JPS60139316A - Preparation of gas separating laminated composite membrane - Google Patents
Preparation of gas separating laminated composite membraneInfo
- Publication number
- JPS60139316A JPS60139316A JP58245470A JP24547083A JPS60139316A JP S60139316 A JPS60139316 A JP S60139316A JP 58245470 A JP58245470 A JP 58245470A JP 24547083 A JP24547083 A JP 24547083A JP S60139316 A JPS60139316 A JP S60139316A
- Authority
- JP
- Japan
- Prior art keywords
- composite membrane
- gas
- membrane
- plasma treatment
- silicon
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000009832 plasma treatment Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims description 22
- 239000010409 thin film Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 abstract description 51
- -1 polydimethylsiloxane Polymers 0.000 abstract description 18
- 229920001577 copolymer Polymers 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 230000035699 permeability Effects 0.000 abstract description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000001307 helium Substances 0.000 abstract description 2
- 229910052734 helium Inorganic materials 0.000 abstract description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 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
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 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
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- 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
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野）
本発明は、気体分離用積層複合膜の製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing a laminated composite membrane for gas separation.
従来、気体透過性に優れ、かつ気体の高選択性を備えた
気体分離用複合膜を得る方法として、気体分離用複合膜
の表面に非重合性ガスで低温プラズマ処理を施す方法が
知られていた。Conventionally, a method for obtaining a gas separation composite membrane with excellent gas permeability and high gas selectivity has been known, in which the surface of the gas separation composite membrane is subjected to low-temperature plasma treatment with a non-polymerizable gas. Ta.
しかしながら、かかる方法によって得られた気体分離用
複合膜は、気体の選択性が経時的に著しく低下していく
という欠点があった。However, the composite membrane for gas separation obtained by such a method has the drawback that the gas selectivity decreases significantly over time.
本発明の目的は、上記欠点のないもの、すなわち、気体
透過性に優れ、気体の高選択性を備え、かつ選択性の経
時変化を抑えた気体分離用積層複合膜の製造方法を提供
せんとするものである。An object of the present invention is to provide a method for producing a laminated composite membrane for gas separation that does not have the above drawbacks, that is, has excellent gas permeability, high gas selectivity, and suppresses changes in selectivity over time. It is something to do.
本発明は、気体分離用複合膜の表面に非重合性ガスで低
温プラズマ処理を施し、次いで該面上に含ケイ素重合体
の薄膜層を形成する気体分離用積層複合膜の製造方法で
ある。The present invention is a method for producing a laminated composite membrane for gas separation, in which the surface of the composite membrane for gas separation is subjected to low-temperature plasma treatment with a non-polymerizable gas, and then a thin film layer of a silicon-containing polymer is formed on the surface.
本発明における気体分離用複合膜は、多孔質支持体上に
、高分子物質よりなる厚さ０．０１μ以上０．５μ以下
の薄膜層が形成されている構成である。・多孔質支持体
は、シート状、管状、繊維状など形状、組成とも特に限
定されない。また高分子物質は、プラズマ作用を受け薄
膜形成性を有するものであれば特に限定されないが、特
に好ましい高分子物質としては、■ポリエチレン、ポリ
プロピレン、ポリブチレンなどのポリオレフィン類、■
ポリスチレン、ポリアクリロニトリル、ポリ塩化ビニル
、ポリ塩化ビニリデン、ポリテトラフルオロエチレン、
ポリビニルイソブチルエーテル、ポリアクリル酸メチル
、ポリメタクリル酸ブチル、ポリメタクリル酸ブチル、
ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルピ
リジンなどビニル系重合体類、■ポリブタジェン、ポリ
イソプレン、ポリクロロプレンなどの共役ジエン重合体
類、■ポリオキシメチレン、ポリオキシエチレン、ポリ
プロピレンオキサイドなどのポリエーテル類、■ポリフ
ェニレンオキサイド、ポリカーボネート、ポリエステル
、ポリアミド、ポリペプチド、ポリイミド、ポリスルホ
ン、ポリウレタン、ポリジメチルシロキサン、ポリシル
フェニレンなど重縮合系高分子類などがある。上記のほ
か、これら重合体を構成する単ｍ体の各種共重合体や共
重縮合体も含まれる。The composite membrane for gas separation in the present invention has a structure in which a thin film layer made of a polymeric substance and having a thickness of 0.01 μm or more and 0.5 μm or less is formed on a porous support. - The porous support is not particularly limited in shape or composition, such as sheet, tubular, or fibrous. The polymeric substance is not particularly limited as long as it has the ability to form a thin film under plasma action, but particularly preferred polymeric substances include: (1) polyolefins such as polyethylene, polypropylene, and polybutylene;
Polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene,
Polyvinyl isobutyl ether, polymethyl acrylate, polybutyl methacrylate, polybutyl methacrylate,
Vinyl polymers such as polyvinyl acetate, polyvinyl alcohol, and polyvinylpyridine, ■ Conjugated diene polymers such as polybutadiene, polyisoprene, and polychloroprene, ■ Polyethers such as polyoxymethylene, polyoxyethylene, and polypropylene oxide, ■ Examples include polycondensation polymers such as polyphenylene oxide, polycarbonate, polyester, polyamide, polypeptide, polyimide, polysulfone, polyurethane, polydimethylsiloxane, and polysilphenylene. In addition to the above, various copolymers and copolycondensates of monomers constituting these polymers are also included.
低温プラズマとは、グロー放電、コロナ放電によって生
成されるプラズマをさす。Low-temperature plasma refers to plasma generated by glow discharge or corona discharge.
低温プラズマで使用する非重合性ガスとは、プラズマ状
態としたときにそれ自身でいわゆるプラズマ重合が起こ
らず、固体が析出沈積しないガスである。例えば、水素
、ヘリウム、アルゴン、窒素、酸素、空気、−酸化炭素
、二酸化炭素、アンモニア等である。なお、重合性ガス
を用いると固体が多量に析出して不均一な膜面の閉塞が
起こり一定した性能が得難く望ましくない。The non-polymerizable gas used in low-temperature plasma is a gas that does not cause so-called plasma polymerization by itself when brought into a plasma state, and does not cause precipitation of solids. For example, hydrogen, helium, argon, nitrogen, oxygen, air, carbon oxide, carbon dioxide, ammonia, etc. It should be noted that if a polymerizable gas is used, a large amount of solids will precipitate, resulting in non-uniform clogging of the membrane surface, making it difficult to obtain consistent performance, which is not desirable.
非重合性ガスの圧力は、０．０１〜５Ｔｏｒｒに設定す
るのが好ましく、４０〜１００Ｗの中の特定の高周波出
力で放電を行なう。The pressure of the non-polymerizable gas is preferably set to 0.01 to 5 Torr, and discharge is performed at a specific high frequency output of 40 to 100W.
含ケイ素重合体とは、主鎖がケイ素原子のみからなるポ
リシラン、主鎖がケイ素と炭素だけから構成される重合
体たとえばポリシルメチレン、ポリシルフェニレン、主
鎖がケイ素とへテロ原子からなる重合体、たとえば、ポ
リシロキサン、ポリシラザン、ポリシルチアン、ポリシ
ルフェニレンシロキサン、ポリフェニレンオキシシロキ
サン、側鎖にケイ素を含む原子団を持つ炭素骨格重合体
たとえば、ポリトリメチルシラン、ポリＰ−トリメチル
シリルスチレンや、これらの各種共重合体である。これ
らの含ケイ素重合体は、低温プラズマ処理を施した気体
分離用複合膜の表面に薄膜を形成させても、気体透過性
をあまり低下させずに、選択性の経時変化を抑えるので
好ましい。Silicon-containing polymers include polysilane whose main chain consists only of silicon atoms, polymers whose main chain consists only of silicon and carbon such as polysylmethylene, polysilphenylene, and polymers whose main chain consists of silicon and heteroatoms. Coalescing, for example, polysiloxane, polysilazane, polysilthian, polysilphenylene siloxane, polyphenyleneoxysiloxane, carbon skeleton polymers with silicon-containing atomic groups in side chains, such as polytrimethylsilane, polyP-trimethylsilylstyrene, and various types thereof. It is a copolymer. These silicon-containing polymers are preferable because even when a thin film is formed on the surface of a composite membrane for gas separation subjected to low-temperature plasma treatment, they do not significantly reduce gas permeability and suppress changes in selectivity over time.
その中でも、特に好ましいのは、ポリシルフェニレンシ
ロキサン／ジメチルシロキサン共重合体、ポリカーボネ
ート／ジメチルシロキサン共重合体などのポリジメチル
シロキサンの共重合体で、気体透過性が高く、かつ薄膜
形成性も優れているため、低温プラズマ処理を施しｔｃ
気体分離用複合膜の気体透過性をはと／ｖど低下させず
に、選択性の経時変化を抑えられるので好ましい。Among these, particularly preferred are polydimethylsiloxane copolymers such as polysilphenylenesiloxane/dimethylsiloxane copolymer and polycarbonate/dimethylsiloxane copolymer, which have high gas permeability and excellent thin film forming properties. Therefore, low-temperature plasma treatment is applied to
This is preferable because changes in selectivity over time can be suppressed without significantly reducing the gas permeability of the composite membrane for gas separation.
含ケイ素重合体薄膜層の膜厚は、０．０１μ以上０．３
μ以下が好ましく、０．０１μより薄いとｗＪ膜層のピ
ンホールが多くなるため、得られた気体分離用積層複合
膜の選択性の軽＋１ｉ変化が大きくなる傾向にあり、０
．３μを越える場合、薄膜層の気体の透過抵抗が大きく
なって気体透過性の大きな気体分離用積層複合膜が得ら
れない傾向がある。The thickness of the silicon-containing polymer thin film layer is 0.01μ or more and 0.3μ
μ or less is preferable, and if it is thinner than 0.01 μ, there will be many pinholes in the wJ membrane layer, so the change in selectivity of the obtained laminated composite membrane for gas separation will tend to increase.
．． When it exceeds 3μ, the gas permeation resistance of the thin film layer increases, and there is a tendency that a laminated composite membrane for gas separation with high gas permeability cannot be obtained.
簿膜層を形成する方法には、含ケイ素重合体を溶媒に溶
解し、得られた溶液を、低温プラズマ処理を施した気体
分離用複合膜に塗布する方法や、含ケイ素重合体の溶液
を水面上に展開し、水面に形成された薄膜を、あらかじ
め低温プラズマ処理を施した気体分離用複合膜に担持す
る方法があるが、選択性の経時変化を抑えるという点で
は、塗布により薄膜層を形成する方法が好ましい。Methods for forming the membrane layer include dissolving a silicon-containing polymer in a solvent and applying the resulting solution to a composite membrane for gas separation that has been subjected to low-temperature plasma treatment; There is a method in which the thin film formed on the water surface is supported on a composite membrane for gas separation that has been previously subjected to low-temperature plasma treatment. A method of forming is preferred.
本発明は上述したように、気体分離用複合膜の表面を非
重合ガスで低温プラズマ処理を施し、次いで該面上に含
ケイ素重合体の薄膜層を形成する気体分離用積層複合膜
の製造方法としたので、得られた複合膜は、高気体透過
性でかつ高気体選択性を備え、選択性の経時変化が少な
いという効果を奏するものである。As described above, the present invention provides a method for producing a laminated composite membrane for gas separation, in which the surface of the composite membrane for gas separation is subjected to low-temperature plasma treatment with a non-polymerized gas, and then a thin film layer of a silicon-containing polymer is formed on the surface. Therefore, the obtained composite membrane has high gas permeability and high gas selectivity, and has the effect of having little change in selectivity over time.
なお、本発明における特性の測定方法および評価基準は
、次の通りである。In addition, the measuring method and evaluation criteria of the characteristics in the present invention are as follows.
（１） 気体分離用複合膜の気体透過性は、一時圧２ａ
ｔｎ＋、二次圧１ ａｔｍの条件下で測定した酸素透過
速度を評価基準とした。(1) The gas permeability of the composite membrane for gas separation is at a temporary pressure of 2a.
The oxygen permeation rate measured under the conditions of tn+ and secondary pressure of 1 atm was used as the evaluation standard.
（２） 気体選択性は、上記条件で測定した酸素透過速
度、窒素透過速度の比である分離係数Ｒを評価基準とし
た。（酸素または窒素の透過速度の単位＝ｔｎ’／ｖｎ
２− ＋１ｒ−ａｔｍ ）〔実施例〕
以下、実施例に基づいて本発明の一実／ＩＩ！ｉ態様を
説明する。(2) Gas selectivity was evaluated using the separation coefficient R, which is the ratio of the oxygen permeation rate and nitrogen permeation rate measured under the above conditions. (Unit of oxygen or nitrogen permeation rate = tn'/vn
2-+1r-atm) [Example] Hereinafter, based on the Example, part of the present invention/II! The i aspect will be explained.
実施例１
ポリジメチルシロキサン／シルフェニレン共重合体ＰＳ
Ｏ９５（チッ素株式会社製シルフェニレン／ジメチルシ
ロキ１ナンの共重合比＝１１５、数平均分子量３０万）
をシクロヘキセンに溶解し、０．１重量部に調製する。Example 1 Polydimethylsiloxane/silphenylene copolymer PS
O95 (Copolymerization ratio of silphenylene/dimethylsiloxinane made by Chisso Co., Ltd. = 115, number average molecular weight 300,000)
was dissolved in cyclohexene to adjust to 0.1 part by weight.
この溶液を水面上に展開し、フッ素樹脂多孔膜（商品名
７０口ボア、住友電工社製）に水面上の薄膜を担持し気
体分離用複合膜を得る。この複合膜を、柳本製、低温沃
化装置、型式ＬＴＡ−２ＳＮの反応容器の中央部に設置
し、Ａｒガスを非重性ガスとして使用し、真空ポンプで
約０．５Ｔｏｒｒに排気し出力５０Ｗで３０秒間低揚湯
ラズマ処理する。得られた複合膜の薄膜層に、ポリジメ
チルシロキサン／シルフェニレン共重合体ＰＳＯ９５の
０．１重量部をシクロヘキセン９９．９重量部に溶かし
た溶液でコーティングし、９０℃で３０分乾燥して積層
複合膜を得る。ｌｎられた積層複合膜の透過性能と経時
変化を表１に示した。This solution is spread on the water surface, and the thin film on the water surface is supported on a fluororesin porous membrane (trade name: 70-bore, manufactured by Sumitomo Electric Industries, Ltd.) to obtain a composite membrane for gas separation. This composite membrane was installed in the center of a reaction vessel using a low-temperature iodination apparatus manufactured by Yanagimoto, model LTA-2SN, and using Ar gas as a non-heavy gas, it was evacuated to approximately 0.5 Torr with a vacuum pump and the output was 50 W. Heat the rice for 30 seconds with a low boiling water plasma treatment. The thin film layer of the resulting composite membrane was coated with a solution of 0.1 part by weight of polydimethylsiloxane/silphenylene copolymer PSO95 dissolved in 99.9 parts by weight of cyclohexene, and dried at 90°C for 30 minutes to form a laminated layer. Obtain a composite membrane. Table 1 shows the permeation performance and changes over time of the laminated composite membrane.
実施例２
実施例１と同様に、ポリジメチルシロキサン／シルフェ
ニレン共重合体ＰＳＯ９５の薄膜をフッ素樹脂多孔膜に
担持して得られた複査膜に、実施例１と同じ条件で低温
プラズマ処理を施した複合膜の薄膜層に、ポリジメチル
シロキサン／カーボネート共重合体ＰＳＯ９９（チッ素
株式会社製、非シロキン−５０〜５５％）０．１重囲部
を塩化メチレン９９，９重量部に溶かした溶液でコーテ
ィングし、５０℃で３０分乾燥して積層複合膜を得る。Example 2 In the same manner as in Example 1, a composite film obtained by supporting a thin film of polydimethylsiloxane/silphenylene copolymer PSO95 on a porous fluororesin membrane was subjected to low-temperature plasma treatment under the same conditions as in Example 1. 0.1 parts of polydimethylsiloxane/carbonate copolymer PSO99 (manufactured by Chisso Co., Ltd., non-siloquine - 50 to 55%) was dissolved in 99.9 parts by weight of methylene chloride to the thin film layer of the composite film. The solution is coated and dried at 50° C. for 30 minutes to obtain a laminated composite membrane.
得られた積層複合膜の透過性能及び経時変化を表１に示
した。Table 1 shows the permeation performance and changes over time of the obtained laminated composite membrane.
比較例１
実施例１〜２で得られた、ポリジメチルシロキサン／シ
ルフェニレン共重合体ＰＳＯ９５の複合膜を低温プラズ
マ処理したものの透過性能及び経時変化を表１に示した
。Comparative Example 1 Table 1 shows the permeation performance and changes over time of the composite membranes of polydimethylsiloxane/silphenylene copolymer PSO95 obtained in Examples 1 and 2 subjected to low temperature plasma treatment.
実施例３
ポリスチレン／ブタジェンブロック共重合体く商品名タ
フブレンＡ１旭化成工業社製）をシクロヘキセンに溶解
し、０．１重囲部の溶液を調製する。得られた溶液を水
面上に展開し薄膜を形成さば、フッ素樹脂多孔膜に担持
して複合膜を得る。Example 3 A polystyrene/butadiene block copolymer (trade name: Toughblen A1 manufactured by Asahi Kasei Kogyo Co., Ltd.) is dissolved in cyclohexene to prepare a 0.1 part solution. The obtained solution is spread on a water surface to form a thin film, and then supported on a fluororesin porous membrane to obtain a composite membrane.
この複合膜を実施例１と同様の条件で低温プラズマ処理
を施した後、ポリジメチルシロキサンＣＹ５４００２（
トーレシリコーン社製）０．１重量部をイソペンタン９
９．９重量部に溶かした溶液をコーティングし４０℃で
３０分乾燥して積層複合膜を１７ｊｏ透過性能及び経時
変化を表１に示した。After subjecting this composite film to low-temperature plasma treatment under the same conditions as in Example 1, polydimethylsiloxane CY54002 (
(manufactured by Toray Silicone) 0.1 part by weight of isopentane 9
The laminated composite membrane was coated with a solution containing 9.9 parts by weight and dried at 40° C. for 30 minutes, and the 17jo permeation performance and changes over time are shown in Table 1.
比較例２
実施例３で作成した、低温プラズマ処理を施したポリス
チレン／ブタジェン共重合体の複合膜の透過性能及び経
時変化を表１に示した。Comparative Example 2 Table 1 shows the permeation performance and changes over time of the polystyrene/butadiene copolymer composite membrane prepared in Example 3 and subjected to low-temperature plasma treatment.
表 １
（但し、Ｒ−酸素透過速度／窒素透過速度）上記から明
らかな様に、本発明は高気体透過性で高気体選択性を備
え、気体選択性の経時変化の少ない気体分離用積層複合
膜を提供出来るという点で優れていることがわかる。Table 1 (However, R - Oxygen permeation rate/Nitrogen permeation rate) As is clear from the above, the present invention is a multilayer composite for gas separation that has high gas permeability and high gas selectivity, and has little change in gas selectivity over time. It can be seen that this method is excellent in that it can provide a membrane.
特許出願人 東 し 株 式 会 社Patent applicant Higashi Shikikai Co., Ltd.
Claims (1)
ラズマ処理を施し、次いで該面上に含ケイ素重合体の薄
膜層を形成することを特徴とする気体分離用積層複合膜
の製造方法。(1) Production of a laminated composite membrane for gas separation, characterized in that the surface of the composite membrane for gas separation is subjected to low-temperature plasma treatment with a non-polymerizable gas, and then a thin film layer of a silicon-containing polymer is formed on the surface. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58245470A JPS60139316A (en) | 1983-12-28 | 1983-12-28 | Preparation of gas separating laminated composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58245470A JPS60139316A (en) | 1983-12-28 | 1983-12-28 | Preparation of gas separating laminated composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60139316A true JPS60139316A (en) | 1985-07-24 |
| JPH0453575B2 JPH0453575B2 (en) | 1992-08-27 |
Family
ID=17134134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58245470A Granted JPS60139316A (en) | 1983-12-28 | 1983-12-28 | Preparation of gas separating laminated composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60139316A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7811359B2 (en) | 2007-01-18 | 2010-10-12 | General Electric Company | Composite membrane for separation of carbon dioxide |
| WO2015046141A1 (en) * | 2013-09-27 | 2015-04-02 | 富士フイルム株式会社 | Gas separation membrane, method for producing gas separation membrane, and gas separation membrane module |
| WO2017098887A1 (en) * | 2015-12-10 | 2017-06-15 | 富士フイルム株式会社 | Method for producing gas separation membrane with protective layer, gas separation membrane with protective layer, gas separation membrane module and gas separation device |
| US10427111B2 (en) | 2014-09-30 | 2019-10-01 | Fujifilm Corporation | Gas separation membrane, method of producing gas separation membrane, gas separation membrane module, and gas separator |
| 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 |
-
1983
- 1983-12-28 JP JP58245470A patent/JPS60139316A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7811359B2 (en) | 2007-01-18 | 2010-10-12 | General Electric Company | Composite membrane for separation of carbon dioxide |
| WO2015046141A1 (en) * | 2013-09-27 | 2015-04-02 | 富士フイルム株式会社 | Gas separation membrane, method for producing gas separation membrane, and gas separation membrane module |
| US10427111B2 (en) | 2014-09-30 | 2019-10-01 | Fujifilm Corporation | Gas separation membrane, method of producing gas separation membrane, gas separation membrane module, and gas separator |
| US11071953B2 (en) | 2014-09-30 | 2021-07-27 | Fujifilm Corporation | Gas separation membrane, method of producing gas separation membrane, gas separation membrane module, and gas separator |
| WO2017098887A1 (en) * | 2015-12-10 | 2017-06-15 | 富士フイルム株式会社 | Method for producing gas separation membrane with protective layer, gas separation membrane with protective layer, gas separation membrane module and gas separation device |
| JPWO2017098887A1 (en) * | 2015-12-10 | 2018-09-13 | 富士フイルム株式会社 | Method for producing gas separation membrane with protective layer, gas separation membrane with protective layer, gas separation membrane module, and gas separation device |
| US10843137B2 (en) | 2015-12-10 | 2020-11-24 | Fujifilm Corporation | Method for producing protective-layer-covered gas separation membrane, protective-layer-covered gas separation membrane, gas separation membrane module, and gas separation apparatus |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0453575B2 (en) | 1992-08-27 |
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