JPH06126138A - Multilayer gas separation film - Google Patents
Multilayer gas separation filmInfo
- Publication number
- JPH06126138A JPH06126138A JP4279946A JP27994692A JPH06126138A JP H06126138 A JPH06126138 A JP H06126138A JP 4279946 A JP4279946 A JP 4279946A JP 27994692 A JP27994692 A JP 27994692A JP H06126138 A JPH06126138 A JP H06126138A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- separation
- gas separation
- membrane
- film
- 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.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、空気中の酸素と窒素を
分離、濃縮する気体分離複合膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas separation composite membrane for separating and concentrating oxygen and nitrogen in air.
【０００２】[0002]
【従来の技術】近年、気体分離膜は簡単な構成で酸素と
窒素を分離できるので燃焼機器，空調機器，医療機器な
どに利用する研究がなされ一部実用化されている。2. Description of the Related Art In recent years, gas separation membranes are capable of separating oxygen and nitrogen with a simple structure, and therefore, research has been conducted for use in combustion equipment, air conditioning equipment, medical equipment and the like, and some of them have been put to practical use.
【０００３】従来、この種の気体分離膜は特開昭56−26
504号公報に示すようなものがあった。すなわち、側鎖
に活性水素を有するポリオリガノシロキサンと側鎖にビ
ニル基を有するポリオリガノシロキサンとの共重合体を
主成分とするものである。この膜の酸素と窒素の分離係
数はＰＯ2／ＰＮ2が約2.2であり、酸素の透過係数は2.8
×10~8cm3(STP)・cm/cm2・sec・cmHg程度である。Conventionally, a gas separation membrane of this type has been disclosed in JP-A-56-26.
There was one as shown in Japanese Patent No. 504. That is, it is mainly composed of a copolymer of a polyorganosiloxane having active hydrogen in the side chain and a polyorganosiloxane having a vinyl group in the side chain. The separation coefficient of oxygen and nitrogen of this membrane is about 2.2 for PO 2 / PN 2 , and the permeability coefficient of oxygen is 2.8.
× 10 to 8 cm 3 (STP) · cm / cm 2 · sec · cmHg.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら上記従来
の気体分離膜では、酸素の分離係数と透過係数は相反す
る特性を有しているので、高濃度でしかも高流量の酸素
を得るためには、膜面積を多く必要としコストが高くな
るという欠点があり、実用化するためには満足が得られ
るものではなかった。However, in the above-mentioned conventional gas separation membrane, since the separation coefficient and the permeability coefficient of oxygen are contradictory to each other, in order to obtain high concentration and high flow rate of oxygen, There is a drawback that a large film area is required and the cost is high, and it is not satisfactory for practical use.
【０００５】本発明は上記従来の問題を解決するもの
で、酸素の分離性能および透過性能を向上させることが
できる気体分離複合膜を提供することを目的とする。The present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide a gas separation composite membrane capable of improving oxygen separation performance and oxygen permeation performance.
【０００６】[0006]
【課題を解決するための手段】本発明は上記目的を達成
するために、多孔質材料からなる支持膜層と、この支持
膜層上に設けた分離層と、この分離層上に設けた保護層
とを備え、前記分離層には(化２)で示される一置換もし
くは二置換ポリジフェニルアセチレンを用いるとともに
前記保護層にはシロキサン系化合物を用いたものであ
る。In order to achieve the above object, the present invention provides a support membrane layer made of a porous material, a separation layer provided on the support membrane layer, and a protection provided on the separation layer. A mono- or di-substituted polydiphenylacetylene represented by the chemical formula 2 is used for the separation layer and a siloxane compound is used for the protective layer.
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】[0008]
【作用】本発明によれば、支持膜層に接着された分離層
は(化２)で示される一置換もしくは二置換ポリジフェニ
ルアセチレンを用い極薄膜化することにより、酸素の分
離係数と透過係数の特性を良くするように作用し、また
シロキサン系化合物からなる保護層を用いることによ
り、支持膜層と分離層の界面における相互作用により、
高い気体分離性を得ることができ、また保護膜層として
設けたシロキサン系化合物は膜の気体透過を活性化させ
るように作用し透過係数を向上させることができる。According to the present invention, the separation layer adhered to the support membrane layer is formed into an ultrathin film using the mono- or di-substituted polydiphenylacetylene represented by the chemical formula (2), whereby the separation coefficient and the permeability coefficient of oxygen are By improving the characteristics of the above, and by using a protective layer made of a siloxane-based compound, by the interaction at the interface between the supporting membrane layer and the separation layer,
A high gas separation property can be obtained, and the siloxane compound provided as the protective film layer can act to activate gas permeation of the film and improve the permeation coefficient.
【０００９】[0009]
【実施例】以下、本発明の各実施例について図１及び図
２に示す気体分離複合膜の断面図を参照しながら説明す
る。図１に示すように、気体分離複合膜１aはポリエー
テルスルホン多孔質材料からなる支持膜層２、この支持
膜層２の上面に設けた分離層３、さらに分離層３の上に
設けた保護層４によって構成されている。EXAMPLES Examples of the present invention will be described below with reference to the cross-sectional views of the gas separation composite membrane shown in FIGS. As shown in FIG. 1, the gas separation composite membrane 1a includes a support membrane layer 2 made of a polyethersulfone porous material, a separation layer 3 provided on the upper surface of the support membrane layer 2, and a protection provided on the separation layer 3. It is constituted by the layer 4.
【００１０】（実施例１） (化２)で示される一置換もしくは二置換ポリジフェニル
アセチレンのＲ1がトリメチルシリル基で置換されるポ
リ(１−(ｐ−トリメチルシリルフェニル)−２−フェニ
ルアセチレン)を0.8重量％用い、水面展開剤としてポリ
フマル酸エステルを0.35重量％となるようにクロロブタ
ン、トルエン、テトラヒドロフランの有機溶媒(クロロ
ブタン，トルエン，テトラヒドロフランそれぞれの重量
の割合は150：８：５である)で調製して分離層３の調整
液とした。Example 1 A poly (1- (p-trimethylsilylphenyl) -2-phenylacetylene) in which R 1 of the mono- or di-substituted polydiphenylacetylene represented by the formula (2) is substituted with a trimethylsilyl group is used. Prepared with 0.8% by weight of polyfumaric acid ester as a water surface developing agent to an organic solvent of chlorobutane, toluene and tetrahydrofuran (the weight ratio of each of chlorobutane, toluene and tetrahydrofuran is 150: 8: 5) so as to be 0.35% by weight. This was used as a preparation liquid for the separation layer 3.
【００１１】また保護層４は、シロキサン系化合物とス
チレンの共重合体を3.4重量％、水面展開剤としてポリ
フマル酸エステルを0.1重量％となるようにクロロブタ
ン、テトラヒドロフランの有機溶媒(クロロブタン、テ
トラヒドロフランの重量の割合は20：１である)で調製
して調製液とした。The protective layer 4 contains 3.4% by weight of a copolymer of siloxane compound and styrene and 0.1% by weight of polyfumarate as a water surface developing agent, and an organic solvent of chlorobutane and tetrahydrofuran (weight of chlorobutane and tetrahydrofuran). The ratio is 20: 1) to prepare a preparation liquid.
【００１２】そして分離層３の調整液を一定量、水面上
に展開し、溶媒を蒸発させることによって平均膜厚0.03
μｍの分離層３を形成し、支持膜層２と接触させること
により、その上に分離層３を２層積層させ、保護層４の
調製液を一定量、水面上に展開し、溶媒を蒸発させるこ
とによって平均膜厚0.02μｍの薄膜を作製し、さらにそ
の表面に保護層４を２層積層している。得られた気体分
離複合膜の性能を(表１)の実施例１に示す。Then, a fixed amount of the adjustment liquid for the separation layer 3 is spread on the water surface, and the solvent is evaporated to obtain an average film thickness of 0.03.
By forming a separation layer 3 having a thickness of μm and bringing it into contact with the supporting membrane layer 2, two separation layers 3 are laminated thereon, and a fixed amount of the preparation liquid of the protective layer 4 is spread on the water surface to evaporate the solvent. By doing so, a thin film having an average film thickness of 0.02 μm is produced, and two protective layers 4 are further laminated on the surface thereof. The performance of the obtained gas separation composite membrane is shown in Example 1 of (Table 1).
【００１３】（実施例２）ポリ(１−(ｐ−トリメチルシ
リルフェニル)−２−フェニルアセチレン)に代えて、
(化２)で示される一置換もしくは二置換ポリジフェニル
アセチレンのＲ1がｔ−ブチル基で置換されるポリ(１−
(ｐ−ｔ−ブチルフェニル)−２−フェニルアセチレン)
を用いた以外は実施例１と同様にして気体分離複合膜を
作製した。得られた気体分離複合膜の性能を(表１)の実
施例２に示す。Example 2 Instead of poly (1- (p-trimethylsilylphenyl) -2-phenylacetylene),
Poly (of 2) R 1 monosubstituted or disubstituted polydiphenylacetylene represented by is substituted with t- butyl (1-
(pt-butylphenyl) -2-phenylacetylene)
A gas separation composite membrane was produced in the same manner as in Example 1 except that was used. The performance of the obtained gas separation composite membrane is shown in Example 2 of (Table 1).
【００１４】（実施例３）ポリ(１−(ｐ−トリメチルシ
リルフェニル)−２−フェニルアセチレン)に代えて、
(化２)で示される一置換もしくは二置換ポリジフェニル
アセチレンのＲ1がトリメチルシリル基，Ｒ2がフッ素原
子で置換されるポリ(１−(ｐ−トリメチルシリルフェニ
ル)−２−(ｐ−フルオロフェニル)アセチレン)を用いた
以外は、実施例１と同様にして気体分離複合膜を作製し
た。得られた気体分離複合膜の性能を(表１)の実施例３
に示す。Example 3 Instead of poly (1- (p-trimethylsilylphenyl) -2-phenylacetylene),
Poly (1- (p-trimethylsilylphenyl) -2- (p-fluorophenyl) in which R 1 of the mono- or di-substituted polydiphenylacetylene represented by the formula (2) is substituted with a trimethylsilyl group and R 2 is substituted with a fluorine atom. A gas separation composite membrane was produced in the same manner as in Example 1 except that acetylene) was used. The performance of the obtained gas separation composite membrane is shown in Example 3 of (Table 1).
Shown in.
【００１５】なお、上記ポリジフェニルアセチレンから
なる分離層の重量1.0に対し、シロキサン系化合物から
なる保護層４の重量が0.2未満では、ちり，ほこり，湿
気，熱等による劣化を防止するのが困難であり、保護層
４の重量が6.0以上では分離層３の酸素の透過性能を妨
げる。If the weight of the separation layer made of polydiphenylacetylene is 1.0, the weight of the protective layer 4 made of a siloxane-based compound is less than 0.2, it is difficult to prevent deterioration due to dust, dust, moisture, heat and the like. When the weight of the protective layer 4 is 6.0 or more, the oxygen permeation performance of the separation layer 3 is impeded.
【００１６】したがって、劣化を防止し酸素の透過性能
に影響を与えないようにするためには、一置換もしくは
二置換ポリジフェニルアセチレンからなる分離層３の重
量1.0に対し、シロキサン系化合物からなる保護層４の
重量は0.4〜3.0が好ましい。Therefore, in order to prevent the deterioration and prevent the oxygen permeation performance from being affected, the weight of the separation layer 3 made of mono- or di-substituted polydiphenylacetylene is 1.0, and the protection layer made of a siloxane compound is used. The weight of layer 4 is preferably 0.4 to 3.0.
【００１７】[0017]
【表１】 [Table 1]
【００１８】また、図２は支持膜層２上に接着層５を設
けた気体分離複合膜１bの構造を示した図であり、前述
の実施例１〜３と相違する点は、支持膜層２と分離層３
との間にシロキサン系化合物からなる接着層５を設けた
ものである。接着層５はシロキサン系化合物からなり、
製法としては調製液を一定量、水面上に展開し、溶媒を
蒸発させることによって平均膜厚0.01μｍの接着層５を
作製し、さらに支持膜２と接触させることにより積層さ
せたものである。FIG. 2 is a view showing the structure of the gas separation composite membrane 1b in which the adhesive layer 5 is provided on the support membrane layer 2. The difference from the above-mentioned Examples 1 to 3 is that the support membrane layer is different. 2 and separation layer 3
An adhesive layer 5 made of a siloxane-based compound is provided between and. The adhesive layer 5 is made of a siloxane compound,
As a manufacturing method, a fixed amount of the prepared liquid is spread on the water surface, the solvent is evaporated to prepare an adhesive layer 5 having an average film thickness of 0.01 μm, and the adhesive layer 5 is further brought into contact with the support film 2 to be laminated.
【００１９】また分離層３の重量1.0に対し、接着層５
の重量が0.1未満では支持膜層２と分離層３との接着が
困難であり、接着層５の重量が2.0以上である場合は分
離層３の酸素の透過性能を妨げてしまう。したがって酸
素の透過性能を維持するためには、分離層３の重量1.0
に対し、接着層５の重量は0.2〜0.6が好ましい。Further, for the weight of the separating layer 3 of 1.0, the adhesive layer 5 is used.
If the weight is less than 0.1, it is difficult to bond the support membrane layer 2 and the separation layer 3, and if the weight of the adhesive layer 5 is 2.0 or more, the oxygen permeation performance of the separation layer 3 is hindered. Therefore, in order to maintain the oxygen permeability, the weight of the separation layer 3 should be 1.0
On the other hand, the weight of the adhesive layer 5 is preferably 0.2 to 0.6.
【００２０】このように接着層５を介在して膜を形成す
ることにより、膜を製造する工程において容易に支持膜
層２に分離層３が製膜ができ、酸素の透過性能を妨げる
こともない。実施例１〜３における分離層３に用いた各
々の一置換もしくは二置換ポリジフェニルアセチレンの
気体分離複合膜１bによる性能は(表１)の実施例１′〜
３′に示す。By thus forming the membrane with the adhesive layer 5 interposed, the separation layer 3 can be easily formed on the supporting membrane layer 2 in the step of producing the membrane, and the oxygen permeation performance may be hindered. Absent. The performance of each mono- or di-substituted polydiphenylacetylene used for the separation layer 3 in Examples 1 to 3 by the gas separation composite membrane 1b is shown in Table 1 as Example 1 '.
3 '.
【００２１】なお本実施例において、支持膜層は、ポリ
エーテルスルホンを用いたが、ポリスルホン、ポリスチ
レン、ポリエチレンテレフタレートなどの重合体から形
成した材料を用いてもよく、支持膜層の形状は平膜、筒
状膜、中空糸膜などいずれでもよく、織布，不織布など
の支持体の上に製膜したものでもよい。また、分離層
は、水面展開において良好な薄膜を得るために、必要に
応じて水面展開助剤を加えてもよく、また保護層シロキ
サン系化合物とスチレンの共重合体を用いたが、速乾脱
アルコールタイプの接着シール剤，剥離用シリコーンの
溶剤型を用いても、また、それらのブレンドを用いても
よい。また、ポリジフェニルアセチレンは淡黄色から橙
色であるので、製膜するときに水面に展開して超薄膜に
しても亀裂、ピンホール等の膜の欠陥を見極めることが
容易である。In this embodiment, polyether sulfone was used for the support film layer, but a material formed of a polymer such as polysulfone, polystyrene, polyethylene terephthalate may be used, and the shape of the support film layer is a flat film. , A tubular membrane, a hollow fiber membrane, or the like, or a membrane formed on a support such as a woven or non-woven fabric. Further, in order to obtain a good thin film on the surface of the separation layer, a water surface development aid may be added if necessary, and a protective layer siloxane compound and a copolymer of styrene are used, but they are fast-drying. A dealcohol type adhesive sealant, a solvent type of silicone for peeling, or a blend thereof may be used. Further, since polydiphenylacetylene is light yellow to orange in color, it is easy to identify cracks, pinholes and other film defects even when the film is spread on the water surface and formed into an ultra thin film.
【００２２】[0022]
【発明の効果】以上説明したように本発明の気体分離複
合膜は、多孔質材料からなる支持膜層と、この支持膜層
上に設けた分離層と、この分離層上に設けた保護層とを
備え、前記分離層には(化２)で示される一置換もしくは
二置換ポリジフェニルアセチレンを用いるとともに前記
保護層にはシロキサン系化合物を用いたものであり、こ
の構成とすることにより、酸素の分離性能および透過性
能を向上できる。As described above, the gas separation composite membrane of the present invention comprises a support membrane layer made of a porous material, a separation layer provided on the support membrane layer, and a protective layer provided on the separation layer. And a siloxane-based compound is used for the protective layer and a mono- or di-substituted polydiphenylacetylene represented by the chemical formula 2 is used for the separation layer. The separation performance and permeation performance of can be improved.
【図１】本発明の実施例１〜３における気体分離複合膜
の断面図である。FIG. 1 is a cross-sectional view of gas separation composite membranes in Examples 1 to 3 of the present invention.
【図２】図１の支持膜層上に接着層を設けた構造の気体
分離複合膜の断面図である。FIG. 2 is a cross-sectional view of a gas separation composite membrane having a structure in which an adhesive layer is provided on the support membrane layer of FIG.
１a，１b…気体分離複合膜、 ２…支持膜層、 ３…分
離層、 ４…保護層、５…接着層。1a, 1b ... Gas separation composite membrane, 2 ... Support membrane layer, 3 ... Separation layer, 4 ... Protective layer, 5 ... Adhesive layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木村 雅典 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 大坪 雅人 神奈川県川崎市川崎区夜光一丁目２番１号 日本ゼオン株式会社研究開発センター内 (72)発明者 渡辺 澄 神奈川県川崎市川崎区夜光一丁目２番１号 日本ゼオン株式会社研究開発センター内 (72)発明者 田原 武志 神奈川県川崎市川崎区夜光一丁目２番１号 日本ゼオン株式会社研究開発センター内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masanori Kimura 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Masato Otsubo 1-2-1, Yokou, Kawasaki-ku, Kanagawa Prefecture Zeon Japan R & D Center Co., Ltd. (72) Inventor Sumi Watanabe 1-2-1, Yokou, Kawasaki-ku, Kawasaki, Kanagawa Prefecture Zeon Corporation R & D Center (72) Inventor Takeshi Tahara 1-chome, Yokou, Kawasaki-ku, Kanagawa Prefecture 2-1 Japan Zeon Co., Ltd. Research and Development Center
Claims (2)
持膜層上に設けた分離層と、この分離層上に設けた保護
層とを備え、前記分離層には(化１)で示される一置換も
しくは二置換ポリジフェニルアセチレンを用いるととも
に前記保護層にはシロキサン系化合物を用いたことを特
徴とする気体分離複合膜。 【化１】 1. A support membrane layer made of a porous material, a separation layer provided on the support membrane layer, and a protective layer provided on the separation layer, wherein the separation layer has the formula (1) A gas separation composite membrane, wherein the mono- or di-substituted polydiphenylacetylene shown is used and a siloxane compound is used for the protective layer. [Chemical 1]
たことを特徴とする請求項１記載の気体分離複合膜。2. The gas separation composite membrane according to claim 1, wherein an adhesive layer is provided between the support membrane layer and the separation layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27994692A JP3295144B2 (en) | 1992-10-19 | 1992-10-19 | Gas separation composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27994692A JP3295144B2 (en) | 1992-10-19 | 1992-10-19 | Gas separation composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06126138A true JPH06126138A (en) | 1994-05-10 |
| JP3295144B2 JP3295144B2 (en) | 2002-06-24 |
Family
ID=17618130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27994692A Expired - Lifetime JP3295144B2 (en) | 1992-10-19 | 1992-10-19 | Gas separation composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3295144B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017098802A1 (en) * | 2015-12-10 | 2017-06-15 | 富士フイルム株式会社 | Gas separation membrane with protective layer, method for producing gas separation membrane with protective layer, gas separation membrane module and gas separation device |
| JP2017164675A (en) * | 2016-03-15 | 2017-09-21 | パナソニックＩｐマネジメント株式会社 | Gas separation composite membrane and gas separation module |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20110063827A (en) | 2008-10-31 | 2011-06-14 | 울박, 인크 | Ion implanting device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017098802A1 (en) * | 2015-12-10 | 2017-06-15 | 富士フイルム株式会社 | Gas separation membrane with protective layer, method for producing gas separation membrane with protective layer, gas separation membrane module and gas separation device |
| US10906008B2 (en) | 2015-12-10 | 2021-02-02 | Fujifilm Corporation | Protective-layer-covered gas separation membrane, method for producing protective-layer-covered gas separation membrane, gas separation membrane module, and gas separation apparatus |
| JP2017164675A (en) * | 2016-03-15 | 2017-09-21 | パナソニックＩｐマネジメント株式会社 | Gas separation composite membrane and gas separation module |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3295144B2 (en) | 2002-06-24 |
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