KR101993908B1

KR101993908B1 - Dispersing agent, its preparation method and dispersed composition of carbon-based material comprising the same

Info

Publication number: KR101993908B1
Application number: KR1020150070987A
Authority: KR
Inventors: 김용욱; 권원종; 손권남; 박희용; 배용진
Original assignee: 주식회사 엘지화학
Priority date: 2015-05-21
Filing date: 2015-05-21
Publication date: 2019-06-27
Also published as: KR20160136860A

Abstract

The present invention relates to a novel dispersant capable of uniformly dispersing various carbonaceous materials in various media including water solvents, a method for producing the same, and a dispersion composition for carbonaceous materials containing the same. The dispersant is in the form of a mixture containing a plurality of polyaromatic hydrocarbon compounds, wherein each polyaromatic hydrocarbon compound contains 5 to 50 benzene rings, has a predetermined molecular weight, and has at least one acyl group bonded thereto.

Description

TECHNICAL FIELD [0001] The present invention relates to a dispersant, a method for producing the same, and a dispersion composition of carbon-based material containing the same. DISPERSING AGENT, ITS PREPARATION METHOD AND DISPERSED COMPOSITION OF CARBON- BASED MATERIAL COMPRISING THE SAME,

The present invention relates to a novel dispersant capable of uniformly dispersing various carbonaceous materials in various media including water solvents, a method for producing the same, and a dispersion composition for carbonaceous materials containing the same.

In recent years, various carbon-based materials have been researched and used in various products or technical fields such as thermoplastic resin compositions, secondary batteries, solar cells, display materials or electronic materials. For example, the use of carbon nanotubes and derivatives thereof has been studied and attempted to further improve the capacity characteristics or electrical characteristics of secondary batteries or solar cells, Application of carbon nanomaterials such as graphene or derivatives thereof has been attempted. In addition, in the thermoplastic resin composition, various carbon-based materials have been attempted for the purpose of improving the mechanical properties or adding new properties such as electrical conductivity.

However, in order to realize the desired properties by applying the carbon-based materials such as the carbon nanotubes, graphenes, carbon black, fullerene materials or derivatives thereof to various fields, it is necessary to add such carbon-based materials to a high concentration It is necessary to disperse them uniformly. For example, in order to further improve the electrical characteristics of the secondary battery by using a conductive material containing carbon nanotubes or the like, it is necessary to uniformly disperse such a carbon-based material in a medium such as a water solvent at a high concentration.

However, in general, most carbon-based materials such as carbon nanotubes, graphenes, and fullerene-based materials are mostly composed of carbon-carbon bonds, and therefore it is most difficult to uniformly disperse these carbon-based materials in a high concentration in the medium. As a result, there has been a limit in which it is difficult to fully utilize the merits of the carbon-based material. To solve this problem, the use of a dispersant for dispersing the carbon-based material in various media at a high concentration has been examined.

However, the dispersant previously known or studied has not been able to sufficiently disperse the carbon-based material depending on the kind of the medium, or it has been often necessary to use an excessive amount of the dispersing agent in order to effectively disperse the carbon-based material. Moreover, previously known dispersants have disadvantages such that the raw material itself is expensive or requires a complicated manufacturing process, resulting in a very high manufacturing cost.

Therefore, it is possible to uniformly disperse various carbon-based materials such as carbon nanotubes, graphene, and fullerene-based materials in various media, for example, in environmentally friendly water solvents, at a high concentration even by using a relatively small amount of dispersant There is a continuing need for the development of a novel dispersant capable of securing a simplified manufacturing process and a low unit cost.

The present invention provides a novel dispersant capable of uniformly dispersing various carbonaceous materials in various media including water solvents at a high concentration and a method for producing the same.

The present invention also provides a dispersion composition of a carbon-based material containing such a novel dispersant and a carbon-based material uniformly dispersed thereby.

According to one embodiment of the present invention, there is provided a dispersant in the form of a mixture containing a plurality of polyaromatic hydrocarbon compounds, wherein each polyaromatic hydrocarbon compound contains 5 to 50 benzene rings and has a molecular weight of 300 to 3000 g / mol , And one or more acyl groups represented by the following formula (1) are bonded.

[Chemical Formula 1]

In Formula 1, R is an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a carboxyl group (-COOH); An alkenyl group having 2 to 10 carbon atoms which is substituted or unsubstituted with a carboxyl group (-COOH); And an aryl group having 6 to 40 carbon atoms substituted or unsubstituted with a carboxyl group (-COOH).

For example, R in Formula 1 is an alkyl group having 2 to 3 carbon atoms substituted with a carboxyl group (-COOH); An alkenyl group having 2 to 3 carbon atoms substituted with a carboxy group (-COOH); And an aryl group having 6 carbon atoms substituted with a carboxyl group (-COOH).

In the above dispersant, each of the polyaromatic hydrocarbon compounds may have on average 1 to 50 acyl groups bonded thereto.

According to another embodiment of the invention, there is provided a process for preparing a dispersant comprising reacting a mixture comprising polyaromatic hydrocarbons having a molecular weight of 200 to 1500 g / mol in the presence of Lewis acid, with a reaction precursor comprising at least one acyl group do.

In the above production process, the mixture containing poly aromatic hydrocarbons having a molecular weight of 200 to 1500 g / mol may contain a plurality of aromatic hydrocarbons containing 5 to 50 benzene rings. Such a mixture comprising polyaromatic hydrocarbons having a molecular weight of 200 to 1500 g / mol may originate from the pitch obtained from the fossil fuel or its product.

As the reaction precursor containing one or more acyl groups, an acid anhydride, an acid halide, or a mixture thereof may be used.

As the Lewis acid, there may be used AlCl ₃ , FeCl ₃ , ZnCl ₂ , CuCl ₂ , GaCl ₃ , BF ₃ , SbCl ₅ , BiCl ₃ , bismuth trifluoromethane sulfonate (Bi (OTf) ₃ ) Can be used.

According to another embodiment of the present invention, a carbon-based material; And a dispersion composition of a carbon-based material containing the above-mentioned dispersant.

In the dispersion composition, the carbon-based material may be at least one selected from the group consisting of graphene, carbon nanotube, graphite, carbon black, fullerene-based materials, and derivatives thereof.

INDUSTRIAL APPLICABILITY According to the present invention, a novel dispersant capable of uniformly dispersing various carbonaceous materials in various media such as water solvents at a high concentration and a method for producing the same are provided. Particularly, such a dispersant has a very low production cost while exhibiting excellent dispersibility with respect to the carbon-based material, because it can be obtained through a very simplified manufacturing process using a low-cost raw material such as a pitch obtained from fossil fuel residue. According to the above production method, a dispersant containing a plurality of polyaromatic hydrocarbon compounds having an acyl group introduced therein can be obtained at a high yield without using an excessive amount of inorganic acid, thereby greatly facilitating the large-scale production of the dispersant.

Accordingly, it is possible to overcome the limitations of conventional dispersants and to uniformly disperse various carbon-based materials in a medium at a high concentration uniformly at a low production cost, For example, for improvement of physical properties using a carbon-based material and the like.

Fig. 1 is a MALDI-TOF mass spectrum of the dispersant prepared in Preparation Example 1 and a pitch not soluble in the DCM obtained in the preparation of the dispersant of Production Example 1. Fig. The upper graph of Fig. 1 is the graph for the pitch, and the lower graph is the graph for the dispersant.
Fig. 2 is an enlarged graph of a molecular weight distribution graph of the dispersant at the bottom of Fig. 1; Fig.
FIG. 3 is a ¹³ C CPMAS NMR spectrum of the pitch obtained by dissolving the DCM in the dispersant of Production Example 1 and the dispersant prepared in Production Example 1. FIG. The black graph is the graph for the pitch, and the red graph is the graph for the dispersant.
4 is a photograph of a basic aqueous solution to which a pitch not soluble in the DCM obtained in the preparation of the dispersant of Production Example 1 is added.
5 is a photograph of a basic aqueous solution to which the dispersant prepared in Production Example 1 is added.
FIG. 6 is a photograph showing the dispersion compositions of Comparative Example 1 and Examples 1 to 4 from the left, FIG. 7 is a photograph showing the dispersion compositions of Comparative Example 2 and Examples 5 to 9 from the left, FIG. Examples 3 to 10 and 13 to 13.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a novel dispersant according to a specific embodiment of the present invention, a method for producing the same, and a dispersion composition of a carbonaceous material containing the same will be described in detail.

First, in the following specification, the term "dispersant" means any agent for uniformly dispersing a carbonaceous material such as a graphene or a carbon nanotube in a water solvent, an organic solvent or other liquid medium . Such a "dispersant" and a composition in which other components to be dispersed, such as a carbon-based material, are dispersed in a liquid medium may be referred to as a " As shown in FIG. Such a "dispersion composition" also includes a conductive composition of a secondary battery; An electrode or a conductive composition applied in a manufacturing process of various cells, displays, or devices; An active material composition such as a secondary battery; A composition for preparing various polymers or resin complexes; Or an ink or a paste composition applied in the production process of various electronic materials or devices, and the use thereof is not particularly limited. As long as the "dispersant" and the component to be dispersed are contained together in the liquid medium , &Quot; dispersion composition "regardless of its state or use.

In the following specification, the term "polyaromatic hydrocarbon" may refer to an aromatic hydrocarbon compound having two or more, or five or more, aromatic rings, for example, a benzene ring, .

In the following description, the term "carbon-based material" refers to any material mainly containing carbon-carbon bonds such as graphene, carbon nanotubes, graphite, carbon black, Fullerene and other similar fullerene materials to be displayed or derivatives thereof may be collectively referred to. However, the category of the "carbon-based material" can be interpreted as not including the " polyaromatic hydrocarbon "or" a derivative thereof into which a certain functional group is introduced "

According to one embodiment of the present invention, there is provided a dispersant in the form of a mixture containing a plurality of polyaromatic hydrocarbon compounds, wherein each polyaromatic hydrocarbon compound contains 5 to 50 benzene rings and has a molecular weight of 300 to 3000 g / mol And one or more acyl groups represented by the following general formula (1) are bonded.

[Chemical Formula 1]

In Formula 1, R is an alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with a carboxyl group (-COOH); An alkenyl group having 2 to 10 carbon atoms which is substituted or unsubstituted with a carboxyl group (-COOH); And an aryl group having 6 to 40 carbon atoms substituted or unsubstituted with a carboxyl group (-COOH).

The pitch discharged from the residue in the refining process of fossil fuels such as petroleum or coal is a by-product used for the production of asphalt, and it is in the form of a viscous mixture containing a plurality of polyaromatic hydrocarbons having a plurality of aromatic rings . Of course, the specific kind, structure, compositional ratio, or molecular weight distribution of the polyaromatic hydrocarbon may vary depending on the raw material or the origin of pitch, but the pitch may be, for example, 5 to 50 aromatic rings, May contain a plurality of polyaromatic hydrocarbons contained in the structure, and may include polyaromatic hydrocarbons generally having a molecular weight of 200 to 1500 g / mol.

As a result of experiments conducted by the inventors of the present invention, introduction of an acyl group through Friedel-Crafts acylation to such a pitch exhibits excellent water-dispersibility per se and remarkably improves the dispersibility of carbon-based materials Based on the total amount of the dispersant.

Specifically, as a result of the Friedel-Crafts acylation reaction of the pitch, at least one acyl group was introduced into each of the polyaromatic hydrocarbons included in the pitch to obtain a mixture containing a plurality of polyaromatic hydrocarbon compounds. The polyaromatic hydrocarbon compound had a skeleton almost similar to the polyaromatic hydrocarbon included in the pitch, and contained an acyl group introduced into the skeleton.

Specifically, the specific kind, structure, and distribution of the polyaromatic hydrocarbon compound may be varied depending on the type and the origin of the pitch as a raw material thereof, the kind of reaction precursor of the Friedel-Crafts acylation reaction, and the like. However, at least the plural kinds of polyaromatic hydrocarbon-based compounds contained in the dispersant of one embodiment include about 5 to 50 benzene rings each, and include one or more acyl groups bonded to about 5 to 50 benzene rings can do.

Accordingly, each polyaromatic hydrocarbon-based compound may have a larger molecular weight than each polyaromatic hydrocarbon contained in the pitch. For example, each polyaromatic hydrocarbon-based compound obtained by this method can have a molecular weight in the range of about 300 to 3000 g / mol, 300 to 2000 g / mol, or 500 to 2000 g / mol when analyzed by MALDI-TOF MS .

Polyaromatic hydrocarbon compounds satisfying the above-described structural characteristics and molecular weight distribution can simultaneously have a hydrophobic π-domain in which aromatic rings are assembled and a hydrophilic region by acyl groups bonded to the aromatic ring or the like. The hydrophobic π-domain can interact with the surface of a carbonaceous material, such as graphene or carbon nanotubes, formed with carbon-carbon bonds, and the hydrophilic region can have a single graphene or carbon nano- So that a repulsive force between the tubes can be generated. As a result, the dispersant of one embodiment including a plurality of the polyaromatic hydrocarbon-based compounds is present in the liquid medium between molecules of the carbon-based material such as graphene or carbon nanotubes to uniformly disperse the carbon-based material have. Accordingly, the dispersant of one embodiment can exhibit an excellent dispersing ability to uniformly disperse the carbonaceous material at a higher concentration even if a relatively small amount is used.

In addition, the dispersant of one embodiment can exhibit water solubility by itself due to the presence of the above-mentioned hydrophilic region, so that the carbonaceous material can be uniformly dispersed even in an environmentally friendly water solvent. In particular, in the dispersant according to an embodiment, the acyl group bonded to the aromatic ring or the like may protonate or deprotonate in a prominent acidic or basic aqueous solution to exhibit a greater polarity. Accordingly, the dispersant exhibits better dispersibility in the acidic or basic aqueous solution, and the dispersibility of the carbon-based material can be further improved.

In addition, the dispersant can disperse the carbon-based material at a high concentration uniformly in various organic solvents such as acetone, tetrahydrofuran (THF), ethanol and N-methyl-2-pyrrolidone Can exhibit excellent dispersing power.

Each of the polyaromatic hydrocarbon compounds contained in the dispersant of one embodiment may have one or more acyl groups bonded thereto. The structure of the acyl group may vary depending on, for example, the kind of the reaction precursor used in the Friedel-Crafts reaction process such as pitch, and may be represented by, for example,

[Chemical Formula 1]

Unless otherwise specifically defined herein, the alkyl group having 1 to 20 carbon atoms may be an alkyl group having 1 to 10 carbon atoms, 1 to 5 carbon atoms, or 1 to 3 carbon atoms, and the alkyl group may be a straight chain, branched chain, or cyclic alkyl group. The alkyl group having 1 to 20 carbon atoms substituted with a carboxyl group may be one in which at least one hydrogen of an alkyl group having 1 to 20 carbon atoms is substituted with a carboxyl group.

The alkenyl group having 2 to 10 carbon atoms includes at least one carbon-carbon double bond and may be an alkenyl group having 2 to 8 carbon atoms, 2 to 5 carbon atoms, or 2 to 3 carbon atoms, and the alkenyl group may have a linear, branched or cyclic Lt; / RTI > The alkenyl group having 2 to 10 carbon atoms substituted with a carboxy group may be one in which at least one hydrogen of an alkenyl group having 2 to 10 carbon atoms is substituted with a carboxy group.

The aryl group having 6 to 40 carbon atoms may be an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and the aryl group may have an aralkyl group or an alkylaryl group. The aryl group having 6 to 40 carbon atoms substituted with a carboxy group may be one in which at least one hydrogen of an aryl group having 6 to 40 carbon atoms is substituted with a carboxyl group.

For example, in order to exhibit better water solubility and dispersibility, the acyl group is an alkyl group having 2 to 3 carbon atoms in which R in the formula (1) is substituted with a carboxy group (-COOH); An alkenyl group having 2 to 3 carbon atoms substituted with a carboxy group (-COOH); And an aryl group having 6 carbon atoms substituted with a carboxyl group (-COOH). More specifically, the acyl group may be a 3-carboxypropanoyl group, a 3-carboxypropenoyl group, a carboxybenzoyl group, or the like.

Such an acyl group can further increase the dispersibility of the carbon-based polar solvent interacting with the dispersing agent and the dispersing agent due to the good mixing property with the polar solvent. Particularly, the acyl group deprotonates in a basic aqueous solution to exhibit a negative charge, thereby exhibiting a higher polarity. Accordingly, the dispersing agent comprising the acyl groups listed above exhibits a very excellent dispersibility with respect to a basic aqueous solution, and the dispersibility of the carbon-based material interacting with the dispersing agent in a basic aqueous solution can be remarkably increased.

On average, 1 to 50, 1 to 20, or 1 to 10 acyl groups may be bonded to each polyaromatic hydrocarbon compound contained in the dispersant so that the dispersant according to one embodiment has adequate hydrophilicity.

The content of the acyl group reflects the degree to which the acyl group is introduced by the Friedel-Crafts acylation reaction step, and the hydrophilic region can be appropriately included as described above according to the satisfaction of the acyl group content. As a result, various carbon-based materials can be uniformly dispersed at a higher concentration in a water solvent using the dispersant of one embodiment.

In addition, since the dispersant of one embodiment can be manufactured from raw materials such as low-cost pitches through one process, it is possible to significantly reduce the cost of producing a dispersant of a carbon-based material and to easily expand the process scale using the carbon-based material .

As a result, the dispersant of one embodiment can overcome the limitations of existing dispersants and can disperse various carbon-based materials in various liquid media at high concentration uniformly at a low manufacturing cost, Or for various products such as electronic materials, etc., for improving physical properties using carbon-based materials, and the like.

The dispersant of one embodiment described above can be used for dispersing in various solvents of solvent-based carbonaceous materials, and can be suitably used for uniformly dispersing the carbonaceous material in a high concentration in a water solvent. Examples of the carbon-based material that can be used to improve dispersibility by using such a dispersant include, but are not limited to, graphene, carbon nanotubes, graphite, carbon black, fullerene Materials and derivatives thereof. However, it goes without saying that a dispersant of one embodiment may be suitably used for dispersing various other carbon-based materials.

On the other hand, according to another embodiment of the invention, a method for producing the above-mentioned dispersant is provided. The process for preparing such a dispersant may comprise reacting, in the presence of a Lewis acid, a mixture comprising polyaromatic hydrocarbons having a molecular weight of 200 to 1500 g / mol with a reaction precursor comprising at least one acyl group.

As already mentioned above, the pitch discharged from the residue in the refining process of fossil fuels such as petroleum or coal may be a mixture containing a plurality of polyaromatic hydrocarbons and having a viscous or powdery form. Of course, the specific kind, structure, compositional ratio, or molecular weight distribution of the polyaromatic hydrocarbon may vary depending on the raw material or the origin of pitch, but the pitch may be, for example, 5 to 50 aromatic rings, May contain a plurality of polyaromatic hydrocarbons contained in the structure, and may include polyaromatic hydrocarbons generally having a molecular weight of 200 to 1500 g / mol.

For example, a mixture (e.g., pitch) comprising polyaromatic hydrocarbons having a molecular weight of from 200 to 1500 g / mol, which is used as a starting material in the manufacturing method of another embodiment, may comprise at least about 80% by weight of polyaromatic hydrocarbons in this molecular weight range, Or about 90% by weight or more.

When a mixture containing polyaromatic hydrocarbons such as pitch is reacted with a predetermined reaction precursor in the presence of a Lewis acid, one or more acyl groups are introduced into each of the polyaromatic hydrocarbons contained in the pitch to convert the polyaromatic hydrocarbon compound into a plurality of In other words, the dispersant of one embodiment can be prepared very simply.

In the method of preparing such a dispersant, as the reaction precursor, one containing at least one acyl group may be used, and one species may be used singly or two or more species may be used together.

More specifically, as the reaction precursor containing one or more acyl groups, an acid anhydride, an acid halide (acyl halide) or a mixture thereof may be used.

Specifically, as the acid anhydride, an aliphatic acid anhydride having 2 to 20 carbon atoms or an aromatic acid anhydride having 8 to 40 carbon atoms can be used as the chained acid anhydride or the cyclic acid anhydride, and as the acid halide, 1 to 20 carbon atoms An acid halide including an alkyl group or an aryl group having 6 to 30 carbon atoms can be used.

As an example, the reaction precursor may be an acid anhydride. Among them, when a cyclic acid anhydride is used, water dispersibility is advantageously increased because of the carboxylic acid generated after the reaction. More specifically, examples of the cyclic acid anhydride include succinic anhydride, maleic anhydride, and phthalic anhydride.

In the method for producing the dispersant, the kind of the Lewis acid is not particularly limited, and any of those commonly used in the Friedel-Crafts reaction can be used. Examples of such Lewis acids include AlCl ₃ , FeCl ₃ , ZnCl ₂ , CuCl ₂ , GaCl ₃ , BF ₃ , SbCl ₅ , BiCl ₃ , bismuth trifluoromethane sulphonate (Bi (OTf) ₃ ) .

In this step, the mixture comprising the polyaromatic hydrocarbons can be reacted with the desired reaction precursor in the presence of Lewis acid at a temperature between about 0 and 200 < 0 > C. The reaction time can be adjusted to about 1 to 48 hours. However, the reaction temperature and time may be appropriately controlled depending on the amount of the introduced acyl group introduced into the polyaromatic hydrocarbon and the like.

As already mentioned above, the mixture containing the polyaromatic hydrocarbons having a molecular weight of 200 to 1500 g / mol as a starting material of the above-mentioned production method may originate from a pitch obtained from the fossil fuel or its product, The kind, structure or molecular weight distribution of the polyaromatic hydrocarbons may be different depending on the kind of the polyaromatic hydrocarbons. Nevertheless, by proceeding with the Friedel-Crafts reaction process for a mixture containing polyaromatic hydrocarbons having a molecular weight of 200 to 1,500 g / mol derived from the above-mentioned pitch and the like, the dispersant of one embodiment exhibiting excellent dispersibility against carbon- As described above.

On the other hand, by using the production method according to another embodiment, the content of the acyl group introduced into the aromatic ring of the polyaromatic hydrocarbon is determined according to the addition ratio of the mixture of the polyaromatic hydrocarbons and the reaction precursor including one or more acyl groups , The introduction amount of an acyl group can be easily controlled. Compared with the oxidation process using an excess amount of inorganic acid as a solvent, an acyl group (hydrophilic group) is introduced into the aromatic ring of the polyaromatic hydrocarbon at a desired level by using a small amount of the reaction precursor containing the acyl group It is very economical. In addition, the above-described production method can produce a mixture containing a plurality of polyaromatic hydrocarbon compounds at an excellent yield, and is suitable for mass production.

On the other hand, the dispersant produced by the above-mentioned production method exhibits excellent water-dispersibility in itself and further shows an effect of improving the dispersibility of the carbonaceous material. Accordingly, a large amount of a dispersing agent capable of improving the dispersibility of the carbon-based material can be supplied by the above-described production method, and this manufacturing method is expected to contribute greatly to the expansion of the process scale using the carbon-based material.

In addition to the above-described steps, the method for producing the dispersant may further include steps that are conventionally employed in the art to which the present invention belongs.

According to another embodiment of the present invention, a carbon-based material; And a dispersant of one embodiment described above.

In such a dispersion composition, the carbon-based material may be at least one selected from the group consisting of graphene, carbon nanotubes, graphite, carbon black, fullerene-based materials, and derivatives thereof.

With such a dispersion composition, the high-concentration carbonaceous material can be dispersed in a liquid medium such as a water solvent at a higher concentration uniformly by the action of the above-mentioned dispersant. In addition, such a dispersion composition can be used in various applications such as a conductive material composition, an electrode composition or an active material composition of a secondary battery depending on the kind of the carbonaceous material, the use of other additional components or the specific composition. The state may also be in various states such as a solution phase, a slurry phase, or a paste phase depending on the kind of the carbonaceous material and the specific composition.

However, since the dispersion composition of these various uses, types, or conditions can be obtained by applying compositions and processes commonly known to those skilled in the art, except for using the dispersant of one embodiment, further description thereof will be omitted.

Due to the use of the dispersant of one embodiment, the above-described dispersion composition can be a liquid composition in which a higher concentration of the carbon-based material is uniformly dispersed. Therefore, such a dispersion composition can be highly suitably applied to various products such as solar cells, display materials, and electronic materials for improving physical properties using carbon-based materials.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. However, this is provided as an example of the invention, and the scope of the invention is not limited thereto in any sense.

Manufacturing example 1: Preparation of dispersant

Pitch, a by-product of petroleum, was added to dichloromethane (DCM). Then, the pitch was mixed so that the pitch was dissolved in the DCM, and some of the pitch was dissolved in the DCM, and the remaining was not dissolved. The mixture was then filtered to separate the pitch not dissolved in DCM and then dried.

The thus obtained pitch (pitch not dissolved in DCM) was reacted with succinic anhydride under Friedel-Crafts under AlCl ₃ as follows to prepare the dispersant of Preparation Example 1.

1 g of succinic anhydride and 1.33 g of AlCl ₃ were added to 20 mL of DCM at 0 ° C, and the mixture was stirred for about 30 minutes. Thereafter, 1 g of the above-obtained pitch was added to the solution, and the mixture was stirred at room temperature for about 20 hours. Next, water was added to the solution, followed by filtration, followed by washing with 0.5 M hydrochloric acid. Then, the obtained product was dried to obtain a dispersant.

Test Example One: Dispersant Characteristic test

(1) The molecular weight distribution of the dispersant obtained through the Friedel-Crafts reaction was compared with the pitch (raw material) not soluble in the DCM through the MALDI-TOF mass spectrum.

Referring to FIG. 1, in the graph of the molecular weight distribution of the upper raw material, peaks having high intensities are observed mainly in the range of 400 to 1,000, but in the graph of the dispersant molecular weight distribution at the bottom, peaks having the highest intensity are observed at 1,000 or more, It was confirmed that a dispersant having an increased molecular weight was obtained.

Referring to FIG. 2, which is an enlarged graph of the molecular weight distribution of the dispersant at the bottom of FIG. 1, peaks having a difference of about 100 Da corresponding to the molecular weight of the acyl group resulting from the Friedel-Crafts reaction of succinic anhydride were observed. As a result, it was confirmed that the 3-carboxypropanoyl group derived from succinic anhydride was introduced into the pitch through the Friedel-Crafts reaction.

(2) Pitches (raw materials) not soluble in the above DCM were compared with dispersants obtained through Friedel-Crafts reaction through ¹³ C CPMAS NMR spectrum.

As shown in Fig. 3, when the black graph of the raw material and the red graph of the dispersant were compared, a peak for the carboxyl group was observed in the red graph of the dispersant. As a result, it was confirmed that the 3-carboxypropanoyl group derived from the succinic anhydride was introduced into the pitch through the Friedel-Crafts reaction as in the foregoing results.

(3) The dispersibility of the pitch (raw material) and the dispersant obtained by the Friedel-Crafts reaction were compared with each other by adding NaOH solution to the pitch (raw material) and dispersant which were not dissolved in DCM. Referring to FIG. 4, in a basic aqueous solution to which a pitch (raw material) was added, a clear liquid phase and a precipitate not dispersed in a liquid phase were observed, and it was confirmed that the dispersibility of the pitch was poor. Referring to FIG. 5, the Friedel- In the basic aqueous solution to which the dispersant was added, the dispersant was dispersed and a turbid liquid phase was observed. Thus, it is confirmed that a dispersant having improved water dispersibility from the pitch can be provided according to the production method according to an embodiment of the present invention.

Example And Comparative Example : Preparation of dispersion composition of carbon-based material

As shown in Table 1, 5 mg of the dispersant prepared in Preparation Example 1 and 50 mg of the carbon-based material were added to 20 mL of the solvent and dispersed for 30 minutes using a sonicator. However, in Comparative Examples 1 to 3, the dispersant of Production Example 1 was not added.

Carbon-based material menstruum Comparative Example 1 black smoke Distilled water Example 1 Aqueous solution of sodium chloride Example 2 Acetone Example 3 THF (tetrahydrofuran) Example 4 ethanol Comparative Example 2 Carbon nanotubes (MWCNT) Distilled water Example 5 Distilled water Example 6 Aqueous solution of sodium chloride Example 7 Acetone Example 8 THF (tetrahydrofuran) Example 9 ethanol Comparative Example 3 Graphene flake Distilled water Example 10 Aqueous solution of sodium chloride Example 11 Acetone Example 12 THF (tetrahydrofuran) Example 13 ethanol

The dispersion compositions of Comparative Example 1 and Examples 1 to 4 were listed and shown in FIG. 6, and the dispersion compositions of Comparative Example 2 and Examples 5 to 9 were listed and shown in FIG. 7, 3 and Examples 10 to 13 were listed and then photographed and shown in Fig.

6 to 8, it is confirmed that the dispersant according to one embodiment of the present invention improves the dispersibility of the carbon-based material to various solvents.

Claims

As a dispersant in the form of a mixture containing a plurality of polyaromatic hydrocarbon compounds,
Wherein each polyaromatic hydrocarbon compound comprises 5 to 50 benzene rings, has a molecular weight of 300 to 3000 g / mol, and has an average of 1 to 50 acyl groups represented by the following formula (1)
[Chemical Formula 1]

In Formula 1, R is an alkyl group having 2 to 3 carbon atoms substituted with a carboxyl group (-COOH); An alkenyl group having 2 to 3 carbon atoms substituted with a carboxy group (-COOH); And an aryl group having 6 carbon atoms and substituted with a carboxyl group (-COOH).

delete

Reacting a mixture comprising polyaromatic hydrocarbons having a molecular weight of 200 to 1500 g / mol with a reaction precursor comprising at least one acyl group in the presence of Lewis acid,
Wherein the reaction precursor is an acid anhydride, an acid halide, or a mixture thereof.

5. The method according to claim 4, wherein the mixture containing poly aromatic hydrocarbons having a molecular weight of 200 to 1500 g / mol contains a plurality of aromatic hydrocarbons containing 5 to 50 benzene rings.

delete

The method of claim 4, wherein the Lewis acid is selected from the group consisting of AlCl ₃ , FeCl ₃ , ZnCl ₂ , CuCl ₂ , GaCl ₃ , BF ₃ , SbCl ₅ , BiCl ₃ , bismuth trifluoromethane sulfonate (Bi (OTf) ₃ ) And mixtures thereof.

5. A process according to claim 4, wherein the mixture comprising polyaromatic hydrocarbons having a molecular weight of from 200 to 1500 g / mol is derived from a pitch obtained from a fossil fuel or a product thereof.

Carbon based materials; And
A dispersion composition of a carbonaceous material comprising the dispersant of claim 1.

The dispersion composition of claim 9, wherein the carbon-based material is at least one selected from the group consisting of graphene, carbon nanotubes, graphite, carbon black, fullerene-based materials, and derivatives thereof.