JP2007153977A - Cured phenol resin particle for carbide, method for producing the same, and method for producing carbide by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cured phenol resin particle for carbide, having high actual carbon ratio, a method for producing the resin particle, and a method for producing the carbide by using the cured phenol resin particle. <P>SOLUTION: The objective carbide is formed by reacting phenols and aldehydes with a protective colloid in the presence of at least one kind of compounds selected from the group consisting of phosphoric acids, phosphate esters, a phosphazene compound and a specific organic phosphonic acid to afford the uncured phenol resin particle, curing the uncured phenol resin particle to provide a cured phenol resin particle containing above compounds, and firing the cured phenol resin particle. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cured phenol resin particle for carbide, a method for producing the same, and a method for producing a carbide using the same, and more particularly to a cured phenol resin particle for carbide useful as a filler, a raw material for various carbon materials, and the like. It is related with the method which can be manufactured advantageously. Furthermore, this invention relates to the manufacturing method of the carbide | carbonized_material using such a hardening phenol resin particle for carbide | carbonized_materials.

  Conventionally, particles or powders made of cured phenolic resin have been widely used as fillers (additives) and as raw materials for carbon materials such as activated carbon. Has been proposed.

  For example, in JP-A-11-60664 (Patent Document 1) and JP-A-2001-114852 (Patent Document 2), a predetermined alkylamine compound as a condensation reaction catalyst and a glucoside as an emulsifying dispersant in an aqueous medium. A method for producing a spherical phenol resin characterized by subjecting a phenol and an aldehyde to a condensation reaction in the presence of a polymer surfactant having a bond has been clarified, and Japanese Patent Publication No. 62-30211. In the gazette (patent document 3), a method for producing a powdered phenol / formaldehyde resin using hydrochloric acid as a condensation reaction catalyst is proposed.

  However, since the cured phenol resin particles and powder produced according to such a method contain a relatively large amount of nitrogen, chlorine ions, etc., the cured phenol resin particles and powder produced by such a method On the other hand, if heat treatment is performed separately, nitrogen oxides and chlorides are generated from nitrogen contained in the particles and powder, and these nitrogen oxides corrode equipment and have an adverse effect on the environment. There was a problem such as affecting.

  On the other hand, the applicant of the present application previously described in JP-A-3-7714 (Patent Document 4), phenols and aldehydes in the presence of an alkylbenzenesulfonic acid having an alkyl group having 10 or more carbon atoms and a protective colloid. And a second step of curing the resin particles by continuing or separating from the first step to form thermosetting resin particles. A method for producing cured phenolic resin particles was proposed. According to this method, since an acid catalyst (alkylbenzene sulfonic acid) with low corrosivity is used, as a reaction vessel of phenols and aldehydes, glass lining or made of Hastelloy is used. The existing stainless steel equipment can be used as it is without the need for expensive corrosion-resistant reaction tanks, and cured phenol resin particles can be produced safely and with high yield under mild reaction conditions. Met.

  However, in the cured phenol resin particles obtained according to such a method, when carbonized, the residual carbon ratio was relatively low, about 50%, and the carbonization yield was low. For this reason, in the recent situation where there is a demand for increasing the carbonization yield with a cured phenol resin, the method previously proposed by the applicant of the present application has not yet been used as a cured phenol resin particle for carbide. There was room for improvement.

Japanese Patent Laid-Open No. 11-60664 JP 2001-114852 A Japanese Examined Patent Publication No. 62-30211 JP-A-3-7714

  Here, the present invention has been made in the background of such circumstances, and the problem to be solved is a cured phenolic resin particle for carbide with a high residual carbon ratio, and a method for advantageously producing the same. It is another object of the present invention to provide an advantageous method for producing a carbide using such a cured phenol resin particle for carbide.

  And as a result of intensive studies based on the technique previously proposed in Patent Document 4 in order to solve such a problem, the present inventors, as a result, together with protective colloids, phosphates, phosphate esters In the presence of at least one compound selected from the group consisting of phosphazene compounds, phosphazene compounds and specific organic phosphonic acids, phenols and aldehydes are reacted to produce uncured phenol resin particles, It has been found that by curing such uncured phenol resin particles, cured phenol resin particles having a high residual carbon ratio can be obtained.

  Therefore, the present invention has been completed based on such findings, and can be suitably implemented in various modes as listed below. However, the modes described below can be combined in any combination. Can be adopted. It should be noted that aspects or technical features of the present invention are not limited to those described below, and can be recognized based on the description of the entire specification or the inventive idea disclosed therein. It should be understood.

(1) Phosphoric acids, phosphate esters, phosphazene compounds, and general formula: R—PO (OH) ₂ [wherein R contains a carbon atom and contains —COOH and / or —PO (OH) ₂ It is a group. A cured phenol resin particle for carbide, comprising at least one compound selected from the group consisting of organic phosphonic acids represented by the formula:

(2) Phosphoric acids, phosphate esters, phosphazene compounds, and general formula: R—PO (OH) ₂ [wherein R contains a carbon atom and —COOH and / or —PO (OH) together with protective colloid ) A group containing ₂ . In the presence of at least one compound selected from the group consisting of organic phosphonic acids represented by the following formula, uncured phenol resin particles are produced by reacting phenols with aldehydes, and then the uncured phenol. A method for producing a cured phenol resin particle for carbide, wherein the resin particle is cured.

(3) Curing for carbide according to the above aspect (2), wherein when the phosphoric acid is present, the reaction between the phenol and the aldehyde is performed in the presence of a phenol resin synthesis catalyst. A method for producing phenol resin particles.

(4) The method for producing cured phenol resin particles for carbide according to the above aspect (3), wherein the phenol resin synthesis catalyst is an alkylbenzene sulfonic acid.

(5) The cured phenol resin particles for carbide according to any one of the above aspects (2) to (4), wherein the reaction is performed under a condition in which the organic phase and the aqueous phase are not separated. Production method.

(6) In any one of the above aspects (2) to (5), the phosphoric acid is present in an amount of 0.01 to 10% by weight based on the phenol resin. The manufacturing method of the hardening phenol resin particle for description of carbide | carbonized_material.

(7) Any one of the above aspects (2) to (5), wherein the phosphoric acid esters are present in a proportion of 0.1 to 30% by weight with respect to the phenol resin. The manufacturing method of the hardening phenol resin particle | grains for carbide | carbonized_materials as described in one.

(8) A method for producing carbide, characterized in that the cured phenol resin particles for carbide according to the aspect (1) are fired.

(9) A method for producing a carbide comprising firing the cured phenol resin particles for carbide obtained by the production method according to any one of the above aspects (2) to (7).

(10) Phosphoric acids, phosphate esters, phosphazene compounds, and general formula: R—PO (OH) ₂ [wherein R contains a carbon atom and contains —COOH and / or —PO (OH) ₂ It is a group. ] The residual-carbon-ratio improvement agent of the phenol resin containing the at least 1 sort (s) of compound chosen from the group which consists of organic phosphonic acid shown by these.

In such a cured phenol resin particle for carbide according to the present invention, phosphoric acids, phosphoric esters, phosphazene compounds, and general formula: R—PO (OH) ₂ [wherein R contains a carbon atom, and − A group containing COOH and / or —PO (OH) ₂ . The residual carbon ratio is effectively improved by containing at least one compound selected from the group consisting of organic phosphonic acids represented by the following formula, and thus such cured phenolic resin particles are fired: In this case, the carbide can be obtained with a high carbonization yield.

  Further, in the method for producing cured phenol resin particles for carbide according to the present invention, the reaction between phenols and aldehydes is allowed to proceed in the presence of a protective colloid and a specific compound as described above. When the cured phenol resin particles obtained by such a method are fired, carbonization can be effectively promoted by the presence of the specific compound, and after firing, a carbide can be obtained with a high residual carbon ratio. Therefore, cured phenol resin particles for carbide that can be used very advantageously as a raw material for carbon materials such as activated carbon can be advantageously obtained.

  By the way, the target cured phenol resin particles for carbide in the present invention can be basically obtained by reacting phenols and aldehydes in the presence of the specific compound according to the present invention. . In this case, as the phenols which are one of the reaction raw materials, any known phenols conventionally used in the production of phenol resins can be used. In addition, as such phenols, usually, phenols having three or more reactive sites for aldehydes in the molecule (hereinafter simply referred to as polyfunctional phenols) and the production of these polyfunctional phenols. Phenol-based purification residues that are sometimes produced as by-products are used, but if necessary, bifunctional phenols (phenols having two reaction sites for aldehydes in the molecule) and monofunctional phenols (molecule It is also possible to use phenols having a single reactive site for aldehydes, etc., together with polyfunctional phenols, as long as the object of the present invention is not impaired.

  Such polyfunctional phenols include, in addition to phenol, m-cresol, m-butylphenol, 3,5-xylenol, m-nitrophenol, m-aminophenol, m-propenylphenol, m-phenyl. M-substituted phenols such as phenol, m-chlorophenol, m-bromophenol, resorcinol, polyhydric phenols such as catechol, pyrogallol, phloroglucinol, and cashew shell oil, bisphenol A, bisphenol F, bisphenol S Examples thereof include bisphenols such as polycondensed ring phenols such as naphthol, and mixtures thereof. Examples of the phenol-based purification residue include a cresol residue, a resorcinol residue, a catechol residue, a bisphenol A residue, and a mixture thereof. Of course, in the present invention, it is needless to say that polyfunctional phenols other than those exemplified here and phenol-based purification residues can be used as appropriate, and target phenol resin particles, etc. Depending on the case, polyfunctional phenols or phenol-based purification residues may be used alone or in combination.

  Moreover, as needed, as bifunctional phenols and monofunctional phenols used with these polyfunctional phenols and / or a phenol-type refinement | purification residue, for example, o-cresol, p-cresol, 2, 5 -Xylenol, p-tert-butylphenol, p-nonylphenol, p-phenylphenol, p-cumylphenol, 2,5-diaminophenol, 2,4-xylenol, 2,6-xylenol and the like can be mentioned.

  On the other hand, the aldehydes that are the other reaction raw materials used in the present invention are not particularly limited, and generally, from the viewpoint of reactivity, raw material prices, etc., formalin, paraformaldehyde, trioxane, tetraoxane, acetal, etc. Formaldehyde feed materials, glyoxal, and mixtures thereof can be suitably used. In addition, acetaldehyde, butyraldehyde, benzaldehyde, hydroxybenzaldehyde, acrolein, furfural and the like can be used as necessary.

  And when manufacturing the hardening phenol resin particle | grains for carbide | carbonized_materials according to this invention, generally such aldehydes are the quantity which will be a ratio of aldehydes: 1.0 mol or more with respect to phenols: 1.0 mol. In this case, it is desirable that the aldehydes are used in a quantitative range of 1.1 to 1.3 mol from the viewpoint of odor during production, economy, and the like.

  Here, when producing the cured phenol resin particles for carbide according to the present invention, advantageously, in the reaction of phenols and aldehydes as described above, the specific compound according to the present invention coexists with the protective colloid. Will be.

  By the way, in such a production method, the protective colloid is added for the purpose of obtaining the produced phenol resin in the form of particles, but the type thereof is not particularly limited and has been conventionally known. Various protective colloids can be used. Here, examples of the compounds that can achieve the object of the present invention more advantageously include water-soluble polymer compounds such as gum arabic, gatch gum, hydroxyalkyl guar gum, partially hydrolyzed polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose. Among them, in particular, gum arabic can be preferably used. Such gum arabic can be more advantageously provided with uncured phenol resin particles having a small average particle diameter by heat treatment.

  Such protective colloids can be used alone or in combination of two or more. The amount used is determined according to the type of protective colloid used and the like. Generally, the amount used is preferably 0.1 to 10% by weight of the phenol. It will be used in an amount such that the proportion is 5 to 5.0% by weight.

On the other hand, the specific compounds according to the present invention which are present together with such protective colloids are phosphoric acids, phosphoric esters, phosphazene compounds, and general formula: R-PO (OH) ₂ [wherein R represents a carbon atom And a group containing —COOH and / or —PO (OH) ₂ . ] Among these, at least one compound selected from the group consisting of organic phosphonic acids, preferably phosphoric acids, phosphoric esters, and more preferably phosphoric acids. Examples of phosphoric acids include polyphosphoric acids such as metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, and tetraphosphoric acid, phosphoric anhydride, and mixtures thereof. An orthophosphoric acid aqueous solution that is easily available at low cost. For example, 75% by mass phosphoric acid, 89% by mass phosphoric acid and the like are advantageously used. Examples of the phosphoric acid esters include methyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isodecyl acid phosphate, monoisodecyl phosphate and the like. In addition to phosphate ester, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, tri-n-butyl phosphite, triphenyl phosphite and the like can be mentioned, and among these, acidic phosphate ester is preferable. .

The phosphazene compounds include cyclophosphazenes that are cyclic compounds and polyphosphazenes that are chain compounds. Cyclophosphazene is represented by the structure shown in the following chemical formula 1, and specifically, chlorinated cyclophosphazene (X = Cl), alkoxylated cyclophosphazene (X = alkoxy) depending on the type of functional group represented by X in the formula. Group), aminated cyclophosphazene (X = NH ₂ ), phenoxylated cyclophosphazene (X = phenoxy group), alkylated cyclophosphazene (X = alkyl group), allylated cyclophosphazene (X = allyl group), etc. Etc. are exemplified. Further, polyphosphazene, structural formula (-PY ₂ = N-) n (where, n = from 3 to 10,000) represented by, specifically, by the kind of functional group represented by Y in the formula, chlorinated Polyphosphazene (Y = Cl), alkoxylated polyphosphazene (Y = alkoxy group), aminated polyphosphazene (Y = NH ₂ ), phenoxylated polyphosphazene (Y = phenoxy group), alkylated polyphosphazene (Y = alkyl group) ), Polyphosphazenes such as allylated polyphosphazene (Y = allyl group) and the like are exemplified, but not particularly limited thereto.

Furthermore, the general formula: R—PO (OH) ₂ [wherein R is a group containing a carbon atom and containing —COOH and / or —PO (OH) ₂ . As the organic phosphonic acid represented by the formula, ethylenediaminetetrakismethylenephosphonic acid, ethylenediaminebismethylenephosphonic acid, aminotrimethylenephosphonic acid, β-aminoethylphosphonic acid-N, N-diacetic acid, aminomethylphosphone, which are aminopolyphosphonic acids Examples include acid-N, N-diacetic acid, 1-hydroxyethane-1,1′-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and the like. Among these, in view of the object of the present invention, aminotrimethylene phosphonic acid, 1-hydroxyethane-1,1′-diphosphonic acid, 2-phosphonobutane-, which are industrially mass-produced and can be obtained at low cost. 1,2,4-tricarboxylic acid and the like are desirable. In addition, these compounds may be contained individually by 1 type, and may be contained combining 2 or more types.

In addition, the usage-amount of this specific compound will be determined suitably according to the kind etc. In general, it is preferably used in such an amount as to be a proportion of 0.01% to 30% by weight with respect to the phenol resin, but when such a specific compound is phosphoric acid, The blending amount is preferably about 0.01 wt% to 10 wt%, more preferably 0.05 wt% to 5 wt%, and more preferably 0.1 wt% to 2 wt% with respect to the phenol resin. Most preferred. Further, when the specific compound is a phosphate ester, the blending amount thereof is preferably about 0.1% by weight to 30% by weight with respect to the phenol resin, and more preferably 0.5% by weight to 20% by weight. Is more preferable, and 1 to 10% by weight is most preferable. Further, the specific compound is a phosphazene compound or a general formula: R—PO (OH) ₂ [wherein R is a group containing a carbon atom and containing —COOH and / or —PO (OH) ₂ . In the case of the organic phosphonic acid represented by the formula (1), the blending amount is preferably about 0.01% by weight to 10% by weight, more preferably 0.05% by weight to 5% by weight, based on the phenol resin. And 0.1% by weight to 2% by weight is most preferable. Incidentally, if the amount of such a specific compound used is excessive, the specific compound contributes not as a residual carbon ratio improver but as a reaction catalyst, and before the desired particles are produced, The tendency to gel is increased. This tendency is particularly large in phosphoric acids and phosphate esters that are originally used as reaction catalysts.

  In the present invention, the reaction between the phenols and the aldehydes can be carried out by various conventionally known methods. For example, it is effective to advance the reaction in the presence of a phenol resin synthesis catalyst. However, in particular, in the case where phosphoric acids are used as the specific compound, it is desirable that such a phenol resin synthesis catalyst coexist and react. In addition, as such a phenol resin synthesis catalyst, any catalyst can be used as long as it is a catalyst conventionally used for synthesizing a phenol resin. For example, alkylbenzene sulfonic acid, various amine compounds, hydrochloric acid, etc. Can be mentioned. Among these various phenol resin synthesis catalysts, alkylbenzene sulfonic acid is preferable from the viewpoint of safety at the time of producing phenol resin particles, and alkylbenzene sulfonic acid having an alkyl group having 10 or more carbon atoms is preferable. Can be used. Examples of the alkylbenzenesulfonic acid having an alkyl group having 10 or more carbon atoms include decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, and mixtures thereof. Among them, dodecylbenzenesulfonic acid can be used particularly advantageously from the viewpoints of economy, availability, catalytic function, and the like.

  Furthermore, the amount of the phenol resin synthesis catalyst used is appropriately determined according to the type of catalyst, the blending ratio of reaction raw materials, reaction conditions, and the like. For example, when the alkylbenzene sulfonic acid as described above is used, it is used in such an amount that the proportion becomes about 0.5 to 2.0% by weight of the phenol. When alkylbenzene sulfonic acid is used as the phenol resin synthesis catalyst in the present invention, the amount used is relatively small compared to the amount used when a conventional alkylamine compound or the like is used as a catalyst. The resulting phenol resin particles have a relatively low impurity content. However, since the formation reaction of the phenol resin proceeds in the presence of alkylbenzene sulfonic acid, the resulting phenol resin particles contain a slight amount of impurities such as sulfur compounds.

  Thus, in the cured phenol resin particles for carbide obtained according to the method for producing cured phenol resin particles for carbide according to the present invention, together with the protective colloid, in the presence of the specific compound defined in the present invention. Since the resin particles are obtained by reacting phenols with aldehydes, such specific compounds are contained in the resin particles.

  That is, the cured phenol resin particle for carbide according to the present invention contains the specific compound defined in the present invention in the particle, and when such cured phenol resin particle is fired, Carbonization is promoted by the action, and a high residual carbon ratio is exhibited after firing. And such a high carbon residue rate, in other words, the hardened phenol resin particles having a high carbonization yield can be used very advantageously as a raw material for carbon materials such as activated carbon.

  By the way, when manufacturing the cured phenol resin particles for carbide according to the present invention, it is advantageously carried out according to the following method.

  First, in a normal reaction vessel equipped with a reflux condenser, a thermometer, and a stirrer, phenols and aldehydes as a reaction raw material, protective colloid, and a specific compound defined in the present invention, if necessary, A phenol resin synthesis catalyst, dilution water (distilled water), various modifiers (for example, urea, melamine, guanamine, aniline, tall oil, etc.) and the like are charged.

  Here, the timing of addition (addition) of the protective colloid to the reaction system is not particularly limited as long as it is before the condensate (reaction product) is cured. It is preferable to add it before or at the time of emulsification), and in particular, from the viewpoint of simplification of the work, it is desirable to add from the start of the reaction. In the present invention, in order to perform granulation smoothly and prevent agglomeration of the generated uncured phenol resin particles, the water content in the reaction system is 80% by weight or more based on phenols. From the viewpoint of waste liquid treatment, production efficiency, etc., it is advantageous to adjust the ratio so that the ratio is preferably about 100 to 180% by weight. It should be noted that the time for adjusting the amount of water is appropriate at the start of the reaction or at the time of addition of protective colloid.

  Next, while stirring the phenols and the like in the reaction tank, the inside of the reaction tank is heated at a rate of temperature rise of about 0.5 to 2.0 ° C./min. Phenols and aldehydes are reacted at a temperature (reaction temperature) for a predetermined time to produce fusible uncured phenol resin particles (step 1). Subsequently, the reaction is continued for a predetermined time at the same temperature as or slightly lower than the reaction temperature, thereby obtaining infusible cured phenol resin particles (step 2). The time required for these series of reactions is usually about 0.5 to 6 hours.

  Thereafter, the inside of the reaction tank is cooled, and if necessary, the phenol resin synthesis catalyst is neutralized, and then the produced cured phenol resin particles are separated by solid-liquid separation means such as filtration or a centrifugal separator. Then, the separated cured phenol resin particles are washed as necessary and dried by various conventionally known drying methods such as air drying and heat drying (for example, heating, hot air circulation, vibration, fluidized bed, etc.). Thus, the desired cured phenol resin particles can be obtained.

  The average particle diameter of the cured phenol resin particles obtained in this way is not particularly limited because it does not affect the yield and the like for the purpose of obtaining a carbide, but the production method according to the present invention In general, it is possible to easily obtain cured phenol resin particles for carbide having a small average particle diameter of 1 nm to 2 mm.

  In the present invention, the fusible uncured phenol resin produced according to the above step 1 is further reacted to a state where it can be handled, and then separated according to the same method as described above, and if necessary. After washing, it is possible to obtain infusible cured phenol resin particles for carbide by thermosetting using the above-described heat drying method.

  Further, the cured phenol resin particles for carbide obtained according to the present invention are originally infusible particles with a small amount of uncured components, but further heat treatment for applications requiring phenol resin particles with a very small amount of uncured components. Alternatively, solvent extraction can be performed.

  Furthermore, the cured phenol resin for light-colored carbides in which a part of the phenolic hydroxyl group in the particle is acetylated by acetylating the cured phenol resin particle for carbide produced according to the present invention according to a conventionally known method. Particles can also be obtained.

  And the carbide | carbonized_material can be obtained with the outstanding yield by baking the hardening phenol resin particle for carbide | carbonized_materials which concerns on this invention as mentioned above. This carbonization yield (residual carbon ratio) is approximately 55% or more, although it depends on the firing conditions. Regarding the firing conditions, the conditions under a reducing atmosphere are preferably employed for the purpose of further improving the yield of carbides.

  Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the above specific description. It should be understood that improvements and the like can be added. In this example, the residual carbon ratio and phosphorus content of the obtained cured phenol resin particles for carbide were measured as follows.

-Measurement of residual coal rate-
In a weighed Pt container, phenol resin particles are weighed and accommodated, and the temperature of the Pt container is increased from room temperature to 800 ° C. at a rate of temperature increase of 10 ° C./min using TG-DTA. The weight reduction rate (%) from room temperature to 100 ° C. and the weight reduction rate (%) from 100 ° C. to 800 ° C. are calculated from the following equation (1). In addition, "high residual carbon ratio" has shown that the carbon atom contained in the structure as an organic compound in a phenol resin particle is efficiently carbonized also under high temperature.
[Equation 1]
[Remaining charcoal rate (%)]
= (1-{(Weight reduction rate from 100 ° C. to 800 ° C. (%)) / [100− (Weight reduction rate from room temperature to 100 ° C.)]}) × 100

-Measurement of phosphorus content-
Measurement was performed in accordance with the method of JIS-K-0102.

  In a 1 L reaction flask equipped with a reflux condenser, a thermometer, and a stirrer, phenol: 300 parts by weight, 92% paraformaldehyde: 125 parts by weight, 3 parts by weight of gum arabic as a protective colloid, and a phenol resin synthesis catalyst 30 parts by weight of a 10% aqueous solution of dodecylbenzenesulfonic acid was added, and 440 parts by weight of diluted water (distilled water) was further added.

  Next, while stirring the flask, the temperature is increased (heated) at a rate of about 1 ° C./min until the temperature in the flask reaches the reflux temperature, and the reaction proceeds while the temperature is maintained at the reflux temperature. After 45 minutes from the formation of the phenol resin particles, the temperature in the flask is slightly lowered and held for another 4 hours in order to prevent the generated particles from being combined. Cured.

  Then, the inside of the flask was neutralized with sodium hydroxide, cooled, filtered, washed (hot water-methanol washed), and further dried by heating under reduced pressure to produce cured phenol resin particles a.

  In addition, in addition to phenol, 92% paraformaldehyde, gum arabic, and 10% aqueous dodecylbenzene sulfonic acid, 89% phosphoric acid is further blended in the proportions listed in Table 1 below to produce the cured phenol resin particles a. According to the same method, four types of cured phenol resin particles b to e were obtained.

  Further, phenol, 92% paraformaldehyde, gum arabic, and isodecyl acid phosphate were blended in the proportions listed in Table 1 below, and cured phenol resin particles f were prepared in the same manner as in the production of the cured phenol resin particles a. Got.

Also, phenol, 92% paraformaldehyde, gum arabic, 89% phosphoric acid and isodecyl acid phosphate were blended in the proportions listed in Table 1 below, and cured according to the same method as in the production of the cured phenol resin particles a. Phenol resin particles g were obtained.

  Cured phenol resin particles h were obtained in the same manner as in the production of the cured phenol resin particles c, except that 3 parts by weight of hydroxyethyl cellulose was used as the protective colloid instead of gum arabic.

  Further, cured phenol resin particles i were obtained in the same manner as in the production of cured phenol resin particles c except that 1-hydroxyethane 1,1-diphosphonic acid was used instead of 89% phosphoric acid.

  Further, cured phenol resin particles j were obtained in the same manner as in the production of cured phenol resin particles c except that phenoxyphosphazene was used instead of 89% phosphoric acid.

  About the various hardening phenol resin particle | grains obtained as mentioned above, the residual carbon ratio and phosphorus content were measured according to said method, respectively, and the result was combined with following Table 1, and was shown.

As is clear from the results in Table 1, the cured phenol resin particles b to j produced according to the method of the present invention are compared with the cured phenol resin particles a produced without using a specific compound. It was confirmed that the residual coal rate was high.

Claims (10)

Phosphoric acids, phosphate esters, phosphazene compounds, and general formula: R—PO (OH) _2, where R is a group containing a carbon atom and containing —COOH and / or —PO (OH) ₂ . A cured phenol resin particle for carbide, comprising at least one compound selected from the group consisting of organic phosphonic acids represented by the formula: Along with protective colloid, phosphoric acid, phosphoric acid ester, phosphazene compound, and general formula: R—PO (OH) _{2 wherein} R contains a carbon atom and —COOH and / or —PO (OH) ₂ It is a group containing. In the presence of at least one compound selected from the group consisting of organic phosphonic acids represented by the following formula, uncured phenol resin particles are produced by reacting phenols with aldehydes, and then the uncured phenol. A method for producing a cured phenol resin particle for carbide, wherein the resin particle is cured.   The production of cured phenol resin particles for carbide according to claim 2, wherein when the phosphoric acid is present, the reaction between the phenol and the aldehyde is performed in the presence of a phenol resin synthesis catalyst. Method.   The method for producing cured phenol resin particles for carbide according to claim 3, wherein the phenol resin synthesis catalyst is alkylbenzene sulfonic acid.   The method for producing cured phenol resin particles for carbide according to any one of claims 2 to 4, wherein the reaction is performed under a condition in which the organic phase and the aqueous phase are not separated.   The hardening for carbide according to any one of claims 2 to 5, wherein the phosphoric acids are present in a proportion of 0.01 to 10% by weight with respect to the phenol resin. A method for producing phenol resin particles.   The carbide according to any one of claims 2 to 5, wherein the phosphate ester is present in a proportion of 0.1 to 30% by weight with respect to the phenol resin. For producing cured phenolic resin particles.   A method for producing a carbide comprising firing the cured phenol resin particles for carbide according to claim 1.   A method for producing a carbide comprising firing the cured phenol resin particles for carbide obtained by the production method according to any one of claims 2 to 7. Phosphoric acids, phosphate esters, phosphazene compounds, and general formula: R—PO (OH) _2, where R is a group containing a carbon atom and containing —COOH and / or —PO (OH) ₂ . ] The residual-carbon-ratio improvement agent of the phenol resin containing the at least 1 sort (s) of compound chosen from the group which consists of organic phosphonic acid shown by these.