KR101270407B1 - Novel fulleren derivatives, fullerene polymers and methods of synthesizing thereof - Google Patents

Abstract

The present invention provides a fullerene derivative having two functional groups, and relates to a fullerene polymer prepared by using the same. More particularly, a fullerene derivative having a functional group may be prepared by bonding two carboxyl groups to the fullerene surface, and condensation thereof. It relates to a novel fullerene polymer that is easily prepared through the reaction.

Functional fullerene derivatives and fullerene polymers prepared according to the present invention have excellent charge mobility and can be usefully used in organic electronic devices such as organic solar cells, organic transistors, organic memories, electromagnetic wave shielding agents, and the like.

Fullerene, carboxyl group, organic electronic device

Description

Novel Fullerene Derivatives, Fullerene Polymers and Methods for Making the Same {NOVEL FULLEREN DERIVATIVES, FULLERENE POLYMERS AND METHODS OF SYNTHESIZING THEREOF}

The present invention relates to a novel fullerene derivative, a fullerene polymer and a method for preparing the same, and more particularly, to the fullerene polymer prepared by using a novel fullerene derivative having a carboxyl group bonded to a fullerene surface. The novel fullerene derivative and the fullerene polymer according to the present invention can be used as an organic electronic device that can be used in various fields such as semiconductors, solar cells, fuel cells, organic transistors and the like because of excellent charge mobility.

Fullerenes represented by C ₆₀ are molecules composed of carbon atoms. Diamonds and graphite are the new carbon allotrope. C ₆₀ was discovered by accident in 1985, and then in 1990, a method of mass synthesis was established and much research has been done to date. Notable studies have been reported in newspapers. In 1996, the Nobel Prize for Chemistry was awarded to Smalley, Kroto for the C ₆₀ discovery. This was the motivation for higher expectations for fullerenes as a new material.

The ball-like, which is composed of 60 pieces of carbon ₆₀ C is the most basic structure is the structure in which the five membered ring of 12 and 20 closed, six-membered ring of the condensed fullerenes in a flow diameter of 7Å. In C _60, there are 30 6-membered to 6-membered ring junctions and 60 5-membered to 5-membered ring junctions. When C ₆₀ increases to a rugby ball shape, it becomes higher order fullerenes such as C ₇₀ and C ₈₄ .

Fullerenes are composed of sp ² carbon like graphite. sp ² carbon is the constituent carbon of benzene and has a planar alignment. In graphite, the one where the benzene ring is in contact with the plane is stacked in a stack. In fullerene nanotubes, there is a structure in which the benzene ring is connected, but the spherical structure includes a five-membered ring structure. Thus, fullerenes have a three-dimensional conformation, which is characterized by a combination of flexible sp ² carbon structures. As a result, fullerenes have unique chemical and physical characteristics not found in conventional organic compounds. Diamond is also composed of carbon atoms and has a three-dimensional structure. In this case sp ³ carbon. Diamonds are characterized by high hardness, transparency and high refractive index. Fullerenes are close to graphite in appearance.

Fullerenes are characterized by being one molecule different from graphite and diamond, and this is one reason to attract attention in the physiological activity of fullerenes. Nanotubes, though one molecule, are very large polymers and differ from fullerenes.

The four physical and chemical properties of fullerenes are listed below.

Optical excitation easily occurs.

-High hydrophobicity.

-May contain metals, etc.

-The movement of electrons occurs easily.

Due to the characteristics of fullerenes as described above, derivatives using fullerenes can be mentioned in electronic fields related to superconductivity in application fields, photovoltaic power generation focusing on good photoexcitation, and development into pharmaceutical fields related to new skeletons. In the field of electronic devices and fuel cell electrodes, the field of application has been widely studied.

Conventional Patent Application No. PCT / JP2001 / 11352 for fullerene derivatives describes a method for preparing fullerene derivatives and fullerene derivatives, proton conductors and electrochemical devices, and more particularly OH groups such as fullereneols suitable as proton conductors. Or an efficient process for producing SO ₃ H-group introduced fullerenes or derivatives thereof, and novel and useful proton conductors obtained using such processes and electrochemical devices such as fuel cells using such proton conductors.

In addition, Korean Patent Laid-Open Publication No. 2008-0063233 discloses a fullerene derivative, and more specifically, a method for preparing an amphiphilic fullerene derivative by combining a hydrophilic functional group containing five branches of sulfur in fullerene. It is described.

However, International Application No. PCT / JP2001 / 11352 and Korean Patent Laid-Open Publication No. 2008-0063233 describe a method for preparing a fullerene derivative by combining a functional group with fullerene, but a florene derivative prepared by inserting a carboxyl functional group It is not described, nor is there any benefit of using a fullerene polymer made using it.

In order to solve the above problems, the present invention is to provide a functional fullerene derivative having two functional groups.

The present invention also provides a fullerene polymer prepared by polymerizing a functional fullerene derivative having two functional groups.

The present invention provides a functional fullerene derivative having two functional groups.

The present invention also provides a fullerene polymer prepared by polymerizing a functional fullerene derivative having two functional groups.

In addition, the present invention comprises the steps of adding and mixing fullerenes, reactants, catalyst 1 and catalyst 2 to the organic solvent (step 1);

Reacting the mixture of step 1 at a high temperature in an inert atmosphere for 50 to 70 hours to obtain an intermediate product (step 2);

Purifying the intermediate product of step 2, and then extracting with alcohol, to obtain a final product to dry it to provide a method for producing a functional fullerene derivative comprising the step (step 3).

In addition, the present invention comprises the steps of adding and mixing the functional fullerene derivative, glycols, diamines, acid chlorides and the catalyst 1 according to the present invention to the organic solvent (step 1);

Reacting the mixture of step 1 at room temperature to obtain an intermediate (step 2);

Purifying the intermediate product of step 2, and then extracting with alcohol, to obtain a final product to dry it provides a method for producing a functional fullerene polymer consisting of (step 3).

The functional fullerene derivative having two functional groups and the fullerene polymer prepared by using the same according to the present invention have excellent charge mobility and can be usefully used in organic electronic devices.

The present invention provides a functional fullerene derivative having two functional groups represented by the following general formula (1).

(A is C ₁ -C ₂₀ alkyl)

It is preferable that the said functional group is a carboxyl group. The alkyl of Formula 1 is not particularly limited, and may be selected from chain, branched and cyclic alkyl. Preferably the alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, cyclopentyl, n-hexyl, sec- Hexyl, nonyl, decanyl and the like can be used.

In addition, the present invention provides a functional fullerene polymer represented by the following formula (2) obtained by polymerizing a fullerene derivative prepared by the formula (1).

(n is an integer of 2 or more, A and C are C ₁ to C ₂₀ alkyl, and B is -O- and -NH-).

The alkyl of Formula 2 is not particularly limited, and chain, branched, and cyclic alkyl may be used. More preferably the alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, cyclopentyl, n-hexyl, sec-hexyl, nonyl, decanyl and the like can be used.

In addition, the present invention comprises the steps of adding and mixing fullerenes, reactants, catalyst 1 and catalyst 2 to the organic solvent (step 1);

Reacting the mixture of step 1 at a high temperature in an inert atmosphere for 50 to 70 hours to obtain an intermediate product (step 2);

Purifying the intermediate product of step 2, and then extracting with alcohol, to obtain a final product to dry it to provide a method for producing a functional fullerene derivative comprising the step (step 3).

First, step 1 is a step of adding and mixing fullerene, reactants, catalyst 1 and catalyst 2 to the organic solvent.

The organic solvent may be used alone or mixed with tetrahydrofuran, toluene, xylene, chlorobenzene, dichlorobenzene and the like, the fullerene is not particularly limited, C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ , C ₉₆ , and more preferably C ₆₀ or C ₇₀ may be selected and used.

The reactants may use 1-bromohexanoic acid, and catalyst 1 is 2-2′-bipyridine, triethylamine, (4- (diethylamino) pyridine, 4-aminopyrimidine, aminopyrazine, 3 -Amino-1,2,4-triazine, aminoquinoline, N, N dimethyldipropylenetriamine, or the like can be used alone or in combination, and the catalyst 2 can be copper bromide, silver bromide or the like.

Next, step 2 is a step of obtaining an intermediate by reacting the mixture of step 1 at a high temperature in an inert atmosphere for 50 to 70 hours.

The inert gas may be nitrogen, helium, neon, argon, krypton, xenon, radon and the like. Although the said high temperature is not specifically limited, Preferably, it can select and apply in 80-130 degreeC range. If the high temperature is less than 80 ℃, it is difficult to induce a sufficient reaction, if it exceeds 130 ℃ has the disadvantage of lowering the yield of the final product is caused by the generation of impurities in addition to the intermediate product. In addition, when the reaction time is less than 50 hours, it is difficult to obtain a sufficient intermediate product, and when the reaction time exceeds 70 hours, the yield of the final product does not increase compared to the reaction time.

Finally, step 3 is a step of obtaining the final product after purification of the intermediate of step 2, followed by extraction with alcohol and drying it.

Although the said alcohol is not specifically limited, Preferably, short-chained methanol and ethanol can be used individually or in mixture.

In addition, the present invention comprises the steps of adding and mixing the functional fullerene derivative, glycols, diamines, acid chlorides and the catalyst 1 according to the present invention to the organic solvent (step 1);

Reacting the mixture of step 1 at room temperature to obtain an intermediate (step 2);

Purifying the intermediate product of step 2, and then extracting with alcohol, to obtain a final product to dry it provides a method for producing a functional fullerene polymer consisting of (step 3).

First, step 1 is a step of adding and mixing the functional fullerene derivative, glycols, diamines, acid chlorides and the catalyst 1 according to the present invention to the organic solvent.

The organic solvent is not particularly limited, but preferably, the organic solvent may be used alone or mixed with tetrahydrofuran, toluene, xylene, chlorobenzene, dichlorobenzene, and the like. The glycols may be ethylene glycol, propylene glycol, Diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol, butylene glycol may be used alone or in combination, diamines may be used alone or in combination with ethyl diamine, propyldiamine, butyldiamine, pentyldiamine, hexyldiamine It can be mixed and used.

In addition, the acid chloride may be used alone or in combination of benzoyl chloride, cinnamoyl chloride, 2-methylphenylacetyl chloride, 4-methylphenylacetyl chloride, 1-naphthylacetyl chloride, etc., the catalyst 1 is 2-2'-ratio Pyridine, triethylamine, (4- (diethylamino) pyridine, 4-aminopyrimidine, aminopyrazine, 3-amino-1,2,4-triazine, aminoquinoline, N, N dimethyldipropylenetriamine, etc. May be used alone or in combination.

Next, the step of obtaining the intermediate product by reacting the mixture of step 1 at room temperature.

The room temperature is not particularly limited, but it is preferable to react the mixture of Step 1 at 10 to 30 ° C. When the reaction temperature is less than 10 ℃ it is difficult to induce the reaction of the polymer, when the reaction temperature exceeds 30 ℃ does not increase the synthesis of the polymer compared to the temperature increase.

Finally, step 3 is a step of obtaining the final product after purification of the intermediate of step 2, followed by extraction with alcohol and drying it.

Although the said alcohol is not specifically limited, Preferably, short-chained methanol and ethanol can be used individually or in mixture.

The functional fullerene derivative and fullerene polymer final product extraction method and drying method according to the invention is not particularly limited, any method can be used as long as the yield and drying efficiency of the final product is good.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

< Example  1> Sensuality Fullerene  Derivative manufacturing

100 ml of toluene was added to a four neck flask, and 0.1 g of fullerene, 19 µl of 1-bromohexanoic acid, 0.04 g of 2-2'-bipyridine, and 0.02 g of copper bromide were mixed. This was reacted for 59 hours at 100 ~ 110 ℃ in the presence of nitrogen gas. The reaction was filtered to remove impurities and the clear solution was concentrated. Methanol was added to the concentrate, which was filtered again to afford 0.04 g of final product.

< Example  2> Fullerene  Composite manufacturing

100 ml of tetrahydrofuran was added to the four-necked flask, 1 g of the functional fullerene derivative obtained in Example 1, 0.062 g of ethylene glycol, 0.28 g of benzoyl chloride, 0.4 g of triethylamine, and 0.06 g of 4- (dimethylamino) pyridine. Silver was mixed and the mixture was prepared at room temperature to produce an intermediate. The solution containing the intermediate was filtered to remove impurities and the clear solution was concentrated. Methanol was added to the concentrate, which was filtered again to give 0.9 g of the final product.

Claims (24)

Functional fullerene derivative having two functional groups represented by the following formula (1). &Lt; Formula 1 >

(A is C ₁ -C ₂₀ alkyl) The functional fullerene derivative according to claim 1, wherein the functional group is a carboxyl group. The functional fullerene derivative according to claim 1, wherein the alkyl is any one of chain, branched and cyclic alkyl. The compound of claim 1, wherein the alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, cyclopentyl, n-hexyl , sec-hexyl, nonyl, and decanyl. A functional fullerene derivative, characterized in that one kind independently selected from the group consisting of. Functional fullerene polymer represented by the following general formula (2) obtained by polymerizing the fullerene derivative of claim 1. <Formula 2>

(n is an integer of 2 or more, A, C is C ₁ ~ C ₂₀ alkyl, B is -O-, -NH- is a linking site.) 6. The functional fullerene polymer of claim 5 wherein the alkyl is any one of chain, branched and cyclic alkyl. 7. The method of claim 5 or 6, wherein the alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, cyclopentyl and n-hexyl, sec-hexyl, nonyl and decanyl. The functional fullerene polymer, characterized in that one kind selected from the group consisting of. Fullerenes in organic solvents; Reactants that are 1-bromohexanoic acid; 2-2'-bipyridine, triethylamine, (4- (diethylamino) pyridine, 4-aminopyrimidine, aminopyrazine, 3-amino-1,2,4-triazine, aminoquinoline and N, N At least one catalyst agent selected from the group consisting of dimethyldipropylenetriamine; and Catalyst 2 which is copper bromide or silver bromide; Adding and mixing (step 1); Reacting the mixture of step 1 at a high temperature in an inert atmosphere for 50 to 70 hours to obtain an intermediate product (step 2); Purifying the intermediate product of step 2, followed by extraction with alcohol and obtaining the final product to dry it (step 3) of the production of a functional fullerene derivative. The method of claim 8, wherein the organic solvent of step 1 is at least one selected from the group consisting of tetrahydrofuran, toluene, xylene, chlorobenzene, and dichlorobenzene. The method of claim 8, wherein the fullerene of step 1 is C ₆₀ or C ₇₀ . delete delete delete The method of claim 8, wherein the inert gas of step 2 is at least one selected from the group consisting of nitrogen, helium, neon, argon, krypton, xenon, and radon. The method of claim 8, wherein the high temperature of the step 2 is 80 ~ 130 ℃. 9. The method of claim 8, wherein the alcohol of step 3 is a mixture of methanol and ethanol alone or in a mixture. A functional fullerene derivative according to any one of claims 1 to 4 in an organic solvent; Glycols; Diamines; Acid chlorides; And 2-2'-bipyridine, triethylamine, (4- (diethylamino) pyridine, 4-aminopyrimidine, aminopyrazine, 3-amino-1,2,4-triazine, aminoquinoline and N, N Adding and mixing one or more catalysts 1 selected from the group consisting of dimethyldipropylenetriamine (step 1); Reacting the mixture of step 1 at room temperature to obtain an intermediate (step 2); Purifying the intermediate product of step 2, followed by extraction with alcohol and obtaining the final product to dry it (step 3) a method for producing a functional fullerene polymer. 18. The method of claim 17, wherein the organic solvent of step 1 is at least one selected from the group consisting of tetrahydrofuran, toluene, xylene, chlorobenzene, and dichlorobenzene. 18. The method of claim 17, wherein the glycols of step 1 is at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol and butylene glycol. Method for producing a functional fullerene polymer. The method for producing a functional fullerene polymer according to claim 17, wherein the diamines of step 1 are at least one selected from the group consisting of ethyldiamine, propyldiamine, butyldiamine, pentyldiamine and hexyldiamine. 18. The method according to claim 17, wherein the acid chloride of step 1 is at least one selected from the group consisting of benzoyl chloride, cinnamoyl chloride, 2-methylphenylacetyl chloride, 4-methylphenylacetyl chloride, and 1-naphthylacetyl chloride. Method of Making Functional Fullerene Polymer. delete The method of claim 17, wherein the room temperature of step 2 is 10 ~ 30 ℃. 18. The method of claim 17, wherein the alcohol of step 3 is sole or mixed with methanol and ethanol.