JP6664401B2 - ポリアクリロニトリル繊維の高密度化 - Google Patents
ポリアクリロニトリル繊維の高密度化 Download PDFInfo
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- JP6664401B2 JP6664401B2 JP2017534649A JP2017534649A JP6664401B2 JP 6664401 B2 JP6664401 B2 JP 6664401B2 JP 2017534649 A JP2017534649 A JP 2017534649A JP 2017534649 A JP2017534649 A JP 2017534649A JP 6664401 B2 JP6664401 B2 JP 6664401B2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
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- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
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- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
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- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- NUHSROFQTUXZQQ-UHFFFAOYSA-N isopentenyl diphosphate Chemical compound CC(=C)CCO[P@](O)(=O)OP(O)(O)=O NUHSROFQTUXZQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
- D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/223—Stretching in a liquid bath
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/228—Stretching in two or more steps, with or without intermediate steps
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/229—Relaxing
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Description
膨潤程度(%)=(Wa−Wf)x(100/Wf)
繊維サンプルの膨潤値が低いほど、典型的には、より低い多孔性又は繊維ネットワーク密度の増加を示す。
PANポリマーは、懸濁液重合又は溶液重合により作製され得る。溶液重合において、アクリロニトリル(AN)モノマーは、溶媒、及び一又は複数のコモノマーと混合され、溶液を形成する。次いで、溶液は室温を超える温度(すなわち25℃を超える温度)、例えば約40℃から約85℃に加熱される。加熱後、開始剤が溶液に添加され、重合反応が開始する。重合が完了すると、未反応のANモノマーは(例えば高真空下の脱気により)取り除かれ、得られるPANポリマー溶液は冷却される。この段階で、PANポリマーは、紡糸の準備が整っている溶液又はドープ形態にある。
a)DMSOをDMSO保存タンクから反応器へ、次いでANをAN保存タンクから反応器へ、メーターを介して供給する;
b)反応器を窒素でパージする;
c)反応器を予熱し、コモノマーを室温(25℃)を上回る温度で反応器に添加する;
d)溶液を加熱し、次いで開始剤/触媒を40〜85℃の所望の温度点で添加する;
e)8〜24時間、60〜80℃の温度で重合を開始する;
f)40〜50℃の温度に冷却し、ポリマー溶液を排出する。
図1に示されるように、ドープ[1]は、複数の毛細管を有する紡糸口金[3]を通して排出される前に、典型的にはフィルター[2]を通して押し出され、ゲル又はその他夾雑物を捕捉する。PANドープは、紡糸口金及び凝固槽液面を分離する周囲空気又は他のガスの空間に、濾過及び計量されたPANドープの連続流として、各紡糸口金毛管を出る。この空隙[4]は、典型的には2〜10mmの範囲であり、PANドープの温度は、凝固槽の温度とは分離して制御及び操作されることになる。凝固槽[5]は溶媒及び非溶媒で構成される液体槽であり、それにより、PANの凝固速度及び得られる繊維構造が制御されるように、濃度及び温度が操作され、制御される。凝固した繊維は凝固槽を出て、一又は複数の加熱された液体洗浄槽[7]及び加熱された伸張槽[9]に入る。被動ロール[6]は、洗浄及び伸張の様々な段階で繊維速度を制御するため及び所望に応じて繊維に伸張又は緩和を加えるために使用される。洗浄及び伸張槽は、凝固した繊維からの溶媒を水で置換しながら同時に繊維を伸張及び配向することを可能にする。洗浄及び伸張槽を出た後、繊維は、典型的にはその後の処理工程における繊維の損傷及び繊維の粘着を最小限にするために適用された紡糸仕上げを有する[8]。紡糸仕上げが適用された後、トウは乾燥され、緩和され、加熱されたロール上の空隙構造が崩壊する[10]。乾燥後及び巻き取り前に、追加の伸張、緩和及び紡糸仕上げ塗布工程が可能である[11]。
処方1から製造されるPANポリマーを、凝固槽中でアクリル繊維に紡糸した。次いで繊維を一連の四つの槽を通して延伸した。槽の温度、繊維の伸張及び膨潤の百分率を下の表3に示す。
白色繊維前駆体を220℃〜285℃の温度範囲の空気中で酸化させ、350℃〜650℃の温度範囲(事前炭化)、次いで800℃〜1300℃の温度範囲の窒素中で炭化させた。
Claims (4)
- 炭素繊維を製造するための方法であって、
凝固槽でアクリルポリマーを紡糸し、それにより複数の単一フィラメントのアクリル繊維を形成すること;
アクリル繊維を二より多い槽で延伸することであって、第一及び第二の槽の温度が、第二の槽から出るアクリル繊維の膨潤により測定されるような繊維ネットワーク密度が第一の槽から出るアクリル繊維の繊維ネットワーク密度よりも低いか又はそれに等しいように設定され、かつアクリル繊維の伸張が最終槽で緩和される、延伸すること;並びに
アクリル繊維を安定化し、続いて炭化させること
を含む方法。 - 炭素繊維を製造するための方法であって、
(a)凝固槽でアクリルポリマーを紡糸し、それにより複数の単一フィラメントのアクリル繊維を形成すること;
(b)4つの加熱槽を通してアクリル繊維を延伸することであって、槽の温度は第一から第四の槽へと増加し、第一の槽の温度が70℃〜80℃の範囲であり、第二の槽の温度が75℃〜85℃の範囲であり、第三の槽の温度が85℃〜95℃の範囲であり、かつ第四の温度が90℃〜100℃であり、槽における繊維の延伸又は伸張比が、第一の槽において1.0〜2.0であり、第二の槽において1.0〜2.0であり、第三の槽において1.5〜4.0であり、第四の槽において0.95〜1.20である、延伸すること;
(c)第四の槽から出るアクリル繊維を酸化して、酸化繊維を形成すること;並びに
(d)酸化繊維を炭化させること
を含む方法。 - 槽における繊維の延伸又は伸張比が、第一の槽において1.0〜1.25であり、第二の槽において1.0〜1.25であり、第三の槽において1.25〜2.0であり、第四の槽において0.90〜1.0である、請求項2に記載の方法。
- (c)における酸化が、220℃〜285℃の温度範囲内の空気中で実施され;かつ
(d)おける炭化が、350℃〜650℃及びその後800℃〜1300℃の温度範囲内の窒素中で実施される
請求項2又は3に記載の方法。
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