JP7254544B2 - Highly structurally controlled organic-inorganic composites - Google Patents

Description

The present invention relates to an organic-inorganic composite.

In light of recent trends toward resource saving and energy saving, lightweight carbon materials have been developed and used in various fields. Carbon-material-containing materials such as carbon-coated inorganic particles and hollow carbon fine particles have been reported as compounds having such lightweight carbon materials in various fields (for example, Patent Documents 1 to 4, Non-Patent References 1-4). Activated carbon, carbon black, and the like are also known as carbon material-containing materials that are industrially produced.

The above carbon material-containing materials, including industrially produced activated carbon and carbon black, have various functional groups. For this reason, it is difficult to precisely control the structure of the carbon material-containing material, and there is a problem that variations in physical properties occur. In recent years, there has been a demand for carbon material-containing materials that can reliably exhibit targeted physical properties, and for this reason, the development of carbon material-containing materials with precisely controlled structures is desired.

JP-A-7-187849 JP-A-7-267618 JP 2005-281065 A JP 2010-168251 A

Dawei Pan et. al. , Langmuir, 22, 5872-5876 (2006) V. Ruiz et. al. , Electrochemistry Communications, 24, 35-38 (2012) H. Nishihara et. al. , Adv. Funct. Mater. , 26, 6418-6427 (2016) Riichiro Saito, "State-of-the-Art Technologies and Spreading Applications of Graphene", Chapter 2. 2. Basic physical properties of graphene; Optoelectronic properties of graphene

An object of the present invention is to provide an organic-inorganic composite with a precisely controlled structure, which is useful for industrial production of carbon material-containing materials such as carbon-coated inorganic particles and hollow carbon fine particles.

The organic-inorganic composite of the present invention is
An organic-inorganic composite containing a carbon material and an inorganic oxide,
By C1sXPS analysis, total carbon oxygen bonds, i.e., C-O bonds and The ratio of the total amount of C=O bonds is 10% or more, and the total amount of carbon oxygen bonds, that is, the total amount of C—O bonds and C=O bonds, is derived from ethers and alcohols. The ratio of the total amount of CO bonds is 50% or more.

The organic-inorganic composite of the present invention is
An organic-inorganic composite containing a carbon material and an inorganic oxide,
By C1sXPS analysis, total carbon oxygen bonds, i.e., C-O bonds and The ratio of the total amount of C=O bonds is 10% or more, and all bonds, that is, the total amount of C—C bonds, C=C bonds, C—H bonds, C—O bonds, and C=O bonds of the total amount of ether-derived CO bonds and alcohol-derived CO bonds is 15% or more.

In one embodiment, the organic-inorganic composite of the present invention shows no peak attributed to C═O stretching vibration between 1700 cm ⁻¹ and 1800 cm ⁻¹ in IR analysis.

In one embodiment, the organic-inorganic composite of the present invention is subjected to TG-DTA analysis under an air atmosphere at a temperature increase of 10 ° C./min, and the oxidation start temperature indicated by the rising temperature of DTA is 200° C. or higher.

In one embodiment, the inorganic oxide is an inorganic oxide particle having a functional group on its surface.

In one embodiment, the inorganic oxide particles are at least one selected from the group consisting of silica particles, alumina particles, titania particles, polyacid particles, and metal particles having at least a portion of the surface oxidized. .

In one embodiment, the inorganic oxide particles are polyacid particles.

In one embodiment, the metal constituting the polyacid particles is at least one selected from the group consisting of molybdenum, vanadium, tungsten, niobium, titanium and tantalum.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an organic-inorganic composite having a precisely controlled structure, which is useful for industrial production of carbon material-containing materials such as carbon-coated inorganic particles and hollow carbon fine particles.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows one preferable embodiment of the organic-inorganic composite of this invention. 1 is a schematic cross-sectional view showing core-shell particles obtainable from the organic-inorganic composite of the present invention. FIG. 1 is an XPS spectrum (C1s) diagram of organic-inorganic composites (1) to (4) obtained in Examples 1 to 4. FIG. 1 is a measurement diagram showing the results of DTA analysis in TG-DTA analysis of organic-inorganic composites (1) to (4) obtained in Examples 1 to 4. FIG. 1 is an IR spectrum diagram of organic-inorganic composites (1) to (4) obtained in Examples 1 to 4. FIG. 1 is a Raman spectrum diagram of organic-inorganic composites (1) to (4) obtained in Examples 1 to 4. FIG. FIG. 3 is an XPS spectrum (C1s) diagram of organic-inorganic composites (5) to (8) obtained in Examples 5 to 8. 1 is a Raman spectrum diagram of the surface of a highly carbonized core-shell particle (9) obtained in Reference Example 1. FIG.

<<<1. Organic-Inorganic Composites≫≫
The organic-inorganic composite of the present invention contains a carbon material and an inorganic oxide. Only one kind of carbon material may be used, or two or more kinds thereof may be used. Only one kind of inorganic oxide may be used, or two or more kinds thereof may be used.

The content of the carbon material in the organic-inorganic composite of the present invention is preferably 0.01% by mass to 99.99% by mass, and particularly preferably 0.1% by mass to 99.9% by mass. is. If the content of the carbon material in the organic-inorganic composite of the present invention is within the above range, the organic-inorganic composite of the present invention can be industrially produced under mild conditions. Hollow carbon microparticles and the like can be industrially produced using the body as a material. The content ratio of these carbon materials can be easily adjusted to an arbitrary ratio by various removal processes described later, etc., depending on the desired physical properties.

The content of the inorganic oxide in the organic-inorganic composite of the present invention is preferably 0.01% by mass to 99.99% by mass, particularly preferably 0.1% by mass to 99.9% by mass. %. If the content of the inorganic oxide in the organic-inorganic composite of the present invention is within the above range, the organic-inorganic composite of the present invention can be industrially produced under mild conditions. Hollow carbon microparticles and the like can be industrially produced using the composite as a material. The content ratio of these inorganic oxides can be easily adjusted to an arbitrary ratio according to the desired physical properties by various removal processes described later.

The organic-inorganic composite of the present invention has all bonds, that is, C-C bonds, C=C bonds, C-H bonds and C-O bonds (alcohol-derived C-O bonds, ether-derived C -O bond, epoxy-derived CO bond, etc.) and C=O bond (carbonyl-derived C=O bond, carboxyl-derived C=O bond, ester-derived C=O bond, lactone-derived C=O The ratio of the total amount of all carbon-oxygen bonds, that is, the total amount of CO bonds and C═O bonds, to the total amount of bonds, etc.) is preferably 10% or more, more preferably 20% or more, and further Preferably it is 25% or more. The upper limit of the above ratio is preferably 35% or less. In the organic-inorganic composite of the present invention, C-O bond and C=O for the total amount of C-C bond, C=C bond, C-H bond, C-O bond and C=O bond by C1sXPS analysis If the ratio of the total amount of bonds is within the above range, the organic-inorganic composite of the present invention contains a novel carbon material having various physical properties such as solubility, unlike conventionally known simple carbon materials. can be a material.

The organic-inorganic composite of the present invention includes all carbon-oxygen bonds, that is, CO bonds (alcohol-derived CO bonds, ether-derived CO bonds, epoxy-derived CO bonds, etc., by C1sXPS analysis. ) and C = O bond (including C = O bond derived from carbonyl, C = O bond derived from carboxyl, C = O bond derived from ester, C = O bond derived from lactone, etc.), C derived from ether -O bond (i.e., C-O-C bond) and alcohol-derived C-O bond (i.e., C-OH bond) is preferably 50% or more, more preferably 60% or more , more preferably 65% or more, particularly preferably 70% or more, and most preferably 75% or more. The upper limit of the above ratio is preferably 90% or less. In the organic-inorganic composite of the present invention, the ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of CO bonds and C=O bonds by C1sXPS analysis is the above Within the range, the organic-inorganic composite of the present invention can increase the structural control rate of the carbon material portion and more precisely control the structure. In addition, the structural control ratio indicates the proportion of bonds derived from a desired reaction with respect to the total number of bonds. In the present invention, the total number of bonds corresponds to the total amount of CO bonds and C=O bonds, and the bonds derived from the desired reaction are the CO bonds derived from ethers and the CO bonds derived from alcohols. corresponds to the total amount of A high structural control rate, in other words, means that there are many bonds derived from desired reactions and few bonds derived from undesired reactions. In the present invention, the bond derived from an undesired reaction is a C=O bond derived from a decomposition reaction, and the decomposition reaction is suppressed as the structure control rate is lower. It can be said that it is controlled more precisely.

The organic-inorganic composite of the present invention has all bonds, that is, C-C bonds, C=C bonds, C-H bonds and C-O bonds (alcohol-derived C-O bonds, ether-derived C -O bond, epoxy-derived CO bond, etc.) and C=O bond (carbonyl-derived C=O bond, carboxyl-derived C=O bond, ester-derived C=O bond, lactone-derived C=O The ratio of the total amount of ether-derived CO bonds (i.e., C-O-C bonds) and alcohol-derived CO bonds (i.e., C-OH bonds) to the total amount of C-OH bonds) is preferably is 15% or more, more preferably 17% or more, and still more preferably 20% or more. The upper limit of the above ratio is preferably 30% or less. In the organic-inorganic composite of the present invention, the CO bond derived from ether (ie, CO bond) and the CO bond derived from alcohol (ie, C- OH bonds) is within the above range, the organic-inorganic composite of the present invention can be said to be an organic-inorganic composite whose structure is more precisely controlled.

The organic-inorganic composite of the present invention is particularly preferably all bonds by C1sXPS analysis, that is, C-C bonds, C=C bonds, C-H bonds and C-O bonds (C-O bonds derived from alcohol, ether-derived CO bond, epoxy-derived CO bond, etc.) and C=O bond (carbonyl-derived C=O bond, carboxyl-derived C=O bond, ester-derived C=O bond, lactone-derived The ratio of the total amount of all carbon oxygen bonds, that is, the total amount of C—O bonds and C=O bonds to the total amount of C=O bonds, etc.) is within the above range, and by C1sXPS analysis, all Carbon oxygen bond, that is, CO bond (including alcohol-derived CO bond, ether-derived CO bond, epoxy-derived CO bond, etc.) and C=O bond (carbonyl-derived C=O bond , carboxyl-derived C=O bond, ester-derived C=O bond, lactone-derived C=O bond, etc.) with respect to the total amount of ether-derived C-O bond (that is, C-O-C bond) and In this embodiment, the ratio of the total amount of alcohol-derived C—O bonds (ie, C—OH bonds) is within the above range. With such an aspect, the organic-inorganic composite of the present invention can further increase the structural control rate of the carbon material portion, and the structure can be controlled more precisely.

The organic-inorganic composite of the present invention is particularly preferably all bonds by C1sXPS analysis, that is, C-C bonds, C=C bonds, C-H bonds and C-O bonds (C-O bonds derived from alcohol, ether-derived CO bond, epoxy-derived CO bond, etc.) and C=O bond (carbonyl-derived C=O bond, carboxyl-derived C=O bond, ester-derived C=O bond, lactone-derived The ratio of the total amount of all carbon oxygen bonds, that is, the total amount of C—O bonds and C=O bonds to the total amount of C=O bonds, etc.) is within the above range, and by C1sXPS analysis, all bonds, namely CC bonds, C=C bonds, CH bonds and CO bonds (including alcohol-derived CO bonds, ether-derived CO bonds, epoxy-derived CO bonds, etc.) and C=O bond (including carbonyl-derived C=O bond, carboxyl-derived C=O bond, ester-derived C=O bond, lactone-derived C=O bond, etc.) relative to ether-derived C-O In this embodiment, the ratio of the total amount of bonds (ie, C—O—C bonds) and alcohol-derived CO bonds (ie, C—OH bonds) is within the above range. With such an aspect, the organic-inorganic composite of the present invention can further increase the solubility of the carbon material portion and further increase the structural control rate of the carbon material portion. Moreover, in such an embodiment, the structure of the organic-inorganic composite of the present invention can be controlled more precisely.

The organic-inorganic composite of the present invention is most preferably all bonds by C1sXPS analysis, that is, C-C bonds, C=C bonds, C-H bonds and C-O bonds (C-O bonds derived from alcohol, ether-derived CO bond, epoxy-derived CO bond, etc.) and C=O bond (carbonyl-derived C=O bond, carboxyl-derived C=O bond, ester-derived C=O bond, lactone-derived The ratio of the total amount of all carbon oxygen bonds, that is, the total amount of C—O bonds and C=O bonds to the total amount of C=O bonds, etc.) is within the above range, and by C1sXPS analysis, all Carbon oxygen bond, that is, CO bond (including alcohol-derived CO bond, ether-derived CO bond, epoxy-derived CO bond, etc.) and C=O bond (carbonyl-derived C=O bond , carboxyl-derived C=O bond, ester-derived C=O bond, lactone-derived C=O bond, etc.) with respect to the total amount of ether-derived C-O bond (that is, C-O-C bond) and The ratio of the total amount of alcohol-derived C-O bonds (that is, C-OH bonds) is within the above range, and by C1sXPS analysis, all bonds, that is, C-C bonds and C=C bonds and C -H bond and C-O bond (including alcohol-derived C-O bond, ether-derived C-O bond, epoxy-derived C-O bond, etc.) and C=O bond (carbonyl-derived C=O bond, carboxyl Ether-derived C-O bonds (that is, C-O-C bonds) and alcohol-derived is within the above range. With such an aspect, the organic-inorganic composite of the present invention can further increase the solubility of the carbon material portion and further increase the structural control rate of the carbon material portion. Moreover, in such an embodiment, the structure of the organic-inorganic composite of the present invention can be controlled even more precisely.

The organic-inorganic composite of the present invention preferably shows no peak due to C═O stretching vibration between 1660 cm ⁻¹ and 1800 cm ⁻¹ in IR analysis. In the IR analysis of the organic-inorganic composite of the present invention, if no peak due to C=O stretching vibration is observed between 1660 cm ^-1 and 1800 cm ^-1 , the organic-inorganic composite of the present invention has a more precise structure. can be controlled.

The reason why the structure of the organic-inorganic composite can be more precisely controlled when no peak due to C=O stretching vibration is observed between 1660 cm ^-1 and 1800 cm ^-1 in the IR analysis of the organic-inorganic composite is It can be considered as follows. That is, when an organic-inorganic composite is formed using a compound and a manufacturing method as described later, the product after the condensation reaction will have the aromatic skeleton and the oxygen functional group remaining in the product after the reaction. At this time, while the aromatic structure is maintained (in other words, when the structure is controlled), the CO bond of the ether bridge or the CO bond derived from the alcohol, and also the oxygen functional group are eliminated and condensed, It is considered that a C—C bond is formed in which the aromatics of the skeleton are bonded to each other. On the other hand, when an undesired decomposition reaction occurs and the aromatic structure of the skeleton is cleaved, a C=O bond resulting from the decomposition reaction is generated. Therefore, the absence of a peak due to C=O stretching vibration between 1660 cm ^-1 and 1800 cm ^-1 in IR analysis means that the decomposition reaction is suppressed, and such an organic-inorganic composite can be said to be an organic-inorganic composite whose structure is more precisely controlled. The above range is particularly preferably between 1700 cm ⁻¹ and 1800 cm ⁻¹ .

The organic-inorganic composite of the present invention is subjected to TG-DTA analysis under an air atmosphere from 40 ° C. under the temperature rising condition of 10 ° C./min, and the oxidation start temperature indicated by the rising temperature of DTA is preferably It is 200° C. or higher, more preferably 250° C. or higher, and most preferably 300° C. or higher. In the organic-inorganic composite of the present invention, when TG-DTA analysis is performed under an air atmosphere from 40 ° C. under the temperature rising condition of 10 ° C./min, the oxidation start temperature indicated by the rising temperature of DTA is within the above range. If it is inside, the organic-inorganic composite of the present invention has high oxidation stability, that is, the structure is controlled and the skeleton structure is maintained, so that oxidation resistance (decomposition resistance) is high. If the skeleton is cleaved to form a C═O bond, the stability of the skeleton may be lowered, and the oxidation resistance (decomposition resistance) may be lowered.

The organic-inorganic composite of the present invention can be produced by any appropriate method as long as the effects of the present invention are not impaired. Such a production method typically includes a heating step (I) of heating a composition containing a compound (A) and an inorganic oxide in which a condensation reaction occurs between the same molecules and/or between different molecules upon heating. . Through this heating step (I), the compound (A) in the composition containing the compound (A) and an inorganic oxide can be heated to become a carbon material.

The heating temperature in the heating step (I) is preferably (T-150)°C or higher when the condensation reaction temperature of compound (A) is T°C. However, the condensation reaction temperature T in this specification means the condensation reaction temperature without a catalyst (support).

In the heating step (I), the composition containing the compound (A) and the inorganic oxide is heated so that a condensation reaction occurs between the same molecules and/or between different molecules by heating. The mixing ratio of the compound (A) and the inorganic oxide is preferably 0.01% by mass to 1,000,000% by mass, more preferably 0.1%, relative to 100% by mass of the inorganic oxide. % to 100,000% by mass, particularly preferably 1% to 1,000% by mass. If the compounding ratio of the compound (A) and the inorganic oxide is within the above range, an organic-inorganic composite having a more precisely controlled structure can be produced more easily under milder conditions. The mixing ratio of these inorganic oxides and the compound (A) can be arbitrarily adjusted according to the physical properties of the desired composite. For example, by adjusting the mixing ratio of the inorganic oxide and the compound (A), the physical properties and morphology of the resulting organic-inorganic composite (e.g., solubility in a solvent, the shape of the carbon component or inorganic component (particulate or non-particulate), size of carbon or inorganic components, etc.) can be controlled.

In the composition containing the compound (A) and an inorganic oxide in which a condensation reaction occurs between the same molecules and/or between different molecules when heated, any appropriate other component may be added to the extent that the effects of the present invention are not impaired. may be included. Such other components include, for example, solvents, catalysts, base materials, carriers, and the like.

The composition to be heated in the heating step (I) may be prepared by any suitable method as long as the effects of the present invention are not impaired. Examples of such a method include a method of mixing the compound (A) and an inorganic oxide in a solid state by any appropriate method (eg, crushing, pulverizing, etc.). Further, the compound (A), the inorganic oxide, the solvent, and, if necessary, other components other than the solvent are mixed by any appropriate method (e.g., ultrasonic treatment, etc.), and any appropriate method ( For example, there is a method of removing the solvent by vacuum drying). Moreover, crushing may be performed as needed.

The heating temperature in the heating step (I) is preferably (T-150)°C or higher, more preferably (T-150 to T+50)°C when the condensation reaction temperature of compound (A) is T°C. There, more preferably (T-130 to T + 45) ° C., more preferably (T-100 to T + 40) ° C., particularly preferably (T-80 to T + 35) ° C., most preferably (T- 50 to T+30)°C. When producing the organic-inorganic composite of the present invention, the catalytic ability of the inorganic oxide and the high reactivity between the functional group on the inorganic oxide and the carbon material are such that the condensation of the compound (A) is performed as described above. The reaction can proceed at a relatively low temperature compared to the reaction temperature, and carbonization can proceed. By adjusting the heating temperature within the above range, an organic-inorganic composite having solubility in a solvent or an organic-inorganic composite having a more precisely controlled structure can be produced more easily under milder conditions.

The condensation reaction temperature of compound (A) can be determined by TG-DTA analysis. Specifically, it is as follows.
(1) When one type of compound is used as compound (A), TG-DTA analysis of compound (A) is performed by heating from 40° C. at a temperature increase rate of 10° C./min in a nitrogen gas atmosphere, The peak top temperature on the lowest temperature side of DTA is determined as the condensation reaction temperature (T° C.) of compound (A).
(2) When a mixture of two or more compounds is used as compound (A), TG-DTA analysis of the mixture is performed by heating from 40° C. at a heating rate of 10° C./min in a nitrogen gas atmosphere. , the peak top temperature on the lowest temperature side of DTA is determined as the condensation reaction temperature (T° C.) of compound (A) (mixture of two or more compounds).

The heating temperature in the heating step (I) is preferably 200 ° C. to 500 ° C., more preferably 220 ° C. to 400 ° C., still more preferably 230 ° C. to 350 ° C., as a specific heating temperature. It is preferably 250°C to 300°C. By adjusting the heating temperature within the above range, an organic-inorganic composite having solubility in a solvent or an organic-inorganic composite having a more precisely controlled structure can be produced more easily under milder conditions. In particular, since the heating temperature in the heating step (I) is thus low, the organic-inorganic composite can be industrially produced under milder conditions.

The specific heating time in the heating step (I) is preferably 0.1 to 120 hours, more preferably 0.5 to 100 hours, still more preferably 1 to 50 hours. and most preferably from 2 hours to 24 hours. By adjusting the heating time within the above range, an organic-inorganic composite having solubility in a solvent or an organic-inorganic composite having a more precisely controlled structure can be produced more easily under milder conditions.

<<1-1. Carbon material≫
The "carbon material" described herein means the carbon material portion contained in the organic-inorganic composite.

The presence of carbon components in the carbon material can be easily confirmed by C1sXPS analysis. Also, the carbon material preferably has a honeycomb structure (graphene structure) derived from benzene rings in its structure. The presence or absence of a graphene structure can be confirmed by Raman spectroscopic analysis (Non-Patent Document 4).

In the carbon material, the total content of metal components that become impurities is usually preferably 0.1 atomic % or less, more preferably 0.01 atomic % or less, based on 100 atomic % of carbon atoms. Preferably it is substantially zero. These can be confirmed by analyzing the carbon material by fluorescent X-ray elemental analysis (XRF). Further, when the organic-inorganic composite is analyzed by X-ray fluorescence elemental analysis (XRF), the content of metal components other than the metal components contained in the inorganic oxides constituting the organic-inorganic composite is 100 atomic% of carbon atoms. is preferably 0.1 atomic % or less, more preferably 0.01 atomic % or less, and particularly preferably substantially zero. For example, when an organic-inorganic composite using alumina as an inorganic oxide is analyzed by X-ray fluorescence elemental analysis (XRF), if the only metal component contained in alumina is aluminum, the content of metal components other than aluminum is preferably 0.1 atomic % or less, more preferably 0.01 atomic % or less, and particularly preferably substantially zero, based on 100 atomic % of carbon atoms.

The carbon material essentially contains carbon as a constituent element, and may contain elements other than carbon. The element other than carbon is preferably at least one element selected from oxygen, hydrogen, nitrogen, sulfur, fluorine, chlorine, bromine and iodine, more preferably oxygen, hydrogen, nitrogen and sulfur. is at least one element selected from, more preferably at least one element selected from oxygen, hydrogen and nitrogen, and particularly preferably at least one element selected from oxygen and hydrogen. When the total amount of elements other than hydrogen among the elements constituting the carbon material is 100 atomic %, carbon is preferably 60 atomic % or more, more preferably 70 atomic % or more, and still more preferably 75 atomic %. That's it. Moreover, elements other than carbon are preferably 10 atomic % or more. When the ratio of each element falls within this range, it is possible to exhibit good solubility even though it is a carbon material. These can be confirmed by quantifying the carbon material by X-ray photoelectron spectroscopy (C1sXPS). Further, when the organic-inorganic composite is quantified by X-ray photoelectron spectroscopy (C1sXPS), when the total amount of elements other than the elements contained in the inorganic oxides constituting the organic-inorganic composite is 100 atomic%, carbon is It is preferably 60 atomic % or more, more preferably 70 atomic % or more, and still more preferably 75 atomic % or more. Moreover, elements other than carbon are preferably 10 atomic % or more. For example, when an organic-inorganic composite using phosphotungstic acid as an inorganic oxide is analyzed by X-ray photoelectron spectroscopy (C1sXPS), phosphorus and tungsten are detected, but phosphorus, tungsten, and phosphorus and tungsten. It is preferable that the ratio of the amount of carbon and the ratio of elements other than carbon to the total amount of elements other than oxygen constituting phosphotungstic acid calculated from the content (excluding hydrogen) fall within the above ranges.

The carbon material is preferably soluble in the solvent. Here, the case where the carbon material is soluble in the solvent means the case where the carbon material has better solubility in the solvent than conventional carbon materials and can realize good handleability.

As an embodiment in which the carbon material is soluble in the solvent, the following embodiments can be preferably adopted.
(Embodiment 1) An embodiment in which all of the carbon material is dissolved in the solvent. That is, an embodiment in which the carbon material consists only of a solvent-soluble component (component A).
(Embodiment 2) An embodiment in which a part of the carbon material is dissolved in the solvent. That is, an embodiment in which the carbon material consists of a solvent-soluble component (component A) and a solvent-insoluble component (component B). In this case, the component B includes, for example, a portion that interacts with the inorganic oxide described below and does not dissolve.

In the present invention, the term "soluble in a solvent" means an aspect in which there is a component that dissolves in any solvent, and the solvent preferably includes N,N-dimethylformamide, N,N-dimethylacetamide, N- Methylpyrrolidone, dimethylsulfoxide, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, dichloromethane and the like. N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, dichloromethane. A preferable aspect is one in which there is a component that dissolves in at least one solvent selected from More preferably, there is a component that dissolves in at least one solvent selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and chloroform, and even more preferably. is an aspect in which there is a component that dissolves in at least one solvent selected from the group consisting of N,N-dimethylformamide and N-methylpyrrolidone, and particularly preferably there is a component that dissolves in N-methylpyrrolidone. be.

One embodiment in which the carbon material is solvent soluble is, for example, an embodiment in which the carbon material comprises a carbon-based compound that is soluble in the solvent.

As a method for determining whether or not it is soluble in a solvent, for example, after mixing the organic-inorganic composite to 0.001% by mass with respect to the solvent, ultrasonic treatment is performed for 1 hour to obtain When the obtained liquid is passed through a PTFE filter paper (pore size: 0.45 μm), it can be determined whether or not the liquid that has passed through the filter paper contains a carbon-based compound. If the liquid that has passed through the filter paper contains a carbon-based compound, it is determined that the carbon material contains a carbon-based compound that is soluble in the solvent. As the PTFE filter paper, for example, GL Chromatodisc (model 13P) manufactured by GL Sciences Co., Ltd. can be used.

The carbon material preferably has (i) a G band (generally within the range of 1550 cm ⁻¹ to 1650 cm ⁻¹ ) and a D band (generally within the range of 1300 cm ⁻¹ to 1400 cm ^{−1 )} in a Raman spectrum obtained by Raman spectroscopy. (ii) further includes a carbon-based compound that is soluble in a solvent.

A carbon material exhibits a peak in the G band (generally within the range of 1550 cm ⁻¹ to 1650 cm ⁻¹ ) in a Raman spectrum obtained by Raman spectroscopic analysis. Therefore, the fact that the carbon material has a peak in the G band (generally within the range of 1550 cm ⁻¹ to 1650 cm ⁻¹ ) in the Raman spectrum obtained by Raman spectroscopic analysis means that the carbon material has a graphene structure or a graphene structure similar to the graphene structure. It means that it has structure. If the G band is high in intensity and sharp, it can be said to have a finer graphene structure or a graphene-like structure.

A carbon material has a peak in the D band (generally within the range of 1300 cm ⁻¹ to 1400 cm ⁻¹ ) in a Raman spectrum obtained by Raman spectroscopic analysis. A carbon material having a structure derived from defects in the graphene structure exhibits a peak in the D band (generally within the range of 1300 cm ⁻¹ to 1400 cm ⁻¹ ) in the Raman spectrum obtained by Raman spectroscopic analysis. Therefore, the fact that the carbon material has a peak in the D band (generally within the range of 1300 cm ^-1 to 1400 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopic analysis is due to defects in the graphene structure of the carbon material. It means having a structure similar to a structure or a structure derived from defects in the graphene structure. If the D band is less intense, it can be said to have a cleaner graphene structure or a graphene-like structure. Moreover, the fact that the D band can be confirmed means that the carbon material has a functional group, which can increase the solubility in a solvent.

A carbon material exhibits a peak in the G' band (generally within the range of 2650 cm ⁻¹ to 2750 cm ⁻¹ ) in a Raman spectrum obtained by Raman spectroscopic analysis. Therefore, the fact that the carbon material has a peak in the G′ band (generally within the range of 2650 cm ⁻¹ to 2750 cm ⁻¹ ) in the Raman spectrum obtained by Raman spectroscopic analysis means that the carbon material has a graphene structure or a graphene structure. It means that it has the structure of The intensity of the G' band is the strongest when the graphene structure is one layer, and gradually decreases as the number of layers of the graphene structure increases. However, the peak of the G' band can be observed even if the intensity gradually decreases as the number of layers of the graphene structure increases. Therefore, having a peak in the G' band means that the carbon material has a graphene structure or a structure similar to the graphene structure. The G' band is sometimes called the 2D band.

The carbon material preferably has a peak in the D+D' band (generally within the range of 2800 cm ^-1 to 3000 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopy. A carbon material having a structure derived from defects in the graphene structure exhibits a peak in the D+D' band (generally within the range of 2800 cm ⁻¹ to 3000 cm ⁻¹ ) in the Raman spectrum obtained by Raman spectroscopic analysis. Therefore, the fact that the carbon material has a peak in the D + D' band (generally within the range of 2800 cm ^-1 to 3000 cm ^-1 ) in the Raman spectrum obtained by Raman spectroscopic analysis is derived from defects in the graphene structure of the carbon material. It means that it has a structure similar to the structure of the graphene structure or the structure derived from defects in the graphene structure. If the D+D' band is less intense, it can be said to have a cleaner graphene structure or a graphene-like structure. The D+D' band is sometimes called the D+G band. The fact that the D+D' band can be confirmed also means that the carbon material has a functional group, which can increase the solubility in the solvent.

When the carbon material contains a functional group and has a defect in a part of the graphene structure, the defect may contribute to the solubility of the carbon material in a solvent.

As described above, unlike conventionally known carbon materials, the carbon material has a graphene structure or a structure similar to a graphene structure, and the solubility of the carbon material in a solvent is superior (for example, carbon that dissolves in a solvent more components of the material, more types of solvents in which the carbon material can be dissolved, etc.).

The molecular weight of the carbon-based compound contained in the carbon material is preferably 1,000 to 1,300,000, more preferably 5,000 to 1,000,000, even more preferably 10,000 to 700,000, particularly preferably 15,000 to 500,000, and most preferably 20,000 to 300,000. If the molecular weight of the carbon-based compound contained in the carbon material is within the above range, the solubility of the carbon material in the solvent can be improved in combination with the above feature (i) (for example, the carbon material component that dissolves in the solvent , and the types of solvents in which carbon materials can be dissolved increase). If the molecular weight of the carbon-based compound contained in the carbon material exceeds 1,300,000, the solubility of the carbon material in the solvent may deteriorate. If the molecular weight of the carbon-based compound contained in the carbon material is less than 1,000, there is a risk that the characteristics of the carbon material may be weakened. These molecular weights can be analyzed by the method described later.

The content of the carbon-based compound in the carbon material is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, still more preferably 90% by mass to 100% by mass, Especially preferred is 95% to 100% by weight, most preferred is substantially 100% by weight. If the content of the carbon-based compound in the carbon material is within the above range, the solubility of the carbon material in a solvent can be improved (e.g., dissolving in a solvent The components of the carbon material are increased, and the types of solvents in which the carbon material can be dissolved are increased).

The carbon material preferably exhibits a peak within the range of 20° to 30° in an XRD spectrum chart obtained by XRD analysis. That is, it is also one of preferred embodiments that the carbon material has a structure in which graphene structures are laminated (graphene laminated structure). Having a laminated structure can make the carbon material stronger and more stable.

A carbon material is typically produced by a heating step (I) of heating a composition containing a compound (A) and an inorganic oxide in which a condensation reaction occurs between the same molecules and/or between different molecules by heating. The compound (A) in is obtained by heating.

<Compound (A)>
Compound (A) causes a condensation reaction between identical molecules and/or different molecules by heating. , the compound (A) can be a carbon material.

Compound (A) is preferably solid and has a melting point at 23°C. Since it has a melting point, it melts during the firing process, and the intermolecular reaction proceeds favorably. If it does not have a melting point, it will not melt during the firing process, so the positions of the molecules will be fixed, the reaction between molecules will be difficult to promote, and it will be difficult to convert it into a carbon material. By adopting such a compound (A), the condensation reaction is promoted, the decomposition reaction is suppressed, and the solubility of the carbon material in the solvent is more excellent (for example, the components of the carbon material dissolved in the solvent are more or more types of solvents in which carbon materials can be dissolved).

The skeleton of compound (A) that does not contribute to condensation preferably has an aromatic structure. By having an aromatic skeleton, the carbon component of the resulting carbon material can be made more stable. Such aromatic structures include, for example, aromatic structures composed of carbon atoms such as benzene, naphthalene; heteroaromatic structures composed of carbon atoms and heteroatoms (such as nitrogen and oxygen) such as pyridine, pyrimidine, furan, thiophene; among these, more preferred are aromatic structures and heteroaromatic structures having a six-membered ring structure such as benzene and pyridine.

Any appropriate molecular weight can be adopted as the molecular weight of the compound (A) as long as the effects of the present invention are not impaired. Such a molecular weight is preferably 500 or less, more preferably 75 to 450, still more preferably 80 to 400, and most preferably 100 to 350, from the viewpoint that the effects of the present invention can be more expressed. is.

Any appropriate condensation reaction temperature can be adopted as the condensation reaction temperature of compound (A) as long as the effects of the present invention are not impaired. Such a condensation reaction temperature is preferably 400° C. or less, more preferably 200° C. to 370° C., and most preferably 250° C. to 350° C. in terms of allowing the effects of the present invention to be exhibited more effectively. .

The weight of the weight M500 at a temperature of 500° C. relative to the initial weight M50 at a temperature of 50° C. when TG-DTA analysis of compound (A) is performed under a nitrogen gas atmosphere from 40° C. under the condition of temperature increase of 10° C./min. The ratio (M500/M50) is preferably 0.2 or more, more preferably 0.2 to 0.9, and most preferably 0.3 to 0, in order to further express the effects of the present invention. .8. By using the compound (A) whose weight ratio (M500/M50) falls within the above range, the carbon material can sufficiently remain in the organic-inorganic composite after heating.

[Representative Embodiment of Compound (A) (Embodiment 1)]
A representative embodiment (Embodiment 1) of compound (A) is an aromatic compound that is decomposed by heating to generate radicals on an aromatic ring. An aromatic compound in which a radical is generated on an aromatic ring causes a condensation reaction between the same molecules and/or between different molecules to become a carbon material.

The aromatic compound that is decomposed by heating to generate radicals on the aromatic ring is preferably an aromatic compound that generates a gas (a gas in a gaseous state at normal temperature and normal pressure) by heating.

As the aromatic compound that generates gas by heating, any appropriate aromatic compound can be adopted as long as it is an aromatic compound that generates gas by heating. At least one selected from CO, CO ₂ and O ₂ is preferable as the gas that is in a gaseous state at normal temperature and normal pressure.

Examples of aromatic compounds that generate CO and/or CO ₂ upon heating include aromatic compounds having a "-C(=O)-" and/or "-O-C(=O)-" structure (e.g. , aromatic ketone derivatives, aromatic ester derivatives, acid anhydrides, etc.).

Examples of aromatic compounds that generate CO and/or CO ₂ upon heating include the following compounds.

Examples of aromatic compounds that generate O ₂ upon heating include aromatic compounds having an “—O—O—” structure (eg, aromatic carbon oxides, aromatic peroxides, etc.).

Examples of aromatic compounds that generate O ₂ by heating include the following compounds. In the compounds below, R represents a hydrogen atom, or an optionally substituted alkyl group, aryl group, or heteroaryl group.

Aromatic compounds that are decomposed by heating to generate radicals on the aromatic ring have decomposability by heating, and at least a part of the skeleton is separated and decomposed into gas molecules (preferably CO, CO ₂ , At least one selected from O ₂ ) is generated, and a radical is generated on the remaining aromatic ring. By using such an aromatic compound, a reaction occurs only by decomposition of itself without the need for a reaction catalyst. Impurities can be suppressed, and a higher quality carbon material can be obtained. Moreover, by using such an aromatic compound, a carbon material can be obtained in a relatively mild temperature environment without using combustible gas. Also, such aromatic compounds may have high reactivity that does not require catalysis.

[Representative Embodiment of Compound (A) (Embodiment 2)]
A representative embodiment (embodiment 2) of compound (A) is a compound in which a neutral molecule is formed and eliminated from two or more groups by a condensation reaction. In Embodiment 2, one compound may have two or more groups, or two or more groups may be combined to form two or more groups. may be Such a compound (A) can cause a condensation reaction between identical molecules and/or different molecules to become a carbon material.

As the condensation reaction, any appropriate condensation reaction may be adopted as long as it is a condensation reaction in which one neutral molecule is formed from two or more groups and eliminated, within a range that does not impair the effects of the present invention. obtain. By setting it as such a condensation reaction, it may become possible to react at a comparatively low temperature. Such condensation reactions include, for example,
(a) a condensation reaction by the formation and elimination of H ₂ O from —H and —OH groups;
(b) a condensation reaction by the formation and elimination of ROH from a -H group and a -OR group (where R is any suitable substituted or unsubstituted alkyl group);
(c) condensation reaction by formation and elimination of RCOOH from -H group and -OOCR group (R is any suitable substituted or unsubstituted alkyl group);
etc. In particular, if the desorbed neutral component is a gaseous component at the desorption temperature (firing temperature), it will not be incorporated into the carbon material and will remain in the gaseous phase, and thus will not easily become an impurity.

As a representative example of the condensation reaction, the condensation reaction (above (a)) in which H ₂ O is formed and eliminated from —H group and —OH group will be described.

One embodiment of the compound (A) in Embodiment 2 (sometimes referred to as embodiment (X)) is a compound (a1) having a skeleton consisting of one carbon six-membered ring structure or two or more carbon A compound (a2) having a skeleton to which a 6-membered ring structure is bonded and/or condensed, half of the substituents not contributing to the structure formation of the skeleton are —OH groups, and the other half are —H is the base.

In embodiment (X),
(i) when the compound (A) is a compound (a1) having a skeleton consisting of one carbon six-membered ring structure,
(ii) when the compound (A) is a compound (a2) having a skeleton in which two or more six-membered carbon ring structures are bonded and/or condensed,
Either of the two cases can be adopted.

In embodiment (X), the "substituent that does not contribute to the formation of the skeleton structure" is the "skeleton consisting of one carbon six-membered ring structure" in the case of (i) above, or the case of (ii) above. means a substituent that does not contribute to the structure formation of the skeleton of the "skeleton in which two or more carbon six-membered ring structures are bonded and/or condensed". For example, in the case of (i) above, when the compound (a1) having a skeleton consisting of one carbon six-membered ring structure is represented by the chemical formula (a1-1) shown later, one carbon six-membered ring structure The substituents that do not contribute to the structure formation of the skeleton consisting of are 6 —OH groups and 6 —H groups, and the compound (a1) having a skeleton consisting of one carbon 6-membered ring structure is shown later In the case represented by the chemical formula (a1-2), three —OH groups and three —H groups are substituents that do not contribute to the structure formation of the skeleton consisting of one carbon six-membered ring structure. Further, for example, as the case of (ii) above, when a compound (a2) having a skeleton in which two or more six-membered carbon ring structures are bonded and/or condensed is represented by the following chemical formula (a2-1) , 6 —OH groups and 6 —H groups are substituents that do not contribute to the structure formation of the skeleton in which two or more carbon 6-membered ring structures are bonded and/or condensed.

In the embodiment (X), half of the substituents not contributing to the structure formation of the skeleton of the compound (a1) having a skeleton consisting of one carbon 6-membered ring structure are —OH groups. Half of the substituents that are -H groups and do not contribute to the structure formation of the skeleton of the compound (a2) having a skeleton in which two or more 6-membered carbon ring structures are bonded and/or condensed are half the number -OH groups and the other half are -H groups. By having such a substituent structure, compound (A) can effectively undergo dehydration reaction between identical molecules and/or different molecules by heating.

The compound (A) that can be employed in the embodiment (X) includes a compound (a1) having a skeleton consisting of one carbon 6-membered ring structure or two or more carbon 6-membered ring structures bonded and/or condensed If it is a compound (a2) having a skeletal structure, half of the number of substituents that do not contribute to the structure formation of the skeletal structure are —OH groups, and the other half are —H groups, the compound of the present invention Any appropriate compound can be employed as long as it does not impair the effect. Examples of such compound (A) include the following compounds.

Among the compounds (A) that can be employed in the embodiment (X), it is presumed that the condensation reaction is likely to occur due to the formation and elimination of H ₂ O from the —H group and the —OH group, and the reaction occurs at a low temperature. Phloroglucinol (compound (a1-2)) and hexahydroxytriphenylene (HHTP) (compound (a2-1)) are preferred because they are presumed to progress easily.

Another embodiment of compound (A) in embodiment 2 (sometimes referred to as embodiment (Y)) is compound (a1) and/or 2 having a skeleton consisting of one carbon six-membered ring structure two or more selected from compounds (a2) having a skeleton in which at least one carbon 6-membered ring structure is bonded and/or condensed, and substituents that do not contribute to the structure formation of the skeleton of the compound (a1) Half of the total number and the number of substituents that do not contribute to the structure formation of the skeleton of the compound (a2) are —OH groups, and the other half are —H groups.

In embodiment (Y),
(i) when the compound (A) consists of two or more compounds selected from compounds (a1) having a skeleton consisting of one carbon six-membered ring structure,
(ii) when compound (A) consists of two or more compounds selected from compound (a2) having a skeleton in which two or more six-membered carbon ring structures are bonded and/or condensed,
(iii) Compound (A) has a skeleton consisting of one carbon 6-membered ring structure, and at least one selected from compound (a1) and two or more carbon 6-membered ring structures are bonded and/or condensed. When it consists of one or more selected from compounds (a2) having a skeleton,
Any one of the three cases can be adopted.

In Embodiment (Y), "the sum of the number of substituents that do not contribute to the formation of the skeleton structure of compound (a1) and the number of substituents that do not contribute to the formation of the skeleton structure of compound (a2)" , has the following meaning. That is, in the case of (i) above, the number of substituents that do not contribute to the structure formation of the “skeleton consisting of one carbon six-membered ring structure” in each of the two or more compounds (a1) is means the total number. In the case of (ii) above, the substitution that does not contribute to the structure formation of the "skeleton in which two or more six-membered carbon ring structures are bonded and/or condensed" in each of the two or more compounds (a2) It means the total number of groups. In the case of (iii) above, the number of substituents that do not contribute to the structure formation of the “skeleton consisting of one carbon six-membered ring structure” in each of the one or more compounds (a1), and one The number of substituents that do not contribute to the structure formation of the skeleton of the "skeleton in which two or more six-membered carbon ring structures are bonded and/or condensed" in each of the above compounds (a2) was totaled. means number.

In embodiment (Y), for example, in the case of (i) above, when two or more compounds (a1) are represented by the following chemical formulas (a1-5) and (a1-6), chemical formula (a1 Substituents that do not contribute to the structure formation of the skeleton consisting of one carbon six-membered ring structure of the compound represented by -5) are two —OH groups and four —H groups, and have the chemical formula (a1 Substituents that do not contribute to the structure formation of the skeleton consisting of one carbon 6-membered ring structure of the compound represented by -6) are 4 -OH groups and 2 -H groups, and the total are 6 —OH groups and 6 —H groups. Further, for example, in the case of (iii) above, one or more compounds (a1) are represented by the following chemical formulas (a1-5) and (a1-7), and one or more compounds (a2) are represented by the following When represented by the chemical formula (a2-3), the substituents that do not contribute to the structure formation of the skeleton consisting of one carbon six-membered ring structure of the compound represented by the chemical formula (a1-5) are two —OH group and four —H groups, which do not contribute to the structure formation of the skeleton consisting of one carbon six-membered ring structure of the compound represented by the chemical formula (a1-7) are six —OH groups, which do not contribute to the structure formation of the skeleton in which two or more six-membered carbon ring structures of the compound represented by the chemical formula (a2-3) are bonded and/or condensed, are two -OH group and 6 -H groups.

By using such a compound (A), a reaction due to its own dehydration reaction occurs without the need for a reaction catalyst. Fatal impurities can be suppressed, and a higher quality carbon material can be obtained. Moreover, by using such a compound (A), a carbon material can be obtained in a relatively mild temperature environment without using a combustible gas. Also, such compounds (A) may have high reactivity that does not require catalysis.

[Representative Embodiment of Compound (A) (Embodiment 3)]
A representative embodiment (Embodiment 3) of compound (A) is a form in which both Embodiment 1 and Embodiment 2 are employed simultaneously. That is, Embodiment 3 is an aromatic compound that is decomposed by heating to generate radicals on an aromatic ring, and that one neutral molecule is formed and eliminated from two or more groups by a condensation reaction. is a compound. Such a compound (A) can cause a condensation reaction between identical molecules and/or different molecules to become a carbon material.

Specific structures of Embodiment 3 include, for example, compound (a3-1). When compound (a3-1) is heated, carbon dioxide molecules are eliminated, radicals (reaction active sites) are generated on the aromatic rings, and hydroxyl groups and hydrogen groups are dehydrated intermolecularly, causing a condensation reaction.

By using such a compound (A), a reaction due to its own dehydration reaction occurs without the need for a reaction catalyst. Fatal impurities can be suppressed, and a higher quality carbon material can be obtained. Moreover, by using such a compound (A), a carbon material can be obtained in a relatively mild temperature environment without using a combustible gas. Also, such compounds (A) may have high reactivity that does not require catalysis.

<<1-2. Inorganic oxide≫
Any appropriate inorganic oxide can be adopted as the inorganic oxide as long as the effects of the present invention are not impaired. Examples of such inorganic oxides include particulate inorganic oxides (inorganic oxide particles), non-particulate inorganic oxides (e.g., fibrous inorganic oxides, thin film inorganic oxides, etc.), and the like. can be adopted.

Examples of the "inorganic oxide" in the present invention include partially oxidized metals, preferably metals at least partially oxidized on the surface thereof. This is because metals are generally partially oxidized, preferably at least partially on the surface, as will be described later.

Specific examples of the "inorganic oxide" in the present invention include, for example, silica, alumina, titania, polyacid, and partially oxidized metal (preferably, at least a portion of the surface of which is oxidized). metal) and the like.

The "inorganic oxide" referred to in the present invention is an inorganic oxide as a whole, regardless of its shape (that is, whether it is an inorganic oxide particle or a non-particulate inorganic oxide). It may be an embodiment, or an embodiment in which a portion is an inorganic oxide. Embodiments in which a portion is an inorganic oxide are preferably embodiments having an inorganic oxide on the surface.

Embodiments in which a portion is an inorganic oxide (preferably, embodiments having an inorganic oxide on the surface) include, regardless of the shape thereof, for example, a metal partially oxidized (preferably, the surface thereof is at least partially oxidized metals). A portion of the metal (preferably at least a portion of its surface) can be oxidized in the presence of oxygen. Therefore, the "embodiment having an inorganic oxide on the surface", which is one form of the inorganic oxide referred to in the present invention, includes a metal having at least a portion of its surface oxidized regardless of its shape.

When inorganic oxide particles are used as the inorganic oxide, the heating step (I) for heating the composition containing the compound (A) and the inorganic oxide typically yields massive organic inorganic particles containing a large number of inorganic oxide particles. A composite can be obtained (in this case, a particulate organic-inorganic composite can be obtained by pulverization or the like). However, by adjusting the blending ratio of the compound (A) and the inorganic oxide, a particulate organic-inorganic composite is obtained by the heating step (I) of heating the composition containing the compound (A) and the inorganic oxide. Sometimes it is.

When a fibrous inorganic oxide is used as the inorganic oxide, for example, fibrous core-shell fibers can be obtained instead of the core-shell particles described later. Further, when fibrous inorganic oxides are used, for example, tubular hollow carbon materials can be obtained instead of hollow carbon fine particles described later.

When a thin-film inorganic oxide is used as the inorganic oxide, for example, a laminated organic-inorganic composite can be obtained by the heating step (I) of heating the composition containing the compound (A) and the inorganic oxide. . Further, by subjecting such a laminated organic-inorganic composite to a heating step (II), a carbon material removing step, an inorganic oxide removing step, etc., which will be described later, for example, various thin film carbon materials can be obtained.

The decomposition temperature of the inorganic oxide is preferably 800° C. or higher, more preferably 850° C. or higher, still more preferably 900° C. or higher, and particularly preferably 950° C. or higher, from the viewpoint that the effects of the present invention can be more exhibited. °C or higher.

In the present invention, inorganic oxide particles are preferable as the inorganic oxide in that the effects of the present invention can be exhibited more effectively.

The “inorganic oxide particles” used in this specification are preferably particles whose whole particles are inorganic oxides, or particles whose particles are partially inorganic oxides. Particles having an inorganic oxide on their surface are preferable as the particles partially composed of an inorganic oxide. The "inorganic oxide particles" referred to in this specification are more preferably particles whose whole particles are inorganic oxides.

Examples of particles partially composed of an inorganic oxide (preferably particles having an inorganic oxide on the surface) include, for example, metal particles partially oxidized (preferably, at least a portion of the surface are oxidized metal particles). A portion of the metal particles (preferably at least a portion of the surface thereof) can be oxidized in the presence of oxygen. Therefore, the "particles having an inorganic oxide on their surface", which is one form of the inorganic oxide particles in the present invention, include metal particles having at least a portion of the surface oxidized.

Inorganic oxide particles other than metal particles (e.g., silica particles, alumina particles, titania particles, etc.) are not only particles in which the whole particle is an inorganic oxide, but also particles in which a part of the particle is an inorganic oxide. (preferably particles having an inorganic oxide on the surface). That is, for example, taking silica particles as an example, silica particles are not only the case where the whole particle is silica, but also the case where a part of the particle is silica (preferably a particle having silica on the surface). It is possible.

The average particle size of the inorganic oxide particles can be appropriately set depending on the purpose. The average particle size of the inorganic oxide particles is preferably from 0.01 μm to 100 μm, and particularly preferably from 0.1 μm to 10 μm, from the viewpoint that the effects of the present invention can be exhibited more effectively.

The average particle size of the inorganic oxide particles is the average particle size in a volume-based particle size distribution, and is preferably measured by a laser diffraction scattering method.

The inorganic oxide particles are preferably inorganic oxide particles having a functional group on the surface, from the viewpoint that the effects of the present invention can be exhibited more effectively. Such functional groups include, for example, hydroxyl functional groups such as M-OH; oxygen functional groups including etheric functional groups such as MOM; M-NHX (where X is 0-3); Nitrogen functional groups containing amine functional groups such as M-NHX-M; Sulfur functional groups containing thiol functional groups such as M-SH, MSM; Others, silicon functional groups, boron functional groups, Phosphorus functional group; ). These functional groups can be easily formed by surface-treating the inorganic oxide with various compounds. Among these, inorganic oxide particles having an oxygen functional group on the surface are preferable as the inorganic oxide particles.

If inorganic oxide particles having a functional group on the surface are employed as the inorganic oxide, the functional group present on the surface of the inorganic oxide particle can form a bond with the carbon material in the organic-inorganic composite of the present invention. The region of the carbon material that contributes to such bonding (carbon material bonding region) is not the carbon material itself. That is, as shown in FIG. 1, in one preferred embodiment of the organic-inorganic composite of the present invention, the organic-inorganic composite 100 is a carbon material 10 as a matrix in which a plurality of inorganic oxide particles 20 are dispersed. At the interface between the carbon material 10 and the inorganic oxide particles 20, there is a carbon material region (carbon material bonding region ) 30 exists. Then, for example, when the carbon material is soluble in a solvent, when the organic-inorganic composite 100 is treated with a solvent that dissolves the carbon material, as shown in FIG. A core-shell particle (core portion: inorganic oxide particle, shell portion: carbon material-bonded region) 200 coated with a material-bonded region (region that is not dissolved by a solvent) 30 can be obtained. By removing the inorganic oxide particles 20 as the core portion from the core-shell particles 200 thus obtained, hollow carbon microparticles having a carbon material can be obtained.

The inorganic oxide particles having functional groups on their surfaces are preferably at least one selected from the group consisting of silica particles, alumina particles, titania particles, polyacid particles, and metal particles having at least part of their surfaces oxidized. is. As the inorganic oxide particles having functional groups on their surfaces, at least one selected from the group consisting of silica particles, alumina particles, titania particles, polyacid particles, and metal particles having at least a portion of their surfaces oxidized may be employed. , the functional groups present on the surface of the inorganic oxide particles can form more bonds with the carbon material.

The inorganic oxide particles having functional groups on their surfaces are more preferably polyacid particles. Examples of polyacids constituting polyacid particles include isopolyacids and heteropolyacids. As described above, when the compound (A) is used, a carbon material-containing material can be obtained without using a catalytic effect. When the organic-inorganic composite of the present invention is formed by the combination of the catalytic effect and the presence of the surface functional group, the dehydration condensation reaction is promoted and the total amount of —OH groups and —O— groups relative to the total amount of CO bonds. can have a high ratio of structural control.

As the isopolyacid, any suitable isopolyacid can be employed as long as the effects of the present invention are not impaired. Such isopolyacids include, for example, molybdenum, vanadium, tungsten, niobium, titanium, tantalum, chromium, manganese, rhenium, iron, ruthenium, cobalt, nickel, palladium, platinum, copper, silver, gold, tin, titanium, Inorganic acids mainly composed of inorganic elements such as zirconium, rhodium, iridium, osmium, zinc, etc., and salts thereof, typically molybdic acid, vanadic acid, tungstic acid, niobic acid, titanic acid, tantalic acid, etc. are mentioned.

As the heteropolyacid, any appropriate heteropolyacid can be adopted as long as the effects of the present invention are not impaired. Such heteropolyacids include, for example, isopolyacids or metal salts thereof into which heteroatoms have been introduced. Heteroatoms include, for example, oxygen, sulfur, phosphorus, ammonium, potassium, sodium, silicon, and the like. Heteropolyacids may be hydrates.

Specific examples of the heteropolyacid include a tungsten-based heteropolyacid obtained by introducing a heteroatom into an isopolyacid containing tungsten, a molybdenum-based heteropolyacid obtained by introducing a heteroatom into an isopolyacid containing molybdenum, and the like. mentioned.

Examples of the tungsten-based heteropolyacid include phosphotungstic acid, silicotungstic acid, cobalt tungstic acid, germanotungstic acid, borotungstic acid, phosphovanadotungstic acid, and phosphotungstomolybdic acid.

Examples of molybdenum-based heteropoly acids include phosphomolybdic acid, silicomolybdic acid, and phosphovanadomolybdic acid.

<<<2. Applications of organic-inorganic composites>>>>
The organic-inorganic composite of the present invention can be applied in various ways. Carbon material-containing particles are a representative product obtained through such development of applications. Typical carbon material-containing particles include core-shell particles, highly carbonized core-shell particles, hollow carbon microparticles, and highly carbonized hollow carbon microparticles.

<<2-1. Core-shell particles≫
In the production of the organic-inorganic composite of the present invention, the core-shell particles are subjected to a carbon material removal step of removing at least part of the carbon material generated by heating the compound (A) after the heating step (I). can be manufactured by That is, after producing the organic-inorganic composite of the present invention through the heating step (I), it is produced by subjecting it to a carbon material removal step of removing at least part of the carbon material contained in the organic-inorganic composite of the present invention. obtain. In the carbon material removing step, the treatment is performed with a solvent that dissolves the carbon material contained in the organic-inorganic composite of the present invention. As a result, as shown in FIG. 2, a core-shell particle (core part: inorganic oxide particle, shell part: carbon material binding area) 200 can be obtained.

Examples of solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, methanol, ethanol, 2-propanol, butanol, chloroform, Examples include dichloromethane and the like, preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and chloroform, more preferably N,N-dimethylformamide and N-methylpyrrolidone. and particularly preferably N-methylpyrrolidone.

<<2-2. High-carbon core-shell particles>>
When producing the organic-inorganic composite of the present invention, the highly carbonized core-shell particles are subjected to the heating step (II) in which the heating step (I) is followed by the carbon material removal step and then the heating step (II). can be manufactured by That is, the core-shell particles (core portion: inorganic oxide particles, shell portion: carbon material bonding region) obtained by the carbon material removing step are further heated. This heating step (II) can carbonize the shell portion. Thereby, highly carbonized core-shell particles (core portion: inorganic oxide particles, shell portion: highly carbonized material) can be obtained. By increasing the carbon content, the strength and heat resistance of the obtained highly carbonized core-shell particles can be improved.

The heating temperature in the heating step (II) may be within a temperature range that the inorganic component of the core can withstand, and the specific heating temperature is preferably 500°C to 3000°C, more preferably 600°C to 2500°C. and most preferably 700°C to 2000°C. By adjusting the heating temperature in the heating step (II) within the above range, the shell portion can be effectively carbonized.

The specific heating time in the heating step (II) is preferably 0.1 to 120 hours, more preferably 0.5 to 100 hours, and still more preferably 1 to 50 hours. and most preferably from 2 hours to 24 hours. By adjusting the heating time within the above range, the shell portion can be effectively carbonized.

<<2-3. Hollow carbon microparticles≫
Hollow carbon microparticles can be produced by including an inorganic oxide removal step of removing inorganic oxides after the heating step (I) when producing the organic-inorganic composite of the present invention (manufacturing mode 1). That is, it can be produced by producing an organic-inorganic composite through the heating step (I) and then subjecting it to an inorganic oxide removal step for removing inorganic oxides contained in the organic-inorganic composite.

In the production of the organic-inorganic composite of the present invention, the hollow carbon microparticles are also subjected to the inorganic oxide removal step of removing the inorganic oxide after the heating step (I) and the carbon material removal step. (Manufacturing Form 2). That is, after manufacturing the core-shell particles through the heating step (I) and the subsequent carbon material removing step, the core-shell particles can be produced by subjecting them to an inorganic oxide removing step for removing inorganic oxides contained in the core-shell particles.

Examples of the method of removing the inorganic oxide in the inorganic oxide removing step include a method of removing with a solvent capable of dissolving the inorganic oxide without dissolving the carbon material. The solvent having the dissolution properties as described above is not particularly limited, but a water-based solvent is preferable. The reason why water-based solvents are preferable is that the carbon material contained in the organic-inorganic composite produced by the production method of the present invention is difficult to dissolve in water, while the inorganic oxide is water (especially acidic water or basic water). ) is soluble in Examples of aqueous solvents include acidic aqueous solutions such as sulfuric acid, hydrochloric acid, and nitric acid; basic aqueous solutions such as sodium hydroxide, potassium hydroxide, and ammonia; and the like. In the removal step, the temperature is not particularly limited, but is preferably 0° C. to 150° C., more preferably 20° C. to 100° C. in terms of effectively expressing the dissolution characteristics of the aqueous solvent. . Furthermore, the physical treatment in the removal step is not particularly limited, but from the point of being able to effectively express the removability, it is preferably standing, stirring, ultrasonic treatment, shearing operation, and more preferably , agitation, sonication, and shearing operations.

<<2-4. High Carbon Hollow Carbon Fine Particles≫
When producing the organic-inorganic composite of the present invention, the high-carbon hollow carbon fine particles are subjected to the heating step (II) of further heating after the heating step (I), followed by the inorganic oxide removal step. can be produced by including That is, the hollow carbon microparticles obtained in the production mode 1 described above are further heated. By this heating step (II), the carbon material portion can be highly carbonized. Thereby, highly carbonized hollow carbon microparticles can be obtained. By increasing the carbon content, the strength and heat resistance of the obtained carbon material or carbon material composite can be improved.

In the production of the organic-inorganic composite of the present invention, the high-carbon hollow carbon fine particles are also subjected to the heating step (I), the carbon material removal step, and the inorganic oxide removal step. After that, it can be produced by including a heating step (II) of further heating. That is, the hollow carbon microparticles obtained in the production mode 2 described above are further heated. By this heating step (II), the carbon material portion can be highly carbonized.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". Moreover, in this specification, "mass" may be read as "weight". However, % in the portion relating to C1sXPS in this specification means atomic %.

<Raman spectroscopic analysis>
Raman spectroscopic analysis was performed using the following equipment and conditions.
Measuring device: Microscopic Raman (JASCO NRS-3100)
Measurement conditions: Use of 532 nm laser, 20x objective lens, CCD capture time of 1 second, integration 64 times (resolution = 4 cm-1)
In Raman analysis, the G' band and the D+D' band may overlap, and the D+D' band may be analyzed as a broad peak having a shoulder. In this case, the point of inflection of the shoulder peak is regarded as the peak of the G' band.

<XRD analysis>
The XRD measurement was performed under the following conditions using a fully automatic horizontal X-ray diffractometer (SMART LAB manufactured by Rigaku Corporation).
CuKα1 line: 0.15406 nm
Scan range: 10°-90°
X-ray output setting: 45kV-200mA
Step size: 0.020°
Scanning speed: 0.5°min ^-1 -4°min ^-1
The XRD measurement was performed in a state in which an inert atmosphere was maintained by loading the sample onto an airtight sample table in a glove box.

<C1s XPS analysis>
C1sXPS measurement was performed under the following conditions using a photoelectron spectrometer (AXIS-ULTRA, manufactured by Shimadzu Corporation).
Source: Mg (dual node)
Emission: 10mA
Anode: 10 kV
Analyzer: Pass Energy: 40
Measurement range: C1s: 296-270eV
Accumulation times: 10 Analysis conditions: Peaks derived from the C1s orbital were separated for each functional group with the energy described below, and the ratio was calculated from each area. The types of functional groups are (1) -COO-, lactones, and some ketones @ 288.3 eV, (2) C=O and epoxy groups @ 286.2 eV, (3) C-OH and C-O-C @ 285.6 eV, (4) 6-membered ring C=C @ 284.3 eV, (5) CC, CH and 5-membered ring C=C @ 283.6 eV. However, (4) and (5) were collectively calculated for the ratio calculation. Note that % in the portion related to C1sXPS means atomic %. In the table, the proportions of peaks corresponding to (1), (2), and (3) are indicated by (A), (B), and (C), and correspond to (4) and (5). The total percentage of peaks is shown in (D).

<TG-DTA analysis>
TG-DTA analysis was performed using the following equipment and conditions.
Measuring device: Suggestive thermogravimetric simultaneous measuring device (TG/DTA6200, manufactured by Seiko Instruments Inc.)
The condensation reaction temperature of compound (A) was performed as follows.
(1) When one type of compound is used as compound (A), TG-DTA analysis of compound (A) is performed by heating from 40° C. at a temperature increase rate of 10° C./min in a nitrogen gas atmosphere, The peak top temperature on the lowest temperature side of DTA was determined as the condensation reaction temperature (T° C.) of compound (A).
(2) When a mixture of two or more compounds is used as compound (A), TG-DTA analysis of the mixture is performed by heating from 40° C. at a heating rate of 10° C./min in a nitrogen gas atmosphere. , the peak top temperature on the lowest temperature side of DTA was determined as the condensation reaction temperature (T° C.) of compound (A) (mixture of two or more compounds).
The oxidation start temperature of the organic-inorganic composite was performed in an air atmosphere from 40° C. at a temperature increase rate of 10° C./min, and was estimated from the lowest DTA rise temperature among the DTA rise temperatures.

<IR analysis>
FT-IR analysis was performed using the following equipment and conditions.
Measuring device: Fourier transform infrared spectrophotometer (FT/IR-4200 manufactured by JASCO Corporation)
Measurement conditions: Diffuse reflectance (DRIFT) method, MCT detector, resolution 4 cm −1 , 128 integration times Sample conditions: A mixture of sample and KBr at a weight ratio of 1:50 was used.

<Measurement of molecular weight>
The molecular weight is measured using gel permeation chromatography (GPC, HLC-8220GPC manufactured by Tosoh Corporation), N,N-dimethylformamide (containing 0.1% LiBr) so that each carbon material is 0.02% by mass. After sonication for 1 hour, it was passed through a PTFE filter paper (0.45 μm) for pretreatment, and the filtrate was N,N-dimethylformamide (containing 0.1% LiBr) as a developing solvent. The molecular weight was calculated in terms of polystyrene. The maximum molecular weight in the carbon material was calculated from the rising point of the peak.

[Example 1]: phloroglucinol + silica particles + 250°C x 1 hour phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 220°C, condensation reaction temperature: 330°C): theoretical specific surface area of 750 m ² /g is silica Silica particles (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “Q-10HT60315”, specific surface area 259 m ² /g) were sufficiently mixed so as to form 1.5 layers with respect to the particles.
After the obtained mixture was vacuum-sealed in a quartz ampoule tube, it was heated in an electric furnace preheated to 250° C. for 1 hour.
As a result, an organic-inorganic composite (1) containing the carbon material (1A) and the inorganic oxide (1B) was obtained.
When the organic-inorganic composite (1) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (1) are shown in FIG. 3 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (1) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (CC bonds, C=C bonds, CH bonds and C The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of -O bonds and C=O bonds) is 26%, and the total amount of carbon-oxygen bonds (C-O bonds The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C-O bonds and C=O bonds) is 62%, and all carbon bonds (C-C bonds and C=C bonds and The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C--H bonds, CO bonds and C=O bonds was 16%. From this, it can be seen that the structural control rate is high.
The weight ratio of the weight M500 at a temperature of 500° C. to the initial weight M50 at a temperature of 50° C. (M500/M50 ) was 0.49. From this, it can be seen that phloroglucinol can sufficiently exist on the inorganic oxide even after carbonization.
FIG. 4 shows the results of DTA analysis in TG-DTA analysis of the obtained organic-inorganic composite (1). According to FIG. 4, the organic-inorganic composite (1) was subjected to TG-DTA analysis under an air atmosphere with a temperature increase of 10 ° C./min from 40 ° C., and the oxidation indicated by the rising temperature of DTA. The starting temperature was 200°C. From this, it can be seen that the oxidation resistance is high.
Furthermore, FIG. 5 shows the results of IR analysis of the obtained organic-inorganic composite (1). According to FIG. 5, in the IR spectrum of the organic-inorganic composite (1), there is no peak at 1660 cm ⁻¹ to 1800 cm ⁻¹ derived from the C=O structure, and the structure is highly controlled.
Furthermore, FIG. 6 shows the Raman spectrum of the obtained organic-inorganic composite (1). Since the Raman spectrum has peaks at 1365 cm ⁻¹ , 1590 cm ⁻¹ , 2650 cm ⁻¹ and 2835 cm ⁻¹ , the carbon material (1A) has a graphene structure and includes a carbon-based compound having a structure in which the graphene structures are laminated. found to be the material
As described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially produced under mild conditions.

[Example 2] Phloroglucinol + alumina particles + 250°C x ¹ hour An organic-inorganic composite (2) containing a carbon material (2A) and an inorganic oxide (2B) was obtained in the same manner as in Example 1.
When the organic-inorganic composite (2) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (2) are shown in FIG. 3 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (2) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (CC bonds, C=C bonds, CH bonds and C The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of -O bonds and C=O bonds) is 29%, and the total amount of carbon-oxygen bonds (C-O bonds The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C-O bonds and C=O bonds) is 59%, and all carbon bonds (C-C bonds and C=C bonds and The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C--H bonds, CO bonds and C=O bonds was 17%. From this, it can be seen that the structural control rate is high.
FIG. 4 shows the results of DTA analysis in TG-DTA analysis of the obtained organic-inorganic composite (2). According to FIG. 4, the organic-inorganic composite (2) was subjected to TG-DTA analysis under an air atmosphere from 40 ° C. under the condition of a temperature increase of 10 ° C./min, and oxidation indicated by the rising temperature of DTA. The starting temperature was 230°C. From this, it can be seen that the oxidation resistance is high.
Furthermore, FIG. 5 shows the results of IR analysis of the obtained organic-inorganic composite (2). According to FIG. 5, in the IR spectrum of the organic-inorganic composite (2), there is a peak at 1660 cm ⁻¹ to 1800 cm ⁻¹ derived from the C=O structure, and the structure control rate by C1sXPS is high. The structural control rate by FT-IR analysis is rather low.
Furthermore, FIG. 6 shows the Raman spectrum of the obtained organic-inorganic composite (2). Since the Raman spectrum has peaks at 1340 cm ⁻¹ , 1585 cm ⁻¹ , 2650 cm ⁻¹ and 2835 cm ⁻¹ , the carbon material (2A) has a graphene structure and a carbon-based compound having a structure in which the graphene structures are laminated. found to be the material
As described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially produced under mild conditions.

[Example 3] Phloroglucinol + titania particles + 250 ° C. × 1 hour Silica particles were changed to titania particles (Catalysis Society of Japan free distribution sample "JRC-TIO-4 (2)", specific surface area 50 m ² /g) An organic-inorganic composite (3) containing a carbon material (3A) and an inorganic oxide (3B) was obtained in the same manner as in Example 1 except that
When the organic-inorganic composite (3) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (3) are shown in FIG. 3 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (3) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (CC bonds, C=C bonds, CH bonds and C The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of -O bonds and C=O bonds) is 27%, and the total amount of carbon-oxygen bonds (C-O bonds and C=O bonds), the ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount is 56%, and the total amount of carbon bonds (CC bonds and C=C bonds and The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C--H bonds, CO bonds and C═O bonds) was 15%. From this, it can be seen that the structural control rate is high.
FIG. 4 shows the results of DTA analysis in TG-DTA analysis of the obtained organic-inorganic composite (3). According to FIG. 4, the organic-inorganic composite (3) was subjected to TG-DTA analysis under an air atmosphere from 40 ° C. under the condition of a temperature increase of 10 ° C./min, and oxidation indicated by the rising temperature of DTA. The starting temperature was 200°C. From this, it can be seen that the oxidation resistance is high.
Furthermore, FIG. 5 shows the results of IR analysis of the obtained organic-inorganic composite (3). According to FIG. 5, in the IR spectrum of the organic-inorganic composite (3), there is a peak at 1660 cm ⁻¹ to 1800 cm ⁻¹ derived from the C=O structure, and the structure control rate by C1sXPS is high, The structural control rate by FT-IR analysis is rather low.
Furthermore, FIG. 6 shows the Raman spectrum of the obtained organic-inorganic composite (3). Since the Raman spectrum has peaks at 1340 cm ⁻¹ , 1580 cm ⁻¹ , 2650 cm ⁻¹ and 2820 cm ⁻¹ , the carbon material (3A) has a graphene structure and includes a carbon-based compound having a structure in which the graphene structures are laminated. found to be the material
As described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially produced under mild conditions.

[Example 4] Phloroglucinol + heteropolyacid particles (HPW) + 250 ° C. × 1 hour Silica particles as heteropolyacid particles HPW (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 12-tungst (VI) phosphoric acid n-hydrate , the specific surface area was changed to 278 m ² /g) in the same manner as in Example 1 to obtain an organic-inorganic composite (4) containing a carbon material (4A) and an inorganic oxide (4B).
When the organic-inorganic composite (4) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (4) are shown in FIG. 3 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (4) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (CC bonds, C=C bonds, CH bonds and C The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of -O bonds and C=O bonds) is 29%, and the total amount of carbon-oxygen bonds (C-O bonds The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C-O bonds and C=O bonds) is 76%, and all carbon bonds (C-C bonds and C=C bonds and The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C--H bonds, CO bonds and C=O bonds was 22%. From this, it can be seen that the structural control rate is high.
FIG. 4 shows the results of DTA analysis in TG-DTA analysis of the obtained organic-inorganic composite (4). According to FIG. 4, the organic-inorganic composite (4) was subjected to TG-DTA analysis under an air atmosphere from 40 ° C. under the condition of a temperature increase of 10 ° C./min. The starting temperature was 300°C. From this, it can be seen that the oxidation resistance is high.
Furthermore, FIG. 5 shows the results of IR analysis of the obtained organic-inorganic composite (4). According to FIG. 5, in the IR spectrum of the organic-inorganic composite (4), there is no peak at 1660 cm ⁻¹ to 1800 cm ⁻¹ derived from the C=O structure, and the structure is highly controlled.
Furthermore, FIG. 6 shows the Raman spectrum of the obtained organic-inorganic composite (4). Since the Raman spectrum has peaks at 1350 cm ⁻¹ , 1585 cm ⁻¹ , 2650 cm ⁻¹ and 2810 cm ⁻¹ , the carbon material (4A) has a graphene structure and a carbon-based compound having a structure in which the graphene structures are laminated. found to be the material Further, when the molecular weight of the carbon material (4A) portion was measured, the weight average molecular weight was 8,000 and the maximum molecular weight was 50,000.
As described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially produced under mild conditions.

[Example 5] Phloroglucinol + heteropolyacid particles (HPMo) + 250°C x 1 hour Silica particles were used as heteropolyacid particles to prepare HPMo (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 12-molybdo (VI) phosphoric acid n-hydrate ) in the same manner as in Example 1 to obtain an organic-inorganic composite (5) containing a carbon material (5A) and an inorganic oxide (5B).
When the organic-inorganic composite (5) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (5) are shown in FIG. 7 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (5) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (CC bonds, C=C bonds, CH bonds and C The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of -O bonds and C=O bonds) is 27%, and the total amount of carbon-oxygen bonds (C-O bonds The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C-O bonds and C=O bonds) is 63%, and all carbon bonds (C-C bonds and C=C bonds and The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C--H bonds, CO bonds and C=O bonds was 17%. From this, it can be seen that the structural control rate is high.
As described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially produced under mild conditions.

[Example 6] Phloroglucinol + heteropolyacid particles (HSiW) + 250°C x 1 hour Same as in Example 1, except that the silica particles were changed to HSiW (manufactured by Nippon New Metals Co., Ltd., silicotungstic acid) as heteropolyacid particles. An organic-inorganic composite (6) containing a carbon material (6A) and an inorganic oxide (6B) was obtained in the same manner.
When the organic-inorganic composite (6) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (6) are shown in FIG. 7 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (5) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (CC bonds, C=C bonds, CH bonds and C The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of -O bonds and C=O bonds) is 29%, and the total amount of carbon-oxygen bonds (C-O bonds The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C-O bonds and C=O bonds) is 72%, and all carbon bonds (C-C bonds and C=C bonds and The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C--H bonds, CO bonds and C=O bonds was 21%. From this, it can be seen that the structural control rate is high.
As described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially produced under mild conditions.

[Example 7] Phloroglucinol + heteropolyacid particles (HPVMo) + 250°C x 1 hour Example 1 except that the silica particles were changed to HPVMo (phosphovanadomolybdic acid, manufactured by Nippon New Metals Co., Ltd.) as heteropolyacid particles. In the same manner as above, an organic-inorganic composite (7) containing a carbon material (7A) and an inorganic oxide (7B) was obtained.
When the organic-inorganic composite (7) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (7) are shown in FIG. 7 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (7) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (CC bonds, C=C bonds, CH bonds and C The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of -O bonds and C=O bonds) is 29%, and the total amount of carbon-oxygen bonds (C-O bonds and C=O bonds), the ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount is 55%, and the total amount of carbon bonds (CC bonds and C=C bonds and The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C--H bonds, CO bonds and C=O bonds was 16%. From this, it can be seen that the structural control rate is high.
As described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially produced under mild conditions.

[Example 8] Phloroglucinol + heteropolyacid particles (HPWMo) + 250°C x 1 hour Example 1 except that the silica particles were changed to HPWMo (manufactured by Nippon New Metals Co., Ltd., lintungstomolybdic acid) as heteropolyacid particles. An organic-inorganic composite (8) containing a carbon material (8A) and an inorganic oxide (8B) was obtained in the same manner.
When the organic-inorganic composite (8) was dispersed in NMP (N-methylpyrrolidone) and the solubility of the carbon component was confirmed by the method described above, it was soluble in the solvent.
The results of C1sXPS analysis of the obtained organic-inorganic composite (8) are shown in FIG. 7 (XPS spectrum (C1s)) and Table 1. From Table 1, it can be seen that the organic-inorganic composite (8) is an organic-inorganic composite containing a carbon material and an inorganic oxide, and all carbon bonds (CC bonds, C=C bonds, CH bonds and C The ratio of the total amount of all carbon-oxygen bonds (C-O bonds and C=O bonds) to the total amount of -O bonds and C=O bonds) is 27%, and the total amount of carbon-oxygen bonds (C-O bonds and C=O bonds), the ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount is 70%, and all carbon bonds (CC bonds and C=C bonds and The ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds to the total amount of C--H bonds, CO bonds and C=O bonds was 19%. From this, it can be seen that the structural control rate is high.
As described above, according to the present invention, it is possible to provide an organic-inorganic composite that is soluble in a solvent, has a precisely controlled structure, and can be industrially produced under mild conditions.

[Reference Example 1]: phloroglucinol + copper particles + 300 ° C. x 2 hours, high-carbon core-shell particles phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 220 ° C., condensation reaction temperature: 330 ° C.): 1 g to 200 g 20 g of copper particles (manufactured by ECKA Granules Germany GmbH, particle size: 95 vol % or more and 36 μm or less): 20 g were added and thoroughly mixed by ultrasonic treatment.
Acetone was removed from the resulting mixture by vacuum drying at room temperature, and the remaining lumps were pulverized, followed by heating at 300° C. for 2 hours.
As a result, an organic-inorganic composite (10) containing the carbon material (9A) and the inorganic oxide (9B) was obtained.
The resulting organic-inorganic composite ( 10 ) was treated with DMF (N,N-dimethylformamide). As a result, the carbon material (9A) is removed, and the core-shell particles (9) in which the surface of the inorganic oxide (9B) is coated with the carbon material bonding region (core part: inorganic oxide particle, shell part: carbon material bonding region )was gotten.
Core-shell particles (9) were further calcined at 700° C. for 1 hour. As a result, the carbon material in the shell portion was highly carbonized, and highly carbonized core-shell particles (9) were obtained. FIG. 8 shows the Raman spectrum of the surface of the highly carbonized core-shell particles (9). It can be seen from FIG. 8 that the surface (shell portion) of the high-carbon core-shell particles (9) is composed of a high-carbon carbon material without impairing the shape.

The organic-inorganic composite of the present invention is lightweight, has excellent lubricity, excellent electrical conductivity, excellent thermal conductivity, and is useful as a filler having excellent antioxidant properties. Carbon-coated inorganic particles and hollow carbon It can be effectively used as a material for industrial production of fine particles and the like.

10 carbon material 20 inorganic oxide particles 30 carbon material bonding region 100 organic-inorganic composite 200 core-shell particles

Claims (7)

An organic-inorganic composite containing a carbon material and an inorganic oxide,
The organic-inorganic composite contains a reaction product of the compound (A) and the inorganic oxide, in which a condensation reaction occurs between the same molecules and/or different molecules when heated, and the carbon material is derived from the compound (A). The compound (A) is a compound in which one neutral molecule is formed and eliminated from two or more groups by a condensation reaction, and the condensation reaction is
(a) a condensation reaction by the formation and elimination of H ₂ O from —H and —OH groups;
(b) a condensation reaction by the formation and elimination of ROH from a -H group and a -OR group (where R is any suitable substituted or unsubstituted alkyl group);
(c) condensation reaction by formation and elimination of RCOOH from -H group and -OOCR group (R is any suitable substituted or unsubstituted alkyl group);
is either
The inorganic oxide is an inorganic oxide particle having a functional group on the surface,
By C1sXPS analysis, total carbon oxygen bonds, i.e., C-O bonds and The ratio of the total amount of C=O bonds is 10% or more, and the total amount of carbon oxygen bonds, that is, the total amount of C—O bonds and C=O bonds, is derived from ethers and alcohols. The ratio of the total amount of CO bonds is 50% or more,
Organic-inorganic composite. An organic-inorganic composite containing a carbon material and an inorganic oxide,
The organic-inorganic composite contains a reaction product of the compound (A) and the inorganic oxide, in which a condensation reaction occurs between the same molecules and/or different molecules when heated, and the carbon material is derived from the compound (A). The compound (A) is a compound in which one neutral molecule is formed and eliminated from two or more groups by a condensation reaction, and the condensation reaction is
(a) a condensation reaction by the formation and elimination of H ₂ O from —H and —OH groups;
(b) a condensation reaction by the formation and elimination of ROH from a -H group and a -OR group (where R is any suitable substituted or unsubstituted alkyl group);
(c) condensation reaction by formation and elimination of RCOOH from -H group and -OOCR group (R is any suitable substituted or unsubstituted alkyl group);
is either
The inorganic oxide is an inorganic oxide particle having a functional group on the surface,
By C1sXPS analysis, total carbon oxygen bonds, i.e., C-O bonds and The ratio of the total amount of C=O bonds is 10% or more, and all bonds, that is, the total amount of C—C bonds, C=C bonds, C—H bonds, C—O bonds, and C=O bonds , the ratio of the total amount of ether-derived CO bonds and alcohol-derived CO bonds is 15% or more,
Organic-inorganic composite. 3. The organic-inorganic composite according to claim 1, wherein no peak attributed to C═O stretching vibration is observed between 1700 cm ⁻¹ and 1800 cm ⁻¹ in IR analysis. 4. Any one of claims 1 to 3, wherein the oxidation start temperature indicated by the rise temperature of DTA is 200° C. or higher when TG-DTA analysis is performed under an air atmosphere at a temperature increase of 10° C./min. The organic-inorganic composite described. Claims 1 to 4, wherein the inorganic oxide particles are at least one selected from the group consisting of silica particles, alumina particles, titania particles, polyacid particles, and metal particles whose surfaces are at least partially oxidized. The organic-inorganic composite according to any one of. The organic-inorganic composite according to any one of claims 1 to 5, wherein the inorganic oxide particles are polyacid particles. 7. The organic-inorganic composite according to claim 6, wherein the metal element constituting said polyacid particles is at least one selected from the group consisting of molybdenum, vanadium, tungsten, niobium, titanium and tantalum.

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