitate which is a nano graphite sheet.
(6) And (4) the graphite nanoplatelets in the steps (4) and (5) can be used as a downstream product of graphene as a lubricant or can be recycled as graphite to be stripped.
Example 6: using naphthalene tetracarboxylic dianhydride as a component non-covalently bonded to graphene to synthesize a dispersant, and using The dispersant is used for preparing graphene aqueous dispersion
(1) And (3) preparing a hyperbranched polymer framework. Polyethylene glycol diglycidyl ether (PEG-DE, Mn ═ 2000g/mol,4.0g), polypropylene glycol diglycidyl ether (PPG-DE, Mn ═ 382g/mol, 7.64g), and N- (2-hydroxyethyl) ethylenediamine (AEEA, 2.29g) were dissolved in 1, 4-dioxane and refluxed at 85 ℃ for 24h under nitrogen. After the reaction is finished, the reaction product is cooled to room temperature, and the solvent is removed to obtain a light yellow viscous solid product, namely the hyperbranched polymer-6, wherein the yield is about 94%.
(2) And (3) synthesis of an amphiphilic hyperbranched polymer. Naphthalene tetracarboxylic dianhydride (0.05mol) and hyperbranched polymer-6 (0.01mol, calculated by the total amount of amino and hydroxyl) are dissolved in toluene and refluxed at 115 ℃ for 24 hours under the protection of nitrogen. And after the reaction is finished, removing the solvent, and performing vacuum drying to obtain the amphiphilic hyperbranched polymer-6 serving as the dispersing agent-6 for dispersing the graphene.
(3) 4.5g of dispersant-6 and 0.5g of graphite were weighed, mixed in 200mL of water, and ground by a sand mill at 10 ℃ for 8 hours to obtain a black suspension-6.
(4) And (4) standing the black suspension liquid-6 obtained in the step (3) for 10 hours to obtain supernatant liquid-6 and nano graphite sheet precipitates.
(5) And (3) centrifuging the supernatant-6 obtained in the step (4) for 50min under the condition of 7500 r/min by using a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-6, and a lower precipitate which is a nano graphite sheet.
(6) And (4) the graphite nanoplatelets in the steps (4) and (5) can be used as a downstream product of graphene as a lubricant or can be recycled as graphite to be stripped.
Fig. 5 shows a photograph showing the stability of an aqueous dispersion of graphene. As can be seen from fig. 5, the aqueous dispersion of graphene prepared using the graphene dispersant according to the present invention was stable even after 150 days of storage. The inventors of the present invention have also surprisingly found that the aqueous dispersion of graphene at high concentration which can be prepared using the carbon material dispersant of the present invention is also stable after 150 days of storage, which was difficult to achieve prior to the present invention.
Example 7: preparation of aqueous carbon nanotube Using amphiphilic hyperbranched Polymer-1 of example 1 as dispersant Dispersion product
(1) The amphiphilic hyperbranched polymer-1 obtained in example 1 above was used as a dispersant for dispersing carbon nanotubes.
(2) 1.5g of carbon nanotube dispersant and 1.0g of carbon nanotube were weighed, mixed in 200mL of water, and ground by a sand mill at room temperature for 2 hours to obtain a black suspension-7.
(3) Filtering the black suspension-1 obtained in the step (2) to obtain a supernatant-7 and grinding beads.
(4) And (3) centrifuging the supernatant-7 obtained in the step (3) for 10min under the condition of 9000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a carbon nano tube aqueous solution-7 and a precipitate which is a carbon nano tube aggregate at the lower layer.
A TEM of the aqueous dispersion 7 of carbon nanotubes is shown in fig. 6. Fig. 7 shows a photograph showing the stability of the aqueous dispersion 7 of carbon nanotubes. As can be seen from fig. 7, the aqueous dispersion of carbon nanotubes prepared using the dispersion of the present invention was also very stable, with no significant precipitation occurring after 150 days of storage at room temperature.
Example 8: preparation of aqueous carbon nanotube Using amphiphilic hyperbranched Polymer-3 of example 3 as dispersant Dispersion product
(1) The amphiphilic hyperbranched polymer-3 obtained in example 3 above was used as a dispersant for dispersing carbon nanotubes.
(2) 2.0g of dispersant-3, 2.0g of carbon nanotubes were weighed, mixed in 200mL of water, and ground by a sand mill at 30 ℃ for 2 hours to obtain a black suspension-8.
(3) And (3) standing the black suspension-8 obtained in the step (2) for 12h to obtain a supernatant-2.
(4) And (3) centrifuging the supernatant-8 obtained in the step (3) for 10min under the condition of 9000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a carbon nano tube aqueous solution-8 and a precipitate which is a carbon nano tube aggregate at the lower layer.
The TEM of the aqueous dispersion of carbon nanotubes-8 is shown in fig. 8. Fig. 9 shows a photograph showing the stability of the aqueous dispersion 8 of carbon nanotubes. As can be seen from fig. 9, the aqueous dispersion of carbon nanotubes prepared using the dispersion of the present invention was also very stable, with no significant precipitation occurring after 150 days of storage at room temperature.
Example 9: the dispersant is prepared by using naphthalene tetracarboxylic dianhydride as a non-covalent bonding component with graphene, and the dispersant is adopted Dispersant preparation of graphene aqueous dispersion
(1) And (3) preparing a hyperbranched polymer framework. Polyethylene glycol diglycidyl ether (PEG-DE, Mn 500g/mol,10.52g) and N-ethyl ethylenediamine (NEED, 1.76g) were dissolved in ethanol, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃, and refluxed for 24 h. After the reaction is finished, the reaction product is cooled to room temperature, and ethanol is removed by reduced pressure distillation to obtain a light yellow viscous solid product, namely the hyperbranched polymer-3, wherein the yield is about 95%.
(2) And (3) synthesizing a functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound. 1,4,5, 8-Naphthalenetetracarboxylic dianhydride (4.00g, 14.92mmol) was dissolved in an aqueous solution (700 ml) of KOH (3.92 g). By H3PO4The resulting brown solution was acidified to pH 6.3 with (1M) solution, to which butylamino (1.09g, 14.92mmol) was added dropwise, again with H3PO4The (1M) solution was acidified to pH 6.4 and the resulting yellow clear mixed solution was transferred to a three-necked flask under N2Heating to 110 ℃ under protection, and stirring to react for 16 h. Cooling to room temperature after reaction, filtering the mixture, acidifying the filtrate with 10mL glacial acetic acid to obtain ice cream-like precipitate, stirring for 20min, and filtering to obtain milky whiteThe white solid was dried in vacuo at 50 ℃ for 48h to give the final product as a cream powder solid with a yield of about 85%. The above milky white solid (100mg, 0.293mmol) and glycine (22.0mg, 0.293mmol) were dissolved in DMAC (2.5mL), to which toluene (0.25mL) was added dropwise in N2Stirring and refluxing at 135 ℃ under protection, removing water in the system for about 20 hours, cooling to room temperature after reaction is finished, precipitating the obtained product in deionized water (10mL), filtering and drying in vacuum at 60 ℃ for 24 hours to obtain a product which is light pink to light brown powder, namely the functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-9, and the yield is about 80%.
(3) And (3) synthesis of an amphiphilic hyperbranched polymer. Functional group-containing monocyclic, polycyclic, fused ring or heterocyclic Compound-9 (1.632g, 4mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (0.920g, 4.8mmol), 1-hydroxybenzotriazole (0.54g, 4mmol) were dissolved in chloroform (30ml), activated at room temperature for 4 hours, and then a solution of hyperbranched polymer-3 (2.46g, 4mmol) in chloroform (5ml) was added dropwise thereto over N2And reacting at 40 ℃ for 12h under protection. And after the reaction is finished, dialyzing the mixture for 2 days in ethanol at the molecular weight cutoff of 3500g/mol, then dialyzing the mixture for 1 day in water, extracting the mixture for 3 to 5 times by using chloroform with the same volume, removing chloroform by rotary evaporation, and drying the mixture in vacuum at the temperature of 50 ℃ to obtain the amphiphilic hyperbranched polymer-9.
(4) 1.5g of dispersant-9 and 2.0g of graphite were weighed, mixed in 200mL of water, and ground by a sand mill at room temperature for 3 hours to obtain a black suspension-9.
(5) And (4) standing the black suspension-9 obtained in the step (4) for 12h to obtain a supernatant-9.
(6) And (3) centrifuging the supernatant-9 obtained in the step (5) for 10min under the condition of 5000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-9, and a lower precipitate which is a nano graphite sheet.
(7) And (4) the graphite nanoplatelets in the step (6) can be used as a downstream product of graphene as a lubricant or can be recycled as graphite to be stripped.
Example 10: synthesis of a dispersant with benzophenone as a non-covalent bonding component to graphene, and use thereof Dispersant preparation of graphene aqueous dispersion
(1) And (3) preparing a hyperbranched polymer framework. Polyethylene glycol diglycidyl ether (PEG-DE, Mn ═ 500g/mol,10.52g), polypropylene glycol diglycidyl ether (PPG-DE, Mn ═ 640g/mol,12.8g), and N-ethyl ethylenediamine (NEED, 3.52g) were dissolved in ethanol, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃, and refluxed for 24 h. After the reaction is finished, the reaction product is cooled to room temperature, and ethanol is removed by reduced pressure distillation to obtain a light yellow viscous solid product, namely the hyperbranched polymer-1, wherein the yield is about 90%.
(2) And (3) synthesizing a functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound. Benzophenone (17.28g,0.087mol), epichlorohydrin (40.37g,0.436mol) and K2CO3(24.12g, 0.174mol) was dissolved in 400ml of butanone and the solution was mixed with N2Protecting, and heating at 80 deg.C for 24 h. And then, cooling the mixed solution to room temperature, performing rotary evaporation to remove butanone, recrystallizing the residues in ethanol, and then placing a sample in a vacuum oven at 70 ℃ for 12 hours to obtain the product 2- (2, 3-epoxypropoxy) benzophenone, namely the functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-10.
(3) And (3) synthesis of an amphiphilic hyperbranched polymer. Functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-10 (0.952g, 4mmol) and hyperbranched polymer-3 (2.46g, 4mmol) were dissolved in 20ml ethanol, and N was2Under protection, refluxing at 80 ℃ for 24h, cooling to room temperature after the reaction is finished, precipitating the reaction mixture in n-hexane with ten times of volume for three times, and vacuum-drying at 50 ℃ for 24h to obtain a light yellow viscous product, namely the amphiphilic hyperbranched polymer-10.
(4) 1.0g of dispersant-10 and 0.5g of graphite were weighed, mixed in 200mL of water, and ground by a sand mill at room temperature for 3 hours to obtain a black suspension-10.
(5) And (4) standing the black suspension-10 obtained in the step (4) for 12h to obtain a supernatant-10.
(6) And (3) centrifuging the supernatant-10 obtained in the step (5) for 30min under the condition of 4000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-10, and a lower precipitate which is a nano graphite sheet.
(7) And (4) the graphite nanoplatelets in the step (6) can be used as a downstream product of graphene as a lubricant or can be recycled as graphite to be stripped.
Example 11 Synthesis of dispersant with 1-pyrene methanol as a non-covalent bonding component to graphene, and use thereof Dispersant preparation of graphene aqueous dispersion
(1) Polyethylene glycol diglycidyl ether (PEG-DE, Mn ═ 500g/mol,10.52g), polypropylene glycol diglycidyl ether (PPG-DE, Mn ═ 640g/mol,12.8g), N-ethyl ethylenediamine (NEED, 1.76g) and N, N' -diethyl ethylenediamine (2.32g) were dissolved in ethanol, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃ and refluxed for 24 h. After the reaction is finished, cooling to room temperature, and removing ethanol through reduced pressure distillation to obtain a light yellow viscous solid product, namely the hyperbranched polymer-11.
(2) And (3) synthesizing a functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound. 1-pyrenemethanol (4.65g,0.02mol) and epichlorohydrin (9.25g,0.1mol) were dissolved in 100ml of DMF, 5g of potassium carbonate was added as a catalyst, and the mixture was refluxed for 12 hours under nitrogen protection. After the reaction is finished, the catalyst and the solvent are removed, and the functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-11 is obtained.
(3) And (3) synthesis of an amphiphilic hyperbranched polymer. Functional group-containing monocyclic, polycyclic or fused ring compound-11 (0.01mol), hyperbranched polymer-11 (0.01mol, calculated as the amount of secondary amine groups) was dissolved in 100ml of ethanol and refluxed for 20h under nitrogen protection. After the reaction is finished, precipitating the obtained mixture in n-hexane, and drying in vacuum to obtain the amphiphilic hyperbranched polymer-11 serving as the dispersing agent-11 for dispersing the graphene.
(4) 0.6g of dispersant-11 and 2.0g of graphite were weighed, mixed in 200mL of water, and ground at 35 ℃ for 1 hour by a sand mill to obtain a black suspension-11.
(5) And (4) filtering the black suspension-11 obtained in the step (4) to obtain supernatant-11 and grinding beads.
(6) And (3) centrifuging the supernatant-11 obtained in the step (5) for 30min under the condition of 4000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-11, and a lower precipitate which is a nano graphite sheet.
(7) The grinding beads obtained in the step (5) can be recycled, and the graphite nanoplatelets obtained in the step (6) can be used as a downstream product of graphene as a lubricant or used as graphite to be stripped for recycling.
Example 12: synthesizing a dispersant with 3-hydroxypyridine as a non-covalent bonding component with graphene, and using The dispersant is used for preparing graphene aqueous dispersion
(1) Polyethylene glycol diglycidyl ether (PEG-DE, Mn ═ 500g/mol,10.52g), polypropylene glycol diglycidyl ether (PPG-DE, Mn ═ 640g/mol,12.8g), N-ethyl ethylenediamine (NEED, 2.64g) and piperazine (0.86g) were dissolved in ethanol, stirred at room temperature for 48h under nitrogen protection, warmed to 80 ℃ and refluxed for 24 h. After the reaction is finished, cooling to room temperature, and removing ethanol through reduced pressure distillation to obtain a light yellow viscous solid product, namely the hyperbranched polymer-12.
(2) And (3) synthesizing a functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound. 3-hydroxypyridine (1.90g,0.02mol) and epichlorohydrin (9.25g,0.1mol) were dissolved in 60ml of butanone, 5g of potassium carbonate was added as a catalyst, and the mixture was refluxed for 12 hours under nitrogen protection. After the reaction is finished, the catalyst and the solvent are removed, and the functional group-containing monocyclic, polycyclic, fused ring or heterocyclic compound-12 is obtained.
(3) And (3) synthesis of an amphiphilic hyperbranched polymer. Functional group-containing monocyclic, polycyclic or fused ring compound-12 (0.01mol), hyperbranched polymer-12 (0.01mol, calculated as the amount of secondary amine groups) was dissolved in 100ml of ethanol and refluxed for 20h under nitrogen protection. After the reaction is finished, precipitating the obtained mixture in n-hexane, and drying in vacuum to obtain the amphiphilic hyperbranched polymer-12 serving as the dispersing agent-12 for dispersing the graphene.
(4) 0.2g of dispersant-12 and 2.0g of graphite were weighed, mixed in 200mL of water, and ground by a sand mill at room temperature for 2 hours to obtain a black suspension-12.
(5) Filtering the black suspension-12 obtained in the step (4) to obtain supernatant-12 and grinding beads.
(6) And (3) centrifuging the supernatant-12 obtained in the step (5) for 60min under the condition of 3000 r/min by using a centrifugal separation technology to obtain a black supernatant which is a two-dimensional graphene aqueous solution-12, and a lower precipitate which is a nano graphite sheet.
(7) The grinding beads obtained in the step (5) can be recycled, and the graphite nanoplatelets obtained in the step (6) can be used as a downstream product of graphene as a lubricant or used as graphite to be stripped for recycling.
While the invention has been described with reference to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the invention as disclosed herein.

Claims (36)

1. A dispersant for carbon materials comprising an amphiphilic hyperbranched polymer having a backbone structure comprising amine groups and a monocyclic, polycyclic, fused ring or heterocyclic aryl group covalently bonded to the backbone structure in non-covalent association with a graphene structure, and the carbon material having a graphene structure,
wherein the amphiphilic hyperbranched polymer further comprises hydrophilic polyether segments and/or hydrophobic organic segments, wherein the molar ratio of the hydrophilic polyether segments to the hydrophobic organic segments is in the range of 10:0 to 0: 10.
2. The carbon material dispersant of claim 1, wherein said monocyclic, polycyclic, fused ring, or heterocyclic aryl group comprises a substituted or unsubstituted group derived from: benzene, naphthalene, pyrene, anthracene, pentacene, benzo [ a ] pyrene, benzophenone, thioxanthone, pyridine, coronene, caryophyllene, tetracene, phenanthrene, benzo [9,10] phenanthrene, ovalene, triphenylene, perylene, benzo [ ghi ] perylene, anthanthrone, pentacene, picene, dibenzo [3, 4; 9,10] pyrene, benzo [3,4] pyrene, dibenzo [3, 4; 8,9] pyrene, dibenzo [3, 4; 6,7] pyrene, dibenzo [1, 2; 3,4] pyrene, naphtho [2, 3; 3,4] pyrene, a porphyrin derivative or any combination thereof.
3. A carbonaceous material as claimed in claim 2A dispersant, wherein said monocyclic, polycyclic, fused ring, or heterocyclic aryl group is substituted with a substituent selected from the group consisting of: c1-C20Alkyl, halo C1-C20Alkyl radical, C1-C20Alkoxy, carboxyl, carbonyl, hydroxyl, halogen, amino, C2-C20Alkynyl, C2-C20Alkenyl, aldehyde, anhydride, cyano.
4. The carbon material dispersant of claim 1 wherein said hydrophilic polyether segment is derived from polyoxyethylene having a molecular weight in the range of 174-6000 g/mol.
5. The carbon material dispersant of claim 1 wherein the hydrophobic organic segment is derived from C having a molecular weight in the range of 382-6000g/mol3-C10Alkoxy polyethers or structures based on bisphenol A, bisphenol F or bisphenol S and derivatives thereof, C1-C20Alkyl groups and derivatives thereof or combinations thereof.
6. The carbon material dispersant of claim 1, wherein the backbone structure of said amphiphilic hyperbranched polymer is formed via an addition reaction of a polyglycidyl compound and a polyfunctional amine.
7. The carbon material dispersant of claim 6, wherein said polyglycidyl compound is selected from the group consisting of polyglycidyl esters, polyglycidyl ethers, or combinations thereof.
8. The carbon material dispersant of claim 6 wherein said polyglycidyl compounds are selected from polyglycidyl ethers.
9. The carbon material dispersant of claim 7 or 8, wherein the polyglycidyl ether is selected from the group consisting of diglycidyl ethers of polyhydric phenols, diglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of phenolic resins, and combinations thereof.
10. The carbon material dispersant of claim 6, wherein the multifunctional amine comprises an aliphatic trifunctional amine, an aromatic trifunctional amine, an alicyclic trifunctional amine, a heterocyclic trifunctional amine, or a combination thereof.
11. The carbon material dispersant of claim 6 wherein said multifunctional amine further comprises an aliphatic difunctional amine, an aromatic difunctional amine, an alicyclic difunctional amine, a heterocyclic difunctional amine, or combinations thereof.
12. The carbon material dispersant of claim 6, wherein the amino hydrogen of said polyfunctional amine is in molar excess relative to the glycidyl groups of said polyglycidyl compound.
13. The carbon material dispersant of claim 6, wherein said amphiphilic hyperbranched polymer has a structure represented by formula I below:
Figure FDA0002784041840000021
in the above formula, the first and second carbon atoms are,
x represents a divalent organic fragment derived from a polyglycidyl compound;
y represents substituted or unsubstituted C2-C10Alkyl, substituted or unsubstituted C2-C10Alkoxy, substituted or unsubstituted C3-C10A cycloalkyl group;
r represents said monocyclic, polycyclic, fused or heterocyclic aryl group; and
r' represents substituted or unsubstituted C1-C10Alkyl radical, C1-C10Alkoxy, cycloalkyl, aryl, heteroaryl.
14. The carbon material dispersant of claim 13 wherein X represents a polyether segment having the structure of formula II:
Figure FDA0002784041840000031
wherein R is1Represents substituted or unsubstituted C1-C20Alkyl radical, C1-C10Alkoxy radical, C1-C10Acyloxy, C3-C10Cycloalkyl radical, C6-C14An aromatic group, a silane group, or a combination thereof.
15. The carbon material dispersant of claim 14 wherein the substituent is selected from the group consisting of C1-C20Alkyl, hydroxy, halogen.
16. The carbon material dispersant of claim 14 wherein X represents-O- (CH)2CH(CH3)-O)n-CH2-、-O-(CH2CH2-O)n-CH2-or a combination thereof, wherein n represents a positive integer from 1 to 150.
17. The carbon material dispersant of claim 16 wherein n represents a positive integer of 1 to 20.
18. The carbon material dispersant of claim 1 wherein the amphiphilic hyperbranched polymer has a weight average molecular weight in the range of 2000-30000 g/mol.
19. The carbon material dispersant of claim 1 wherein said carbon material comprises graphene, carbon nanotubes or other carbon materials having a graphene structure.
20. A method for preparing a carbon material dispersant comprising i) reacting a polyglycidyl compound with a polyfunctional amine, thereby forming a hyperbranched polymer bearing secondary amine groups at the ends, wherein the amino hydrogens of the polyfunctional amine are in molar excess relative to the glycidyl groups of the polyglycidyl compound; and ii) introducing a mono-, multi-, fused-or heterocyclic aromatic group non-covalently associated with the graphene structure into the hyperbranched polymer via a reaction with a secondary amine group, thereby forming a dispersant comprising an amphiphilic hyperbranched polymer, wherein the carbon material has a graphene structure, wherein the polyglycidyl compound is selected from the group consisting of polyglycidyl esters, polyglycidyl ethers, or a combination thereof.
21. The method for producing a carbon material dispersant as claimed in claim 20 wherein said polyglycidyl compound is selected from polyglycidyl ethers.
22. The method for producing a carbon material dispersant of claim 20 or 21 wherein said polyglycidyl ether is selected from the group consisting of diglycidyl ethers of polyhydric phenols, diglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of phenolic resins, and combinations thereof.
23. The method for preparing a carbon material dispersant of claim 20 wherein said multifunctional amine comprises an aliphatic trifunctional amine, an aromatic trifunctional amine, an alicyclic trifunctional amine, a heterocyclic trifunctional amine, or a combination thereof.
24. The method for preparing a carbon material dispersant of claim 20 wherein said multifunctional amine further comprises an aliphatic difunctional amine, an aromatic difunctional amine, an alicyclic difunctional amine, a heterocyclic difunctional amine or a combination thereof.
25. The method for preparing a carbon material dispersant of claim 20 wherein a monocyclic, polycyclic, fused ring or heterocyclic aryl compound carrying an amino-reactive functional group selected from the group consisting of a carboxyl group, an epoxy group, an ester group, an acid chloride group, or a combination thereof is employed.
26. The method for producing a carbon material dispersant of claim 20 wherein said steps i) and ii) are both carried out in an organic solvent selected from the group consisting of alcohols, ethers, ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, 1, 4-dioxane, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
27. A stable aqueous dispersion of carbon material comprising a carbon material dispersant non-covalently associated with the carbon material, wherein the carbon material dispersant is as defined in any one of claims 1 to 19 or prepared by the method of any one of claims 20 to 26, and wherein the carbon material has a graphene structure.
28. The aqueous dispersion of carbon material of claim 27, wherein the carbon material comprises carbon nanotubes, graphene or other carbon materials having a graphene structure.
29. The aqueous dispersion of carbon material of claim 28, wherein the graphene has an average side length of 0.5-20 microns.
30. The aqueous dispersion of carbon material of claim 28, wherein the number of graphene layers is no more than 10.
31. The aqueous dispersion of carbon material as claimed in claim 28, wherein the aqueous dispersion of graphene is formed by milling a mixture of graphite and the carbon material dispersant in the presence of an aqueous solvent.
32. The aqueous dispersion of carbon material as claimed in claim 31 wherein the milling is carried out using a milling device selected from the group consisting of a mill, a horizontal sand mill, a vertical sand mill, a multi-function disperser, a vibratory disperser.
33. The aqueous dispersion of carbon material as claimed in claim 31 wherein the milling is carried out at a temperature of 3-95 ℃.
34. The aqueous dispersion of carbon material of claim 31, wherein the weight ratio of the graphite to the amphiphilic hyperbranched dispersant is in the range of 1:10 to 40: 1.
35. Use of an aqueous dispersion of the carbon material according to any one of claims 27 to 34 in hydrogen storage materials, ultra light aircraft, ultra light body armor, aerospace materials, flexible devices, light sensitive elements, sensors, liquid crystal display materials, transparent electrically conductive electrodes.
36. An amphiphilic hyperbranched polymer having a backbone structure comprising amine groups and a single, multi, fused or heterocyclic aromatic group covalently bonded to the backbone structure in non-covalent association with a graphene structure, wherein the backbone structure of the amphiphilic hyperbranched polymer is formed by an addition reaction of a polyglycidyl compound and a polyfunctional amine.
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