JPH0450056B2 - - Google Patents
Info
- Publication number
- JPH0450056B2 JPH0450056B2 JP26362984A JP26362984A JPH0450056B2 JP H0450056 B2 JPH0450056 B2 JP H0450056B2 JP 26362984 A JP26362984 A JP 26362984A JP 26362984 A JP26362984 A JP 26362984A JP H0450056 B2 JPH0450056 B2 JP H0450056B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- oxygen
- plasma
- gas separation
- rate
- 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
Links
- 239000012528 membrane Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 6
- 229920005990 polystyrene resin Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 polysiloxane Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- 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、気体分離膜に関する。更に詳しく
は、酸素富化膜などとして有効に使用される気体
分離膜に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a gas separation membrane. More specifically, the present invention relates to a gas separation membrane that is effectively used as an oxygen enrichment membrane.
従来酸素富化膜には、ポリシロキサン、ポリカ
ーボネート、ポリビニルピリジン、ポリエステル
などの高分子材料が素材として用いられており、
これらの素材をキヤスト法、水面展開法、プラズ
マ重合法、コーテイング法などによつて酸素富化
膜としている。酸化富化膜として使用する場合に
は、酸素の透過性、透過速度および他の気体、一
般には窒素との分離率（透過速度比）が共に良好
であるものが望まれている。しかるに、上記各素
材を用いたとき、例えばポリシロキサンでは透過
性（透過係数として10-8cm3・cm／cm2・秒・cmHg）
が良好な反面分離率が約２〜３と低く、逆に分離
率が約４〜５と高いポリエステルでは透過性（透
過係数として10-11〜10-12cm3・cm／cm2・秒・cm
Hg）が小さい。
Conventionally, oxygen enrichment membranes have been made of polymeric materials such as polysiloxane, polycarbonate, polyvinylpyridine, and polyester.
Oxygen-enriched membranes are made from these materials by casting methods, water surface spreading methods, plasma polymerization methods, coating methods, etc. When used as an oxidation-enriching membrane, it is desired that the membrane has good oxygen permeability and permeation rate as well as separation rate (permeation rate ratio) from other gases, generally nitrogen. However, when using each of the above materials, for example, polysiloxane has a low permeability (permeability coefficient of 10 -8 cm 3 cm/cm 2 seconds cmHg).
On the other hand, polyester has a low separation rate of about 2 to 3, while polyester has a high separation rate of about 4 to 5 . cm
Hg) is small.
かかる状況に鑑み、酸素の透過性および分離率
が共に良好で、しかも透過速度の点でもすぐれて
いる酸素富化膜が待望されている訳であるが、本
発明者は素材として分離率の良好なポリエステル
を選択し、しかもその膜厚を薄くするためにプラ
ズマ重合法を用いてポリエステル樹脂薄膜を形成
させることにより、かかる課題が効果的に達成さ
れることを先に見出した（特願昭59−163265号）。
In view of this situation, there has been a long-awaited demand for an oxygen-enriching membrane that has both good oxygen permeability and separation rate, and is also excellent in terms of permeation rate. We have previously discovered that this problem can be effectively achieved by selecting a polyester that has the same properties and forming a polyester resin thin film using a plasma polymerization method to reduce the film thickness (Patent Application No. 1983). −163265).
即ち、プラズマ重合法で得られた重合体は、例
えば界面重合法などの他の重合法で得られた重合
体と比較して、化学組成が異なるといわれてお
り、これによつて透過係数の変化、望ましくは向
上が期待できる。また、プラズマ重合法で得られ
た重合体膜は膜厚が薄く、これによつて透過速度
の向上が期待できる。本発明の結果は、かかる期
待に十分こたえることのできるものであつた。 In other words, it is said that polymers obtained by plasma polymerization have different chemical compositions than polymers obtained by other polymerization methods, such as interfacial polymerization, and this causes a decrease in the permeability coefficient. Change, preferably improvement, can be expected. Furthermore, the polymer film obtained by plasma polymerization has a thin film thickness, which can be expected to improve the permeation rate. The results of the present invention were able to fully meet these expectations.
本発明者は、この種の気体分離膜について更に
検討の結果、多孔質膜状体の表面に形成せしめる
プラズマ重合樹脂膜として、ポリエステルと同様
にポリスチレンも使用し得ることを新たに見出し
た。 As a result of further studies on this type of gas separation membrane, the present inventors have newly discovered that polystyrene as well as polyester can be used as a plasma polymerized resin membrane formed on the surface of a porous membrane.
〔問題点を解決するための手段〕および〔作用〕
従つて、本発明は酸素富化膜などとして有効に
使用される気体分離膜に係り、この気体分離膜
は、多孔質膜状体の表面にプラズマ重合ポリスチ
レン樹脂薄膜を形成せしてなる。[Means for Solving the Problems] and [Operation] Therefore, the present invention relates to a gas separation membrane that is effectively used as an oxygen enrichment membrane, etc. A thin film of plasma-polymerized polystyrene resin is formed on the substrate.
多孔質膜状体としては、ポリプロピレン、ポリ
カーボネート、ポリスルホン、ポリフツ化ビニリ
デン、酢酸セルロースなどの多孔質体であつて、
支持体としての十分な強度を保持する厚さの平膜
状、中空糸状などの膜状体が用いられる。この膜
状体表面に形成されるプラズマ重合ポリスチレン
樹脂薄膜は、非置換または置換スチレンモノマー
をプラズマ重合させることにより得られる。 Porous membrane-like materials include porous materials such as polypropylene, polycarbonate, polysulfone, polyvinylidene fluoride, and cellulose acetate.
A membrane-like body such as a flat membrane or a hollow fiber having a thickness that maintains sufficient strength as a support is used. The plasma-polymerized polystyrene resin thin film formed on the surface of this film-like body is obtained by plasma polymerizing unsubstituted or substituted styrene monomer.
プラズマ重合反応は、例えば次のようにして行
われる。即ち、一端側が細長くなつており、そこ
に高周波発振器に接続されたコイルを巻き付けた
円筒状反応容器内を、真空ポンプに連結された容
器他端側の排気口から排気して10-4〜10-5Torr
の圧力迄減圧した後、スチレンモノマーを反応容
器内に0.2Torrの圧力になる迄導入し、前記コイ
ルから出力20Wの電力を30分間印加してプラズマ
を発生させることにより重合反応が行われる。 The plasma polymerization reaction is performed, for example, as follows. That is, the inside of the cylindrical reaction vessel, which is elongated at one end and has a coil connected to a high-frequency oscillator wound around it, is evacuated from the exhaust port at the other end of the vessel connected to a vacuum pump, and the temperature is 10 -4 to 10. -5 Torr
After reducing the pressure to a pressure of 0.2 Torr, styrene monomer is introduced into the reaction vessel until the pressure reaches 0.2 Torr, and a polymerization reaction is performed by applying power of 20 W from the coil for 30 minutes to generate plasma.
このように、多孔質膜状体の表面にプラズマ重
合ポリスチレン樹脂薄膜を形成せしめた本発明の
気体分離膜は、酸素の透過性および分離率の点で
いずれもすぐれており、従つて酸素富化膜として
酸素と窒素との分離などに有効に使用することが
できる。
As described above, the gas separation membrane of the present invention, in which a plasma-polymerized polystyrene resin thin film is formed on the surface of a porous membrane, has excellent oxygen permeability and separation rate. It can be effectively used as a membrane to separate oxygen and nitrogen.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
多孔質膜状体として、ポリプロピレン樹脂製ミ
クロフイルター（ポリプラスチツク社製ジユラガ
ード2400；孔径0.02μｍ×0.2μｍ、膜厚25μｍ）を
用い、前記プラズマ重合条件下で反応させること
により、ミクロフイルターの表面に膜厚0.5μｍ
（日本真空技術製膜厚モニターモデルCRMによ
る）のポリスチレン樹脂薄膜を形成させた。な
お、モノマーとしては、窒素気流中で減圧蒸留
し、沸点46℃／20mmHgの留分のスチレンが用い
られた。Example A polypropylene resin microfilter (Jyuragard 2400 manufactured by Polyplastics; pore diameter 0.02 μm x 0.2 μm, film thickness 25 μm) was used as the porous membrane, and the microfilter was reacted under the plasma polymerization conditions described above. Film thickness 0.5μm on the surface
A thin polystyrene resin film (based on the film thickness monitor model CRM manufactured by Japan Vacuum Technology) was formed. As the monomer, styrene, which was distilled under reduced pressure in a nitrogen stream and had a boiling point of 46° C./20 mmHg, was used.
得られた気体分離膜について、圧力法による膜
の評価を行ない、酸素と窒素とをそれぞれ単独で
通過させたときの透過速度を求め、その比から分
離率を算出した。 The obtained gas separation membrane was evaluated by a pressure method, and the permeation rate when oxygen and nitrogen were passed through each alone was determined, and the separation rate was calculated from the ratio.
酸素の透過速度 1.83×10-5cm3／cm2・秒・cm
Hg
窒素の透過速度 0.35×10-5cm3／cm2・秒・cm
Hg
分離率 5.3
上記酸素の透過速度から、多孔質膜状部分の抵
抗を考えずに、酸素の透過係数を換算すると9.15
×10-10cm3／cm2・秒・cmHgの値が得られた。 Oxygen permeation rate 1.83×10 -5 cm 3 /cm 2・sec・cm
Hg Nitrogen permeation rate 0.35×10 -5 cm 3 /cm 2・sec・cm
Hg separation rate 5.3 Based on the above oxygen permeation rate, without considering the resistance of the porous membrane part, the oxygen permeation coefficient is converted to 9.15
A value of ×10 -10 cm 3 /cm 2 ·sec·cmHg was obtained.
Claims (1)
チレン樹脂薄膜を形成せしめてなる気体分離膜。 ２ 酸素富化膜として使用される特許請求の範囲
第１項記載の気体分離膜。[Claims] 1. A gas separation membrane comprising a plasma polymerized polystyrene resin thin film formed on the surface of a porous membrane. 2. The gas separation membrane according to claim 1, which is used as an oxygen enrichment membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26362984A JPS61141914A (en) | 1984-12-13 | 1984-12-13 | Gas separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26362984A JPS61141914A (en) | 1984-12-13 | 1984-12-13 | Gas separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61141914A JPS61141914A (en) | 1986-06-28 |
| JPH0450056B2 true JPH0450056B2 (en) | 1992-08-13 |
Family
ID=17392165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26362984A Granted JPS61141914A (en) | 1984-12-13 | 1984-12-13 | Gas separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61141914A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376314C (en) * | 2006-03-24 | 2008-03-26 | 华南农业大学 | An ultra permeable membrane of high polymer polystyrene resin and method for preparing same |
-
1984
- 1984-12-13 JP JP26362984A patent/JPS61141914A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61141914A (en) | 1986-06-28 |
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