JPH0259179B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for obtaining a carbonized product having a fine mosaic-like anisotropic structure. Carbonized materials have excellent properties such as heat resistance, abrasion resistance, and chemical resistance, so they are used in a variety of applications. Conventionally, tar pitch has been mainly used as a raw material for forming carbon structures. On the other hand, there is a phenolic resin as a raw material for forming a carbon structure. Phenol resin has a higher percentage of residual carbon after carbonization than other materials. For this reason, the carbonized product is dense and has excellent properties such as strength, abrasion resistance, and chemical resistance.There are many types of phenolic resins, but the one that best suits the application and usage conditions. It has excellent features such as being able to select and use different materials, and being a general-purpose resin, the quality is consistent. However, carbonized products obtained from phenolic resins also have drawbacks such as poorer oxidation resistance when exposed to high temperature atmospheres than carbonized products obtained from tar pitch. Furthermore, the carbonized product obtained by simply mechanically mixing tar pitch and phenolic resin may have the effect of promoting an increase in the residual carbon ratio, but the carbonized product itself has a large anisotropy with a flow structure generated from tar pitch. This results in a heterogeneous mixture of a carbonized part with a structure and a carbonized part with an isotropic structure generated from the phenolic resin. The reality is that such mixtures are of low quality and have limited practical applications. Generally, when carbonized products are observed using a polarizing microscope, the carbonized products of tar pitch have a large anisotropic structure with a flow structure, and the carbonized products of phenolic resin alone have an isotropic structure. In addition, after simply mechanically mixing phenolic resin and tar pitch,
The fact is that the carbonized product obtained by carbonizing this could not be expected to uniformly form a fine mosaic-like anisotropic structure. That is,
Even if it is observed that a fine mosaic-like anisotropic structure is generated locally, it is extremely difficult to form a fine mosaic-like structure over a wide area, and it is difficult to put it into practical use as an industrially useful material. It was possible. The large mosaic-like anisotropic structure that is originally produced by carbonizing tar pitch is resistant to air oxidation and adheres well to aggregate, but it is prone to cracking, and its low strength is a fatal drawback. It was hot. This has been a major obstacle to the practical application of tarpitz carbonized products. As a result of intensive research by the inventors to overcome the above-mentioned drawbacks, we found that by carbonizing a solution consisting of a solvent in which more than 50% of the total weight of tar pitch and phenol resin are soluble in an aromatic hydrocarbon system, We obtained a new finding that carbonized products with a uniform and fine anisotropic mosaic structure are formed. It has also been found that the carbonized product produced in this way has a significant reduction in brittleness, which is a drawback of isotropic carbonized products, even though the phenol resin, which is an isotropic carbonized product component, is present. The uniform and fine mosaic-like anisotropic structure according to the present invention improves properties such as strength, wear resistance, and air oxidation resistance of carbonized materials, and is widely useful in various applications that require these properties. . Here, the characteristics of the substances constituting the composition according to the present invention will be described. First, regarding the separation of tar pitch according to the present invention, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, etc. are used alone as aromatic hydrocarbon solvents for separating tar pitch. Or they can be used together. In particular, benzene, toluene, and xylene are preferably used alone or in combination. In order to carry out the present invention preferably, it is sufficient to use a tar pitch which is separated in this way and which dissolves 50% by weight or more of the tar pitch in the aromatic hydrocarbon solvent. In order to carry out the present invention more preferably, a substance that can be completely dissolved in the aromatic hydrocarbon solvent by fractionation is used. After separating tar pitsu, 50% of tar pitch was found to be an aromatic hydrocarbon solvent.
Those that dissolve less than % by weight should be avoided because they contain too much insoluble matter, which makes the structure of the carbonized material non-uniform. The type of tar pitch used in the present invention is preferably coal tar pitch, petroleum tar pitch, or a mixture of both. The phenolic resin used in the present invention can be a resol type phenolic resin, a novolak type phenolic resin, or a mixture of the two, and among these, a resol type phenolic resin is preferred. The organic solvent in which these tarpitz and phenol resin are soluble is one selected from compounds having alcohol groups, ketone groups, ester groups, and ether groups, hydrocarbons, and nitrogen-containing compounds that are liquid at room temperature. Although the solvent contains more than one type of solvent, a mixed solvent of two or more of these types is often most effective. The blending ratio of tar pitch, phenolic resin, and solvent used in the composition for forming a carbonized product having a finely anisotropic structure of the present invention is 20 to 80% by weight of tar pitch that is soluble at least 50% by weight in an aromatic hydrocarbon solvent.
and phenolic resin 80-20% by weight total weight 100
10 parts by weight of each soluble organic solvent
Parts by weight or more. Among them, Tarpitz 30 to 70% by weight, which is soluble at least 50% by weight in aromatic hydrocarbon solvents, and 70 to 30% by weight of resol type phenolic resin (calculated as non-volatile content), or the above-mentioned Tarpitz 40 to 70% by weight.
It is preferable that the above-mentioned tarpitch and the solvent in which the phenolic resin is soluble is 20 parts by weight or more relative to the total weight of 100 parts by weight in each case of 80% by weight and 60 to 20% by weight of novolak type phenolic resin. If the tar pitch, which is soluble at least 50% by weight in the aromatic hydrocarbon solvent, is outside the range of 20 to 80% by weight, and the phenolic resin is outside the range of 80 to 20% by weight, the total weight is 100 parts by weight. On the other hand, if the organic solvent in which each is soluble is less than 10 parts by weight, the carbonized product will not form a fine anisotropic structure over a wide area, and even if it does form, it will only be localized. Since it only remains in the tissue, it has no characteristics compared to conventional phenolic resins or carbonized tarpitz. The phenols used in the production of the phenolic resin of the present invention include phenol, cresol, xylenol, ethylphenol, propylphenol,
These include propenylphenol, butylphenol, octylphenol, nonylphenol, phenylphenol, catechol, resorcinol, hydroquinone, and bisphenol A, and the practice of the present invention also involves by-products produced when producing these phenols. include. on the other hand,
As the aldehyde used in the production of this phenolic resin, formaldehyde, paraformaldehyde, trioxane, polyoxymethylene, etc. can be used, but in short, as long as the composition expresses formaldehyde in a desired amount, any composition may be used for the purposes of this invention. Can be used. Further, the usage ratio of phenols P and aldehydes F (molar ratio: F/P) is preferably 0.8 to 2.0, more preferably 1.0 to 1.6 in the case of producing a resol type phenolic resin. On the other hand, in the case of novolak type phenolic resin production, the usage ratio is
0.55~0.90 is preferable, more preferably 0.65~
It is 0.85. The catalysts used in the production of resol-type phenolic resins include oxides, hydroxides, and carbonates of alkali metals such as sodium, potassium, and lithium, and oxides and hydroxides of alkaline earth metals such as calcium, magnesium, and barium. Furthermore, amine compounds such as ammonia, triethylamine and triethanolamine, naphthenic acid metal salts such as lead naphthenate, zinc naphthenate, lead naphthenate, nickel naphthenate, and cobalt naphthenate can be used alone or in combination. . On the other hand, the catalysts used in the production of novolac type phenolic resins include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as oxalic acid, phenolsulfonic acid, p-toluenesulfonic acid, and metaxylenesulfonic acid; One or more substances selected from organic metal salts such as zinc acetate are used. The composition according to the present invention has a specific composition of tar pitch, the phenolic resin enhances the caking action of the tar pitch, and the presence of an organic solvent in which both of these components are soluble allows the composition to be uniformly distributed. Compared to raw materials for carbonized products, carbonized products having a fine mosaic-like anisotropic structure can be easily and reliably produced over a wide range of areas. Therefore, carbonized products with industrially useful properties can only be obtained by using the constituent components of the present invention. Therefore, the produced carbonized product has a wide range of uses, including carbon fiber/carbon composite materials, carbon product molding, carbon product impregnation, refractory molding, refractory modeling, and refractory impregnation. EXAMPLES The present invention will be explained in detail below using Examples, but the present invention is not limited by the Examples. Note that "parts" and "%" described in the production examples, examples, and comparative examples all represent "parts by weight" and "percent by weight." Production example 1 Sorting of tar pitch Softening point according to JIS K 2425 is 109.5℃, BI amount is
Coal-based tar pitch 100 with 38.3% and QI amount of 16.0%
400 parts of benzene was added to the mixture, and the mixture was stirred at room temperature for 24 hours. After evaporation, the liquid was freeze-dried to obtain 62 parts of benzene-soluble tarpitch (BS). 120 parts of pyridine was added to 30 parts of the residue, and the mixture was stirred at room temperature for 24 hours.
After this, the liquid was heated to 80-90°C under reduced pressure to remove most of the pyridine. Further decompression 150
Pyridine was removed by holding at ℃ for 3 hours, and benzene-insoluble-pyridine-soluble tarpitz (BI-PS) was prepared.
I got the department. Production Example 2 Fractionation of Tar Pitch 400 parts of benzene was added to 100 parts of petroleum tar pitch having a softening point of 114.0° C. according to JIS K 2425, and the mixture was stirred at room temperature for 24 hours. After evaporation, the liquid was freeze-dried to obtain 93 parts of benzene-soluble tarpitch (BS). Production Example 3 Production of resol type phenolic resin 1000 parts of phenol and 1120 parts of 37% formalin were charged into a reaction apparatus equipped with a stirrer, a reflux condenser and a thermometer, and 80 parts of a 25% aqueous sodium hydroxide solution was added. After the contents are heated and the temperature reaches 80℃
The reaction was allowed to proceed for 150 minutes. Thereafter, the pH was adjusted to 7.0 with formic acid, and a dehydration reaction was performed under reduced pressure of 40 to 60 mmHg.
When the internal temperature reached 85°C, the pressure was returned to normal to obtain 1380 parts of resol type phenolic resin. This resol type phenolic resin had a viscosity of 110 poise at 40°C and a non-volatile content of 85% (the measurement method was JIS
K 6909). Production Example 4 Production of resol type phenolic resin 1000 parts of phenol and 1000 parts of 37% formalin were charged into a reaction apparatus of the same type as Production Example 2, and 45 parts of 28% ammonia water and 40 parts of 25% sodium hydroxide aqueous solution were added. After the contents are heated and the temperature reaches 70℃ 5
Allowed time to react. Then adjust the pH to 7.5 with acetic acid,
The dehydration reaction was carried out under reduced pressure of 40-60 mmHg. When the internal temperature reached 88°C, the pressure was returned to normal to obtain 1330 parts of resol type phenolic resin. This resol type phenolic resin had a viscosity of 320 poise at 40°C and a non-volatile content of 86% (all measurement methods were JIS K).
6909). Production Example 5 Production of novolac type phenolic resin 1000 parts of phenol and 710 parts of 37% formalin were charged into a reaction apparatus equipped with a stirrer, a reflux condenser, and a thermometer, and 10 parts of oxalic acid was added thereto and the temperature was raised. After the temperature reached 100°C, a reflux reaction was carried out for 90 minutes, and then the pressure was gradually reduced from normal pressure to carry out a dehydration reaction. When the internal temperature reaches 150℃ under a reduced pressure of 40mmHg, the dehydration reaction ends and the novolak type phenolic resin
Obtained 1030 copies. The above novolak type phenolic resin
1000 parts hexamethylenetetramine as curing agent
Add 100 parts, pulverize together, and mix thoroughly.
A powdered novolak type phenolic resin was obtained. This powdered novolac-type phenolic resin containing hexamethylenetetramine has a melting point determined by the capillary method.
The sieve residue when measured at 89°C and a 105μ sieve was 3%, and the gelation time by the hot plate method at 150°C was 121 seconds (all measurement methods were in accordance with JIS K 6909). Example 1 300 parts of pyridine was charged into a mixing apparatus equipped with a stirrer, a reflux condenser, and a thermometer, and while stirring,
The softening point according to JIS K 2425 is 112.5℃, and the amount of BI is
Coal-based tar pitch 100 with 33.5% and QI amount of 13.3%
part was gradually added and dissolved at room temperature. Thereafter, 200 parts of a mixture of 100 parts of resol type phenolic resin obtained in Production Example 3 and 100 parts of ethylene glycol was added to obtain a mixed solution, and a microscopic difference consisting of tarpitz/resol type phenolic resin/solvent system was added. 600 parts of a composition for forming a carbonized product having an orthogonal structure was obtained. Example 2 300 parts of pyridine was charged into a mixing device of the same type as in Example 1, and while stirring, the coal-based mixture obtained in Production Example 1 was added.
100 parts of BS was gradually added and dissolved at room temperature. After that, the resol type phenolic resin obtained in Production Example 3
Add and mix 200 parts of a mixture of 100 parts of 100 parts of ethylene glycol and 100 parts of ethylene glycol to make a homogeneous solution, and create a composition for forming a carbonized product with a finely anisotropic structure consisting of BS/resol type phenolic resin/solvent system. Obtained 600 copies. Example 3 300 parts of toluene was charged into a mixing device of the same type as in Example 1, and while stirring, the coal-based mixture obtained in Production Example 2 was added.
100 parts of BS was gradually added and dissolved at room temperature. After that, the resol type phenolic resin obtained in Production Example 4
Add and mix 200 parts of a mixed solution of 100 parts of Cellosolve and 100 parts of Cellosolve to make a homogeneous solution,
Composition for forming carbonized products with fine anisotropic structure consisting of BS/resol type phenolic resin/solvent system
Got 600 copies. Example 4 300 parts of benzene was charged into a mixing device of the same type as in Example 1, and while stirring, the coal-based mixture obtained in Production Example 1 was added.
100 parts of BS was gradually added and dissolved at room temperature. After that, the resol type phenolic resin obtained in Production Example 3
Add and mix 200 parts of a mixture of 100 parts of 100 parts of ethylene glycol and 100 parts of ethylene glycol to make a homogeneous solution, and create a composition for forming a carbonized product with a finely anisotropic structure consisting of BS/resol type phenolic resin/solvent system. Obtained 600 copies. Example 5 300 parts of toluene was charged into a mixing device of the same type as in Example 1, and while stirring, the coal-based mixture obtained in Production Example 1 was added.
100 parts of BS was gradually added and dissolved at room temperature. After that, the resol type phenolic resin 50 obtained in Production Example 4 was
and 100 parts of ethylene glycol were mixed in advance, and 100 parts of the novolak type phenolic resin containing hexamethylenetetramine obtained in Production Example 5 were gradually added to make a homogeneous solution.
600 parts of a composition for forming a carbonized product having a finely anisotropic structure consisting of BS/resol type phenolic resin/novolac type phenolic resin/solvent system was obtained. Example 6 300 parts of pyridine was charged into a mixing device of the same type as in Example 1, and while stirring, the coal-based mixture obtained in Production Example 1 was added.
100 parts of BS was gradually added and dissolved. Thereafter, 100 parts of ethylene glycol and 100 parts of the novolak type phenolic resin containing hexamethylenetetramine obtained in Production Example 5 were gradually added to make a homogeneous solution.
600 parts of a composition for forming a carbonized product having a finely anisotropic structure consisting of a novolak type phenolic resin/solvent system was obtained. Comparative Example 1 The coal-based BS obtained in Production Example 1 was pulverized using a mortar. Amount of finely ground coal-based BS that passes through a 105μ sieve
Thoroughly knead 100 parts and 100 parts of the resol type phenolic resin obtained in Production Example 3 into a paste at room temperature.
200 parts of a composition for carbonized products consisting of a BS/resol type phenolic resin system was obtained. Comparative Example 2 The coal-based BS obtained in Production Example 1 was pulverized using a mortar. 100 parts of the finely ground BS that passed through a 105 μ sieve and 100 parts of the novolak type phenolic resin containing hexamethylenetetramine obtained in Production Example 5 were thoroughly mixed mechanically into powder using a laboratory mixer, and the BS/novolak type phenolic resin system was mixed. 200 parts of a composition for carbonide was obtained. Comparative Example 3 The coal-based BI-PS obtained in Production Example 1 was pulverized using a mortar. 100 parts of the finely ground BI-PS that passed through a 105μ sieve and 100 parts of the resol type phenolic resin obtained in Production Example 4 were sufficiently kneaded into a paste at room temperature to obtain a composition for carbonized products consisting of a BS/resol type phenolic resin system. Got 200 copies. Comparative Example 4 200 parts of pyridine was charged into a mixing device of the same type as in Example 1, and while stirring, the coal-based mixture obtained in Production Example 1 was added.
Gradually add and dissolve 100 parts of BS at room temperature, and
300 parts of a composition for carbonized material consisting of a solvent system was obtained. Comparative Example 5 200 parts of pyridine was charged into a mixing device of the same type as Example 1, and while stirring, 100 parts of the resol type phenolic resin obtained in Production Example 3 was gradually added and dissolved at room temperature to form a resol type phenolic resin/solvent. 300 parts of a composition for carbonized material consisting of the system was obtained. Comparative Example 6 200 parts of pyridine was charged into a mixing device of the same type as in Example 1, and while stirring, 100 parts of the novolak type phenolic resin obtained in Production Example 5 was gradually added and dissolved at room temperature to form a novolak type phenolic resin/solvent. 300 parts of a composition for carbonized material consisting of the system was obtained. The compositions for forming carbonized products having a fine anisotropic structure obtained in Examples 1 to 6 and the compositions for forming carbonized products obtained in Comparative Examples 1 to 6 were each maintained at a maximum temperature of 60°C for one day and night while being suctioned with an aspirator. to remove the solvent. After that, it was kept at 120℃ for 5 hours in a dryer, and then placed in an electric furnace for 200℃ in a nitrogen stream.
Post-curing took 5 hours at .degree. The post-cured solid material was placed in a test tube, heated to 600°C at a rate of 1°C per minute in a nitrogen stream, and held at the same temperature for 3 hours. The results of polarizing microphotographs of the carbonized products produced were as shown in Table 1 and Figures 1 to 10. It has been revealed that the carbonized product obtained from the composition of the present invention consists of an almost perfect fine mosaic-like anisotropic structure. On the other hand, formation of such a structure was hardly observed in the carbonized products obtained from the carbonized product compositions shown in each comparative example. 【table】

[Brief explanation of drawings]

Figures 1, 2, 3, 4, 5, and 6 are polarized light micrographs at 300x magnification, showing that the structure of the carbonide is almost completely micro-anisotropic. Figures 7, 8, and 9 are polarized light micrographs taken at 300x magnification, showing that the carbonized structure is a mixture of flow-type anisotropy and isotropy. Figure 10 is a polarized light micrograph at 300x magnification, showing that the structure of the carbonide is of a flow type.

Claims (1)

[Scope of Claims] 1. Fine anisotropy comprising a dissolved substance consisting of tar pitch which is soluble at least 50% by weight in an aromatic hydrocarbon solvent, a phenolic resin, and an organic solvent in which each is soluble. A composition for forming carbonized products having a structure. 2. For 100 parts by weight of the total weight of 20-80% by weight of tar pitch, which is soluble at least 50% by weight in aromatic hydrocarbon solvents, and 80-20% by weight of phenolic resin,
A composition for forming a carbonized product having a finely anisotropic structure according to claim 1, having a composition in which each of the organic solvents is soluble in an amount of 10 parts by weight or more. 3. Claim 1, wherein the tar pitch that is soluble at least 50% by weight in the aromatic hydrocarbon solvent is one selected from coal tar pitch, petroleum tar pitch, or a mixture of coal tar pitch and petroleum tar pitch, or 3. The composition for forming a carbonized product having a finely anisotropic structure according to item 2. 4. The composition for forming a carbonized product having a finely anisotropic structure according to claim 1 or 2, wherein the phenolic resin is a resol type phenolic resin. 5. The composition for forming a carbonized product having a finely anisotropic structure according to claim 1 or 2, wherein the phenolic resin is a novolak type phenolic resin. 6. The composition for forming a carbonized product having a finely anisotropic structure according to claim 1 or 2, wherein the phenolic resin is a mixture of a resol type phenolic resin and a novolak type phenolic resin. 7. The organic solvent is a solvent that is liquid at room temperature and contains one or more compounds selected from alcohol groups, ketone groups, ester groups, ether groups, hydrocarbons, and nitrogen-containing compounds. A composition for forming a carbonide having a finely anisotropic structure according to item 1 or 2.