JPH04198331A - Production of fluorine-containing bipolar film - Google Patents
Production of fluorine-containing bipolar filmInfo
- Publication number
- JPH04198331A JPH04198331A JP2322354A JP32235490A JPH04198331A JP H04198331 A JPH04198331 A JP H04198331A JP 2322354 A JP2322354 A JP 2322354A JP 32235490 A JP32235490 A JP 32235490A JP H04198331 A JPH04198331 A JP H04198331A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- group
- layer
- amine
- sulfonic acid
- 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.)
- Granted
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 13
- 239000011737 fluorine Substances 0.000 title claims description 13
- 239000012528 membrane Substances 0.000 claims abstract description 54
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical group NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims abstract description 4
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 3
- 229910052783 alkali metal Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims 5
- 229910052739 hydrogen Inorganic materials 0.000 claims 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 24
- 238000005349 anion exchange Methods 0.000 description 13
- 238000005341 cation exchange Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- -1 alkali metal salt Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003014 ion exchange membrane Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000565 sulfonamide group Chemical group 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000003012 bilayer membrane Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229920006303 teflon fiber Polymers 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、含フッ素系バイポーラ膜の製造方法に関する
。バイポーラ膜とは、二層構造を持ち、一方の層にカチ
オン交換基を有し、他方の層にアニオン交換基を有する
膜であり、工業廃棄物として生じる塩の酸と塩基への分
解による再利用、各種酸洗液の回収、酸や塩基の製造等
に利用できる。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a fluorine-containing bipolar membrane. A bipolar membrane is a membrane that has a two-layer structure, with a cation exchange group in one layer and an anion exchange group in the other. It can be used for recovery of various pickling solutions, production of acids and bases, etc.
［従来技術］
従来、このようなバイポーラ膜の製造方法として多くの
提案がなされている。[Prior Art] Conventionally, many proposals have been made as methods for manufacturing such bipolar membranes.
例えば、特公昭６０−３１８６０と特開昭６３−９５２
３５には、ベンゼン環を含有する高分子膜の片面にスル
ホン化処理によりカチオン交換基を導入し、もう一方の
面にアニオン交換基として四級化アンモニウム基を導入
する方法が開示されている。また、特公昭６０−３５９
３６には、ポリビニルベンジルクロライドとポリフッ化
ビニリデン溶液を塗布して作製されるバイポーラ膜が開
示され、更に、特公昭５９−４７２３５には、アニオン
交換膜とカチオン交換膜の積層界面に塩化鉄などの無機
化合物を介在させて接合させた膜が開示されている。For example, JP 60-31860 and JP 63-952
No. 35 discloses a method in which a cation exchange group is introduced into one side of a polymer membrane containing a benzene ring by sulfonation treatment, and a quaternized ammonium group is introduced as an anion exchange group into the other side. In addition, special public service 60-359
No. 36 discloses a bipolar membrane prepared by applying a solution of polyvinylbenzyl chloride and polyvinylidene fluoride, and Japanese Patent Publication No. 59-47235 discloses a bipolar membrane prepared by coating a solution of polyvinylbenzyl chloride and polyvinylidene fluoride. A membrane bonded with an inorganic compound interposed therein is disclosed.
更に、特公昭６０−１２３４には、機械的強度や耐薬品
性を改善する目的で主鎖骨格がパーフルオロカーボン重
合体としたフッ素系バイポーラ膜が開示されている。Furthermore, Japanese Patent Publication No. 60-1234 discloses a fluorine-based bipolar membrane in which the main chain skeleton is a perfluorocarbon polymer for the purpose of improving mechanical strength and chemical resistance.
従来の含フッ素系バイポーラ膜の製造方法としては均質
なフッ素系スルホン酸膜を出発物質として片面のみスル
ホン酸基をカルボン酸基に変換し、エステル化の後アミ
ンを導入し四級化することで、片面がスルホン酸型のカ
チオン膜もう一方の面が四級アンモニウム型のアニオン
膜とする方法。均質なフッ素系フルホニルフロリド膜の
片面のみにジアミンを導入した後、膜全体をアルカリ処
理し、アミン部分を四級化することで片面がスルホン酸
型のカチオン膜もう一方の面か四級アンモニウム型のア
ニオン膜とする方法かある。しかし、片面のみの反応を
行うにあたり、細やかな反応厚みのコントロールが難し
いという問題点を有していた。The conventional method for manufacturing fluorine-containing bipolar membranes is to use a homogeneous fluorine-containing sulfonic acid membrane as a starting material, convert the sulfonic acid groups to carboxylic acid groups on one side only, and then introduce amines after esterification to quaternize the membrane. , a method in which one side is a sulfonic acid type cation membrane and the other side is a quaternary ammonium type anion membrane. After introducing diamine into only one side of a homogeneous fluorine-based fluorinyl fluoride membrane, the entire membrane is treated with alkali and the amine portion is quaternized. There is a method to create a class ammonium type anion film. However, when performing the reaction on only one side, there was a problem in that it was difficult to precisely control the reaction thickness.
特にアニオン層よりもカチオン層の薄いバイポーラ膜の
製造は事実上不可能であった。In particular, it has been virtually impossible to manufacture bipolar membranes in which the cation layer is thinner than the anion layer.
［発明が解決しようとする問題点］
本発明の目的は、このような従来の含フッ素系バイポー
ラ膜の製造方法の問題点を改善し、新規な含フッ素系バ
イポーラ膜の製造方法を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to improve the problems of the conventional method for manufacturing a fluorine-containing bipolar membrane, and to provide a novel method for manufacturing a fluorine-containing bipolar membrane. It is in.
［問題を解決するための手段］
本発明者らは、二層構造をもち一方の層のペンダント鎖
にスルホニルフルオライド基を有し、他方の層のペンダ
ント鎖にスルホン酸基を有し、かつ主鎖がパーフルオロ
カーボン重合体からなる膜体にアミンを反応させ、スル
ホン酸基を変性させることなくスルホニルフルオライド
基にスルホアミド基を介して三級アミンを導入し、更に
三級アミンの窒素原子を四級化することを特徴とする特
フッ素系バイポーラ膜の製造方法を見い出し、本発明を
完成した。[Means for Solving the Problems] The present inventors have developed a material that has a two-layer structure, has a sulfonyl fluoride group in the pendant chain of one layer, has a sulfonic acid group in the pendant chain of the other layer, and A membrane body whose main chain is a perfluorocarbon polymer is reacted with an amine, a tertiary amine is introduced into the sulfonyl fluoride group via the sulfamide group without modifying the sulfonic acid group, and the nitrogen atom of the tertiary amine is We have discovered a method for producing a special fluorine-based bipolar membrane characterized by quaternization, and completed the present invention.
［作用］ 本発明の詳細な説明する。[Effect] The present invention will be described in detail.
四フッ化エチレンと、例えば下記に示すコモノＣＦ２−
ＣＦ−０−ＣＦ２−ＣＦ２−８Ｏ２ＦＣＦ２−ＣＦ−０
−ＣＦ２−ＣＰ （ＣＦ３）−０−ＣＦ２−ＣＦ２−９
Ｏ２ＦＣＦ２−ＣＦ−０−ＣＦ２−ＣＦ （ＣＦ３ ）
−０−ＣＦ２−ＣＦ （ＣＦ３ ）−０−ＣＦ２−ＣＰ
２〜５Ｏ２Ｆ
ＣＦ２−ＣＦ−ＣＦ２−ＣＦ２−８Ｏ２Ｆとをフリーラ
ジカル開始剤の存在下において０〜２００℃及び１〜２
００気圧の範囲の条件下で共重合することにより、ペン
ダント鎖にスルホニルフルオライドを有する式
で表される重合体を得ることが出来る。もちろん本発明
に用いられる膜は、上記のコモノマーによって得られる
ものに制限されるものではない。これらの共重合体は、
膜体に成型される。この成型は通常溶融して薄い膜を成
型する一般の技術を用いることが出来る。本発明で使用
される膜の厚さは通常５０μｍないし５００μｍのもの
が用いられ、膜の強度、比電導度、電流効率等を考慮し
て適当な厚みを選択できる。また、このような膜は、膜
の強度を向上させるためテフロン繊維布等で補強された
ものであってよい。Tetrafluoroethylene and, for example, the following co-mono CF2-
CF-0-CF2-CF2-8O2FCF2-CF-0
-CF2-CP (CF3)-0-CF2-CF2-9
O2FCF2-CF-0-CF2-CF (CF3)
-0-CF2-CF (CF3)-0-CF2-CP
2-5O2F CF2-CF-CF2-CF2-8O2F in the presence of a free radical initiator at 0-200°C and 1-2
By copolymerizing under conditions in the range of 000 atm, it is possible to obtain a polymer represented by the formula having a sulfonyl fluoride in a pendant chain. Of course, the membranes used in the present invention are not limited to those obtained using the above-mentioned comonomers. These copolymers are
Molded into a membrane body. For this molding, a general technique of melting and molding a thin film can be used. The thickness of the film used in the present invention is usually 50 μm to 500 μm, and an appropriate thickness can be selected taking into consideration the strength, specific conductivity, current efficiency, etc. of the film. Further, such a membrane may be reinforced with Teflon fiber cloth or the like to improve the strength of the membrane.
膜の形状は平膜状あるいはチューブ状のいずれでもよい
。The shape of the membrane may be either a flat membrane or a tube.
この様な膜体の片面のみをアルカリ雰囲気下または酸雰
囲気下で水を作用させて加水分解を起こし、スルホニル
フルオライド基の部分をスルホン酸基に変換する。作用
させる水は、液体、気体のいずれでもよく、水を作用さ
せる時間でスルホン酸基に変換する層の厚みを制御する
ことが出来、結果としてカチオン交換層の厚みを制御す
ることが可能となる。Water is applied to only one side of such a membrane in an alkaline or acidic atmosphere to cause hydrolysis, converting the sulfonyl fluoride groups into sulfonic acid groups. The water to be acted on can be either liquid or gas, and the thickness of the layer converted to sulfonic acid groups can be controlled by the time for which water is applied, and as a result, the thickness of the cation exchange layer can be controlled. .
別に、スルホン酸基を有する膜とスルホニルフルオライ
ド基を有する膜とを張り合わせることによってもスルホ
ニルフルオライド／スルホン酸二層膜を得ることが可能
である。Alternatively, a sulfonyl fluoride/sulfonic acid bilayer membrane can also be obtained by laminating a membrane having a sulfonic acid group and a membrane having a sulfonyl fluoride group.
このようにして、二層からなっており、一方の層が上記
のスルホニルフルオライド層であり、他方の層がペンダ
ント鎖にスルホン酸基を有する下記の式
で表される膜体を得ることが出来る。この内、スルホニ
ルフルオライド基を有する層は、以下で説明する反応に
より、陰イオン交換基である第４級アンモニウム基を導
入して、陰イオン交換層となる。一方、スルホン酸のア
ルカリ金属塩層は、反応により変化せず陽イオン交換層
として残る。従って、最初のスルホニルフルオライド基
を有する層とスルホン酸のアルカリ金属塩層との厚みを
規定しておけば、任意に陰イオン交換層／陽イオン交換
層の膜厚を制御したバイポーライオン交換膜の製造が可
能である。In this way, it is possible to obtain a membrane body consisting of two layers, one layer being the above-mentioned sulfonyl fluoride layer, and the other layer having the sulfonic acid group on the pendant chain represented by the following formula. I can do it. Among these, the layer having a sulfonyl fluoride group becomes an anion exchange layer by introducing a quaternary ammonium group, which is an anion exchange group, through the reaction described below. On the other hand, the alkali metal salt layer of sulfonic acid is not changed by the reaction and remains as a cation exchange layer. Therefore, if the thicknesses of the first layer having a sulfonyl fluoride group and the alkali metal salt layer of sulfonic acid are specified, the bipolar ion exchange membrane can control the thickness of the anion exchange layer/cation exchange layer as desired. It is possible to manufacture
以下、スルホニルフルオライド基層を第４級アンモニウ
ム基に変換する反応を以下に説明する。The reaction for converting the sulfonyl fluoride base layer into a quaternary ammonium group will be described below.
次の一般式で表されるジアミン
Ｈ２Ｎ−（ＣＨ２）ｎ−Ｃ（Ｒ１）（Ｒ２）−（Ｃ）１
２）ｍ−Ｎ（Ｒ３） （Ｒ４）、を作用させスルホニル
フルオライド部分にアミンを導入する。上記−数式で表
されるアミンの構造としては、
）１２１？−ＣＨ２−ＣＨ２−Ｎ（（ＪＩＳ）２）１２
Ｎ−Ｃ）（２−Ｃ）＋２−Ｃ）＋２−Ｎ （Ｃ）＋３）
２８２Ｎ−Ｃ）１２−ＣＨ２−ＣＨ２−ＣＨ２−Ｎ （
ＣＨ３）２Ｈ２Ｎ−ＣＨ２−Ｃ（ＣＨ５）２−ＣＨ２−
Ｎ（ＣＨ３）２）１２Ｎ−ＣＨ２−Ｃ（Ｃ）１２ｃＨ３
）２−ＣＨ２−Ｎ（ＣＨ３）２Ｈ２Ｎ−ＣＨ２−Ｃ）１
２−Ｃ（ＣＨ３）２−ＣＨ２−ＣＨ２−Ｎ（ＣＨ２ＣＨ
３）２）１２Ｎ−ＣＨ２−ＣＨ２＝Ｃ（Ｃ）１３）２−
ＣＨ２−ＣＨ２−Ｎ（ＣＨ２Ｃ）１２ＣＨ２ＣＨ３）２
Ｈ２八ｌ−ＣＨ２−Ｃ）！２−Ｃ（ＣＨ３） ２−ＣＨ
２−ＣＪ（２−Ｎ （ＣＨ３） ２等を例示することが
できる。Diamine H2N-(CH2)n-C(R1)(R2)-(C)1 represented by the following general formula
2) m-N(R3) (R4) is applied to introduce an amine into the sulfonyl fluoride moiety. The structure of the amine represented by the above formula is: )121? -CH2-CH2-N ((JIS)2)12
N-C) (2-C)+2-C)+2-N (C)+3)
282N-C) 12-CH2-CH2-CH2-N (
CH3)2H2N-CH2-C(CH5)2-CH2-
N(CH3)2)12N-CH2-C(C)12cH3
)2-CH2-N(CH3)2H2N-CH2-C)1
2-C(CH3)2-CH2-CH2-N(CH2CH
3)2)12N-CH2-CH2=C(C)13)2-
CH2-CH2-N(CH2C)12CH2CH3)2 H28l-CH2-C)! 2-C(CH3) 2-CH
Examples include 2-CJ(2-N (CH3) 2).
また、これらのアミン類との反応は、それらのアミン中
あるいは他の溶媒を用いて行うことができる。溶媒を用
いる場合はジエチルエーテル、テトラヒドロフラン、ジ
オキサン等のエーテル類、ベンゼン、トルエン、ヘキサ
ン等の炭化水素類を用いることかできる。Further, the reaction with these amines can be carried out in the amine or using another solvent. When a solvent is used, ethers such as diethyl ether, tetrahydrofuran and dioxane, and hydrocarbons such as benzene, toluene and hexane can be used.
反応温度は、室温〜８０℃、反応時間は１００時間で十
分である。A reaction temperature of room temperature to 80°C and a reaction time of 100 hours are sufficient.
このようにして得られたスルホンアミド基を有するフィ
ルムをナトリウム化液を作用させることによりスルホン
アミド基のアルカリ金属塩に変換すると同時にスルホニ
ルフルオライド基をスルホン酸のアルカリ金属塩に変換
する。The thus obtained film having sulfonamide groups is treated with a sodium-containing solution to convert it into an alkali metal salt of the sulfonamide group, and at the same time convert the sulfonyl fluoride group into an alkali metal salt of sulfonic acid.
ナトリウム化液としては、水酸化アルカリ金属の水溶液
とアルコールの混合系、アルコラードのアルコール溶液
などを用いることができる。反応温度は、室温〜９０℃
の範囲で十分である。As the sodium-containing liquid, a mixed system of an aqueous alkali metal hydroxide solution and alcohol, an alcohol solution of Alcolade, etc. can be used. Reaction temperature is room temperature to 90℃
is sufficient.
得られたスルホンアミド基のアルカリ金属塩とスルホン
酸のアルカリ金属塩の二層からなるフィルムにジメチル
スルホキシドとヨウ化アルキルの混合系を作用させてア
ルキル化することにより陽イオン交換基であるスルホン
酸基を破壊することなく陰イオン交換基である第四級ア
ンモニウム基を導入して、バイポーライオン交換膜を得
ることができる。このバイポーライオン交換膜は陰イオ
ン交換層及び陽イオン交換層の厚みが制御された膜であ
る。The obtained film consisting of two layers of an alkali metal salt of sulfonamide group and an alkali metal salt of sulfonic acid is alkylated with a mixed system of dimethyl sulfoxide and alkyl iodide to form sulfonic acid, which is a cation exchange group. A bipolar ion exchange membrane can be obtained by introducing a quaternary ammonium group, which is an anion exchange group, without destroying the group. This bipolar ion exchange membrane is a membrane in which the thicknesses of the anion exchange layer and the cation exchange layer are controlled.
ヨウ化アルキルとしては、例えばヨウ化メチル、ヨウ化
エチル、ヨウ化ブチル等を用いることができる。As the alkyl iodide, for example, methyl iodide, ethyl iodide, butyl iodide, etc. can be used.
ここで得られる陽イオン交換基と陰イオン交換基を有す
る膜の対イオンを交換する必要がある場合は、常法によ
りアルカリ金属塩ハロゲン化物または酸またはアルカリ
などで処理することで交換できる。If it is necessary to exchange the counter ions of the membrane having a cation exchange group and an anion exchange group obtained here, it can be exchanged by treatment with an alkali metal salt halide, acid, or alkali using a conventional method.
［本発明の効果コ
本発明はスルホニルフルオライド基層／スルホン酸のア
ルカリ塩基の二層膜を経由することに特徴がある。この
特徴により、任意に陰イオン交換層／陽イオン交換層の
膜厚を制御したバイポーライオン交換膜の製造が可能で
ある。[Effects of the Present Invention] The present invention is characterized by passing through a two-layer film of a sulfonyl fluoride base layer/alkaline base of sulfonic acid. Due to this feature, it is possible to manufacture a bipolar ion exchange membrane in which the thickness of the anion exchange layer/cation exchange layer is arbitrarily controlled.
［実施例］
以下、実施例を示すが、本発明は以下の実施例に特に限
定されるものではない。[Examples] Examples will be shown below, but the present invention is not particularly limited to the following examples.
以下の実施例において、膜の抵抗は０．５Ｎ塩化ナトリ
ウム水溶液または１Ｎ水酸化ナトリウム水溶液に十分浸
種させたのち、交流１０００サイクル、温度２５℃で測
定した。In the following examples, the resistance of the membrane was measured at 25° C. for 1000 cycles of AC after sufficiently soaking in a 0.5N aqueous sodium chloride solution or a 1N aqueous sodium hydroxide solution.
実施例Ｉ
ＣＦ２−ＣＦ２とＣＦ２−ＣＦ−０−ＣＦ２−ＣＦ （
ＣＦ３）−０−ＣＦ２−ＣＦ２−９０２Ｆとの共重合に
より得られた共重合体を平膜に成型した（膜厚さ１７０
μｍ、ｐ／ｑ−６，５）。Example I CF2-CF2 and CF2-CF-0-CF2-CF (
The copolymer obtained by copolymerization with CF3)-0-CF2-CF2-902F was molded into a flat film (film thickness 170
μm, p/q-6,5).
この膜の片面に水蒸気を２時間接触させて加水分解を実
施し、スルホニルフルオライド／スルホン酸の二層膜を
得た。 この二層膜を
Ｈ２Ｎ−ＣＨ２−Ｃ（ＣＨ５）２−Ｃ）１２−Ｎ（Ｃ）
１３）２の構造のアミンに浸漬し、４０℃で６０時間反
応させた。反応後、１０ ｗ ｔ％水酸化ナトリウム水
溶液／メタノール（容積比２ニア）に浸漬し、６０℃で
６日間処理した後、メタノールで洗浄した。Hydrolysis was carried out by contacting one side of this membrane with water vapor for 2 hours to obtain a sulfonyl fluoride/sulfonic acid bilayer membrane. This bilayer film is converted into H2N-CH2-C(CH5)2-C)12-N(C)
13) It was immersed in the amine having the structure 2 and reacted at 40°C for 60 hours. After the reaction, it was immersed in a 10 wt% aqueous sodium hydroxide solution/methanol (volume ratio 2nia), treated at 60° C. for 6 days, and then washed with methanol.
次いでヨウ化エチル／ジメチルスルホキシド（容積比１
：２０）中、５０℃で２日間処理した。Then ethyl iodide/dimethyl sulfoxide (volume ratio 1
:20) for 2 days at 50°C.
次に塩化リチウムのｌ Ｑ ｗ ｔ％メタノール溶液中
、６０℃で２４時間処理した後、０．５Ｎ塩化ナトリウ
ム水溶液中に３日間浸漬した。得られた膜はクレゾール
レッドで染色したところ片面の陰イオン交換層（膜厚−
１５０μｍ）のみ着色した。Next, it was treated in a 1 Q w t % methanol solution of lithium chloride at 60° C. for 24 hours, and then immersed in a 0.5N aqueous sodium chloride solution for 3 days. When the obtained membrane was stained with cresol red, the anion exchange layer on one side (film thickness -
150 μm) was colored.
一方、クリスタルバイオレットで染色したところ他方の
片面の陽イオン交換層（膜厚−２０ｕｍ）のみ着色した
。On the other hand, when it was stained with crystal violet, only the cation exchange layer (film thickness -20 um) on the other side was colored.
実施例２
加水分解時間を８時間とする以外は実施例１と同様の条
件でバイポーライオン交換膜を製造した。Example 2 A bipolar ion exchange membrane was produced under the same conditions as in Example 1 except that the hydrolysis time was 8 hours.
得られた膜はクレゾールレッドで染色したところ片面の
陰イオン交換層（膜厚−１３０μｍ）のみ着色した。一
方、クリスタルバイオレットで染色したところ他方の片
面の陽イオン交換層（膜厚−４０μｍ）のみ着色した。When the obtained membrane was stained with cresol red, only the anion exchange layer on one side (film thickness -130 μm) was colored. On the other hand, when it was stained with crystal violet, only the cation exchange layer (film thickness -40 μm) on the other side was colored.
実施例３
ＣＦ２−ＣＦ２とＣＦ２−ＣＰ−０−ＣＦ２−ＣＦ（Ｃ
Ｆ３）−０−ＣＦ、２−ＣＦ２−８０２Ｆとの共重合に
より得られた共重合体を平膜に成型した（膜厚さ１７０
μｍ、ｐ／ｑ−６，５）。Example 3 CF2-CF2 and CF2-CP-0-CF2-CF (C
F3) The copolymer obtained by copolymerization with -0-CF and 2-CF2-802F was molded into a flat film (film thickness 170
μm, p/q-6,5).
この膜の一部を切取り（膜厚−２０μｍ）、加水分解を
しだ後よく水洗してから乾燥した。加水分解をした膜（
膜厚−２０μｍ）と加水分解をしていない膜（膜厚−１
５０，ａｍ）とを圧着貼り合わせして、スルホニルフル
オライド／スルホン酸の二層膜を得た。 この二層膜を
実施例１と同様の方法でバイポーライオン交換膜を製造
した。A part of this membrane was cut out (film thickness -20 μm), and after hydrolysis had stopped, it was thoroughly washed with water and then dried. Hydrolyzed membrane (
(film thickness -20 μm) and non-hydrolyzed film (film thickness -1
50, am) were bonded together under pressure to obtain a two-layer film of sulfonyl fluoride/sulfonic acid. A bipolar ion exchange membrane was produced from this two-layer membrane in the same manner as in Example 1.
得られた膜はクレゾールレッドで染色したところ片面の
陰イオン交換層（膜厚−１５０μｍ）のみ着色した。一
方、クリスタルバイオレットで染色したところ他方の片
面の陽イオン交換層（膜厚−２０μｍ）のみ着色した。When the obtained membrane was stained with cresol red, only the anion exchange layer (film thickness -150 μm) on one side was colored. On the other hand, when it was stained with crystal violet, only the cation exchange layer (film thickness -20 μm) on the other side was colored.
得られた膜の抵抗及び塩化カリウム水溶液に対するアニ
オン輸率を表１に示す。Table 1 shows the resistance of the obtained membrane and the anion transfer number with respect to an aqueous potassium chloride solution.
実施例２
実施例１中の
８２Ｎ−ＣＨ２−Ｃ（ＣＨ３）２−ＣＨ２−Ｎ（Ｃ）１
３）２の構造のアミンのかわりに
Ｈ２Ｎ−Ｃ）１２−Ｃ）１２−ＣＨ２−Ｎ （Ｃ）１３
）２で表されるアミンを用いた以外は実施例１と同様の
方法で含フッ素系バイポーラ膜を得た。得られた膜はク
レゾールレッドで染色したところ片面の陰イオン交換層
（膜厚−１５０μｍ）のみ着色した。一方、クリスタル
バイオレットで染色したところ他方の片面の陽イオン交
換層（膜厚−２０μｍ）のみ着色した。Example 2 82N-CH2-C(CH3)2-CH2-N(C)1 in Example 1
3) H2N-C)12-C)12-CH2-N (C)13 instead of the amine in structure 2
) A fluorine-containing bipolar membrane was obtained in the same manner as in Example 1 except that the amine represented by 2 was used. When the obtained membrane was stained with cresol red, only the anion exchange layer (film thickness -150 μm) on one side was colored. On the other hand, when it was stained with crystal violet, only the cation exchange layer (film thickness -20 μm) on the other side was colored.
膜の抵抗及び塩化カリウム水溶液に対するアニオン輸率
を表１に示す。Table 1 shows the resistance of the membrane and the anion transfer number with respect to an aqueous potassium chloride solution.
表１ 測定結果Table 1 Measurement results
Claims (3)
ニルフルオライド基を有し、他方の層のペンダント鎖に
スルホン酸基を有し、かつ主鎖がパーフルオロカーボン
重合体からなる膜体にアミンを反応させ、スルホン酸基
を変性させることなくスルホニルフルオライド基にスル
ホアミド基を介して三級アミンを導入し、更に三級アミ
ンの窒素原子を四級化することを特徴とする含フッ素系
バイポーラ膜の製造方法。(1) A film body with a two-layer structure, with a sulfonyl fluoride group in the pendant chains of one layer, a sulfonic acid group in the pendant chains of the other layer, and a main chain made of a perfluorocarbon polymer. A fluorine-containing system characterized by reacting an amine, introducing a tertiary amine into a sulfonyl fluoride group via a sulfamide group without modifying the sulfonic acid group, and further quaternizing the nitrogen atom of the tertiary amine. Method for manufacturing bipolar membranes.
層が下記の一般式 ▲数式、化学式、表等があります▼ 〔Ｘ＝ＦまたはＣＦ＿３、ｌ＝０または１〜５の整数、
ｍ＝０または１、ｎ＝１または２〜５の整数、ｐおよび
ｑは正の数であって、その比ｐ／ｑは２〜１６である。 〕 で表される繰り返し単位よりなり、ペンダント鎖にスル
ホン酸基を有する層が下記の一般式 ▲数式、化学式、表等があります▼ 〔Ｘ、ｌ、ｍ、ｎ、ｐおよびｑは上記と同一、Ｍは水素
またはアルカリ金属〕 で表される繰り返し単位よりなる特許請求の範囲第１項
に記載の含フッ素系バイポーラ膜の製造方法。(2) The layer with sulfonyl fluoride in the pendant chain has the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [X = F or CF_3, l = 0 or an integer from 1 to 5,
m=0 or 1, n=1 or an integer from 2 to 5, p and q are positive numbers, and the ratio p/q is from 2 to 16. ] The layer consisting of repeating units represented by , and having a sulfonic acid group in the pendant chain has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [X, l, m, n, p and q are the same as above , M is hydrogen or an alkali metal] The method for producing a fluorine-containing bipolar membrane according to claim 1, comprising a repeating unit represented by the following formula.
−（ＣＨ＿２）＿ｍ−Ｎ（Ｒ＿３）（Ｒ＿４）、ｎは０
〜１５の整数、ｍは１〜１５までの整数Ｒ＿１は水素ま
たはＣ１〜Ｃ４のアルキル基、Ｒ＿２は水素またはＣ１
〜Ｃ４のアルキル基、Ｒ＿３は水素またはＣ１からＣ６
のアルキル基、Ｒ＿４は水素またはＣ１〜Ｃ６のアルキ
ル基〕である特許請求の範囲第１項に記載の含フッ素系
バイポーラ膜の製造方法。(3) The amine is H_2N-(CH_2)_n-C(R_1)(R_2)
-(CH_2)_m-N(R_3)(R_4), n is 0
-15 integer, m is an integer from 1 to 15 R_1 is hydrogen or a C1-C4 alkyl group, R_2 is hydrogen or C1
~C4 alkyl group, R_3 is hydrogen or C1 to C6
The method for producing a fluorine-containing bipolar membrane according to claim 1, wherein R_4 is hydrogen or a C1 to C6 alkyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322354A JP3044784B2 (en) | 1990-11-28 | 1990-11-28 | Method for producing fluorine-containing bipolar membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322354A JP3044784B2 (en) | 1990-11-28 | 1990-11-28 | Method for producing fluorine-containing bipolar membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04198331A true JPH04198331A (en) | 1992-07-17 |
| JP3044784B2 JP3044784B2 (en) | 2000-05-22 |
Family
ID=18142709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2322354A Expired - Fee Related JP3044784B2 (en) | 1990-11-28 | 1990-11-28 | Method for producing fluorine-containing bipolar membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3044784B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582333A (en) * | 2015-10-20 | 2017-04-26 | 辽宁易辰膜科技有限公司 | Manufacturing method of monolithic bipolar membrane |
-
1990
- 1990-11-28 JP JP2322354A patent/JP3044784B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582333A (en) * | 2015-10-20 | 2017-04-26 | 辽宁易辰膜科技有限公司 | Manufacturing method of monolithic bipolar membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3044784B2 (en) | 2000-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1094982A (en) | Single film, high performance bipolar membrane | |
| CA1046457A (en) | Electrolytic diaphragms, and method of electrolysis using the same | |
| US4147844A (en) | Reverse-side treatment of fabric reinforced membranes | |
| CN105924587A (en) | Branched side chain polymer anion exchange membrane and preparation method thereof | |
| JPS5833886B2 (en) | Cation exchange membrane and its manufacturing method | |
| US4126589A (en) | Method for preparation of cation exchange membranes | |
| JPH08506613A (en) | Single film membrane, its manufacturing method and its use | |
| US5066682A (en) | Process for preparing an ion exchange membrane | |
| JP2609524B2 (en) | Hydrolysis method of fluorine ion exchange resin membrane | |
| JPS59155435A (en) | Tubular anion exchange membrane | |
| JPH04198331A (en) | Production of fluorine-containing bipolar film | |
| US4030988A (en) | Process for producing halogen and metal hydroxides with cation exchange membranes of improved permselectivity | |
| JPS609053B2 (en) | Manufacturing method of cation exchange membrane | |
| JPH0786126B2 (en) | Polymer having betaine structure, solution diffusion film, method for producing the same, and use thereof | |
| JPS601234A (en) | Fluorine-containing bipolar membrane | |
| CA1145236A (en) | Process for fusion bonding of fluorocarbon type polymers | |
| JPH01311132A (en) | Production of anion exchange membrane having excellent alkali resistance | |
| JPS59202227A (en) | Anion exchange membrane and its production | |
| JPS609529B2 (en) | Manufacturing method of cation exchange membrane | |
| TW200410990A (en) | Ionic electroactive graft copolymer with a fluorine-containing backbone and a carbazole-containing side chain, blend thereof and actuator | |
| JPH082975B2 (en) | Method for producing anion exchange membrane having excellent alkali resistance | |
| JPS61185507A (en) | Production of anion exchange material | |
| JPS5858366B2 (en) | Manufacturing method of cation exchange membrane | |
| JPH01297433A (en) | Production of anion exchange membrane having excellent alkali resistance | |
| JPH05125205A (en) | Production of unusually shaped ion-exchange membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |