JPS58134179A - Preparation of mesophase pitch - Google Patents

Abstract

PURPOSE:To prepare mesophase pitch, economically, in high efficiency, by heating and stirring a petroleum pitch under specific conditions, leaving the heat- treated pitch at rest to effect the exclusive growth and fusion of the mesophase, and separating the mesophaase from the non-mesophase. CONSTITUTION:A petroleum pitch or tar pitch available at an extremely low cost is heated under stirring preferably at 360-450 deg.C in a non-oxidizing gas flow under atmospheric or positive pressure to develop the mesocomponent in the thermally produced pitch. The pitch is left at rest to effect the exclusive growth and fusion of the mesophase in the thermally produced pitch, and the meso phase is separated from the non-mesophase. A 100% mesophase pitch composed of Q.I component and Q.S component can be obtained by this process. The content of mesophase in the pitch produced by the heating under stirring is preferably 10-50%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention describes the use of 100% carbon fiber as a raw material for high strength and high modulus carbon fiber.
The present invention relates to the production of Chimesophase pitch, and aims to provide a method for producing highly acidic and highly elastic carbon fibers, which are particularly suitable as raw materials for composite materials, with high efficiency and low cost.

The present invention deals with petroleum-based carbonization of residual carbon substances produced by thermal catalytic fractionation (FCC) of vacuum gas oil or thermal decomposition of naphtha:
A pitch containing 101 to 501 mesophases was produced by heat-treating petroleum tar at a temperature of 360"C to 450"C under a non-oxidizing gas stream under normal or increased pressure, and the latter 2 was a non-oxidizing pitch. Lower temperature than the heat treatment temperature under a positive air flow290
Separate and separate into an upper non-men layer and a lower men layer (which can be easily measured with a polarized light microscope) by holding still at 1 °C to 370"C to produce an ion 4 men phase pitch. In recent years, the rapid growth of the aircraft, automobile, and other transportation manufacturing industry has resulted in the rapid growth of the industry in manufacturing aircraft, automobiles, and other transportation vehicles. There has been an increasing demand for materials that can exhibit specific properties, and there is a strong demand for materials that have special characteristics, high strength, high elasticity, and are lightweight and inexpensive for recycling. Since it is not possible to stably supply materials that meet certain demands with current technology, research is being actively conducted on the production of highly reinforced materials (reinforced resins) to meet these demands. One of the most promising materials for use in reinforcing resins is high-strength, high-modulus carbon fiber. This material appeared on the market at the beginning of the rapid growth of the aforementioned industries.
When this carbon fiber is used in combination with a resin, it is possible to produce a reinforced resin that exhibits properties that are completely unrivaled by any other similar material. Unfortunately, however, the high strength acid and high modulus carbon fibers for reinforced resins as mentioned above are extremely expensive.
Although the reinforced resin using this material exhibits extremely remarkable properties, the demand for it has not been developed much.

It is known that the raw materials for currently available high-strength, high-elastic carbon fibers are mainly polyacrylonitrile fibers spun using special manufacturing and spinning methods.
+) Acryloni) IJ rut fibers are not only expensive as a carbon fiber precursor and t12, but also the yield of carbon fiber from this precursor is extremely poor at less than 45%. This complicates the process for producing superior carbon weave11 and increases the cost of producing the final carbon fiber product.

In order to create a particularly inexpensive raw material for carbon fiber, the inventor of the present invention has conducted extensive research.1. Ta. As a result, extremely inexpensive petroleum-based and tar-based pitches were heat-treated with stirring at 360°C to 450°C in a non-oxidizing air flow to generate meng components in the heated pitch, and the post-heated pitch was non-allocated. By keeping it stationary at 280°C to 370°C under an oxidizing air flow, and keeping it at that temperature sufficiently, the men component fuses with each other in the heated pitch and grows to a large size. Due to the difference in specific gravity and other physical properties of men (anisotropic) pitch, under the conditions of static holding, the upper layer non-meso pitch and the lower layer men pitch are separated from the side heat, and 100 tons of men pitch are separated. Discovered manufacturing scales [7] Completed the present invention. In addition, when the heated raw age pitch is maintained at 280°C to 370°C, it is stirred gently at a level that does not prevent the separation of the folded non-menu layer from the cymene layer, which promotes the fusion and enlargement of the menen balls in the pitch. Kotomoashougure.

The manufacturing method of inexpensive raw materials for carbon fiber was published in the Japanese Patent Publication No. 48-36.
160, Special Publication Showa 48-122.122 and Special Publication Publication Showa-6
In these production methods, petroleum-based and tar-based pitches are heat-treated to a temperature of 380°C to 440°C; 〈 produces pitch containing M≧6≦, which is directly used as a raw material for carbon fibers. Therefore, this pitch contains a large amount of non-meso pitch, and cannot be said to be the 100-chimeso phase pitch required as a raw material for high-strength, high-elastic carbon fibers, and does not have the characteristics sufficiently, and furthermore, it is essentially 100%. □Method for producing bitsea containing mesophase of 5% - 1972-
55.625(7). That is, a very large amount of inert gas such as 9 elements, argon, xenon, helium, and water vapor is press-injected into the flexible pitch for at least 877 minutes per raw noodle L7, and vigorously stirred 1. We are attempting to produce a so-called 100 mesophase pitch by heating it at 380°C to 430"C for 5 to 44 hours until it converts to a single-phase system. Isotropic pitch, which is a raw material, is a so-called macromolecule and is not a complex and pure compound, but also contains impurities and forms an emulsion. Even if the emulsion is mixed, it is impossible to completely unify the emulsion, and no matter how much (2) I can't say 1001 mesophases 7.

Residual carbon substances produced by thermal catalytic cracking (FCC) of vacuum gas oil are preheated as necessary under normal pressure and non-oxidizing gas to create a precursor.
0 ``C'' to 450°C, stirring treatment for 5 minutes to 308 seconds to achieve a content of menphase in the heated pitch of 10 to 50%. Heating temperature 380° to streamline processing conditions
C to 440"C1 By selecting heat treatment conditions for a reaction time of 1 to 6 hours, heat-generated pitch containing 20% to 40% mesophase can be produced. This heat-generated pitch is heated under a non-acidic gas flow. Hold at 280"C to 370°C, which is lower than the heat treatment temperature, for 2 hours to (a) (7) The menphase part is fused and grown to form a large size, and the heat-generated pinch is separated into a non-meso layer and a menslayer. It is classified as side heat.

If the heating temperature is 280° C. or lower, the wide pitch during heating cannot be separated into a non-menu layer and a meso layer. 17 Non-oxidizing gases used during heat treatment and when separating JtC boiled beef pitch into non-menu layer and meso layer include methane, ethane, and gros/! ? Carbohydrates with a small number of carbon atoms such as carbon, butane, low boiling points\heavy, 1L
The naphtha fraction that does not have any However, the most economical gas from bittern is the dry gas (mainly a mixture of hydrocarbons with a small number of carbon atoms) produced by coloring the raw material.

It should be noted that the meso layer can be easily confirmed to be 1004 memphase using a polarizing microscope. In order to rationalize the static holding conditions, it is preferable to select electrostatic holding conditions of a standing temperature of 300° C. to 340° C. and a holding time of 5 hours to 15 hours to separate the non-meso layer and the meso layer.

Furthermore, the inventor of the present invention has developed a segmented men layer Q, ■,
It is composed of two main components: (quinoline soluble content, measured by quinoline extraction at 130"C) and OoS, (quinoline soluble content), and this 100-time phase is not only Q, 1. component, but also Q,,S We have found that the spinnability of this mesophase can be improved by configuring it with other components.

The feature of the present invention is that 100 chimen phase is produced, and at the same time, this men phase contains Q, L men components and Q, S men.

This 100 is composed of
An example of producing carbon fiber by spinning % menphase is as follows. Spinning temperature li 320″C viscosity (at spinning temperature), spinning speed 10t) 1111
The yarn obtained by spinning at 300°C/min was infusible (crosslinked) with air at 300°C for 15 minutes, and then carbonized at a final temperature of 1.400″C for 15 minutes at a heating rate of 10°C/min. In winter, we were able to produce long-lasting, high-strength, high-elastic carbon fiber.

Example 1 Thermal catalytic cracking (FCC) of vacuum gas oil [Thus, the residual carbon material produced as a by-product was heat treated at 400°r for 2 hours under a non-oxidizing air flow to produce precursor pitch.

Precursor yield: 54 Precursor softening point (RAB equivalent): 67
It was °C.

This precursor was treated under the following heat treatment conditions7, and then the heated pitch was left standing at 300"C for U hours to divide it into a non-menu layer and a meso layer. Example 2 The heat-generated pitch produced in Experiment No. 2 of Example 1 was maintained under static holding conditions such as the direct method after generation. Layer bifurcation tests were conducted.

Under the electrostatic holding conditions of Experiment No. 6, the electrostatic holding conditions were not sufficient as the electrostatic holding conditions were not sharply separated into two layers, the non-men layer and the men layer, but could be divided into three layers. Ta.

Example 3 B, P, by-produced by pyrolysis of naphtha at 200°
The residual carbon material of C or higher was treated under the following heat treatment conditions under a non-oxidizing stream of methane gas.

The method for measuring the R&B equivalent softening point as a result of normal pressure heat treatment is based on JI8-2531.

After the heated pitch produced in Experiment No. 11 was produced, a men layer separation test was conducted directly under the non-oxidizing flow of methane gas under the following electrostatic holding conditions.

Men's layer separation test results Applicant: Shozo Watanabe""'-1 Agent: Yatabe Sasai; August 8th, -19, 11, -111: Mr. Kazuo Wakasugi, Commissioner of the Patent Office (Mr. Chief Adjudicator of the Patent Office) (Mr. Examiner of the Patent Office) 1, Display of the case 1932
7 Year Patent Application No. 15521 2, Title of Invention Method for Manufacturing Menphase Pitch 3, Relationship with Amendment Case Patent Applicant fE l! Ii j4L) Rah & 45-18-2 Torienji, Ward Name: Watanabe Tome
3 [Phase] 4, Agent address: 2-8 Shinjuku, Shinjuku-ku, Tokyo 160
No. 1 Shinjuku Seven Building Room 608 (6601) Name Patent Attorney Yata Tosasai', @ (Telephone 35
4-1285 & 6) l-5, date of amendment order
Spontaneous Sleeve IE 6. The number of inventions increased by the amendment No increase 8. Contents of the amendment The following circular (1) The description of the scope of the patent Bpi request will be changed as follows.

1) Petroleum-based pitch is stirred and heat-treated in a non-oxidizing air flow under normal pressure or pressurization, and the latter is held stationary to grow only the men phase in the pitch produced by heating and deposit #l111, forming a non-men layer. ζ, 1. A method for manufacturing 100% menphase pitch consisting only of components Q, s, and components.

2) The mesophase-containing lid is made 10 to 50 scratches in the pinch produced by stirring and heating petroleum pitch at a temperature of 360 ° C to 450 ° C under normal pressure or under pressure in a non-oxidizing gas flow. tf! It is assumed to be f-symptom. Q, i, component and Q
, S. A method for producing 100-wound Memphaze pitches composed only of ingredients.

3) The above-mentioned heat-generated pitch was treated under completely different treatment conditions than the heat treatment conditions - under a non-oxidizing air flow and at a lower temperature than the heat treatment temperature.
Q characterized in that only the menphase in the heat-generated pitch grows and fuses after one degree of temperature treatment at 80°C to 350°C, and the heat-generated pitch becomes a non-meso layer.
, 1. A method for manufacturing 100% menphase pitch composed only of the components Q, s, and the component '.

(2) The following amendments will be made in the detailed description of the invention.

(1) Page 3 top, line 99 "Pitch, petroleum tar" Change the pitch to "Pitch".

411 8th line from directly below 3 "290℃" to "280℃" Change "370℃" to "350℃".

(III) In the 6th line from the bottom of page 3, insert "Consisted only of Q, i, component) Q, 8. component" between "divided," and "100 scratches."

11V) In the 5th line from the bottom of page 3, insert "(can be easily confirmed with a polarizing microscope)" between "face pitch" and "manufactured".

(v) 10th line from the top of page 5 "Fine threads and tar-based pitch" Change to "Hoisito Pisona".

6/1) 8th line from the bottom of page 5 Between “flowing down” and “280℃” Enter "heat treatment temperature υ low temperature".

-5 7th line from directly below Change "370℃" to "350℃".

(V-)δ 6th line from you Between “Tsute” and “Men” Insert "Only begin."

(IX) In the 5th line from the bottom of page 5, change ``Rusama nishi,'' to ``i''.

(→ In the first line from the bottom of page 5, insert ``It is composed only of Q, i, component and Q, 8. component'' between ``Release,'' and 1100 valence.''

(XI) 6 negative upper 92nd line Change "1370℃" to "350℃".

@6th line from the bottom of page 6 Put "Only" in box 11 of "Ingredients" and "Heating".

kil) 4th line from the bottom of page 6 Between “physical properties” and “no” Enter "e.g. viscosity)".

04ν) 4th line from the bottom of page 7 Change "350℃" to "360℃".

(c) In the 6th line from the top of page 8, change "370°C J to "350°C,""2hours" to "5 hours," and "60 hours" to "30 hours J."

Hook 1) 7th line from 8 Sadaka Change [-z part] to "-z only".

(Skin 11) 3rd line from the top of page 9 Change "15 hours" to "25 hours".

(Leak-) 9N4 In the 6th line from the top, insert "I will set the above f19 position holding conditions:" between "person" and "category". Medial country From line 10 to line 11 from the top of page 9 [Men 7
AIDS as Q, i, not only the components but also Q, 6. [depending on the component] is defined as "Mesophase tiQ,i, the component is 75 to 8
Machi and JS, the ingredients will be changed to 13 饅～2Φ 俤.

(c) 9th line from the bottom of page 9 Insert "extremely" between "sexually" and "good."

6oC1) 6th line from you Insert "only" between "ingredients" and "by".

Cooking 11) Column 7 of the table on page 15 Change i2,96J to l'296J.

The sentinel writes the name of the letter: Phrase 4 2・4・1・・′[・・+'7;Rv'j ・1. i
z 1iij・-Number of inventions recorded/made 3ZJIF entry V
Substituted” 4'51111j;y, go, γ, 4-,
, (1-ii-B in ,7.

lχ I Revenue 1 Procedural Amendment j Stamp 1 September 1981 lo date:, -1.21. -0. -1. -1: Mr. Kazuo Wakasugi, Commissioner of the Patent Office (Mr. Chief Adjudicator of the Patent Office) (Mr. Examiner of the Patent Office) 1. Display of the case 1937
Patent Application No. 15521, filed in 2007 2, Title of the invention: Mesophase pitch tentative propagation method 3, Relationship with the case of the person making the amendment Patent applicant Address: Iku Tsukanaga 5-18-2 Koenji Minami, Suginami-ku Name: Tadashi Watanabe three
J4, agent address 2-8 Shinjuku, Shinjuku-ku, Tokyo 160
No. 1 Shinjuku Seven Building Room 608 (6601) Name Patent Attorney Yata Tosasai Department
[Phase] (Telephone: 354-1285 - 6) 5. Date of amendment order Voluntary amendment 6. Number of inventions increased by amendment Increase f (1) Change the description of the scope of claims as follows 1゜1) Petroleum-based pitch is stirred and heat-treated in a non-oxidizing air flow under normal pressure or pressurization, and the latter is held stationary to grow and melt only the mesophase in the heated pitch, forming a non-menu layer and a mesophase I. -Q characterized by segmentation into 1. Ingredients and Q, 8. A method for producing 100% Menzez Bich, which is composed only of ingredients.

2) The above stirring and force treatment conditions are applied to petroleum pitch at 360°C.
Claim 1: The content of mesophase in the pitch produced by stirring and heating treatment in a non-oxidizing gas flow at a temperature of 450° C. to 450° C. under normal pressure or increased pressure is 10 to 50.
Method 3) The above-mentioned static holding conditions are completely different from the heat treatment conditions for the heat-generated pitch described in MiJ, and the υ11 heat treatment is performed at a low temperature of 280°C to 3.5' under a non-oxidizing air flow. Claim 1, wherein only the mesophase in the heat-generated pitch grows and fuses at a temperature of 0°C, and the heat-generated pitch separates the non-men layer and the men layer from the side heat, and separates the men layer. Method The following amendments are made in the amendment dated August 18, 1157.

4th line from the bottom of page 5 [(X11) 6 negative bottom, 6th line” ((xll
) 6th line from the bottom of page 5 r (x+ii) 1st line from the bottom of page 5 r (x+ii) 4th line from the bottom of page 6 r (x
ii+) Correct to `` from the 5th F on the 4th line.

Claims (1)

[Scope of Claims] 1) Petroleum-based and tar-based pitches are stirred and heat-treated under a non-oxidizing air flow at normal pressure or 9 pressures, and the remaining 2 is kept stationary to remove isophase in the heated pitch. A method for manufacturing a 100-layer mesophase pitch characterized by growing and fusing it and separating it into a non-men layer and a men layer. 2) Petroleum-based and tar-based pitches at 350°C to 450°C
At a temperature of °C, the IEt is heated under a non-oxidizing gas stream with stirring for 7 hours to produce a mesophase content of 10 to 51M and kept at 12.2f. The main feature is that the layer is divided into a non-meko layer and 12 layers.
A method of manufacturing 00% mesophase pitch. 280''C to 370'C (lower than the heat treatment temperature)
Production of 100% mesophase pitch characterized in that the mesophase in the heat-generated pitch is successfully fused at temperature D, and the heat-generated pitch separates the meso layer into a non-men layer and a meso layer, and separates the meso layer. One way to do it