JPS61132507A - Carbonaceous fine strands - Google Patents

Abstract

PURPOSE:Carbonaceous fine strands that are obtained by pyrolyzing hydrocarbons in the presence of a specific organometallic compound so that a plurality of carbon spherical particles are connected in the lengthwise direction, thus showing good wettability with a resin and high conductivity. CONSTITUTION:hydrocarbon such as anthracene, benzene or ethylene and an organometallic compound such as bis (cyclopentadienyl) iron or nickel carbonyl are introduced, when needed, together with a carrier gas such as helium or argon, into the reaction zone where the hydrocarbon is catalytically pyrolyzed at 900-1,300 deg.C. Thus, primary carbon particles of 1-3 micron diameter are connected in the lengthwise direction to give the objective carbon strands of an aspect ratio less than 500. The carbon strands are suitable for use as a reinforcement material for resins and as electrode plates.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a carbonaceous chain, and more particularly to a carbonaceous chain having properties intermediate between carbon fibers and carbon granules (carbon black). It is.

BACKGROUND OF THE INVENTION Carbon materials have excellent mechanical and physical properties, so they are rapidly gaining popularity as various composite materials in recent years. These materials can be broadly divided into two types: carbon fibers and carbon particles (carbon blanks), but the carbonaceous chain body of the present invention is located between carbon fibers and carbon black, and takes advantage of its unique properties. It is expected that this material will be used in various composite materials and other applications.

(Prior art and its problems) Among the carbon materials mentioned above, carbon fiber has poor wettability with the base resin, so it is desirable to make the diameter as thin as possible and increase the contact area. There is an upper limit.

On the other hand, carbon blank has a small particle size, so there is no problem with wettability, but since each particle is dispersed and exists in the base resin, mechanical and physical properties are poor. Many of them were inferior to carbon fibers, and also lacked easy graphitization, which is advantageous as a conductive material. For this reason, it has been desired to develop a carbon material that overcomes these drawbacks.

An object of the present invention is to eliminate the drawbacks of conventional carbon fibers and granular carbon, and to provide an easily graphitizable carbonaceous chain body having properties intermediate between these.

(Means for solving the problem) In order to achieve the above object, the carbonaceous chain body of the present invention has 1
A chain carbonaceous particle formed by longitudinally connecting a plurality of carbonaceous spherical particles each having a diameter of 1 to 3μ, the ratio of the length of the chain carbon particle to the diameter of the spherical particle being 500 or less. (
preferably from 10 to 500).

The carbonaceous chain bodies of the present invention include not only one-dimensional chain bodies but also two-dimensional and three-dimensional chain bodies.

If the diameter of the carbonaceous spherical particles does not reach 1μ, the bonding force between the particles will be weak, and the strength of the composite will decrease.
Moreover, if it exceeds 3μ, the adhesiveness of the resin will deteriorate. When the ratio of the length of the chain particles to the diameter of the spherical carbon particles (p) exceeds 500, the strength of the composite material tends to be insufficient. This is considered to be because the strength of the chain particles decreases with respect to stress in the radial direction.

In addition, the carbonaceous chain particles of the present invention have a crystal size in the C-axis direction measured by powder X-ray diffraction method (Carbon Materials Experimental Technology (1), p. 55, published by Science and Technology Company, June 1, 1978). When Lc=50Å or less, the (002) plane spacing (iooz”3
．． It is preferable to have a thickness of 45 Å or more. In addition, when the carbonaceous chain particles are heat-treated at 2000°C or higher to graphitize, the crystal size in the C-axis direction Lc = LOOÅ or more and the (002) plane spacing dooz = 3.45Å or less. It is desirable to have high orientation. Graphitized chain particles with such high orientation were found to have extremely high electrical conductivity compared to carbon black and the like. Furthermore, since the primary particles were connected, it was found that the electrical conductivity was significantly improved even when the resin was filled into a resin as a composite material.

The carbonaceous chain particles of the present invention are produced by introducing a hydrocarbon and a specific organometallic compound into a reaction zone together with a carrier gas if necessary, and subjecting the hydrocarbon to thermal decomposition and catalytic reaction.

The hydrocarbons used in the present invention are not particularly limited, and include hydrocarbons that are solid at room temperature including anthracene, naphthalene, etc., hydrocarbons that are liquid at room temperature including benzene, toluene, hexane, isooctane, etc., or methane. , propane, ethylene, acetylene, and the like.

Examples of the organometallic compound used in the present invention include compounds of metals belonging to Group 1 Va, Group Va, Group Vla, and Group II of the periodic table, particularly cyclopentadienyl metal compounds, carbonyl metal compounds, and benzene. - metal compounds, alkyl, allyl or alkynyl metal compounds, β-diketone metal complexes, keto acid ester metal complexes, substituted products thereof,
Derivatives and the like are preferably used. Among these, cyclopentagenyl compounds such as bis(cyclopentagenyl) iron, nickel or cobalt, iron carbonyl, nickel carbonyl, cobalt carbonyl, bis(cyclopentadienyl carbonyl) iron, nickel, or cobalt, etc. β-diketone metal complexes such as iron, nickel or cobalt complexes of di- or triacetylacetone, iron, nickel or cobalt complexes of di- or triacetoacetic acid esters, or derivatives thereof, etc. give good results.

As a carrier gas, helium, argon, xenon, hydrogen, nitrogen, or a mixture thereof can be used. Inert gases such as argon are used for displacement, and hydrogen etc. are used for controlling the concentration of hydrocarbons, etc. be done. The amount of these carrier gases varies depending on the type of hydrocarbon and the size of the reaction tube, but is, for example, 1000 to 5000 mj! It is set to a certain degree.

The method for supplying the organometallic compound includes directly heating them and supplying them in a gaseous state, or dissolving the organometallic compound in a hydrocarbon liquid and heating it and supplying it or ejecting it. Methods such as doing this are used.

Supply amount of the above organometallic compound (supply weight % per light per minute)
) is 0.01% by weight or more based on the mixture with hydrocarbon,
Preferably it is 0.5 to 20% by weight.

For example, when the organometallic compound is bis(cyclopentadienyl) iron and the hydrocarbon is benzene, good results can be obtained if the amount of bis(cyclopentadienyl) iron used is set to 1 to 10% by weight.

The temperature range for introducing hydrocarbons and organometallic compounds is 50
A suitable temperature is 0°C or lower, preferably 100 to 500°C.

Further, the appropriate reaction heating temperature range is 900 to 1300°C. Note that the organometallic compound and the hydrocarbon may be mixed in advance and then supplied to the reaction zone.

Hereinafter, the manufacturing method and characteristics of the carbonaceous chain body of the present invention will be explained in detail with reference to drawings and photographs substituted for drawings.

FIG. 1 shows an experimental apparatus for producing the carbonaceous chain body of the present invention. This device includes a furnace core tube 2 inserted into an electric furnace 1 and a seal plug 16 provided on the inlet side of the furnace core tube 2.
an inert gas etc. introduction pipe 4 and a hydrocarbon introduction pipe 3 provided through the furnace core tube 2; a gas discharge pipe 14 inserted into a seal plug 13 provided on the outlet side of the furnace core tube 2;
A receiver for the carbonaceous chain body provided at the lower part of the furnace core tube is a plate 12.
, a metering pump 5, valves 7 and 8 provided on the hydrocarbon introduction pipe 3, and the hydrocarbon introduction pipe 4.
a sealed container 89 for supplying hydrocarbons to the container, hydrocarbons 6 and an inert gas supply pipe 10 contained in the sealed container;
It mainly consists of.

In the above device, the temperature of the furnace core tube 2 is set to 500 to 1300.
After setting the temperature to about .degree. C., hydrogen gas or inert gas (nitrogen, argon, etc.) is introduced from the introduction pipe 4 to replace the inside of the furnace core tube. Inert gas is supplied from the introduction pipe 10 to the sealed container 9 of the hydrocarbon 6, the valve 7.8 is opened, and the metering pump 5 is operated to supply the hydrocarbon from the introduction pipe 3 and at the same time, the carrier is introduced from the introduction pipe 4. Gas is supplied to simultaneously supply hydrocarbons and metal compounds to the reaction temperature range. After reacting for a predetermined period of time, the produced carbonaceous chains are collected in a tray 12 at the bottom of the furnace core tube, and after the reaction is completed and the furnace is cooled, it is taken out to the outside.

The carbonaceous chain body thus obtained has a diameter of 1 to 3 μm.
A plurality of carbonaceous spherical particles connected in the longitudinal direction,
The ratio of the length of the connected particles to the diameter of the spherical particles is 10 to 50.
It was within the range of 0.

(Effects of the invention) The carbonaceous chain body of the present invention has good wettability with resin, provides an excellent reinforcing effect when made into a composite material, and has excellent electrical conductivity because it has connected particles. It is something. Therefore, the carbonaceous particles of the present invention can be widely used not only as reinforcing materials for resins but also as electrical materials such as electrode plates.

(Example) Example 1 An alumina furnace core tube 2 with an inner diameter of 60 m and both ends sealed with rubber plugs was installed in the tube furnace shown in Fig. 1, and one of the rubber plugs 1 was installed.
An alumina pipe 4 having an inner diameter of 6 mm was passed through the tube 6, and the outlet of the pipe 4 was placed at a position of 450° C. when the temperature rose to the set temperature of the furnace core tube (1100° C.). on the other hand,
The inlet side of the pipe 4 is connected to a metering pump 5 via a soft tube.
and further inserted into the closed container 9 via a pipe. A raw material solution 6 in which 10% by weight of biscyclopentadienyl iron was dissolved in benzene was placed in a closed container so that it could be supplied to the furnace core tube 2 by the metering pump 5. Further, the rubber stopper 16 was set so that an inert gas for replacing the inside of the furnace and hydrogen gas as an aid for fiber growth could be introduced from the pipe 4. Raw material liquid 1cc/mi at furnace temperature 1100℃
While carrying n with 1200 cc/+nin of hydrogen gas, it was supplied for about 10 minutes. After that, the furnace is cooled and the receiver is placed in the tray 12.
The carbonaceous filaments collected were taken out. The yield is about 4.
It was 5g.

When the obtained carbonaceous chain was observed with an electron microscope, it was found that
The particle size was 2 to 2.5 microns, and the chain length/particle size was about 300 or less. Figure 2 shows this scanning electron micrograph. Further, when this material was examined by the powder X-ray diffraction method described above, Lc = 33 people, dooz = 3.4g, and ivy.

Example 2 The carbonaceous chain body obtained in Example 1 was heated at 2700°C for 30 minutes.
After heat treatment in an argon gas atmosphere, powder X-ray diffraction was performed, and it was found that Lc = 250 people and dooz - 3.40 people.

Example 3 25% by weight of the carbonaceous chain obtained in Example 1 was mixed into an epoxy resin to obtain a compression molded product. This volume resistivity was 3Ω.

Comparative Example 1 Commercially available acetylene black was mixed into an epoxy resin in an amount of 40% by weight and molded in the same manner as in Example 3. The volume resistivity was 10Ω.

The bending strength of the resin molded products obtained in Example 3 and Comparative Example 1 was measured according to ASTM 0790. The results are shown below.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of an experimental apparatus for producing the carbonaceous chain body of the present invention, and FIG. 2 is a diagram showing a scanning electron micrograph of the carbonaceous chain body obtained by the present invention. be. 1... Electric furnace, 2... Furnace core tube, 3.4... Introducing pipe, 5... Metering pump, 6... Electric power, 7.8...
・Valve, 9... Airtight container, 12... Receiver is a plate, 13
．． 16... Seal plug, 14... Discharge pipe, 15.
...Produced carbonaceous chains. Agent: Takeshi Kawakita (Long procedural amendment writing method) March 29, 1985 1, Indication of the case 1982 Patent Application No. 253553 2, Title of the invention Carbonaceous chain body 3, Person making the amendment Relationship to the incident Patent applicant address 1-2-6 Eijimahama, Kita-ku, Osaka-shi, Osaka Name (003) Asahi Kasei Corporation Representative Teru Miyazaki 4, agent 103 Address Nihonbashi, Chuo-ku, Tokyo Kayabacho-chome 11-8 (
(Shipping date: March 26, 1985) 6. Subject of amendment: Brief description of drawings in the specification. 7. Contents of the amendment (1) "Diagram showing a scanning electron micrograph" on page 12, lines 2 to 3 of the specification has been changed to micrograph 1 of the r-connected grain structure. that's all

Claims (2)

[Claims] (1) A chain carbonaceous particle formed by connecting a plurality of carbonaceous spherical particles with a primary particle diameter of 1 to 3μ in the longitudinal direction,
The ratio of the length of the chain carbon particles to the diameter of the spherical particles is 50
A carbonaceous chain body characterized by having a carbonaceous chain of 0 or less. (2) The carbonaceous spherical particles are formed by arranging layers of graphite or carbon that is easily converted into graphite in an annual ring shape parallel to the longitudinal axis. carbonaceous chains.