JPH0691928B2 - Gas permeable membrane - Google Patents
Gas permeable membraneInfo
- Publication number
- JPH0691928B2 JPH0691928B2 JP60171540A JP17154085A JPH0691928B2 JP H0691928 B2 JPH0691928 B2 JP H0691928B2 JP 60171540 A JP60171540 A JP 60171540A JP 17154085 A JP17154085 A JP 17154085A JP H0691928 B2 JPH0691928 B2 JP H0691928B2
- Authority
- JP
- Japan
- Prior art keywords
- permeable membrane
- gas permeable
- oxygen
- film
- metal chelate
- 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
Links
- 239000012528 membrane Substances 0.000 title claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000013522 chelant Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 10
- 229920001197 polyacetylene Polymers 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000035699 permeability Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical group CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- RLLPVAHGXHCWKJ-IEBWSBKVSA-N (3-phenoxyphenyl)methyl (1s,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-IEBWSBKVSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LVTCZSBUROAWTE-UHFFFAOYSA-N diethyl(phenyl)phosphane Chemical compound CCP(CC)C1=CC=CC=C1 LVTCZSBUROAWTE-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- UDEISTCPVNLKRJ-UHFFFAOYSA-N oct-3-yne Chemical compound CCCCC#CCC UDEISTCPVNLKRJ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229950003776 protoporphyrin Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、空気中より酸素を濃縮分離するための気体透
過膜に関するものである。Description: TECHNICAL FIELD The present invention relates to a gas permeable membrane for concentrating and separating oxygen from the air.
従来の技術 気体透過性に秀れる膜材料として既に幾つかの提案がな
されている。特に透過の大きい材料としてはポリオルガ
ノシロキサン系高分子が秀れる。更に最近、これらオル
ガノシロキサン系高分子の透過性を凌ぐものとして、ポ
リアセチレン系、たとえばポリトリメチルシリルプロピ
ン（特開昭57−154106号公報参照）が提案されており、
この場合前記オルガノシロキサン系ポリマーにくらべ一
桁程度酸素の透過がすぐれるものである。2. Description of the Related Art Several proposals have already been made as membrane materials having excellent gas permeability. In particular, polyorganosiloxane-based polymers are excellent as a material having a large transmission. More recently, polyacetylene-based compounds such as polytrimethylsilylpropyne (see Japanese Patent Laid-Open No. 57-154106) have been proposed to exceed the permeability of these organosiloxane polymers.
In this case, oxygen permeation is superior to the organosiloxane polymer by about one digit.
発明が解決しようとする問題点 前記ポリトリメチルシリルプロピンは極めて気体透過性
にすぐれるが、本発明者らの観測に依れば、例えば空気
を分離する場合、その酸素と窒素の分離比は、1.5〜1.8
と極めて小さく、またその気体透過性は不安定であり、
数時間の運転により透過係数は初期値の一桁以上低下し
てしまうことが認められた。この不安定さに対する原因
は明らかでは無いが、本ポリマーは第三物質を包含し易
く、包含された第三物質によって気体透過性が阻害され
たものと想像しうる。Problems to be Solved by the Invention The polytrimethylsilylpropyne has excellent gas permeability, but according to the observation of the present inventors, for example, when separating air, the separation ratio of oxygen and nitrogen is: 1.5 to 1.8
Is extremely small, and its gas permeability is unstable,
It was confirmed that the permeation coefficient decreased by more than one digit of the initial value after several hours of operation. Although the cause for this instability is not clear, the present polymer is likely to include the third substance, and it can be imagined that the gas permeability is inhibited by the included third substance.
問題点を解決するための手段 本発明者らは斯かる欠点を克服し、上記置換ポリアセチ
レンが有する性質を利用すべく、このポリマーに各種材
料をドーピングしその気体透過性、安定性を検討した。
その結果、上記置換ポリアセチレンをベースとし、これ
に酸素親和性を有する金属キレートを含有せしめた膜
が、すぐれた気体透過性を有し、且つ安定性にすぐれる
事を見出し本発明に到達した。Means for Solving the Problems In order to overcome such drawbacks and utilize the properties of the above-mentioned substituted polyacetylene, the present inventors have doped this polymer with various materials and investigated its gas permeability and stability.
As a result, they have found that a film based on the above-mentioned substituted polyacetylene and containing a metal chelate having an oxygen affinity has excellent gas permeability and excellent stability, and has reached the present invention.
即ち本発明は、モノ、またはジ置換ポリアセチレンをホ
スト高分子とし、前記ホスト高分子に酸素親和性を有す
る金属キレート分子を含有せしめたことを特徴とする気
体透過膜である。ここで、ホスト高分子とは、金属キレ
ート分子がドープされて含有せられる側の高分子をいう
（以下同様）。That is, the present invention is a gas-permeable membrane characterized in that a mono- or di-substituted polyacetylene is used as a host polymer, and the host polymer contains a metal chelate molecule having oxygen affinity. Here, the host polymer means a polymer on the side where the metal chelate molecule is doped and contained (the same applies hereinafter).
作用 本発明はホスト高分子に、酸素親和性を有する金属キレ
ート分子を含有させることにより、極れた気体透過性と
安定性を得ている。Action In the present invention, by incorporating a metal chelate molecule having an oxygen affinity into the host polymer, excellent gas permeability and stability are obtained.
本発明のホスト高分子として用いるモノ、またはジ置換
ポリアセチレンは、嵩高い置換基を有し、その置換基
が、炭素数１から10のアルキル基、炭素数１から３のト
リアルキルシリル基より選ばれたグループより成る比較
的歪みの大きいと考えられる高分子であり、例えば、ポ
リトリメチルシリルプロピン、ポリゾメチルエチルシリ
ルプロピン、ポリtert−ブチルプロピン、ポリ−tert−
ブチルアセチレン、ポリ−tertペンチルアセチレン、ポ
リ−２−ヘキサン、ポリ−２−オクチン、これらの共重
合体、などが好適である。The mono- or di-substituted polyacetylene used as the host polymer of the present invention has a bulky substituent, and the substituent is selected from an alkyl group having 1 to 10 carbon atoms and a trialkylsilyl group having 1 to 3 carbon atoms. Polymers that are considered to have relatively large strains, and include, for example, polytrimethylsilylpropyne, polyzomethylethylsilylpropyne, polytert-butylpropyne, poly-tert-
Butylacetylene, poly-tert-pentylacetylene, poly-2-hexane, poly-2-octyne, copolymers thereof, and the like are preferable.
また本発明の酸素親和性を有する金属キレートとして
は、Mn,Fe,Co,Cuなどを金属として含む、これに窒素
系、リン系、酸素系などのリガンドから成るものが好適
で、ポリフィリン類、フタロシアニン類、などがすぐれ
ている。たとえば、鉄ポロトポリフィリン、銅プロトポ
リフィリン、あるいはジ（Ｎ−メチルイミダゾール）メ
ソーラトラ（α，α，α，α−Ｏ−ピバルアミドフェニ
ル）ポリフィナート鉄などのピケットフェンスポリフィ
リン、Mnフタロシアニン、鉄フタロシアニン、銅フタロ
シアニン、Coフタロシアニン、などが良い。Further, as the metal chelate having an oxygen affinity of the present invention, Mn, Fe, Co, Cu, etc. are included as a metal, and nitrogen-based, phosphorus-based, and oxygen-based ligands are preferable, and porphyrins, Phthalocyanines are excellent. For example, iron porotoporphyrin, copper protoporphyrin, or picket fence porphyrin such as di (N-methylimidazole) mesolatra (α, α, α, α-O-pivalamidophenyl) polyfinate iron, Mn phthalocyanine, iron phthalocyanine, copper Phthalocyanine and Co phthalocyanine are preferable.
あるいはサルコミン、のごときCo錯体、ポリエチレンイ
ミン−Co錯体も好適である。臭化マンガンとホスフィン
類、例えば、トリフエニルホスフィン、ジメチルフエニ
ルホスフィン、ジエチルフエニルホスフィンなどとの錯
体も好適であった。Alternatively, a Co complex such as salcomine and a polyethyleneimine-Co complex are also suitable. Complexes of manganese bromide with phosphines such as triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine and the like were also suitable.
これらの錯体は、適当な溶媒中に溶解させた状態で、こ
れにポリアセチン系のフィルムを含浸させる事により容
易に膜中に取り込ませる事が出来る。またはキレートと
ポリアセチレン系の共溶媒両者を溶解しておき、キャス
トしても良い。あるいは、ポリアセチレンフィルムに対
し、キレート類を真空含浸させる事も可能であった。These complexes can be easily incorporated in the film by dissolving them in a suitable solvent and impregnating them with a polyacetin film. Alternatively, both the chelate and the polyacetylene-based cosolvent may be dissolved and cast. Alternatively, it was possible to impregnate the polyacetylene film with the chelates in vacuum.
このようにして得られた膜に対し、酸素、窒素などの気
体の透過を調べたところ、ホスト高分子単独の透過性に
対し、キレートを含む膜では、透過係数は若干低下する
ものの、酸素／窒素の分離比は大きく向上し、例えば分
離比として２〜５程度の大きい値が得られた。また安定
性も向上し、長期にわたって、初期特性が維持された。When the permeation of gases such as oxygen and nitrogen was examined with respect to the membrane thus obtained, the permeation coefficient of the chelate-containing membrane was slightly lower than that of the host polymer alone. The separation ratio of nitrogen was greatly improved, and for example, a large separation ratio of about 2 to 5 was obtained. The stability was also improved, and the initial characteristics were maintained for a long time.
実施例 以下本発明の代表的な実施例につき具体的に詳述する。Examples Hereinafter, typical examples of the present invention will be described in detail.
（実施例−１） テトラカルボン酸フタロシアニン鉄１部をベンゼンに溶
解し、この溶液にフタロシアニンに対し約10倍のポリト
リメチルシリルプロピンを加え均一溶液とした。溶液を
濾過し、濾液をガラス板上にてキャスト乾燥後、フィル
ムを得た。フィルムの厚さは約35μで、このフィルムを
用いた酸素、窒素の透過率を低真空透過測定法により測
定した。酸素透過係数として、2.8×10-8cc・cm/cm2・s
ec・cmHg、酸素／窒素透過係数比（α）は、3.4であっ
た。(Example-1) 1 part of iron tetracarboxylic acid phthalocyanine was dissolved in benzene, and about 10 times as much polytrimethylsilylpropyne as phthalocyanine was added to this solution to obtain a uniform solution. The solution was filtered, and the filtrate was cast and dried on a glass plate to obtain a film. The thickness of the film was about 35μ, and the oxygen and nitrogen transmittances using this film were measured by the low vacuum transmission measurement method. 2.8 × 10 -8 cc ・ cm / cm 2・ s as oxygen permeability coefficient
The ec · cmHg and oxygen / nitrogen permeation coefficient ratio (α) were 3.4.
（実施例−２） サルコミン１部をクロロホルムに溶解し、これにサルコ
ミンに対し約10部のポリ−ｔ−ブチルアセチレンを溶解
させ、均一溶液とした。溶液を濾過し、濾液をガラス板
上にキャストし、約50μのフィルムを得た。(Example-2) 1 part of salcomine was dissolved in chloroform, and about 10 parts of poly-t-butylacetylene was dissolved in this solution to form a uniform solution. The solution was filtered and the filtrate was cast on a glass plate to give a film of about 50μ.
このフィルムの酸素透過係数は4.3×10-8cc・cm/cm2・s
ec・cmHg、αは、4.1を示した。The oxygen permeability coefficient of this film is 4.3 × 10 -8 cc ・ cm / cm 2・ s
ec · cmHg, α was 4.1.
（実施例−３） 臭化マンガン及びシメチルフェニルホスフィンを等モ
ル、シトラヒドロフランに加え約２時間加熱置流させ
た。生成した沈殿を冷却後濾別した。沈殿を乳鉢中で微
粉化し。ポリ−３−オクチンのフィルム（〜70μ）上に
一様に分散させ、これを真空乾燥機内にセットした。減
圧下乾燥機を約150℃に加熱し、３時間放置した。冷却
後フィルムを取り出し、フィルム表面上の粉末を除去
後、透過率を測定した。酸素の透過係数は7.8×10-8cc
・cm/cm2・sec・cmHg、α2.2を示した。(Example-3) Manganese bromide and cymethylphenylphosphine were added in equimolar amounts to citrahydrofuran, and the mixture was heated and left standing for about 2 hours. The precipitate formed was cooled and then filtered off. Micronize the precipitate in a mortar. It was evenly dispersed on a film of poly-3-octyne (~ 70μ) and set in a vacuum dryer. The dryer was heated to about 150 ° C. under reduced pressure and left for 3 hours. After cooling, the film was taken out, the powder on the film surface was removed, and the transmittance was measured. Oxygen permeability coefficient is 7.8 × 10 -8 cc
・ Cm / cm 2・ sec ・ cmHg and α2.2 were shown.
発明の効果 以上要するに本発明は、モノまたはジ置換ポリアセチレ
ンからなるホスト高分子に、酸素親和性を有する金属キ
レート分子を含有せしめてなる気体透過膜を提供するも
ので、気体透過性に秀れ、また極めて安定しており使用
による経時劣化が少ない利点を有する。EFFECTS OF THE INVENTION In summary, the present invention provides a gas permeable membrane obtained by containing a metal chelate molecule having an oxygen affinity in a host polymer composed of mono- or di-substituted polyacetylene, which is excellent in gas permeability, In addition, it is extremely stable and has the advantage of little deterioration over time due to use.
Claims (3)
モノ、またはジ置換ポリアセチレンの高分子に含有せし
めたことを特徴とする気体透過膜。1. A metal chelate molecule having an oxygen affinity,
A gas permeable membrane characterized by being contained in a polymer of mono- or di-substituted polyacetylene.
基が、炭素数が１から10のアルキル基および炭素数が１
から３のトリアルキルシリル基より選ばれたものの１つ
であることを特徴とする特許請求の範囲第１項記載の気
体透過膜。2. The mono- or di-substituted polyacetylene has a substituent having a carbon number of 1 to 10 and a carbon number of 1.
3. The gas permeable membrane according to claim 1, wherein the gas permeable membrane is one selected from the trialkylsilyl groups of 3 to 3.
属が、Mn,Fe,Co,Cuの内の少なくとも１つを含むことを
特徴とする特許請求の範囲第１項または第２項記載の気
体透過膜。3. A metal chelate molecule having oxygen affinity, wherein the metal of the metal chelate molecule includes at least one of Mn, Fe, Co and Cu. Gas permeable membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60171540A JPH0691928B2 (en) | 1985-08-02 | 1985-08-02 | Gas permeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60171540A JPH0691928B2 (en) | 1985-08-02 | 1985-08-02 | Gas permeable membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6233526A JPS6233526A (en) | 1987-02-13 |
| JPH0691928B2 true JPH0691928B2 (en) | 1994-11-16 |
Family
ID=15925014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60171540A Expired - Lifetime JPH0691928B2 (en) | 1985-08-02 | 1985-08-02 | Gas permeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0691928B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62136226A (en) * | 1985-12-07 | 1987-06-19 | Agency Of Ind Science & Technol | Gas separation membrane |
| US5176724A (en) * | 1987-11-10 | 1993-01-05 | Matsushita Electric Industrial Co., Ltd. | Permselective composite membrane having improved gas permeability and selectivity |
| US4859215A (en) * | 1988-05-02 | 1989-08-22 | Air Products And Chemicals, Inc. | Polymeric membrane for gas separation |
| US5501722A (en) * | 1992-11-04 | 1996-03-26 | Membrane Technology And Research, Inc. | Natural gas treatment process using PTMSP membrane |
| US5707423A (en) * | 1996-06-14 | 1998-01-13 | Membrane Technology And Research, Inc. | Substituted polyacetylene separation membrane |
| JP7107494B2 (en) * | 2019-03-19 | 2022-07-27 | フィガロ技研株式会社 | gas detector |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5998706A (en) * | 1982-11-29 | 1984-06-07 | Toshiba Corp | Oxygen gas permselective composite membrane |
| JPS6012103A (en) * | 1983-06-29 | 1985-01-22 | Sanyo Chem Ind Ltd | Gas separation membrane |
-
1985
- 1985-08-02 JP JP60171540A patent/JPH0691928B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6233526A (en) | 1987-02-13 |
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