JPS63141626A - Permselective membrane for gas - Google Patents
Permselective membrane for gasInfo
- Publication number
- JPS63141626A JPS63141626A JP28702386A JP28702386A JPS63141626A JP S63141626 A JPS63141626 A JP S63141626A JP 28702386 A JP28702386 A JP 28702386A JP 28702386 A JP28702386 A JP 28702386A JP S63141626 A JPS63141626 A JP S63141626A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- permselective membrane
- polyacetylene
- acid ester
- dicarboxylic acid
- 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 13
- -1 dicarboxylic acid ester Chemical class 0.000 claims abstract description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001197 polyacetylene Polymers 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000007870 radical polymerization initiator Substances 0.000 abstract description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JHYLUAZDEONDSF-UHFFFAOYSA-N dibutyl but-2-ynedioate Chemical compound CCCCOC(=O)C#CC(=O)OCCCC JHYLUAZDEONDSF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BLTIOLPUMPDFSF-UHFFFAOYSA-N methyl(prop-1-ynyl)silane Chemical compound C[SiH2]C#CC BLTIOLPUMPDFSF-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 230000005855 radiation Effects 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
- 238000003756 stirring Methods 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は混合気体から特定の気体を濃縮分離するのに用
いる選択性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 selective gas permeable membrane used to concentrate and separate a specific gas from a gas mixture.
従来の技術
近年、混合気体より特定の気体を濃縮分離するために選
択的透過性を有する高分子膜を用いる方法が盛んに研究
、実用化されている。2. Description of the Related Art In recent years, methods using selectively permeable polymer membranes have been actively researched and put into practical use in order to concentrate and separate a specific gas from a mixed gas.
例えば天然ガスからのヘリウム採取や、工場排ガスより
の水素回収、などがあるが、中でも大気中から酸素を選
択的に透過させて酸素富化空気を作る技術は応用分野が
広く、各種化学プロセス、汚泥処理、燃焼プロセス、医
療用等、産業界に与える影響は極めて犬である。このよ
うな技術に利用される高分子膜に求められる特性として
は、分離すべき気体の選択性と気体透過性が共に大きく
、且つ長時間の運用に際し、耐熱性、耐湿性、耐薬品性
があり、機械的にも十分な強度があることである。Examples include helium extraction from natural gas and hydrogen recovery from factory exhaust gas, but the technology to create oxygen-enriched air by selectively permeating oxygen from the atmosphere has a wide range of applications, including various chemical processes, The impact it has on industries such as sludge treatment, combustion processes, and medical uses is extremely significant. The properties required of polymer membranes used in such technology include high selectivity for the gases to be separated and gas permeability, as well as high heat resistance, moisture resistance, and chemical resistance for long-term operation. It also has sufficient mechanical strength.
発明が解決しようとする問題点
現在知られている高分子の中でも、特に気体透過性に浸
れるものさして、ポＩＪ ト１，１メチルシリルプロピ
ン（ＰＭＳＰ）では酸素透過係数ｐ ｏ２が１．６０
：＜ １０ ｃｃ −ｃｍｌｃｒＡ ・ｓｅｃ・ｃｍｌ
（ｇシリコーンゴムでばＦｏ２が〜６．ＯＸ １０’
ｃｃ −ｃｒｒｙｃｒｉｌ ・ｓｅｃ・ｃｍＨｇ等があ
るが、これらは酸素と窒素の分離係数α （Ｐｏｚ／
ＰＪ）は前者が約１．４後者で約２０程度でしかない。Problems to be Solved by the Invention Among currently known polymers, one that has particularly high gas permeability is POIJ 1,1 methylsilylpropyne (PMSP), which has an oxygen permeability coefficient po2 of 1. 60
:< 10 cc-cmlcrA ・sec・cml
(For silicone rubber, Fo2 is ~6.OX 10'
cc - crrycril ・sec・cmHg, etc., but these are based on the separation coefficient α of oxygen and nitrogen (Poz/
PJ) is only about 20, with the former being about 1.4 and the latter.
一方分離係数が大きい高分子材料は多数あるが、いずれ
も気体透過性が悪く、例えばポリフェニレンオキサイド
ではαが約４０と大きくなるがＰＯ２は２．８ Ｘ １
０ｃｃ −ｃｒｒｙ’ｃｒＡ−ｓｅｅ−ｃｍ Ｉ−Ｉ
ｇと極めて小さい。このように高分子膜では一般に気体
透過性と気体選択性とは一方が大きくなるともう一方が
低下するという関係にあり、特定の気体を高濃度で多量
に分離できるという選択性気体透過膜はまだ得られてい
なかった。On the other hand, there are many polymeric materials with large separation coefficients, but they all have poor gas permeability.For example, polyphenylene oxide has a large α of about 40, but PO2 is 2.8 x 1
0cc -crry'crA-see-cm I-I
g, which is extremely small. In general, the relationship between gas permeability and gas selectivity in polymer membranes is such that as one increases, the other decreases, and selective gas permeable membranes that can separate large amounts of specific gases at high concentrations have not yet been developed. I wasn't getting it.
本発明は上記のような問題点を解決するもので、気体透
過性と気体選択性の両方に優れた特性を有する選択性気
体透過膜を提供することを目的とするものである。The present invention solves the above-mentioned problems, and aims to provide a selective gas permeable membrane having excellent characteristics in both gas permeability and gas selectivity.
問題点を解決するための手段
本発明は、一般式が
０Ｒ１
（但し、Ｊ Ｒ，’は炭素数が１〜１０の範囲である
アルキル基、フェニル基を示し′、ｎは重合度を示す）
で示されるポリアセチレンジカルボン酸エステルより成
る選択性気体透過膜により、上記の問題点を解決するも
のである。Means for Solving the Problems The present invention has a general formula of 0R1 (wherein JR,' represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n represents the degree of polymerization).
The above-mentioned problems are solved by a selective gas permeable membrane made of a polyacetylene dicarboxylic acid ester shown in the following.
作用
上記の本発明のポリアセチレンジカルボン酸エステルは
該尚するモノマーの単独、又は他のモノマーとの共重合
により、容易に成膜性、酸素透過性にすぐれたポリマー
を与えることが判明した。Function: It has been found that the above-mentioned polyacetylene dicarboxylic acid ester of the present invention can easily provide a polymer with excellent film-forming properties and oxygen permeability by copolymerizing the monomer alone or with other monomers.
本発明に特徴的に用いられるポリアセチレンジカルボン
酸エステルのＲ，Ｒ’としては炭素数が１〜１０のアル
キル基、例えばメチル基、エチル基、インプロピル基、
ｎ−ブチル基、インブチル基、ｆｅｒｆ −７’ｆル基
、シクロヘキシル基、ネオペンチル基、フェニル基など
を例示することが出来る。これらのエステルモノマーは
通常当業者にとって既知のエステル化法により容易に合
成可能であり、或は一部市販の試薬の利用が可能である
。R and R' of the polyacetylene dicarboxylic acid ester characteristically used in the present invention include an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an inpropyl group,
Examples include n-butyl group, inbutyl group, ferf-7'f group, cyclohexyl group, neopentyl group, and phenyl group. These ester monomers can be easily synthesized by esterification methods known to those skilled in the art, or some commercially available reagents can be used.
本発明の特徴である気体透過性にすぐれた高分子物を得
るには、適当なラジカル重合開始剤の存在下、溶媒中で
加熱重合することにより目的の重合物を得ることができ
る。重合開始剤としては、一般的な重合開始剤、例えば
有機過酸化物、アゾ化合物、ハロゲン化チタン、ハロゲ
ン化モリブデン、光、放射線などを利用することが出来
、特に金属ハロゲン化物が有効でちった。得られた高分
子物の重合度は数１ｏｏｏ〜数１０万であり、気体透過
膜用としては、致方程度以上が好ましい特性を与えた。In order to obtain a polymer with excellent gas permeability, which is a feature of the present invention, the desired polymer can be obtained by heating polymerization in a solvent in the presence of a suitable radical polymerization initiator. As a polymerization initiator, general polymerization initiators such as organic peroxides, azo compounds, titanium halides, molybdenum halides, light, and radiation can be used, and metal halides are particularly effective. . The degree of polymerization of the obtained polymer was from several 10,000 to several 100,000, and for gas permeable membranes, a degree of polymerization of about 100,000 or more gave preferable characteristics.
生成重合体は、例えばテトラヒドロフラン、トルエンの
有機溶媒に可溶で、これらの溶液からキャスト法、水面
展開法などにより容易に成膜することが可能であった。The resulting polymer was soluble in organic solvents such as tetrahydrofuran and toluene, and it was possible to easily form a film from these solutions by a casting method, a water surface spreading method, or the like.
生成薄膜の気体透過性は酸素の透過係数が１０〜１０
ｃｃ −ｃｒｇ／ｃｒ＋Ｌｓｅｃ・■Ｈｇと極めて犬き
く、また酸素／窒素の選択性も、２８〜４．５を示し、
極めてすぐれた特性を有するものである。The gas permeability of the produced thin film is such that the oxygen permeability coefficient is 10 to 10.
cc-crg/cr+Lsec・■Hg, which is extremely high, and the oxygen/nitrogen selectivity is 28 to 4.5,
It has extremely excellent properties.
実施例
以下実施例を用いて本発明を説明するが、本発明はこれ
らによって、何らの制限を受けるものでは無い。EXAMPLES The present invention will be explained below using examples, but the present invention is not limited in any way by these examples.
過剰のｎ−ブチルアルコール中に硫酸触媒下、アセチレ
ンジカルボン酸を加え、加熱下４日間攪拌反応させた。Acetylene dicarboxylic acid was added to excess n-butyl alcohol under a sulfuric acid catalyst, and the mixture was stirred and reacted with heating for 4 days.
反応抜水を加え、エーテルにて抽出した。エーテル及び
溶媒回収後、ジ−ｎ−ブチルアセチレンジカルボキシレ
ートを沸点（ｂｐ、）１００〜１０２：／ １ ｍｍＨ
ｇの減圧蒸留によって得た。Reaction water was added, and the mixture was extracted with ether. After ether and solvent recovery, di-n-butyl acetylene dicarboxylate was heated to boiling point (bp, ) 100-102:/1 mmH.
It was obtained by vacuum distillation of g.
トルエン１００ ｍｌ中に前記ジ−ｎ−ブチルカルボン
酸エステル１０ｇを溶解し、五塩化タンタル０１ｇを加
え８００窒素気流化２４時間攪拌反応させた。反応後メ
タノール中に投入し、重合物を得た。ＧＰＣ測定による
分子量は約１５万を示した。10 g of the above di-n-butylcarboxylic acid ester was dissolved in 100 ml of toluene, 01 g of tantalum pentachloride was added, and the mixture was reacted with stirring for 24 hours under a stream of nitrogen at 800 ml. After the reaction, the mixture was poured into methanol to obtain a polymer. The molecular weight determined by GPC measurement was approximately 150,000.
このポリマーをトルエンに溶解しキャストしてフィルム
を得、気体透過性を測定した結果、酸素の透過係数が３
．２Ｘ １０ ｃｃ −ｃｒｒｙ’ｃｒＡ・５代・巾１
−Ｉ ｇを示し、窒素との分離係数は４．３を示した。This polymer was dissolved in toluene and cast to obtain a film, and as a result of measuring gas permeability, the oxygen permeability coefficient was 3.
．． 2X 10 cc -crry'crA, 5th generation, width 1
-Ig, and the separation coefficient from nitrogen was 4.3.
発明の効果
以上要するに本発明は、一般式が
（但し、Ｊ Ｒ’は炭素数が、１〜１０の範囲である
アルキル基、フェニル基を示し、ｎは重合度を示す）で
示されるポリアセチレンジカルボン酸エステルより成る
選択性気体透過膜を提供するもので、選択性、透過性と
もに優れた特性を有する利点を有する。Effects of the Invention In short, the present invention provides a polyacetylene dicarboxylic compound represented by the general formula (wherein JR' represents an alkyl group or phenyl group having a carbon number ranging from 1 to 10, and n represents the degree of polymerization). It provides a selective gas permeable membrane made of acid ester, and has the advantage of having excellent properties in both selectivity and permeability.
Claims (1)
ルキル基、フェニル基を示し、ｎは重合度を示す） で示されるポリアセチレンジカルボン酸エステルより成
る選択性気体透過膜。[Claims] General formulas include ▲mathematical formulas, chemical formulas, tables, etc.▼ (However, R and R' represent an alkyl group or phenyl group having 1 to 10 carbon atoms, and n is a polymerized A selective gas permeable membrane made of polyacetylene dicarboxylic acid ester (indicating the degree of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28702386A JPS63141626A (en) | 1986-12-02 | 1986-12-02 | Permselective membrane for gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28702386A JPS63141626A (en) | 1986-12-02 | 1986-12-02 | Permselective membrane for gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63141626A true JPS63141626A (en) | 1988-06-14 |
Family
ID=17712040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28702386A Pending JPS63141626A (en) | 1986-12-02 | 1986-12-02 | Permselective membrane for gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63141626A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015029980A (en) * | 2013-08-06 | 2015-02-16 | 国立大学法人室蘭工業大学 | Carbon dioxide separation material |
-
1986
- 1986-12-02 JP JP28702386A patent/JPS63141626A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015029980A (en) * | 2013-08-06 | 2015-02-16 | 国立大学法人室蘭工業大学 | Carbon dioxide separation material |
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