JPS62277123A - Production of membrane for separating gas - Google Patents
Production of membrane for separating gasInfo
- Publication number
- JPS62277123A JPS62277123A JP12005686A JP12005686A JPS62277123A JP S62277123 A JPS62277123 A JP S62277123A JP 12005686 A JP12005686 A JP 12005686A JP 12005686 A JP12005686 A JP 12005686A JP S62277123 A JPS62277123 A JP S62277123A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- modified
- epoxy
- gas
- separating gas
- 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 description 9
- -1 polysiloxane Polymers 0.000 claims abstract description 17
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 16
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 230000035699 permeability Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000035515 penetration Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は王にシロキサン構造による高分子と！ＶＢ、と
の化合物で大きな気体透過速度と良好な選択性をもった
気体分離用膜の製造方法に関するものである。[Detailed Description of the Invention] Industrial Application Field The present invention is primarily a polymer with a siloxane structure! The present invention relates to a method for producing a gas separation membrane having a high gas permeation rate and good selectivity using a compound of VB.
従来の技術
従来、主として用いられているガス分離、濃縮の方法は
Ｑ）深冷分離方法、■吸着による方法が挙げられる。BACKGROUND OF THE INVENTION Conventionally, methods of gas separation and concentration that have been mainly used include Q) Cryogenic separation method, and (2) Adsorption method.
深冷分離方法は混合χ体を冷却してその各々の沸点差を
利用して蒸留する方法であり、現在大型プラントによっ
て大量に処理されている。The cryogenic separation method is a method of cooling the mixed x-form and distilling it using the difference in their boiling points, and is currently being processed in large quantities in large-scale plants.
深冷分離は分離に賛するエネルギー効率が低いことが欠
点であり、小型化非常に困難である。Cryogenic separation has the disadvantage of low energy efficiency for separation, and is extremely difficult to miniaturize.
吸着による方法は主にゼオライトの各ガスに対する吸着
力の差を利用したものであり、吸着という特性上どうし
てもパッチシステムにならざるを得す、そのため目的分
離ガスが経時時間に対して圧力や濃度が変化したり水蒸
気ガス等が吸着力へ影響を及ぼす等の欠点があった、膜
による分離の方法は原理的に連続方式であリ、分離、濃
縮に要するエネルギーも少くて済むＯ
発明が解決しようとする問題点
気体系の分離、濃縮についての実用化のレベルは液体系
に較べて低い。その理由は気体の透過速度が遅く、選択
比も低いので装置が大型化するためにエネルギー損失も
多くなるためであった。The adsorption method mainly utilizes the difference in the adsorption power of zeolite for each gas, and due to the characteristics of adsorption, it is inevitable to use a patch system. Separation methods using membranes have shortcomings such as changes in adsorption capacity and water vapor gas, etc., which affect the adsorption power.In principle, the separation method using membranes is a continuous method, and requires less energy for separation and concentration.The invention will solve this problem. The practical level of separation and concentration of gas systems is lower than that of liquid systems. The reason for this is that the gas permeation rate is slow and the selectivity is low, which increases the size of the device and increases energy loss.
しだがって、膜によるガスの分離濃縮にとって最も望ま
れていることは、通過速度を速く、選択性を高くするこ
とである。Therefore, what is most desired for gas separation and concentration using a membrane is to increase the passage rate and increase the selectivity.
現在実用化されたもので、両者を満足させる分離濃縮膜
はない。Currently, there is no separation/concentration membrane in practical use that satisfies both requirements.
発明の目的
本発明は上記の事情に鑑みなされたもので、従来の透過
速度より速く且つ比較的高い選択性を合わせもった特性
のある気体分離用膜を製造することができる気体分離用
膜の製造方法を提供することを目的とする。Purpose of the Invention The present invention has been made in view of the above-mentioned circumstances, and provides a gas separation membrane capable of producing a gas separation membrane having characteristics of higher permeation rate than conventional membranes and relatively high selectivity. The purpose is to provide a manufacturing method.
問題点を解決するための手段及び作用
上記の目的を達成するたｂに本発明は多孔質支持膜上に
付着させた両末端エポキシ変−成ジメチルポリシロキサ
ン
（ルー２〜３０ 、 Ｒ−ＣＨｓ 、）と）ＷＥ
、を反応させて両末端アミノ変成ポリシロキサンとした
ものを再度両末端エポキシ変成ポリシロキサンを反応さ
せ必要に応じて上記の反応のうち１つまたは全てを繰り
返して行うように１７だ。Means and Effects for Solving the Problems In order to achieve the above objects, the present invention provides a double-end epoxy-modified dimethylpolysiloxane (R-2-30, R-CHs, R-CHs, ) and) WE
, to form a polysiloxane modified with amino at both ends, and then reacted again with a polysiloxane modified with epoxy at both ends, and one or all of the above reactions are repeated as necessary.
実施例 以下本発明の詳細な説明する。Example The present invention will be explained in detail below.
気体分離用透過膜材料としてジメチルポリシロキサン類
は気体透過係数が高いので主として用いられている。Dimethylpolysiloxanes are mainly used as permeable membrane materials for gas separation because they have a high gas permeability coefficient.
ジメチルポリシロキサンの気体透過係数が高い理由は硅
素原子の直径および原子間結合距離が大きく、さらに分
子同志の絡みつきの原因となる水素結合の傾向が少ない
ので分子間の空間が犬きぐなるためと考えられる。The reason for the high gas permeability coefficient of dimethylpolysiloxane is thought to be that the diameter of the silicon atom and the bond distance between atoms are large, and the space between molecules is narrow because there is less tendency for hydrogen bonds to cause entanglement between molecules. It will be done.
Ｌ７かしポリシロキサン類は一般に物理的強度が弱いの
でその改善のために他の樹脂との共重合が行われたが強
度の上昇のためには透過係数がどうしても犠牲になって
いた。Since L7 polysiloxanes generally have low physical strength, copolymerization with other resins has been carried out to improve this, but the increase in strength inevitably comes at the expense of permeability coefficient.
本発明に係る気体分離膜の製造方法は、両末端エポキシ
変成ポリシロキサンをアンモニヤやアミン等でアミン化
したものを支持膜上で合成したものに再度両末端エポキ
シ変成ポリシロキサンを支持膜上で反応させて分離膜と
したので必要に応じての反応を繰り返すことを骨子とす
る。In the method for producing a gas separation membrane according to the present invention, polysiloxane modified with epoxy at both ends is aminated with ammonia or amine, synthesized on a support membrane, and then polysiloxane modified with epoxy at both ends is reacted again on the support membrane. Since the separation membrane has been made by using this method, the main point is to repeat the reaction as necessary.
すなわち、本発明に係る気体分離用膜の製造方法は、多
孔質支持膜上に付着させた両末端エポキシ変成ジメチル
ポリシロキサン
Ａ ｌｌ
（ルー２〜３０ 、 Ｒ−ＣＭ、 ）とＮＨ，を
反応させて両末端アミン変成ポリシロキサンとしたもの
を再度両末端エポキシ変成ポリシロキサンを反応させ必
要に応じて上記の反応のうち１つまたは全てを繰り返し
て行うことを特徴とするものである。That is, the method for producing a gas separation membrane according to the present invention involves reacting a double-end epoxy-modified dimethylpolysiloxane All (Rue 2-30, R-CM, ) deposited on a porous support membrane with NH. The polysiloxane modified with amine at both ends is reacted again with a polysiloxane modified with epoxy at both ends, and one or all of the above reactions are repeated as necessary.
上記の本発明の方法によりジメチルポリシロキサンの特
徴である分子空間をさらに増大させたところ透過係数は
非常に増加したにもかかわらず膜の物理的強度の低下は
針入度試験結果によるとほとんど見受けられなかった。When the molecular space, which is a characteristic of dimethylpolysiloxane, was further increased by the above method of the present invention, the permeability coefficient was greatly increased, but the penetration test results show that there was almost no decrease in the physical strength of the membrane. I couldn't.
実験の結果、両末端エポキシ変成ポリシロキサンの硅素
原子の数は２〜３０個が適していたが３０個以上では物
理的強度は低下することが針入度試験結果から分った。As a result of experiments, it was found that the suitable number of silicon atoms for the polysiloxane modified with epoxy at both ends was 2 to 30, but it was found from the penetration test results that when the number of silicon atoms exceeded 30, the physical strength decreased.
実施例１
両末端エポキシ変成ジメチルポリシロキサンの２０Ｉｉ
量％ベンゼン溶液中ば平均孔径０．２μの弗素樹脂多孔
質膜を浸析する８引き上げた後に室温で１０分間重直に
して室内放置することによって表面の余乗分を除去する
。その後アンモニャガスと１時間１００℃、ｌ ａ ｔ
ｍ／ ｃｔｄの条件で接触させてアミン化した物を室内
に１時間室温で放置して未反応のアンモニヤを拡散除去
する８表面にアミン化物を付着させた弗素樹脂製多孔質
膜を再度同じ両末端エポキシ変成ジメチルポリシロキサ
ンの２０嘩でベンゼン溶液中に浸析する。Example 1 20Ii of dimethylpolysiloxane modified with epoxy at both ends
A fluororesin porous membrane having an average pore diameter of 0.2 .mu.% is soaked in a % benzene solution.After being pulled up for 8 minutes, the membrane is left in an upright position indoors for 10 minutes at room temperature to remove the surface copolymers. After that, add ammonia gas and heat at 100℃ for 1 hour.
The aminated material was brought into contact under m/ctd conditions and left indoors at room temperature for 1 hour to diffuse and remove unreacted ammonia. Twenty tons of epoxy-terminated dimethylpolysiloxane are immersed in a benzene solution.
その後引き上げて室温で前回向機に１ｏ分間重直にし７
て室内放置して表面の余剰分がなくなツタら１００℃、
１時間エアオーブン中に放ｔし７てエポキシ基とアミノ
基を反応させて高分子化を行ってから取出１て室温まで
放冷の後、ベンゼン中に浸し１．て表面の未反応物を除
去する。After that, lift it up and place it on a rotating machine for 10 minutes at room temperature.
I left it indoors and there was no excess on the surface and the ivy reached 100℃.
The sample was placed in an air oven for 1 hour to react with the epoxy group and amino group to form a polymer, then taken out, left to cool to room temperature, and immersed in benzene. to remove unreacted substances on the surface.
室温でベンゼンをＷ表面から追い出し７た後に重量測定
法により分離用膜の膜厚を求める。表１は両末端エポキ
シ変成ジメチルポリシロキサンの主鎖の長さが変化ｊた
ものを用いて上記した本発明の方法に従って分離用膜を
各々作成また後各棹ガスに対する透過試験を行った結果
である。After benzene is expelled from the W surface at room temperature, the thickness of the separation membrane is determined by gravimetry. Table 1 shows the results of creating separation membranes according to the method of the present invention described above using dimethylpolysiloxane modified with epoxy at both ends and varying the main chain length, and then conducting a permeation test for each rod gas. be.
比較のためにシリコンゴムのベンゼン１０％溶液中に同
じ多孔質膜を浸析させたのちに引き上げ溶剤を除去させ
てから１００℃”２気浴中で１０分間加硫（加硫剤、ビ
ス２−４ジクロールベンゾパーオキサイド）１．たもの
も試料として用いた。For comparison, the same porous membrane was soaked in a 10% benzene solution of silicone rubber, pulled up to remove the solvent, and then vulcanized for 10 minutes in a 100°C gas bath (vulcanizing agent, bis 2 -4 dichlorobenzoperoxide) 1. was also used as a sample.
又試料の物理的強度も針入度試験によって実験を行った
。The physical strength of the sample was also tested using a penetration test.
（以下余白）
表１の結果から、本発明方法によって得らセた膜のＮ、
、 ０． 、 Ｃへ、Ｃ，Ｈ，各ガスに対する透過係
数はポリシロキサン骨格の主鎖の長さが２以上の場合シ
リコンゴム製の分離用膜よりいずれのガスにおいても高
い値を示した。(Left below) From the results in Table 1, it can be seen that the N of the film obtained by the method of the present invention,
, 0. , C, C, and H, the permeability coefficients for each gas showed higher values for all gases than for silicone rubber separation membranes when the main chain length of the polysiloxane skeleton was 2 or more.
オリシロキサンの骨格主鎖の硅素数が大きくなるに従っ
て各気体の透過係数は上昇するが、３０個以上の場合、
膜強度が低下（２て膜破壊が生じた。また針入度試験の
結果からもそれを確認することができた。The permeability coefficient of each gas increases as the number of silicon atoms in the main chain of the orisiloxane skeleton increases, but when it is 30 or more,
The membrane strength decreased (2) and membrane destruction occurred. This was also confirmed from the results of the penetration test.
そのために硅素数は３０個以下、２個以上が望ましい。For this purpose, the number of silicon primes is preferably 30 or less, and preferably 2 or more.
一般に透過係数が上昇すハば” ／７ｖ、の選択比は低
下するがシリコンゴム製の分離用膜に比べて主項の硅素
数が２個〜３０個の範囲では選択比も透過係数も上昇し
ていることがわかる、発明の効果
以上詳述したように、本発明に係る気体分離用膜の製造
方法は、多孔質支持膜上に付着させた両末端エポキシ変
成ジメチルボリシロキサンＨＥ
Ｉ Ｈ（ｒＬ−２〜３０ 、 Ｒ−ＣＨｓ
、 ）とＩＶＨ，、を反応させて両末端アミン変成ポ
リシロキサンとしたものを再度両末端エポキシ変成ポリ
シロキサンを反応させ必要に応じて上記の反応のうち１
つまたは全てを繰り返して行うことを特徴とするもので
ある。In general, the permeability coefficient increases and the selectivity decreases when the permeability coefficient increases, but compared to silicone rubber separation membranes, the selectivity and permeability coefficient increase when the number of silicon atoms in the main term ranges from 2 to 30. Effects of the Invention As described in detail above, the method for producing a gas separation membrane according to the present invention is characterized in that the method for producing a gas separation membrane according to the present invention is characterized in that a double-end epoxy-modified dimethylborosiloxane HE adhered to a porous support membrane is
IH(rL-2~30, R-CHs
, ) and IVH, , to form a polysiloxane modified with amine at both terminals, the polysiloxane modified with epoxy at both terminals is reacted again, and one of the above reactions is carried out as necessary.
It is characterized by repeating one or all of the steps.
また上記の気体分離用膜の製造方法により、従来の透過
速度より速く且つ比較的高い選択性を合わせもった特性
のある気体分離用膜を製造することができる。Further, by the above-described method for producing a gas separation membrane, it is possible to produce a gas separation membrane having characteristics that have a higher permeation rate than conventional membranes and a relatively high selectivity.
Claims (1)
ルポリシロキサン ▲数式、化学式、表等があります▼ （ｎ＝２〜３０、Ｒ＝ＣＨ＿３、） とＮＨ＿３を反応させて両末端アミノ変成ポリシロキサ
ンとしたものを再度両末端エポキシ変成ポリシロキサン
を反応させ必要に応じて上記の反応のうち１つまたは全
てを繰り返して行うことを特徴とする気体分離用膜の製
造方法。[Claims] A double-terminated epoxy-modified dimethylpolysiloxane adhered on a porous support membrane (numerical formulas, chemical formulas, tables, etc.) (n = 2 to 30, R = CH_3,) and NH_3 are reacted. A method for producing a gas separation membrane, which comprises reacting a polysiloxane modified with amino at both ends and a polysiloxane modified with epoxy at both ends, and repeating one or all of the above reactions as necessary.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12005686A JPS62277123A (en) | 1986-05-27 | 1986-05-27 | Production of membrane for separating gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12005686A JPS62277123A (en) | 1986-05-27 | 1986-05-27 | Production of membrane for separating gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62277123A true JPS62277123A (en) | 1987-12-02 |
Family
ID=14776797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12005686A Pending JPS62277123A (en) | 1986-05-27 | 1986-05-27 | Production of membrane for separating gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62277123A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012138755A1 (en) * | 2011-04-08 | 2012-10-11 | Dongchan Ahn | Method of preparing gas selective membrane using epoxy-functional siloxanes |
| CN110461450A (en) * | 2017-03-29 | 2019-11-15 | 环球油品有限责任公司 | For isolated rubber-like polymer film |
-
1986
- 1986-05-27 JP JP12005686A patent/JPS62277123A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012138755A1 (en) * | 2011-04-08 | 2012-10-11 | Dongchan Ahn | Method of preparing gas selective membrane using epoxy-functional siloxanes |
| CN103534012A (en) * | 2011-04-08 | 2014-01-22 | 道康宁公司 | Method of preparing gas selective membrane using epoxy-functional siloxanes |
| US20140060324A1 (en) * | 2011-04-08 | 2014-03-06 | Dow Corning Corporation | Method of preparing gas selective membrane using epoxy-functional siloxanes |
| JP2014523334A (en) * | 2011-04-08 | 2014-09-11 | アン ドンチャン | Method for preparing gas selective membranes using epoxy functional siloxanes |
| CN110461450A (en) * | 2017-03-29 | 2019-11-15 | 环球油品有限责任公司 | For isolated rubber-like polymer film |
| CN110461450B (en) * | 2017-03-29 | 2022-04-08 | 环球油品有限责任公司 | Rubbery polymer membrane for separation |
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