JPH058238B2 - - Google Patents
Info
- Publication number
- JPH058238B2 JPH058238B2 JP58038182A JP3818283A JPH058238B2 JP H058238 B2 JPH058238 B2 JP H058238B2 JP 58038182 A JP58038182 A JP 58038182A JP 3818283 A JP3818283 A JP 3818283A JP H058238 B2 JPH058238 B2 JP H058238B2
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- mesophase
- weight
- carbon
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011295 pitch Substances 0.000 claims description 64
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 27
- 239000004917 carbon fiber Substances 0.000 claims description 27
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 239000011302 mesophase pitch Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000011280 coal tar Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011338 soft pitch Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000000835 fiber Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011294 coal tar pitch Substances 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000011301 petroleum pitch Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000002641 tar oil Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011339 hard pitch Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は軟化点が50〜75℃のコールタール軟ピ
ツチまたは中ピツチを２段階の熱処理によりメソ
フエーズピツチを生成する炭素繊維用プリカーサ
ーピツチの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing precursor pitch for carbon fibers, which produces mesophase pitch through two-step heat treatment of coal tar soft pitch or medium pitch with a softening point of 50 to 75°C. .
炭素繊維の製造は原料から大別すると、ポリア
クリロニトリル等の合成繊維を原料とする方法
と、石油ピツチやコールタールピツチを原料とす
る方法に分類できる。ポリアクリロニトリル等の
合成繊維を原料とする場合、原料繊維の価格が高
いこと、原料繊維の炭化収率が低いこと等が欠点
として挙げられる。 The production of carbon fiber can be roughly divided into two types: methods using synthetic fibers such as polyacrylonitrile as raw materials, and methods using petroleum pitch or coal tar pitch as raw materials. When synthetic fibers such as polyacrylonitrile are used as raw materials, drawbacks include high cost of the raw fibers and low carbonization yield of the raw fibers.
一方、石油ピツチやコールタールピツチを原料
とする場合、これらの原料は一般に紡糸性の良い
ものは不融化が困難であり、不融化性の良いもの
は紡糸が困難であるという性質を有している。現
在、市場に出ている炭素繊維は殆ど石油ピツチを
原料としている。しかし、石油ピツチを原料とす
る場合、原料ピツチを調整するための不溶性固型
分の除去、および水添、熱処理等の物理化学的に
種々の特殊な処理を施す事が不可欠であると言わ
れており、このピツチ調整および特殊処理に多大
の労力と時間をかけているのが実情である。 On the other hand, when using petroleum pitch or coal tar pitch as raw materials, these raw materials generally have the property that those with good spinnability are difficult to make infusible, and those with good infusibility are difficult to spin. There is. Currently, most of the carbon fibers on the market are made from petroleum pits. However, when petroleum pitch is used as a raw material, it is said that it is essential to remove insoluble solids and perform various special physicochemical treatments such as hydrogenation and heat treatment to adjust the raw material pitch. The reality is that a great deal of effort and time is spent on this pitch adjustment and special processing.
コールタールピツチを原料とする場合、不溶性
固型分としてピツチ中に含まれる直径1μｍ以下
の微粒子であるフリーカーボンの分離除去が必要
であり、更に紡糸性、不融化性を改善する為に、
溶剤分割、水素化処理、熱処理等の特殊なピツチ
調整を行わなければならない。一般に炭素繊維用
プリカーサーピツチとして要求される特性は、
(1) 灰分、フリーカーボン等の不溶性固型分を含
まない事、
(2) 熱安定性に優れている事、
(3) 溶融紡糸性に優れている事、
(4) 不融化処理が容易な事、
(5) 炭化収率が大きい事、
(6) プリカーサーピツチに溶融紡糸、不融化、炭
化の一連の処理を施した時、得られた炭素繊維
が黒鉛化性および配向性に優れ、炭素繊維とし
ての充分な強度および弾性率を有する事
である。 When using coal tar pitch as a raw material, it is necessary to separate and remove free carbon, which is fine particles with a diameter of 1 μm or less, contained in the pitch as an insoluble solid content.In order to further improve spinnability and infusibility,
Special pitch adjustments such as solvent splitting, hydrogenation treatment, heat treatment, etc. must be performed. In general, the characteristics required for precursor pitch for carbon fibers are (1) no insoluble solid content such as ash or free carbon, (2) excellent thermal stability, and (3) good melt spinnability. (4) Easy to infusible treatment; (5) High carbonization yield; The carbon fibers have excellent graphitizability and orientation, and have sufficient strength and elastic modulus as carbon fibers.
本発明者らは鋭意研究の結果、コールタールピ
ツチ中のフリーカーボンを容易に取除くことがで
き、水素化処理等の特殊な処理を経由しないで、
しかも炭素繊維用のプリカーサーピツチとして必
要な上記(1)〜(6)の条件を同時に充分に満足し得る
炭素繊維用プリカーサーピツチの製造方法を発明
するに至つた。 As a result of intensive research, the present inventors have found that free carbon in coal tar pitch can be easily removed without going through special treatments such as hydrogenation.
In addition, we have invented a method for producing a precursor pitch for carbon fibers that satisfies the conditions (1) to (6) above, which are necessary for a precursor pitch for carbon fibers.
本発明は軟化点が50〜75℃のコールタール軟ピ
ツチまたは中ピツチを、第１段階で350〜500℃の
温度にて不活性ガスの雰囲気で熱処理し、メソフ
エーズを生成させ、溶剤で抽出し、メソフエーズ
を含む溶剤不溶分を分離除去後、フリーカーボン
を含まない熱安定性に富むピツチを得て、このピ
ツチを、第２段階で不活性ガスの雰囲気で常圧ま
たは減圧下に350〜500℃にて熱処理し、キノリン
不溶分20〜60重量％を有するメソフエーズピツチ
を生成させることを特徴とする高強度、高弾性の
特性を有する炭素繊維用プリカーサーピツチの製
造方法を提供するものである。 In the present invention, coal tar soft pitch or medium pitch with a softening point of 50 to 75°C is heat treated in an inert gas atmosphere at a temperature of 350 to 500°C in the first step to generate mesophase, which is extracted with a solvent. After separating and removing solvent-insoluble components including mesophase, a thermally stable pitch containing no free carbon is obtained. In the second step, this pitch is heated under normal pressure or reduced pressure in an inert gas atmosphere for 350 to 500 °C. Provided is a method for producing a precursor pitch for carbon fibers having high strength and high elasticity properties, which is characterized by heat-treating at ℃ to produce a mesophase pitch having a quinoline insoluble content of 20 to 60% by weight. be.
即ち、本発明によれば、第１段階でコールター
ルピツチを熱処理し、メソフエーズを発生させ、
溶剤抽出によりメソフエーズを含む溶剤不溶分を
分離除去して、ピツチ中に含まれるフリーカーボ
ンを容易に取除くことができ、フリーカーボンを
含まないピツチが得られる。この方法によれば、
水素化等の特殊な処理を特に経由することなく、
非常に熱安定性が良く、紡糸性、不融化性に優
れ、炭化収率が高く、しかも黒鉛化性、配向性に
優れた炭素繊維用のプリカーサーピツチを容易に
製造することができる。 That is, according to the present invention, in the first step, coal tar pitch is heat-treated to generate mesophase,
Free carbon contained in pitch can be easily removed by separating and removing solvent-insoluble components including mesophase by solvent extraction, and pitch free of free carbon can be obtained. According to this method,
without going through any special treatment such as hydrogenation,
It is possible to easily produce a precursor pitch for carbon fibers that has very good thermal stability, excellent spinnability and infusibility, high carbonization yield, and excellent graphitization and orientation properties.
ピツチを熱処理した時のメソフエーズの発生
と、その生長合体の進行とは、当然ピツチの種類
によつて若干異なる。しかし、通常メソフエーズ
は加熱温度が350℃位から発生し始め、更に温度
を上げると発生量が増えると共に大きな球体へと
生長する。加熱温度が470℃位からメソフエーズ
の球体が合体し始め、更に500℃付近になると全
面的な異方性化に至る。この反応の過程におい
て、コールタールピツチに元来存在する直径1μ
ｍ以下の微粒子であるフリーカーボン及び灰分と
なる無機質は、メソフエーズの球体の生長と共に
球体の周囲に付着するため、これらを容易に除去
することができる。 The generation of mesophases and the progress of their growth and coalescence when pitches are heat-treated naturally differ slightly depending on the type of pitches. However, mesophases usually begin to be generated when the heating temperature is around 350°C, and as the temperature is raised further, the amount of mesophases generated increases and they grow into large spheres. The mesophase spheres begin to coalesce when the heating temperature reaches around 470°C, and when the heating temperature reaches around 500°C, complete anisotropy occurs. In the process of this reaction, the diameter of 1 μm originally present in the coal tar pitch
Free carbon, which is fine particles with a size of less than m, and inorganic substances that become ash adhere to the periphery of the mesophase sphere as it grows, so they can be easily removed.
更にフリーカーボンや無機質のみでなく、ピツ
チ中に存在する熱反応性の大きい高分子量成分
や、微量の官能基を有する成分は、熱処理により
容易に重縮合化しメソフエーズとなる。従つてこ
れらの成分も容易に除去することができ、その結
果得られたピツチは、ヘテロ原子が低下してお
り、ピツチとして均質であり熱安定性に非常に優
れたものとなる。 Furthermore, not only free carbon and inorganic substances but also high-molecular weight components with high thermal reactivity and components having a trace amount of functional groups present in the pitch are easily polycondensed by heat treatment to form mesophase. Therefore, these components can be easily removed, and the pitch obtained as a result has a reduced number of heteroatoms, is homogeneous, and has excellent thermal stability.
本発明では第１段階でメソフエーズの発生温度
である約350℃から全面的なコークス化が進行す
る約500℃までの温度でピツチを熱処理した。熱
処理温度が高過ぎるとメソフエーズが多く発生
し、その結果硬ピツチの収率が低下し、逆に熱処
理温度が低過ぎると硬ピツチ中に熱反応性の大き
い成分が残存しやすい欠点がある。この２つの相
反する条件を考慮すると、熱処理温度は前記のよ
うに約350℃〜約500℃が最適であり、この温度範
囲でメソフエーズを10〜30重量％程度発生させる
ことが好ましい。 In the first step of the present invention, pitch is heat-treated at a temperature ranging from about 350°C, which is the temperature at which mesophase occurs, to about 500°C, at which complete coking occurs. If the heat treatment temperature is too high, a large amount of mesophase will be generated, resulting in a decrease in the yield of hard pitches.On the other hand, if the heat treatment temperature is too low, highly thermally reactive components will tend to remain in the hard pitches. Considering these two contradictory conditions, the optimal heat treatment temperature is about 350°C to about 500°C, as described above, and it is preferable to generate about 10 to 30% by weight of mesophase within this temperature range.
この条件下で熱処理しメソフエーズを発生させ
た硬ピツチに芳香族系の溶剤を添加する事によ
り、自然沈降または過によつて容易にメソフエ
ーズを含む溶剤不溶分を分離できる。この分離
は、フリーカーボンのみの分離と異なり極めて容
易である。その後、蒸留により溶剤を除去しフリ
ーカーボンを含まないピツチを得る。更にこのピ
ツチを第２段階で熱処理し、メソフエーズを生成
させて炭素繊維用プリカーサーピツチを得る。こ
のプリカーサーピツチの特性は、軟化点が300℃
以上、ベンゼン不溶分が80〜95重量％、キノリン
不溶分が20〜60重量％、灰分が300ppm以下であ
る。 By adding an aromatic solvent to the hard pitch that has been heat-treated under these conditions to generate mesophases, solvent-insoluble components including mesophases can be easily separated by natural sedimentation or filtration. This separation is extremely easy, unlike separation of only free carbon. Thereafter, the solvent is removed by distillation to obtain pitch free of free carbon. Furthermore, this pitch is heat-treated in a second step to generate mesophase and obtain precursor pitch for carbon fiber. This precursor pitch has a softening point of 300℃.
Above, the benzene insoluble content is 80 to 95% by weight, the quinoline insoluble content is 20 to 60% by weight, and the ash content is 300 ppm or less.
本発明により得られた炭素繊維用プリカーサー
ピツチは、キノリン不溶分を20〜60重量％含有し
ている、いわゆるバルクメソフエーズピツチであ
る。このピツチを偏光顕微鏡下に観察すると、全
面的な光学的異方性組織の中に等方性ピツチ成分
が分散しているのが見られる。偏光顕微鏡下で観
察される光学的異方性組織の割合は80〜95体積％
である。このようなピツチは紡糸性、不融化性に
優れており、高強度、高弾圧率の炭素繊維を与え
ることを見出した。メソフエーズピツチから得ら
れる炭素繊維は、メソフエーズを全く含有しない
等方性プリカーサーピツチから得られる炭素繊維
には見られない数々の特性を有している。つま
り、本発明によるメソフエーズピツチからの炭素
繊維は、処理温度が1000℃であつても高弾性率を
示し、更に黒鉛化処理により、引張強度、弾性率
とも著しく増大する。 The carbon fiber precursor pitch obtained according to the present invention is a so-called bulk mesophase pitch containing 20 to 60% by weight of quinoline insoluble matter. When this pitch is observed under a polarizing microscope, it can be seen that isotropic pitch components are dispersed within the overall optically anisotropic structure. The percentage of optically anisotropic tissue observed under a polarizing microscope is 80-95% by volume.
It is. It has been found that such pitch has excellent spinnability and infusibility, and provides carbon fibers with high strength and high elastic modulus. Carbon fibers obtained from mesophase pitches have a number of properties not found in carbon fibers obtained from isotropic precursor pitches containing no mesophases. In other words, the carbon fibers produced from the mesophase pitch according to the present invention exhibit a high modulus of elasticity even at a treatment temperature of 1000°C, and furthermore, both tensile strength and modulus of elasticity are significantly increased by the graphitization treatment.
炭素繊維用プリカーサーピツチとして最も適し
ているものは、ベンゼン不溶分が80〜95重量％、
キノリン不溶分が20〜60重量％のメソフエーズピ
ツチである。ベンゼン不溶分が80重量％以下、キ
ノリン不溶分が20重量％以下ではメソフエーズピ
ツチ中のメソフエーズ部分と等方性ピツチ部分と
が分離してしまい紡糸不能となる。又、ベンゼン
不溶分が95重量％以上、キノリン不溶分が60重量
％以上ではメソフエーズピツチの溶融粘度が著し
く高くなり紡糸不能となる。前記のようにベンゼ
ン不溶分が80〜95重量％、キノリン不溶分が20〜
60重量％のメソフエーズピツチは、メソフエーズ
部分と等方性ピツチ部分とが均一な系として存在
し、紡糸温度における溶融粘度も高くなく紡糸性
に優れている。 The most suitable precursor pitch for carbon fiber has a benzene insoluble content of 80 to 95% by weight.
It is a mesophase pitch with a quinoline insoluble content of 20 to 60% by weight. If the benzene insoluble content is less than 80% by weight and the quinoline insoluble content is less than 20% by weight, the mesophase portion and the isotropic pitch portion in the mesophase pitch will separate, making spinning impossible. Furthermore, if the benzene insoluble content is 95% by weight or more and the quinoline insoluble content is 60% by weight or more, the melt viscosity of the mesophase pitch becomes extremely high and spinning becomes impossible. As mentioned above, the benzene insoluble content is 80 to 95% by weight, and the quinoline insoluble content is 20 to 95% by weight.
The 60% by weight mesophase pitch exists as a homogeneous system of mesophase portions and isotropic pitch portions, does not have a high melt viscosity at the spinning temperature, and has excellent spinnability.
まとめると、軟化点が300℃以上、ベンゼン不
溶分が80〜95重量％、キノリン不溶分が20〜60重
量％のメソフエーズピツチが炭素繊維用プリカー
サーピツチとして適当であり、系の均一化、熱安
定性、紡糸性、不融化性に優れ、炭化収率が高
く、フリーカーボン、ヘテロ原子、無機質等の不
純物が少なく、しかもこのピツチから得られる炭
素繊維は高強度、高弾性率の特性を有する。 In summary, mesophase pitch with a softening point of 300°C or higher, a benzene-insoluble content of 80 to 95% by weight, and a quinoline-insoluble content of 20 to 60% by weight is suitable as a precursor pitch for carbon fibers, and is effective in homogenizing the system and The carbon fiber obtained from this pitch has excellent thermal stability, spinnability, and infusibility, has a high carbonization yield, and has low impurities such as free carbon, heteroatoms, and inorganic substances. Moreover, the carbon fiber obtained from this pitch has the characteristics of high strength and high elastic modulus. have
本発明の第１段階での熱処理により得られるフ
リーカーボンを含まないピツチを用いく、第２段
階で熱処理し、炭素繊維のプリカーサーピツチに
調整する方法は、上述のように、不活性ガスの雰
囲気で常圧または減圧下に加熱しメソフエーズピ
ツチを生成させるという簡便な方法で充分であ
る。得られたプリカーサーピツチは、第１段階の
熱処理により、原料のピツチに存在した熱反応性
の大きい高分子量成分やヘテロ原子が除かれたも
のであるから、熱安定性に優れ紡糸に適してい
る。更に、原料のピツチが芳香族性に富んだコー
ルタールピツチであること、第１段階で熱処理を
受けたことにより、得られたフリーカーボンを含
まないピツチは比較的大きな芳香族分子から構成
されている。従つて第２段階で得られるメソフエ
ーズピツチは、メソフエーズ成分と等方性成分と
が均一な系とし存在する。 As described above, the method of using the pitch that does not contain free carbon obtained by the heat treatment in the first step and heat-treating it in the second step to adjust the pitch to a carbon fiber precursor pitch is as follows. A simple method of heating under normal pressure or reduced pressure to produce a mesophase pitch is sufficient. The obtained precursor pitch has thermally reactive high molecular weight components and heteroatoms present in the raw material pitch removed through the first heat treatment, so it has excellent thermal stability and is suitable for spinning. . Furthermore, because the raw material pitch is coal tar pitch that is rich in aromaticity, and because it was heat-treated in the first step, the resulting pitch, which does not contain free carbon, is composed of relatively large aromatic molecules. There is. Therefore, the mesophase pitch obtained in the second step exists as a homogeneous system of mesophase components and isotropic components.
プリカーサーピツチ中の不純物である灰分は炭
素繊維のボイドの発生や強度の低下などの原因と
なるものであり、できる限り少ない方が好まし
い。本発明によるプリカーサーピツチは灰分が
300ppm以下と非常にクリーンなものであり、炭
素繊維のプリカーサーピツチとして非常に優れて
いる。 The ash content, which is an impurity in the precursor pitch, causes voids in the carbon fibers and a decrease in strength, so it is preferable to have as little as possible. The precursor pitch according to the present invention has a low ash content.
It is very clean at less than 300ppm, making it an excellent precursor pitch for carbon fiber.
このプリカーサーピツチは、通常の溶融紡糸法
で軟化点より20〜40℃高い温度にて紡糸する。紡
糸した繊維は、オゾン酸化あるいは硫酸等の酸化
剤による前処理を施す事なく、簡単に空気酸化に
よる不融化処理が可能である。この不融化処理の
後、Ar、N2の如き不活性ガス雰囲気中で約1000
℃まで昇温、焼成、炭化することにより、炭素繊
維を得ることができる。更に2000℃以上で焼成、
黒鉛化することにより、延伸工程などを施す事な
く、高強度、高弾性率の黒鉛繊維とすることがで
きる。 This precursor pitch is spun at a temperature 20 to 40°C higher than the softening point using a normal melt spinning method. The spun fibers can be easily rendered infusible by air oxidation without pretreatment with ozone oxidation or oxidizing agents such as sulfuric acid. After this infusibility treatment, about 1000
Carbon fibers can be obtained by raising the temperature to ℃, firing, and carbonizing. Furthermore, firing at over 2000℃,
By graphitizing, graphite fibers with high strength and high modulus of elasticity can be obtained without performing a drawing process or the like.
以下、実施例に基づき本発明を詳細に説明す
る。 Hereinafter, the present invention will be explained in detail based on Examples.
実施例 １
フリーカーボンを含むコールタール軟ピツチを
450℃にて不活性ガスの雰囲気で60分間加熱処理
し、25重量％のメソフエーズを生成させ、タール
油で抽出し、メソフエーズを主体とする高分子量
成分を別した。液を真空蒸留して溶剤を回収
し、軟化点が90℃、ベンゼン不溶分が12重量％、
キノリン不溶分がこん跡量であるフリーカーボン
を含まないピツチを得た。得られたピツチを不活
性ガスとしてN2ガスの雰囲気で真空度20mmHg、
465℃にて60分間加熱処理し、軟化点が355℃、ベ
ンゼン不溶分が91.9重量％、キノリン不溶分が
55.2重量％であるメソフエーズピツチを得た。こ
のメソフエーズピツチを偏光顕微鏡下に観察する
と全面的な光学的異方性組織の中に等方性ピツチ
成分が分散しているのが見られた。この光学的異
方性組織の割合は約86体積％であつた。このメソ
フエーズピツチを385℃にて、300〜500ｍ／分の
まき取り速度で溶融紡糸し、得られたピツチ繊維
を320℃にて空気酸化した後、引き続きアルゴン
中で1000℃にて炭化処理し炭素繊維を得た。この
繊維は繊維径が12〜14μｍ、引張強度が140Kg／
mm2、弾性率が8.4t／mm2であつた。更にアルゴン中
で2600℃にて黒鉛化処理し、黒鉛繊維を得た。こ
の繊維は繊維径が11〜13μｍ、引張強度が240
Kg／mm2、弾性率が43t／mm2であつた。Example 1 Coal tar soft pitch containing free carbon
Heat treatment was performed at 450°C for 60 minutes in an inert gas atmosphere to produce 25% by weight of mesophase, which was extracted with tar oil to separate high molecular weight components mainly consisting of mesophase. The solvent was recovered by vacuum distillation, and the softening point was 90℃, the benzene insoluble content was 12% by weight,
Pitch containing no free carbon and a trace amount of quinoline insoluble matter was obtained. The resulting pitch was vacuumed at 20 mmHg in an atmosphere of N2 gas as an inert gas.
Heat treated at 465℃ for 60 minutes, softening point is 355℃, benzene insoluble content is 91.9% by weight, quinoline insoluble content is
A mesophasic pitch of 55.2% by weight was obtained. When this mesophase pitch was observed under a polarizing microscope, it was found that isotropic pitch components were dispersed within the overall optically anisotropic structure. The proportion of this optically anisotropic structure was approximately 86% by volume. This mesophase pitch was melt-spun at 385°C at a winding speed of 300 to 500 m/min, and the resulting pitch fibers were air oxidized at 320°C, followed by carbonization at 1000°C in argon. Carbon fiber was obtained. This fiber has a fiber diameter of 12 to 14 μm and a tensile strength of 140 kg/
mm 2 , and the elastic modulus was 8.4t/mm 2 . Further, graphitization treatment was performed at 2600°C in argon to obtain graphite fibers. This fiber has a fiber diameter of 11 to 13 μm and a tensile strength of 240
Kg/mm 2 and elastic modulus was 43t/mm 2 .
実施例 ２
実施例１の途中で得られた軟化点が90℃であつ
てフリーカーボンを含まないピツチを、常圧下で
465℃にて45分間加熱処理した。この時、原料ピ
ツチ300ｇに対して不活性ガスであるN2ガスを５
／分の流量で流した。この結果、軟化点350℃
で、ベンゼン不溶分が93.7重量％、キノリン不溶
分が45.1重量％のメソフエーズピツチを得た。こ
のメソフエーズピツチを偏光顕微鏡下に観察した
結果、光学的異方性組織の割合は約94体積％であ
つた。このメソフエーズピツチを370℃にて、300
〜500ｍ／分のまき取り速度で溶融紡糸し、得ら
れたピツチ繊維を320℃にて空気酸化した後、引
き続きアルゴン中で1000℃にて炭化処理し炭素繊
維を得た。この繊維は繊維径が12〜14μｍ、引張
強度が130Kg／mm2、弾性率が8.6t／mm2であつた。
更にアルゴン中で2600℃にて黒鉛化処理し、黒鉛
繊維を得た。この繊維は繊維径が11〜13μｍ、引
張強度が280Kg／mm2、弾性率が43t／mm2であつた。Example 2 The pitch obtained in the middle of Example 1 with a softening point of 90°C and containing no free carbon was heated under normal pressure.
Heat treatment was performed at 465°C for 45 minutes. At this time, 50 g of N2 gas, which is an inert gas, is added to 300 g of raw material pitch.
It was flowed at a flow rate of /min. As a result, the softening point is 350℃
Thus, a mesophase pitch containing 93.7% by weight of benzene insoluble matter and 45.1% by weight of quinoline insoluble matter was obtained. When this mesophase pitch was observed under a polarizing microscope, the proportion of optically anisotropic structure was approximately 94% by volume. This mesophase pitch was heated to 300℃ at 370℃.
Melt spinning was carried out at a winding speed of ~500 m/min, and the resulting pitch fibers were air oxidized at 320°C, followed by carbonization treatment at 1000°C in argon to obtain carbon fibers. This fiber had a fiber diameter of 12 to 14 μm, a tensile strength of 130 Kg/mm 2 , and an elastic modulus of 8.6 t/mm 2 .
Further, graphitization treatment was performed at 2600°C in argon to obtain graphite fibers. This fiber had a fiber diameter of 11 to 13 μm, a tensile strength of 280 Kg/mm 2 , and an elastic modulus of 43 t/mm 2 .
比較例 １
フリーカーボンを含むコールタール軟ピツチを
加熱処理しないで直接タール油で抽出し、過に
よりキノリン不溶分がこん跡量であり軟化点が90
℃のまだフリーカーボンを含むピツチを得た。こ
のピツチを不活性ガスとしてN2ガスの雰囲気で
真空度20mmHg、450℃にて60分間加熱処理し、ベ
ンゼン不溶分が82.3重量％、キノリン不溶分が
43.2重量％であるメソフエーズピツチを得た。こ
のメソフエーズピツチは、溶融状態でメソフエー
ズ部分と等方性ピツチ部分との間に相分離が起こ
り、紡糸が不能であつた。Comparative Example 1 Coal tar soft pitch containing free carbon was directly extracted with tar oil without heat treatment.
A pitch was obtained that still contained free carbon at °C. This pitch was heat-treated at 450°C for 60 minutes at a vacuum degree of 20 mmHg in an atmosphere of N2 gas as an inert gas, and the benzene-insoluble content was 82.3% by weight and the quinoline-insoluble content was reduced.
A mesophase pitch of 43.2% by weight was obtained. In this mesophase pitch, phase separation occurred between the mesophase portion and the isotropic pitch portion in the molten state, making spinning impossible.
Claims (1)
１段階で350〜500℃の温度にて熱処理しメソフエ
ーズを生成させ、溶剤で抽出しメソフエーズを含
む溶剤不溶分を分離除去後、得られたフリーカー
ボンを含まないピツチを、第２段階で不活性ガス
の雰囲気で常圧または減圧下に350〜500℃の温度
にて熱処理し、キノリン不溶分20〜60重量％を有
するメソフエーズピツチを生成させることを特徴
とする炭素繊維用プリカーサーピツチの製造方
法。1 Coal tar soft pitch or medium pitch is heat-treated at a temperature of 350 to 500°C in the first step to generate mesophase, extracted with a solvent, and after separating and removing solvent-insoluble components including mesophase, the resulting free carbon is extracted. In a second step, the pitch that does not contain quinoline is heat-treated at a temperature of 350 to 500°C under normal pressure or reduced pressure in an inert gas atmosphere to produce mesophase pitch having a quinoline insoluble content of 20 to 60% by weight. A method for producing a carbon fiber precursor pitch characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3818283A JPS59164386A (en) | 1983-03-10 | 1983-03-10 | Preparation of precursor pitch for carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3818283A JPS59164386A (en) | 1983-03-10 | 1983-03-10 | Preparation of precursor pitch for carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59164386A JPS59164386A (en) | 1984-09-17 |
| JPH058238B2 true JPH058238B2 (en) | 1993-02-01 |
Family
ID=12518237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3818283A Granted JPS59164386A (en) | 1983-03-10 | 1983-03-10 | Preparation of precursor pitch for carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59164386A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100717702B1 (en) * | 2002-11-29 | 2007-05-11 | 신토 브레이터 가부시키가이샤 | Barrel polishing method, and barrel polishing device |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6123686A (en) * | 1984-07-11 | 1986-02-01 | Kawasaki Steel Corp | Carbon fiber precursor pitch and production thereof |
| JPS61179319A (en) * | 1985-02-04 | 1986-08-12 | Kawasaki Steel Corp | Production of high performance carbon yarn |
| JPH0629437B2 (en) * | 1985-09-04 | 1994-04-20 | 川崎製鉄株式会社 | Method for producing carbon fiber plicator pitch |
| JPS62277491A (en) * | 1986-05-26 | 1987-12-02 | Maruzen Petrochem Co Ltd | Production of meso-phase pitch |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5938280A (en) * | 1982-08-27 | 1984-03-02 | Kawasaki Steel Corp | Preparation of precursor pitch for carbon fiber |
-
1983
- 1983-03-10 JP JP3818283A patent/JPS59164386A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5938280A (en) * | 1982-08-27 | 1984-03-02 | Kawasaki Steel Corp | Preparation of precursor pitch for carbon fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100717702B1 (en) * | 2002-11-29 | 2007-05-11 | 신토 브레이터 가부시키가이샤 | Barrel polishing method, and barrel polishing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59164386A (en) | 1984-09-17 |
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