JPH03167315A - Production of pitch-based hollow carbon yarn - Google Patents
Production of pitch-based hollow carbon yarnInfo
- Publication number
- JPH03167315A JPH03167315A JP30466489A JP30466489A JPH03167315A JP H03167315 A JPH03167315 A JP H03167315A JP 30466489 A JP30466489 A JP 30466489A JP 30466489 A JP30466489 A JP 30466489A JP H03167315 A JPH03167315 A JP H03167315A
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- raw material
- yarn
- hollow carbon
- metal
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title 1
- 229910052799 carbon Inorganic materials 0.000 title 1
- 239000011295 pitch Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004698 Polyethylene Substances 0.000 claims abstract description 4
- -1 polyethylene Polymers 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011337 anisotropic pitch Substances 0.000 claims abstract 2
- 239000000835 fiber Substances 0.000 claims description 32
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 21
- 239000004917 carbon fiber Substances 0.000 claims description 21
- 238000003763 carbonization Methods 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005087 graphitization Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000005011 phenolic resin Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- 239000011302 mesophase pitch Substances 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野］ 本発明は、ピッチ系中空炭素繊維の製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing pitch-based hollow carbon fiber.
［従来の技術］
炭素繊維は、耐薬品性、耐熱性等の特性に優れるため各
種の機能性物質の材料として使用されている。例えば、
中空炭素繊維は、これらの性質を利用して各種の分離膜
や断熱材として使用されている。[Prior Art] Carbon fiber is used as a material for various functional substances because of its excellent properties such as chemical resistance and heat resistance. for example,
Hollow carbon fibers are used as various separation membranes and heat insulating materials by taking advantage of these properties.
従来、炭素繊維の原料としては、ポリアクリロニトリル
（ＰＡＮ）系原料が使用されていた。これに対して、現
在ではピッチ系原料が使用されつつある。このピッチ系
原料は、原料コストが安価である。この中でも、炭化時
の収率が高いピッチ原料には、等方性ピッチ原料とバル
クメソフェーズピッチ原料の２Ｆｉ類があるので、好ま
しいものとされている。このバルクメソフェーズピッチ
は、石油系または石災系ピッチを４００ないし４５０℃
の温度範囲で熱処理して得られるもので、光学的異方性
組織（液品）が全面的に展開されている。Conventionally, polyacrylonitrile (PAN)-based raw materials have been used as raw materials for carbon fibers. In contrast, pitch-based raw materials are now being used. This pitch-based raw material is inexpensive in raw material cost. Among these, pitch raw materials with a high yield during carbonization include 2Fi, which is an isotropic pitch raw material and a bulk mesophase pitch raw material, and are therefore considered preferable. This bulk mesophase pitch is produced by heating oil-based or stone-based pitch to 400 to 450°C.
It is obtained by heat treatment in the temperature range of , and an optically anisotropic structure (liquid product) is fully developed.
これらの原料を用いて中空炭素繊維を製造する方法は、
例えば、特開昭６１−８３３２１号公報に開示されてい
る。この方法は、粘度が１０ないし１５０ボイズである
溶融ピッチを押出用、ガス背圧が０．２ないし１ ．
０ ｋｇ ／ ｃｊ ，紡糸ノズル径（ｄ）が０．１
ないし０．５ｍｍ，紡糸ノズル長（Ｌ）が１．０ないし
１．５ｕ＋，Ｌ／ｄが２ないし５である条件下で紡糸し
、紡糸繊維を紡糸ノズル直下で冷却用ガスによって急冷
するものである。The method for producing hollow carbon fibers using these raw materials is as follows:
For example, it is disclosed in Japanese Patent Application Laid-Open No. 61-83321. This method is used for extruding molten pitch with a viscosity of 10 to 150 voids and a gas back pressure of 0.2 to 1.
0 kg/cj, spinning nozzle diameter (d) is 0.1
to 0.5 mm, the spinning nozzle length (L) is 1.0 to 1.5 u+, and L/d is 2 to 5, and the spun fibers are rapidly cooled by cooling gas directly below the spinning nozzle. be.
［発明が解決しようとする課題］
しかしながら、この方法は、安定して所望の中空炭素繊
維を得ることができない。このため、得られる中空炭素
繊維は、一定した径の中空部を持たない。したがって、
この方法によって冑られた中空炭素繊維は、優れた性能
を発揮することができない。[Problems to be Solved by the Invention] However, this method cannot stably obtain desired hollow carbon fibers. Therefore, the obtained hollow carbon fiber does not have a hollow portion with a constant diameter. therefore,
Hollow carbon fibers cracked by this method cannot exhibit excellent performance.
本発明はかかる点に鑑みてなされたものであり、連続し
て、かつ、安定に優れた性能を持つ中空炭素繊維を容易
に製造することができるピッチ系中空炭素繊維の製造方
法を提供することを目的とする。The present invention has been made in view of the above points, and an object of the present invention is to provide a method for producing pitch-based hollow carbon fibers that can continuously and easily produce hollow carbon fibers with excellent performance in a stable manner. With the goal.
［課題を角タ決するための手段〕
本発明は、フェノール系あるいはポリエチレン系等の樹
脂系繊維上に金属を彼着し、次に、該金属被着繊維上に
等方性ピッチ原料あるいはバルクメソフェーズピッチ原
料を不活性雰囲気下で披覆し、その後、これに炭化処即
および黒鉛化処理を順次施すことを特徴とするピッチ系
中空炭素繊維の製造方法である。ここで、炭化処理およ
び黒鉛化処理は、等方性ピッチ原料被覆物に不融化処理
が施された後に施すことが好ましい。[Means for solving the problem] The present invention involves depositing metal on resin fibers such as phenolic or polyethylene fibers, and then depositing isotropic pitch raw material or bulk mesophase on the metal-coated fibers. This is a method for producing a pitch-based hollow carbon fiber, which is characterized in that a pitch raw material is coated in an inert atmosphere, and then subjected to carbonization treatment and graphitization treatment sequentially. Here, the carbonization treatment and the graphitization treatment are preferably performed after the isotropic pitch raw material coating is subjected to the infusibility treatment.
ここで、繊維は、炭化処理および黒鉛化処理で灰化して
、得られるピッチ系中空炭素繊維の中空部を形成させる
ものであればよい。このようなものとして、フェノール
樹脂系繊維、ポリエチレン系繊維等が挙げられる。その
中でもフェノール樹脂系繊維は、炭化時の発泡が少ない
ので好ましい。フェノール樹脂系繊維の径は、１０ない
し５００μｍが好ましい。これは、繊維径が１０μｍ未
満であると生成する中空径が小さすぎ、繊維径が５００
μｍを超えると生成する中空径が大きすぎるからである
。Here, the fiber may be any fiber as long as it is incinerated by carbonization treatment and graphitization treatment to form a hollow portion of the resulting pitch-based hollow carbon fiber. Examples of such fibers include phenolic resin fibers and polyethylene fibers. Among these, phenol resin fibers are preferred because they cause less foaming during carbonization. The diameter of the phenolic resin fiber is preferably 10 to 500 μm. This is because if the fiber diameter is less than 10 μm, the hollow diameter produced is too small, and the fiber diameter is less than 500 μm.
This is because when the diameter exceeds μm, the hollow diameter produced is too large.
金属は、繊維上に容易に被着可能なものであればよい。The metal may be any metal as long as it can be easily deposited on the fibers.
このようなものとして、ニッケル、銅等が挙げられる。Examples of such materials include nickel and copper.
また、繊維への金属の披着方法は、無電解メッキ等を用
いることができる。このときの繊維上の金属被着厚みは
、１ないし１０μｍであることが好ましい。これは、厚
みが１μｍ未満であると溶融したピッチを被覆する際の
耐熱性が不十分となり、厚みが１０μｍを超えると形成
される中空部が不規則なものとなるからである。Furthermore, electroless plating or the like can be used as a method for depositing metal onto the fibers. The thickness of the metal deposited on the fiber at this time is preferably 1 to 10 μm. This is because if the thickness is less than 1 μm, the heat resistance when covering molten pitch will be insufficient, and if the thickness exceeds 10 μm, the hollow portions formed will be irregular.
等方性ピッチ原料あるいはバルクメソフェーズピッチ原
料は、軟化点が約３２０℃以下のものが好ましい。これ
は、等方性ピッチ原料の軟化点が約３２０℃を超えると
溶融時の粘度が高く、被覆の際に、その被覆層の厚さが
不均一となるからである。The isotropic pitch raw material or the bulk mesophase pitch raw material preferably has a softening point of about 320°C or lower. This is because if the softening point of the isotropic pitch raw material exceeds about 320° C., the viscosity during melting will be high, and the thickness of the coating layer will become non-uniform during coating.
不活性雰囲気は、アルゴン、窒素等の通常の不活性ガス
を使用することにより達成される。An inert atmosphere is achieved by using common inert gases such as argon, nitrogen, etc.
金馬被着繊維上に等方性ピッチ原料あるいはノ《ルクメ
ソフエーズピッチ原料を披覆する方法は、金属繊維表面
上に所望の厚みのピッチ原料層を形成させるものであれ
ばよい。例えば、溶融状態の等方性ピッチ原料中に金属
披着繊維を通過させる方法等が挙げられる。The method of coating the isotropic pitch raw material or the mesophase pitch raw material on the metallic fibers may be any method as long as it forms a pitch raw material layer of a desired thickness on the surface of the metal fiber. For example, a method may be used in which metallized fibers are passed through a molten isotropic pitch raw material.
不融化処理は、空気等の気体酸化剤、硝酸等の液体酸化
剤を用いる酸化処理、またはキノリン等の溶媒を使用す
る溶剤抽出処理により行われる。The infusibility treatment is performed by oxidation treatment using a gaseous oxidizing agent such as air, liquid oxidizing agent such as nitric acid, or solvent extraction treatment using a solvent such as quinoline.
炭化処理は、１０００ないし１２００℃にまで昇温しで
行う。また、黒鉛化処理は、２００ｏないし２５００℃
にまで昇温して行う。The carbonization treatment is performed by raising the temperature to 1000 to 1200°C. In addition, graphitization treatment is carried out at 200o to 2500℃.
Raise the temperature to .
［作用〕
本発明のピッチ系中空炭素繊維の製造方法によれば、フ
ェノール樹脂系繊維上に金属を被着し、次に、金属被着
繊維上に等方性ピッチ原料あるいはバルクメソフェーズ
ピッチ原料を不活性雰囲気下で被覆し、その後、これに
不融化処理、炭化処理および黒鉛化処理を順次施してい
る。[Function] According to the method for producing pitch-based hollow carbon fibers of the present invention, a metal is deposited on a phenolic resin fiber, and then an isotropic pitch raw material or a bulk mesophase pitch raw material is deposited on the metal-coated fiber. It is coated under an inert atmosphere, and then subjected to infusibility treatment, carbonization treatment, and graphitization treatment sequentially.
金属が彼着している繊維は、耐熱性に優れ、また、等方
性ピッチ原料あるいはバルクメソフェーズピッチ原料と
の濡れ性も悪くないので、金属彼着繊維上に容易に等方
性ピッチ原料層を形成することができる。The metal-adhered fiber has excellent heat resistance and has good wettability with isotropic pitch raw material or bulk mesophase pitch raw material, so it is easy to form an isotropic pitch raw material layer on the metal-adhered fiber. can be formed.
また、金属披着繊維は、得られる中空炭素繊維の中空部
に対応している。このため、金篇披着繊維を炭化処理お
よび黒鉛化処理で灰化除表することによって、容易に所
望孔径の中空部をｈ゜する中空災素繊維を得ることがで
きる。Further, the metallized fibers correspond to the hollow portions of the obtained hollow carbon fibers. Therefore, by ashing and removing the gold-plated fibers through carbonization and graphitization, it is possible to easily obtain hollow fibers having a hollow portion with a desired pore diameter.
［実施例］ 以下、本発明の実施例について具体的に説明する。[Example] Examples of the present invention will be specifically described below.
実施例
繊維径が２０μｍであるフェノール樹脂繊維に無電解ニ
ッケルメッキを施して、フェノール樹脂繊維上に厚さ２
μｍのニッケル層を設けた。次に、ニッケル被着フェノ
ール樹脂繊維を３８０”Ｃに加熱した゜等方性ビ゛ツチ
原料（軟化点３００’Ｃ）融液中にアルゴン雰囲気下で
浸漬させ、通過させて、ニツケ“ル披着フェノール樹脂
繊維に厚み１０μｍで等方性ピッチ原料層を設けた。Example: Electroless nickel plating was applied to phenolic resin fibers with a fiber diameter of 20 μm, and a thickness of 2 μm was applied to the phenol resin fibers.
A nickel layer of μm was provided. Next, the nickel-coated phenolic resin fibers were immersed in a melt of isotropic vinyl raw material (softening point 300'C) heated to 380'C under an argon atmosphere, and passed through to coat the nickel. An isotropic pitch raw material layer with a thickness of 10 μm was provided on the phenol resin fiber.
その後、等方性ピッチ原料層を有するニッケル被着フェ
ノール樹脂繊維に空気を用いて不融化処理を施した。続
けて、これに、１℃／分の昇温速度で１０００℃まで昇
温しで、炭化処理を施した。Thereafter, the nickel-coated phenolic resin fiber having the isotropic pitch raw material layer was subjected to an infusibility treatment using air. Subsequently, this was heated to 1000° C. at a heating rate of 1° C./min to undergo carbonization treatment.
さらに、これに１℃／分の昇温速度で２０００℃まで昇
温しで、黒鉛化処理を施した。このようにして、本発明
のピッチ系中空炭素繊維を作製した。Furthermore, this was heated to 2000° C. at a heating rate of 1° C./min to undergo graphitization treatment. In this way, the pitch-based hollow carbon fiber of the present invention was produced.
得られたピッチ系中空炭素繊維は、所望の中空部を有し
ているものであった。The obtained pitch-based hollow carbon fiber had a desired hollow portion.
［発明の効果］
以上説明した如く、本発明のピッチ系中空炭素繊維の製
造方法は、連続して、かつ、安定に優れた性能を持つ中
空炭素繊維を容易に製造することができるものである。[Effects of the Invention] As explained above, the method for producing pitch-based hollow carbon fibers of the present invention can easily produce hollow carbon fibers that have excellent performance continuously and stably. .
Claims (3)
繊維上に金属を被着し、次に、該金属被着繊維上に等方
性あるいは異方性ピッチ原料を不活性雰囲気下で被覆し
、その後、これに炭化処理および黒鉛化処理を順次施す
ことを特徴とするピッチ系中空炭素繊維の製造方法。(1) A metal is deposited on resin fibers such as phenolic or polyethylene, and then an isotropic or anisotropic pitch raw material is coated on the metal-coated fibers in an inert atmosphere, and then A method for producing a pitch-based hollow carbon fiber, which comprises sequentially subjecting the same to carbonization treatment and graphitization treatment.
被覆物に不融化処理が施された後に施す請求項１記載の
ピッチ系中空炭素繊維の製造方法。(2) The method for producing a pitch-based hollow carbon fiber according to claim 1, wherein the carbonization treatment and the graphitization treatment are performed after the isotropic pitch raw material coating is subjected to an infusibility treatment.
料である請求項１または２記載のピッチ系中空炭素繊維
の製造方法。(3) The method for producing a pitch-based hollow carbon fiber according to claim 1 or 2, wherein the pitch raw material is a pitch raw material containing bulk mesophase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30466489A JPH03167315A (en) | 1989-11-27 | 1989-11-27 | Production of pitch-based hollow carbon yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30466489A JPH03167315A (en) | 1989-11-27 | 1989-11-27 | Production of pitch-based hollow carbon yarn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03167315A true JPH03167315A (en) | 1991-07-19 |
Family
ID=17935744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30466489A Pending JPH03167315A (en) | 1989-11-27 | 1989-11-27 | Production of pitch-based hollow carbon yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03167315A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987926A (en) * | 2017-04-14 | 2017-07-28 | 河北民族师范学院 | Pitch based carbon fiber, preparation method and its application in lithium ion battery |
-
1989
- 1989-11-27 JP JP30466489A patent/JPH03167315A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987926A (en) * | 2017-04-14 | 2017-07-28 | 河北民族师范学院 | Pitch based carbon fiber, preparation method and its application in lithium ion battery |
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