JPH0761426B2 - Selective gas permeable composite membrane - Google Patents
Selective gas permeable composite membraneInfo
- Publication number
- JPH0761426B2 JPH0761426B2 JP62283533A JP28353387A JPH0761426B2 JP H0761426 B2 JPH0761426 B2 JP H0761426B2 JP 62283533 A JP62283533 A JP 62283533A JP 28353387 A JP28353387 A JP 28353387A JP H0761426 B2 JPH0761426 B2 JP H0761426B2
- Authority
- JP
- Japan
- Prior art keywords
- composite membrane
- selective gas
- permeable composite
- porous support
- polymer
- 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 37
- 239000002131 composite material Substances 0.000 title claims description 26
- 229920000642 polymer Polymers 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 230000035699 permeability Effects 0.000 claims description 9
- 229920006254 polymer film Polymers 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920001197 polyacetylene Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/122—Separate manufacturing of ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は混合気体からある一つの気体を選択透過させる
気体分離用の選択気体透過性複合膜に関するものであ
る。TECHNICAL FIELD The present invention relates to a selective gas permeable composite membrane for gas separation that selectively permeates a single gas from a mixed gas.
従来の技術 近年、混合気体より特定の気体を、高分子の膜を介して
分離濃縮する技術が実用化され始め、既に空気中よりの
酸素の濃縮、工業用水素分離濃縮及び炭酸ガスの回収な
どの分離膜が用いられている。特に空気中より酸素を濃
縮するいわゆる酸素富化膜は、その用途が広く産業界に
与える影響は大きい。Conventional technology In recent years, the technology of separating and concentrating a specific gas from a mixed gas through a polymer membrane has begun to be put into practical use, and has already concentrated oxygen from the air, industrial hydrogen separation and concentration, carbon dioxide recovery, etc. The separation membrane of is used. In particular, a so-called oxygen-enriched film that concentrates oxygen from the air has a wide range of uses and has a great influence on the industrial world.
発明が解決しようとする問題点 しかしながら現在実用化されている酸素富化膜で考える
と、大気空気を処理するものとしては、ポリオルガノシ
ロキサン系の膜が多く、膜材料固有の酸素透過速度とし
ては、約10-1cc/cm2・sec・atmオーダーのものである。
この系統の膜は、比較的気体透過性は大きいが、一般的
には酸素／窒素の分離比が〜２と小さく、生成される酸
素富化空気中の酸素濃度としては〜30％程度である。一
方、医療用などに用いられる酸素富化膜では、酸素／窒
素の分離比が３〜４で、40％前後の酸素富化空気が得ら
れるが、気体の処理量が少く、用いられている膜材料、
例えばポリオレフィン系膜では酸素の透過速度は、10-2
〜10-3cc/cm2・sec・atmと小さい。透過流量、及び分離
性の大きい膜の出現は、現在の酸素富化空気の用途を大
きく拡大することが予想されており、新しい高性能膜の
開発が期待されている。Problems to be Solved by the Invention However, considering oxygen-enriched membranes currently in practical use, many of them are polyorganosiloxane-based membranes for treating atmospheric air, and the oxygen permeation rate peculiar to the membrane material is , About 10 -1 cc / cm 2 · sec · atm order.
The membrane of this system has a relatively high gas permeability, but generally has a small oxygen / nitrogen separation ratio of ~ 2, and the oxygen concentration in the oxygen-enriched air produced is ~ 30%. . On the other hand, oxygen-enriched membranes used for medical purposes have an oxygen / nitrogen separation ratio of 3 to 4, and oxygen-enriched air of about 40% can be obtained, but the amount of gas treated is small and used. Membrane material,
For example, in a polyolefin membrane, the oxygen transmission rate is 10 -2.
Small as ~ 10 -3 cc / cm 2 · sec · atm. The advent of membranes with high permeation flow rates and separability is expected to greatly expand the current applications of oxygen-enriched air, and the development of new high-performance membranes is expected.
本発明は上記気体透過膜の必要性に対し、従来にない、
高透過性でかつ高分離性、そしてさらには実用上最も重
要である安定性の優れた膜を提供することを目的とする
ものである。The present invention is unconventional to the need for the gas permeable membrane,
It is an object of the present invention to provide a highly permeable and highly separable membrane, and further, a stable membrane which is most important for practical use.
問題点を解決するための手段 本発明は上記目的を達成するもので、その技術的手段
は、多孔質支持体と第１の高分子超薄膜との間に、多孔
質支持体材料と第１の高分子超薄膜材料からなる界面層
を設け、前記第１の高分子超薄膜表面に、酸素透過係数
が10-8cc・cm/cm2・sec・cmHg以上の第２の高分子超薄
膜を設けたものである。Means for Solving the Problems The present invention achieves the above object, and its technical means is to provide a porous support material and a first support between the porous support and the first ultrathin polymer film. And a second polymer ultrathin film having an oxygen permeability coefficient of 10 −8 cc · cm / cm 2 · sec · cmHg or more on the surface of the first polymer ultrathin film. Is provided.
作用 本発明の構成の選択気体透過性複合膜は非常に高気体透
過性で、かつ気体の分離性もシリュー系酸素富化膜より
向上する。そして実用上最も重要である特性の安定性も
十分のものとなる。例えば第１の高分子材料としてポリ
〔−１−（トリメチルシリル）１−プロピン（PMSP）
を、第２の高分子としてポリヒドロキシスチレン−ポリ
スルホン−ポリジメチルシロキサン共重合体（HS）を、
そして多孔質支持体としてポリスルホン非対称膜を使用
すると酸素の透過速度が約0.6cc/cm2・sec・atmに達
し、かつ酸素と窒素の分離性は約2.7にまで高性能化で
きた。そしてこの複合膜に圧力を印加した状態でそのラ
イフ試験をした所、500時間経過で流量低下率が10％以
内に留まり、分離性の変化は何等検出されなかった。Action The selective gas-permeable composite membrane of the constitution of the present invention has a very high gas permeability, and the gas separability is also improved as compared with the siliu-based oxygen-enriched membrane. In addition, the stability of the characteristics, which is most important in practical use, becomes sufficient. For example, as the first polymer material, poly [-1- (trimethylsilyl) 1-propyne (PMSP) is used.
A polyhydroxystyrene-polysulfone-polydimethylsiloxane copolymer (HS) as the second polymer,
When a polysulfone asymmetric membrane was used as the porous support, the oxygen permeation rate reached about 0.6cc / cm 2 · sec · atm, and the separability of oxygen and nitrogen was improved to about 2.7. When a life test was performed with pressure applied to this composite membrane, the flow rate reduction rate remained within 10% after 500 hours, and no change in separability was detected.
この選択気体透過性複合膜での重要なポイントは高透過
性であると同時に、この複合膜構成材料のいずれの素材
よりも高分離性になることである。つまりここで用いた
PMSPは酸素と窒素の透過係数比が約1.6であり一方HSは
約2.1である、多孔質支持体は本質的に分離性はなく、
実際の複合膜の分離性2.7よりいずれの素材とも小さ
い。そこで本発明者らは第１の高分子層と多孔質支持体
界面にそれぞれの材料から成る高分離性の界面層ができ
ていることを想定し実験した結果、複合膜モデルとして
の界面層を発見したわけである。そしてその存在がきわ
めて有効に選択気体透過性複合膜特性に反映され高性能
化が可能となった。表面に存在するHS層はこの選択気体
透過性複合膜の特性を安定化させるためのものであり、
透過特性に本質的には関与していない。An important point in this selective gas permeable composite membrane is that it has high permeability and at the same time has higher separability than any of the constituent materials of the composite membrane. I.e. used here
PMSP has a permeability coefficient ratio of oxygen to nitrogen of about 1.6, whereas HS has a ratio of about 2.1, the porous support is essentially non-separable,
Both materials are smaller than the actual separability of composite membranes of 2.7. Therefore, the present inventors have conducted experiments assuming that a highly separable interface layer made of each material is formed at the interface of the first polymer layer and the porous support, and as a result, the interface layer as a composite membrane model was formed. I discovered it. And its existence was very effectively reflected in the characteristics of the selective gas permeable composite membrane, and the high performance became possible. The HS layer present on the surface is for stabilizing the properties of this selective gas permeable composite membrane,
There is essentially no contribution to the transmission properties.
本発明の第１の高分子超薄膜の材料としては一般式が （但しR1は水素原子、炭素数が４以下のアルキル基のい
ずれかで示され、R2はCH2）ｍ−CH3のｍが０〜３で示
される。）で表わされるポリアセチレンもしくは一般式
が （但しR1はハロゲン原子、水素原子、炭素数が４以下の
アルキル基のいずれかで示され、R2はフェニル基、炭素
数が３〜６個のアルキル基のいずれかで示される。）で
表わされるポリアセチレン系高分子が好適である。これ
らの高分子はいずれも主鎖に２重結合をもち、かつこの
２重結合の炭素上にバルキーな置換基を有するため、ガ
ラス転移温度が約160℃以上の無定形の高分子となる。
従ってアセチレン系の高分子でなくても同様の性質を有
する高分子であれば好適な材料となり得る。The general formula for the material of the first ultra-thin polymer film of the present invention is (However, R 1 is represented by any one of a hydrogen atom and an alkyl group having 4 or less carbon atoms, and R 2 is CH 2 ) m —CH 3 is represented by m of 0 to 3. ) Polyacetylene or general formula (However, R 1 is a halogen atom, a hydrogen atom, or an alkyl group having 4 or less carbon atoms, and R 2 is a phenyl group or an alkyl group having 3 to 6 carbon atoms.) A polyacetylene-based polymer represented by is preferable. Each of these polymers has a double bond in the main chain, and has a bulky substituent on the carbon of this double bond, and thus is an amorphous polymer having a glass transition temperature of about 160 ° C. or higher.
Therefore, even if it is not an acetylene-based polymer, a polymer having similar properties can be a suitable material.
多孔質支持体の材料としては芳香族ポリスルホン もしくは芳香族ポリエーテルスルホン が適当である。Aromatic polysulfone as a material for the porous support Or aromatic polyether sulfone Is appropriate.
また第２の高分子材料としてはポリオルガノシロキサン
もしくはポリオルガノシロキサンを主成分とするブロッ
ク、グラフトあるいはグラフト架橋型共重合体で、酸素
透過係数が〜10-8cc・cm/cm2・sec・cmHg以上のものが
適当である。The second polymeric material is a polyorganosiloxane or a block, graft or graft-crosslinked copolymer containing polyorganosiloxane as a main component and having an oxygen permeability coefficient of up to 10 −8 cc · cm / cm 2 · sec · A value of cmHg or more is suitable.
実施例 以下に本発明の実施例について詳細に述べる。Examples Examples of the present invention will be described in detail below.
〈実施例〉 第１の高分子としてポリ〔−１−（トリメチルシリル）
−１−プロピン〕（PMSP）、多孔質支持体としてポリエ
ーテルスルホン（東洋クロス社製、Ko−２タイプ）を用
い、第２の高分子としてポリヒドロキシスチレン−ポリ
スルホン−ポリジメチルシロキサン（HS）共重合体（シ
ロキサン含有率〜70％）をそれぞれ用い、第１と第２の
ベンゼン希薄溶液を用いて水面上に超薄膜を形成し、上
記多孔質支持体上に第１、第２高分子超薄膜の順で積層
した。第１の高分子（PMSP）超薄膜の膜厚の特性への影
響を見るため、この層数を１〜10層までの範囲で特性を
検討したその結果を第１表に示す。第１表に示すように
第１の高分子（PMSP）の層数を増加するに従い、Fo2、
分離性も下がり、さらに経時のFo2の低下も大きくなっ
た。つまり高性能特性を発揮し、かつ経時変化を押える
ためには出来るだけこのPMSP層を薄くすれば良好な特性
となる。しかし第２の高分子層及び多孔質支持体の種類
でもこの特性は変わるため、その複合膜構成に 合わせた考察が必要である。いずれにしてもこの様な構
成にすることで従来にない高性能な選択気体透過性複合
膜が可能となった。<Example> As the first polymer, poly [-1- (trimethylsilyl)] was used.
-1-propyne] (PMSP), polyether sulfone (Koyo type, manufactured by Toyo Cross Co., Ltd.) as the porous support, and polyhydroxystyrene-polysulfone-polydimethylsiloxane (HS) as the second polymer An ultrathin film is formed on the water surface by using a dilute solution of benzene and a dilute solution of benzene each containing a polymer (a siloxane content of 70%), and the first and second polymers are superposed on the porous support. The thin films were laminated in this order. In order to see the effect of the film thickness of the first ultra-thin polymer (PMSP) film on the characteristics, Table 1 shows the results of examining the characteristics in the range of 1 to 10 layers. As shown in Table 1, as the number of layers of the first polymer (PMSP) increases, Fo 2 ,
The separability also decreased, and the decrease in Fo 2 over time also increased. In other words, in order to exhibit high-performance characteristics and suppress changes over time, it is desirable to thin the PMSP layer as much as possible. However, this property changes depending on the type of the second polymer layer and the porous support, so that the composite membrane structure is Combined consideration is necessary. In any case, by adopting such a structure, a high-performance selective gas-permeable composite membrane which has never existed before becomes possible.
〈比較例〉 実施例と同様の手法で、HS層の存在しない複合膜を作製
し、その特性を第２表に示す。<Comparative Example> A composite film having no HS layer was prepared in the same manner as in the example, and the characteristics are shown in Table 2.
第２表に示すようにFo2と分離性の関係は層数に対して
実施例と同様の傾向を示し、表面に設置されるHS層の初
期特性への影響は殆んど見られない。これに対し経時に
よる特性は大きく影響され不安定な複合膜になってしま
う。 As shown in Table 2 , the relationship between Fo 2 and separability shows the same tendency with respect to the number of layers as in the example, and there is almost no effect on the initial characteristics of the HS layer placed on the surface. On the other hand, the characteristics over time are greatly affected, resulting in an unstable composite film.
本実施例の複合膜モデルは図の様に想定される。つまり
図に示すような界面層２を多孔質支持体１と第１の高分
子層３の間に形成することで高分離性が発現され、更に
第２の高分子層４を設けることにより安定化を図ってい
るわけである。図において第１の高分子層３の酸素透過
係数を▲▼、膜厚をl1、界面層２がそれぞれ▲
▼、l2とすると第２の高分子層４のない状態（複合膜と
しての）のFo2は（多孔質支持体１は抵抗層とならない
ため無視する。） （ここでＡは膜面積、dPは圧力差） となり分離性α０（Fo2／FN2）は （ここでα１、α２はそれぞれ第１層、第２層の分離性
である。）で示される。The composite membrane model of this embodiment is assumed as shown in the figure. That is, by forming the interface layer 2 between the porous support 1 and the first polymer layer 3 as shown in the figure, high separability is exhibited, and by providing the second polymer layer 4, it becomes stable. That is what we are trying to achieve. In the figure, the oxygen permeability coefficient of the first polymer layer 3 is ▲ ▼, the film thickness is l 1 , and the interface layer 2 is ▲.
▼, l 2 represents Fo 2 without the second polymer layer 4 (as a composite membrane) (the porous support 1 does not serve as a resistance layer and is ignored). (Where A is the membrane area and dP is the pressure difference) and the separability α0 (Fo 2 / FN 2 ) is (Here, α 1 and α 2 are the separability of the first layer and the second layer, respectively.).
ここで生成する界面層の厚さが、第１層の層数（厚さ）
に関係なく一定であると仮定すると、（１）式は、第１
層の層数をｎとすると （２）式は に書ける。さらに（３）式は に変形でき、この式からわかるように界面層が積層数に
関係なく一定の膜厚であるとするとFo2の逆数と積層数
が１次式の関係になることになる。第２表のデータを基
にプロットするとこの式に良く対応し、この解析から界
面層の存在と特性が明確となった。そしてその相関より
（５）式 の値が概算され、その得られた値を（４）式に代入する
ことで界面層の分離性（α２）を計算すると約2.9とな
り積層数でこの値に影響はなかった。本実施例では安定
化のために第１の高分子層３の上に第２の高分子層４を
設けている。第２の高分子層４により複合膜の特性を劣
化させずに高安定化がはかれる。The thickness of the interface layer generated here is the number of layers (thickness) of the first layer.
Assuming that it is constant regardless of
If the number of layers is n Equation (2) is Can be written on. Furthermore, equation (3) is As can be seen from this equation, if the interface layer has a constant film thickness regardless of the number of stacked layers, the reciprocal of Fo 2 and the number of stacked layers have a linear relationship. Plotting based on the data in Table 2 corresponds well to this equation, and this analysis clarified the existence and properties of the interfacial layer. And from the correlation, equation (5) When the separability (α 2 ) of the interface layer was calculated by substituting the obtained value into the equation (4), the value was about 2.9, and this value was not affected by the number of layers. In this embodiment, the second polymer layer 4 is provided on the first polymer layer 3 for stabilization. The second polymer layer 4 provides high stability without deteriorating the characteristics of the composite film.
上記実施例においては第１の高分子としてPMSPについて
のみ示したが、同類のアセチレン系高分子でも同様の効
果が得られた。また第２の高分子としてはポリオルガノ
シロキサンを主成分とするものも同様の気体透過性を有
し、同様の効果が得られた。In the above examples, only PMSP was shown as the first polymer, but similar effects were obtained with the same kind of acetylene polymer. The second polymer having polyorganosiloxane as a main component also had the same gas permeability, and the same effect was obtained.
発明の効果 以上要するに本発明は、多孔質支持体と第１の高分子超
薄膜の間に界面層を生成させることで非常に高性能の複
合膜とすると同時に、さらに表面に第２の高分子層を設
けることで複合膜の特性を劣化せず実用レベルにまで高
安定化できる利点を有する。EFFECTS OF THE INVENTION In summary, according to the present invention, by forming an interface layer between the porous support and the first polymer ultrathin film, a highly efficient composite film is obtained, and at the same time, the second polymer is further formed on the surface. By providing the layer, there is an advantage that the characteristics of the composite film are not deteriorated and can be highly stabilized to a practical level.
【図面の簡単な説明】 図は本発明の一実施例における選択気体透過性複合膜の
モデルを示す断面図である。 １……多孔質支持体、２……界面層、３……第１の高分
子層、４……第２の高分子層。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a model of a selective gas-permeable composite membrane according to an embodiment of the present invention. 1 ... Porous support, 2 ... Interface layer, 3 ... First polymer layer, 4 ... Second polymer layer.
Claims (6)
前記多孔質支持体表面と第１の高分子超薄膜の間に設け
られた、多孔質支持体材料と第１の高分子超薄膜材料か
らなる界面層と、前記第１の高分子超薄膜表面に設けら
れた、酸素透過係数が10-8cc・cm/cm2・sec・cmHg以上
の第２の高分子超薄膜とを具備する選択気体透過性複合
膜。1. A porous support and a first ultra-thin polymer film,
An interface layer comprising a porous support material and a first ultra-thin polymer film, provided between the surface of the porous support and the first ultra-thin polymer film, and the surface of the first ultra-thin polymer film A selective gas-permeable composite membrane, comprising a second ultra-thin polymer film having an oxygen permeability coefficient of 10 −8 cc · cm / cm 2 · sec · cmHg or more.
である特許請求の範囲第１項記載の選択気体透過性複合
膜。2. The selective gas permeable composite membrane according to claim 1, wherein the material of the porous support is aromatic polysulfone.
スルホンである特許請求の範囲第１項記載の選択気体透
過性複合膜。3. The selective gas-permeable composite membrane according to claim 1, wherein the material of the porous support is aromatic polyether sulfone.
ずれかで示され、R2は−（CH2）ｍCH3のｍが０〜３で示
される。）で表わされるポリアセチレンである特許請求
の範囲第１項から第３項のいずれか記載の選択気体透過
性複合膜。4. The first polymer ultrathin film material has a general formula. (Provided that R 1 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R 2 is — (CH 2 ) m CH 3 wherein m is 0 to 3). A selective gas-permeable composite membrane according to any one of claims 1 to 3.
アルキル基のいずれかで示され、R2はフェニル基、炭素
数が３〜６個のアルキル基のいずれかで示される。）で
表わされるポリアセチレン系高分子である特許請求の範
囲第１項から第３項のいずれか記載の選択気体透過性複
合膜。5. The first polymer ultrathin film material has a general formula. (However, R 1 is a halogen atom, a hydrogen atom, or an alkyl group having 4 or less carbon atoms, and R 2 is a phenyl group or an alkyl group having 3 to 6 carbon atoms.) The selective gas-permeable composite membrane according to any one of claims 1 to 3, which is a polyacetylene-based polymer represented by.
ロキサンあるいはポリオルガノシロキサンを主成分とす
るブロック、グラフトもしくはグラフト架橋型共重合体
のいずれかである特許請求の範囲第１項から第５項のい
ずれか記載の選択気体透過性複合膜。6. The second polymer ultrathin film material is a polyorganosiloxane or a block, graft or graft cross-linking copolymer containing polyorganosiloxane as a main component. Item 7. The selective gas-permeable composite membrane according to any one of items 5.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62283533A JPH0761426B2 (en) | 1987-11-10 | 1987-11-10 | Selective gas permeable composite membrane |
| US07/753,020 US5176724A (en) | 1987-11-10 | 1991-08-26 | Permselective composite membrane having improved gas permeability and selectivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62283533A JPH0761426B2 (en) | 1987-11-10 | 1987-11-10 | Selective gas permeable composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01123619A JPH01123619A (en) | 1989-05-16 |
| JPH0761426B2 true JPH0761426B2 (en) | 1995-07-05 |
Family
ID=17666763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62283533A Expired - Lifetime JPH0761426B2 (en) | 1987-11-10 | 1987-11-10 | Selective gas permeable composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761426B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105935557A (en) * | 2016-06-28 | 2016-09-14 | 深圳中物兴华科技发展有限公司 | Oxygen permeable membrane, oxygen permeable membrane oxygen generator, and oxygen enriched air conditioner |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5707423A (en) * | 1996-06-14 | 1998-01-13 | Membrane Technology And Research, Inc. | Substituted polyacetylene separation membrane |
| JP2019166443A (en) * | 2018-03-22 | 2019-10-03 | 東芝ライフスタイル株式会社 | Oxygen enrichment membrane |
-
1987
- 1987-11-10 JP JP62283533A patent/JPH0761426B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105935557A (en) * | 2016-06-28 | 2016-09-14 | 深圳中物兴华科技发展有限公司 | Oxygen permeable membrane, oxygen permeable membrane oxygen generator, and oxygen enriched air conditioner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01123619A (en) | 1989-05-16 |
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