JPS61191573A - Resin reinforced porous carbon material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a porous carbon material reinforced by impregnation with a thermoplastic resin or a thermosetting resin, and a method for producing the same. The resin-reinforced porous carbon material of the present invention has excellent properties such as electrical conductivity, thermal conductivity, and corrosion resistance that carbon materials inherently have, as well as strength such as bending strength that is stronger than conventional porous carbon materials. It is particularly useful as a dust collection electrode for, for example, a Cottrell type electric collector II.

[Prior Art] In recent years, carbonaceous molded products based on carbonaceous materials such as carbon 111ft and carbon particles have been used in various industrial fields, and as technology advances and demand increases, Higher demands such as improved productivity and physical properties are increasing.

For example, porous carbon materials have excellent physical properties inherent to carbon materials, such as touch resistance, thermal conductivity, electrical conductivity, and strength, and they also have high porosity. It is used effectively in various fields by taking advantage of this.

Methods for manufacturing such porous carbon materials have already been described in many patent documents. For example, JP-A-58-1176
See 49.59-141170. According to the methods described in these patent documents, a porous carbon material molded product having a large porosity (a sharp pore size distribution) can be obtained.

One possible method of effectively utilizing the porosity, conductivity, strength, etc. of a porous carbon material is to use, for example, a Cottrell type dust collection electrode for an electrostatic precipitator. Such dust collection electrodes collect microparticles in the air by applying a high voltage to a porous conductor, but the ones used in the past are usually made of metal and have several drawbacks that need improvement. are doing. In other words, in the case of metals, it is difficult to obtain porous products with small pore diameters and a sharp size distribution, metals are easily susceptible to oxidative corrosion, and if they are made of metal, attached microparticles may discharge. metal is relatively heavy (for example, 2 to 6 times as heavy as carbon).

[Problems to be solved by the invention] The present inventors have discovered that the drawbacks of the metal dust collecting electrodes described above can be overcome by using a porous carbon material as the collecting v1 electrode. Furthermore, by coating the inner surface of the pores of the porous carbon material with a resin, it is possible to prevent the adhering microparticles from being discharged or re-scattering, and the strength of the porous carbon material of the product is greatly increased, making it possible to produce metal fruits! We have discovered that this method is comparable to or superior to Iden, and have arrived at the present invention.

That is, the present invention provides a collection Im! for, for example, a Cottrell type electrostatic precipitator. The purpose of the present invention is to provide a resin-reinforced porous carbon material that exhibits excellent performance as an electrode.

[Means for Solving the Problems] The resin-reinforced porous carbon material of the present invention has thermosetting resin or thermoplastic resin in the pores of the porous carbon material as a raw material in an amount of 1 to 70% of the pore volume; It is preferably impregnated at a ratio of 10 to 60%, has a bending strength of 150 kg/cm2 or more, and has a residual porosity of 10 to 60%, preferably 15 to 60%.
50% and gas permeability is 10I11/CII-hr
-1lIIIH20 or more.

The resin-reinforced porous carbon material of the present invention is manufactured as follows.

In one method, a predetermined amount of thermoset or thermoplastic resin is press-injected into the pores of a porous carbon material as a starting material. Pressing conditions are temperature 8 for thermosetting resin.
0-200℃, pressure 5-200Kg/co+2, for thermoplastic resin temperature 130-350℃, pressure 5-500K
g/cII2.

The thermosetting resin is appropriately selected from phenol resins, epoxy resins, furfuryl alcohol resins, and the like. The thermoplastic resin used in the present invention is appropriately selected from polyethylene, polyvinyl chloride, polystyrene, polymethacrylate, polyethylene oxide, polyethyl vinyl ether, polytetrafluoroethylene, polyvinylidene fluoride, polyphenylene sulfide, and the like.

In another method of the present invention, the thermosetting resin or thermoplastic resin as described above is dissolved in an organic solvent in a proportion of 1 to 50% by weight, preferably 5 to 40% by weight, and the resulting solution is used to form a porous carbonaceous material. It is impregnated into the pores of the material by an appropriate means, and then the organic solvent is removed by evaporation, followed by heat treatment at a temperature of 80 to 350° C. or higher for several minutes to several hours.

The organic solvent used in this method may be appropriately selected depending on the resin to be used, but organic compounds such as ethyl alcohol, methyl alcohol, methyl ethyl ketone, acetone, benzene, dilunaphthalene, toluene, and xylene are generally preferred. In yet another method, particles of the resin as described above are dispersed in water at a concentration of 1 to 80% by weight, preferably 10 to 70% by weight, and the resulting dispersion is dispersed into fine particles of a porous carbon material by an appropriate means. The resin is impregnated into the pores, and then the water is evaporated off by heating or in a vacuum, and the resin is further heated to a temperature of 80 to 400° C. for several minutes to several hours to melt and bond the resin.

In this case, it is preferable to use water containing a nonionic surfactant having an HLB of 8 or more at a concentration of 0.01 to 10% by weight as a dispersion medium. Examples of such surfactants include polyoxyethylene octylphenol ether (
TRITON X-100), etc.

In addition, in both methods, the starting material has a porosity of 50
~80% of its pores are 60. A porous carbon material in which % or more of the pore diameters are in the range of 10 to 80 μm is preferred. Methods for producing such materials are well known, and for example, the methods described in the above-mentioned patent documents can be used.

For example, 100 parts by weight of short flame fiber and 2 parts by weight of binder resin.
20 to 250 parts by weight of a pore-forming particulate material having a predetermined particle size distribution is added to a mixture consisting of 0 to 200 parts by weight per 100 parts by weight of the mixture, molded under heat and pressure, and fired to form fine pores. A method consisting of pyrolyzing the pore-forming particulate material can be used.

In this method, the pore-forming particulate material has an average particle size in the range of 10 to 200μ and a particle size distribution with a standard deviation of within 15μ, and the short flame fibers have a fiber diameter of 3 to 30μ and a fiber length of 2am.
It is preferable that the binder resin is a phenol resin or a furfuryl alcohol resin. Particularly preferable short flame fibers are oxidized pitch fibers in an inert gas atmosphere.
It is obtained by firing at a temperature of 0 to 3000°C.

The resin-reinforced porous carbon material of the present invention thus obtained has a bending strength of 150 to 9/cm2 or more, a residual porosity of 10 to 60%, preferably 15 to 50%, and gas permeability. The degree is 10ydllam -hr・jw+82
It is 0 or more. The short carbon m fibers in the resin-reinforced porous carbon material of the product are continuously bonded to each other by carbon without being interrupted by the thermosetting resin or thermoplastic resin. In addition, the electrical resistivity of the product when measured in the pressure direction during molding of the raw material porous carbon material is 50X10-3Ωα or less, and the thermal conductivity is 1, OkcaI2Im-hr.
Theal over −℃.

Note that this measurement value was measured after removing the resin covering the outer surface of the carbon material.

[Operations and Effects of the Invention] As described above, the resin-reinforced porous carbon material of the present invention has electrical resistance and thermal conductivity comparable to that of conventional porous carbon materials not impregnated with resin, and is porous. However, it can prevent carbon from peeling off due to friction from the carbon material surface, and has greater bending strength than conventional porous carbon materials.
For example, a collection of Cottrell type electrostatic precipitators! Particularly useful as an electrode. That is, when the resin-reinforced porous carbon material of the present invention is used as a collector electrode, it has higher resistance to oxidative corrosion than conventional metal electrodes.
It has remarkable effects such as being 2 to 1/6 lighter in weight, and furthermore, it is possible to prevent discharge of attached microparticles, thereby preventing re-scattering. Another advantage is that a porous conductor having a smaller diameter and a sharper pore size distribution than metals can be easily obtained.

In addition, the present invention is particularly applicable to electric precipitators! ! Although the case where it is used in electrodes has been described, various electrodes such as bioelectrodes, electrolytic cell electrodes, electromagnetic shielding materials, etc. can also be considered as applications that effectively utilize the above-mentioned excellent properties of the resin-reinforced porous carbon material of the present invention. .

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

30 parts by weight of Tomo Lfl short flame fiber (manufactured by Kenbetsu Kagaku Kogyo Co., Ltd., M-2048, average diameter 14 μm, average length 400 μm) and phenol resin (manufactured by Asahi Yokuzai Co., Ltd., RM-210, resol type) ), 60 parts by weight of polyethylene particles (manufactured by Mitsui Petrochemicals, Hi-ZEX 5100EP, average particle size 120μ, standard deviation 14μ) were added to a mixture consisting of 30 parts by weight, and the resulting homogeneous mixture was supplied to a press molding die. ,1
Molded at 40℃, 50Kg/CI2, about 30 minutes,
After curing at 140-'C10,5N9/cm2 for about 2 hours, the temperature was slowly raised to 700°C at a rate of 100°C/hour, and then to 2000°C and fired for about 1 hour.

The porous carbon material obtained had a porosity of 60%, an average pore diameter of 40μ, and a gas permeability of 290JIi! /cIR・hr
・awrH20, bending strength is 50Ky/CI2,
The electrical resistivity measured in the pressure direction during molding is 30×10-
3Ωα, thermal conductivity 1.2 kca! 2/m-hr-℃
Met.

Phenol resin (manufactured by Asahi Yokuzai Co., Ltd., RM-21O8,
(average particle size: 25 μm) was dissolved in methyl ethyl ketone in an amount of 20% by weight, and the porous carbon material was immersed in the solution at room temperature to impregnate the resin.

After impregnation, methyl ethyl ketone was removed by evaporation at room temperature for 1 hour.
It was heated at 140°C for 2 hours.

The obtained product (100 aw x 100 shoes x 3 shoes) has a carbon material part of 40% by volume, a resin part of 10% by volume, and a porosity of 50% by volume.
and the gas permeability is 180Id/α・hr・s+H2
0, bending strength is 170 Kff/cm2, electrical resistivity measured in the same manner as above (resin remaining on the surface of the product was removed) is 32X10-3Ω1, thermal conductivity is 1,
2kca! 2/TrL-hr-'C.

! 1u12 The phenolic resin RM-21O8 of Example 1 was placed on the upper and lower surfaces of the porous carbon material of Example 1, and heated at 150°C and 100K.
Press injection was performed at s/cm2.

The resin-reinforced porous carbon material thus obtained is the carbon material portion 40.
The volume is r%, the resin part is 30% by volume, and the porosity is 30% by volume,
Gas permeability is 35d/a・hr-a+H20, bending strength is 230 phantom/cm2, and electrical resistivity is 35X10.
'Ω drawing, thermal conductivity is 1.1kcau/m -hr-'
It was C.

At the end of the day, a solution of Teflon particles dispersed in an aqueous surfactant solution (60% Teflon, manufactured by Mitsui Fluorochemical Co., Ltd., 30-J, average diameter of dispersed particles 0.2μ) was applied to the porous carbon material of Example 1 at room temperature. Impregnated with After that, dry it at room temperature for about 1 hour, and then dry it for about 1 hour.
The dispersion medium was removed by evaporation at 0 Torr for 20 minutes, and then at 350 Torr.
Heated at ℃ for 30 minutes.

The obtained resin-reinforced porous carbon material has a carbon material portion of 40% by volume,
The Teflon part has a volumetric capacity of 30%, a porosity of 30% by volume, a gas permeability of 20ml/cm, a hr-amH20° bending strength of 160Ks/cm2, and an electrical resistivity of 30X1.
0-3Ωα, thermal conductivity 1.2 kcau/m-hr・
It was ℃. In addition, the product showed water repellency.

Example 4 Polyethylene (Mitsui Petrochemical Co., Ltd., 51'OOE)
P ) was injected into the porous carbon material of Example 1 at 180° C. and 100 Ky/cm 2 .

The resin-reinforced porous carbon material thus obtained is the carbon material portion 40.
The volume is 30% by volume, the resin part is 30% by volume, and the porosity is 30% by volume.
Gas permeability is 20d/as・hr-gH, 20, bending strength is 25 (1g/cm2), electrical resistivity is 38
X10'Ωα, thermal conductivity is 1.1kcau/m-hr-
'C was there.

Polyphenylene sulfide (manufactured by Kenbetsu Kagaku, average particle size 5)
00μ) was dissolved in chlornaphthalene at 220-230℃ (10% by weight), and the resulting solution was heated at 250℃, 1QTo
The porous carbon material of Example 1 was impregnated under reduced pressure of rr.

Thereafter, the solvent was removed by evaporation at 250° C. for 1 hour, and further heated in air at 300° C. for 10 minutes to perform an oxidative crosslinking reaction.

The resin-reinforced porous carbon material thus obtained is the carbon material portion 40.
The resin part is 5% by volume, the porosity is 55% by volume, and the gas permeability is 200ml/cIR-hr-trnH20.
, the bending strength is 240Ky/cm2, the electrical resistivity is 35X10'Ωcrn, and the thermal conductivity is 1.2kcau.
/m-hr-'C.

Example 6 The polyphenylene sulfide powder of Example 5 was heated to 300°C.
, 100 Kg/Cl12 was injected into the porous carbon material of Example 1.

The resin-reinforced porous carbon material thus obtained is the carbon material portion 40.
volume%, resin part 20% by volume, porosity 40% by volume,
Gas permeability is 60 d/cm・hr・wear H20, bending strength is 250 Ky/cm2, and electrical resistivity is 40
X10-3Ωα, thermal conductivity is 1.3 kcau/m −
hr-'Ctea OL.

Additionally, the product was alkali resistant.

Claims (23)

[Claims] (1) Thermosetting resin or thermoplastic resin is impregnated into the pores of the porous carbon material at a ratio of 1 to 70% of the pore volume, the bending strength is 150 kg/cm^2 or more, and the residual porosity is is 10-60%, gas permeability is 10ml/cm・hr
・Resin-reinforced porous carbon material with a value of mmH_2O or more. (2) The porosity of the porous carbon material as a raw material is 50 to 8
The resin-reinforced porous carbon material according to claim 1, wherein at least 60% of the pores have a pore diameter in the range of 10 to 80 μm. (3) The porous carbon material as a raw material is short carbon fiber 10
0 parts by weight and 20 to 200 parts by weight of a binder resin, 20 to 250 parts by weight of a pore-forming particulate material having a predetermined particle size distribution is added to 100 parts by weight of the mixture, and the mixture is heated and pressed. The resin-reinforced porous carbon material according to claim 2, wherein the resin-reinforced porous carbon material is produced by firing and thermally decomposing the pore-forming particulate material. (4) The resin-reinforced porous structure according to claim 3, wherein the short carbon fibers are continuously bonded to each other by carbon without being interrupted by thermosetting resin or thermoplastic resin. Quality carbon material. (5) Claim 3 or 4, characterized in that the pore-forming particulate material has an average particle size in the range of 10 to 200μ and a particle size distribution with a standard deviation of within 15μ. resin-reinforced porous carbon material. (6) Short carbon fibers have a fiber diameter of 3 to 30μ and a fiber length of 2m.
m or less
The resin-reinforced porous carbon material according to any one of Item 5. (7) The resin-reinforced porous structure according to claim 6, wherein the short carbon fibers are obtained by firing oxidized pitch fibers at a temperature of 400 to 3000°C in an inert gas atmosphere. Quality carbon material. (8) The resin-reinforced porous carbon material according to any one of claims 3 to 7, wherein the binder resin is a phenol resin or a furfuryl alcohol resin. (9) The resin-reinforced porous resin according to any one of claims 1 to 8, wherein the thermosetting resin is selected from the group consisting of phenolic resin, epoxy resin, and furfuryl alcohol resin. Quality carbon material. (10) A patent claim characterized in that the thermoplastic resin is selected from the group consisting of polyethylene, polyvinyl chloride, polystyrene, polymethacrylate, polyethylene oxide, polyethyl vinyl ether, polytetrafluoroethylene, polyvinylidene fluoride, and polyphenylene sulfide. The resin-reinforced porous carbon material according to any one of items 1 to 8. (11) Claims 3 to 1 characterized in that the electrical resistivity of the porous carbon material as a raw material measured in the pressurizing direction during molding is 50 x 10^-^3 Ωcm or less.
The resin-reinforced porous carbon material according to any one of Item 0. (12) Thermal conductivity measured in the pressing direction during molding of the porous carbon material as a raw material is 1.0 Kcal/m・hr・℃
The resin-reinforced porous carbon material according to any one of claims 3 to 11, which has the above properties. (13) The resin-reinforced porous material according to any one of claims 1 to 12, characterized in that a thermosetting resin or a thermoplastic resin is press-injected into the pores of the porous carbon material. Method of manufacturing carbon material. 14. The method of claim 13, wherein the thermosetting resin is selected from the group consisting of phenolic resins, epoxy resins and furfuryl alcohol resins. (15) Temperature of 80-200℃, 5-200kg/cm
15. The method according to claim 14, characterized in that a predetermined amount of thermosetting resin is press-injected at a pressure of ^2. (16) A patent claim characterized in that the thermoplastic resin is selected from the group consisting of polyethylene, polyvinyl chloride, polystyrene, polymethacrylate, polyethylene oxide, polyethyl vinyl ether, polytetrafluoroethylene, polyvinylidene fluoride, and polyphenylene sulfide. The method according to item 13. (17) Temperature of 130-350℃, 5-500kg/c
17. The method according to claim 16, characterized in that a predetermined amount of thermoplastic resin is press-injected at a pressure of m^2. (18) Thermosetting resin or thermoplastic resin is dissolved in an organic solvent at a ratio of 1 to 50% by weight, impregnated into the pores of the porous carbon material, then the organic solvent is removed by evaporation, and further heat-treated. A method for producing a resin-reinforced porous carbon material according to any one of claims 1 to 12. (19) As an organic solvent, ethyl alcohol, methyl alcohol, methyl ethyl ketone, acetone, benzene,
19. Process according to claim 18, characterized in that an organic compound selected from the group consisting of chlornaphthalene, toluene and xylene is used. (20) 1 to 1 particles of thermoplastic resin or thermosetting resin
Any of claims 1 to 12, which comprises dispersing in water at a concentration of 80% by weight, impregnating into the pores of a porous carbon material, then removing water by evaporation, and further heat-treating. A method for producing a resin-reinforced porous carbon material according to claim 1. (21) During dispersion, a surfactant selected from the group consisting of nonionic surfactants with an HLB of 8 or more is added to
21. A method according to claim 20, characterized in that water containing water in a concentration of ~10% by weight is used. (22) The porosity of the porous carbon material as a raw material is 50~
Claim 1, wherein at least 60% of the pores have a pore diameter in the range of 10 to 80μ.
The method according to any one of Items 3 to 21. (23) The porous carbon material as a raw material is short carbon fiber 1
00 parts by weight and 20 to 200 parts by weight of a binder resin with an average particle size in the range of 10 to 200 μm.
20 to 250 parts by weight of a pore-forming granular material having a particle size distribution with a standard deviation within μ is added to 100 parts by weight of the mixture, molded under heat and pressure, and fired to form a pore-forming granular material. 23. A method according to claim 22, characterized in that it is produced by a method comprising pyrolysis.