JPS6135824A - Gas permeable membrane - Google Patents
Gas permeable membraneInfo
- Publication number
- JPS6135824A JPS6135824A JP59157831A JP15783184A JPS6135824A JP S6135824 A JPS6135824 A JP S6135824A JP 59157831 A JP59157831 A JP 59157831A JP 15783184 A JP15783184 A JP 15783184A JP S6135824 A JPS6135824 A JP S6135824A
- Authority
- JP
- Japan
- Prior art keywords
- group
- oxygen
- permeable membrane
- gas permeable
- perfluoride
- 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 23
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 20
- 229920001197 polyacetylene Polymers 0.000 claims abstract description 20
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229950011087 perflunafene Drugs 0.000 claims description 2
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 claims description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 claims description 2
- UEOZRAZSBQVQKG-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluorooxolane Chemical compound FC1(F)OC(F)(F)C(F)(F)C1(F)F UEOZRAZSBQVQKG-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 19
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- -1 Polydimethylsiloxane Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- DCGLONGLPGISNX-UHFFFAOYSA-N trimethyl(prop-1-ynyl)silane Chemical group CC#C[Si](C)(C)C DCGLONGLPGISNX-UHFFFAOYSA-N 0.000 description 3
- IVILBNIXEFKQHQ-UHFFFAOYSA-N 1-fluoro-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2C(F)CCCC21 IVILBNIXEFKQHQ-UHFFFAOYSA-N 0.000 description 2
- 239000002473 artificial blood Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical group CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZDWYFWIBTZJGOR-UHFFFAOYSA-N bis(trimethylsilyl)acetylene Chemical group C[Si](C)(C)C#C[Si](C)(C)C ZDWYFWIBTZJGOR-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000002640 oxygen therapy Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- B01D71/44—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)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は空気から酸素を濃縮分離する場合に特に好適な
気体透過膜に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a gas permeable membrane particularly suitable for concentrating and separating oxygen from air.
従来例の構成とその問題点
近年、低濃度酸素、すなわち含有酸素濃度が２１チ以上
４０チ程度のいわゆる酸素富化空気の利用技術の開発が
盛に行なわれている。これらの酸素富化空気は、燃焼シ
ステムに於ける省エネルギー化、あるいは医療分野にお
ける酸素療法、その他汚泥処理、化学工業における酸化
プロセスでの利用などさまざまな用途が期待されている
。この酸素富化空気の製造法に関しては、経済性、安全
性、取扱いの容易さなどから、いわゆる気体透過膜によ
る膜分離法が脚光を浴びている。気体の分離濃縮におい
て、用いられる気体透過膜に対し要求される性能のポイ
ントは、目的とする気体の透過係数、及び他の気体との
分離における選択性の大なるこ走である。特に・燃焼シ
ステムの省エネルギー化を目的とした酸素富化空気の製
造などの場合には、大量の空気量が必要で、より透過係
数の大きい膜材料が必要となってくる。従来より透過係
数の大きい材料としては、ポリジメチルシロキサン（い
わゆるシリコーンゴム）が良く知られておりＰｏ２（酸
素透過係数）〜６ Ｘ １０−８ｃｃ蜘〆ｄ・五・Ｃ＃
＆Ｈｇ の値を有している。この材料の成膜性を改善し
、実用に供するだめの技術は既に幾つか提案、実用化さ
れている。たとえば、特開昭５１−８９５６４号公報、
特開昭５６−２８６０５号公報、特開昭５６−２６５０
６号公報などである。Conventional Structures and Problems There has been active development in recent years of techniques for utilizing low-concentration oxygen, that is, so-called oxygen-enriched air having an oxygen content of 21 to 40 degrees. This oxygen-enriched air is expected to have a variety of uses, including energy saving in combustion systems, oxygen therapy in the medical field, sludge treatment, and oxidation processes in the chemical industry. Regarding the method for producing oxygen-enriched air, a membrane separation method using a so-called gas-permeable membrane is attracting attention because of its economic efficiency, safety, and ease of handling. In the separation and concentration of gases, the performance points required of the gas permeable membrane used are the permeability coefficient of the target gas and the high selectivity in separation from other gases. In particular, in the case of producing oxygen-enriched air for the purpose of energy saving in combustion systems, a large amount of air is required, and a membrane material with a higher permeability coefficient is required. Polydimethylsiloxane (so-called silicone rubber) is well known as a material with a higher permeability coefficient than before, and Po2 (oxygen permeability coefficient) ~6
&Hg. Several techniques for improving the film formability of this material and putting it into practical use have already been proposed and put into practical use. For example, Japanese Patent Application Laid-Open No. 51-89564,
JP-A-56-28605, JP-A-56-2650
Publication No. 6, etc.
しかしながらより小面積で大量の空気を処理し、大幅な
コスト低減を図るためにはこれらのオルガノシロキサン
系の膜材料より更に透過の秀れた材料が望まれている。However, in order to treat a large amount of air in a smaller area and to significantly reduce costs, a material with even better permeability than these organosiloxane-based membrane materials is desired.
発明の目的
本発明は前記従来の欠点を解消するもので、透過性の優
れた気体透過膜を得ることを目的とするものである。OBJECTS OF THE INVENTION The present invention solves the above-mentioned conventional drawbacks, and aims to provide a gas permeable membrane with excellent permeability.
発明の構成
本発明は前記目的を達成するもので、ハロゲン原子、ア
ルキル基、ハロゲン化アルキル基、フェニル基、オルガ
ノシリル基よ構成る群から選ばれた基または原子を置換
基として有する、１置換ポリアセチレンと１，２置換ポ
リアセチレンのいずれかまたは両方を母材とし、これに
酸素溶解性の大なる過弗化物を添加してなることを特徴
とする気体透過膜を提供するものである。Structure of the Invention The present invention achieves the above-mentioned object, and provides a monosubstituted compound having as a substituent a group or atom selected from the group consisting of a halogen atom, an alkyl group, a halogenated alkyl group, a phenyl group, and an organosilyl group. The present invention provides a gas permeable membrane characterized by using either or both of polyacetylene and 1,2-substituted polyacetylene as a base material, to which a perfluoride with high oxygen solubility is added.
本発明に有用なポリアセチレン類としては、ポリメチル
アセチレン、ポリエチルアセチレン、ポリ−ｎ−プロピ
ルアセチレン、ポリ−１８０−プロピルアセチン、ポリ
ｎ−ブチルアセチレン、ポリー七ｅｈｔ−ブチルアセチ
レン、ポリへブチン、ポリオクチンなどのアルキル置換
ポリアセチレン、ポリトリメチルシリルアセチレン、ポ
リトリエチルシリルアセチレンなどのオルガノシリル置
換アセチレン、ポリフェニルアセチレン、ポリ−１−７
００−２フエニルアセチンなどのフェニル置換アセチレ
ン、ポリ−２−ヘキシン、ポリ１メチル−２−トリメチ
ルシリルアセチレン、ポリ−１，２−ビス（トリメチル
シリル）アセチレンなどの１゜２−ジ置換ア↓チレンな
どであり、特に嵩だかめ置換 を有するものが、気体透
過性にすぐれる。Polyacetylenes useful in the present invention include polymethylacetylene, polyethylacetylene, poly-n-propylacetylene, poly-180-propylacetin, poly-n-butylacetylene, poly-7eht-butylacetylene, polyhebutyne, Alkyl-substituted polyacetylene such as polyoctin, organosilyl-substituted acetylene such as polytrimethylsilylacetylene, polytriethylsilylacetylene, polyphenylacetylene, poly-1-7
Phenyl-substituted acetylenes such as 00-2 phenylacetin, 1°2-disubstituted a↓tylenes such as poly-2-hexyne, poly-1methyl-2-trimethylsilylacetylene, poly-1,2-bis(trimethylsilyl)acetylene, etc. In particular, those with bulky substitution have excellent gas permeability.
これらのポリ２−は、ベンゼン、トルエン、キシレンな
どの芳香族溶媒に易溶であり、通常の方法により、これ
らの高分子を含む溶液から、キャスト法、水面展開法な
どによって容易に薄膜を得ることが出来る。得られた薄
膜は、多孔性基材に移しとられ、複合化される。あるい
は多孔性基材を前記高分子溶液に含浸させても良い。と
ころがこのようにして得られた薄膜は、その透過特性が
と元の材料が有する値より低下していることが認められ
た。例えば、典型的な例を挙げると、化タンタルを用い
、トルエン中で重合させたポリ１−メチル−２−トリメ
チルシリルアセチレン（分子量、約１２０万）は、透過
特性の初期値が、Ｐ（）２＝ｙｘ １ｏ−７ｃｃ −ｔ
ｘ／ｃｄ −ｓｅｃ−ｍＨｇ 、 Ｐ０２／ ｙ、２−
１．８を示した。一方、この材料をベンゼンに溶解し、
この溶液から水面に展開して得られた膜をポリブタピレ
ン多孔膜上に移しとり測定すると、都、（換算値） ＝
：２ Ｘ １０−８ｃｃ ＊偏μ拳ｓｅｃ＊ｃｍＨｇ
。These poly-2- are easily soluble in aromatic solvents such as benzene, toluene, and xylene, and thin films can be easily obtained from solutions containing these polymers by conventional methods such as casting or water surface development. I can do it. The obtained thin film is transferred to a porous substrate and composited. Alternatively, a porous substrate may be impregnated with the polymer solution. However, the thin film thus obtained was found to have lower transmission properties than the original material. For example, to give a typical example, poly-1-methyl-2-trimethylsilylacetylene (molecular weight, about 1.2 million) polymerized in toluene using tantalum oxide has an initial value of permeability of P()2 =yx 1o-7cc -t
x/cd-sec-mHg, P02/y, 2-
It showed 1.8. Meanwhile, dissolve this material in benzene,
When the membrane obtained by developing this solution on the water surface was transferred onto a polybutapyrene porous membrane and measured, the result was: (converted value) =
:2 X 10-8cc *Unbalanced fist sec*cmHg
.
′）２／ＦＮ２−２−６と変化した。あるいは多孔基材
に含浸し、５０″Ｃ程度に熱処理して得られた膜も、同
程度の変化を示した。この傾向は、特に高透過性のポリ
アセチレン類で顕著であり、且つ、表面積の大きい形状
にする 顕著であった。')2/FN2-2-6. Alternatively, a membrane obtained by impregnating a porous substrate and heat-treating it at about 50"C showed a similar change. This tendency is particularly remarkable for highly permeable polyacetylenes, and Making the shape larger was noticeable.
とじて用いた多孔膜中に存在する各種の充填材による゛
影響が一因であると判明した。すなわち嵩高い置換基を
有する、歪のか＼ったポリアセチレンに有っては、通常
吸蔵し難いと考えられる分子を容易に吸蔵してしまうこ
とが判明した。しかも一端吸蔵された分子は、その分子
を溶解するような溶媒などで抽出しない限シ、安定にと
のポリマー中に存在していることが判明した。そこで本
発明者らは、吸蔵させる分子として、酸素溶解性が大き
く、人工血液などで用いられろ過弗化物を用いたところ
、酸素透過性にすぐれ、且つ酸素選択透過能の大きい気
体透過膜を得ることが出来た。It was found that one of the causes was the influence of various fillers present in the porous membrane used. In other words, it has been found that a strained polyacetylene having bulky substituents easily occludes molecules that are normally considered difficult to occlude. Moreover, it has been found that molecules that have been occluded remain stably present in the polymer unless they are extracted with a solvent that dissolves the molecules. Therefore, the present inventors used filtration fluoride, which has high oxygen solubility and is used in artificial blood, as the molecule to be occluded, and obtained a gas permeable membrane with excellent oxygen permeability and high oxygen selective permeability. I was able to do it.
此処で用いられろ過弗化物としては、高弗素化されたハ
イドロカーボン、フルコール、エーテルカルボン酸アミ
ンなど、一般に良く知られているように、表面張力が小
さく、従って気体透過性にすぐれた弗化物ならどれでも
利用することが可能である。またこれら単分子だけでな
く、パーフルオロカーボンオリゴマーも好適であった。The filtration fluorides used here include highly fluorinated hydrocarbons, flucols, ether carboxylic acid amines, etc. As is generally well known, fluorides with low surface tension and excellent gas permeability are used. It is possible to use any of them. In addition to these single molecules, perfluorocarbon oligomers were also suitable.
特に秀れたものとしては、既に人工血液として用いられ
ているパーフルオロデカリン、バーフルオロラトラヒド
ロフラン、パーフルオロトリブチルアミンなどが好適で
あった。これらの過弗化物をポリアセチレンに吸蔵させ
る方法は、特に限定されるものでは無いが、弗素を含む
バゲン化炭化水素のごとき溶媒に、該過弗化物とポリア
セチレンを溶解して混合溶液と成し、キャストする方法
、あるいは、過弗化物の蒸気にポリアセチレンを曝露す
る方法などにより導入することが可能である。過弗化物
のポリアセチレンに対する含有比率は、１〜８０％、好
ましくは、２〜４５チであった。このようにして得られ
る過弗化物含有ポリアセチレン複合膜は、そのポリアセ
チレンの特異な吸蔵能力によって安定で、他の酸素キャ
リアーを多孔膜に含浸して成るようないわゆる液膜にく
らべ著しい特性向上が発揮された。Especially suitable were perfluorodecalin, perfluorolatrahydrofuran, perfluorotributylamine, etc., which are already used as artificial blood. The method for occluding these perfluorides in polyacetylene is not particularly limited, but includes dissolving the perfluoride and polyacetylene in a solvent such as a fluorine-containing vaporized hydrocarbon to form a mixed solution, It can be introduced by casting, or by exposing polyacetylene to perfluoride vapor. The content ratio of perfluoride to polyacetylene was 1 to 80%, preferably 2 to 45%. The perfluoride-containing polyacetylene composite membrane obtained in this way is stable due to the unique storage ability of the polyacetylene, and exhibits significantly improved properties compared to so-called liquid membranes made by impregnating other oxygen carriers into a porous membrane. It was done.
実施例の説明 以下本発明を幾つかの実施例を用いて詳述する。Description of examples The present invention will be explained in detail below using some examples.
本発明は以下に述べる実施例に限られるのでは無く、上
述のごとき組合せの系において充分な効果が得られるこ
とは云う迄も無い。。It goes without saying that the present invention is not limited to the embodiments described below, and that sufficient effects can be obtained in combinations such as those described above. .
〈実施例−１〉
ポリアセチレンとして、ポリ−１−メチル−２トリメチ
ルシリルアセチレン、（Ｍω：〜１２０万）を用いた。<Example-1> Poly-1-methyl-2-trimethylsilylacetylene (Mω: ~1.2 million) was used as polyacetylene.
このポリマーをベンゼンに溶解しキャスト法によって、
厚さ約１８０μのフィルムを得た。パー７／ｌ／オロト
リプチルアミンをガラス製シャーレに入れ、シャーレを
前記フィルムで覆い該シャーレを真空乾燥機中に設置し
た。系全体をロータリーポンプで減圧にし、６０°Ｃに
て約３時間放置した。冷却後、常圧に戻し、フィルムを
取り出した。フィルムの処理前後の容量測定から、パー
フルオロ） ＩＪブチルアミン約８％フィルムに混入し
ていることが分った。このフィルムの気体透過性を測定
したところ、常温で、酸素透過係数として、４．５×１
Ｏ−６（ｃｃ−ａｍ／ｃ４−気・偏Ｈｑ）、酸素／窒素
の選択性は３．２を示した。By dissolving this polymer in benzene and casting,
A film with a thickness of about 180μ was obtained. Par7/l/otriptylamine was placed in a glass Petri dish, the Petri dish was covered with the film, and the Petri dish was placed in a vacuum dryer. The entire system was evacuated using a rotary pump and left at 60°C for about 3 hours. After cooling, the pressure was returned to normal and the film was taken out. Capacity measurements of the film before and after processing revealed that about 8% of perfluoro)IJ butylamine was mixed in the film. When the gas permeability of this film was measured, the oxygen permeability coefficient was 4.5×1 at room temperature.
O-6 (cc-am/c4-air/partial Hq), oxygen/nitrogen selectivity was 3.2.
〈実施例−２〉
ポリアセチレンとして、ポリ−ｔ−ブチルア方チレン（
Ｍω；〜４０万）を用い、溶媒として（商品名）グイフ
ーン ３に溶解した。これにノく−フルオロデカリンを
溶かし、ボリューとノ（−フルオロデカリンの比を１０
：１とした。この溶液をキャストし、フィルムを得た。<Example-2> As polyacetylene, poly-t-butyl abutylene (
Mω; ~400,000) was used and dissolved in Guihoon 3 (trade name) as a solvent. Dissolve fluorodecalin in this and adjust the ratio of volume to fluorodecalin to 10.
:1. This solution was cast to obtain a film.
このフィルムの気体透過性は、酸素透過係数が、１．２
５Ｘ １０ （ｃｃ・ｃｍ、／Ｃｄ−π・ｃｔａｌｉ
ｑ ） 、酸素と窒素の分離比として、３．６が得られ
た。The gas permeability of this film has an oxygen permeability coefficient of 1.2.
5X 10 (cc・cm, /Cd−π・ctali
q), a separation ratio of 3.6 between oxygen and nitrogen was obtained.
〈実施例−３〉
実施例−１または２の方法を用い、フィルムを作成し、
気体透過性を測定した。結果を表に示す。<Example-3> Using the method of Example-1 or 2, a film was created,
Gas permeability was measured. The results are shown in the table.
以下余白
発明の効果
以上要するに本発明は嵩高い置換基を有し、歪のかかっ
たポリアセチレンに過弗化物を混入してなる気体透過膜
を提供するもので、気体透過性に極めて優れる利点を有
する。The following is a margin. Effects of the Invention In short, the present invention provides a gas permeable membrane made by mixing perfluoride into strained polyacetylene having bulky substituents, and has the advantage of extremely excellent gas permeability. .
Claims (2)
基、フェニル基、オルガノシリル基よりなる群から選ば
れた基または原子を置換基として有する、１置換ポリア
セチレン１，２置換ポリアセチレンのいずれか一方また
は両方からなる母材に、酸素溶解性の大なる過弗化物を
添加してなることを特徴とする気体透過膜。(1) One or both of 1-substituted polyacetylene and 1- and 2-substituted polyacetylene having as a substituent a group or atom selected from the group consisting of a halogen atom, an alkyl group, a halogenated alkyl group, a phenyl group, and an organosilyl group. A gas permeable membrane characterized by being made by adding a perfluoride having a high oxygen solubility to a base material consisting of.
ロテトラヒドロフラン、パーフルオロトリブチルアミン
より選ばれた一種類またはその混合物であることを特徴
とする特許請求の範囲第１項記載の気体透過膜。(2) The gas permeable membrane according to claim 1, wherein the perfluoride is one selected from perfluorodecalin, perfluorotetrahydrofuran, and perfluorotributylamine, or a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59157831A JPS6135824A (en) | 1984-07-27 | 1984-07-27 | Gas permeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59157831A JPS6135824A (en) | 1984-07-27 | 1984-07-27 | Gas permeable membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6135824A true JPS6135824A (en) | 1986-02-20 |
| JPH0365223B2 JPH0365223B2 (en) | 1991-10-11 |
Family
ID=15658279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59157831A Granted JPS6135824A (en) | 1984-07-27 | 1984-07-27 | Gas permeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6135824A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657564A (en) * | 1985-12-13 | 1987-04-14 | Air Products And Chemicals, Inc. | Fluorinated polymeric membranes for gas separation processes |
| JPS62227411A (en) * | 1986-03-28 | 1987-10-06 | Shin Etsu Chem Co Ltd | Production by separation membrane |
| JPS6349221A (en) * | 1986-08-19 | 1988-03-02 | Matsushita Electric Ind Co Ltd | Hybrid membrane for separating gas |
| WO2010104044A1 (en) * | 2009-03-09 | 2010-09-16 | 住友化学株式会社 | Co2 permeation barrier membrane |
| WO2016047351A1 (en) * | 2014-09-22 | 2016-03-31 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separator and gas separation method |
-
1984
- 1984-07-27 JP JP59157831A patent/JPS6135824A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657564A (en) * | 1985-12-13 | 1987-04-14 | Air Products And Chemicals, Inc. | Fluorinated polymeric membranes for gas separation processes |
| JPS62227411A (en) * | 1986-03-28 | 1987-10-06 | Shin Etsu Chem Co Ltd | Production by separation membrane |
| JPH0423571B2 (en) * | 1986-03-28 | 1992-04-22 | Shinetsu Chem Ind Co | |
| JPS6349221A (en) * | 1986-08-19 | 1988-03-02 | Matsushita Electric Ind Co Ltd | Hybrid membrane for separating gas |
| WO2010104044A1 (en) * | 2009-03-09 | 2010-09-16 | 住友化学株式会社 | Co2 permeation barrier membrane |
| WO2016047351A1 (en) * | 2014-09-22 | 2016-03-31 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separator and gas separation method |
| JPWO2016047351A1 (en) * | 2014-09-22 | 2017-06-08 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separation device, and gas separation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0365223B2 (en) | 1991-10-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |