JPH02242921A - Production of carbon fiber - Google Patents
Production of carbon fiberInfo
- Publication number
- JPH02242921A JPH02242921A JP6454289A JP6454289A JPH02242921A JP H02242921 A JPH02242921 A JP H02242921A JP 6454289 A JP6454289 A JP 6454289A JP 6454289 A JP6454289 A JP 6454289A JP H02242921 A JPH02242921 A JP H02242921A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- precursor
- flame
- heat
- heat treatment
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 32
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 238000007380 fibre production Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- -1 acryl Chemical group 0.000 abstract description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 3
- 239000008187 granular material Substances 0.000 abstract 2
- 230000001404 mediated effect Effects 0.000 abstract 2
- 239000002245 particle Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- KTHAEJQIULVVPV-UHFFFAOYSA-N 3-(2-methylpropoxycarbonyl)but-3-enoic acid Chemical compound CC(C)COC(=O)C(=C)CC(O)=O KTHAEJQIULVVPV-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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、炭素繊維の製造方法−１特に効率的に高品質
、高性能を有する炭素繊維を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a carbon fiber manufacturing method-1, particularly a method for efficiently manufacturing carbon fibers having high quality and high performance.
［従来の技術］
アクリル系繊維から炭素繊維を製造する方法は広く知ら
れており、まず、空気または他の酸化性ガス雰囲気中に
て、２００〜３００℃で耐炎化して耐炎化繊維となし、
次いでこれを窒素、アルゴン等の不活性ガス雰囲気中に
て８００〜２０００℃で炭化して製造される。また、さ
らに２０００℃以上の否活性ガス雰囲気中で黒鉛化を行
ない、弾性率が一段と高い黒鉛゛繊維を製造することも
行なわれる。[Prior Art] A method for producing carbon fiber from acrylic fiber is widely known. First, carbon fiber is made flame-resistant by making it flame-resistant at 200 to 300°C in an atmosphere of air or other oxidizing gas.
This is then carbonized at 800 to 2000° C. in an inert gas atmosphere such as nitrogen or argon. Furthermore, graphitization is carried out in an inert gas atmosphere at a temperature of 2000° C. or higher to produce graphite fibers with even higher modulus of elasticity.
上記耐炎化工程は酸化と環化による発熱をともない、そ
の反応を十分コントロールしながら処理する必要がある
。また、物性の高い炭素繊維を得るためには、耐炎化反
応に必要な酸素を充分に単糸内部へ拡散させるのに長時
間を要するため、この耐炎化工程が炭素繊維の製造費に
占める割合は高い。The above-mentioned flameproofing step involves heat generation due to oxidation and cyclization, and it is necessary to perform the process while sufficiently controlling the reaction. In addition, in order to obtain carbon fibers with high physical properties, it takes a long time to sufficiently diffuse the oxygen necessary for the flame-retardant reaction into the single fibers, so this flame-retardant process accounts for a large proportion of the manufacturing cost of carbon fibers. is expensive.
そこで、耐炎化時間短縮を図るために、前駆体繊維に熱
風を吹き付けたり、また、加熱固体表面に間欠的に接触
させる方法が示されている。Therefore, in order to shorten the flame resistance time, methods have been proposed in which the precursor fibers are blown with hot air or brought into contact with a heated solid surface intermittently.
［本発明が解決しようとする課題］
しかしながら、上記の方法によれば耐炎化時間は従来に
比べて短縮されるものの、得られる炭素繊維の物性は大
幅に低下する。たとえば、一定の弾性率を得るためには
炭化温度を上げるなどして対処しなければならなかフた
。一方、炭素ｗＡＱ製進用プリカーサ−を分散手段上の
流動層中で加熱処理することにより、耐炎化時間が大幅
に短縮できることを提案したく特願昭６２−１９０３０
１号）。そこで本発明者らは、さらに該炭素繊維製造用
プリカーサ−をアクリルｗｃ維とし、かつその共重合組
成を特定することにより、耐炎化時間の大幅な短縮とと
もに、得られる炭素繊維の物性低下が抑制できることを
見出し、本発明に至ったものである。[Problems to be Solved by the Present Invention] However, although the above method shortens the flame resistance time compared to the conventional method, the physical properties of the obtained carbon fibers are significantly reduced. For example, in order to obtain a constant elastic modulus, measures such as increasing the carbonization temperature were required. On the other hand, we would like to propose that the flame resistance time can be significantly shortened by heat-treating a precursor made of carbon wAQ in a fluidized bed on a dispersing means.
No. 1). Therefore, the present inventors further determined that by using acrylic WC fiber as the precursor for carbon fiber production and specifying its copolymer composition, the flame resistance time was significantly shortened, and the deterioration of the physical properties of the obtained carbon fiber was suppressed. This is what led to the present invention.
すなわち、本発明の課題は、高品質、高性能な炭素繊維
を、短時間で効率よく製造することにある。That is, an object of the present invention is to efficiently produce high-quality, high-performance carbon fiber in a short time.
［課題を解決するための手段］
本発明の上記課題は、アクリロニトリル８５％以上、重
合性不飽和カルボン酸のアルキルエステル１〜ｌＯ％か
らなる共重合体で構成される炭素繊維製造用プリカーサ
−を、分散手段」二の流動層中で加熱処理することを特
徴とする炭素繊維の製造方法によって解決することがで
きる。[Means for Solving the Problems] The above object of the present invention is to provide a precursor for carbon fiber production composed of a copolymer consisting of 85% or more acrylonitrile and 1 to 10% alkyl ester of a polymerizable unsaturated carboxylic acid. This problem can be solved by a carbon fiber manufacturing method characterized by heat treatment in a fluidized bed.
すなわち、本発明において炭素繊維製造用プリカーサ−
（以下単にプリカーサ−という）は、アクリロニトリル
８５％以上、重合性不飽和カルボン酸のアルキルエステ
ル１〜１０％からなる共重合体で構成される。前記共重
合成分量が少ないと得られる効果が小さく、一方、多す
ぎると得られる炭素繊維の物性や炭化収率が低下するよ
うになる。従って、共重合量としては２〜９％がより好
ましく、３〜８％がさらに好ましい。That is, in the present invention, the precursor for carbon fiber production is
(hereinafter simply referred to as precursor) is composed of a copolymer consisting of 85% or more acrylonitrile and 1 to 10% alkyl ester of a polymerizable unsaturated carboxylic acid. If the amount of the copolymerized component is small, the effect obtained will be small, while if it is too large, the physical properties and carbonization yield of the obtained carbon fiber will decrease. Therefore, the amount of copolymerization is more preferably 2 to 9%, and even more preferably 3 to 8%.
重合性不飽和カルボン酸のアルキルエステルの具体例と
しては、アクリル酸メチル、メタクリル酸メチル、イタ
コン酸ジエチル、アクリル酸ノルマルプロピル、メタク
リル酸ノルマルブチル、メタクリル酸イソブチル、イタ
コン酸イソブチル、エタクリル酸ラウリル、アクリル酸
シクロヘキシル、メタクリル酸ステアリル等を挙げるこ
とができるが、汎用性、効果の点からアクリル酸、メタ
クリル酸のエステルが好ましく、また、炭素数が３以上
であるアルキルのエステルが好ましく、ノルマルプロピ
ルエステル、ノルマルブチルエステル、イソブチルエス
テルがより好ましい。Specific examples of alkyl esters of polymerizable unsaturated carboxylic acids include methyl acrylate, methyl methacrylate, diethyl itaconate, n-propyl acrylate, n-butyl methacrylate, isobutyl methacrylate, isobutyl itaconate, lauryl ethacrylate, and acrylic. Examples include cyclohexyl acid and stearyl methacrylate, but esters of acrylic acid and methacrylic acid are preferred from the viewpoint of versatility and effectiveness, and esters of alkyl having 3 or more carbon atoms are preferred, such as normal propyl ester, Normal butyl ester and isobutyl ester are more preferred.
これらの共重合成分は、それ自身耐炎化反応を促進する
ことはないが、酸素透過性を改善するため、酸素濃度分
布が均一で、そして、不飽和化が進行した単糸内部の水
素濃度が低い耐炎化糸が得られ、しかも、この耐炎化糸
を焼成すると、極めて高い物性の炭素繊維を得ることが
でき、特に、耐炎化時間を短縮した時にも極めて物性低
下を小さくできる。These copolymerized components do not themselves promote flame-retardant reactions, but they improve oxygen permeability so that the oxygen concentration distribution is uniform and the hydrogen concentration inside the unsaturated single fibers is reduced. A yarn with low flame resistance can be obtained, and when this flame resistance yarn is fired, carbon fibers with extremely high physical properties can be obtained, and in particular, even when the flame resistance time is shortened, the decrease in physical properties can be extremely small.
また、本発明中のプリカーサ−には、−層耐炎化時間を
短縮するため、不飽和カルボン酸等、耐炎化反応を促進
する重合性不飽和単量体を共重合することが好ましい。Further, in order to shorten the time required for flame-proofing the layer, it is preferable to copolymerize the precursor in the present invention with a polymerizable unsaturated monomer that promotes the flame-proofing reaction, such as an unsaturated carboxylic acid.
不飽和カルボン酸の具体例としては、アクリル酸、メタ
クリル酸、イタコン酸、クロトン酸、シトラコン酸、エ
タクリル酸、マレイン酸゛、メサコン酸等があるが、こ
の中でも、アクリル酸、メタクリル酸、イタコン酸が好
ましい。そして、不飽和カルボン酸の共重合量は０゜２
５〜５％が好ましく、０．５〜４％がより好ましい。Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconic acid, ethacrylic acid, maleic acid, mesaconic acid, etc. Among these, acrylic acid, methacrylic acid, itaconic acid is preferred. And the amount of copolymerization of unsaturated carboxylic acid is 0゜2
5% to 5% is preferable, and 0.5% to 4% is more preferable.
また、その他のアクリロニトリルと共重合可能な重合性
不飽和単量体と共重合することも可能である。It is also possible to copolymerize with other polymerizable unsaturated monomers that can be copolymerized with acrylonitrile.
重合方法は、溶液重合、懸濁重合、乳化重合等、公知の
方法いずれに仕ってもよい。The polymerization method may be any known method such as solution polymerization, suspension polymerization, and emulsion polymerization.
紡糸に用いる溶媒は、有機、無機の公知の溶媒を使用す
ることができる。本発明においてはこのアクリル系重合
体溶液を公知の方法に従って、紡糸、浴中延伸、乾燥緻
密化する。紡糸は直接凝固浴中に紡出してもよいし、−
度、空気中に紡出した後浴中凝固させてもよい。浴中延
伸は紡出糸を直接性なってもよいし、また、−度水洗し
て溶媒を除去したのちに行なってもよい。浴中延伸は通
常５０〜９８℃の延伸浴中で約２〜６倍に延伸されるが
本発明はこれに限定されない。乾燥緻密化は、浴中延伸
後の糸条をホットドラムなどで乾燥することによって行
なわれるが、乾燥温度、時間等は適宜選択することがで
きる。また、必要に応じて乾燥緻密化後の糸条を加圧ス
チーム延伸することも行なわれる。さらに、前駆体繊維
には、高温で処理して耐炎化時間を短縮しうる耐熱性を
持だせるため、シリコン油剤で処理することもできる。As the solvent used for spinning, known organic and inorganic solvents can be used. In the present invention, this acrylic polymer solution is subjected to spinning, bath stretching, and drying and densification according to known methods. Spinning may be carried out directly into a coagulation bath, or -
It may also be spun into air and then coagulated in a bath. The bath drawing may be carried out directly on the spun yarn, or may be carried out after washing with water to remove the solvent. The in-bath stretching is usually carried out by about 2 to 6 times in a stretching bath at a temperature of 50 to 98°C, but the present invention is not limited thereto. Drying and densification is carried out by drying the yarn after drawing in a bath using a hot drum or the like, and the drying temperature, time, etc. can be selected as appropriate. Further, if necessary, the yarn after drying and densification is stretched with pressurized steam. Furthermore, the precursor fibers can be treated with a silicone oil agent to impart heat resistance that can be treated at high temperatures to shorten the flame resistance time.
付与の方法としては、工程油剤として伺与する等通常の
方法をとることができる。As a method of application, usual methods such as application as a process oil agent can be used.
次に、本発明における流動層とは、固体熱媒粒子を気体
で流動化した状態で加熱処理する手段であって、前記熱
媒粒子が酸化性気体で流動化された状態と、所定の温度
、好ましくは２００℃以上、より好ましくは２４０℃以
上に加熱された状態がこの流動層内で共存された状態を
言う。Next, the fluidized bed in the present invention is a means for heat-treating solid heat transfer particles in a state in which they are fluidized with a gas, and the heat transfer particles are in a state in which they are fluidized in an oxidizing gas and at a predetermined temperature. , preferably at 200° C. or higher, more preferably at 240° C. or higher, coexisting in the fluidized bed.
本発明において酸化性気体とは、空気の他、含硫黄気体
５等、前記前駆体繊維に対して加熱時広義の酸化反応を
生ずる気体が含まれる。In the present invention, the oxidizing gas includes, in addition to air, gases such as sulfur-containing gas 5 that cause an oxidation reaction in a broad sense on the precursor fibers when heated.
本発明における熱媒粒子とは、気体で流動化された状態
で用いる固体粒子を言い、耐炎化に必要な加熱温度に耐
えうる耐熱性を有するもので、たとえば、主成分として
炭素、アルミナ、炭化ケイ素、ジルコニア、シリカ等が
単独あるいは共存して構成されるセラミックやガラス等
の無機物粒子を用いることができる。特に前記熱媒粒子
のうち、炭素を主成分とする粒子が好ましく、さらには
重量の８０％が２８メツシユより小さい粒径の黒鉛粒子
が好ましい。The heating medium particles in the present invention refer to solid particles that are used in a gaseous fluidized state and have heat resistance that can withstand the heating temperature required for flame resistance. Inorganic particles such as ceramic or glass made of silicon, zirconia, silica, etc. singly or in combination can be used. Particularly, among the heat transfer particles, particles whose main component is carbon are preferable, and graphite particles in which 80% of the weight of the particles have a particle size smaller than 28 meshes are particularly preferable.
次に、流動層は次の条件にて形成されるのが好ましい。Next, the fluidized bed is preferably formed under the following conditions.
すなわち、上面レベルから分散手段までの熱媒粒子の静
置時深さＨ［ｍ］を下記の範囲として分散板上に流動層
を形成せしめ、前記流動層中で前駆体繊維を加熱する。That is, a fluidized bed is formed on the dispersion plate by setting the standing depth H [m] of the heating medium particles from the upper surface level to the dispersion means in the following range, and the precursor fibers are heated in the fluidized bed.
２０Ｍｆ／（ρυＣｐＡ）＜Ｈ＜５００／ρυここで、
Ｍｆ ：流動層中に存在する前駆体繊維重量［ｋ８］ρ
υ：熱媒粒子の嵩密度［ｋｇ／ｍ３］Ｃｐ ：熱媒粒子
の比熱［ｋｃａｌ／ｋｇ’ｃ］Ａ ：流動層の流動化面
積［ｍ２］
である。20Mf/(ρυCpA)<H<500/ρυwhere, Mf: weight of precursor fibers present in the fluidized bed [k8]ρ
υ: Bulk density of heating medium particles [kg/m3] Cp: Specific heat of heating medium particles [kcal/kg'c] A: Fluidized area of fluidized bed [m2].
また、流動層で耐炎化する前に、２００℃以上２６０℃
以下の空気中で６０秒以下の緊張前処理を施してもよい
。In addition, before making it flame resistant in a fluidized bed,
The following tension pretreatment may be performed in air for 60 seconds or less.
また、耐炎化処理中の延伸比は、緊張状態を保ち、また
、得られる耐炎化糸に損傷を与えない範囲で適宜選択す
ることができるが、高物性の炭素繊維を得るためには延
伸比が好ましくは０．８以上、より好ましくは０．９以
上、さらに好ましくは１．０以上である。In addition, the stretching ratio during the flame-retardant treatment can be appropriately selected within a range that maintains tension and does not damage the resulting flame-retardant yarn, but in order to obtain carbon fiber with high physical properties, the stretching ratio is preferably 0.8 or more, more preferably 0.9 or more, still more preferably 1.0 or more.
さらに、高品質、高性能な炭素繊維を、短時間で効率よ
く製造するという本発明の趣旨から、流動層内の総滞留
時間、すなわち耐炎化時間は短いほうがよく、好ましく
は３０分以内、より好ましくは２０分以内、さらに好ま
しくは１０分以内である。Furthermore, since the purpose of the present invention is to efficiently produce high-quality, high-performance carbon fibers in a short period of time, the total residence time in the fluidized bed, that is, the flame resistance time, is preferably short, preferably within 30 minutes, and more preferably within 30 minutes. Preferably it is within 20 minutes, more preferably within 10 minutes.
以上のようにして得られる耐炎化糸は、引き続き不活性
ガス雰囲気にて最高熱処理温度が８００〜２０００℃で
炭化し炭素繊維とする。また、必要に応じてさらに２０
００℃以上の不活性ガス雰囲気中で黒鉛化して黒鉛化糸
とすることもてきる。The flame-resistant yarn obtained as described above is subsequently carbonized in an inert gas atmosphere at a maximum heat treatment temperature of 800 to 2000°C to form carbon fiber. In addition, if necessary, an additional 20
It is also possible to graphitize in an inert gas atmosphere at 00° C. or higher to obtain a graphitized yarn.
［実施例］ 以下、実施例を挙げて本発明を具体的に説明する。[Example] The present invention will be specifically described below with reference to Examples.
実施例１
ジメチルスルホキシドを溶媒とする溶液重合法により、
重合体濃度２０％の紡糸原液を得て、それを３０００ホ
ールの口金を用いてジメチルスルホキシド水溶液中に紡
出した後、沸水中で延伸しながら水洗し、乾燥緻密化し
た後に、加圧スチーム中でさらに延伸することにより、
単糸デニール１、Ｏｄ、３０００フイラメント、第１表
に示した共重合組成の繊維Ａ−Ｅを得た。この繊維を加
熱空気で流動化した黒鉛粉末熱媒中２６０〜２８０℃に
おいて１０分間で耐炎化し、窒素気流中１３００℃まで
加熱処理して炭素繊維を得た。結果を第２表に示す。Example 1 By solution polymerization method using dimethyl sulfoxide as a solvent,
A spinning stock solution with a polymer concentration of 20% was obtained, which was spun into a dimethyl sulfoxide aqueous solution using a 3000-hole spinneret, washed with water while being stretched in boiling water, dried and densified, and then spun in a pressurized steam bath. By further stretching with
Fibers AE having a single filament denier of 1, Od, 3000 and a copolymer composition shown in Table 1 were obtained. The fibers were made flame resistant for 10 minutes at 260 to 280°C in a graphite powder heat medium fluidized with heated air, and then heat-treated to 1300°C in a nitrogen stream to obtain carbon fibers. The results are shown in Table 2.
比較例１
実施例１と同様の方法にて第１表に示した共重合組成の
繊維Ｆ−Ｈを得た。この繊維を実施例１と同様の方法で
焼成して炭素繊維を得た。結果を第２表に示す。Comparative Example 1 Fibers F-H having the copolymerization composition shown in Table 1 were obtained in the same manner as in Example 1. This fiber was fired in the same manner as in Example 1 to obtain carbon fiber. The results are shown in Table 2.
実施例２
水を溶媒とする懸濁重合法により、アクリロニトリル９
２％１．イタコン酸１％、メタクリル酸イソブチル７％
よりなる共重合体を得て、それを重合体濃度２５％のジ
メチルホルムアミド溶液とし、ジメチルホルムアミド水
溶液中に紡出する以外は、実施例１と同様に紡糸し、３
０００フイラメント、単繊維繊度１．Ｏｄの繊維Ｉを得
た。この繊維を加熱空気で流動化したアルミナ熱媒中て
２７０〜２９０℃において５分間で耐炎化し、窒素気流
中１３００℃まで加熱処理して炭素繊維を得た。結果を
第２表に示す。Example 2 Acrylonitrile 9 was produced by a suspension polymerization method using water as a solvent.
2%1. Itaconic acid 1%, Isobutyl methacrylate 7%
A copolymer composed of
000 filament, single fiber fineness 1. Fiber I of Od was obtained. The fibers were made flame resistant for 5 minutes at 270 to 290°C in an alumina heat medium fluidized with heated air, and then heat treated to 1300°C in a nitrogen stream to obtain carbon fibers. The results are shown in Table 2.
比較例２
実施例２で得た繊維Ｉを、空気中にて、約２４０℃の熱
風中、６０分間耐炎化した。次に、この耐炎化糸を実施
例２と同様に炭化した。得られた炭素繊維は引張強度が
４６３ ｋｇ／ｍｍ”、引張弾性率は２５ 、４ ｔ、
／ｍｍ２であった。Comparative Example 2 The fiber I obtained in Example 2 was flame resistant in air at about 240° C. for 60 minutes. Next, this flame-resistant yarn was carbonized in the same manner as in Example 2. The obtained carbon fiber had a tensile strength of 463 kg/mm", a tensile modulus of 25.4 t,
/mm2.
（以下余白）
第１表
第２表
［発明の効果コ
本発明の炭素繊維の製造方法によって、高品質、高性能
の炭素繊維を、短時間で効率的に製造することができ、
大幅な炭素繊維のコストダウンが可能となる。また、こ
れにより炭素繊維の用途が一段と拡大するなどの効果が
大である。(The following are blank spaces) Table 1 Table 2 [Effects of the invention] By the method for producing carbon fiber of the present invention, high quality and high performance carbon fiber can be produced efficiently in a short time,
This makes it possible to significantly reduce the cost of carbon fiber. Additionally, this has the effect of further expanding the uses of carbon fiber.
Claims (1)
のアルキルエステル１〜１０％からなる共重合体で構成
される炭素繊維製造用プリカーサーを、分散手段上の流
動層中で加熱処理することを特徴とする炭素繊維の製造
方法。A precursor for producing carbon fibers made of a copolymer consisting of 85% or more acrylonitrile and 1 to 10% alkyl ester of a polymerizable unsaturated carboxylic acid is heat-treated in a fluidized bed on a dispersion means. Carbon fiber manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6454289A JPH02242921A (en) | 1989-03-15 | 1989-03-15 | Production of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6454289A JPH02242921A (en) | 1989-03-15 | 1989-03-15 | Production of carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02242921A true JPH02242921A (en) | 1990-09-27 |
Family
ID=13261214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6454289A Pending JPH02242921A (en) | 1989-03-15 | 1989-03-15 | Production of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02242921A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997045576A1 (en) * | 1996-05-24 | 1997-12-04 | Toray Industries, Inc. | Carbon fiber, acrylic fiber, and method of manufacturing them |
-
1989
- 1989-03-15 JP JP6454289A patent/JPH02242921A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997045576A1 (en) * | 1996-05-24 | 1997-12-04 | Toray Industries, Inc. | Carbon fiber, acrylic fiber, and method of manufacturing them |
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