JPH0418922A - Production of mosaic electrifying membrane - Google Patents
Production of mosaic electrifying membraneInfo
- Publication number
- JPH0418922A JPH0418922A JP12266290A JP12266290A JPH0418922A JP H0418922 A JPH0418922 A JP H0418922A JP 12266290 A JP12266290 A JP 12266290A JP 12266290 A JP12266290 A JP 12266290A JP H0418922 A JPH0418922 A JP H0418922A
- Authority
- JP
- Japan
- Prior art keywords
- film
- acrylic acid
- porous polymer
- polymer film
- ethylenimine
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000012528 membrane Substances 0.000 title description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009832 plasma treatment Methods 0.000 claims abstract description 9
- 229920006254 polymer film Polymers 0.000 claims abstract 5
- 239000007864 aqueous solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 4
- 229920002301 cellulose acetate Polymers 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 229920005597 polymer membrane Polymers 0.000 description 5
- 229920000447 polyanionic polymer Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 3
- 239000012466 permeate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229930091051 Arenine Natural products 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、モザイク荷電膜の製造法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing a mosaic charged film.
更に詳しくは、製作の容易性の点ですぐれたモザイク荷
電膜の製造法に関する。More specifically, the present invention relates to a method for manufacturing a mosaic charged film that is easy to manufacture.
〔従来の技術〕および〔発明が解決しようとする課題〕
モザイク荷電膜は、逆の符号を有する高分子電解質の領
域が交互にモザイク状に配列した膜である。このような
膜を濃度の異なる電解質溶液の間に置くと、ポリカチオ
ン領域とポリアニオン領域の間に正の循環電流が流れ、
そのためポリカチオン領域ではアニオンの、またポリア
ニオン領域ではカチオンの透過が自由となり、結果的に
塩濃度の高い相から低い相への電解質の輸送が起こるこ
とになる。この場合、高濃度側に圧力をかけ、低濃度側
を水にすると、圧透析によって塩の分離が行われる。[Prior art] and [Problem to be solved by the invention]
A mosaic charged membrane is a membrane in which regions of polyelectrolyte having opposite signs are arranged in an alternating mosaic. When such a membrane is placed between electrolyte solutions of different concentrations, a positive circulating current flows between the polycation and polyanion regions.
Therefore, anions can freely permeate through the polycation region, and cations can freely permeate through the polyanion region, resulting in electrolyte transport from the phase with high salt concentration to the phase with low salt concentration. In this case, by applying pressure to the high concentration side and using water to the low concentration side, the salt is separated by pressure dialysis.
このように作用するモザイク荷電膜は、従来不活性なマ
トリックス中にポリカチオンおよびポリアニオンの粒子
をそ九ぞれ埋め込む方法、ポリカチオン膜とポリアニオ
ン膜とを貼り合せ、次いで膜面に垂直に裁断する方法な
どによって製造さ九ている。しかしながら、前者の方法
はポリマー同志の相溶性の問題があり、それの最適な配
合条件を見出すことが難しく、また後者の方法は工程的
に煩雑である。A mosaic charged film that acts in this way has conventionally been produced by embedding polycation and polyanion particles in an inert matrix, pasting together a polycation film and a polyanion film, and then cutting the film perpendicular to the film surface. There are nine manufactured by such methods. However, the former method has the problem of compatibility between polymers, making it difficult to find the optimum blending conditions, and the latter method is complicated in terms of steps.
本発明の目的は、こうした従来法とは全く異なり、製作
の容易性の点ですぐれたモザイク荷電膜の製造法を提供
することにある。An object of the present invention is to provide a method for manufacturing a mosaic charged film that is completely different from such conventional methods and is superior in terms of ease of manufacture.
かかる本発明の目的は、多孔質高分子膜状物をエチレン
イミンガス雰囲気中で低温プラズマ処理した後アクリル
酸水溶液中に浸漬し、モザイク荷電膜を製造することに
よって達成される。This object of the present invention is achieved by subjecting a porous polymer membrane to low-temperature plasma treatment in an ethyleneimine gas atmosphere and then immersing it in an acrylic acid aqueous solution to produce a mosaic charged membrane.
多孔質高分子膜状物としては、一般に膜厚が約０．０５
〜１ｍ＋ｎ程度の酢酸セルロース多孔質膜、ポリスルホ
ン多孔質膜、ポリプロピレン多孔質膜、ポリフッ化ビニ
リデン多孔質膜などが用いられる。As a porous polymer membrane, the membrane thickness is generally about 0.05 mm.
Cellulose acetate porous membranes, polysulfone porous membranes, polypropylene porous membranes, polyvinylidene fluoride porous membranes, etc. of about 1 m+n are used.
これらの多孔質高分子膜状物のエチレンイミンガス雰囲
気中での低温プラズマ処理は、多孔質高分子膜状物を収
容したプラズマ反応容器内を１Ｏ−３Ｔｏｒｒのオーダ
ーに減圧した後、外部モノマー管より約０．０１〜０．
ＩＴｏｒｒの圧力になる迄エチレンイミンを導入し、１
３．５６ＭＨｚの高周波を用い、出力約３０〜８０ｖ５
時間約１〜２０分間の条件下で行われる。The low-temperature plasma treatment of these porous polymer membranes in an ethyleneimine gas atmosphere involves reducing the pressure in the plasma reaction vessel containing the porous polymer membranes to the order of 10-3 Torr, and then removing the external monomer tube. From about 0.01 to 0.
Introduce ethyleneimine until the pressure reaches 1 Torr,
Using 3.56MHz high frequency, output approximately 30~80v5
The test is carried out for about 1 to 20 minutes.
次いで、この低温プラズマ処理された多孔質高分子膜状
物を濃度約５〜２０重量％のアクリル酸水溶液中に浸漬
し、プラズマ処理時から残存するラジカルを用いてアク
リル酸を結合させる。その後、約５０〜７０℃の窒素ガ
ス雰囲気中に約１〜３時間放置し、水洗する。アクリル
酸水溶液に代えて、他の水溶性不飽和カルボン酸の水溶
液を用いることもできる。Next, the porous polymer film-like material subjected to the low-temperature plasma treatment is immersed in an aqueous acrylic acid solution having a concentration of about 5 to 20% by weight, and the acrylic acid is bonded using radicals remaining from the plasma treatment. Thereafter, it is left in a nitrogen gas atmosphere at about 50 to 70°C for about 1 to 3 hours, and then washed with water. Instead of the acrylic acid aqueous solution, an aqueous solution of another water-soluble unsaturated carboxylic acid can also be used.
多孔質高分子膜状物をエチレンイミンで低温プラズマ処
理し、その後アクリル酸水溶液中に浸漬するという簡単
な工程だけで、膜中にエチレンイミンによってプラスに
チャージされ、またアクＩＪル酸によってマイナスにチ
ャージされた分子鎖を導入することができ、結局容易か
つ確実な方法で、分離、濃縮などに有効に利用されるモ
ザイク荷電膜を製造することができる。A simple process of subjecting a porous polymer membrane to low-temperature plasma treatment with ethyleneimine and then immersing it in an acrylic acid aqueous solution will cause the membrane to be positively charged by ethyleneimine and negatively charged by acrylic acid. Charged molecular chains can be introduced, and a mosaic charged membrane that can be effectively used for separation, concentration, etc. can be produced in an easy and reliable manner.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
酢酸セルロース多孔質膜（膜厚０．２ｍｍ）をプラズマ
反応容器内に収容し、容器内を０．００５Ｔｏｒｒとし
た後、外部モノマー管よりエチレンイミンを導入した。Example A cellulose acetate porous membrane (film thickness: 0.2 mm) was placed in a plasma reaction vessel, and after the inside of the vessel was adjusted to 0.005 Torr, ethyleneimine was introduced from an external monomer tube.
圧力が０．０５Ｔｏｒｒとなった段階で、 １３．５６
ＭＨｚの高周波を用い、出力４０１ｉ１．１分間の条件
下で低温プラズマ処理した。次いで、この膜を１０重ｉ
ｔ％アクリル酸水溶液中に１０分間浸漬した後表面の水
をきり、６０℃の窒素ガス雰囲気中に２時間放置した。When the pressure reached 0.05 Torr, 13.56
Low-temperature plasma treatment was performed using a high frequency of MHz under conditions of an output of 401i for 1.1 minutes. Next, this film was
After being immersed in a t% acrylic acid aqueous solution for 10 minutes, the surface was drained of water and left in a nitrogen gas atmosphere at 60° C. for 2 hours.
最後に、洗液が酸性を示さなくなる迄水洗し、た。Finally, it was washed with water until the washing liquid no longer showed acidity.
このようにして得られたモザイク荷電膜を１１型セルに
装着し、Ａ室側にはＯ，１ＭＫＣ１）を、またＢ室側に
は０．０５Ｍ ＫＣＱをそれぞれ入れてＡ、 Ｂ両室を
密封し、Ａ室側には窒素ガスで圧力１０ｋｇ／−迄加圧
し。The mosaic charged membrane obtained in this way was attached to an 11-type cell, and O, 1MKC1) was placed in the A chamber side, and 0.05M KCQ was placed in the B chamber side, and both chambers A and B were sealed. Then, pressurize the A room side with nitrogen gas to a pressure of 10 kg/-.
８時間室温下に放置した。その後、両者のＫＣＱ濃度を
電導度計で測定すると、Ａ室では０．１２Ｍ、Ｂ室では
０．０３Ｍとなっており、モザイク荷電膜の特性を示し
た。It was left at room temperature for 8 hours. Thereafter, when the KCQ concentrations in both were measured using a conductivity meter, they were found to be 0.12M in room A and 0.03M in room B, indicating the characteristics of a mosaic charged film.
Claims (1)
で低温プラズマ処理した後アクリル酸水溶液中に浸漬す
ることを特徴とするモザイク荷電膜の製造法。1. A method for producing a mosaic charged film, which comprises subjecting a porous polymer film to a low-temperature plasma treatment in an ethyleneimine gas atmosphere and then immersing it in an acrylic acid aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12266290A JPH0418922A (en) | 1990-05-11 | 1990-05-11 | Production of mosaic electrifying membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12266290A JPH0418922A (en) | 1990-05-11 | 1990-05-11 | Production of mosaic electrifying membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0418922A true JPH0418922A (en) | 1992-01-23 |
Family
ID=14841532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12266290A Pending JPH0418922A (en) | 1990-05-11 | 1990-05-11 | Production of mosaic electrifying membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0418922A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003051498A1 (en) * | 2001-12-14 | 2003-06-26 | 3M Innovative Properties Company | Plasma treatment of porous materials |
| JP2018012084A (en) * | 2016-07-22 | 2018-01-25 | 国立大学法人山口大学 | Mosaic charged film manufacturing method and mosaic charged film |
-
1990
- 1990-05-11 JP JP12266290A patent/JPH0418922A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003051498A1 (en) * | 2001-12-14 | 2003-06-26 | 3M Innovative Properties Company | Plasma treatment of porous materials |
| US6878419B2 (en) | 2001-12-14 | 2005-04-12 | 3M Innovative Properties Co. | Plasma treatment of porous materials |
| US7125603B2 (en) | 2001-12-14 | 2006-10-24 | 3M Innovative Properties Company | Plasma treatment of porous materials |
| EP1632280A3 (en) * | 2001-12-14 | 2008-01-09 | 3M Innovative Properties Company | Plasma treated porous materials |
| KR100970025B1 (en) * | 2001-12-14 | 2010-07-16 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Plasma Treatment of Porous Materials |
| JP2018012084A (en) * | 2016-07-22 | 2018-01-25 | 国立大学法人山口大学 | Mosaic charged film manufacturing method and mosaic charged film |
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