JPS63100917A - Gas permselective membrane and its manufacture - Google Patents
Gas permselective membrane and its manufactureInfo
- Publication number
- JPS63100917A JPS63100917A JP24626986A JP24626986A JPS63100917A JP S63100917 A JPS63100917 A JP S63100917A JP 24626986 A JP24626986 A JP 24626986A JP 24626986 A JP24626986 A JP 24626986A JP S63100917 A JPS63100917 A JP S63100917A
- Authority
- JP
- Japan
- Prior art keywords
- permeable membrane
- selectively permeable
- amine
- gas
- crosslinking agent
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 150000002894 organic compounds Chemical class 0.000 claims abstract 7
- 239000007789 gas Substances 0.000 claims description 40
- 125000001174 sulfone group Chemical group 0.000 claims description 17
- 238000010382 chemical cross-linking Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- 150000001412 amines Chemical group 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims 2
- 150000003141 primary amines Chemical class 0.000 claims 2
- 238000000034 method Methods 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 14
- 229920006380 polyphenylene oxide Polymers 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 6
- -1 Poly(2,6-dimethylphenylene oxide) Polymers 0.000 abstract description 6
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 abstract description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 150000003457 sulfones Chemical class 0.000 abstract 2
- 229920002863 poly(1,4-phenylene oxide) polymer Polymers 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- ICMZFZGUTLNLAJ-UHFFFAOYSA-N 2,6-dimethyl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound CC1=CC=CC2(C)OC12 ICMZFZGUTLNLAJ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はガス選択透過性膜に関し、更に詳しくはスルホ
ン基を置換基として有するポリフェニレンオキサイドが
化学架橋剤によって架橋されたガス選択透過性膜に関す
る。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a gas selectively permeable membrane, and more particularly to a gas selectively permeable membrane in which polyphenylene oxide having a sulfone group as a substituent is crosslinked with a chemical crosslinking agent. .
（従来の技術〕
近年ガス混合物の分離、精製をガス選択透過性膜で行な
うことが、積極的に検討されている。(Prior Art) In recent years, the use of gas selectively permeable membranes to separate and purify gas mixtures has been actively studied.
即ち空気より酸素を選択的に透過させて酸素富化空気を
得、医療あるいは燃焼システムに利用する試み、あるい
は石炭、天然ガス、オイルサンド等を原料に、改質、熱
処理を施すことにより得られる合成ガス又はコークス炉
の廃ガスから水素を選 □択的に透過させ、−酸化炭素
、メタン等のガスと分離、精製し、これらガスを出発原
料としてメタノール、エタノール等の基礎化学品を製造
する試み、更には天然ガスからのヘリウム回収の試み等
がある。In other words, oxygen-enriched air can be obtained by selectively permeating oxygen from air and used in medical treatment or combustion systems, or it can be obtained by reforming or heat-treating coal, natural gas, oil sand, etc. as raw materials. Hydrogen is selectively permeated from synthesis gas or coke oven waste gas, separated from gases such as carbon oxide and methane, and purified, and these gases are used as starting materials to produce basic chemicals such as methanol and ethanol. There are also attempts to recover helium from natural gas.
これらの用途に期待されるガス選択透過性膜に必要な特
性はガス選択透過性、ガス透過速度とも大きく、耐熱性
、耐薬品性に優れていることである。しかしながら市販
されている高分子重合体だけではこれらの特性を全て満
足することはできない０
このような中で、コスト、耐熱性に優れたポリフェニレ
ンオキサイドが検討されている、例えば米国特許第３，
５５０，８４４号は、２，６−シメチルフエニレンオキ
サイドが機械的強度、フィルム形成能と共に高いガス透
過速度を示している。しかしながら、耐薬品性やガス選
択透過性は低い。The characteristics required for gas selectively permeable membranes that are expected to be used in these applications are high gas selective permeability and gas permeation rate, and excellent heat resistance and chemical resistance. However, commercially available polymers alone cannot satisfy all of these properties. Under these circumstances, polyphenylene oxide, which has excellent cost and heat resistance, is being studied; for example, U.S. Patent No. 3,
No. 550,844 discloses that 2,6-dimethylphenylene oxide exhibits high gas permeation rate as well as mechanical strength and film-forming ability. However, chemical resistance and gas selective permeability are low.
米国特許第３，７０９，７７４号、第８，７６２，１３
６号及び第３，８５２，３８８ 号にも同様なことが
示されている。U.S. Patent Nos. 3,709,774 and 8,762,13
No. 6 and No. 3,852,388 also show the same thing.
米国特許第３，７３５，５５９ 号にはスルホン化ポリ
フェニレンオキサイド膜が高い選択透過性を有スルこと
が示されている。しかしながら水素イオン型スルホン基
を有するポリフェニレンオキサイドは熱的に不安定で、
架橋や脱水反応による劣化があることも併記されている
。同様なことが米国特許第３，７８０，４９６ 号にも
示されている。これに対しハロゲン化ポリフェニレンオ
キサイドをアミン架橋した膜が特開昭６０−５１５２５
に提案されており、機械的強度、耐熱性、耐薬品性とも
浸れているが、ガス選択透過性は低い。US Pat. No. 3,735,559 shows that sulfonated polyphenylene oxide membranes have high permselectivity. However, polyphenylene oxide with hydrogen ion-type sulfone groups is thermally unstable;
It is also stated that there is deterioration due to crosslinking and dehydration reactions. A similar situation is shown in US Pat. No. 3,780,496. On the other hand, a film in which halogenated polyphenylene oxide was crosslinked with amine was disclosed in Japanese Patent Application Laid-Open No. 60-51525.
Although it has excellent mechanical strength, heat resistance, and chemical resistance, its gas selective permeability is low.
（発明の構成）
本発明のガス選択透過性膜は、構造式；で示される繰り
返し単位を有し、Ｒ１，Ｒ２が各々独立に水素原子また
はスルホン基であり、該スルホン基の数が、該繰り返し
単位当り０．０１個以上である重合体が化学架橋剤によ
って架橋されていることを特徴とする。(Structure of the Invention) The gas selectively permeable membrane of the present invention has a repeating unit represented by the structural formula; R1 and R2 are each independently a hydrogen atom or a sulfone group, and the number of the sulfone groups is It is characterized in that 0.01 or more polymers per repeating unit are crosslinked with a chemical crosslinking agent.
この結果、本発明の膜はガス選択透過性、ガス透過速度
が大きい上に、耐熱性、耐薬品性にも匿れた特長を有す
る。すなわち、スルホン化ポリフェニレンオキサイド単
独では、ガス選択透過性、ガス透過速度共に大きく、例
えば、酸素の窒素に対する選択透過性（αＯ”／Ｎ２）
は７にも達するが、耐熱性、安定性に欠ける問題点があ
る。例えば、１２０°Ｃの温度雰囲気で１時間加熱する
と脱水反応が起こり、膜は著しく劣化し、ガス透過特性
や機械的強度を維持するのが困難となる。このような膜
はガス選択透過性膜として実用には供し得ない。しかし
ながら本発明によれば、化学架橋剤がスルホン化ポリフ
ェニレンオキサイドの不安定な水素イオンを除去し、こ
の位置で共有結合を形成させると同時に高分子鎖間で架
橋を生ぜしめるため、耐熱性、安定性が向上し、その結
果高いガス分離性能を維持することが可能となり、さら
にはより高いガス選択透過性を得ることもできる。As a result, the membrane of the present invention not only has high gas selective permeability and high gas permeation rate, but also has excellent heat resistance and chemical resistance. That is, when sulfonated polyphenylene oxide alone is used, both the gas selective permeability and the gas permeation rate are high; for example, the selective permeability of oxygen to nitrogen (αO''/N2) is high.
Although it reaches a value of 7, it has the problem of lacking heat resistance and stability. For example, when heated in an atmosphere at a temperature of 120° C. for 1 hour, a dehydration reaction occurs and the membrane deteriorates significantly, making it difficult to maintain gas permeability and mechanical strength. Such a membrane cannot be used practically as a gas selectively permeable membrane. However, according to the present invention, the chemical crosslinking agent removes unstable hydrogen ions from the sulfonated polyphenylene oxide, forms a covalent bond at this position, and at the same time creates crosslinks between polymer chains, resulting in improved heat resistance and stability. As a result, it is possible to maintain high gas separation performance, and even higher gas selective permeability can be obtained.
本発明で用いるスルホン化ポリフェニレンオキサイドの
原料であるポリフェニレンオキサイド（以下ＰＰＯと略
記する〕は、２，６−シメチルフエノールを塩化第１銅
−ビリジンコンプレックスを触媒として、酸化カップリ
ング反応が得られ構造式；
で示される繰り返し単位を有するボ！Ｊ（２，６−シメ
チルフエニレンオキサイド）である。 このＰＰＯのク
ロロホルム溶液をクロロスルホン酸で反応させてクロロ
スルホン化ＰＰＯを得た後、加水分解することによって
構造式；
（ｎ；自然数、Ｒ１，Ｒ２；各々独立に水素原子もしく
はスルホン基）
で示される繰り返し単位を有するスルホン化ＰＰＯが得
られる。Polyphenylene oxide (hereinafter abbreviated as PPO), which is the raw material for the sulfonated polyphenylene oxide used in the present invention, has a structure obtained by an oxidative coupling reaction of 2,6-dimethylphenol using a cuprous chloride-pyridine complex as a catalyst. It is Bo!J (2,6-dimethylphenylene oxide) having a repeating unit represented by the formula: A chloroform solution of this PPO is reacted with chlorosulfonic acid to obtain chlorosulfonated PPO, and then hydrolyzed. By doing so, a sulfonated PPO having a repeating unit represented by the structural formula: (n: natural number, R1, R2: each independently a hydrogen atom or a sulfone group) is obtained.
このスルホン化ＰＰＯは、繰り返し単位当り０．０１個
以上のスルホン基を有していることが好ましく、０．１
個以上であることがさらに好ましい。This sulfonated PPO preferably has 0.01 or more sulfone groups per repeating unit, and 0.1
It is more preferable that the number is at least 1.
スルホン基の数が繰り返し単位当り０．０１個未満の場
合は、重合体全体の特性に与えるスルホン基の影響が小
さく本発明の特徴が得られにくいためで、０．１個以上
となると本発明の特徴はより顕在化してくる。しかしな
がら、スルホン基の数があまり大きくなりすぎると重合
体の極性が大きくなりすぎて架橋等の処理を行なう際の
取扱いが困難になることがある。従ってスルホン基を導
入する個数の上限は後処理条件との兼ねおいて適宜決定
されることが好ましい。If the number of sulfone groups is less than 0.01 per repeating unit, the effect of the sulfone groups on the properties of the entire polymer is small and it is difficult to obtain the characteristics of the present invention, and if the number is 0.1 or more, the present invention characteristics become more apparent. However, if the number of sulfone groups becomes too large, the polarity of the polymer may become too large, making it difficult to handle during treatments such as crosslinking. Therefore, it is preferable that the upper limit of the number of sulfone groups to be introduced is appropriately determined in consideration of the post-treatment conditions.
スルホン化ＰＰＯの溶媒としては、メタノール、エタノ
ール、イソプロパツール、【−ブタノール等のアルコー
ル類、ジメチルホルムアミド、ジメチルアセトアミド等
のアミド類、ジメチルスルオキシド、Ｎメチル２ピロリ
ドン等の極性有機溶媒やその混合物、もしくはそれらの
水との混合物のホカ、クロロホルム、ジクロルメタン等
の塩素系溶媒も用いることができ適宜選択されるが、持
に好ましくはアルコール類が選択される。Solvents for sulfonated PPO include alcohols such as methanol, ethanol, isopropanol, [-butanol, amides such as dimethylformamide and dimethylacetamide, polar organic solvents such as dimethyl sulfoxide, N-methyl 2-pyrrolidone, and mixtures thereof. or a mixture thereof with water, chlorinated solvents such as chloroform, dichloromethane, etc. can also be used and are appropriately selected, but alcohols are most preferably selected.
スルホン化ＰＰＯの溶液は、ドクターナイフ等でフィル
ム状に成形され、溶媒を蒸発させて乾燥されてもよいが
、実用的には多孔性のフィルム上や孔内部もしくは多孔
性中空系の外面、内面や孔内部に薄層に塗布され、溶媒
を蒸発させ乾燥される。The sulfonated PPO solution may be formed into a film with a doctor knife or the like and dried by evaporating the solvent, but in practical terms, it may be formed on a porous film, inside the pores, or on the outer or inner surface of a porous hollow system. It is applied in a thin layer inside the pores and dried by evaporating the solvent.
このようにして複合化される際には、溶液の展延性をよ
くするために界面活性剤を適量添加してもよい。When compounding in this way, an appropriate amount of surfactant may be added to improve the spreadability of the solution.
このようにして得られたスルホン化ＰＰＯは化学架橋剤
によって架橋される。架橋剤としては、アミン系有機化
合物が好ましく用いられる。The sulfonated PPO thus obtained is crosslinked with a chemical crosslinker. As the crosslinking agent, amine organic compounds are preferably used.
ｗに好ｔｔ、＜は、メチルアミン、エチルアミン、ｎ−
ブチルアミン等の１級アミン、ジメチルアミン、エチル
メチルアミン等の２級アミン、エチレンジアミン、ｐ−
フェニレンジアミン等のジアミン、トリエチレンテトラ
ミン等のポリアミンのいずれかもしくはこれら２種以上
の混合物が選ばれさらにはエチレンジアミン、トリエチ
レンテトラミンが好ましく用いられる。これらの化学架
橋剤は、気体状で用いられてもよいが、さらに骸好まし
くは水溶液として用いられる。化学架橋剤水溶液の濃度
は得ようとする膜の架橋の程度により適宜選択されるべ
きである。ここで化学架橋剤水溶液中にスルホン化ポリ
スルホンの膜を浸漬する際に膜の劣化をおこさない条件
でしかも充分な架橋反応をおこさせるためには化学架橋
剤水溶液の水素イオン濃度をｐＨ１１以下の弱アルカリ
性とすることが好ましい。tt is preferable to w, < is methylamine, ethylamine, n-
Primary amines such as butylamine, secondary amines such as dimethylamine and ethylmethylamine, ethylenediamine, p-
Diamines such as phenylenediamine, polyamines such as triethylenetetramine, or a mixture of two or more thereof are selected, and ethylenediamine and triethylenetetramine are preferably used. These chemical crosslinking agents may be used in gaseous form, but are more preferably used in the form of an aqueous solution. The concentration of the chemical crosslinking agent aqueous solution should be appropriately selected depending on the degree of crosslinking of the membrane to be obtained. When immersing a sulfonated polysulfone membrane in an aqueous solution of a chemical crosslinking agent, in order to cause a sufficient crosslinking reaction without causing deterioration of the membrane, the hydrogen ion concentration of the aqueous solution of a chemical crosslinking agent must be kept at a pH of 11 or less. It is preferable to make it alkaline.
化学架橋剤蒸気や水溶液に接触させ架橋を完了させた膜
は充分に水洗された後、乾燥されて本発明のガス選択透
過性膜が得られる。The membrane that has been brought into contact with chemical crosslinking agent vapor or an aqueous solution to complete crosslinking is sufficiently washed with water and then dried to obtain the gas selectively permeable membrane of the present invention.
以下実施例をもって本発明をさらに説明する。The present invention will be further explained below with reference to Examples.
実施例１゜
重合体の繰り返し単位当り０．２９個のスルホン基を有
するスルホン化ポリフェニレンオキサイド３．５ｇをメ
タノール２０ｇに溶解させた。この溶液を平滑な平面を
有するガラス基板上に、ドクターナイフを用いてＱ、０
１ｍｍの厚みに流延した後５０°Ｃの温度雰囲気で乾燥
させ膜を得た。この膜を１０％エチレンジアミン水溶液
に１時間浸漬した。このエチレンジアミン水溶液は塩酸
にてｐＨ８としたものである。架橋後、脱イオン化水で
十分水洗したのち５０’Ｃの温度雰囲気にて乾燥させ緻
密な膜を得た。この膜の透過特性を評価したところ
酸素、窒素分離特性
二酸化炭素、メタン分離特性
であった。Example 1 3.5 g of sulfonated polyphenylene oxide having 0.29 sulfone groups per repeating unit of the polymer was dissolved in 20 g of methanol. Using a doctor knife, apply this solution onto a glass substrate with a smooth surface, Q, 0.
After casting to a thickness of 1 mm, the film was dried in an atmosphere at a temperature of 50°C to obtain a film. This membrane was immersed in a 10% aqueous ethylenediamine solution for 1 hour. This aqueous ethylenediamine solution was adjusted to pH 8 with hydrochloric acid. After crosslinking, it was thoroughly washed with deionized water and then dried in an atmosphere at a temperature of 50'C to obtain a dense film. When the permeation characteristics of this membrane were evaluated, it was found to have good oxygen and nitrogen separation characteristics and carbon dioxide and methane separation characteristics.
実施例２゜
実施例１と同一条件でスルホン化ポリフェニレンオキサ
イド膜を得た。Example 2 A sulfonated polyphenylene oxide film was obtained under the same conditions as in Example 1.
この膜を１５％トリエチレンテトラミン水溶液に１時間
浸漬した。このトリエチレンテトラミン水溶液は塩酸に
てｐＨ１０としたものである。架橋後説イオン化水で十
分水洗したのち５０°Ｃの温度雰囲気にて乾燥させ緻密
な膜を得た。この膜の透過特性を評価したところ
酸素、窒素分離特性
二酸化炭素、メタン分離特性
であった。This membrane was immersed in a 15% triethylenetetramine aqueous solution for 1 hour. This triethylenetetramine aqueous solution was adjusted to pH 10 with hydrochloric acid. Post-Crosslinking After thorough washing with ionized water, it was dried in an atmosphere at a temperature of 50°C to obtain a dense film. When the permeation characteristics of this membrane were evaluated, it was found to have good oxygen and nitrogen separation characteristics and carbon dioxide and methane separation characteristics.
（発明の効果）
本発明によれば、ガス選択透過性、ガス透過速度共にす
ぐれ、耐熱性、耐薬品性にも優れたガス選択透過性膜が
得られる。かかる膜は、空気からの酸素濃縮、石油化学
副生ガスや天然ガスからの炭酸ガスの分離精製やメタン
濃縮などに有用である。(Effects of the Invention) According to the present invention, a gas selectively permeable membrane having excellent gas selective permeability and gas permeation rate as well as excellent heat resistance and chemical resistance can be obtained. Such membranes are useful for oxygen concentration from air, separation and purification of carbon dioxide from petrochemical by-product gases and natural gas, and methane concentration.
Claims (12)
独立に水素原子またはスルホン基であり、該スルホン基
の数が、該繰り返し単位当り０．０１個以上である重合
体が化学架橋剤によって架橋されていることを特徴とす
るガス選択透過性膜。(1) Structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n: natural number) It has a repeating unit represented by, R_1 and R_2 are each independently a hydrogen atom or a sulfone group, and the number of the sulfone groups is A gas selectively permeable membrane, characterized in that 0.01 or more polymers per repeating unit are crosslinked with a chemical crosslinking agent.
個以上であることを特徴とする特許請求の範囲第１項記
載のガス選択透過性膜。(2) The number of sulfone groups is 0.1 per repeating unit.
2. The gas selectively permeable membrane according to claim 1, wherein the gas selectively permeable membrane is at least 1.
特徴とする特許請求の範囲第１項記載のガス選択透過性
膜。(3) The gas selectively permeable membrane according to claim 1, wherein the chemical crosslinking agent is an amine-based organic compound.
ン、ジアミン、ポリアミンのいずれか、もしくはこれら
２種以上の混合物であることを特徴とする特許請求の範
囲第３項記載のガス選択透過性膜。(4) Gas selection according to claim 3, wherein the amine-based organic compound is any one of a primary amine, a secondary amine, a diamine, a polyamine, or a mixture of two or more thereof. Permeable membrane.
はトリエチレンテトラミンであることを特徴とする特許
請求の範囲第４項記載のガス選択透過性膜。(5) The gas selectively permeable membrane according to claim 4, wherein the amine-based organic compound is ethylenediamine or triethylenetetramine.
独立に水素原子またはスルホン基であり、該スルホン基
の数が、該繰り返し単位当り０．０１個以上である重合
体を溶媒に溶解させ、製膜し、溶媒を蒸発、乾燥させた
のちに、化学架橋剤によって架橋することを特徴とする
ガス選択透過性膜の製造方法。(6) Structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n: natural number) It has a repeating unit represented by: R_1 and R_2 are each independently a hydrogen atom or a sulfone group, and the number of the sulfone groups A polymer having 0.01 or more per repeating unit is dissolved in a solvent, formed into a film, the solvent is evaporated and dried, and then crosslinked with a chemical crosslinking agent. Membrane manufacturing method.
個以上であることを特徴とする特許請求の範囲第６項記
載のガス選択透過性膜の製造方法。(7) The number of sulfone groups is 0.1 per repeating unit.
7. The method for producing a gas selectively permeable membrane according to claim 6, wherein the number of gas selectively permeable membranes is 2 or more.
特徴とする特許請求の範囲第６項記載のガス選択透過性
膜の製造方法。(8) The method for producing a gas selectively permeable membrane according to claim 6, wherein the chemical crosslinking agent is an amine-based organic compound.
ン、ジアミン、ポリアミンのいずれか、もしくはこれら
２種以上の混合物であることを特徴とする特許請求の範
囲第８項記載のガス選択透過性膜の製造方法。(9) Gas selection according to claim 8, wherein the amine-based organic compound is any one of a primary amine, a secondary amine, a diamine, a polyamine, or a mixture of two or more thereof. Method for manufacturing a permeable membrane.
くはトリエチレンテトラミンであることを特徴とする特
許請求の範囲第９項記載のガス選択透過性膜の製造方法
。(10) The method for producing a gas selectively permeable membrane according to claim 9, wherein the amine-based organic compound is ethylenediamine or triethylenetetramine.
架橋剤水溶液に浸漬することにより架橋を行なうことを
特徴とする特許請求の範囲第６項記載のガス選択透過性
膜の製造方法。(11) A method for producing a gas selectively permeable membrane according to claim 6, characterized in that crosslinking is carried out by using a chemical crosslinking agent as an aqueous solution and immersing the membrane in the aqueous solution of the chemical crosslinking agent.
を加えることによりｐＨ１１以下の弱アルカリ性とする
ことを特徴とする特許請求の範囲第１１項記載のガス選
択透過性膜の製造方法。(12) The method for producing a gas selectively permeable membrane according to claim 11, wherein the chemical crosslinking agent aqueous solution is made weakly alkaline with a pH of 11 or less by adding an inorganic or organic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24626986A JPS63100917A (en) | 1986-10-15 | 1986-10-15 | Gas permselective membrane and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24626986A JPS63100917A (en) | 1986-10-15 | 1986-10-15 | Gas permselective membrane and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63100917A true JPS63100917A (en) | 1988-05-06 |
Family
ID=17146016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24626986A Pending JPS63100917A (en) | 1986-10-15 | 1986-10-15 | Gas permselective membrane and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63100917A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348569A (en) * | 1993-06-30 | 1994-09-20 | Praxair Technology, Inc. | Modified poly(phenylene oxide) based membranes for enhanced fluid separation |
| US5356459A (en) * | 1993-06-30 | 1994-10-18 | Praxair Technology, Inc. | Production and use of improved composite fluid separation membranes |
| US5364454A (en) * | 1993-06-30 | 1994-11-15 | Praxair Technology, Inc. | Fluid separation composite membranes prepared from sulfonated aromatic polymers in lithium salt form |
-
1986
- 1986-10-15 JP JP24626986A patent/JPS63100917A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348569A (en) * | 1993-06-30 | 1994-09-20 | Praxair Technology, Inc. | Modified poly(phenylene oxide) based membranes for enhanced fluid separation |
| US5356459A (en) * | 1993-06-30 | 1994-10-18 | Praxair Technology, Inc. | Production and use of improved composite fluid separation membranes |
| US5364454A (en) * | 1993-06-30 | 1994-11-15 | Praxair Technology, Inc. | Fluid separation composite membranes prepared from sulfonated aromatic polymers in lithium salt form |
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