JPH0649236A - Production of ion exchange resin - Google Patents
Production of ion exchange resinInfo
- Publication number
- JPH0649236A JPH0649236A JP4208046A JP20804692A JPH0649236A JP H0649236 A JPH0649236 A JP H0649236A JP 4208046 A JP4208046 A JP 4208046A JP 20804692 A JP20804692 A JP 20804692A JP H0649236 A JPH0649236 A JP H0649236A
- Authority
- JP
- Japan
- Prior art keywords
- ion exchange
- monomer
- graft polymerization
- group
- exchange group
- 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.)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は放射線グラフト共重合に
よる産業上有用なイオン交換樹脂の製造法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing an industrially useful ion exchange resin by radiation graft copolymerization.
【０００２】[0002]
【従来の技術】イオン交換樹脂は幅広く産業界に使用さ
れている。従来のイオン交換樹脂は、その多くがスチレ
ンとジビニルベンゼンの共重合体にイオン交換基を導入
したもので、カチオン交換基であるスルホン基の導入工
程は濃硫酸、クロロ硫酸中での高温、長時間の反応が必
要で極めて苛酷な条件が必要であり、基材の損傷劣化を
伴い物理的強度の低下、低分子溶出物の発生などの問題
が生じている。またスルホン化工程に耐えうるよう架橋
を施された基材は成型が非常に困難であるため、その形
状はイオン交換膜を除いてそのほとんどが球状か、それ
を微細化した粉末状である。Ion exchange resins are widely used in industry. Most of the conventional ion exchange resins are those in which an ion exchange group is introduced into a copolymer of styrene and divinylbenzene, and the step of introducing a sulfo group, which is a cation exchange group, is carried out in concentrated sulfuric acid or chlorosulfuric acid at high temperature and long time. Since time reaction is required and extremely severe conditions are required, problems such as deterioration of physical strength and generation of low-molecular-weight eluate occur with damage and deterioration of the base material. Further, since the base material cross-linked so as to withstand the sulfonation step is very difficult to mold, the shape thereof is almost spherical except for the ion exchange membrane, or it is a fine powder.
【０００３】成型加工の問題を解決するために、織布、
不織布、ネット等へ成型加工した基材へスチレンまたは
メタクリン酸グリシジルを放射線グラフト重合した後、
スルホン基を導入する方法が提案されたが、スチレンを
グラフト重合した場合、重合後に濃硫酸、クロロ硫酸を
用いたスルホン化が必要で劣化による上記問題点は解決
されていない。また、メタクリル酸グリシジルの場合
は、亜硫酸ソーダ水溶液と反応させスルホン基を導入で
きるがエステル結合を有しており使用条件によってはそ
の化学的安定性に問題がある。In order to solve the problem of molding process, woven cloth,
After the radiation graft polymerization of styrene or glycidyl methacrylate onto a base material molded into a non-woven fabric, net, etc.,
A method of introducing a sulfone group has been proposed, but when styrene is graft-polymerized, sulfonation using concentrated sulfuric acid and chlorosulfuric acid is required after the polymerization, and the above problems due to deterioration have not been solved. Further, in the case of glycidyl methacrylate, it is possible to introduce a sulfone group by reacting it with an aqueous solution of sodium sulfite, but it has an ester bond and there is a problem in its chemical stability depending on the use conditions.
【０００４】スルホン基を有するモノマー、スチレンス
ルホン酸塩をグラフト重合させる手法も提案されている
が、スチレンスルホン酸塩は単独でのグラフト重合が困
難で２段グラフト重合法が必要であり、照射工程と反応
工程を２回繰り返すことになり非常に不経済的で現実的
な手法とは言い難い。Although a method of graft-polymerizing a monomer having a sulfone group and styrenesulfonate has been proposed, it is difficult to graft-polymerize styrenesulfonate alone, and a two-step graft polymerization method is required. Since the reaction step is repeated twice, it is difficult to say that it is a very uneconomical and realistic method.
【０００５】アニオン交換基である４級アンモニウム基
の導入は、スチレン−ジビニルベンゼン共重合体のクロ
ロメチル化、それに続く、トリメチルアミンによる処理
で行われる。このクロロメチル化には発ガン性物質であ
るクロロメチルメチルエーテルが必要であり、さらに４
級化では法定悪臭物質であるトリメチルアミンを使用す
るため、環境へ悪影響を与えないプロセスを用いねばな
らず製造は容易ではない。Introduction of a quaternary ammonium group which is an anion exchange group is carried out by chloromethylation of a styrene-divinylbenzene copolymer, followed by treatment with trimethylamine. This chloromethylation requires chloromethyl methyl ether, a carcinogen, and
Since trimethylamine, which is a legal malodorous substance, is used in the grading, a process that does not adversely affect the environment must be used and the production is not easy.
【０００６】また、成型加工した基材へスチレン、クロ
ロメチルスチレンまたはメタクリル酸グリシジルを放射
線グラフト重合した後、４級アンモニウム基を導入でき
るが、スチレンをグラフト重合した場合、クロロメチル
化、４級アンモニウム化が容易でないことは上記のとお
りである。クロロメチルスチレンは、催涙性のモノマー
で扱いにくい。また、メタクリル酸グリシジルの場合
は、トリメチルアミン塩酸塩との反応で４級アンモニウ
ム基を導入できるが、化学的安定性、耐久性に問題があ
る。[0006] Further, after styrene, chloromethylstyrene or glycidyl methacrylate is radiation-grafted on the molded base material, a quaternary ammonium group can be introduced. As described above, it is not easy to make the conversion. Chloromethylstyrene is a lacrimatory monomer that is difficult to handle. Further, in the case of glycidyl methacrylate, a quaternary ammonium group can be introduced by reaction with trimethylamine hydrochloride, but there are problems in chemical stability and durability.
【０００７】四級アンモニウム基を有するモノマー、ビ
ニルベンジルトリメチルアンモニウム塩の基材への直接
グラフト重合は困難である。Direct graft polymerization of vinylbenzyltrimethylammonium salt, a monomer having a quaternary ammonium group, onto a substrate is difficult.
【０００８】[0008]
【発明が解決しようとする課題】従来技術では満たしえ
なかった要件、すなわち、穏和な条件でのイオン交換基
の導入、用途に適した形状への成型加工の容易さ、化学
的に安定な構造であること、を同時に満たすイオン交換
樹脂の製造法を提供することが本発明の目的である。DISCLOSURE OF INVENTION Problems to be Solved by the Invention Requirements that cannot be met by the prior art, namely, introduction of ion-exchange groups under mild conditions, ease of molding into a shape suitable for the purpose, and chemically stable structure It is an object of the present invention to provide a method for producing an ion exchange resin that simultaneously satisfies
【０００９】[0009]
【課題を解決するための手段】本発明は前項に記した要
件を満たすイオン交換樹脂の製造法として、成型加工し
た有機重合体に電離性放射線を照射した後、親水性モノ
マー、カチオン交換基を持つモノマーそしてアニオン交
換基を持つモノマーから２種類またはおよび３種類のモ
ノマーの組合せによるグラフト共重合を用いてイオン交
換基を導入したことを特徴とするイオン交換樹脂の製造
法を解決手段として提供するものである。Means for Solving the Problems The present invention is a method for producing an ion exchange resin satisfying the requirements described in the preceding paragraph, in which a molded organic polymer is irradiated with ionizing radiation, and then a hydrophilic monomer and a cation exchange group are added. Provided as a solution means is a method for producing an ion exchange resin, which is characterized in that an ion exchange group is introduced from a monomer having a monomer and a monomer having an anion exchange group by graft copolymerization with a combination of two or three types of monomers. It is a thing.
【００１０】スチレンスルホン酸塩およびビニルベンジ
ルトリメチルアンモニウム塩の疎水性基材へのグラフト
重合は、単独では進行しにくいが、親水性モノマーとの
共存下では、親水性モノマーのグラフト重合によって疎
水性基材が親水化され、共存するスチレンスルホン酸
塩、ビニルベンジルトリメチルアンモニウム塩の基材へ
のグラフト重合が進行する。Graft polymerization of styrene sulfonate and vinylbenzyltrimethylammonium salt onto a hydrophobic substrate is difficult to proceed by itself, but in the presence of a hydrophilic monomer, the graft polymerization of the hydrophilic monomer results in a hydrophobic group. The material is hydrophilized, and the graft polymerization of the coexisting styrene sulfonate and vinylbenzyl trimethyl ammonium salt on the base material proceeds.
【００１１】本発明に用いる基材の材質としては、ボリ
エチレン、ポリプロビレンなどのポリオレフィンや、ハ
ロゲン化ポリオレフィン系のものが好適であるが、これ
らに限定されるものではない。放射線グラフト重合は、
基材の形状を比較的自由に選択できるので、用途に適し
た形状の基材を選ぶことができる。As the material of the substrate used in the present invention, polyolefins such as polyethylene and polypropylene and halogenated polyolefins are preferable, but not limited to these. Radiation graft polymerization
Since the shape of the base material can be selected relatively freely, a base material having a shape suitable for the application can be selected.
【００１２】ここで放射線グラフト重合に用いられる電
離性放射線は、α、β、γ線、電子線、紫外線などがあ
り、何れも使用可能であるが、γ線や電子線などが本発
明に適している。照射線量は基材によって異なるが、５
０ＫＧｙ〜３００ＫＧｙ、好ましくは１００ＫＧｙ〜２
００ＫＧｙである。過少な照射では、必要なグラフト重
合に十分なラジカルの生成量が得られず、過剰な照射
は、不経済であるばかりか、基材の不必要な架橋や、部
分的な分解によってグラフト重合を妨げることがある。The ionizing radiation used in the radiation graft polymerization includes α, β, γ rays, electron beams, ultraviolet rays and the like, and any of them can be used, but γ rays and electron beams are suitable for the present invention. ing. Irradiation dose depends on the substrate, but 5
0KGy to 300KGy, preferably 100KGy to 2
It is 00KGy. With excessive irradiation, a sufficient amount of radicals can not be obtained for the required graft polymerization, and excessive irradiation is not only uneconomical, but also causes unnecessary crosslinking or partial decomposition of the base material to cause graft polymerization. May interfere.
【００１３】基材に放射線を照射する方法としては、基
材とモノマーの共存下に放射線を照射する同時照射と、
予め基材を照射した後、モノマーと接触させる前照射法
があるが、モノマーの単独重合物の生成の少ない前照射
法の方が有利である。As the method of irradiating the substrate with radiation, simultaneous irradiation with radiation in the coexistence of the substrate and the monomer,
Although there is a pre-irradiation method in which the base material is previously irradiated and then contacted with the monomer, the pre-irradiation method which produces less homopolymer of the monomer is more advantageous.
【００１４】本発明で使用するモノマーは、親水性モノ
マーとして、ヒドロキシエチルメタクリレート、ビニル
ピロリドンそしてジメチルアクリルアミドなどがあり、
カチオン交換基を持つモノマーとしてアクリル酸、メタ
クリル酸そしてスチレンスルホン酸塩が、そしてアニオ
ン交換基を持つモノマーとしてビニルベンジルトリメチ
ルアンモニウム塩そしてジエチルアミノエチルメタクリ
レートがあるが、これらに限定されるものではない。ま
た、アクリル酸、メタクリル酸およびジエチルミアノエ
チルメタクリレートは、親水性モノマーとしても使用さ
れる。The monomers used in the present invention include, as hydrophilic monomers, hydroxyethyl methacrylate, vinylpyrrolidone and dimethylacrylamide.
Monomers having cation exchange groups include acrylic acid, methacrylic acid and styrene sulfonate, and monomers having anion exchange groups include, but are not limited to, vinylbenzyl trimethyl ammonium salt and diethylaminoethyl methacrylate. Acrylic acid, methacrylic acid and diethylmianoethylmethacrylate are also used as hydrophilic monomers.
【００１５】照射を受けた基材へのグラウト重合は、基
材とモノマー溶液とを無酸素下、液相で接触させる、ま
たは含浸させるだけでよい。モノマー水溶液との接触時
間は、基材や照射線量により異なるが、含浸の場合、グ
ラフト重合の完結には２時間あれば十分である。液相で
の場合、３時間〜５時間で、十分なグラフト重合体が得
られる。The grout polymerization of the irradiated substrate may be performed by contacting or impregnating the substrate and the monomer solution in the liquid phase in the absence of oxygen. The contact time with the aqueous monomer solution varies depending on the substrate and the irradiation dose, but in the case of impregnation, 2 hours is sufficient to complete the graft polymerization. In the liquid phase, a sufficient graft polymer can be obtained in 3 to 5 hours.
【００１６】反応温度は、含浸グラフト重合の場合、３
０°Ｃ〜５０°Ｃが好ましい。液相グラフト重合の場合
は、３０°Ｃ〜８０°Ｃ、好ましくは、５０°Ｃ〜７０
°Ｃである。The reaction temperature is 3 in the case of impregnation graft polymerization.
0 ° C to 50 ° C is preferable. In the case of liquid phase graft polymerization, 30 ° C to 80 ° C, preferably 50 ° C to 70 ° C.
° C.
【００１７】本発明の利点は、種々の形状に成型加工し
た有機重合体へ放射線前照射グラフト重合するだけで、
スチレングラフト重合体や、メタクリル酸グリシジルグ
ラフト重合体の場合のような、イオン交換基導入工程を
必要とせずに、イオン交換基を導入できる点である。The advantage of the present invention is that by pre-irradiating radiation-induced graft polymerization onto organic polymers molded into various shapes,
The point is that an ion exchange group can be introduced without the need for an ion exchange group introduction step as in the case of a styrene graft polymer or a glycidyl methacrylate graft polymer.
【００１８】[0018]
【実施例】以下に本発明による製造法の実施例を説明す
る。EXAMPLES Examples of the production method according to the present invention will be described below.
【００１９】[0019]
【実施例１】繊維径４０μｍのポリプロピレン製繊維よ
りなる不織布に電子線加速器を用いて、２００ＫＧｙを
照射した後、予め脱酸素したアクリル酸とスチレンスル
ホン酸ナトリウムの混合３３％水溶液中、５°Ｃで２時
間３０分反応させ、１７０％のグラフト率を得た。この
グラフト重合体は、強酸基であるスルホン基を２．０ｍ
ｅｑ／ｇ及び弱酸基であるカルボキシル基を３．０ｍｅ
ｑ／ｇを有するカチオン交換樹脂であった。Example 1 A non-woven fabric made of polypropylene fiber having a fiber diameter of 40 μm was irradiated with 200 KGy using an electron beam accelerator, and then pre-deoxygenated acrylic acid and sodium styrenesulfonate were mixed at a temperature of 5 ° C. in a 33% aqueous solution. And reacted for 2 hours and 30 minutes to obtain a graft ratio of 170%. This graft polymer has a sulfone group, which is a strong acid group, of 2.0 m.
eq / g and a carboxyl group, which is a weak acid group, at 3.0 me
It was a cation exchange resin having a q / g.
【００２０】比較例１ 上記と同様の条件下、スチレンスルホン酸ナトリウムの
みの溶液中、グラフト重合を試みたが重合は進行しなか
った。Comparative Example 1 Graft polymerization was attempted in a solution of sodium styrenesulfonate alone under the same conditions as above, but the polymerization did not proceed.
【００２１】[0021]
【実施例２】繊維径４０μｍのポリプロピレン製繊維よ
りなる不織布に電子線加速器を用いて、２００ＫＧｙを
照射した後、アクリル酸とスチレンスルホン酸ナトリウ
ムの混合溶液に含浸した後、残液を除いて反応容器に入
れ、脱酸素して４０°Ｃ、２時間反応させ、１３５％の
グラフト率を得た。得られたカチオン交換樹脂は、スル
ホン基を１．２ｍｅｑ／ｇ及びカルボキシル基を３．６
ｍｅｑ／ｇ有していた。Example 2 A non-woven fabric made of polypropylene fiber having a fiber diameter of 40 μm was irradiated with 200 KGy using an electron beam accelerator, impregnated with a mixed solution of acrylic acid and sodium styrenesulfonate, and then the residual liquid was removed to react. It was put in a container, deoxidized and reacted at 40 ° C. for 2 hours to obtain a graft ratio of 135%. The obtained cation exchange resin had a sulfone group of 1.2 meq / g and a carboxyl group of 3.6.
had meq / g.
【００２２】比較例２ 同様にスチレンスルホン酸塩のみの溶液では、重合は進
行しなかった。Comparative Example 2 Similarly, polymerization did not proceed with a solution containing only styrene sulfonate.
【００２３】[0023]
【実施例３】厚さ５０μｍの低密度ポリエチレン膜に電
子線加速器を用いて、２００ＫＧｙを照射した後、予め
脱酸素したヒドロキシエチルメタクレートとビニルベン
ジルトリメチルアンモニウム塩の混合溶液中、７０°Ｃ
で３時間反応させ、１５８％のグフラト率を得た。この
グラフト重合体は、強塩基である４級アンモニウム基を
１．４ｍｅｑ／ｇ有していた。Example 3 A low-density polyethylene film having a thickness of 50 μm was irradiated with 200 KGy using an electron beam accelerator, and then 70 ° C. in a mixed solution of previously deoxygenated hydroxyethyl methacrylate and vinylbenzyltrimethylammonium salt.
And reacted for 3 hours to obtain a gflat rate of 158%. This graft polymer had 1.4 meq / g of a quaternary ammonium group which is a strong base.
【００２４】比較例３ 同様にビニルベンジルトリメチルアンモニウム塩のみの
溶液でグラフト重合を試みたが重合は進行しなかった。Comparative Example 3 Similarly, a graft polymerization was tried with a solution of vinylbenzyltrimethylammonium salt alone, but the polymerization did not proceed.
【００２５】[0025]
【実施例４】直径２ｍｍのポリエチレン粒子に電子線加
速器を用いて、２００ＫＧｙを照射した後、予め脱酸素
したアクリル酸、スチレンスルホン酸ナトリウムそして
ビニルベンジルトリメチルアンモニウム塩の混合溶液
中、５０°Ｃ、５時間反応させ、グフラト率５２％のグ
ラフト重合体を得た。Example 4 Polyethylene particles having a diameter of 2 mm were irradiated with 200 KGy using an electron beam accelerator, and then pre-deoxygenated acrylic acid, sodium styrenesulfonate and vinylbenzyltrimethylammonium salt in a mixed solution at 50 ° C. The reaction was carried out for 5 hours to obtain a graft polymer having a gflat rate of 52%.
【００２６】[0026]
【発明の効果】本発明により、スチレンスルホン酸塩お
よびビニルベンジルトリメチルアンモニウム塩の直接グ
フラト共重合が可能となり、従来のイオン交換樹脂の製
造法では困難だった。形状選択の自由化、グラフト重合
後のイオン交換基導入工程の省略が可能となった。EFFECTS OF THE INVENTION According to the present invention, it is possible to carry out a direct gfurato copolymerization of styrene sulfonate and vinylbenzyltrimethylammonium salt, which is difficult with the conventional method for producing an ion exchange resin. It has become possible to liberate shape selection and to omit the ion-exchange group introduction step after graft polymerization.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｊ 7/18 7310−4Ｆ (72)発明者 筒井 ▲つよし▼ 新潟県新津市滝谷本町１番26号 日揮化学 株式会社新津事業所内Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical indication location C08J 7/18 7310-4F (72) Inventor Tsutsui ▲ Tsuyoshi ▼ No. 26 Takitanimotocho Niitsu City Niigata Prefecture JGC Chemical Inside Niitsu Co., Ltd.
Claims (5)
して、親水基とイオン交換基を導入するイオン交換樹脂
の製造法。1. A method for producing an ion exchange resin, wherein a hydrophilic group and an ion exchange group are introduced into a polymer substrate by using radiation graft polymerization.
ノマーとカチオン交換基をもつモノマーおよびアニオン
交換基を持つモノマーより選ばれた２種類または及び３
種類のモノマーの組合せによる共存重合である特許請求
の範囲第１項記載の製造法。2. The radiation graft polymerization method comprises two or three types selected from a hydrophilic monomer, a monomer having a cation exchange group and a monomer having an anion exchange group.
The method according to claim 1, wherein the co-polymerization is a combination of monomers.
ノマーは、カチオン交換基を持つモノマーとしてアクリ
ル酸、メタクリル酸そしてスチレンスルホン酸塩であ
り、アニオン交換基を持つモノマーとしてビニルベンジ
ルトリメチルアンモニウム塩そしてジエチルアミノエチ
ルメタクリレートより選択されたものである特許請求の
範囲第１項記載の製造法。3. A monomer used for the radiation graft polymerization is acrylic acid, methacrylic acid and styrene sulfonate as a monomer having a cation exchange group, and vinylbenzyl trimethyl ammonium salt and diethylaminoethyl as a monomer having an anion exchange group. The method according to claim 1, which is selected from methacrylate.
単繊維、単繊維の集合体である織布および不織布、それ
らの加工品、膜状材料およびその加工品、空隙性材料お
よびその加工品より選択されたものである特許請求の範
囲第１項記載の製造法。4. A base material used for the radiation graft polymerization is a monofilament, a woven fabric or a non-woven fabric which is an aggregate of monofilaments, a processed product thereof, a film-shaped material and a processed product thereof, a void material and a processed product thereof. The manufacturing method according to claim 1, which is selected.
交換基を導入する方法は、液相及び含浸法である特許請
求の範囲第１項記載の製造法。5. The production method according to claim 1, wherein the method of introducing an ion exchange group by the radiation graft polymerization method is a liquid phase and impregnation method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20804692A JP3245454B2 (en) | 1992-08-04 | 1992-08-04 | Production method of ion exchange resin |
| US08/491,307 US5648400A (en) | 1992-08-04 | 1995-06-16 | Process for producing polymeric electrolyte complex and ion-exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20804692A JP3245454B2 (en) | 1992-08-04 | 1992-08-04 | Production method of ion exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0649236A true JPH0649236A (en) | 1994-02-22 |
| JP3245454B2 JP3245454B2 (en) | 2002-01-15 |
Family
ID=16549751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20804692A Expired - Fee Related JP3245454B2 (en) | 1992-08-04 | 1992-08-04 | Production method of ion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3245454B2 (en) |
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|---|---|---|---|---|
| JPH10279713A (en) * | 1997-04-04 | 1998-10-20 | Ebara Corp | Anion exchanger, its production and chemical filter |
| JP2000258592A (en) * | 1999-03-08 | 2000-09-22 | Japan Atom Energy Res Inst | Filter and device for removing iodine |
| JP2001048923A (en) * | 1999-06-04 | 2001-02-20 | Reitekku:Kk | Functional polytetrafluoroethylene resin and its production |
| JP2004337749A (en) * | 2003-05-16 | 2004-12-02 | Kankyo Joka Kenkyusho:Kk | Boron catching material and its production method |
| JP2007007575A (en) * | 2005-06-30 | 2007-01-18 | Ebara Corp | Microorganism carrier and its production method |
| JP2008255350A (en) * | 2007-03-14 | 2008-10-23 | Solt Industry Center Of Japan | Cation exchange membrane for salt production and method for producing the same |
| JP2008255351A (en) * | 2007-03-14 | 2008-10-23 | Solt Industry Center Of Japan | Anion exchange membrane for salt production and method for producing the same |
| JP2009532551A (en) * | 2006-04-04 | 2009-09-10 | メトローム・アクチェンゲゼルシャフト | Ion exchange material, ion exchange column, and production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10279713A (en) * | 1997-04-04 | 1998-10-20 | Ebara Corp | Anion exchanger, its production and chemical filter |
| JP2000258592A (en) * | 1999-03-08 | 2000-09-22 | Japan Atom Energy Res Inst | Filter and device for removing iodine |
| JP2001048923A (en) * | 1999-06-04 | 2001-02-20 | Reitekku:Kk | Functional polytetrafluoroethylene resin and its production |
| JP2004337749A (en) * | 2003-05-16 | 2004-12-02 | Kankyo Joka Kenkyusho:Kk | Boron catching material and its production method |
| JP2007007575A (en) * | 2005-06-30 | 2007-01-18 | Ebara Corp | Microorganism carrier and its production method |
| JP2009532551A (en) * | 2006-04-04 | 2009-09-10 | メトローム・アクチェンゲゼルシャフト | Ion exchange material, ion exchange column, and production method |
| JP2008255350A (en) * | 2007-03-14 | 2008-10-23 | Solt Industry Center Of Japan | Cation exchange membrane for salt production and method for producing the same |
| JP2008255351A (en) * | 2007-03-14 | 2008-10-23 | Solt Industry Center Of Japan | Anion exchange membrane for salt production and method for producing the same |
| JP2012513546A (en) * | 2008-12-23 | 2012-06-14 | スリーエム イノベイティブ プロパティズ カンパニー | Functionalized non-woven articles |
| JP2010155195A (en) * | 2008-12-26 | 2010-07-15 | Japan Atomic Energy Agency | Catalyst for producing biodiesel, method for producing the catalyst and method for producing biodiesel |
| WO2014103338A1 (en) * | 2012-12-28 | 2014-07-03 | 日東電工株式会社 | Method for producing anion exchange membrane, membrane-electrode assembly for fuel cells, and fuel cell |
| JP2014143197A (en) * | 2012-12-28 | 2014-08-07 | Nitto Denko Corp | Method for producing anion exchange membrane, membrane-electrode assembly for fuel cell, and fuel cell |
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|---|---|
| JP3245454B2 (en) | 2002-01-15 |
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