JPS63305904A - Modifying method for sulfonic acid-type semi permeable membrane - Google Patents
Modifying method for sulfonic acid-type semi permeable membraneInfo
- Publication number
- JPS63305904A JPS63305904A JP14140287A JP14140287A JPS63305904A JP S63305904 A JPS63305904 A JP S63305904A JP 14140287 A JP14140287 A JP 14140287A JP 14140287 A JP14140287 A JP 14140287A JP S63305904 A JPS63305904 A JP S63305904A
- Authority
- JP
- Japan
- Prior art keywords
- sulfonic acid
- semipermeable membrane
- polyamine
- membrane
- sulfonated
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 21
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 5
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 4
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 4
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 3
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000000108 ultra-filtration Methods 0.000 abstract description 2
- 230000003204 osmotic effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000002131 composite material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000035699 permeability Effects 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920002873 Polyethylenimine Polymers 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 for example Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KOAWAWHSMVKCON-UHFFFAOYSA-N 6-[difluoro-(6-pyridin-4-yl-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methyl]quinoline Chemical compound C=1C=C2N=CC=CC2=CC=1C(F)(F)C(N1N=2)=NN=C1C=CC=2C1=CC=NC=C1 KOAWAWHSMVKCON-UHFFFAOYSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 101100365756 Omphalotus olearius omo1 gene Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- ZQESQBVNDBLWAM-WMZHIEFXSA-N n-[(3s,4r)-1-[2-(4-isothiocyanatophenyl)ethyl]-3-methylpiperidin-4-yl]-n-phenylpropanamide Chemical compound C([C@H]([C@H](C1)C)N(C(=O)CC)C=2C=CC=CC=2)CN1CCC1=CC=C(N=C=S)C=C1 ZQESQBVNDBLWAM-WMZHIEFXSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、逆浸透膜あるいは限外ｐ過膜として有用であ
り、％に水処理系における低分子有機物の分離に好適に
用いられると考えられる半透膜に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention is useful as a reverse osmosis membrane or an ultrapolar membrane, and is considered to be suitably used for the separation of low-molecular organic substances in water treatment systems. The invention relates to semipermeable membranes.
（従来の技術）
スルホン酸型半透膜は、主に脱塩用逆浸透膜として、以
前より研究がなされてきた。その例としては、スルホン
化ポリフェニレンオキサイド膜（Ｉｎｄ、 Ｅｎｇ、
Ｃｈｅｍ、 Ｐｒｏｄ、 Ｒｅｓ、 Ｄｅｖｅｌｏｐ、
、Ｖｏ７１０、＆３．ｐ３３５−３３９．１９７１）、
スルホン化ポリスルホン膜（大阪古文工業研究所報告、
第７３回）、スルホン化ポリエーテルイミド膜（％開昭
６Ｏ−２）６８０）などが挙げられる。また、近年ハ膜
の高性能化のために、これらスルホン化ポリマーを支持
膜上にコーティングして得られる複合膜に関する研究も
なされている。その例としては、スルホン化ポリフェニ
レンオキサイド複合膜（％願昭６２−５９９２８）、ス
ルホン化ポリスルホン複合膜（特開昭６ｌ−４５０６）
などが挙げられる。(Prior Art) Sulfonic acid type semipermeable membranes have been studied for some time mainly as reverse osmosis membranes for desalination. Examples include sulfonated polyphenylene oxide membranes (Ind, Eng,
Chem, Prod, Res, Develop,
, Vo710, &3. p335-339.1971),
Sulfonated polysulfone membrane (Reported by Osaka Kobun Kogyo Research Institute,
73rd), sulfonated polyetherimide membrane (% Kaisho 6O-2) 680), and the like. Furthermore, in recent years, in order to improve the performance of membranes, research has been conducted on composite membranes obtained by coating these sulfonated polymers on support membranes. Examples include sulfonated polyphenylene oxide composite membrane (% patent application No. 62-59928), sulfonated polysulfone composite membrane (JP-A No. 61-4506).
Examples include.
これらスルホン酸型半透膜は、他の半透膜（例えば、ポ
リアミド膜など）と比較して、塩類の排除能は高いが、
中性有機物の排除能は低いという特徴を有していた（例
えは、膜、ｖｏｔ８．＆２゜ｐ９７−１）２ 、１９８
３参照）。近年においては、いろいろな工業分野で低分
子有機物の除去が要求される場面が多くなってきており
、従来のスルホン酸型半透膜でに、かかる場面での使用
は困難であった。These sulfonic acid type semipermeable membranes have a higher ability to exclude salts than other semipermeable membranes (e.g., polyamide membranes), but
It was characterized by a low ability to eliminate neutral organic matter (e.g. membrane, vot8.&2゜p97-1)2, 198
(See 3). In recent years, there have been many situations in which the removal of low-molecular-weight organic substances is required in various industrial fields, and it has been difficult to use conventional sulfonic acid type semipermeable membranes in such situations.
（発明が解決しようとする問題点）
本発明は、高い有機物排除能を有する、改質されたスル
ホン酸型半透膜を提供しようとするものである。(Problems to be Solved by the Invention) The present invention aims to provide a modified sulfonic acid type semipermeable membrane having high organic matter removal ability.
（問題点を解決するための手段）
本発明者らは、スルホン酸型半透膜の有機物に対する排
除能を向上させる目的で鋭意研究した結果、スルホン酸
型半透膜のスルホン酸基含有ポリマーをポリアミンで架
橋させることにより、従来のスルホン酸型半透膜には見
られない、有機物に対して高い排除能を示す半透膜が得
られることを見い出し、本発明に到達した。(Means for Solving the Problems) As a result of extensive research aimed at improving the ability of sulfonic acid type semipermeable membranes to exclude organic substances, the present inventors found that the sulfonic acid group-containing polymer of sulfonic acid type semipermeable membranes We have discovered that by crosslinking with polyamine, it is possible to obtain a semipermeable membrane that exhibits a high ability to exclude organic substances, which is not seen in conventional sulfonic acid type semipermeable membranes, and have arrived at the present invention.
本発明における架橋剤としては、ポリアミンが用いられ
る。ただし、ここで言うポリアミンとけ、主鎖または側
鎖中に一級あるいけ二級あるいは三級のアミノ基を有す
る、少なくとも分子量が５００以上の複数アミン基含有
化合物のことである。なはスルホン酸アミド結合（−８
ｏ、−Ｎ＼）が形成されることにより起こると考えられ
る。また、本発明者らは、スルホン酸基含有ポリマーと
ポリアミンとの間で架橋反応が起こることを、次のよう
な実験を行なうことにより見い出している。すなわち、
その実験例を述べれば、イオン交換容量が１．９ミリ当
−ｆｉｔ／ｌのスルホン化ポリ−２，６−シメチルー１
，４−フェニレンオキサイド（以下、５ＰＰＯと略記す
る）２重量部とエチレングリコールモノ−ｎ−ブチルエ
ーテル９８重量部とより成る溶液（以下、該組成の溶液
をＡ溶液と称する）と、ポリエチレンイミン２重量部と
純水５重量部とエタノール９６重量部より成る溶液（以
下、該組成の溶液をＢ溶液と称する）とを室温で等量ず
つ混合したところ、瞬時にして多量の不溶性淡茶色沈で
んが生成した。Ａ溶液に、これと等量の純水５重量部と
エタノール９３重量部とより成る溶液を加えても、また
、Ｂ溶液に、これと等量のエチレンクリコールモノ−ｎ
−ブチルエーテルを加えても、ともに沈でんは生成しな
かった。以上の実験結果より、５ｐｐｏとポリエチレン
イミンの両者が速やかに架橋反応を起こし、不溶性の沈
でんを形成することを知ることができる。Polyamine is used as the crosslinking agent in the present invention. However, the polyamine referred to herein refers to a compound containing multiple amine groups having a primary, secondary, or tertiary amino group in the main chain or side chain and having a molecular weight of at least 500 or more. is a sulfonic acid amide bond (-8
o, -N\) is thought to occur. Furthermore, the present inventors have discovered through the following experiment that a crosslinking reaction occurs between a sulfonic acid group-containing polymer and a polyamine. That is,
To describe an experimental example, sulfonated poly-2,6-dimethyl-1 with an ion exchange capacity of 1.9 mE-fit/l
, 2 parts by weight of 4-phenylene oxide (hereinafter abbreviated as 5PPO) and 98 parts by weight of ethylene glycol mono-n-butyl ether (hereinafter, a solution with this composition is referred to as solution A), and 2 parts by weight of polyethyleneimine. When a solution consisting of 5 parts by weight of pure water and 96 parts by weight of ethanol (hereinafter, a solution with this composition is referred to as solution B) were mixed in equal amounts at room temperature, a large amount of insoluble light brown precipitate was instantly formed. did. Even if a solution consisting of an equal amount of 5 parts by weight of pure water and 93 parts by weight of ethanol is added to solution A, an equal amount of ethylene glycol mono-n is added to solution B.
- Even when butyl ether was added, no precipitate was formed. From the above experimental results, it can be seen that both 5ppo and polyethyleneimine quickly undergo a crosslinking reaction to form an insoluble precipitate.
ポリアミンがなぜ架橋剤として％に有効であるのか、そ
の理由は不明である。しかしながら、ポリアミンは、（
１）近距離間のスルホン酸基同士たけでなく、遠距離間
のスルホン酸基同士の架橋を可能にでき、かつ、１２＋
二つのスルホン酸基同士だけでなく、三つ以上のスルホ
ン酸基同士の架橋も可能にでき、さらに、（３）スルホ
ン酸基含有ポリマーとの架橋後も、架橋には関与してい
ないフリーのアミノ基がおそらくは残存していることが
考えられるなど、他の架橋剤（例えば、低分子ジアミン
や多価カチオンなど）には見られない特徴を有している
。したがって、これらの特徴が本発明の効果（スルホン
酸型半透膜の有機物に対する排除能の向上）に対して大
きく寄与しているのではないかと考えられる。The reason why polyamines are so effective as crosslinking agents is unknown. However, polyamines (
1) It is possible to cross-link not only sulfonic acid groups at short distances, but also sulfonic acid groups at long distances, and 12+
It is possible to crosslink not only two sulfonic acid groups, but also three or more sulfonic acid groups, and (3) even after crosslinking with the sulfonic acid group-containing polymer, free particles that are not involved in the crosslinking are removed. It has characteristics not found in other crosslinking agents (for example, low-molecular diamines, polyvalent cations, etc.), such as the possibility that amino groups may remain. Therefore, it is considered that these characteristics greatly contribute to the effect of the present invention (improvement in the ability of the sulfonic acid type semipermeable membrane to exclude organic matter).
ポリアミンとしては、例えば、ポリエチレンイＭａｋｒ
ｏｍｏ１． Ｃｈｅｍ、、 １７０ 、２５（１９７Ｆ
）記載のなどの含窒素系の高分子凝集剤（例えば、地人
書館刊、高分子凝集剤、「水処理の高分子科学と技術（
下）高分子水処理剤」参照）を中心とした高分子群を挙
げることができ、いずれを用いても効果がある。したが
って、どれを用いるかは％に限定はされないが、経済性
の面でポリエチレンイミンが好ましく用いられる。As the polyamine, for example, polyethylene Makr
omo1. Chem,, 170, 25 (197F
) Nitrogen-containing polymer flocculants such as those described in ``Polymer Science and Technology of Water Treatment''
Examples of polymers include "Polymer Water Treatment Agents" below), and any of them can be effective. Therefore, although there is no limit to the percentage, polyethyleneimine is preferably used from the economic point of view.
また、スルホン酸型半透膜におけるスルホン酸基含有ポ
リマーが、いかなる化学種のポリマーであるかも％に限
定はされないが、スルホン化ポリフェニレンオキサイド
、スルホン化ポリスルホン、スルホン化ポリエーテルス
ルホン、スルホン化ポリエーテルイミドが、主に耐熱性
に優れている点で好ましく用いられる。Furthermore, the sulfonic acid group-containing polymer in the sulfonic acid type semipermeable membrane is not limited to any chemical species, but examples include sulfonated polyphenylene oxide, sulfonated polysulfone, sulfonated polyether sulfone, and sulfonated polyether sulfone. Imide is preferably used mainly because it has excellent heat resistance.
本発明によるスルホン酸型半透膜の改質は、スルホン酸
型半透膜をポリアミン溶液と接触させることによシ行な
うことができる。また、ポリアミン溶液との接触を終え
た半透膜を、さらに熱処理することにより、半透膜の溶
質排除能力をさらに向上させることもできる。Modification of the sulfonic acid type semipermeable membrane according to the present invention can be carried out by bringing the sulfonic acid type semipermeable membrane into contact with a polyamine solution. Moreover, the solute removal ability of the semipermeable membrane can be further improved by further heat-treating the semipermeable membrane after contact with the polyamine solution.
架橋に供するスルホン酸型半透膜は、乾燥状態でも湿潤
状態でもどちらでもよい。ポリアミン溶液の調製に用い
る溶媒は、ポリアミンを溶解し、かつ、架橋に供された
スルホン酸型半透膜金おかさないものであれば伺でもよ
いが、通常、さしつかえがなければ水あるいは水とアル
コールの混合溶媒が、取り扱いの容易さから好ましく用
いられる。ポリアミン溶液中のポリアミン濃度も特に限
定されるものではないが、高濃度では溶液の粘度が高く
なって取り扱いに不便をきたし、希薄すぎる場合には効
果的な架橋が困難になるため、通常は５重量％〜０．０
５重量％の濃度範囲で用いられる。スルホン酸型半透膜
とポリアミン溶液との接触時間も特に限定されるもので
はないが、通常に数秒から１分間程度で充分である。熱
処理についても、その方法は特に限定はされず、例えば
、水中での熱処理でも、空気中での熱処理でもよい。The sulfonic acid type semipermeable membrane to be subjected to crosslinking may be in either a dry state or a wet state. The solvent used to prepare the polyamine solution may be any solvent as long as it dissolves the polyamine and does not disturb the sulfonic acid type semipermeable membrane used for crosslinking, but it is usually water or water and alcohol unless otherwise prohibited. A mixed solvent of is preferably used because of ease of handling. The polyamine concentration in the polyamine solution is not particularly limited, but if the concentration is too high, the viscosity of the solution will increase, making handling inconvenient, and if it is too dilute, effective crosslinking will be difficult. Weight%~0.0
It is used in a concentration range of 5% by weight. The contact time between the sulfonic acid type semipermeable membrane and the polyamine solution is also not particularly limited, but a period of several seconds to about 1 minute is usually sufficient. The method of heat treatment is not particularly limited, and may be, for example, heat treatment in water or heat treatment in air.
熱処理温度は比較的低い温度でも効果はあるが、効率良
く熱処理を行なうためには、５０Ｃ以上、ベースとなる
スルホン酸型半透膜の変質温度未満の温度範囲であるこ
とが好捷しい。熱処理時間については、熱処理温度との
兼ね合いもあるが、概ねそれほど長い時間を必要とはせ
ず、熱処理温度が適当であれば、１時間程度で充分であ
る。Although a relatively low heat treatment temperature is effective, in order to perform the heat treatment efficiently, it is preferable that the temperature range is 50C or higher and lower than the deterioration temperature of the sulfonic acid type semipermeable membrane serving as the base. Regarding the heat treatment time, there is a balance with the heat treatment temperature, but generally it does not require a very long time, and if the heat treatment temperature is appropriate, about 1 hour is sufficient.
（実施例）
以下に実施例を挙げて本発明を具体的に説明するが、本
発明は、これら実施例により何ら限定されるものではな
い。(Examples) The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
ポリスルホンより成る外径１．５５ｔｔｒｘ、内径０．
７２冨鳳、分画分子量６０００、透水率１）．０ ｍｌ
／ｍ。Example 1 Made of polysulfone, outer diameter 1.55 ttrx, inner diameter 0.
72 Tomiho, molecular weight cut off 6000, water permeability 1). 0ml
/m.
ｍ（ｋｌ／ｍ” ） ａｔ ２ ｓ Ｃの中空繊維状限
外濾過膜の外表面上に、イオン交換容量が１，９ミ’）
当量／１の５ＰＰ０２重量部とエチレングリコールモノ
−ｎ−ブチルエーテル９８重量部とから成る溶液をコー
ティングした後に風乾することにより、５ｐｐｏ複合半
透膜を得た。この５ｐｐｏ複合半透膜の性能は、後述の
表１に付記した方法で測定したところ、ショ糖の排除率
６４．０％、イソプロピルアルコールの排除率７．１チ
、溶質濾過時の透水率１．００ ｍ”７ｍ”・日であっ
た。m (kl/m") at 2 s C on the outer surface of the hollow fiber ultrafiltration membrane with an ion exchange capacity of 1.9 m')
A 5ppo composite semipermeable membrane was obtained by coating a solution consisting of 2 parts by weight of 5PP0 at equivalent weight/1 and 98 parts by weight of ethylene glycol mono-n-butyl ether and then air drying. The performance of this 5ppo composite semipermeable membrane was measured using the method listed in Table 1 below, and found that the sucrose rejection rate was 64.0%, the isopropyl alcohol rejection rate was 7.1%, and the water permeability during solute filtration was 1%. It was .00 m"7 m"・day.
次に、この５ｐｐｏ複合半透膜を、以下のようにして本
発明による改質を行なった。Next, this 5ppo composite semipermeable membrane was modified according to the present invention as follows.
５ｐｐｏ複合半透膜の外表面を、ポリエチレンイミン〔
東京化成（株）の市販品９０．５重量部と純水７０重量
部とエタノール６０重量部とから成る溶液中に約１０秒
間浸漬した後、取り出し、改質５ｐｐｏ複合半透膜を得
た。得られた改質ｓｐｐ。The outer surface of the 5ppo composite semipermeable membrane was coated with polyethyleneimine [
After being immersed for about 10 seconds in a solution consisting of 90.5 parts by weight of a commercially available product from Tokyo Kasei Co., Ltd., 70 parts by weight of pure water, and 60 parts by weight of ethanol, it was taken out to obtain a modified 5ppo composite semipermeable membrane. The resulting modified spp.
複合半透膜の性能全表１に示した。The complete performance of the composite semipermeable membrane is shown in Table 1.
比較例１
実施例１で用いた５ｐｐｏ複合半透膜の外表面を、１モ
ル／リットルのＣａＣ４水溶液中に２０時間浸漬した後
、取り出した。得られたＣａＣム処理膜の性能を表１に
示した。Comparative Example 1 The outer surface of the 5ppo composite semipermeable membrane used in Example 1 was immersed in a 1 mol/liter CaC4 aqueous solution for 20 hours and then taken out. Table 1 shows the performance of the obtained CaC-treated membrane.
比較例２
実施例１で用いたｓ ｐｐｏ複合半透膜の外表面を、ヒ
ヘラジン０．５重量部と純水７０重量部とエタノール５
０重量部とから成る溶液中に約１０秒−１〇 −
間浸漬した後、取シ出した。得られたピペラジン処理膜
の性能を表１に示した。Comparative Example 2 The outer surface of the sppo composite semipermeable membrane used in Example 1 was coated with 0.5 parts by weight of hyherazine, 70 parts by weight of pure water, and 5 parts by weight of ethanol.
After being immersed in a solution consisting of 0 parts by weight for about 10 seconds to 10 minutes, it was taken out. Table 1 shows the performance of the obtained piperazine-treated membrane.
実施例２
実施例１で得られた改質５ｐｐｏ複合半透膜を、８０Ｃ
の純水中で１時間熱処理を行なった。得られた熱処理膜
の性能を表１に示した。Example 2 The modified 5ppo composite semipermeable membrane obtained in Example 1 was heated to 80C
Heat treatment was performed in pure water for 1 hour. Table 1 shows the performance of the heat-treated film obtained.
実施例３
実施例１で得られた改質５ｐｐｏ複合半透膜を、８０Ｃ
の乾燥機中で１時間熱処理を行なった。得られた熱処理
膜の性能を表１に示した。Example 3 The modified 5ppo composite semipermeable membrane obtained in Example 1 was heated to 80C
Heat treatment was performed in a dryer for 1 hour. Table 1 shows the performance of the heat-treated film obtained.
表 １
なお、膜性能の評価は、外圧濾過方式、圧力１０にノ／
（ｎ”、温度２５Ｃ１溶質濃度５００ａｐｌで行ない、
安定してからの値を用いた。また、表１中なる式によっ
て定義され、透水率は溶質濾過時の透水率を用いた。Table 1 The evaluation of membrane performance is based on the external pressure filtration method and pressure 10.
(n'', temperature 25C, solute concentration 500 apl,
The value after stabilization was used. Moreover, it was defined by the formula in Table 1, and the water permeability at the time of solute filtration was used as the water permeability.
実施例４
ｓｐｐｏをイオン変換容量が１．５ミリ当量／ｌのスル
ホン化ポリスルホン（以下、ＳＰＳと略記する）にかえ
た以外は、実施例１と同様にして、本発明による改質Ｓ
ＰＳ複合半透膜を得た。得られた改質ＳＰＳ複合半透膜
の性能を表２に示した。Example 4 The modified S according to the present invention was produced in the same manner as in Example 1, except that sppo was changed to sulfonated polysulfone (hereinafter abbreviated as SPS) with an ion conversion capacity of 1.5 meq/l.
A PS composite semipermeable membrane was obtained. Table 2 shows the performance of the obtained modified SPS composite semipermeable membrane.
なお、ポリエチレンイミンによる改質前のＳＰＳ複合半
透膜の性能は、後述の表２に付記した方法により測定し
たところ、イソプロピルアルコールの排除率５．４％、
溶質濾過時の透水率１．０７ｍ３／が・日であった。The performance of the SPS composite semipermeable membrane before modification with polyethyleneimine was measured using the method described in Table 2 below, and the rejection rate of isopropyl alcohol was 5.4%.
The water permeability during solute filtration was 1.07 m3/day.
実施例５
実施例１で用いたｓｐｐｏ複合半透膜の外表面を、キト
サン（片倉チツカリン（株）製） ０．２５重量部と酢
酸９重量部と純水９０．７５重量部とから成る溶液中に
約１０秒間浸漬した後、取り出した。Example 5 The outer surface of the sppo composite semipermeable membrane used in Example 1 was coated with a solution consisting of 0.25 parts by weight of chitosan (manufactured by Katakura Chitsukarin Co., Ltd.), 9 parts by weight of acetic acid, and 90.75 parts by weight of pure water. After being immersed in it for about 10 seconds, it was taken out.
得られた改質５ＰＰＯ複合半透膜の性能を表２に示した
。Table 2 shows the performance of the obtained modified 5PPO composite semipermeable membrane.
実施例６
実施例５で得られた改質５ｐｐｏ複合牛透膜を、８０Ｃ
の乾燥機中で１時間熱処理を行なった。得られた熱処理
膜の性能を表２に示した。Example 6 The modified 5ppo composite bovine permeable membrane obtained in Example 5 was heated to 80C
Heat treatment was performed in a dryer for 1 hour. Table 2 shows the performance of the obtained heat-treated film.
実施例７ 実施例２および実施例６で得られた改質ｓｐｐ。Example 7 Modified spp obtained in Example 2 and Example 6.
熱処理膜を、８０Ｃの純水中に４時間浸漬した。The heat-treated membrane was immersed in pure water at 80C for 4 hours.
熱水浸漬処理後の各膜の性能を表２に示した。膜性能は
、いずれも熱水浸漬の前後で実質的に変化しておらず、
これらの膜は、いずれも耐熱性に優れていることがわか
る。Table 2 shows the performance of each membrane after hot water immersion treatment. The membrane performance was virtually unchanged before and after immersion in hot water.
It can be seen that all of these films have excellent heat resistance.
表 ２
なお、膜性能の評価は、外圧沖過方式、圧力１０にノ／
−２、温度２５［、溶質濃度５００ｐｐｍで行ない、安
定してからの値を用いた。また、表２中なる式によって
定義され、透水率は、溶質沖過時の透水率を用いた。Table 2 The membrane performance was evaluated using the external pressure offshore method and pressure 10
-2, the temperature was 25[deg.], and the solute concentration was 500 ppm, and the values after stabilization were used. Moreover, it was defined by the formula in Table 2, and the water permeability at the time of solute passage was used as the water permeability.
（発明の効果）
上記実施例および比較例から明らかなように、本発明に
より得られるスルホン酸型半透膜は、従来のスルホン酸
型半透膜に比べて、きわめて高い有機物排除能を有する
。(Effects of the Invention) As is clear from the above Examples and Comparative Examples, the sulfonic acid type semipermeable membrane obtained by the present invention has an extremely high ability to remove organic matter compared to the conventional sulfonic acid type semipermeable membrane.
手続補正書
昭和６２年７月６日
特許庁長官 小 川 邦 夫 殿
１ 事件の表示
特願昭６２−１４１４０２号
２ 発明の名称
スルホン酸型半透膜の改質方法
３ 補正をする者
事件との関係・特許出願人
（００３） 旭化成工業株式会社
４代理人
東京都港区虎ノ門−丁目２番２９号虎ノ門産業ビル５階
明細書の発明の詳細な説明の欄
６ 補正の内容
明細書の記載を次のとおり補正する。Procedural amendment July 6, 1988 Director General of the Patent Office Kunio Ogawa 1 Indication of the case Patent application No. 141402/1982 Title of the invention Method for modifying sulfonic acid type semipermeable membrane 3 Person making the amendment Case and Relationship/Patent Applicant (003) Asahi Kasei Kogyo Co., Ltd. 4 Agent 5th Floor, Toranomon Industrial Building, 2-29 Toranomon-chome, Minato-ku, Tokyo Column 6 for Detailed Explanation of the Invention in the Specification Detailed Description of the Amendment Contents of the Specification shall be corrected as follows.
（１）第１）頁の表１を削除する。(1) Delete Table 1 on page 1).
（２）第１２頁１〜６行の
「なお、膜性能の評価は・・・・・・・・・透水率を用
いた。」を削除する。(2) Delete "The membrane performance was evaluated using water permeability" in lines 1 to 6 on page 12.
（３）第１２頁１２行、同１４行、第１３頁４行、同９
行、同１３行の「表２に」を「表１に」と補正する。(3) Page 12, line 12, line 14, page 13, line 4, line 9
In line 13, "in Table 2" is corrected to "in Table 1."
（４）第１４頁１行の「表２」の表示を「表１」と補正
する。(4) Correct the display of "Table 2" on page 14, line 1 to "Table 1."
（５）第１５頁３行の「表２中」を「表１中」と補正す
る。(5) Correct “in Table 2” in line 3 of page 15 to “in Table 1”.
Claims (3)
をポリアミンで架橋させることを特徴とするスルホン酸
型半透膜の改質方法。(1) A method for modifying a sulfonic acid type semipermeable membrane, which comprises crosslinking a sulfonic acid group-containing polymer of the sulfonic acid type semipermeable membrane with a polyamine.
せる方法が、スルホン酸基を有する半透膜にポリアミン
溶液を接触させるか、あるいはポリアミン溶液に接触さ
せた後に熱処理を施す方法である特許請求の範囲第１項
記載のスルホン酸型半透膜の改質方法。(2) A method for crosslinking a sulfonic acid group-containing polymer with a polyamine is a method in which a semipermeable membrane having a sulfonic acid group is brought into contact with a polyamine solution, or a method is performed in which a semipermeable membrane having a sulfonic acid group is brought into contact with a polyamine solution and then subjected to heat treatment. 2. A method for modifying a sulfonic acid type semipermeable membrane according to item 1.
ェニレンオキサイド、スルホン化ポリスルホン、スルホ
ン化ポリエーテルスルホン、スルホン化ポリエーテルイ
ミドから成るポリマー群の中より選ばれるスルホン酸基
含有ポリマーである特許請求の範囲第１項または第２項
記載のスルホン酸型半透膜の改質方法。(3) Claims in which the sulfonic acid group-containing polymer is a sulfonic acid group-containing polymer selected from the polymer group consisting of sulfonated polyphenylene oxide, sulfonated polysulfone, sulfonated polyether sulfone, and sulfonated polyetherimide. A method for modifying a sulfonic acid type semipermeable membrane according to item 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14140287A JPS63305904A (en) | 1987-06-08 | 1987-06-08 | Modifying method for sulfonic acid-type semi permeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14140287A JPS63305904A (en) | 1987-06-08 | 1987-06-08 | Modifying method for sulfonic acid-type semi permeable membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63305904A true JPS63305904A (en) | 1988-12-13 |
Family
ID=15291169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14140287A Pending JPS63305904A (en) | 1987-06-08 | 1987-06-08 | Modifying method for sulfonic acid-type semi permeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63305904A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02157026A (en) * | 1988-12-08 | 1990-06-15 | Sumitomo Bakelite Co Ltd | Charge type ultrafiltration film and its manufacture |
| US5348569A (en) * | 1993-06-30 | 1994-09-20 | Praxair Technology, Inc. | Modified poly(phenylene oxide) based membranes for enhanced fluid separation |
| US5356459A (en) * | 1993-06-30 | 1994-10-18 | Praxair Technology, Inc. | Production and use of improved composite fluid separation membranes |
| US5364454A (en) * | 1993-06-30 | 1994-11-15 | Praxair Technology, Inc. | Fluid separation composite membranes prepared from sulfonated aromatic polymers in lithium salt form |
| WO1997024777A1 (en) * | 1995-12-28 | 1997-07-10 | Research Foundation Of The State University Of New York | Blend membranes based on sulfonated poly(phenylene oxide) for enhanced polymer electrochemical cells |
| FR2894984A1 (en) * | 2005-12-20 | 2007-06-22 | Millipore Corp | (EN) COMPOSITION FOR INCREASING THE PERMEABILITY OF MICRO - ORGANISM WALLS AND METHOD FOR MEMBRANE DETECTION OF MICROORGANISMS. |
| US7345135B2 (en) | 2001-10-10 | 2008-03-18 | Mitsui Chemicals, Inc. | Crosslinkable aromatic resin having protonic acid group, and ion conductive polymer membrane, binder and fuel cell using the resin |
| JP2014000568A (en) * | 2012-05-22 | 2014-01-09 | Daicen Membrane Systems Ltd | Internal pressure type hollow fiber type nf membrane and manufacturing method of the same |
-
1987
- 1987-06-08 JP JP14140287A patent/JPS63305904A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02157026A (en) * | 1988-12-08 | 1990-06-15 | Sumitomo Bakelite Co Ltd | Charge type ultrafiltration film and its manufacture |
| US5348569A (en) * | 1993-06-30 | 1994-09-20 | Praxair Technology, Inc. | Modified poly(phenylene oxide) based membranes for enhanced fluid separation |
| US5356459A (en) * | 1993-06-30 | 1994-10-18 | Praxair Technology, Inc. | Production and use of improved composite fluid separation membranes |
| US5364454A (en) * | 1993-06-30 | 1994-11-15 | Praxair Technology, Inc. | Fluid separation composite membranes prepared from sulfonated aromatic polymers in lithium salt form |
| WO1997024777A1 (en) * | 1995-12-28 | 1997-07-10 | Research Foundation Of The State University Of New York | Blend membranes based on sulfonated poly(phenylene oxide) for enhanced polymer electrochemical cells |
| US7345135B2 (en) | 2001-10-10 | 2008-03-18 | Mitsui Chemicals, Inc. | Crosslinkable aromatic resin having protonic acid group, and ion conductive polymer membrane, binder and fuel cell using the resin |
| FR2894984A1 (en) * | 2005-12-20 | 2007-06-22 | Millipore Corp | (EN) COMPOSITION FOR INCREASING THE PERMEABILITY OF MICRO - ORGANISM WALLS AND METHOD FOR MEMBRANE DETECTION OF MICROORGANISMS. |
| EP1801239A3 (en) * | 2005-12-20 | 2007-08-15 | Millipore Corporation | Composition for increasing microorganism wall permeability and method for detecting said microorganisms on a membrane |
| US8148081B2 (en) | 2005-12-20 | 2012-04-03 | Emd Millipore Corporation | Method for detecting microorganisms on a membrane |
| JP2014000568A (en) * | 2012-05-22 | 2014-01-09 | Daicen Membrane Systems Ltd | Internal pressure type hollow fiber type nf membrane and manufacturing method of the same |
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