JPH025446B2 - - Google Patents
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- Publication number
- JPH025446B2 JPH025446B2 JP57186370A JP18637082A JPH025446B2 JP H025446 B2 JPH025446 B2 JP H025446B2 JP 57186370 A JP57186370 A JP 57186370A JP 18637082 A JP18637082 A JP 18637082A JP H025446 B2 JPH025446 B2 JP H025446B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- reverse osmosis
- monomer
- monomers
- porous
- 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.)
- Expired - Lifetime
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- Separation Using Semi-Permeable Membranes (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、逆浸透膜の製造方法、さらに詳しく
は、単量体を多孔性支持膜中に含浸させ光重合さ
せることにより一段で逆浸透膜を製造する方法に
関するものである。
従来、逆浸透用複合膜は、逆浸透性を示す重合
体を製造し、これを多孔性膜にキヤストする方法
で一般に製造されている。この方法は単量体をい
つたん重合させて逆浸透性を有する重合体を合成
し、再沈殿、精製したのち、溶媒に溶解させてキ
ヤステイング溶液を調製し、これを支持膜上へ塗
布し乾燥するもので、多くの煩雑な工程を必要と
するものである。
本発明者は、このような従来の煩雑な工程を必
要としない逆浸透膜の製造方法を開発するために
研究を行い、先に４−メタクリロイロキシカルコ
ンと親水性基をもつ一官能性単量体とを共重合さ
せて光可溶性感光ポリマーを調製し、次いでこれ
を多孔質膜に塗布し光照射して架橋させることに
より逆浸透膜を製造する方法を提案したが（特公
昭57−41281号公報）、さらに研究を重ねた結果、
親水性基をもつ一官能性単量体と二官能性単量体
の液状混合物に光重合開始剤を加え、これを多孔
性支持膜に含浸させたのち、光照射すれば、一挙
に逆浸透膜が得られることを見出し、この知見に
基づいて本発明をなすに至つた。
すなわち、本発明は、光重合開始剤を含んだ、
親水性基をもつ一官能性単量体と二官能性単量体
との液状混合物を、多孔性支持膜の微孔中に充て
んしたのち、これに光照射して単量体の光重合及
び光架橋化を同時に起させ、微孔中に担持された
親水ゲルを形成させることを特徴とする逆浸透膜
の製造方法を提供するものである。
本発明の方法に用いられる一官能性単量体とし
ては、例えば２−ジメチルアミノエチルメタクリ
レート、アクリル酸、メタクリル酸、Ｎ，Ｎ−ジ
メチルアクリルアミド、２−ヒドロキシエチルメ
タクリレート、２−アクリルアミド−２−メチル
プロパンスルホン酸等の親水性基を有するアクリ
ル系単量体を挙げることができるが、その他の光
重合性を示、かつ親水性基をもつ一官能性単量体
も、もちろん使用可能である。また、二官能性単
量体としては、例えばエチレングリコールジメタ
クリレート、ジエチレングリコールジメタクリレ
ート、４−メタクリロイルオキシカルコン、Ｎ，
Ｎ−（２−ヒドロキシ−３−メタクリロイルオキ
シプロピル）ピペラジン等を挙げることができ
る。
これら一官能性単量体と二官能性単量体の使用
割合は、逆浸透により排除すべき塩の種類や濃度
により適宜選択されるが、二官能性単量体の量が
多すぎると膜透過流束が小さくなり、少なすぎる
と溶存塩類の排除率が低くなり、逆浸透膜の性能
が低下するので好ましくなく、通常二官能性単量
体は一官能性単量体に対し、0.5〜15％の範囲量
が有利に用いられる。また、一官能性単量体は単
一成分でもよいし２成分以上を組み合わせて使用
することができ、二官能性単量体も同様に１種又
は２種以上を組み合わせて使用できる。
また、これら単量体中に含有せしめる好ましい
光重合開始剤としては、例えば２，２−ジエトキ
シアセトフエノン、ベンゾイン、ベンゾフエノ
ン、ベンゾインイソプロピルエーテル、２，２−
ジメトキシ２−フエニルアセトフエノン等の光増
感剤を挙げることができる。このうち、液状の上
記単量体類に溶解し得る２，２−ジエトキシアセ
トフエノンが特に好都合である。
本発明方法に用いられる多孔性支持膜は、多孔
性の膜状物であつて、例えば多孔性ポリプロピレ
ンフイルムのような多孔性高分子フイルムが有利
に使用される。本発明においては、このような多
孔性支持膜に、まず光重合開始剤を含有させた単
量体混合液を含浸し、好ましくは空気非接触条件
下に光照射して単量体を重合させるが、例えばフ
ツ素樹脂板に多孔性高分子フイルムを載せ、これ
に単量体混合液を含浸させたのち、その上を透明
なフイルムで覆い、次いで例えばローラーなどで
上側からしごくように空気を追い出して密着さ
せ、光照射処理される。空気を遮断するための透
明なフイルムは、単量体に溶解、膨潤などする素
材は好ましくなく、好都合なものは透明なポリプ
ロピレンフイルム、ポリエチレンフイルム、フツ
素化エチレン−プロピレン共重合体フイルムなど
である。
光照射は、通常高圧水銀灯が有利に使用され、
例えば100Wの高圧水銀灯では、10〜15cmの距離
で透明フイルム側から光照射させると直ちに重合
がはじまり、多孔性高分子支持フイルム中の単量
体は容易に重合体を形成する。この光照射処理は
数分〜数十分程度の比較的短時間に完了するが、
好ましくは光照射後に例えば100〜110℃程度の温
度で３〜10分間熱処理される。熱処理後、カバー
した透明フイルムをはがして容易に逆浸透性複合
膜を得ることができる。
本発明の方法においては、前記のように親水性
基を有する一官能性単量体が有利に使用されるの
で、例えばＮ，Ｎ−ジメチルアミノエチルメタク
リレートのような塩基が重合体中に導入されてい
るときは塩酸水溶液に浸し、またアクリル酸を用
いたような場合には水酸化ナトリウムの水溶液に
浸すなどして高分子塩にすることが好ましく、こ
のような処理により透水性を向上させることがで
きる。
本発明の方法は、従来の逆浸透膜の製造方法に
おけるような煩雑な工程がなく、取扱いや操作が
極めて容易であり、しかも単量体のロスを大幅に
減少させることができるので工業的に有利であ
る。また、本発明の方法により得られる逆浸透膜
は、従来の逆浸透膜の有する溶存塩排除率、例え
ば0.3％塩化ナトリウム水溶液に適用した場合の
排除率70〜80％程度に匹敵する逆浸透性能を有
し、充分実用に供しうるものである。
本発明の方法により得られた逆浸透膜は、従来
品と同様にかん水の淡水化、無機塩水溶液からの
脱塩水の製造に有用であり、またイオン交換膜と
して使用することもできる。
以下、実施例により本発明をさらに詳細に説明
する。
実施例 １
２−ジメチルアミノエチルメタクリレート
（DAEMAと略記する）の1.0c.c.に所定量の二官能
性単量体すなわち４−メタクリロイルオキシカル
コン（MC）又はエチレングリコールジメタクリ
レート（EG）及び光重合開始剤として、２，２
−ジエトキシアセトフエノン（EAP）0.02c.c.を混
合して単量体混合液を調製した。この液を多孔性
ポリプロピレン膜（Celgard 2400、疎水性、直
径7.5cm）に含浸させ、その含浸膜をテフロン板
と透明ポリプロピレンフイルムに狭み、透明ポリ
プロピレンフイルムの上からハンドローラーでし
ごくようにして空気を追い出し密着させた。次い
で、100W高圧水銀灯により15cmの距離から透明
ポリプロピレン側に向つて10分間光照射を行い、
照射後、110℃で３分間熱処理を施し、水中で膜
をはがした。得られた複合膜を稀塩酸水溶液（濃
塩酸２c.c.を10c.c.の水で稀釈した水溶液）に浸漬し
て一夜放置した。この段階でジメチルアミノ基は
塩酸塩の形になり、膜はいくらか膨潤して広がつ
た。水で十分洗浄した後、この膜をAbcor RO−
３型逆浸透計（180c.c.容量）を用い、0.3％の塩化
ナトリウム水溶液を用いて逆浸透実験を行つた。
操作圧は70Kg／cm2、有効膜面積は30.2cm2である。
MC又はEGの使用量を変えて製造した種々の逆
浸透膜について得た結果を第１表に示す。また、
二官能性単量体を添加しない膜を同様に製造し、
その測定値を表中に併記した。
The present invention relates to a method for manufacturing a reverse osmosis membrane, and more particularly to a method for manufacturing a reverse osmosis membrane in one step by impregnating a monomer into a porous support membrane and photopolymerizing it. Conventionally, composite membranes for reverse osmosis have generally been manufactured by a method in which a polymer exhibiting reverse osmosis properties is manufactured and this is cast into a porous membrane. This method involves polymerizing monomers to synthesize a polymer with reverse osmosis properties, reprecipitating and purifying it, then dissolving it in a solvent to prepare a casting solution, which is then applied onto a support membrane. It is dry and requires many complicated steps. The present inventor conducted research to develop a method for manufacturing reverse osmosis membranes that does not require such conventional complicated steps, and first developed a method for manufacturing reverse osmosis membranes that does not require such conventional complicated steps. proposed a method for producing a reverse osmosis membrane by copolymerizing the polymer with a photopolymer and a photopolymer, and then applying this to a porous membrane and crosslinking it by irradiating it with light (Japanese Patent Publication No. 57-41281). As a result of further research,
A photopolymerization initiator is added to a liquid mixture of a monofunctional monomer and a difunctional monomer having a hydrophilic group, and a porous support membrane is impregnated with this, and then irradiated with light, resulting in reverse osmosis. It was discovered that a membrane could be obtained, and based on this knowledge, the present invention was accomplished. That is, the present invention includes a photopolymerization initiator,
A liquid mixture of a monofunctional monomer and a difunctional monomer having a hydrophilic group is filled into the micropores of a porous support membrane, and then it is irradiated with light to photopolymerize the monomers. The present invention provides a method for producing a reverse osmosis membrane, which is characterized by simultaneously causing photocrosslinking and forming a hydrophilic gel supported in micropores. Monofunctional monomers used in the method of the present invention include, for example, 2-dimethylaminoethyl methacrylate, acrylic acid, methacrylic acid, N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, 2-acrylamido-2-methyl Acrylic monomers having a hydrophilic group such as propanesulfonic acid can be used, but other monofunctional monomers that exhibit photopolymerizability and have a hydrophilic group can also be used. In addition, examples of the bifunctional monomer include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 4-methacryloyloxychalcone, N,
Examples include N-(2-hydroxy-3-methacryloyloxypropyl)piperazine. The ratio of these monofunctional monomers and difunctional monomers to be used is appropriately selected depending on the type and concentration of salts to be removed by reverse osmosis, but if the amount of difunctional monomers is too large, the membrane The permeation flux becomes small, and if it is too small, the rejection rate of dissolved salts will be low, and the performance of the reverse osmosis membrane will deteriorate, which is not preferable. A range amount of 15% is advantageously used. Moreover, the monofunctional monomer may be used as a single component or in combination of two or more components, and the difunctional monomer can be similarly used alone or in combination of two or more components. Preferred photoinitiators to be included in these monomers include, for example, 2,2-diethoxyacetophenone, benzoin, benzophenone, benzoin isopropyl ether, 2,2-diethoxyacetophenone, benzoin, benzophenone, benzoin isopropyl ether,
Photosensitizers such as dimethoxy 2-phenylacetophenone can be mentioned. Of these, 2,2-diethoxyacetophenone, which is soluble in the liquid monomers mentioned above, is particularly advantageous. The porous support membrane used in the method of the present invention is a porous membrane-like material, and for example, a porous polymer film such as a porous polypropylene film is advantageously used. In the present invention, such a porous support membrane is first impregnated with a monomer mixture containing a photopolymerization initiator, and the monomers are polymerized by irradiation with light, preferably under air-free conditions. However, for example, a porous polymer film is placed on a fluororesin plate, impregnated with the monomer mixture, and then covered with a transparent film, and then air is squeezed from above using a roller or the like. They are expelled, brought into close contact, and treated with light. The transparent film used to block air is not preferably a material that dissolves or swells in monomers, but suitable materials include transparent polypropylene film, polyethylene film, and fluorinated ethylene-propylene copolymer film. . For light irradiation, a high-pressure mercury lamp is usually used to advantage;
For example, with a 100W high-pressure mercury lamp, polymerization begins immediately when light is irradiated from the transparent film side at a distance of 10 to 15 cm, and the monomers in the porous polymer support film easily form a polymer. This light irradiation process is completed in a relatively short time of several minutes to several tens of minutes, but
Preferably, after the light irradiation, heat treatment is performed at a temperature of about 100 to 110° C. for 3 to 10 minutes. After heat treatment, the covered transparent film can be peeled off to easily obtain a reverse osmosis composite membrane. In the method of the present invention, since a monofunctional monomer having a hydrophilic group is advantageously used as described above, a base such as N,N-dimethylaminoethyl methacrylate may be introduced into the polymer. When using acrylic acid, it is preferable to immerse it in an aqueous solution of hydrochloric acid, and when using acrylic acid, it is preferable to immerse it in an aqueous solution of sodium hydroxide to make it into a polymer salt.This treatment improves water permeability. Can be done. The method of the present invention does not require complicated steps unlike conventional reverse osmosis membrane manufacturing methods, is extremely easy to handle and operate, and can significantly reduce monomer loss, making it industrially viable. It's advantageous. In addition, the reverse osmosis membrane obtained by the method of the present invention has reverse osmosis performance comparable to the dissolved salt rejection rate of conventional reverse osmosis membranes, for example, the rejection rate of about 70 to 80% when applied to a 0.3% sodium chloride aqueous solution. , and is fully usable for practical use. The reverse osmosis membrane obtained by the method of the present invention, like conventional products, is useful for desalinating brine and producing desalinated water from an aqueous inorganic salt solution, and can also be used as an ion exchange membrane. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 1.0 cc of 2-dimethylaminoethyl methacrylate (abbreviated as DAEMA) was added with a predetermined amount of a bifunctional monomer, i.e., 4-methacryloyloxychalcone (MC) or ethylene glycol dimethacrylate (EG), and a photopolymerization initiator. As, 2,2
- A monomer mixture was prepared by mixing 0.02 cc of diethoxyacetophenone (EAP). A porous polypropylene membrane (Celgard 2400, hydrophobic, diameter 7.5 cm) is impregnated with this liquid, the impregnated membrane is sandwiched between a Teflon plate and a transparent polypropylene film, and air is squeezed with a hand roller from above the transparent polypropylene film. I chased him out and brought him into close contact with him. Next, the transparent polypropylene side was irradiated with light for 10 minutes from a distance of 15 cm using a 100W high-pressure mercury lamp.
After irradiation, heat treatment was performed at 110°C for 3 minutes, and the film was peeled off in water. The resulting composite membrane was immersed in a dilute aqueous hydrochloric acid solution (an aqueous solution prepared by diluting 2 c.c. of concentrated hydrochloric acid with 10 c.c. of water) and left overnight. At this stage, the dimethylamino group became the hydrochloride salt, and the membrane expanded with some swelling. After thorough washing with water, the membrane was placed in Abcor RO−
A reverse osmosis experiment was conducted using a 0.3% sodium chloride aqueous solution using a Type 3 reverse osmosis meter (180 c.c. capacity).
The operating pressure is 70Kg/cm 2 and the effective membrane area is 30.2cm 2 .
Table 1 shows the results obtained for various reverse osmosis membranes manufactured using different amounts of MC or EG. Also,
Membranes without the addition of difunctional monomers were similarly produced,
The measured values are also listed in the table.
【表】
実施例 ２
実施例１において、２−ジメチルアミノエチル
メタクリレートの代りにアクリル酸を用い、二官
能性単量体及び光重合開始剤（EAP）を混合し
て多孔性膜に含浸し、実施例１と同様にして光重
合膜を作成した。この膜を５％カセイソーダ水溶
液に30分間浸せきし、塩の形にすると膨潤して膜
は広がつた。十分水洗した後、この膜をカツトし
て逆浸透計にかけ塩排除率及び流束を測定した。
その結果を第２表に示す。
なお、表中の二官能性単量体bpは、Ｎ，Ｎ−
（２−ヒドロキシ−３−メタクリロイルオキシプ
ロピル）ピペラジンである。[Table] Example 2 In Example 1, acrylic acid was used instead of 2-dimethylaminoethyl methacrylate, a difunctional monomer and a photopolymerization initiator (EAP) were mixed, and the mixture was impregnated into a porous membrane. A photopolymerized film was prepared in the same manner as in Example 1. This membrane was immersed in a 5% caustic soda aqueous solution for 30 minutes to form a salt, which caused it to swell and spread. After thorough washing with water, the membrane was cut and subjected to a reverse osmosis meter to measure the salt rejection rate and flux.
The results are shown in Table 2. In addition, the bifunctional monomer bp in the table is N,N-
(2-hydroxy-3-methacryloyloxypropyl)piperazine.
【表】
実施例 ３
２−アクリルアミド−２−メチルプロパンスル
ホン酸0.21ｇ、MC0.02ｇをＮ，Ｎ−ジメチルア
クリルアミド２c.c.に溶解させ、その一部をとり、
実施例１と同様にして多孔性ポリプロピレン膜中
で光重合させ、逆浸透膜を作成した。0.3％塩化
ナトリウム水溶液に対する塩排除率は70Kg／cm2の
操作圧で67％、流束は0.73／hr・m2であつた。[Table] Example 3 Dissolve 0.21 g of 2-acrylamido-2-methylpropanesulfonic acid and 0.02 g of MC in 2 c.c. of N,N-dimethylacrylamide, take a portion of it,
A reverse osmosis membrane was prepared by photopolymerizing in a porous polypropylene membrane in the same manner as in Example 1. The salt rejection rate for a 0.3% sodium chloride aqueous solution was 67% at an operating pressure of 70 Kg/cm 2 , and the flux was 0.73/hr·m 2 .
Claims (1)
能性単量体と二官能性単量体との液状混合物を、
多孔性支持膜の微孔中に充てんしたのち、これに
光照射して単量体の光重合及び光架橋化を同時に
起させ、微孔中に担持された親水ゲルを形成させ
ることを特徴とする逆浸透膜の製造方法。1 A liquid mixture of a monofunctional monomer and a difunctional monomer having a hydrophilic group and containing a photopolymerization initiator,
It is characterized by filling the micropores of a porous support membrane and then irradiating it with light to simultaneously cause photopolymerization and photocrosslinking of the monomer to form a hydrophilic gel supported in the micropores. A method for manufacturing reverse osmosis membranes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18637082A JPS5976504A (en) | 1982-10-22 | 1982-10-22 | Production of reverse osmotic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18637082A JPS5976504A (en) | 1982-10-22 | 1982-10-22 | Production of reverse osmotic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5976504A JPS5976504A (en) | 1984-05-01 |
| JPH025446B2 true JPH025446B2 (en) | 1990-02-02 |
Family
ID=16187189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18637082A Granted JPS5976504A (en) | 1982-10-22 | 1982-10-22 | Production of reverse osmotic membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5976504A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4976897A (en) * | 1987-12-16 | 1990-12-11 | Hoechst Celanese Corporation | Composite porous membranes and methods of making the same |
| US5102552A (en) * | 1987-12-16 | 1992-04-07 | Hoechst Celanese Corporation | Membranes from UV-curable resins |
| JP2521884B2 (en) * | 1993-08-24 | 1996-08-07 | 工業技術院長 | Method for manufacturing plasma-treated film |
| KR20110016434A (en) * | 2008-04-08 | 2011-02-17 | 후지필름 매뉴팩츄어링 유럽 비.브이. | Membrane manufacturing process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5741281A (en) * | 1980-08-25 | 1982-03-08 | Honda Motor Co Ltd | Rear fork for autobicycle |
-
1982
- 1982-10-22 JP JP18637082A patent/JPS5976504A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5976504A (en) | 1984-05-01 |
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