JPS62279805A - Separation membrane using polysulfone containing carboxyl group and its production - Google Patents
Separation membrane using polysulfone containing carboxyl group and its productionInfo
- Publication number
- JPS62279805A JPS62279805A JP12344486A JP12344486A JPS62279805A JP S62279805 A JPS62279805 A JP S62279805A JP 12344486 A JP12344486 A JP 12344486A JP 12344486 A JP12344486 A JP 12344486A JP S62279805 A JPS62279805 A JP S62279805A
- Authority
- JP
- Japan
- Prior art keywords
- polysulfone
- carboxylic acid
- separation membrane
- acid group
- formulas
- 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
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 61
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 238000000926 separation method Methods 0.000 title claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000005911 haloform reaction Methods 0.000 claims abstract description 6
- 239000002841 Lewis acid Substances 0.000 claims abstract description 3
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 238000006276 transfer reaction Methods 0.000 claims description 3
- 230000000397 acetylating effect Effects 0.000 claims description 2
- 230000021736 acetylation Effects 0.000 claims 2
- 238000006640 acetylation reaction Methods 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012346 acetyl chloride Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 3
- 239000004745 nonwoven fabric Substances 0.000 abstract description 3
- 239000012074 organic phase Substances 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- FFOSOACFZGOCHY-UHFFFAOYSA-N 4-bromobutyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CCCCBr FFOSOACFZGOCHY-UHFFFAOYSA-N 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000013505 freshwater Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- -1 heated steam Substances 0.000 description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- OKTJSMMVPCPJKN-BJUDXGSMSA-N carbon-11 Chemical compound [11C] OKTJSMMVPCPJKN-BJUDXGSMSA-N 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〔産業上の利用分野〕
本発明は、液状混合物の成分、特に海水およびカン水を
脱塩して淡水化することができる逆浸透膜や、コロイド
次元の浮遊粒子の分離に使用される限外濾過、精密濾過
膜として有用なカルボン酸基含有ポリスルホン分離膜に
関する。Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention provides a reverse osmosis membrane and a membrane that can desalinate and desalinate components of a liquid mixture, particularly seawater and can water. , relates to a carboxylic acid group-containing polysulfone separation membrane useful as an ultrafiltration or precision filtration membrane used to separate colloidal suspended particles.
従来からポリスルホンおよびスルホン化ポリスルホンは
、逆浸透膜、限外濾過膜、精密濾過膜用素材として有効
であることが知られている。ここでいう膜はポリスルホ
ン又はスルホン化ポリスルホンを適当な溶媒に溶解し、
これをシート状にした後、浴中で凝固するか又は、高分
子支持体上にコーティングし、溶媒を蒸発させることに
よって形成せしめた膜である。このようにして得られた
逆浸透膜、限外濾過膜、精密濾過膜は熱水、加熱スチー
ム、酸、アルカリの他多くの薬品に絶える膜として開発
が進められている。It has been known that polysulfone and sulfonated polysulfone are effective as materials for reverse osmosis membranes, ultrafiltration membranes, and microfiltration membranes. The membrane here is prepared by dissolving polysulfone or sulfonated polysulfone in a suitable solvent.
A film is formed by forming this into a sheet, coagulating it in a bath, or coating it on a polymeric support and evaporating the solvent. The reverse osmosis membranes, ultrafiltration membranes, and microfiltration membranes thus obtained are being developed as membranes that can withstand hot water, heated steam, acids, alkalis, and many other chemicals.
（発明が解決しようとする問題点〕
従来、ポリスルホン膜は、耐久性の優れた膜でおる事が
知られているが、その分離性能が低い点や、目づまりに
よる造水量の低下が問題であった。(Problems to be solved by the invention) Conventionally, polysulfone membranes are known to have excellent durability, but they have problems such as low separation performance and a decrease in the amount of water produced due to clogging. there were.
本発明者らは、イオン性基であるカルボン酸基をポリス
ルホン鎖に導入することによってアニオン性物質による
造水量低下を防ぐことを目的として鋭意検討した結果、
カルボン酸基を有するポリスルホン膜は、造水量が低下
する事なく目的物質を分離する事を見い出し本発明に到
達した。As a result of intensive study by the present inventors with the aim of preventing a decrease in the amount of water produced due to anionic substances by introducing a carboxylic acid group, which is an ionic group, into a polysulfone chain,
The present invention was achieved by discovering that a polysulfone membrane having carboxylic acid groups can separate target substances without reducing the amount of water produced.
（問題点を解決するための手段） 上記目的を達成するため本発明は下記の構成からなる。(Means for solving problems) In order to achieve the above object, the present invention consists of the following configuration.
［（１） ポリスルホンからなる分離膜において、該
ポリスルホンの主鎖を構成するベンゼン環のいずれかの
位置にカルボン１１を有することを特徴とするカルボン
酸基含有ポリスルホン分離膜。[(1) A polysulfone separation membrane containing a carboxylic acid group, which has carbon 11 at any position of a benzene ring constituting the main chain of the polysulfone.
（２） カルボン酸基を有するポリスルホン分離膜の
製造方法において、ポリスルホンをアセチル化し、その
後ハロホルム反応によりアセチル基をカルボン酸基に変
換し分離膜とすることを特徴とするカルボン酸基含有ポ
リスルホン分離膜の製造方法。」
本発明により、工業的に生産されているポリスルホンに
イオン性基であるカルボンｌの導入が可能となりその結
果長期運転による造水量低下の原因となる目づまり物質
とカルボン酸基含有ポリスルホンとの電子的反発が起こ
り、目づまりによる造水量低下を防ぐことが可能となっ
た。(2) A method for producing a polysulfone separation membrane containing a carboxylic acid group, which comprises acetylating polysulfone and then converting the acetyl group into a carboxylic acid group through a haloform reaction to obtain a separation membrane. manufacturing method. According to the present invention, it is possible to introduce carboxyl, which is an ionic group, into industrially produced polysulfone, and as a result, the electrons between clogging substances and carboxylic acid group-containing polysulfone, which cause a decrease in the amount of water produced during long-term operation, are enabled. This made it possible to prevent a decrease in the amount of water produced due to clogging.
本発明の一般式［Ｉ］、［ｎ］中のＲ１〜Ｒ１Ｂ、式［
ＩＩＩ］中のＲ１−Ｒ１゜、式［ＩＶ］中のＲ１−Ｒ８
のうちカルボン酸基以外の置換基として、水素、低級ア
ルキル基、アミノ基、アミノメチル基、アミノエチル基
、水酸基、ヒドロキシメチル基、ヒドロキシエチル基、
クロロメチル基、クロロエチル基、ブロモメチル基、ブ
ロモエチル基、ヨードメチル基、ヨードエチル基、フッ
素、塩素、臭素、ヨウ素、メトキシ基、エトキシ基、ス
ルホン酸基、カルボキシメチル基、カルボキシエチル基
などが挙げられるが、膜の分離性能を左右する水との親
和性および化合物の安定性から好ましくはスルホン酸基
および水素でおる。R1 to R1B in the general formula [I] and [n] of the present invention, the formula [
R1-R1° in formula [III], R1-R8 in formula [IV]
Among these, substituents other than carboxylic acid groups include hydrogen, lower alkyl groups, amino groups, aminomethyl groups, aminoethyl groups, hydroxyl groups, hydroxymethyl groups, hydroxyethyl groups,
Examples include chloromethyl group, chloroethyl group, bromomethyl group, bromoethyl group, iodomethyl group, iodoethyl group, fluorine, chlorine, bromine, iodine, methoxy group, ethoxy group, sulfonic acid group, carboxymethyl group, carboxyethyl group, etc. Sulfonic acid groups and hydrogen are preferred from the viewpoint of affinity with water and stability of the compound, which affect the separation performance of the membrane.
式［１］、［ｎ］中のＲ１−Ｒ１６、式［Ｉ［］中のＲ
１−Ｒ１２、式［Ｎ］中のＲ１−Ｒ８の中で、水素以外
の置換基であるカルボン酸基は、１繰り返し巾位尚たり
平均０．０３〜３個のうちから任意に選ぶことができ、
膜の分離性能を考慮すると０．２〜１個であることが好
ましい。R1-R16 in formula [1], [n], R in formula [I[]
1-R12, among R1-R8 in formula [N], the carboxylic acid group which is a substituent other than hydrogen can be arbitrarily selected from among 0.03 to 3 on average per repeat width. I can,
Considering the separation performance of the membrane, the number is preferably 0.2 to 1.
本発明においては、ポリスルホンは公知のいかなるもの
でおってもよいが、１例を示すと下記の如きものでおる
。In the present invention, the polysulfone may be any known polysulfone, but one example is as follows.
（ただし式［Ｉ］、［ｎ］中のＲ１〜ＲＩＢ、式［ＩＩ
Ｉ］中のＲ１〜Ｒ１□、式［ＩＶ］中のＲ１−Ｒ８のう
ち少なくとも１つはカルボキシル基を示す。）本発明に
おいて分離膜とする技術は、公知のいかなる装膜技術も
使用できる。たとえば、上記のカルボキシル化ホリスル
ホンをジメチルホルムアミドなどの溶媒に溶かしてキャ
スト液とし、これを布帛などの支持体のうえにキャスト
して脱溶媒する方法などである。(However, R1 to RIB in formula [I], [n], formula [II]
At least one of R1 to R1□ in I] and R1 to R8 in formula [IV] represents a carboxyl group. ) In the present invention, any known membrane coating technology can be used to form a separation membrane. For example, the above-mentioned carboxylated folysulfone is dissolved in a solvent such as dimethylformamide to form a casting liquid, which is then cast onto a support such as a fabric and the solvent is removed.
本発明の式［Ｉ］〜［ＩＶ］の重合体は、好ましくは第
１段階において、前記一般式［Ｉ］、［］Ｉ］中のＲ１
−Ｒ１６、式［ＩＩＩ］中のＲ１−Ｒ１２、式［Ｉυコ
コ中Ｒ１−Ｒ８が全て水素原子であるポリスルホンに、
フリーデルクラフッ反応によりアセチル基を導入する。The polymers of formulas [I] to [IV] of the present invention are preferably prepared in the first step by R1
-R16, R1-R12 in formula [III], polysulfone in which R1-R8 in formula [Iυ here are all hydrogen atoms,
An acetyl group is introduced by Friedel-Kraf reaction.
この時用いられる触媒としては各種のルイス酸、例えば
、塩化アルミニウム１、五塩化アンチモン、塩化第二鉄
、塩化第一鉄、四塩化チタン、三フッ化ホウ素、塩化第
二スズ、塩化ビスマス、塩化亜鉛、塩化水銀などが用い
られる仙、フッ化水素、硫酸、ポリリン酸なども用いら
れる。しかし、反応性を考慮すると塩化アルミニウムが
特に好ましいが、塩化第二スズ、塩化亜鉛もよく用いら
れる。）８媒としては、ニトロベンゼン、二硫化炭素、
ジクロロメタン、四塩化炭素、１．２−ジクロロエタン
が用いられるが、溶解性および反応性を考慮すると１．
２−ジクロロエタンが好ましい。第１段階で得られた、
アセチル化ポリスルホンは、第２段階における相間移動
反応によるハロホルム反応を行なう事によってカルボキ
シル基含有ポリスルホンを１ｑる。相間移動反応の触媒
としては、ヨウ化テトラメチルアンモニウム、臭化テト
ラエチルアンモニウム、塩化プロピルアンモニウム、臭
化７１〜５７口ピルアンモニウム、硫酸水素テトラブチ
ルアンモニウム、塩化テトラブチルアンモニウム、臭化
テトラブチルアンモニウム、ヨウ化テトラブチルアンモ
ニウム、過塩素酸テトラブチルアンモニウム、臭化テト
ラペンタアンモニウム、臭化テトラヘキサアンモニウム
、臭化テトラヘプタアンモニウム、臭化テトラオクタア
ンモニウムなどのアンモニウム塩が用いられるが、反応
性および取り扱い易さの点から臭化テトラブチルアンモ
ニウムが好ましい。この臭化テトラブチルアンモニウム
は、水相しか溶解しない次亜塩素酸イオンをアセチル化
ポリスルホンが溶解している有殿相へ移動させ、その為
にハロホルム反応を行なう事が可能となる。Catalysts used at this time include various Lewis acids, such as aluminum 1 chloride, antimony pentachloride, ferric chloride, ferrous chloride, titanium tetrachloride, boron trifluoride, stannic chloride, bismuth chloride, and chloride. Zinc, mercury chloride, etc. are used, and hydrogen fluoride, sulfuric acid, polyphosphoric acid, etc. are also used. However, in consideration of reactivity, aluminum chloride is particularly preferred, but stannic chloride and zinc chloride are also often used. ) As the 8 medium, nitrobenzene, carbon disulfide,
Dichloromethane, carbon tetrachloride, and 1,2-dichloroethane are used, but considering solubility and reactivity, 1.
2-dichloroethane is preferred. obtained in the first stage,
Acetylated polysulfone is converted into 1q of carboxyl group-containing polysulfone by performing haloform reaction by phase transfer reaction in the second step. Catalysts for phase transfer reactions include tetramethylammonium iodide, tetraethylammonium bromide, propylammonium chloride, 71-57 pylammonium bromide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium chloride, tetrabutylammonium bromide, and iodine. Ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium perchlorate, tetrapentaammonium bromide, tetrahexaammonium bromide, tetraheptaammonium bromide, and tetraoctaammonium bromide are used, but they have low reactivity and ease of handling. From this point of view, tetrabutylammonium bromide is preferred. This tetrabutylammonium bromide transfers hypochlorite ions, which are dissolved only in the aqueous phase, to the precipitate phase in which acetylated polysulfone is dissolved, thereby making it possible to carry out the haloform reaction.
具体的な製造方法を以下に示す。A specific manufacturing method is shown below.
本発明の上記式［Ｉ］の共重合体は、例えば次の製造方
法に従って製造される。The copolymer of the above formula [I] of the present invention is produced, for example, according to the following production method.
第１段階 １
第２段階
第１段階：２塩化エタンに溶解したポリスルホンに、塩
化アルミニウム存在下塩化アセ
チルを反応させて、式［Ｂ］の化合物
を製造する。1st Step 1 2nd Step 1st Step: Polysulfone dissolved in ethane dichloride is reacted with acetyl chloride in the presence of aluminum chloride to produce a compound of formula [B].
第２段階：式［Ｂ］の化合物を塩化メチレンに溶解し、
これを臭化テトラブチルアンモ
ニウム水溶液と共に攪拌することによ
って、式［Ｃ’］の化合物を製造する。Second step: Dissolving the compound of formula [B] in methylene chloride,
By stirring this with an aqueous tetrabutylammonium bromide solution, a compound of formula [C'] is produced.
本発明で原料化合物として用いるポリスルホンは市販さ
れており（例えば、ユニオン・カーバイト社製の商品名
Ｕｄｅｌ Ｐ−１７００）容易に入手することができる
。Polysulfone used as a raw material compound in the present invention is commercially available (for example, trade name Udel P-1700 manufactured by Union Carbide Company) and can be easily obtained.
上記した反応プロセスにより、前記式［Ｉ］のカルボキ
シル化ポリスルホンはもちろん、その他の共重合体（た
とえば式［■］、式［■］、式［１１１１１］などの共
重合体も製造することができる。Through the reaction process described above, not only the carboxylated polysulfone of formula [I] but also other copolymers (for example, copolymers of formula [■], formula [■], formula [11111], etc.) can be produced. .
次に、同様の例についての実施例により本発明を更に詳
しく説明する。The invention will now be explained in more detail by means of similar examples.
カルボキシル化ポリスルホンの前駆体であるアセチル化
ポリスルホンは参考例に示す方法によって合成した。Acetylated polysulfone, which is a precursor of carboxylated polysulfone, was synthesized by the method shown in Reference Example.
参考例１
■ アセチル化ポリスルホンの合成
窒素気流下、４．３０Ｃ］の塩化アセチルをジクロロエ
タンに溶解し、更に７．’１１ＣＪの塩化アルミニウム
を溶解した。この溶液を、窒素気流下、１１、ＯＯｇ、
ポリスルホン（ユニオン・カーバイト社製の商品名Ｕｄ
ｅｌ Ｐ−１７００）のジクロロエタン溶液１００ｍ１
中に、滴下した。この時の溶液温度は、３℃であった。Reference Example 1 ■ Synthesis of acetylated polysulfone Under a nitrogen atmosphere, acetyl chloride of 4.30C] was dissolved in dichloroethane, and further 7. '11CJ aluminum chloride was dissolved. This solution was mixed with 11,00 g of nitrogen under a stream of nitrogen.
Polysulfone (trade name Ud manufactured by Union Carbide)
el P-1700) dichloroethane solution 100ml
It dripped inside. The solution temperature at this time was 3°C.
更に４°Ｃで７０分間攪拌した後に、反応溶液を１αの
メタノール中に注いだ、析出した白色沈澱を１戸別し、
更に、４５℃／ ２ ｍｍＨｇの条件下で乾燥を行なっ
た。After further stirring at 4°C for 70 minutes, the reaction solution was poured into 1α methanol, and the precipitated white precipitate was separated.
Furthermore, drying was performed under the conditions of 45° C./2 mmHg.
収徂＝１１．５２に］
■ 分析結果
赤外吸収：’１６８０，１５８２，１２５０゜１ ’１
４５ｃｍ−１
核磁気共鳴（ＣＤ（４３，ＴＭＳ）：δ７，８９８〜６
．８８０ （ｍ＞、２．５１１
（Ｓ）、１．６９２ （Ｓ）ｐｐｍ
核磁気共鳴スペクトル分析より、１．３８ｍｍｏｌ／ｇ
アセチル化されている。Convergence = 11.52] ■ Analysis result Infrared absorption: '1680, 1582, 1250°1 '1
45cm-1 Nuclear magnetic resonance (CD(43, TMS): δ7,898~6
．． 880 (m>, 2.511 (S), 1.692 (S) ppm From nuclear magnetic resonance spectrum analysis, 1.38 mmol/g
Acetylated.
カルボキシル化ポリスルホンは、実施例１，２で示す方
法によって合成した。Carboxylated polysulfone was synthesized by the method shown in Examples 1 and 2.
実施例１
アセチル化ポリスルホン１．ＯＯＣ］を１００ｍ１のジ
オキサンに溶解し、そこに市販次亜塩素酸ナトリウム水
溶液（２０ｍｌ）を滴下し、その後６０°Ｃで３時間加
熱した。反応溶液を酸性にしてから４００ｍ１の水中に
沈澱した後、）戸別し、これを再び１００１ｉ１１のジ
オキサンに溶かした後に２０ｍ１の次亜塩素酸ナトリウ
ムを滴下した。６０℃で１時間加熱すると２相に分離し
たので有機相を分離した。更に５０ｍ１の次亜塩素酸ナ
トリウム水滴液を滴下し、６０’Ｃで１時間加熱したと
ころ、不溶性の化合物が得られたので、溶液を酸性にし
た後に戸別、乾燥した。赤外吸収スペクトルは第１図に
示す。Example 1 Acetylated polysulfone 1. OOC] was dissolved in 100 ml of dioxane, and a commercially available aqueous sodium hypochlorite solution (20 ml) was added dropwise thereto, followed by heating at 60°C for 3 hours. After the reaction solution was acidified and precipitated in 400 ml of water, it was separated and dissolved again in 1001i11 dioxane, and 20 ml of sodium hypochlorite was added dropwise. When heated at 60° C. for 1 hour, the mixture separated into two phases, and the organic phase was separated. Further, 50 ml of aqueous sodium hypochlorite solution was added dropwise and heated at 60'C for 1 hour. Since an insoluble compound was obtained, the solution was made acidic and then dried from house to house. The infrared absorption spectrum is shown in FIG.
実施例２
２００ｆｆ１１３つロフラスコに、次亜塩素酸ナトリウ
ム水溶液３Ｑｍｌ、０．５００の臭化テトラブチルアン
モニウムそれに、３０ｍ１の塩化メチレンに溶解した０
、５０に］のアシル化ポリスルホンを入れ、空温で激し
く澄拌した。反応溶液をビー力に移し、２０ｍ１の塩化
メチレンと２Ｑｍｌの水を加えた。亜硫酸水素ナトリウ
ムを加えた後に、１ＮＨＣ０，で水相を酸性にした。有
機相を分離後、ｎ−ヘキサンで再沈澱すると白色粉末が
析出したのでこれを戸別、乾燥した。イオン交換容量は
、１．０５ｍｅＱ／ｇ＜１繰り返し単位当たり０．３個
）であった。得られたポリマの赤外吸収スペクトルを第
２図に示す。実施例２で得られたカルボン酸基含有ポリ
スルホン化合物の製膜法を実施例３に示す。Example 2 In 113 200ff flasks, 3Qml of sodium hypochlorite aqueous solution, 0.500ml of tetrabutylammonium bromide, and 0.5ml of tetrabutylammonium bromide dissolved in 30ml of methylene chloride were added.
, 50] was added, and the mixture was vigorously clarified at air temperature. The reaction solution was transferred to a beaker and 20ml of methylene chloride and 2Qml of water were added. After adding sodium bisulfite, the aqueous phase was made acidic with 1N HCO. After separating the organic phase, it was reprecipitated with n-hexane to precipitate a white powder, which was then dried separately. The ion exchange capacity was 1.05 meQ/g<0.3 molecules per repeating unit). FIG. 2 shows the infrared absorption spectrum of the obtained polymer. Example 3 shows a method for forming a film of the carboxylic acid group-containing polysulfone compound obtained in Example 2.
実施例３
タテ３０ｃｍ、ヨコ２０ｃｍの大きさのポリエステル繊
維からなる不織布をガラス板上に固定し、その上にポリ
スルホン（ユニオン・カーム４１〜社製）Ｕｄｅｌ Ｐ
−３５００）とカルボン酸基含有ポリスルホン化合物を
６：４（ｆｆｌｉ比）の割合で含む１６重伍％ジメチル
ホルムアミド（ＤＭＦ）溶液を２５０μｍの厚みで空温
（２０’Ｃ）でキャストし、ただちに純水中に浸漬して
５分間放置することによって繊維補強ポリスルホン膜を
作製した。このようにして得られた膜を、温度２５°Ｃ
１圧力５に９／ｍ２、原水１１０００ｐｌ）ポリエチレ
ングリコール（ＰＥＧ−１０００００）水溶液で運転開
始３時間後と２１時間後のポリエチレングリコール排除
率と造水量を第１表に示す。Example 3 A nonwoven fabric made of polyester fibers measuring 30 cm in length and 20 cm in width was fixed on a glass plate, and polysulfone (manufactured by Union Calm 41~) Udel P was placed on top of it.
-3500) and a carboxylic acid group-containing polysulfone compound at a ratio of 6:4 (ffli ratio), a 16% dimethylformamide (DMF) solution was cast to a thickness of 250 μm at air temperature (20'C), and immediately purified. A fiber-reinforced polysulfone membrane was prepared by immersing it in water and leaving it for 5 minutes. The film thus obtained was heated at a temperature of 25°C.
Table 1 shows the polyethylene glycol rejection rate and water generation amount 3 hours and 21 hours after the start of operation using a polyethylene glycol (PEG-100000) aqueous solution (1 pressure 5 to 9/m2, raw water 11000 pl).
比較例
タテ３Ｑｃｍ、ヨコ２０ｃｍの大きさのポリエステル繊
維からなる不織布をガラス板上に固定し、その上にポリ
スルホン（ユニオン・カーバイト社製の商品名Ｕｄｅｌ
Ｐ−１７００）の１５＠０％ジメチルホルムアミド（
ＤＭＦ＞溶液を２００μｍの厚みで空温（２０’Ｃ）で
キャストし、ただちに純水中に浸漬して５分間放置する
ことによって繊維補強ポリスルホン膜を得た。このよう
にして得られたポリスルホン膜を実施例と同様の方法に
よって評価を行なった。その結果を第１表に示す。Comparative Example A nonwoven fabric made of polyester fibers with a length of 3 Q cm and a width of 20 cm was fixed on a glass plate, and polysulfone (trade name: Udel manufactured by Union Carbide Co., Ltd.) was placed on top of it.
P-1700) in 15@0% dimethylformamide (
A fiber-reinforced polysulfone membrane was obtained by casting the DMF> solution to a thickness of 200 μm at air temperature (20'C), immediately immersing it in pure water, and leaving it for 5 minutes. The polysulfone membrane thus obtained was evaluated in the same manner as in the examples. The results are shown in Table 1.
第１表
第１表において膜性能を示す数字は、
［排除率（％）−造水＠（ｍ３／ｍ２・日〉１の形式％
式％
（発明の効果〕
本発明により、市販されている化合物を用いてカルボン
酸基含有ポリスルホンを容易に供給することができるよ
うになる。このカルボン酸基含有ポリスルホンは製膜す
ることにより、良好な分離膜性能を示し、運転時間によ
り造水量の低下する事のない膜を製造することができる
。Table 1 In Table 1, the numbers indicating membrane performance are as follows:
Formula % (Effect of the invention) According to the present invention, it becomes possible to easily supply a polysulfone containing a carboxylic acid group using a commercially available compound. It is possible to produce a membrane that exhibits excellent separation membrane performance and that does not reduce the amount of water produced due to operating time.
第１図は本発明の実施例１のカルボン酸基含有ポリスル
ホンの赤外吸収スペクトルを示す。
第２図は本発明の実施例２のカルボン酸基含有ポリスル
ホンの赤外吸収スペクトルを示す。
特許出願人 東 し 株 式 会 社１２図FIG. 1 shows an infrared absorption spectrum of the carboxylic acid group-containing polysulfone of Example 1 of the present invention. FIG. 2 shows an infrared absorption spectrum of the carboxylic acid group-containing polysulfone of Example 2 of the present invention. Patent applicant Toshi Co., Ltd. Figure 12
Claims (1)
ルホンの主鎖を構成するベンゼン環のいずれかの位置に
カルボン酸基を有することを特徴とするカルボン酸基含
有ポリスルホン分離膜。 （２）ポリスルホンが、下記式［ I ］〜［IV］から選
ばれることを特徴とする特許請求の範囲第（１）項記載
のカルボン酸基含有ポリスルホン分離膜。 ▲数式、化学式、表等があります▼［ I ］ ▲数式、化学式、表等があります▼［II］ ▲数式、化学式、表等があります▼［III］ ▲数式、化学式、表等があります▼［IV］ （ただし式［ I ］、［II］中のＲ＿１〜Ｒ＿１＿６、
式［III］中のＲ＿１〜Ｒ＿１＿２、式［IV］中のＲ＿
１〜Ｒ＿８のうち少なくとも１つはカルボキシル基を示
す。）（３）カルボン酸基が、ポリスルホンの１繰り返
し単位当り０．０３〜３個であることを特徴とする特許
請求の範囲第（１）項記載のカルボン酸基含有ポリスル
ホン分離膜。 （４）カルボン酸基が、ポリスルホンの１繰り返し単位
当り０．２〜１個であることを特徴とする特許請求の範
囲第（１）項記載のカルボン酸基含有ポリスルホン分離
膜。 （５）カルボン酸基を有するポリスルホン分離膜の製造
方法において、ポリスルホンをアセチル化し、その後ハ
ロホルム反応によりアセチル基をカルボン酸基に変換し
分離膜とすることを特徴とするカルボン酸基含有ポリス
ルホン分離膜の製造方法。 （６）アセチル化触媒がルイス酸から選ばれることを特
徴とする特許請求の範囲第（５）項記載のカルボン酸基
含有ポリスルホン分離膜の製造方法。 （７）アセチル化触媒が、塩化アルミニウムまたは塩化
第二スズから選ばれることを特徴とする特許請求の範囲
第（５）項記載のカルボン酸基含有ポリスルホン分離膜
の製造方法。 （８）ハロホルム反応が、テトラアルキルアンモニウム
塩を触媒とし、アルカリハイポハライトを相間移動反応
によって反応させることを特徴とする特許請求の範囲第
（５）項記載のカルボン酸基含有ポリスルホン分離膜の
製造方法。Claims: (1) A polysulfone separation membrane containing a carboxylic acid group, characterized in that the separation membrane is made of polysulfone and has a carboxylic acid group at any position of a benzene ring constituting the main chain of the polysulfone. (2) The carboxylic acid group-containing polysulfone separation membrane according to claim (1), wherein the polysulfone is selected from the following formulas [I] to [IV]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[ IV] (However, R_1 to R_1_6 in formulas [I] and [II],
R_1 to R_1_2 in formula [III], R_ in formula [IV]
At least one of 1 to R_8 represents a carboxyl group. )(3) The carboxylic acid group-containing polysulfone separation membrane according to claim (1), wherein the number of carboxylic acid groups is 0.03 to 3 per one repeating unit of the polysulfone. (4) The carboxylic acid group-containing polysulfone separation membrane according to claim (1), wherein the number of carboxylic acid groups is 0.2 to 1 per repeating unit of the polysulfone. (5) A method for producing a polysulfone separation membrane having a carboxylic acid group, which comprises acetylating polysulfone and then converting the acetyl group into a carboxylic acid group through a haloform reaction to obtain a separation membrane. manufacturing method. (6) The method for producing a carboxylic acid group-containing polysulfone separation membrane according to claim (5), wherein the acetylation catalyst is selected from Lewis acids. (7) The method for producing a carboxylic acid group-containing polysulfone separation membrane according to claim (5), wherein the acetylation catalyst is selected from aluminum chloride or stannic chloride. (8) The carboxylic acid group-containing polysulfone separation membrane according to claim (5), wherein the haloform reaction is carried out by using a tetraalkylammonium salt as a catalyst and reacting alkali hypohalite by a phase transfer reaction. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12344486A JPS62279805A (en) | 1986-05-30 | 1986-05-30 | Separation membrane using polysulfone containing carboxyl group and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12344486A JPS62279805A (en) | 1986-05-30 | 1986-05-30 | Separation membrane using polysulfone containing carboxyl group and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62279805A true JPS62279805A (en) | 1987-12-04 |
Family
ID=14860752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12344486A Pending JPS62279805A (en) | 1986-05-30 | 1986-05-30 | Separation membrane using polysulfone containing carboxyl group and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62279805A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1099468A3 (en) * | 1999-11-10 | 2002-04-24 | DEUTSCHE INSTITUTE FÜR TEXTIL- UND FASERFORSCHUNG STUTTGART Stiftung des öffentlichen Rechts | Microporous hydrophilic membrane |
-
1986
- 1986-05-30 JP JP12344486A patent/JPS62279805A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1099468A3 (en) * | 1999-11-10 | 2002-04-24 | DEUTSCHE INSTITUTE FÜR TEXTIL- UND FASERFORSCHUNG STUTTGART Stiftung des öffentlichen Rechts | Microporous hydrophilic membrane |
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