JPH06277438A - Gas separation membrane and production thereof - Google Patents
Gas separation membrane and production thereofInfo
- Publication number
- JPH06277438A JPH06277438A JP6437993A JP6437993A JPH06277438A JP H06277438 A JPH06277438 A JP H06277438A JP 6437993 A JP6437993 A JP 6437993A JP 6437993 A JP6437993 A JP 6437993A JP H06277438 A JPH06277438 A JP H06277438A
- Authority
- JP
- Japan
- Prior art keywords
- gas separation
- separation membrane
- compound containing
- polymer compound
- membrane
- 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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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、気体分離膜に関し、詳
しくは、ガス分離に用いる透過選択性に優れた気体分離
膜及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas separation membrane, and more particularly to a gas separation membrane having excellent permeation selectivity used for gas separation and a method for producing the same.
【０００２】[0002]
【従来の技術】気体を分離するのに気体分離膜を用いる
いわゆるガス分離に関しては、操作が容易であること、
使用する装置が簡便であること、あるいは省エネルギー
効果を期待できる等のことから、種々検討されてきてい
る。特に、ガス分離の大規模な産業用途への適用を考え
た場合、使用する膜の気体透過性能は、装置容量、動力
費、装置価格等に大きく影響するので、その性能向上等
について検討がなされてきた。2. Description of the Related Art With regard to so-called gas separation, which uses a gas separation membrane for separating a gas, it is easy to operate,
Various studies have been conducted because the device used is simple and the energy saving effect can be expected. In particular, when considering the application of gas separation to large-scale industrial applications, the gas permeation performance of the membrane to be used has a great effect on the equipment capacity, power cost, equipment price, etc., so improvement of the performance is studied. Came.
【０００３】これまで気体分離膜として、高分子膜につ
いては、均質な緻密膜から成るもの、例えばポリシロキ
サンとポリカーボネートとの共重合膜（特開昭４８−６
４１９９号）や、ポリシロキサンとポリフェニレンオキ
シドとのブレンド膜（特開昭５８−９５５３８号）が知
られているが、これらは分離性能はよいとしても透過性
能が不十分である。Up to now, as a gas separation membrane, a polymer membrane composed of a homogeneous and dense membrane, for example, a copolymer membrane of polysiloxane and polycarbonate (JP-A-48-6).
No. 4199) and a blend film of polysiloxane and polyphenylene oxide (JP-A-58-95538) are known, but these have insufficient separation performance even if they have good separation performance.
【０００４】他方、多孔質支持体上に薄い均質膜を担持
させたものとしては、多孔質支持体表面にポリスルホン
のようなポリマーを溶液として塗布し乾燥させたもの
（特公昭５９−３２０１号）、ポリマーの非水溶液を水
面上に展開させて薄膜を形成させ、これを多孔質支持体
表面に付着させたもの（特開昭５８−１４９２８号）、
多孔質支持体上で前駆体を架橋又は重合させたもの（特
開昭５７−１０５２０３号）などが提案されている。On the other hand, as a support having a thin homogeneous film supported on a porous support, a polymer such as polysulfone is applied as a solution on the surface of the porous support and dried (Japanese Patent Publication No. 59-3201). , A non-aqueous solution of a polymer is spread on the surface of water to form a thin film, and the thin film is attached to the surface of a porous support (JP-A-58-14928),
Those obtained by crosslinking or polymerizing a precursor on a porous support (JP-A-57-105203) have been proposed.
【０００５】しかし、これらは薄膜にピンホールを生じ
たり、調製方法が複雑であったり、細孔の閉塞を生じた
り、あるいは透過性と分離性のバランスの調整が困難で
あるなどの問題があり、必ずしも満足し得る結果は得ら
れていない。However, these have problems that a pinhole is formed in the thin film, the preparation method is complicated, pores are blocked, and it is difficult to adjust the balance between permeability and separability. , But not always satisfactory results have been obtained.
【０００６】また、特開平２−２８５８号には、多孔質
基材に反応性ポリシロキサンを含浸して特定の架橋度と
なるように反応させた後、未反応物を除去して、気体透
過性の高い分離膜を得る方法が開示されているが、この
方法により得られる膜の気体分離係数が十分とはいいが
たい。Further, in JP-A-2-2858, a porous base material is impregnated with a reactive polysiloxane to cause a reaction so as to have a specific degree of crosslinking, and then unreacted substances are removed to give a gas permeation. Although a method of obtaining a separation membrane having high properties is disclosed, it cannot be said that the membrane obtained by this method has a sufficient gas separation coefficient.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、このような
観点からなされたものであり、選択性の優れた新しい膜
材料を提供することを課題とする。The present invention has been made from such a point of view, and an object thereof is to provide a new membrane material having excellent selectivity.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意研究を行った結果、無水酸基を含
む高分子化合物とアミノ基を含むシロキサン化合物を反
応させると、選択性の高い気体分離膜素材が得られるこ
とを見出し、本発明に至った。Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that when a polymer compound containing a non-hydroxyl group is reacted with a siloxane compound containing an amino group, selectivity is increased. It was found that a gas separation membrane material with high efficiency can be obtained, and the present invention has been completed.
【０００９】すなわち本発明の気体分離膜は、無水酸基
を含む高分子化合物とアミノ基を含むシロキサン化合物
との反応により生成する共重合体のフィルムまたはシー
トからなる気体分離膜、及び無水酸基を含む高分子化合
物とアミノ基を含むシロキサン化合物との反応により生
成する共重合体で多孔質膜基材を被覆してなる気体分離
膜である。That is, the gas separation membrane of the present invention comprises a gas separation membrane composed of a film or sheet of a copolymer produced by the reaction of a polymer compound containing a hydroxyl group and a siloxane compound containing an amino group, and a hydroxyl group-free film. A gas separation membrane comprising a porous membrane substrate coated with a copolymer produced by the reaction of a polymer compound and a siloxane compound containing an amino group.
【００１０】また、本発明の気体分離膜の製造方法は、
無水酸基を含む高分子化合物をフィルム状またはシート
状に成形し、これにアミノ基を含むシロキサン化合物を
反応させることを特徴とする気体分離膜の製造方法、及
び多孔質膜基材に無水酸基を含む高分子化合物を含浸さ
せた後、この高分子化合物にアミノ基を含むシロキサン
化合物を反応させることを特徴とする気体分離膜の製造
方法である。Further, the method for producing a gas separation membrane of the present invention comprises:
A method for producing a gas separation membrane, which comprises molding a polymer compound containing a hydroxyl group into a film or a sheet, and reacting a siloxane compound containing an amino group with this, and a hydroxyl group-free porous membrane substrate. The method for producing a gas separation membrane is characterized in that after impregnating a polymer compound containing it, the polymer compound is reacted with a siloxane compound containing an amino group.
【００１１】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【００１２】＜１＞本発明の気体分離膜 本発明の気体分離膜は、無水酸基を含む高分子化合物
（以下、単に「高分子化合物」ということがある）にア
ミノ基を含むシロキサン化合物（以下、単に「シロキサ
ン化合物」ということがある）が反応付加した共重合体
のフィルムまたはシートからなる気体分離膜である。<1> Gas Separation Membrane of the Present Invention The gas separation membrane of the present invention comprises a polymer compound containing a non-hydroxyl group (hereinafter sometimes referred to simply as “polymer compound”) and a siloxane compound containing an amino group (hereinafter referred to as “polymer compound”). , Sometimes referred to simply as "siloxane compound") is a gas separation membrane comprising a film or sheet of a copolymer to which a reaction is added.
【００１３】上記高分子化合物としては、分子中に無水
酸基を含むものであれば、特に制限はない。例えば、ス
チレン／無水マレイン酸共重合体、あるいはイソブチレ
ン／無水マレイン酸共重合体、ブタジエン／無水マレイ
ン酸共重合体、アクリル酸エステル或はメタクリル酸エ
ステル／無水マレイン酸共重合体や、二次工程で無水酸
基を導入した石油樹脂、マレイン化液状ゴムなどが挙げ
られる。The polymer compound is not particularly limited as long as it contains a non-hydroxyl group in the molecule. For example, styrene / maleic anhydride copolymer, isobutylene / maleic anhydride copolymer, butadiene / maleic anhydride copolymer, acrylic acid ester or methacrylic acid ester / maleic anhydride copolymer, and the secondary step Examples of the non-hydroxyl-introduced petroleum resin and maleated liquid rubber.
【００１４】シロキサン化合物としては、分子中にアミ
ノ基を含むシロキサン化合物であればよく、１分子鎖中
のアミノ基の数は、２個以上であることが好ましい。以
上の化合物は、後記の製造方法においても同様である。The siloxane compound may be any siloxane compound containing an amino group in the molecule, and the number of amino groups in one molecular chain is preferably 2 or more. The above compounds are the same in the production method described later.
【００１５】本発明の気体分離膜の別の態様は、上記高
分子化合物にシロキサン化合物が反応付加した共重合体
で多孔質膜基材を被覆してなる気体分離膜である。この
場合も、高分子化合物及びシロキサン化合物は前記と同
様である。また、多孔質膜基材としては、酢酸セルロー
スメンブレン、テトラフロロエチレンからなるメンブレ
ン、ポリスルホンメンブレン、ポリプロピレンメンブレ
ン、ポリアクリロニトリルメンブレン等が挙げられ、孔
径は、０．００５〜５μｍ程度が好ましい。これらの膜
基材を用いると、膜剤に機械的強度を与える支持体とな
り、十分な強度を有する膜剤が得られる。また、製膜す
る際の操作が簡便になる点でも好ましい。Another embodiment of the gas separation membrane of the present invention is a gas separation membrane obtained by coating a porous membrane substrate with a copolymer obtained by reacting and adding a siloxane compound to the above-mentioned polymer compound. Also in this case, the polymer compound and the siloxane compound are the same as described above. Examples of the porous membrane substrate include a cellulose acetate membrane, a membrane made of tetrafluoroethylene, a polysulfone membrane, a polypropylene membrane, a polyacrylonitrile membrane, and the like, and the pore diameter is preferably about 0.005 to 5 μm. When these membrane base materials are used, they serve as a support for imparting mechanical strength to the membrane agent, and a membrane agent having sufficient strength can be obtained. It is also preferable in that the operation at the time of film formation becomes simple.
【００１６】上記構成を有する本発明の気体分離膜は、
以下の方法で製造することができる。The gas separation membrane of the present invention having the above structure is
It can be manufactured by the following method.
【００１７】＜２＞本発明の気体分離膜の製造方法 本発明の気体分離膜は、無水酸基を含む高分子化合物を
フィルム状またはシート状に成形し、これにアミノ基を
含むシロキサン化合物を反応付加することにより得られ
る。この反応の温度や圧力は任意でよく、室温でも反応
は進行する。また、触媒も不要である。<2> Method for Producing Gas Separation Membrane of the Present Invention In the gas separation membrane of the present invention, a polymer compound containing a non-hydroxyl group is formed into a film or a sheet, and a siloxane compound containing an amino group is reacted therewith. It is obtained by adding. The temperature and pressure of this reaction may be arbitrary, and the reaction proceeds even at room temperature. Also, no catalyst is required.
【００１８】この反応の際に、高分子化合物を溶解、或
は膨潤させる溶剤を共存させると、反応を促進させるこ
とができる。この溶剤としては、例えば高分子化合物と
してスチレン／無水マレイン酸共重合体を用いる場合に
は、トルエン、アセトン等が挙げられる。この場合、こ
の溶剤がシロキサン化合物を溶解するものであれば、こ
の溶剤にシロキサン化合物を溶解させた溶液に、フィル
ム状またはシート状の高分子化合物を浸漬し、反応を行
えばよい。During the reaction, the reaction can be promoted by coexisting with a solvent that dissolves or swells the polymer compound. Examples of the solvent include toluene and acetone when a styrene / maleic anhydride copolymer is used as the polymer compound. In this case, if the solvent dissolves the siloxane compound, the film-shaped or sheet-shaped polymer compound may be immersed in the solution prepared by dissolving the siloxane compound in the solvent to carry out the reaction.
【００１９】また、反応後に、未反応あるは反応が不十
分なシロキサン化合物を、ヘキサン等の溶剤で洗滌する
と、気体透過性能の安定した気体分離膜を得ることがで
きるので好ましい。洗滌した後は、風乾、あるいは減圧
乾燥等により溶剤を乾燥させるとよい。After the reaction, it is preferable to wash the unreacted or insufficiently reacted siloxane compound with a solvent such as hexane because a gas separation membrane having stable gas permeation performance can be obtained. After washing, the solvent may be dried by air drying, vacuum drying or the like.
【００２０】多孔質膜基材に無水酸基を含む高分子化合
物を含浸させた後、この高分子化合物にアミノ基を含む
シロキサン化合物を反応付加させることにより、本発明
の別の態様の気体分離膜が得られる。多孔質膜基材に無
水酸基を含む高分子化合物を含浸させるには、高分子化
合物を膜基材に塗布すればよい。また、液状高分子化合
物に膜基材を浸漬させればよい。高分子化合物が液状で
ない場合は、溶剤に溶解し、この溶液に膜基材を浸漬さ
せればよい。この場合、シロキサン化合物の付加量をコ
ントロールするために、溶液の濃度を変えてもよい。A gas separation membrane according to another embodiment of the present invention is obtained by impregnating a porous membrane substrate with a polymer compound containing a non-hydroxyl group and then adding a siloxane compound containing an amino group to the polymer compound by reaction. Is obtained. In order to impregnate the porous membrane substrate with the polymer compound containing a non-hydroxyl group, the polymer compound may be applied to the membrane substrate. Further, the membrane base material may be immersed in the liquid polymer compound. When the polymer compound is not liquid, it may be dissolved in a solvent and the membrane substrate may be dipped in this solution. In this case, the concentration of the solution may be changed in order to control the addition amount of the siloxane compound.
【００２１】本発明により得られる気体分離膜は、選択
性に優れ、例えば燃焼炉、加熱炉、ボイラー、鍛造炉、
ガラス溶解炉、金属処理炉、セラミックス焼成炉、医療
用、健康用、排水処理、焼却炉等の他、防爆用、シール
用、食品貯蔵等に用いるのに好適である。The gas separation membrane obtained by the present invention is excellent in selectivity, and includes, for example, a combustion furnace, a heating furnace, a boiler, a forging furnace,
It is suitable for use in glass melting furnaces, metal treatment furnaces, ceramics firing furnaces, medical, health, wastewater treatment, incinerators, etc., as well as explosion-proof, sealing, food storage, etc.
【００２２】[0022]
【作用】本発明の方法において、無水酸基を含む高分子
化合物とアミノ基を含むシロキサン化合物との反応につ
いて説明する。高分子化合物に含まれる無水酸基とシロ
キサン化合物に含まれるアミノ基とが反応し、アミド結
合により両化合物が結合し、例えば無水酸基を含む高分
子化合物がスチレン−無水マレイン酸共重合体の場合に
ついては、下記化１のように反応すると推定される。In the method of the present invention, the reaction between the polymer compound containing a non-hydroxyl group and the siloxane compound containing an amino group will be described. In the case where the non-hydroxyl group contained in the polymer compound reacts with the amino group contained in the siloxane compound and both compounds are bound by an amide bond, for example, the polymer compound containing the non-hydroxyl group is a styrene-maleic anhydride copolymer Is presumed to react as shown below.
【００２３】[0023]
【化１】 [Chemical 1]
【００２４】本発明の気体分離膜は、このような構造を
有する共重合体を用いることにより、高い選択性を有す
ると考えられる。The gas separation membrane of the present invention is considered to have high selectivity by using the copolymer having such a structure.
【００２５】[0025]
【実施例】以下に、本発明の実施例を説明する。EXAMPLES Examples of the present invention will be described below.
【００２６】[0026]
【実施例１】スチレン／無水マレイン酸共重合体（無水
マレイン酸含量１４モル％）を溶融プレス加工して、厚
さ２０μのフィルムを作製した。このフィルムをジアミ
ノシロキサン（分子量１０００）の５０％トルエン溶液
に浸漬し、室温で６時間重合反応を行った。反応後、こ
のフィルムをトルエンで３回繰り返し洗滌し、トルエン
を乾燥させて気体分離膜を得た。Example 1 A styrene / maleic anhydride copolymer (maleic anhydride content 14 mol%) was melt-pressed to prepare a film having a thickness of 20 μm. This film was immersed in a 50% toluene solution of diaminosiloxane (molecular weight 1000), and a polymerization reaction was carried out at room temperature for 6 hours. After the reaction, this film was repeatedly washed with toluene three times, and the toluene was dried to obtain a gas separation membrane.
【００２７】[0027]
【比較例１】実施例１の気体分離膜に対し、上記スチレ
ン／無水マレイン酸共重合体（無水マレイン酸含量１４
モル％）フィルムを、比較例の気体分離膜とした。Comparative Example 1 The gas separation membrane of Example 1 was prepared using the above styrene / maleic anhydride copolymer (maleic anhydride content 14%).
Mol%) film was used as the gas separation membrane of the comparative example.
【００２８】[0028]
【実施例２】ジアミノシロキサンとして、分子量５００
０のものを使用した以外は実施例１と同じ操作により、
気体分離膜を得た。Example 2 As diaminosiloxane, a molecular weight of 500
By the same operation as in Example 1 except that 0 was used,
A gas separation membrane was obtained.
【００２９】[0029]
【実施例３】多孔質膜基材として酢酸セルロースメンブ
レン（孔径０．０２５μ、厚さ８０μｍ）を用い、これ
をスチレン／無水マレイン酸共重合体（無水マレイン酸
含量１４モル％）の３％トルエン溶液に浸漬し、乾燥
後、ジアミノシロキサン（分子量１０００）の５０％ト
ルエン溶液に浸漬した。室温で５時間反応させ、次いで
乾燥して気体分離膜を得た。Example 3 A cellulose acetate membrane (pore size: 0.025 μm, thickness: 80 μm) was used as a porous membrane substrate, and this was used as a 3% toluene solution of a styrene / maleic anhydride copolymer (maleic anhydride content: 14 mol%). After being dipped in the solution and dried, it was dipped in a 50% toluene solution of diaminosiloxane (molecular weight 1000). The mixture was reacted at room temperature for 5 hours and then dried to obtain a gas separation membrane.
【００３０】[0030]
【実施例４】酢酸セルロースメンブレンとして、孔径
０．０５μのものを用いた以外は実施例３と同じ操作で
気体分離膜を得た。Example 4 A gas separation membrane was obtained by the same operation as in Example 3 except that a cellulose acetate membrane having a pore size of 0.05 μ was used.
【００３１】[0031]
【実施例５】多孔質膜基材として、テトラフロロエチレ
ンのメンブレン（孔径０．１μ、厚さ８０μｍ）を用い
た。このメンブレンをスチレン／無水マレイン酸共重合
体（無水マレイン酸含量５０モル％）の１０％アセトン
溶液に浸漬し、乾燥させた。次いでジアミノシロキサン
（分子量５０００）の５０％トルエン溶液に浸漬した。
室温で５時間反応後、乾燥して気体分離膜を得た。Example 5 A tetrafluoroethylene membrane (pore size 0.1 μm, thickness 80 μm) was used as the porous film substrate. This membrane was immersed in a 10% acetone solution of a styrene / maleic anhydride copolymer (maleic anhydride content 50 mol%) and dried. Then, it was immersed in a 50% toluene solution of diaminosiloxane (molecular weight 5000).
After reacting at room temperature for 5 hours, it was dried to obtain a gas separation membrane.
【００３２】[0032]
【比較例２】実施例５に対し、酢酸セルロースメンブレ
ン（孔径０．０５μ）に、ジアミノシロキサン（分子量
５０００）を含浸させたものを、比較例の気体分離膜と
した。Comparative Example 2 In contrast to Example 5, a cellulose acetate membrane (pore size 0.05 μ) impregnated with diaminosiloxane (molecular weight 5000) was used as a gas separation membrane of Comparative Example.
【００３３】以上各実施例及び比較例で得られた気体分
離膜のガス透過性能を、差圧法により測定した。結果を
表１に示す。尚、表中ＰＯ2、ＰＮ2は、各々Ｏ2の透過
性、Ｎ2の透過性を表し、単位は、×１０-9ｃｍ3．ｃｍ
／ｃｍ2．ｓｅｃ．ｃｍＨｇである。また、αは分離係
数（ＰＯ2／ＰＮ2）を表す。The gas permeation performance of the gas separation membranes obtained in the above Examples and Comparative Examples was measured by the differential pressure method. The results are shown in Table 1. In the table, PO 2 and PN 2 represent O 2 permeability and N 2 permeability, respectively, and the unit is × 10 -9 cm 3 . cm
/ Cm 2 . sec. It is cmHg. Further, α represents a separation coefficient (PO 2 / PN 2 ).
【００３４】[0034]
【表１】 この結果から、各実施例で得られた気体分離膜は、比較
例に比べて分離係数が高いことが明らかである。[Table 1] From this result, it is clear that the gas separation membranes obtained in the respective examples have a higher separation coefficient than the comparative examples.
【００３５】[0035]
【発明の効果】本発明により得られる気体分離膜は、選
択性に優れた新しい膜材料である。また、透過性におい
ても、これまで実用化されている膜材の中で優秀と言わ
れてきたシロキサン系化合物と同等の性能を有するもの
も得られる。The gas separation membrane obtained by the present invention is a novel membrane material having excellent selectivity. Further, also in terms of permeability, a film having performance equivalent to that of a siloxane compound which has been said to be excellent among the film materials that have been put into practical use can be obtained.
Claims (6)
を含むシロキサン化合物との反応により生成する共重合
体のフィルムまたはシートからなる気体分離膜。1. A gas separation membrane comprising a film or sheet of a copolymer produced by the reaction of a polymer compound containing a non-hydroxyl group and a siloxane compound containing an amino group.
を含むシロキサン化合物との反応により生成する共重合
体で多孔質膜基材を被覆してなる気体分離膜。2. A gas separation membrane obtained by coating a porous membrane substrate with a copolymer produced by the reaction of a polymer compound containing a non-hydroxyl group and a siloxane compound containing an amino group.
ン／無水マレイン酸共重合体またはマレイン化液状ゴム
である請求項１また２記載の気体分離膜。3. The gas separation membrane according to claim 1, wherein the polymer compound containing a non-hydroxyl group is a styrene / maleic anhydride copolymer or a maleated liquid rubber.
状またはシート状に成形し、これにアミノ基を含むシロ
キサン化合物を反応させることを特徴とする気体分離膜
の製造方法。4. A method for producing a gas separation membrane, which comprises molding a polymer compound containing a non-hydroxyl group into a film or a sheet, and reacting this with a siloxane compound containing an amino group.
合物を含浸させた後、この高分子化合物にアミノ基を含
むシロキサン化合物を反応させることを特徴とする気体
分離膜の製造方法。5. A method for producing a gas separation membrane, which comprises impregnating a porous membrane base material with a polymer compound containing a non-hydroxyl group and then reacting the polymer compound with a siloxane compound containing an amino group.
チレン−無水マレイン酸共重合体またはマレイン化液状
ゴムである請求項４または５記載の気体分離膜の製造方
法。6. The method for producing a gas separation membrane according to claim 4, wherein the polymer compound containing a non-hydroxyl group is a styrene-maleic anhydride copolymer or a maleated liquid rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6437993A JPH06277438A (en) | 1993-03-23 | 1993-03-23 | Gas separation membrane and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6437993A JPH06277438A (en) | 1993-03-23 | 1993-03-23 | Gas separation membrane and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06277438A true JPH06277438A (en) | 1994-10-04 |
Family
ID=13256618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6437993A Pending JPH06277438A (en) | 1993-03-23 | 1993-03-23 | Gas separation membrane and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06277438A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341605C (en) * | 1998-01-10 | 2007-10-10 | 谷田博 | Method and materials for treatment of purifying harmful gases and cinders at bottom of cremator |
| DE102008041477A1 (en) | 2008-08-22 | 2010-02-25 | Wacker Chemie Ag | Porous membranes of organopolysiloxane copolymers |
| WO2014131673A1 (en) | 2013-02-26 | 2014-09-04 | Wacker Chemie Ag | Asymmetrically porous membranes made of cross-linked thermoplastic silicone elastomer |
-
1993
- 1993-03-23 JP JP6437993A patent/JPH06277438A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341605C (en) * | 1998-01-10 | 2007-10-10 | 谷田博 | Method and materials for treatment of purifying harmful gases and cinders at bottom of cremator |
| DE102008041477A1 (en) | 2008-08-22 | 2010-02-25 | Wacker Chemie Ag | Porous membranes of organopolysiloxane copolymers |
| US9475010B2 (en) | 2008-08-22 | 2016-10-25 | Wacker Chemie Ag | Porous membranes made up of organopolysiloxane copolymers |
| WO2014131673A1 (en) | 2013-02-26 | 2014-09-04 | Wacker Chemie Ag | Asymmetrically porous membranes made of cross-linked thermoplastic silicone elastomer |
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