JPH0274615A - Carbon fiber-based porous hollow fiber membrane and production thereof - Google Patents
Carbon fiber-based porous hollow fiber membrane and production thereofInfo
- Publication number
- JPH0274615A JPH0274615A JP1060648A JP6064889A JPH0274615A JP H0274615 A JPH0274615 A JP H0274615A JP 1060648 A JP1060648 A JP 1060648A JP 6064889 A JP6064889 A JP 6064889A JP H0274615 A JPH0274615 A JP H0274615A
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- fiber membrane
- polymer
- acrylonitrile
- thermally decomposable
- 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
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 80
- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 25
- 239000004917 carbon fiber Substances 0.000 title claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000011148 porous material Substances 0.000 claims abstract description 69
- 229920000642 polymer Polymers 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000009987 spinning Methods 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 27
- 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 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 24
- 239000000178 monomer Substances 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000578 dry spinning Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002959 polymer blend Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 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
- KFCDDRTYJQZGKK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enenitrile Chemical compound C=CC#N.CC(=C)C(O)=O KFCDDRTYJQZGKK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001891 gel spinning Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000007791 liquid phase 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
- 239000010446 mirabilite Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CUTKVJUFVWFBQP-UHFFFAOYSA-N C(C(=C)C)(=O)O.C(C=C)#N.C(C=C)(=O)OC Chemical compound C(C(=C)C)(=O)O.C(C=C)#N.C(C=C)(=O)OC CUTKVJUFVWFBQP-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- -1 dichlorohexanone peroxide Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- VRAHSRHQTRYBJV-UHFFFAOYSA-M sodium;2-methyl-1-oxoprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)C(=O)S([O-])(=O)=O VRAHSRHQTRYBJV-UHFFFAOYSA-M 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱性に優れた新規な炭素繊維系多孔質中空
糸膜およびその製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel carbon fiber-based porous hollow fiber membrane with excellent heat resistance and a method for producing the same.
吸着分離のための活性炭素繊維は、既に数種のものが知
られている。例えば再生セルロース系繊維、アクリロニ
トリル系繊維、フェノール系繊維およびピッチ系繊維を
原料とするもの等である。繊維状活性炭は粒状活性炭に
比較して、接触面積が著しく大きく、吸着や脱着の速度
が早い等の形態上の利点が多い。さらに中空糸にするこ
とＫより、吸着、脱着等の繁雑な工程から解放され、流
体を加圧下で中空糸内部を通過させるだけで、流体から
の分離を可能とし、省エネルギープロセスを可能とする
。Several types of activated carbon fibers for adsorption separation are already known. Examples include those made from regenerated cellulose fibers, acrylonitrile fibers, phenol fibers, and pitch fibers. Fibrous activated carbon has many advantages over granular activated carbon, such as a significantly larger contact area and faster adsorption and desorption rates. Furthermore, by using hollow fibers, it is freed from complicated processes such as adsorption and desorption, and by simply passing the fluid through the inside of the hollow fibers under pressure, it is possible to separate the fluid from the fluid, making an energy-saving process possible.
一方、中空状活性炭素繊維については、特開昭４８−８
７１２１号公報に中空率１０〜８０％で、比表面積４０
０ ｍ２７ｇ以上の炭素材中にボイドを形成した、気体
や液体中の微量物質を吸着する機能を有する、中空繊維
が開示されている。この中空繊維の製法は、フェノール
を原料とする繊維のスキン部分を架橋させ、未架橋のコ
ア部を溶媒で溶出して得た中空繊維を炭素化し、さらに
水蒸気等の酸化性ガスで賦活処理して多孔質化する方法
である。そのため細孔半径も１０〜２０Ｘのミクロ孔で
あり、しかも得られる中空繊維の中空部は均一性に欠は
流体抵抗が大きく、透過速度も小さいものである。On the other hand, regarding hollow activated carbon fiber, Japanese Patent Application Laid-Open No. 48-8
Publication No. 7121 has a hollow ratio of 10 to 80% and a specific surface area of 40%.
A hollow fiber is disclosed in which voids are formed in a carbon material of 0 m27 g or more and has the function of adsorbing trace substances in gas or liquid. The manufacturing method for this hollow fiber is to crosslink the skin part of a fiber made from phenol, elute the uncrosslinked core part with a solvent, carbonize the obtained hollow fiber, and then activate it with an oxidizing gas such as water vapor. This method makes the material porous. Therefore, the pore radius is micropores of 10 to 20×, and the hollow portions of the hollow fibers obtained lack uniformity, have high fluid resistance, and have a low permeation rate.
特開昭５８−９１８２６号公報には、ピッチ系中空炭素
繊維が開示されているが、中空内径が１０μｍ以下と小
さく、膜壁への細孔もな（、分離膜を意図したものでは
ない。JP-A-58-91826 discloses a pitch-based hollow carbon fiber, but the hollow inner diameter is as small as 10 μm or less, and there are no pores in the membrane wall (it is not intended as a separation membrane.
また特開昭６０−１７９１０２号公報および特開昭６０
−２０２７０３号公報には多層構造の炭素膜が開示され
ているが、前者の炭素膜は、微多孔質緻密層を少なくと
も一層有し、また少なくとも一層は透過速度を早める為
の大きな細孔を有し、しかも多層構造全体としての配向
係数が０．７と小さいものである。さらに後者の炭素膜
も、分離能を有する多孔質層と透過速度を早めるための
最大孔直径５μｍ以上のボイドな有するスポンジ構造の
多孔質層とからなるものであり、極めて脆弱な膜構造で
あり実用に耐えないものである。Also, JP-A-60-179102 and JP-A-60
Publication No. 202703 discloses a carbon membrane with a multilayer structure, but the former carbon membrane has at least one microporous dense layer, and at least one layer has large pores to accelerate the permeation rate. Moreover, the orientation coefficient of the multilayer structure as a whole is as small as 0.7. Furthermore, the latter carbon membrane also has an extremely fragile membrane structure, consisting of a porous layer with separation ability and a sponge-structured porous layer with voids with a maximum pore diameter of 5 μm or more to accelerate the permeation rate. It is impractical.
さらに特開昭６１−４７８２７号公報には、ポリビニル
アルコール系繊維からの炭素化中空繊維が開示されてい
るが、脱水剤を表層部のみに浸透させ、乾留工程で不融
化し、脱水剤の浸透しなかった中心部分を溶融除去して
中空状とするものであり、しかも、水蒸気で賦活処理し
て多孔質中空炭素繊維を製造するものである。Furthermore, Japanese Patent Application Laid-open No. 61-47827 discloses carbonized hollow fibers made from polyvinyl alcohol fibers, in which a dehydrating agent is infiltrated only into the surface layer, and the dehydrating agent is infusible in the carbonization process. The remaining central portion is melted and removed to make it hollow, and the porous hollow carbon fiber is produced by activation treatment with steam.
また特開昭６３−４８１２号公報には、孔を有する炭素
膜の製法として、予め抽出法で孔を設けた中空糸膜をヒ
ドラジン水溶液で処理してから耐炎化および炭素化する
ことが提案されている。Furthermore, JP-A No. 63-4812 proposes a method for producing a carbon membrane with pores, in which a hollow fiber membrane in which pores have been previously formed by an extraction method is treated with an aqueous hydrazine solution, and then flame-resistant and carbonized. ing.
しか１−ながらこれらの従来技術からの多孔質中空炭素
繊維は、孔の形態はいずれも１〜５ ｎｍのミクロ孔が
多（また実用見地からは強度等の物性が不足している。However, these porous hollow carbon fibers from the prior art have many micropores with a size of 1 to 5 nm (and from a practical standpoint, they lack physical properties such as strength).
従来技術による活性炭素繊維および多孔質中空炭素繊維
の細孔の平均半径は、何れも１〜５ｎｍと小さいため、
分子量が比較的小さい物質の気相からの吸着や分離には
適するが、本発明が意図する比較的大きい分子量を有す
る物質の気相や液相からの吸着、分離には適さない。ま
た、これら従来技術による繊維はその伸度が低く、しな
やかさに欠けるものがほとんどである。The average radius of the pores of activated carbon fibers and porous hollow carbon fibers according to the prior art are both as small as 1 to 5 nm.
Although it is suitable for the adsorption and separation of substances with a relatively small molecular weight from the gas phase, it is not suitable for the adsorption and separation of substances with a relatively large molecular weight from the gas and liquid phases as intended by the present invention. Furthermore, most of the fibers produced by these prior art techniques have low elongation and lack flexibility.
かかる現状に鑑み、本発明は細孔半径が１０〜１１００
０ｎのマクロ孔と称される範囲に鋭いピークの細孔分布
を有する、炭素繊維系多孔質中空糸膜、およびその効率
的な製法を提供することにある。In view of this current situation, the present invention has a pore radius of 10 to 1100.
The object of the present invention is to provide a carbon fiber-based porous hollow fiber membrane having a pore distribution with a sharp peak in a range called 0n macropores, and an efficient method for producing the same.
本発明は、中空糸膜の内壁表面から外壁表面に連続的に
つながった細孔を有し、細孔容積微分曲線から求めた細
孔半径の極大値が１０〜１０００ ｎｍに存在し、全細
孔容積が０．１〜１ｃｒｎ３／Ｉで、屈曲時の曲率半径
が１０ｃｍ以下であり、かつＴＧＡにより測定した中空
糸膜の１０重量％分解する温度が少なくとも約３００°
Ｃである耐熱性に優れた炭素繊維系多孔質中空糸膜であ
る。The present invention has pores that are continuously connected from the inner wall surface to the outer wall surface of the hollow fiber membrane, and the maximum value of the pore radius determined from the pore volume differential curve exists in the range of 10 to 1000 nm, and the total pore diameter is 10 to 1000 nm. The pore volume is 0.1 to 1 crn3/I, the radius of curvature when bent is 10 cm or less, and the temperature at which 10% by weight of the hollow fiber membrane decomposes as measured by TGA is at least about 300°.
It is a carbon fiber porous hollow fiber membrane with excellent heat resistance.
なお本発明の炭素繊維系多孔質中空糸膜はその単繊維の
引張伸度が少なくとも０．８％であることが好ましい。In the carbon fiber porous hollow fiber membrane of the present invention, it is preferable that the tensile elongation of the single fibers is at least 0.8%.
本発明における細孔容積微分曲線から求めた細孔半径の
極大値とは、水銀圧入法により測定される円筒換算細孔
の細孔半径分布曲線の極大値を示すものである。また全
細孔容積は、細孔容積の累積値を示すものである。The maximum value of the pore radius determined from the pore volume differential curve in the present invention refers to the maximum value of the pore radius distribution curve of cylindrical equivalent pores measured by mercury intrusion method. Further, the total pore volume indicates the cumulative value of pore volumes.
本発明の炭素繊維系多孔質中空糸膜の最も犬きな特色は
前記の中空糸膜の内壁表面から外壁表面に連通した細孔
を有し、しかも細孔容積微分曲線から求めた細孔半径の
極大値が１０〜１Ｄ ００ ｎｍであるため、従来の活
性炭素繊維に比較して大きな細孔半径を有するものであ
り、比較的大きい分子量を有する物質を含有する気相や
液相からの該物質の吸着、分離に好適である。The most important feature of the carbon fiber porous hollow fiber membrane of the present invention is that it has pores that communicate from the inner wall surface to the outer wall surface of the hollow fiber membrane, and the pore radius determined from the pore volume differential curve. Since the maximum value of is 10 to 1D00 nm, it has a large pore radius compared to conventional activated carbon fibers, and it is difficult to absorb substances from the gas phase or liquid phase that contain substances with relatively large molecular weights. Suitable for adsorption and separation of substances.
しかも特に屈曲時の曲率半径が１０ｃｒｎ以下であるた
め柔軟性にも優れたものである。炭素繊維系多孔質中空
糸膜が前記の種々の物性のいずれか一つでも満たされな
い場合には、本発明の目的とする多孔質中空糸膜として
の効果を発揮しに（いため好ましくない。In addition, it has excellent flexibility, especially since the radius of curvature when bent is 10 crn or less. If the carbon fiber-based porous hollow fiber membrane does not satisfy any one of the various physical properties described above, it is not preferable because it will not be able to exhibit the effects as a porous hollow fiber membrane that is the object of the present invention.
本発明の炭素繊維系多孔質中空糸膜を製造する好ましい
方法としては、例えばアクリロニトリル単位が９０〜１
００モル％であるアクリロニトリル系重合体（Ａ）と６
００°Ｃ以下の温度で熱分解して低分子量化する熱分解
性重合体（Ｂ）および溶剤（Ｃ）とを混合した後、紡糸
し、延伸して得たアクリロニトリル系中空繊維を耐炎化
処理し、次いで４００℃以上の温度で炭素化処理して多
孔質化する方法が挙げられる。As a preferable method for producing the carbon fiber porous hollow fiber membrane of the present invention, for example, the acrylonitrile unit is 90 to 1
00 mol% acrylonitrile polymer (A) and 6
The acrylonitrile-based hollow fiber obtained by mixing the pyrolyzable polymer (B), which is thermally decomposed to lower the molecular weight at a temperature of 00°C or less and the solvent (C), and then spinning and drawing, is subjected to flame-retardant treatment. An example of this method is to perform a carbonization treatment at a temperature of 400° C. or higher to make the material porous.
炭素繊維系多孔質中空糸膜を製造するに際しては、アク
リロニトリル系重合体（Ｎの溶解パラメーターδは一般
に１５．４付近であり、また熱分解性重合体（Ｂ）のそ
れは９〜１２．２の範囲のものがほとんどであることが
多く、お互いに相溶性に乏しい場合が多いため、アクリ
ロニトリル系重合体囚と熱分解性重合体（Ｂ）との組み
合わせ如何によっては、さらに任意成分として相溶剤（
Ｄ）を混合することによってお互いの相溶性を向上させ
ることができる。When producing a carbon fiber porous hollow fiber membrane, the solubility parameter δ of the acrylonitrile polymer (N is generally around 15.4, and that of the thermally decomposable polymer (B) is 9 to 12.2. Most of them are within this range, and they are often poorly compatible with each other. Therefore, depending on the combination of the acrylonitrile polymer prisoner and the thermally decomposable polymer (B), a compatibilizer (
By mixing D), mutual compatibility can be improved.
本発明の実施に際して用いるアクリロニトリル系重合体
（Ａ）とは、アクリロニトリル単位が９０〜１００モル
％と、アクリロニトリルと共重合可能な単量体０〜１０
モル％とから構成されるアクリロニトリル単独重合体ま
たは共重合体である。共重合可能な単量体の具体例とし
ては、アクリル酸、メタクリル酸、イタコン酸およびそ
れらの誘導体、例えばメチルアクリレート、エチルアク
リレート、ベンジルアクリレート、メチルメタクリレー
ト、エチルメタクリレート等、またアクリルアミド、メ
タクリルアミド等のアミド誘導体、酢酸ビニル、塩化ビ
ニル、塩化ビニリデン等のハロゲン化単量体、メタクリ
ルスルホン酸ソーダやスチレンスルホン酸ソーダ等のス
ルホン酸誘導体等が挙げられるが、必ずしもこれらに限
定されるものでない。The acrylonitrile polymer (A) used in the practice of the present invention includes 90 to 100 mol% of acrylonitrile units and 0 to 10% of monomers copolymerizable with acrylonitrile.
It is an acrylonitrile homopolymer or copolymer composed of mol%. Specific examples of copolymerizable monomers include acrylic acid, methacrylic acid, itaconic acid and derivatives thereof, such as methyl acrylate, ethyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, and acrylamide, methacrylamide, etc. Examples include amide derivatives, halogenated monomers such as vinyl acetate, vinyl chloride, and vinylidene chloride, and sulfonic acid derivatives such as sodium methacrylsulfonate and sodium styrene sulfonate, but are not necessarily limited to these.
アクリロニトリル系重合体（Ａ）としてはポリアクリロ
ニトリル、アクリロニトリル−メタクリル酸共重合体、
アクリロニトリル−メチルアクリレート−イタコン酸共
重合体、アクリロニトリル−メチルアクリレート−メタ
クリル酸共重合体等が特に好ましい。アクリロニトリル
系重合体（ロ）の比粘度で示される重合度としては、比
粘度が０．１〜０．４特に０．２〜０．３の範囲のもの
が好ましい。この範囲を外れると、紡糸操作が困難にな
ったり、また紡糸して得られる繊維の性能も劣悪なもの
になったりする傾向があるため好ましくない。As the acrylonitrile polymer (A), polyacrylonitrile, acrylonitrile-methacrylic acid copolymer,
Particularly preferred are acrylonitrile-methyl acrylate-itaconic acid copolymer, acrylonitrile-methyl acrylate-methacrylic acid copolymer, and the like. The degree of polymerization indicated by the specific viscosity of the acrylonitrile polymer (b) is preferably from 0.1 to 0.4, particularly from 0.2 to 0.3. If it is outside this range, it is not preferable because the spinning operation becomes difficult and the performance of the fiber obtained by spinning tends to be poor.
熱分解性重合体（Ｂ）とは、６００℃以下の温度で熱分
解して低分子量化するものであり、かつアクリロニトリ
ル系重合体囚の溶剤に溶解し得るものである。このよう
な熱分解性重合体の具体例としては、スチレン、α−メ
チルスチレン、ビニルトルエン等の芳香族ビニル系単量
体、ビニルクロライド、ビニルアルコール、ビニルアセ
テート等の脂肪族ビニル系単量体、メチルメタクリレー
ト、エチルメタクリレート、ｎ−メチルメタクリレート
等のメタクリレート系単量体等の単独重合体もしくはこ
れらの単量体単位５１モル％以上と、アクリロニトリル
以外の他の共重合可能な単量体単位４９モル％以下とか
ら構成される共重合体が挙げられる。特にスチレン系重
合体、ビニルクロライド系重合体、またはメチルメタク
リレート系重合体が好ましく・。The thermally decomposable polymer (B) is one that is thermally decomposed at a temperature of 600° C. or lower to reduce its molecular weight, and is soluble in the solvent of the acrylonitrile polymer. Specific examples of such thermally decomposable polymers include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene, and aliphatic vinyl monomers such as vinyl chloride, vinyl alcohol, and vinyl acetate. , a homopolymer of methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-methyl methacrylate, or 51 mol% or more of these monomer units, and other copolymerizable monomer units other than acrylonitrile 49 Examples include copolymers composed of mol% or less. Particularly preferred are styrene polymers, vinyl chloride polymers, and methyl methacrylate polymers.
共重合可能な他の単量体の具体例としてはメチルアクリ
レート、エチルアクリレート、ｎ−フチルアクリレート
等のアクリレート系単量体ならびにアクリル酸、メタク
リル酸等が挙げられる。Specific examples of other copolymerizable monomers include acrylate monomers such as methyl acrylate, ethyl acrylate, and n-phthyl acrylate, as well as acrylic acid and methacrylic acid.
熱分解性重合体（Ｂ）の比粘度で示される重合度として
はアクリロニトリル系重合体（Ａｌと混合分散液とする
とき粘度の調整を容易にするために上記アクリロニトリ
ル系重合体（Ａ）の比粘度の測定法と同じ方法で求めら
れる比粘度が０，１〜０゜４特に０．２〜０．６の範囲
のものが好ましい。The degree of polymerization indicated by the specific viscosity of the thermally decomposable polymer (B) is determined by adjusting the ratio of the acrylonitrile polymer (A) to facilitate adjustment of the viscosity when preparing a mixed dispersion with the acrylonitrile polymer (Al). It is preferable that the specific viscosity determined by the same method as the viscosity measuring method is in the range of 0.1 to 0.4, particularly 0.2 to 0.6.
溶剤（Ｃ）は、前記アクリロニトリル系重合体（Ｎおよ
び熱分解性重合体（Ｂ）ならびに相溶剤（Ｄ）に対して
共通の溶剤となり得るものである。このような溶剤（Ｃ
）としてはジメチルアセトアミド、ジメチルホルムアミ
ドおよびジメチルスルホキシド等が好ましい。The solvent (C) can be a common solvent for the acrylonitrile polymer (N) and the thermally decomposable polymer (B) and the compatibilizer (D).
) is preferably dimethylacetamide, dimethylformamide, dimethylsulfoxide, or the like.
相溶剤（Ｄ）は、アクリロニ） ＩＪル系重合体（Ａ）
および熱分解性重合体ＣＢ）の両者に対して相溶効果を
示す相溶化剤となり得る重合体である。相溶効果を示す
ものとしてはオリゴマーのような低分子のものから高分
子のものまで種々あるが具体的にはアクリロニトリル系
重合体（Ａ）と相溶性を有するか、あるいは同一の単量
体から構成されるセグメン） （ａ）と、同様に熱分解
性重合体（Ｂ）と相溶性を有するか、または同一の単量
体から構成されるセグメン） （ｂ）とを、同一重合体
鎖中に含む重合体、例えばブロック共重合体あるいはグ
ラフト共重合体が好ましく用いられる。このようなブロ
ック共重合体或いはグラフト共重合体は公知の方法、例
えば特公昭６１−３９９７８号公報に記載のブロック共
重合体或いはグラフト共重合体の製造例の方法により製
造することができる。Compatibility agent (D) is acrylonitrile) IJ-based polymer (A)
and thermally decomposable polymer CB), which can act as a compatibilizer that exhibits a compatibility effect with both. There are a variety of substances that exhibit a compatibility effect, from low molecular weight ones such as oligomers to high molecular weight ones, but specifically, those that are compatible with the acrylonitrile polymer (A), or those that are made from the same monomer. Segment composed of (a) and segment) (b) that is similarly compatible with the thermally decomposable polymer (B) or composed of the same monomer, in the same polymer chain. For example, a block copolymer or a graft copolymer is preferably used. Such a block copolymer or graft copolymer can be produced by a known method, for example, by the method described in Japanese Patent Publication No. 61-39978 as an example of producing a block copolymer or graft copolymer.
相溶剤（Ｄ）は、アクリロニトリル系重合体（Ａ）と熱
分解性重合体（Ｂ）とを溶剤（Ｃ）と共に混合する際に
７クリロニトリル系重合体囚溶液と熱分解性重合体（Ｂ
）溶液とを均一な小さな分散粒子とし、得られる分散溶
液を安定な状態にする作用を有するものである。さらに
この相溶剤（Ｄ）は相溶効果を上げるばかりでなく、島
成分となる熱分解性重合体（Ｂ）の分散相としての大き
さの制御にも用いられ、このことは最終的に得られる炭
素繊維系多孔質中空糸膜の細孔径の基となる熱分解性重
合体（Ｂ）のフィブリルの大きさを制御することにつな
がる。従ってこの相溶剤（ＤＪの使用量の多少は最終的
に得られる。多孔質中空糸膜の細孔半径の大小にも関係
し、その使用量が多くなると細孔の半径を小さくし、細
孔の大きさの分布を小さ（し、細孔半径が均一な分布傾
向となる。The compatibilizer (D) is used to mix the acrylonitrile polymer (A) and the thermally decomposable polymer (B) together with the solvent (C).
) It has the effect of making the solution into uniform small dispersed particles and making the resulting dispersion solution stable. Furthermore, this compatibilizer (D) not only improves the compatibility effect, but also controls the size of the dispersed phase of the thermally decomposable polymer (B), which becomes the island component, which ultimately improves the compatibility effect. This leads to controlling the size of the fibrils of the thermally decomposable polymer (B), which is the basis of the pore diameter of the carbon fiber porous hollow fiber membrane. Therefore, the amount of compatibilizer (DJ) used depends on the final amount obtained.It is also related to the size of the pore radius of the porous hollow fiber membrane. The size distribution of the pores becomes small (and the pore radius tends to be uniformly distributed).
相溶剤（Ｄ）としてはアクリロニトリル６０モル％以上
、熱分解性重合体（Ｂ）の構成成分である単量体１０モ
ル％以上およびこれらと共重合可能な他の単量体１０モ
ル％以下から構成されるブロック共重合体やグラフト共
重合体が好ましい。The compatibilizer (D) includes 60 mol% or more of acrylonitrile, 10 mol% or more of monomers that are constituent components of the thermally decomposable polymer (B), and 10 mol% or less of other monomers copolymerizable with these. A block copolymer or a graft copolymer composed of these materials is preferred.
炭素繊維系多孔質中空糸膜を製造するに際してのアクリ
ロニトリル系重合体（Ａ）、熱分解性重合体（Ｂ）およ
び相溶剤（ＤＪの好ましい混合割合はアクリロニトリル
系重合体（Ａ）が１０〜９０重量％好ましくは２０〜８
０重量％、熱分解性重合体（Ｂ）が１０〜９０重量％好
ましくは２０〜８０重量％、相溶剤（Ｄ）が０〜・、１
０重量％好ましくは０〜５重量％〔ただしくＡ）成分、
（Ｂ）成分および（Ｄ）成分の合計量が１００重量％〕
である。When producing a carbon fiber porous hollow fiber membrane, the preferred mixing ratio of the acrylonitrile polymer (A), the thermally decomposable polymer (B), and the compatibilizer (DJ) is 10 to 90% of the acrylonitrile polymer (A). Weight% preferably 20-8
0% by weight, 10 to 90% by weight of the thermally decomposable polymer (B), preferably 20 to 80% by weight, and 0 to 1% of the compatibilizer (D)
0% by weight, preferably 0 to 5% by weight [with the exception of component A),
The total amount of component (B) and component (D) is 100% by weight]
It is.
熱分解性重合体（Ｂ）の混合量が１０重量％より少ない
と、最終的に得られる多孔質中空糸膜の内壁表面から外
壁表面に連通ずる細孔が得られにくいので好ましくない
。また熱分解性重合体（Ｂ）の混合量が多くなるに従っ
て連通孔が増加し細孔容積も増加し、その混合量が９０
重量％を超えると全細孔容積が大きくなり、その結果最
終的に得られる多孔質中空糸膜の強度が低下するので好
ましくない。If the amount of the thermally decomposable polymer (B) mixed is less than 10% by weight, it is not preferable because it is difficult to obtain pores communicating from the inner wall surface to the outer wall surface of the porous hollow fiber membrane finally obtained. Furthermore, as the amount of the thermally decomposable polymer (B) mixed increases, the number of communicating pores increases and the pore volume also increases.
If it exceeds % by weight, the total pore volume increases, resulting in a decrease in the strength of the finally obtained porous hollow fiber membrane, which is not preferable.
相溶剤（Ｄ）はその混合量が増加するに従って分散粒子
の大きさが小さくなり、この結果、分散溶液の安定性が
増加する。そしてこのことは最終的に得られる多孔質中
空糸膜の細孔の半径を小さくし、細孔の大きさの分布を
小さくするのに寄与するが、その混合量が５重量％を超
えるとその添加効果は飽和するため５重量％までの混合
量で十分である。As the mixing amount of the compatibilizer (D) increases, the size of the dispersed particles decreases, and as a result, the stability of the dispersion solution increases. This contributes to reducing the radius of the pores and the distribution of pore sizes in the porous hollow fiber membrane that is finally obtained, but if the mixing amount exceeds 5% by weight, Since the effect of addition is saturated, a mixing amount of up to 5% by weight is sufficient.
混合重合体と溶剤（Ｃ）との混合溶液中の重合体濃度は
１０〜６５重量％、好ましくは１５〜３０重量％である
。混合は溶解時に同時に行ってもよい。またそれぞれ単
独で溶解し、紡糸直前に公知の駆動部分不要の静的混練
素子等を用いて溶液同志の混合を行ってもよい。この場
合相溶剤（ＤＪは必ずしも必要ではない。混合の効果は
エレメントの個数で制御される。即ち、エレメントの数
が多くなると最終的に得られる多孔質中空糸膜の細孔の
半径は小さくなる。The polymer concentration in the mixed solution of mixed polymer and solvent (C) is 10 to 65% by weight, preferably 15 to 30% by weight. Mixing may be performed simultaneously during dissolution. Alternatively, each may be dissolved individually, and the solutions may be mixed together immediately before spinning using a known static kneading element that does not require a driving part. In this case, a compatibilizer (DJ is not necessarily required). The effect of mixing is controlled by the number of elements. In other words, as the number of elements increases, the radius of the pores of the porous hollow fiber membrane finally obtained becomes smaller. .
混合溶液中の重合体の濃度が１０重量％より少ないと最
終的に得られる多孔質中空糸膜の強度特性が低下するた
め好ましくない。また３５重量％を超えると混合溶液の
粘度が高くなり、混合溶液の安定性が欠け、濾過が困難
になる等のトラブルの要因となるため好ましくない。If the concentration of the polymer in the mixed solution is less than 10% by weight, the strength characteristics of the finally obtained porous hollow fiber membrane will deteriorate, which is not preferable. Moreover, if it exceeds 35% by weight, the viscosity of the mixed solution becomes high, which causes problems such as lack of stability of the mixed solution and difficulty in filtration, which is not preferable.
混合分散溶液は、例えば環状スリット、あるいは硝石型
のノズル等を用いて中空状に紡糸する。紡糸方式は湿式
紡糸、乾湿式紡糸、乾式紡糸の何れかで紡糸することが
できるが、特に乾湿式紡糸が好ましい。The mixed dispersion solution is spun into a hollow shape using, for example, an annular slit or a saltpeter-type nozzle. The spinning method can be any of wet spinning, wet-dry spinning, and dry spinning, and wet-dry spinning is particularly preferred.
乾湿式紡糸法で紡糸する場合を例にして説明すると、例
えば硝石型ノズルから吐出された溶液は、いったん空気
中を走行した後、凝固浴中に導かれ凝固される。凝固剤
は、比較的凝固力のゆるやかなものが、相分離も穏やか
に進み強靭な膜が得られやすいので好ましい。通常は溶
剤の水溶液が用いられ、溶剤濃度４０〜８５重量％特に
６０〜８０重量％、４０℃以下特に２０℃以下の温度で
凝固することが好ましい。この範囲を外れると脆弱な中
空糸膜と成りやすいので好ましくない。To explain the case of spinning using a dry-wet spinning method, for example, a solution discharged from a saltpeter type nozzle once travels in the air, and then is introduced into a coagulation bath and coagulated. It is preferable to use a coagulant that has a relatively gentle coagulating force because phase separation proceeds gently and a strong film is easily obtained. Usually, an aqueous solution of a solvent is used, and the solvent concentration is preferably 40 to 85% by weight, particularly 60 to 80% by weight, and solidification is preferably carried out at a temperature of 40°C or lower, particularly 20°C or lower. If it is outside this range, it is not preferable because the hollow fiber membrane tends to be fragile.
次いで温水又は熱水中で洗浄され、延伸される。延伸は
二段階以上で施し、全延伸倍率３倍以上、好ましくは５
倍以上た延伸される。延伸は繊維の構造の破壊が生じな
い範囲で高いほど好ましいが全延伸倍率の上限は延伸法
、延伸媒体により異なるが、延伸破断が生じる延伸倍率
の約８割が目安となる。次いで得られた延伸糸は乾燥さ
れて、主にアクリロニトリル系重合体（ト）と熱分解性
重合体（Ｂ）とのブレンド中空糸膜が製造される。It is then washed in warm or hot water and stretched. Stretching is performed in two or more stages, and the total stretching ratio is 3 times or more, preferably 5 times.
Stretched more than twice as long. It is preferable that the stretching is as high as possible without causing destruction of the fiber structure, but the upper limit of the total stretching ratio varies depending on the stretching method and the stretching medium, but a guideline is approximately 80% of the stretching ratio at which stretch breakage occurs. Next, the obtained drawn fiber is dried to produce a hollow fiber membrane blend mainly of an acrylonitrile polymer (I) and a thermally decomposable polymer (B).
中空糸膜の大きさは、ノズル、溶液吐出量、および延伸
条件等により変更できるが、おおよそ内径２０〜１００
０μｍ１膜厚は内径の１７４〜１／１０の範囲が製造し
易い。次いで得られた前記重合体のブレンド中空糸膜は
、例えば２００〜３００℃の温度の酸化性ガス（０２、
ｏ８、Ｓ、 Ｎｏ、 Ｓｏ□等を含むガス）雰囲気中、
通常は空気中で処理して耐炎化処理を施す。なお耐炎化
処理を施す際には、中空糸膜繊維は長さ方向に収縮が生
じないように制御する。耐炎化工程での過度の収縮は中
空糸膜繊維の機械的強度を低下させるので好ましくない
。また過度の伸張は中空糸膜繊維の切断の要因になるの
で好ましくない。従って耐炎化工程での伸張は０〜１５
％の範囲に制御して耐炎化処理することが好ましい。The size of the hollow fiber membrane can be changed depending on the nozzle, solution discharge amount, stretching conditions, etc., but the inner diameter is approximately 20 to 100 mm.
It is easy to manufacture a film thickness of 0 μm in a range of 174 to 1/10 of the inner diameter. Then, the obtained polymer blend hollow fiber membrane is heated with an oxidizing gas (02,
gas containing o8, S, No, So□, etc.) in the atmosphere,
It is usually treated in air to make it flame resistant. When flame-retardant treatment is performed, the hollow fiber membrane fibers are controlled so as not to shrink in the length direction. Excessive shrinkage in the flameproofing process is undesirable because it reduces the mechanical strength of the hollow fiber membrane fibers. Excessive stretching is also undesirable as it may cause the hollow fiber membrane fibers to break. Therefore, the elongation during the flameproofing process is 0 to 15
It is preferable to carry out the flame-retardant treatment by controlling the amount within a range of 1.
次いで得られた耐炎化処理を施した中空糸膜を４００〜
１２００°Ｃ１好ましくは６００〜１２００℃の温度の
不活性ガス（Ｎ２、Ａｒ、Ｈｅ等）雰囲気中でまたは不
活性ガスと酸化性ガス（ＨＣＩ、Ｎ２０、Ｃ０１０□等
）の混合ガス中で、好ましくは不活性ガス中で、通常は
窒素ガス中で張力を制御しつつ炭素化処理する。この過
程で熱分解性重合体（Ｂ）の、繊維軸に配列したフイフ
リル成分は熱分解、解重合し、単量体等の低分子に分解
し逃散することにより本発明の炭素繊維系多孔質中空糸
膜とすることができる。Next, the obtained hollow fiber membrane subjected to flame-retardant treatment was heated to 400~
1200°C1 Preferably in an inert gas (N2, Ar, He, etc.) atmosphere at a temperature of 600 to 1200°C or in a mixed gas of an inert gas and an oxidizing gas (HCI, N20, CO10□, etc.) is carbonized in an inert gas, usually nitrogen gas, while controlling the tension. In this process, the fifuryl components of the thermally decomposable polymer (B), which are arranged along the fiber axis, are thermally decomposed and depolymerized, decomposed into low molecules such as monomers, and released. It can be a hollow fiber membrane.
本発明の炭素繊維系多孔質中空糸膜の多孔質構造は、ス
ポンジ構造とは異なり、繊維軸に並行な無数の細孔より
構成され、しかもこの細孔が中空糸膜の内壁表面から外
壁表面に連続的につながった細孔である。これはＸ線小
角の散乱強度または走査型電子顕微鏡によって観測する
ことができる。かかる特異な多孔質構造は次のような理
由により形成されるものと考えられる。Unlike a sponge structure, the porous structure of the carbon fiber-based porous hollow fiber membrane of the present invention is composed of countless pores parallel to the fiber axis, and these pores extend from the inner wall surface to the outer wall surface of the hollow fiber membrane. These are pores that are connected continuously. This can be observed by small-angle X-ray scattering intensity or by a scanning electron microscope. It is thought that such a unique porous structure is formed for the following reasons.
即ち混合溶液からの紡糸に際して、それぞれの分散粒子
は剪断応力や延伸の作用を受けて、繊維軸に並行に配列
し、それぞれの重合体のフィブリルは互いに相分離し、
絡み合い網目構造な形成する。従って炭素化での熱分へ
重合体（ＢＪの繊維軸に平行に配列したフィブリルが熱
分解して逃散して無数の細孔が形成される結果、このよ
うな多孔質構造が最終的に得られ多孔質中空糸膜の強度
特性並びに柔軟特性に優れたものとしている。アクリロ
ニトリル系重合体（匂のフィブリル構造よりなる炭素質
構造もまた繊維軸に平行に細く連なった構造であり、こ
のことが本発明の中空糸膜を強靭なものとしている。さ
らに炭素質であるため耐熱性にも優れている。That is, during spinning from a mixed solution, each dispersed particle is subjected to the action of shear stress and stretching, and is arranged parallel to the fiber axis, and the fibrils of each polymer phase separate from each other.
Intertwined to form a network structure. Therefore, due to the heat generated during carbonization, the fibrils arranged parallel to the fiber axis of the polymer (BJ) thermally decompose and escape, forming countless pores, and as a result, such a porous structure is finally obtained. This makes the porous hollow fiber membrane superior in strength and flexibility properties.The carbonaceous structure of the acrylonitrile polymer (which has a fibrillar structure) is also a structure in which thin fibrils are connected parallel to the fiber axis; The hollow fiber membrane of the present invention is made strong.Furthermore, since it is carbonaceous, it also has excellent heat resistance.
本発明の炭素繊維系多孔質中空糸膜の特徴は、細孔容積
微分曲線から求めた細孔半径の孔径分布が非常にシャー
プであるため、高い分離性能を示し、全細孔容積が大き
く単位膜厚当りの孔数が多く透水速度を高いものにして
いる。また本発明の炭素膜は化学的な安定性も高（、あ
らゆるＩ）Ｈ領域及びほとんどの薬液に対して強い抵抗
力を示す。The carbon fiber porous hollow fiber membrane of the present invention is characterized by a very sharp pore size distribution of pore radii determined from a pore volume differential curve, so it exhibits high separation performance and has a large total pore volume per unit. The number of pores per membrane thickness is large, making the water permeation rate high. The carbon film of the present invention also has high chemical stability (and exhibits strong resistance to all I)H regions and most chemical solutions.
本発明の炭素繊維系多孔質中空糸膜は空気中での重量減
少が１０％に達する温度は６００℃から６５０℃の範囲
でより高い温度で使用可能なモジュールを提供すること
が可能である。このように優れた性質を有するため、種
々の用途例えば薬品工業分野におけるパイロジエン、高
分子物質等の分離および精製、化学工業分野におけるガ
ス分離、特に有機ガスの分離および有機薬品の精製等、
食料品工業分野における酒類、清涼飲料水、醤油、酢等
の清澄に効果的に用いることができる。さらにはパイオ
ニ業分野における酵素からの生成物の精製、蛋白質や酵
素等の分離等、メディカル分野における蛋白質やウィル
ス、菌等の分離や、高温度での滅菌、殺菌を必要とする
分野で特に有用である。耐熱性を必要とする分野例えば
発電所の復水タービンヒータードレイン用濾過膜として
も使用できる。The carbon fiber porous hollow fiber membrane of the present invention can provide a module that can be used at a higher temperature in the range of 600°C to 650°C at which the weight loss in air reaches 10%. Because of these excellent properties, it is used for various purposes, such as the separation and purification of pyrogenes and polymer substances in the pharmaceutical industry, gas separation in the chemical industry, especially the separation of organic gases and the purification of organic chemicals.
It can be effectively used for clarifying alcoholic beverages, soft drinks, soy sauce, vinegar, etc. in the food industry. Furthermore, it is particularly useful in fields that require purification of products from enzymes and separation of proteins and enzymes in the pioneering industry, separation of proteins, viruses, bacteria, etc. in the medical field, and fields that require sterilization and sterilization at high temperatures. It is. It can also be used in fields that require heat resistance, such as filtration membranes for condensate turbine heater drains in power plants.
以下、実施例により本発明を具体的に説明する。なお以
下の記載中「部」は重量部を示す。Hereinafter, the present invention will be specifically explained with reference to Examples. Note that "parts" in the following description indicate parts by weight.
１）重合体の比粘度は、重合体０．１ｙを０．１Ｎのロ
ダンノーダを含むジメチルホルムアミド１００ｍ１に溶
解し２５°Ｃで測定した。1) The specific viscosity of the polymer was measured at 25°C by dissolving 0.1y of the polymer in 100ml of dimethylformamide containing 0.1N Rodan Noda.
２）炭素繊維系多孔質中空糸膜の細孔分布構造はＣＡＲ
ＬＯＥＲＢＡ社製ポロシメーター２００を用いて測定し
、細孔半径は円筒換算半径として求めた。2) The pore distribution structure of the carbon fiber porous hollow fiber membrane is CAR
It was measured using Porosimeter 200 manufactured by LOERBA, and the pore radius was determined as a cylindrical equivalent radius.
３）比表面積はメタノール等温吸着曲線を測定、ＢＥＴ
の式を適用して計算した。3) Specific surface area is measured by methanol isothermal adsorption curve, BET
Calculated by applying the formula.
４）単繊維強伸度は、テンシロンＵＴＭ −ＩＩ型（東
洋側機（株）製）を用いて、引張速度１００％／分で測
定した。4) Single fiber strength and elongation were measured using Tensilon UTM-II type (manufactured by Toyo Sideki Co., Ltd.) at a tensile rate of 100%/min.
５）屈曲時の曲率半径は、半径只のシリンダに多孔質中
空糸膜を１８００以上巻きつけたとき、折れや、切断が
生じないとき、その最低の半径を曲率半径とし、柔軟性
の目安とした。5) The radius of curvature at the time of bending is the minimum radius of curvature when no bending or cutting occurs when the porous hollow fiber membrane is wound around a cylinder with a radius of 1800 or more, and is used as a guideline for flexibility. did.
６）耐熱性は、試料を動的熱重サオ分析（ダイナミック
・サーモ・グラピメトリック・アナリシス（ＴＧＡ））
により空気雰囲気中で昇温速度１０℃／分で測定したと
きの、試料が１０重量％分解するときの温度で示した。6) Heat resistance was determined by dynamic thermograpimetric analysis (TGA) of the sample.
It is shown as the temperature at which 10% by weight of the sample decomposes when measured in an air atmosphere at a heating rate of 10° C./min.
７）透水速度は、有効長さ１０ｃｒｎ、実効表面積１
ｍｌの試作モジュールの一方から圧力１ｋｇ／ｃｒｎ２
で中空糸の内壁から外壁へ通過した水の透過量を測定し
て求めた。7) Water permeation rate is effective length 10 crn, effective surface area 1
Pressure 1kg/crn2 from one side of ml prototype module
The amount of water permeated from the inner wall of the hollow fiber to the outer wall was measured.
実施例１
アクリロニトリル（以下ＡＮと略記する）９８モル％、
メタクリル酸（以下ＭＡＡと略記する）２モル％から構
成される比粘度０．２４のＡＮ／ＭＡＡ共重合体（Ａ）
６０部とメチルメタクリレート（以下−と略記する）９
９モル％、アクリル酸メチル（以下ＭＡと略記する）１
モル％から構成される比粘度０．２１のＭＭＡ ／ Ｍ
Ａ共重合体である熱分解性共重合体（Ｂ） ４０部と、
下記の方法にて調製した相溶剤（Ｄ、）の混合量を０〜
５部変更して、第１表に示した４種類の混合溶液を調製
した。Example 1 Acrylonitrile (hereinafter abbreviated as AN) 98 mol%,
AN/MAA copolymer (A) with a specific viscosity of 0.24 composed of 2 mol% of methacrylic acid (hereinafter abbreviated as MAA)
60 parts and methyl methacrylate (hereinafter abbreviated as -) 9
9 mol%, methyl acrylate (hereinafter abbreviated as MA) 1
MMA with specific viscosity 0.21 composed of mol%/M
40 parts of a thermally decomposable copolymer (B) which is a copolymer A;
The mixing amount of the compatibilizer (D,) prepared by the following method is 0 to 0.
Four types of mixed solutions shown in Table 1 were prepared by changing 5 parts.
なお、溶剤（Ｃ）はジメチルホルムアミド（以下ＤＭＦ
と略記する）を用い、重合体濃度２６重量％とし、混合
溶液は温度６０℃に保持し脱泡した。Note that the solvent (C) is dimethylformamide (hereinafter referred to as DMF).
), the polymer concentration was set to 26% by weight, and the mixed solution was kept at a temperature of 60° C. to defoam.
相溶剤（Ｄｌ）の調製ニ
ジクロヘキサノ／パーオキシド（バーオキサＩ（、日本
油脂社製）１部を、馬仏１００部に溶かし、純水８００
部と乳化剤としてペレックスＯＴＰ （日本油脂社製）
１部を反応釜に加えて、不活性ガスで十分に置換した後
、４０°Ｃに保持し、ロンガリット０．７６部と硫酸水
溶液でｐＨ３とした後、重合を開始した。そのまま攪拌
を続け１５０分で第一段目の乳化重合を完結させた。次
いで第二段目として、この乳化液にハフ２部を加えた後
、温度を７０℃に昇温して、再び１５０分攪拌を続け、
さらに芒硝４部を加え３０分攪拌して重合を完了させた
。重合体を取出し、濾過、水洗および乾燥して重合率６
５゜７％の比粘度０．１９のブロック共重合体の相溶剤
（Ｄ、）を得た。Preparation of compatibilizer (Dl) Dissolve 1 part of dichlorohexano/peroxide (Veroxa I (manufactured by NOF Corporation) in 100 parts of Mabutsu, and add 800 parts of pure water.
and Pellex OTP as an emulsifier (manufactured by NOF Corporation)
After adding 1 part to the reaction vessel and sufficiently purging with an inert gas, the temperature was maintained at 40°C, and the pH was adjusted to 3 with 0.76 parts of Rongalit and an aqueous sulfuric acid solution, and then polymerization was started. Stirring was continued to complete the first stage emulsion polymerization in 150 minutes. Next, in the second stage, after adding 2 parts of Hough to this emulsion, the temperature was raised to 70°C and stirring was continued for 150 minutes again.
Furthermore, 4 parts of Glauber's salt was added and stirred for 30 minutes to complete the polymerization. The polymer was taken out, filtered, washed with water, and dried until the polymerization rate was 6.
A block copolymer compatibilizer (D,) with a specific viscosity of 0.19 and 5.7% was obtained.
外形’１． Ｏｍｍφ、内径１．５朋φの鞘部と１．０
ｍ尻φの８部よりなる、硝石型ノズルの鞘部より調整し
た４種類の混合溶液を１種類毎に、８部より空気を１０
朋の水注圧でそれぞれ吐出し、空気中を５ｃ７ｎ走行さ
せた後、ＤＭＦ ７０重量％水溶液、２℃の温度の凝固
浴に導き紡糸し、凝固させ、次いで６０°Ｃの温水中で
洗浄と２．８倍の延伸を施した。次いで、９８℃の熱水
中で２倍延伸した。この全延伸倍率５．６倍の繊維を１
６０℃の熱ロールを通して乾燥して、４種類の重合体ブ
レンド系中空糸を製造した。Outline '1. Ommφ, inner diameter 1.5mmφ sheath and 1.0
For each type of mixed solution prepared from the sheath of the saltpetre nozzle, which consists of 8 parts of m-butt φ, 10 parts of air is mixed with 8 parts of the mixed solution.
After each was discharged with water injection pressure and run in the air for 5c7n, it was introduced into a coagulation bath containing a 70% by weight DMF solution at a temperature of 2°C, spun and coagulated, and then washed in warm water at 60°C. It was stretched 2.8 times. Then, it was stretched twice in hot water at 98°C. This fiber with a total stretching ratio of 5.6 times is
The fibers were dried through a hot roll at 60° C. to produce four types of polymer blend hollow fibers.
これら４種類の中空糸を、それぞれ長さ５０ｍのステン
レススチール製の枠にセットして定長で２３０℃の温度
、空気雰囲気中で３時間処理し耐炎化した。次いで窒素
ガス雰囲気中で常温から８００℃まで５０分、８００℃
で２０分炭素化処理して乳化して、本発明の炭素繊維系
多孔質中空糸膜を製造した。These four types of hollow fibers were each set in a stainless steel frame with a length of 50 m, and were treated at a constant length in an air atmosphere at a temperature of 230° C. for 3 hours to make them flame resistant. Then, in a nitrogen gas atmosphere, the temperature was raised from room temperature to 800°C for 50 minutes at 800°C.
The mixture was carbonized and emulsified for 20 minutes to produce the carbon fiber porous hollow fiber membrane of the present invention.
これら４種類の中空糸膜はそれぞれ内径が３８０±１０
μｍ、膜厚が５０±５μｍであった。Each of these four types of hollow fiber membranes has an inner diameter of 380±10
The film thickness was 50±5 μm.
これら中空糸膜の単繊維強伸度、比表面積、細孔半径極
大値、全細孔容積、屈曲時の曲率半径、透水速度および
耐熱性を測定した結果を第１表に示した。Table 1 shows the results of measuring single fiber strength and elongation, specific surface area, maximum pore radius, total pore volume, radius of curvature when bent, water permeation rate, and heat resistance of these hollow fiber membranes.
第１表より、相溶剤（Ｄ、）である（ＡＮ／ＭＭＡ）ブ
ロック共重合体の混合量が多くなるに従って細孔半径極
大値が小さくなることがわかる。From Table 1, it can be seen that the maximum value of the pore radius becomes smaller as the amount of the (AN/MMA) block copolymer that is the compatibilizer (D) increases.
なお、第１図にこれら４種類の中空糸膜（実験腐１〜４
）の細孔容積微分曲線を示す。Furthermore, Figure 1 shows these four types of hollow fiber membranes (experimental corrosion 1 to 4).
) shows the pore volume differential curve.
第 １
表
実施例２
ＡＮ ９５モル％、ＭＡ４モル％、イタコン酸（以下Ｉ
Ａと略記する）１モル％から構成される比粘度０．２１
のＡＮ／ＭＡ／ＩＡ共重合体囚と凪仏８７モル％、ＭＡ
１３モル％から構成される比粘度０．１９のＭＭＡ／Ｍ
Ａ共重合体である熱分解性重合体′（Ｂ）および下記の
方法で調製したＡＮ ３０モル％、 ＭＭＡ ６５モル
％、酢酸ビニル（以下ＶＡｃと略記する）５モル％から
構成される比粘度０゜１８のブロック重合体である相溶
剤（Ｄ２）とを、第２表に示した混合比で、溶剤（Ｃ）
であるジメチルアセトアミド（以下ＤＭＡｃと略記する
）に、重合体濃度２４重量％で溶解した。Table 1 Example 2 AN 95 mol%, MA 4 mol%, itaconic acid (hereinafter referred to as I
Specific viscosity 0.21 composed of 1 mol% (abbreviated as A)
AN/MA/IA copolymer and Nagibutsu 87 mol%, MA
MMA/M with a specific viscosity of 0.19 composed of 13 mol%
A specific viscosity composed of a thermally decomposable polymer '(B) which is a copolymer and 30 mol% of AN prepared by the method below, 65 mol% of MMA, and 5 mol% of vinyl acetate (hereinafter abbreviated as VAc). Solvent (C) was mixed with compatibilizer (D2), which is a block polymer of 0°18, at the mixing ratio shown in Table 2.
The polymer was dissolved in dimethylacetamide (hereinafter abbreviated as DMAc) at a polymer concentration of 24% by weight.
相溶剤（Ｄ２）の調製ニ
ジクロヘキサノンパーオキシド（パーオキサＨ１日本油
脂社製）１部をＭＭＡ １００部に溶かし、純水８００
部と乳化剤としてペレックス０ＴＰ（日本油脂社製）１
部を反応釜に加えて、不活性ガスで十分に置換した後、
４０℃に保持し、ロンガリツ） ０．、７６部と硫酸水
溶液でｐＨ３とした後、重合を開始した。そのまま攪拌
を続け１２０分で第一段目の乳化重合を完結させた。Preparation of compatibilizer (D2) Dissolve 1 part of dichlorohexanone peroxide (Peroxa H1 manufactured by NOF Corporation) in 100 parts of MMA, and dissolve 800 parts of pure water.
and Pellex 0TP (manufactured by Nippon Oil & Fats Co., Ltd.) as an emulsifier.
After adding part to the reaction vessel and thoroughly replacing with inert gas,
0. After adjusting the pH to 3 with 76 parts of sulfuric acid and an aqueous sulfuric acid solution, polymerization was started. Stirring was continued to complete the first stage emulsion polymerization in 120 minutes.
次いで第二段目としてこの乳化液にＡＮ ６０部、ＶＡ
ｃ １０部を加えた後、温度を７０℃に昇温して、再び
１５０分攪拌を続け、さらに芒硝４部を加え３０分攪拌
して重合を完了させた。重合体を取出し、濾過、水洗お
よび乾燥して重合率６５％の比粘度０．１８、組成ＡＮ
３０モル％／ＭＭＡ ６５モル％／ Ｖ’Ａｃ ５モ
ル％のブロック重合体の相溶剤（Ｄ２）を得た。Then, in the second stage, 60 parts of AN and VA were added to this emulsion.
After adding 10 parts of C, the temperature was raised to 70°C and stirring was continued again for 150 minutes.Furthermore, 4 parts of Glauber's salt was added and stirred for 30 minutes to complete polymerization. The polymer was taken out, filtered, washed with water, and dried to give a polymerization rate of 65%, a specific viscosity of 0.18, and a composition of AN.
A block polymer compatibilizer (D2) of 30 mol%/MMA 65 mol%/V'Ac 5 mol% was obtained.
実施例１と同様のノズルを用いて実施例１と同様に吐出
し、空気中を５Ｃ！ｎ走行させた後、ＤＭＡｃ ７２重
量％水溶液、温度７°Ｃの凝固浴中に導き紡糸し、凝固
させた。次いで６０℃の温水中で洗浄し、２倍の延伸を
施した。さらに９８℃の熱水中で６．２倍延伸した。一
方、比較試料（実験Ａ６９）として、熱水中で延伸せず
、定長で通過させる以外は全て同じ条件で処理し、それ
ぞれ乾燥させて５種類の重合体ブレンド系中空糸を製造
した。実施例１と同じ方法により、これら５種類の中空
糸を金枠にセットして、２４０℃の温度の空気雰囲気中
で３時間耐炎化処理した。Using the same nozzle as in Example 1, discharge in the same manner as in Example 1, and 5C! After running for n times, the fiber was introduced into a coagulation bath containing a 72% by weight DMAc aqueous solution at a temperature of 7°C, and was spun and coagulated. Then, it was washed in warm water at 60°C and stretched twice. Furthermore, it was stretched 6.2 times in hot water at 98°C. On the other hand, as a comparative sample (Experiment A69), five types of polymer blend hollow fibers were manufactured by processing under the same conditions except that the fibers were not stretched in hot water and passed through at a constant length, and then dried. By the same method as in Example 1, these five types of hollow fibers were set in a metal frame and flame resistant treated in an air atmosphere at a temperature of 240° C. for 3 hours.
次いで窒素雰囲気中９００℃の温度で１０分間炭素化処
理して、炭素繊維系多孔質中空糸膜を製造した。第２表
に得られた５種類の中空糸膜の各種性能を示す。Next, carbonization treatment was performed at a temperature of 900° C. for 10 minutes in a nitrogen atmosphere to produce a carbon fiber-based porous hollow fiber membrane. Table 2 shows various performances of the five types of hollow fiber membranes obtained.
第２表
系中空繊維目付
第２表より、熱分解性重合体のブレンド量が多くなると
、全細孔容積が増加することがわかる。比較試料の実験
／１６５は閉孔で連通孔のないものであった。比較試料
である実験層９のものは柔軟性に劣るため使用に耐えな
いものであった。Table 2 Hollow fiber basis weight Table 2 shows that as the blend amount of the thermally decomposable polymer increases, the total pore volume increases. The comparative sample Experiment/165 had closed pores and no communicating pores. The comparative sample, Experimental Layer 9, had poor flexibility and could not be used.
なお第２図にこれら５種類の中空糸膜（実験Ａ５〜９）
の細孔容積累積分布曲線を示す。Figure 2 shows these five types of hollow fiber membranes (Experiments A5 to 9).
The pore volume cumulative distribution curve of FIG.
実施例３
実施例２の実験屋７で製造されたアクリル系中空糸を用
いて、２５６／２３９／２４２／２５０ ’Ｃの４段階
の温度分布の空気雰囲気中を、２０ ｍ／ Ｈｒの速度
で耐炎化処理した。次いで第３表に示した窒素雰囲気の
炭素化温度中を１５ｍ／Ｈｒの速度で多孔質化処理して
、本発明の多孔質中空糸膜を製造した。これらの繊維の
各種性能を第３表に示す。Example 3 Using the acrylic hollow fiber manufactured in Experimental Shop 7 of Example 2, it was heated at a speed of 20 m/Hr in an air atmosphere with a four-stage temperature distribution of 256/239/242/250'C. Flame resistant treated. Next, porous hollow fiber membranes of the present invention were manufactured by performing porous treatment at a rate of 15 m/Hr at the carbonization temperature in a nitrogen atmosphere shown in Table 3. Table 3 shows the various performances of these fibers.
また、第６図にこれら４種類の中空糸膜（実験Ａ １０
〜１６）の細孔容積累積分布曲線を示す。Figure 6 also shows these four types of hollow fiber membranes (Experiment A 10
The pore volume cumulative distribution curves of ~16) are shown.
第 ６ 表
第３表より、炭素化温度が高くなるに従って、細孔半径
極大値は小さく、全細孔容積も小さくなるが、耐熱性は
高くなることがわかる。Table 6 From Table 3, it can be seen that as the carbonization temperature increases, the maximum value of the pore radius decreases and the total pore volume decreases, but the heat resistance increases.
付記
１、 アクリロニトリル系重合体（Ａ）がポリアクリロ
ニトリル、アクリロニトリル−メタクリル酸共重合体、
アクリロニトリル−メチルアクリレート−イタコン酸共
重合体またはアクリロニトリル−メチルアクリレート−
メタクリル酸共重合体であることを特徴とする第３項ま
たは第４項記載の製法。Additional note 1, the acrylonitrile polymer (A) is polyacrylonitrile, acrylonitrile-methacrylic acid copolymer,
Acrylonitrile-methyl acrylate-itaconic acid copolymer or acrylonitrile-methyl acrylate-
4. The method according to item 3 or 4, wherein the copolymer is a methacrylic acid copolymer.
２、熱分解性重合体（Ｂ）が芳香族ビニル系単量体、脂
肪族ビニル系単量体もしくはメタクリレート系単量体の
単独重合体またはこれら単量体単位５１モル％以上とア
クリロニトリル以外の他の共重合可能な単量体単位４９
モル％以下から構成される共重合体であることを特徴と
する第３項または第４項記載の製法。2. The thermally decomposable polymer (B) is a homopolymer of an aromatic vinyl monomer, an aliphatic vinyl monomer, or a methacrylate monomer, or a polymer containing 51 mol% or more of these monomer units and a polymer other than acrylonitrile. Other copolymerizable monomer units 49
5. The method according to item 3 or 4, wherein the copolymer is composed of mol % or less.
６、 熱分解性重合体（Ｂ）がスチレン系重合体、ビニ
ルクロライド系重合体またはメチルメタクリレート系重
合体であることを特徴とする第３項または第４項記載の
製法。6. The method according to item 3 or 4, wherein the thermally decomposable polymer (B) is a styrene polymer, a vinyl chloride polymer, or a methyl methacrylate polymer.
４、 アクリロニトリル系重合体（Ａ）の比粘度が０゜
１〜０．４であることを特徴とする第３項または第４項
記載の製法。4. The method according to item 3 or 4, wherein the acrylonitrile polymer (A) has a specific viscosity of 0°1 to 0.4.
５、 アクリロニトリル系重合体（Ａ）の比粘度が０゜
２〜０．６であることを特徴とする第６項または第４項
記載の製法。5. The method according to item 6 or 4, wherein the acrylonitrile polymer (A) has a specific viscosity of 0°2 to 0.6.
６、熱分解性重合体（Ｂ）の比粘度が０．１〜０．４で
あることを特徴とする第３項または第４項記載の製法。6. The method according to item 3 or 4, wherein the thermally decomposable polymer (B) has a specific viscosity of 0.1 to 0.4.
Ｚ 熱分解性重合体（Ｂ）の比粘度が０．２〜０．３で
あることを特徴とする第３項または第４項記載の製法。Z. The method according to item 3 or 4, wherein the thermally decomposable polymer (B) has a specific viscosity of 0.2 to 0.3.
８、相溶剤（Ｄ）が、アクリロニトリル系重合体（蜀と
相溶性を有するか、あるいは同一の単量体から構成され
るセグメント仏）と、熱分解性重合体（Ｂ）と相溶性を
有するか、あるいは同一の単量体から構成されるセグメ
ント（ｂ）とを同一重合体鎖中に含むグラフト共重合体
またはブロック共重合体であることを特徴とする第４項
記載の製法。8. The compatibilizer (D) is compatible with the acrylonitrile polymer (segmented polymer that is compatible with Shu or composed of the same monomer) and the thermally decomposable polymer (B). or a graft copolymer or a block copolymer containing segment (b) composed of the same monomer in the same polymer chain.
９ 相溶剤（Ｄ）が、アクリロニトリル６０モル％以上
、熱分解性重合体（Ｂ）の構成成分である単量体１０モ
ル％以上及びこれらと共重合可能な他の単量体１０モル
％以下から構成されたものであることを特徴とする第４
項記載の製法。9 The compatibilizer (D) is 60 mol% or more of acrylonitrile, 10 mol% or more of monomers that are constituent components of the thermally decomposable polymer (B), and 10 mol% or less of other monomers copolymerizable with these. The fourth item is characterized in that it is composed of
Manufacturing method described in section.
１０、アクリロニトリル系重合体（Ａ１１０〜９０重量
％、熱分解性重合体（Ｂ） １０〜９０重量％及び相溶
剤（Ｄ）０〜５重量％〔ただしくＡ）成分、（Ｂ）成分
及びＣＤ）成分の合計量が１００重量％〕となるように
混合することを特徴とする第３項または第４項記載の製
法。10. Acrylonitrile polymer (A1 10-90% by weight, thermally decomposable polymer (B) 10-90% by weight, and compatibilizer (D) 0-5% by weight [A) component, (B) component and CD) The method according to item 3 or 4, characterized in that the ingredients are mixed so that the total amount of the ingredients is 100% by weight.
１１、アクリロニトリル系重合体ｆＡ） ２０〜８０重
量％、熱分解性重合体（Ｂ） ２０〜８０重量％及び相
溶剤（Ｄ）０〜５重量％〔ただしくＡ）成分、（Ｂｌ成
分及び（Ｄ）成分の合計量が１００重量％〕となるよう
に混合することを特徴とする第３項または第４項記載の
製法。11. Acrylonitrile polymer fA) 20 to 80% by weight, thermally decomposable polymer (B) 20 to 80% by weight, and compatibilizer (D) 0 to 5% by weight [provided that A) component, (Bl component and (D 4. The method according to item 3 or 4, characterized in that the ingredients are mixed so that the total amount of the components is 100% by weight.
１２゜溶剤（Ｃ）がジメチルホルムアミド、ジメチルア
セトアミド及びジメチルスルホキシドから選ばれたもの
であることを特徴とする第６項または第４項記載の製法
。12. The process according to item 6 or 4, wherein the solvent (C) is selected from dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
１３、乾湿式紡糸法により紡糸することを特徴とする第
３項または第４項記載の製法。13. The manufacturing method according to item 3 or 4, characterized in that spinning is performed by a dry-wet spinning method.
１４、多段延伸法により全延伸倍率が３倍以上の条件で
延伸することを特徴とする第６項または第４項記載の製
法。14. The manufacturing method according to item 6 or 4, characterized in that the film is stretched by a multi-stage stretching method at a total stretching ratio of 3 times or more.
１５、耐炎化処理での伸張を１５％以下の範囲に制御し
て耐炎化処理することを特徴とする第６項または第４項
記載の製法。15. The manufacturing method according to item 6 or 4, wherein the flame resistant treatment is performed by controlling the elongation in the flame resistant treatment to a range of 15% or less.
１６、張力を制御しながら炭素化処理することを特徴と
する第３項または第４項記載の製法。16. The manufacturing method according to item 3 or 4, characterized in that the carbonization treatment is carried out while controlling tension.
第１図は、実施例１の実験Ａ１〜４で得られた中空糸膜
の細孔容積微分曲線、第２図は、実施例２の実験＆５〜
９で得られた中空糸膜の細孔容積累積積分右曲線、第６
図は、実施例６の実験煮１０〜１３で得られた中空糸膜
の細孔容積累積分布曲線である。Figure 1 shows the pore volume differential curves of hollow fiber membranes obtained in experiments A1 to A4 of Example 1, and Figure 2 shows the pore volume differential curves of experiments A1 to A4 of Example 2.
Hollow fiber membrane pore volume cumulative integral right curve obtained in 9, No. 6
The figure shows the pore volume cumulative distribution curves of the hollow fiber membranes obtained in Experiments 10 to 13 of Example 6.
Claims (1)
つた細孔を有し、細孔容積微分曲線から求めた細孔半径
の極大値が１０〜１０００ｎｍに存在し、全細孔容積が
０．１〜１ｃｍ＾３／ｇで、屈曲時の曲率半径が１０ｃ
ｍ以下であり、かつＴＧＡにより測定した中空糸膜の１
０重量％分解する温度が少なくとも約３００℃である耐
熱性に優れた炭素繊維系多孔質中空糸膜。 ２、引張伸度が少なくとも０．８％である第１項記載の
中空糸膜。 ３、アクリロニトリル単位が９０〜１００モル％である
アクリロニトリル系重合体（Ａ）と６００℃以下の温度
で熱分解して低分子量化する熱分解性重合体（Ｂ）およ
び溶剤（Ｃ）とを混合した後、紡糸し、延伸して得たア
クリロニトリル系中空繊維を耐炎化処理し、次いで４０
０℃以上の温度で炭素化処理して多孔質化することを特
徴とする、第１項記載の中空糸膜の製法。 ４、アクリロニトリル系重合体（Ａ）、熱分解性重合体
（Ｂ）および溶剤（Ｃ）に、さらに相溶剤（Ｄ）を混合
することを特徴とする第３項記載の製法。[Claims] 1. The hollow fiber membrane has pores continuously connected from the inner wall surface to the outer wall surface, and the maximum value of the pore radius determined from the pore volume differential curve exists in the range of 10 to 1000 nm. , the total pore volume is 0.1~1cm^3/g, and the radius of curvature when bent is 10c.
1 of the hollow fiber membrane measured by TGA.
A carbon fiber porous hollow fiber membrane having excellent heat resistance and having a decomposition temperature of 0% by weight of at least about 300°C. 2. The hollow fiber membrane according to item 1, which has a tensile elongation of at least 0.8%. 3. Mixing an acrylonitrile polymer (A) containing 90 to 100 mol% of acrylonitrile units, a thermally decomposable polymer (B) that is thermally decomposed at a temperature of 600°C or lower to reduce its molecular weight, and a solvent (C). After that, the acrylonitrile-based hollow fibers obtained by spinning and drawing were subjected to flame-retardant treatment, and then
2. The method for producing a hollow fiber membrane according to item 1, wherein the hollow fiber membrane is made porous by carbonization treatment at a temperature of 0° C. or higher. 4. The method according to item 3, characterized in that a compatibilizer (D) is further mixed with the acrylonitrile polymer (A), the thermally decomposable polymer (B), and the solvent (C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1060648A JPH0274615A (en) | 1988-03-15 | 1989-03-15 | Carbon fiber-based porous hollow fiber membrane and production thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-60928 | 1988-03-15 | ||
| JP6092888 | 1988-03-15 | ||
| JP1060648A JPH0274615A (en) | 1988-03-15 | 1989-03-15 | Carbon fiber-based porous hollow fiber membrane and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0274615A true JPH0274615A (en) | 1990-03-14 |
Family
ID=26401716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1060648A Pending JPH0274615A (en) | 1988-03-15 | 1989-03-15 | Carbon fiber-based porous hollow fiber membrane and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0274615A (en) |
Cited By (9)
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| JPH0398624A (en) * | 1989-09-11 | 1991-04-24 | Mitsubishi Rayon Co Ltd | Carbon fiber-based porous hollow fiber membrane and its preparation |
| WO2011004660A1 (en) * | 2009-07-10 | 2011-01-13 | 日本碍子株式会社 | Method for producing carbon film, carbon film and separator |
| JP2013071073A (en) * | 2011-09-28 | 2013-04-22 | Toyobo Co Ltd | Hollow fiber carbon membrane, separation membrane module and method for producing hollow fiber carbon membrane |
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-
1989
- 1989-03-15 JP JP1060648A patent/JPH0274615A/en active Pending
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| WO2011004660A1 (en) * | 2009-07-10 | 2011-01-13 | 日本碍子株式会社 | Method for producing carbon film, carbon film and separator |
| US8343348B2 (en) | 2009-07-10 | 2013-01-01 | Ngk Insulators, Ltd. | Method for producing carbon film, carbon film and separator |
| JP5624542B2 (en) * | 2009-07-10 | 2014-11-12 | 日本碍子株式会社 | Carbon membrane manufacturing method, carbon membrane, and separation apparatus |
| JP2013071073A (en) * | 2011-09-28 | 2013-04-22 | Toyobo Co Ltd | Hollow fiber carbon membrane, separation membrane module and method for producing hollow fiber carbon membrane |
| WO2015129488A1 (en) * | 2014-02-26 | 2015-09-03 | 東レ株式会社 | Porous carbon material, composite material reinforced with carbon material, porous carbon material precursor, porous carbon material precursor production method, and porous carbon material production method |
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| US10159943B2 (en) | 2014-07-24 | 2018-12-25 | Toray Industries, Inc. | Carbon membrane for fluid separation, fluid separation membrane module, and method for producing carbon membrane for fluid separation |
| JP2016060991A (en) * | 2014-09-19 | 2016-04-25 | 東レ株式会社 | Polyacrylonitrile-based flame resistant fiber, sheet like article using the same and manufacturing method of polyacrylonitrile-based flame resistant fiber |
| WO2017126501A1 (en) * | 2016-01-22 | 2017-07-27 | 東レ株式会社 | Fluid separation membrane, fluid separation membrane module, and porous carbon fiber |
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| JPH0345717A (en) | Flameproof fiber and production thereof |