JP2006096780A - Phenol resin composition for carbon material, carbon material and method for producing the carbon material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenol resin composition for carbon materials in which pore amount and pore diameters formed on the surface can be controlled and a carbon material and to provide a production method which is applicable for producing the carbon material without carrying out activation treatment of the carbon material. <P>SOLUTION: The phenol resin composition for carbon materials comprises a phenol resin and a compound in which the boiling point is ≤800°C. The carbon material is obtained by carrying out curing treatment of the resin composition and carrying out carbonization treatment of the cured material. The method for producing the carbon material comprises (a) a step for preparing the phenol resin composition for carbon materials comprising a phenol resin and a compound in which the boiling point is ≤800°C, (b) a step for obtaining a phenol resin cured material by carrying out curing treatment of the phenol resin composition for carbon materials and (c) a step for obtaining the carbon material by carrying out carbonization treatment of the phenol resin cured material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a phenol resin composition for a carbon material, a carbon material, and a method for producing the same.

  Activated carbon, which is a typical porous carbon material, is manufactured by performing activation treatment using steam or chemicals using coconut shell, coal, petroleum pitch, phenol resin, or the like as a raw material. Among these raw materials, activated carbon using phenol resin as raw material has few impurities, and since the pore size distribution on the surface of activated carbon is sharper than activated carbon using other raw materials, the adsorption performance is high, It has attracted attention (see, for example, Patent Documents 1 to 4).

In recent years, to improve the performance of the adsorption characteristics when activated carbon is used for treatment of water and sewage, and the electrical characteristics when used for activated carbon electrodes typified by electric double layer capacitors, control of the pore diameter on the surface of activated carbon Has become an important technology.
For this reason, attempts have been made to adjust the amount of water vapor and chemicals used in the activation treatment of activated carbon, the activation time, and the like, and the specific surface area of the activated carbon surface can be controlled to some extent by such a method.
However, activation by water vapor or chemicals is a reaction that scrapes the surface of the carbon material, so that control of the pores is difficult, and there is a problem that the performance of the activated carbon cannot be sufficiently improved. For this reason, development of the activated carbon which can control the quantity and pore diameter of the pore formed in the surface, and the method of manufacturing this without an activation process was desired.

JP 05-43345 A Japanese Patent Laid-Open No. 11-1314 2004-193570 No. 2004-221332

  The present invention is applicable to a phenolic resin composition for a carbon material from which a carbon material capable of controlling the amount of pores formed on the surface and the pore diameter can be obtained, and the carbon material, and to produce it without activation treatment. The manufacturing method which can be provided is provided.

Such an object is achieved by the present invention described in the following (1) to (8).
(1) A phenol resin composition for a carbon material containing a phenol resin and a compound having a boiling point of 800 ° C. or less.
(2) The phenol resin composition for carbon materials according to (1) above, containing 10 to 100% by weight of the compound relative to the phenol resin.
(3) A carbon material obtained by subjecting the phenol resin composition for a carbon material according to the above (1) or (2) to a carbonization treatment after curing.
(4) In the above (3), the volume of micropores (pore diameter of 0.4 nm or more and less than 1 nm) among the pores formed on the surface of the carbon material is 0.1 to 2 ml / g. The carbon material described.
(5) In the carbon material, among the pores formed on the surface of the carbon material, the volume of mesopores (pore diameter of 1 nm or more and 25 nm or less) is 0.1 to 2 ml / g (3) or (4 ).
(6) The method for producing a carbon material according to any one of (3) to (5) above,
(A) a step of preparing a phenol resin composition for a carbon material containing a phenol resin and a compound having a boiling point of 800 ° C. or less;
(B) a step of curing the carbon material phenol resin composition to obtain a phenol resin cured product;
(C) a step of carbonizing the phenol resin cured product to obtain a carbon material;
A method for producing a carbon material, comprising:
(7) The method for producing a carbon material according to (6), wherein the curing treatment in the step (b) is a heat treatment at a temperature lower than the boiling point of the compound.
(8) The carbon material according to (6) or (7), wherein the carbonization treatment in the step (c) is performed at a temperature of 500 ° C. or higher.

  The present invention relates to a phenol resin composition for a carbon material characterized by containing a phenol resin and a compound having a boiling point of 800 ° C. or lower, a carbon material obtained by subjecting this to curing treatment, and carbonization treatment thereof, and It is a manufacturing method, and a carbon material capable of controlling the amount of pores formed on the surface and the pore diameter can be obtained. And such a carbon material can be manufactured without an activation process.

Hereinafter, the phenol resin composition for carbon material of the present invention, the carbon material, and the production method thereof will be described in detail.
The phenol resin composition for carbon materials of the present invention (hereinafter sometimes simply referred to as “resin composition”) contains a phenol resin and a compound having a boiling point of 800 ° C. or less.
In addition, the carbon material of the present invention is characterized by being carbonized after curing the resin composition of the present invention.
And the manufacturing method of the carbon material of the present invention (hereinafter sometimes simply referred to as “manufacturing method”) is the above-described manufacturing method of the carbon material of the present invention,
(A) a step of preparing a phenol resin composition for a carbon material containing a phenol resin and a compound having a boiling point of 800 ° C. or less;
(B) a step of curing the carbon material phenol resin composition to obtain a phenol resin cured product;
(C) a step of carbonizing the phenol resin cured product to obtain a carbon material;
It is characterized by having.
First, the resin composition of the present invention will be described.

First, the phenol resin used in the resin composition of the present invention will be described.
The phenol resin used in the resin composition of the present invention is obtained by reacting phenols and aldehydes in the presence of an alkaline or acidic catalyst.

  Although it does not specifically limit as phenols used here, For example, cresol, such as phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, xylenol such as 3,5-xylenol, ethylphenol such as o-ethylphenol, m-ethylphenol, p-ethylphenol, isopropylphenol, butylphenol, p-tert-butylphenol Such as butylphenol, p-tert-amylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol and other alkylphenols, fluorophenol, chlorophenol, bromophenol, iodophenol, etc. Monohydric phenol substitutes such as genated phenol, p-phenylphenol, aminophenol, nitrophenol, dinitrophenol and trinitrophenol, and monohydric phenols such as 1-naphthol and 2-naphthol, resorcin, alkylresorcin, Examples thereof include polyphenols such as pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, and dihydroxynaphthalene. These can be used alone or in combination of two or more.

  The aldehydes are not particularly limited, but examples include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde. Benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. These can be used alone or in combination of two or more.

  It does not specifically limit as a method with which the said phenols and aldehydes are made to react, A well-known method is employable.

  Although it does not specifically limit as a form of the phenol resin used with the resin composition of this invention, For example, solid, powder form, solution form, liquid form etc. are mentioned, Any form can be used.

Although it does not specifically limit as a compound (henceforth only a "addition compound") which has a boiling point of 800 degrees C or less used for the resin composition of this invention, For example, water, methanol, a butanol, ethylene glycol, glycerin , Ethylene carbonate, propylene carbonate, triacetin, butyl lactone, toluene, xylene, petroleum aromatic hydrocarbons and other organic solvents, phenol, cresol, aniline, and the like. These can be used alone or in combination of two or more.
Among these, organic solvents such as ethylene glycol, glycerin, ethylene carbonate, and propylene carbonate having a boiling point of 100 ° C. or higher, and phenol, cresol, and aniline are preferable. These are excellent in compatibility with the phenol resin, and a highly uniform resin composition can be easily obtained. In addition, since the boiling point is 100 ° C. or higher, volatilization of the additive compound can be suppressed even in a temperature range suitable for mixing with the phenol resin, and the additive compound can be easily dispersed and included in the resin composition. It becomes.

In the resin composition of the present invention, those having a boiling point of 800 ° C. or lower can be used as the additive compound, and those having a boiling point of 500 ° C. or lower are particularly preferable.
Thereby, control of the pore diameter and pore volume of the carbon material can be performed more efficiently.
When the boiling point of the additive compound exceeds 800 ° C., it becomes difficult for the additive compound to sublime before the ring condensation during the carbonization treatment, and it becomes difficult to control pore formation by destroying the structure of the carbon material.

Moreover, it is preferable that the residual carbon rate of the said addition compound is 30 weight% or less, More preferably, it is 20 weight% or less. If the residual carbon ratio is larger than the above upper limit value, the amount of components remaining as carbides during carbonization treatment increases, and the proportion contributing to the generation of pores decreases, so that pore control may be difficult in some cases.
In addition, the said remaining-carbon rate calculates the ratio of the residual weight after a process with respect to before a process at the time of heat-processing an additional compound at 800 degreeC for 0.5 hour.

In the composition of the present invention, the blending ratio of the phenol resin and the additive compound is not particularly limited, but it is preferable to contain 10 to 100% by weight of the additive compound with respect to the phenol resin. More preferably, it is 10 to 70% by weight. Thereby, sufficient pore production | generation can be performed at the time of carbon material manufacture.
If the amount of the additive compound is less than the above lower limit, the dispersibility of the additive compound in the phenol resin is lowered, and the number of pores that can be generated during carbonization is reduced. On the other hand, when the amount is larger than the above upper limit value, the curing reaction of the phenol resin may be hindered, or it may be difficult to produce a cured resin including the additive compound. In such a case, when producing a carbon material, it may be difficult to control the amount of generated pores.

Next, the carbon material of the present invention and the manufacturing method thereof will be described.
The carbon material of the present invention is obtained by curing the resin composition of the present invention, followed by carbonization. Specifically,
(A) preparing the resin composition;
(B) a step of curing the resin composition to obtain a phenol resin cured product;
(C) a step of carbonizing the phenol resin cured product to obtain a carbon material;
It can obtain by the manufacturing method of this invention which has these.

First, the step (a) will be described.
The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of simply mixing a phenol resin and an additive compound, a method of melt-mixing, or a method of mixing by dissolving in a solvent. . Moreover, after mixing by these methods, it can carry out also by the method of heating before the hardening process mentioned later. In addition, when a solvent is used at the time of mixing, it can be normally used as the resin composition of this invention by removing this before a hardening process.

Next, the step (b) will be described.
Although it does not specifically limit as a method of hardening the resin composition of this invention, When a resol type phenol resin is used as a phenol resin, it can mix with an additive compound and can be hardened by heating.
Moreover, when a novolak type phenol resin is used as the phenol resin, a curing agent such as hexamethylenetetramine is mixed with an additive compound and heated to cure, a thermosetting resin such as an epoxy resin, a polyisocyanate, or a melamine resin. May be mixed with an additive compound and cured by normal temperature or heating, or may be a method of mixing acids such as paratoluenesulfonic acid and phenolsulfonic acid together with an additive compound and curing by normal temperature or heating.

Although it does not specifically limit as hardening processing temperature in the said (b) process, When carrying out hardening by normal temperature or heating, it can carry out at 100-300 degreeC.
In particular, the curing treatment is preferably performed at a temperature lower than the boiling point of the additive compound used. Thereby, many used additive compounds can be included in a phenol resin hardened | cured material inside, and it can make it easy to control pore production | generation in (c) process.

Next, the step (c) will be described.
In the production method of the present invention, the step (c) is performed in a substantially inert atmosphere using carbon monoxide, nitrogen, helium, or the like.

  The carbonization temperature (maximum temperature) when carbonizing the phenol resin cured product to obtain a carbon material is not particularly limited, but is preferably 500 ° C or higher. If it is less than the above lower limit value, a large amount of elements other than carbon such as hydrogen, oxygen, etc. will remain in the carbon material. Deterioration of adsorption performance due to use may increase.

  Other conditions for the carbonization treatment are not particularly limited. For example, the carbonization treatment time can usually be 0.1 to 15 hours. Moreover, although the temperature increase rate is not particularly limited, the temperature can be increased normally at 5 to 200 ° C./hour. Moreover, although it does not specifically limit about a cooling rate, The temperature which open | releases an inert gas can be made into room temperature-100 degreeC.

The pores formed on the surface of the carbon material of the present invention preferably have a micropore volume (pore diameter of 0.4 nm or more and less than 1 nm) of 0.1 to 2 ml / g. More preferably, it is 0.4-1.5 ml / g.
Similarly, the volume of mesopores (pore diameter of 1 nm to 25 nm) is preferably 0.1 to 2 ml / g. More preferably, it is 0.3-1.2 ml / g.
Thereby, it can be set as the carbon material excellent in the adsorption | suction characteristic. In addition, by controlling the pore diameter in this way, it is possible to selectively adsorb an adsorbed substance having a size suitable for the pore diameter, and to obtain a porous carbon material with high adsorption efficiency.
When the micropore volume is less than the above lower limit value, there are few effective pores, and the characteristics such as adsorption characteristics may not be sufficient as a porous carbon material. Moreover, when larger than the said upper limit, the bulk density of a carbon material may become small and the characteristic per volume of a carbon material may fall.
In addition, when the volume of the mesopores is less than the lower limit value, the characteristics as a porous carbon material such as adsorption characteristics may not be sufficient. Moreover, when larger than the said upper limit, the mechanical strength of a carbon material will become low and a crack etc. may generate | occur | produce at the time of use.

  In the carbon material of the present invention, the micropores and mesopores are microscopically based on an adsorption isotherm obtained using Shimadzu Corporation's “pore distribution measuring device ASAP2010” and using nitrogen gas as a probe gas. The pores were calculated by the MP method (Micro Pore Method) and the mesopores were measured by the DH method (Dollimore & Heal Method).

  In the present invention, as a method for obtaining a carbon material having such a pore volume, the resin composition of the present invention is used, preferably after performing a curing treatment at a temperature equal to or lower than the boiling point of the additive compound in the resin composition. The carbonization can be performed at a maximum temperature of 500 ° C. or higher.

According to the production method of the present invention, a porous carbon material in which the amount of micropores and mesopores is controlled can be obtained by curing and carbonizing the resin composition of the present invention. The reason for this is not clear, but is considered as follows.
In the production method of the present invention, a resin composition containing a phenol resin and an additive compound is used. Then, by curing the resin composition preferably at a temperature equal to or lower than the boiling point of the additive compound, a cured phenol resin containing a large amount of the added additive compound can be obtained.
And in the process of carbonizing the cured product, if the additive compound volatilizes or the additive compound inhibits the curing of the phenolic resin, it is considered that the inhibited part of the phenolic resin unit also volatilizes. And when these volatilize, it is thought that a suitable amount of pores having relatively large pore diameters are generated on the surface of the carbon material, and thus a porous carbon material can be obtained.

  Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to the examples. In the examples and comparative examples, “part” indicates “part by weight”, and “%” indicates “% by weight”.

Example 1
40 parts of ethylene glycol is added to and mixed with 100 parts of a commercially available resol-type phenolic resin (“PR-50087” manufactured by Sumitomo Bakelite Co., Ltd.), heat treated for 24 hours with a drying apparatus at 150 ° C., and cured with phenolic resin including ethylene glycol. I got a thing.
The obtained cured product was heated at 100 ° C./h in a nitrogen atmosphere, maintained at 800 ° C. for 30 minutes, carbonized, and then pulverized to obtain a carbon material.

(Example 2)
40 parts of glycerin was added to and mixed with 100 parts of a commercially available resol-type phenolic resin (“PR-50087” manufactured by Sumitomo Bakelite Co., Ltd.), and heat treated for 10 hours with a drying apparatus at 200 ° C. to obtain a cured phenol resin containing glycerin. Obtained.
The obtained cured product was heated at 200 ° C./h in a nitrogen atmosphere, maintained for 10 minutes after reaching 900 ° C., carbonized, and then pulverized to obtain a carbon material.

(Example 3)
After adding 10 parts of water to 100 parts of a commercially available resol type phenolic resin (“PR-HR-45” manufactured by Sumitomo Bakelite Co., Ltd.), 15 parts of a 63% aqueous solution of phenolsulfonic acid is further added and mixed, followed by drying at 60 ° C. It heat-processed for 20 minutes with the apparatus, and the phenol resin hardened | cured material which included water was obtained.
The obtained cured product was carbonized in the same manner as in Example 1 to obtain a porous carbon material.

Example 4
After mixing 50 parts of phenol and 10 parts of hexamethylenetetramine with 100 parts of a commercially available novolac-type phenolic resin ("PR-50731" manufactured by Sumitomo Bakelite Co., Ltd.) with a pressure kneader, 20 hours in a drying device at 160 ° C. It heat-processed and the phenol resin hardened | cured material which included phenol was obtained.
The obtained cured product was carbonized in the same manner as in Example 2 to obtain a porous carbon material.

(Example 5)
After mixing 40 parts of xylene and 50 parts of isocyanate (“HP-21” manufactured by Sumitomo Bakelite Co., Ltd.) with 50 parts of a commercially available resol type phenolic resin (“PR-51402” manufactured by Sumitomo Bakelite Co., Ltd.), drying at 60 ° C. It heat-processed for 30 minutes with the apparatus, and the phenol resin hardened | cured material which included xylene was obtained.
The obtained cured product was carbonized in the same manner as in Example 1 to obtain a carbon material.

(Comparative Example 1)
100 parts of a commercially available resol type phenolic resin (“PR-50087” manufactured by Sumitomo Bakelite Co., Ltd.) was heat-treated for 10 hours with a drying apparatus at 200 ° C. to obtain a cured phenolic resin.
The obtained cured product was heated at 100 ° C./h in a nitrogen atmosphere, reached 500 ° C., held for 1 hour, cooled, pulverized to obtain a carbide.
The obtained carbide was steam activated at 900 ° C. in a nitrogen atmosphere to obtain a carbon material.

(Comparative Example 2)
100 parts of a commercially available resol type phenolic resin (“PR-50087” manufactured by Sumitomo Bakelite Co., Ltd.) was heat-treated for 24 hours with a drying apparatus at 150 ° C. to obtain a cured phenolic resin.
The obtained cured product was heated at 100 ° C./h in a nitrogen atmosphere, maintained at 800 ° C. for 30 minutes, carbonized, and then pulverized to obtain a carbon material.

(Remaining additive compound (evaluation of porous carbon material)
1. Specific surface area Measured by nitrogen gas, BET three-point method.

2. Pore distribution Micropores and mesopores were measured using the “Porosity distribution measuring device ASAP2010” manufactured by Shimadzu Corporation, and based on the adsorption isotherm obtained using nitrogen gas as a probe gas, the micropores were measured by the MP method (Micro Pore Method). ) And mesopores were calculated by the DH method (Dollimore & Heal Method).

3. Carbon Material Yield Based on the weight of the cured product including volatile components or the weight of a normal cured product, the carbon material yield was measured from the yield of the weight of the porous carbon material obtained therefrom.

  The above evaluation results are shown in Table 1.

Each of Examples 1 to 5 is formed by using a phenol resin composition for a carbon material of the present invention containing a phenol resin and a compound having a boiling point of 800 ° C. or less, followed by carbonization treatment after curing the phenol resin composition. The carbon material of the present invention, which was a carbon material having an appropriate level of micropores and mesopores formed on the surface, could be produced without activation treatment.
In Comparative Example 1, the same resin as in Examples 1 and 2 was used, and a carbon material was obtained by activation treatment without adding a compound having a boiling point of 800 ° C. or lower. The rate fell.
In Comparative Example 2, the same resin as in Comparative Example 1 was used, and a carbon material was obtained by performing carbonization treatment after adding a compound having a boiling point of 800 ° C. or less, followed by carbonization treatment. In both cases, the amount of pores formed was greatly reduced.

The present invention relates to a phenol resin composition for a carbon material characterized by containing a phenol resin and a compound having a boiling point of 800 ° C. or lower, a carbon material obtained by subjecting this to curing treatment, and carbonization treatment thereof, and It is a manufacturing method, and a carbon material capable of controlling the amount of pores formed on the surface and the pore diameter can be obtained. And such a carbon material can be manufactured with high yield, without carrying out an activation process.
The carbon material of the present invention is suitable as a porous carbon material used for the treatment of water and sewage or the like, or a porous carbon material used for an activated carbon electrode typified by an electric double layer capacitor.

Claims (8)

A phenol resin composition for carbon materials, comprising a phenol resin and a compound having a boiling point of 800 ° C. or less. The phenol resin composition for carbon materials of Claim 1 which contains the said compound 10 to 100weight% with respect to the said phenol resin. A carbon material obtained by subjecting the phenol resin composition for a carbon material according to claim 1 or 2 to a curing treatment and then a carbonization treatment. The carbon material according to claim 3, wherein the carbon material has a micropore (pore diameter of 0.4 nm or more and less than 1 nm) volume of 0.1 to 2 ml / g among the pores formed on the surface of the carbon material. . 5. The carbon material according to claim 3, wherein the carbon material has a mesopore volume (pore diameter of 1 nm to 25 nm) of 0.1 to 2 ml / g among the pores formed on the surface of the carbon material. . A method for producing a carbon material according to any one of claims 3 to 5,
(A) a step of preparing a phenol resin composition for a carbon material containing a phenol resin and a compound having a boiling point of 800 ° C. or less;
(B) a step of curing the carbon material phenol resin composition to obtain a phenol resin cured product;
(C) carbonizing the phenolic resin cured product to obtain a carbon material;
A method for producing a carbon material, comprising: The method for producing a carbon material according to claim 6, wherein the curing treatment in the step (b) is a heat treatment at a temperature lower than the boiling point of the compound. The carbon material according to claim 6 or 7, wherein the carbonization treatment in the step (c) is a heat treatment at 500 ° C or higher.