JPH0479687B2 - - Google Patents
Info
- Publication number
- JPH0479687B2 JPH0479687B2 JP59114513A JP11451384A JPH0479687B2 JP H0479687 B2 JPH0479687 B2 JP H0479687B2 JP 59114513 A JP59114513 A JP 59114513A JP 11451384 A JP11451384 A JP 11451384A JP H0479687 B2 JPH0479687 B2 JP H0479687B2
- Authority
- JP
- Japan
- Prior art keywords
- gas separation
- membrane
- thin film
- composite membrane
- polyorganosiloxane
- 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 56
- 238000000926 separation method Methods 0.000 claims description 48
- 239000002131 composite material Substances 0.000 claims description 33
- 229920001577 copolymer Polymers 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000007789 gas Substances 0.000 description 47
- 239000010409 thin film Substances 0.000 description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000035699 permeability Effects 0.000 description 9
- -1 poly(4-methylpentene-1) Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 229920006380 polyphenylene oxide Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000306 polymethylpentene Polymers 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920005527 TPX™ MX001 Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
- B01D71/701—Polydimethylsiloxane
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
〔産業上の利用分野〕
本発明は気体分離複合膜に関する。更にくわし
くは膜分離法により空気から酸素富化空気を得る
ために有効な気体分離複合膜に関する。
〔従来の技術〕
近年、膜法による気体分離、特に膜分離による
酸素富化空気を得る方法が注目されている。この
膜分離に実用上使用され得る膜は、気体分離性能
が高く、かつ気体透過性能も高いという条件を満
たさなければならない。その為、膜の形態は気体
分離性を有する膜素材を薄膜とし、多孔質支持体
上に複合化した複合膜とする必要がある。従来ま
でに、該複合膜としてポリオルガノシロキサンシ
ルフエニレン共重合体複合膜（特開昭57−
122906）が知られているが、ポリオルガノシロキ
サンシルフエニレン共重合体は、分離性能が低い
という欠点があつた。
一方、気体分離性能の高い膜素材であるポリフ
エニレンオキサイドやポリ（４−メチルペンテン
−１）などの重合体を薄膜とし多孔質支持体に直
接複合化したものは、接着性が悪い為、複合膜の
取り扱いの際、薄膜が剥離するという欠点があつ
た。この問題を解消する為に、米国特許第
3874986号に記載されているごとく、気体分離性
能の高いポリフエニレンオキサイドの薄膜と多孔
質支持体との間に接着性の高いポリカーボネー
ト／ポリジメチルシロキサン（PC−PDMS）共
重合体薄膜を介在せしめた複合膜が提唱されてい
る。
しかしながら、PC−PDMS共重合体は酸素透
過係数PO2が２〜３（CCS（TP）・cm／cm2・sec・
cmHg）と小さく、接着性を向上させる為に介在
した該薄膜層が複合膜の透過性能を低下させると
いう欠点があつた。
〔発明が解決しようとする問題点〕
本発明の目的は、上記欠点を解消せしめ、薄膜
層が多孔質支持膜から剥離せず、気体分離性能と
気体透過性能がともに優れている気体分離複合膜
を提供せんとするものである。
〔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ため次の構成、
すなわち、多孔質支持体Ａと、高気体分離性を有
する重合体からなる極薄膜Ｂとの間に、構造式が
で表わされるポリオルガノシロキサンシルフエニ
レン共重合体からなる極薄膜Ｃが介在されてなる
気体分離複合膜である。
本発明におけ多孔質支持体Ａとは、薄膜を支持
するものであればよく、和紙、不織布、合成紙、
紙、布、金網、過膜、限外過膜等があげら
れるが、その中でも表面の平滑性および孔の小さ
い方が補強上好ましいので限外過膜が好適であ
る。限外過膜を具体的に例示すると、ポリスル
ホン多孔質支持膜、ポリエーテルスルホン多孔質
支持膜、ポリプロピレン多孔質支持膜、ポリテト
ラフルオロエチレン多孔質支持膜など挙げること
ができる。これら多孔質支持体Ａの形状は、シー
ト状、管状、繊維状などあるが特に限定されな
い。
次に本発明における高気体分離性を有する重合
体からなる極薄膜Ｂとは、気体分離性が高く、か
つ気体透過性の比較的すぐれた重合体であれば何
でも良いが、薄膜形成性、気体分離性、気体透過
性のバランスの点で以下の重合体が好ましい。
ポリ（４−メチルペンテン−１）．ポリエチレ
ン／プロピレン共重合体．ポリビニルトリメチル
シランのビニル系重合体。
一般式が、
（但し、ｍは１，２，３の整数。R1は−CH3，
−C2H5，−C3H7，−C4H9，−C5H11のアルキル基
から成る群より選ばれる。）で表わされるポリフ
エニレンオキサイド、あるいは一般式が、
（但し、R3，R4は
[Industrial Application Field] The present invention relates to a gas separation composite membrane. More specifically, the present invention relates to a gas separation composite membrane effective for obtaining oxygen-enriched air from air by a membrane separation method. [Prior Art] In recent years, gas separation by membrane methods, particularly methods for obtaining oxygen-enriched air by membrane separation, have attracted attention. A membrane that can be practically used for this membrane separation must satisfy the conditions of high gas separation performance and high gas permeation performance. Therefore, the form of the membrane needs to be a composite membrane in which a thin membrane material with gas separation properties is formed on a porous support. Up until now, polyorganosiloxane silphenylene copolymer composite membrane (Unexamined Japanese Patent Publication No. 1983-1999) has been used as the composite membrane.
122906), but the polyorganosiloxane silphenylene copolymer had the drawback of low separation performance. On the other hand, membrane materials with high gas separation performance, such as polyphenylene oxide and poly(4-methylpentene-1), are made into thin films and composited directly onto a porous support because of poor adhesion. There was a drawback that the thin film peeled off when handling the composite film. In order to solve this problem, US Patent No.
As described in No. 3874986, a highly adhesive polycarbonate/polydimethylsiloxane (PC-PDMS) copolymer thin film is interposed between a polyphenylene oxide thin film with high gas separation performance and a porous support. Composite membranes have been proposed. However, the PC-PDMS copolymer has an oxygen permeability coefficient PO 2 of 2 to 3 (CCS (TP) cm/cm 2 sec
cmHg), and the thin film layer interposed to improve adhesion had the disadvantage that the permeation performance of the composite membrane was reduced. [Problems to be Solved by the Invention] The object of the present invention is to solve the above-mentioned drawbacks, and to provide a gas separation composite membrane in which the thin film layer does not peel off from the porous support membrane and has excellent gas separation performance and gas permeation performance. We aim to provide the following. [Means for solving the problems] In order to achieve the above object, the present invention has the following configuration:
That is, the structural formula is This is a gas separation composite membrane in which an ultra-thin membrane C made of a polyorganosiloxane silphenylene copolymer represented by is interposed. The porous support A in the present invention may be anything that supports a thin film, such as Japanese paper, nonwoven fabric, synthetic paper,
Examples include paper, cloth, wire mesh, permeable membrane, ultrapermeable membrane, etc. Among them, ultrapermeable membrane is preferable because smoothness of the surface and smaller pores are preferable for reinforcement. Specific examples of ultrafiltration membranes include polysulfone porous support membranes, polyethersulfone porous support membranes, polypropylene porous support membranes, polytetrafluoroethylene porous support membranes, and the like. The shape of these porous supports A may be sheet-like, tubular, fibrous, etc., but is not particularly limited. Next, the ultra-thin film B made of a polymer having high gas separation property in the present invention may be any polymer as long as it has high gas separation property and relatively good gas permeability. The following polymers are preferred in terms of the balance between separability and gas permeability. Poly(4-methylpentene-1). Polyethylene/propylene copolymer. A vinyl polymer of polyvinyltrimethylsilane. The general formula is (However, m is an integer of 1, 2, 3. R 1 is −CH 3 ,
selected from the group consisting of the alkyl groups -C2H5 , -C3H7 , -C4H9 , -C5H11 . ), or the general formula is (However, R 3 and R 4 are
【式】−
C2H4−，−C3H6−，−C4H8−，−C5H10−，R2は
−C2H4O−，（―C2H4O）―2，（―C3H6O）―，（―
C4H8O）―，（―C5H10O）―から成る群より選ばれ
る。）で表わされるポリウレタン、あるいは、一
般式が
（但し、R5は[Formula] −C 2 H 4 −, −C 3 H 6 −, −C 4 H 8 −, −C 5 H 10 −, R 2 is −C 2 H 4 O−, (−C 2 H 4 O) ― 2 , (―C 3 H 6 O)―, (―
C 4 H 8 O)―, (―C 5 H 10 O)―. ), or the general formula is (However, R 5 is
【式】【formula】
【式】【formula】
【式】【formula】
次に、実施例に基づいて本発明の実施態様を説
明する。
実施例 １
ポリオルガノシロキサンシルフエニレン共重合
体PSO95（チツ素株式会社製シルフエニレン／ジ
メチルシロキサンの共重合比＝１／５、数平均分
子量30万）をシクロヘキセンに溶解し、0.1wt％
に調製する。この溶液を水面上に展開し、フツ素
樹脂多孔膜（商品名フロロポア、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。次に、ポリ（４メチルペンテン−１）（商品
名TPX−MX001、三井石油化学社製）をシクロ
ヘキセンに溶解し、0.1wt％に調製する。この溶
液を水面上に展開し、先ほど作成したポリオルガ
ノシロキサンシルフエニレン共重合体複合膜の薄
膜表面に、水面上のポリ（４メチルペンテン−
１）薄膜を担持し、気体分離用複合膜を作成し
た。
なお、ポリ（４メチルペンテン−１）薄膜の膜
厚は約0.02μ、ポリオルガノシロキサンシルフエ
ニレン共重合体薄膜の膜厚は約0.1μであつた。こ
の気体分離複合膜の酸素透過速度ならびに酸素と
窒素の分離係数を測定した結果を表−１に示す。
ポリオルガノシロキサンシルフエニレン共重合
体の薄膜を介在させたにもかかわらず、高気体透
過性で、かつ高気体分離性の性能であつた。
実施例 ２
ポリフエニレンオキサイド（重量平均分子量≒
50000）をベンゼンに溶解し、0.5wt％の溶液を調
製する。この溶液を水面上に展開し、薄膜を形成
させる。実施例１と同様の作成方法で作成したポ
リオルガノシロキサンシルフエニレン共重合体複
合膜の表面に、水面上に形成されているポリフエ
ニレンオキサイド薄膜を担持し、気体分離複合膜
を作成した。該複合膜のポリフエニレンオキサイ
ド薄膜の膜厚は約0.04μ、ポリオルガノシロキサ
ンシルフエニレン共重合体薄膜の膜厚は約0.1μで
あつた。この気体分離複合膜の酸素透過速度なら
びに酸素と窒素の分離係数を測定した結果を表１
に示す。気体透過性と気体分離性はともに優れて
いる。
実施例 ３
実施例１で作成した気体分離複合膜の薄膜表面
にフツ素多孔質支持膜（商品名フロロポア、住友
電工社製）を圧力２ｇ／cm2で加圧接着させ、その
後剥離した気体分離複合膜の酸素透過速度ならび
に酸素と窒素の分離係数を測定した結果を表２に
示す。
実施例 ４
実施例２で作成した気体分離複合膜に実施例３
と同様にして行なつた接着剥離後の結果を表２に
示す。
実施例３、実施例４とも接着剥離前後で気体分
離性能、気体透過性能ともに変化せず、本発明が
接着性に優れていることがわかる。
比較例 １
実施例１で調製したポリ（４メチルペンテン−
１）シクロヘキセン0.1wt％溶液を水面に展開し、
薄膜を形成させる。この薄膜をフツ素多孔質支持
膜に担持し、気体分離用複合膜を作製する。ポリ
（４メチルペンテン−１）薄膜の膜厚は約0.02μで
あつた。この気体分離用複合膜の酸素透過速度お
よび酸素と窒素の分離係数を測定した結果を表１
に示す。実施例１で作成したポリオルガノシロキ
サンシルフエニレン共重合体薄膜を介在せしめた
気体分離用複合膜が、気体透過性の点で劣つてい
ないことがわかる。
比較例 ２
実施例２で調製したポリフエニレンオキサイド
のベンゼン0.5wt％溶液を水面上に展開し、薄膜
を形成せしめ、フツ素多孔質支持膜に担持して気
体分離用複合膜を作成する。ポリフエニレンオキ
サイド薄膜の膜厚は約0.04μであつた。この気体
分離用複合膜の酸素透過速度および酸素と窒素の
分離係数を測定した結果を表１に示す。実施例２
で作成したポリオルガノシロキサンフエニレン共
重合体薄膜を介在せしめた気体分離用複合膜が気
体透過性の点で劣つていないことがわかる。
比較例 ３
比較例１で作成した気体分離複合膜の薄膜表面
に、フツ素多孔質支持膜を圧力２ｇ／cm2で接触さ
せ剥がした後、酸素透過速度ならびに酸素と窒素
の分離係数を測定しその結果を表２に示す。
比較例 ４
比較例２で作成した気体分離複合膜に比較例３
と同様の接着テストを施し、その結果を表２に示
す。
比較例３、比較例４ともポリオルガノシロキサ
ンシルフエニレン共重合体薄膜を介在させない気
体分離複合膜は、接着性が悪く分離性能が失われ
てしまうことがわかる。
上記から明らかなように本発明は、薄膜層が多
孔質支持体から剥離しにくい為、取扱い性が良く
気体透過性、気体分離性が優れていることがわか
る。
Next, embodiments of the present invention will be described based on Examples. Example 1 Polyorganosiloxane silphenylene copolymer PSO95 (manufactured by Chitsuso Co., Ltd., silphenylene/dimethylsiloxane copolymerization ratio = 1/5, number average molecular weight 300,000) was dissolved in cyclohexene, and the concentration was 0.1 wt%.
Prepare to. This solution is spread on the water surface and a fluorine resin porous membrane (trade name: Fluoropore, manufactured by Sumitomo Electric Industries, Ltd.) is used.
A thin film is supported on the water surface to obtain a composite membrane for gas separation. Next, poly(4-methylpentene-1) (trade name TPX-MX001, manufactured by Mitsui Petrochemicals) is dissolved in cyclohexene and adjusted to 0.1 wt%. This solution was spread on the water surface and applied to the thin film surface of the polyorganosiloxane silphenylene copolymer composite film prepared earlier.
1) A composite membrane for gas separation was created by supporting a thin film. The thickness of the poly(4-methylpentene-1) film was about 0.02 μm, and the thickness of the polyorganosiloxane silphenylene copolymer film was about 0.1 μm. Table 1 shows the results of measuring the oxygen permeation rate and oxygen/nitrogen separation coefficient of this gas separation composite membrane. Despite the presence of a thin film of polyorganosiloxane silphenylene copolymer, it had high gas permeability and high gas separation performance. Example 2 Polyphenylene oxide (weight average molecular weight≒
50000) in benzene to prepare a 0.5wt% solution. This solution is spread on the water surface to form a thin film. A polyphenylene oxide thin film formed on the water surface was supported on the surface of a polyorganosiloxane silphenylene copolymer composite membrane prepared in the same manner as in Example 1 to prepare a gas separation composite membrane. The polyphenylene oxide thin film of the composite membrane had a thickness of about 0.04 μm, and the polyorganosiloxane silphenylene copolymer thin film had a film thickness of about 0.1 μm. Table 1 shows the results of measuring the oxygen permeation rate and oxygen and nitrogen separation coefficient of this gas separation composite membrane.
Shown below. Both gas permeability and gas separation are excellent. Example 3 A fluorine porous support membrane (trade name: Fluoropore, manufactured by Sumitomo Electric Industries, Ltd.) was adhered to the thin film surface of the gas separation composite membrane prepared in Example 1 at a pressure of 2 g/cm 2 and then peeled off. Table 2 shows the results of measuring the oxygen permeation rate and oxygen/nitrogen separation coefficient of the composite membrane. Example 4 Example 3 was applied to the gas separation composite membrane prepared in Example 2.
Table 2 shows the results after adhesive peeling performed in the same manner as above. In both Examples 3 and 4, both gas separation performance and gas permeation performance did not change before and after adhesive peeling, indicating that the present invention has excellent adhesive properties. Comparative Example 1 Poly(4-methylpentene-
1) Spread a 0.1wt% cyclohexene solution on the water surface,
Form a thin film. This thin film is supported on a fluorine porous support membrane to produce a composite membrane for gas separation. The thickness of the poly(4-methylpentene-1) film was about 0.02μ. Table 1 shows the results of measuring the oxygen permeation rate and oxygen and nitrogen separation coefficient of this composite membrane for gas separation.
Shown below. It can be seen that the composite membrane for gas separation in which the polyorganosiloxane silphenylene copolymer thin film prepared in Example 1 was interposed was not inferior in terms of gas permeability. Comparative Example 2 A 0.5 wt% benzene solution of polyphenylene oxide prepared in Example 2 is spread on a water surface to form a thin film and supported on a fluorine porous support membrane to prepare a composite membrane for gas separation. The thickness of the polyphenylene oxide thin film was approximately 0.04μ. Table 1 shows the results of measuring the oxygen permeation rate and oxygen/nitrogen separation coefficient of this composite membrane for gas separation. Example 2
It can be seen that the composite membrane for gas separation in which the polyorganosiloxane phenylene copolymer thin film prepared in the above is interposed is not inferior in terms of gas permeability. Comparative Example 3 After contacting the thin film surface of the gas separation composite membrane prepared in Comparative Example 1 with a fluorine porous support membrane at a pressure of 2 g/cm 2 and peeling it off, the oxygen permeation rate and the separation coefficient between oxygen and nitrogen were measured. The results are shown in Table 2. Comparative Example 4 Comparative Example 3 was applied to the gas separation composite membrane prepared in Comparative Example 2.
An adhesion test similar to that was conducted and the results are shown in Table 2. It can be seen that in both Comparative Examples 3 and 4, the gas separation composite membranes without the polyorganosiloxane silphenylene copolymer thin film had poor adhesion and lost separation performance. As is clear from the above, in the present invention, since the thin film layer is difficult to peel off from the porous support, it is easy to handle and has excellent gas permeability and gas separation properties.
【表】【table】
本発明の気体分離複合膜は多孔質支持体Ａと、
高気体分離性を有する重合体からなる極薄膜Ｂの
間に、ポリオルガノシロキサンシルフエニレン共
重合体からなる極薄膜Ｃが介在されているのでポ
リオルガノシロキサンシルフエニレン共重合体の
優れた接着性ならびに気体透過性により、次のご
とき優れた効果を得ることができる。
(1) 複合膜は使用に際して、薄膜が剥離しない
為、取り扱い性に優れている。
(2) 気体分離性能および気体透過性能がともに優
れている。
The gas separation composite membrane of the present invention includes a porous support A,
Since the ultra-thin film C made of polyorganosiloxane silphenylene copolymer is interposed between the ultra-thin film B made of a polymer with high gas separation properties, excellent adhesion of the polyorganosiloxane silphenylene copolymer is achieved. The following excellent effects can be obtained due to the properties and gas permeability. (1) Composite membranes are easy to handle because the thin film does not peel off during use. (2) Both gas separation performance and gas permeation performance are excellent.
Claims (1)
合体からなる極薄膜Ｂの間に、構造式が、 で表わされるポリオルガノシロキサンシルフエニ
レン共重合体からなる極薄膜Ｃが介在されてなる
気体分離複合膜。[Claims] 1 Between the porous support A and the ultrathin membrane B made of a polymer having high gas separation properties, A gas separation composite membrane comprising an ultra-thin membrane C made of a polyorganosiloxane silphenylene copolymer represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59114513A JPS60257820A (en) | 1984-06-06 | 1984-06-06 | Gas separation composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59114513A JPS60257820A (en) | 1984-06-06 | 1984-06-06 | Gas separation composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60257820A JPS60257820A (en) | 1985-12-19 |
| JPH0479687B2 true JPH0479687B2 (en) | 1992-12-16 |
Family
ID=14639631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59114513A Granted JPS60257820A (en) | 1984-06-06 | 1984-06-06 | Gas separation composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60257820A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8897359B2 (en) | 2008-06-03 | 2014-11-25 | Microsoft Corporation | Adaptive quantization for enhancement layer video coding |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62180708A (en) * | 1986-02-03 | 1987-08-08 | Agency Of Ind Science & Technol | Production of porous membrane |
| US5073175A (en) * | 1988-08-09 | 1991-12-17 | Air Products And Chemicals, Inc. | Fluorooxidized polymeric membranes for gas separation and process for preparing them |
| JP2015112502A (en) * | 2013-12-07 | 2015-06-22 | 住友化学株式会社 | Laminate and gas separation membrane, and method of manufacturing the laminate |
-
1984
- 1984-06-06 JP JP59114513A patent/JPS60257820A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8897359B2 (en) | 2008-06-03 | 2014-11-25 | Microsoft Corporation | Adaptive quantization for enhancement layer video coding |
| US9185418B2 (en) | 2008-06-03 | 2015-11-10 | Microsoft Technology Licensing, Llc | Adaptive quantization for enhancement layer video coding |
| US9571840B2 (en) | 2008-06-03 | 2017-02-14 | Microsoft Technology Licensing, Llc | Adaptive quantization for enhancement layer video coding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60257820A (en) | 1985-12-19 |
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