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JPH04310224A - Production of gas diffusible membrane - Google Patents

Production of gas diffusible membrane

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Publication number
JPH04310224A
JPH04310224A JP15420491A JP15420491A JPH04310224A JP H04310224 A JPH04310224 A JP H04310224A JP 15420491 A JP15420491 A JP 15420491A JP 15420491 A JP15420491 A JP 15420491A JP H04310224 A JPH04310224 A JP H04310224A
Authority
JP
Japan
Prior art keywords
membrane
polymer
radiation
gas
thin membrane
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
Application number
JP15420491A
Other languages
Japanese (ja)
Inventor
Toshihiro Nakabo
年宏 中坊
Hiroyuki Takagi
裕幸 高木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissin Electric Co Ltd
Original Assignee
Nissin Electric Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nissin Electric Co Ltd filed Critical Nissin Electric Co Ltd
Priority to JP15420491A priority Critical patent/JPH04310224A/en
Publication of JPH04310224A publication Critical patent/JPH04310224A/en
Pending legal-status Critical Current

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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

PURPOSE:To form a gas diffusible membrane which is prevented from the lowering of its performance with the passage of time by irradiating with radiation a thin membrane formed by mixing together a polysubstituted acetylene represented by a specific structural formula and reactive monomers to cross-link the polymer in the mixture. CONSTITUTION:The polysubstituted acetylene represented by the formula (wherein R is 1-4C alkyl) and reactive monomer or its oligomer are mixed together in suitable amounts. The resulting mixture is dissolved in a solvent such as aromatic hydrocarbon, alicyclic hydrocarbon and halogenated hydrocarbon, the solution is spread over a base such as glass plate or a flat surface of liquid and vaporized, and then the formed film is separated therefrom to obtain a thin membrane. This polymerized thin membrane is thereafter irradiated with radiation to cross-link the polymer therein, thereby producing a gas diffusibility membrane. As the example of the radiation for use in the aforesaid irradiation, electron beam and gamma rays are afforded. The gas diffusible membrane thus obtained retains a stable gas diffusibility over an extended period of time.

Description

【発明の詳細な説明】[Detailed description of the invention]

【0001】0001

【産業上の利用分野】本発明は気体透過性膜の製造方法
に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing gas permeable membranes.

【0002】0002

【従来の技術】気体の分離、精製において、省エネルギ
ー化などを理由に、気体透過性高分子膜を用いる方法が
注目されている。この種高分子膜を用いて空気から分離
、製造された酸素富化空気は、その燃焼効率向上性によ
る省エネルギー化、完全燃焼性による排出有害物質の低
減、動植物育成への利用などに期待されている。
2. Description of the Related Art In the separation and purification of gases, methods using gas-permeable polymer membranes are attracting attention for reasons such as energy saving. Oxygen-enriched air separated from air and produced using this type of polymer membrane is expected to save energy by improving combustion efficiency, reduce harmful substances emitted due to its complete combustibility, and be used for raising animals and plants. There is.

【0003】このような用途からみて、この種高分子膜
が具備すべき性能として、■気体透過性が高いこと、■
気体分離性(分離しようとする気体と分離が不必要な気
体との透過性の比)が高いこと、があげられる。特に用
途などを考慮した場合、気体透過性が高いことが強く要
望される。このような性能を最も充足する素材として化
2によって示される構造式で表されるポリ置換アセチレ
ンがあげられる。
[0003] From the viewpoint of such uses, the performances that this type of polymer membrane should have are: (1) high gas permeability; (2) high gas permeability;
One example is that it has a high gas separation property (ratio of permeability between the gas to be separated and the gas that does not require separation). Especially when considering the intended use, high gas permeability is strongly desired. A polysubstituted acetylene represented by the structural formula shown by Chemical Formula 2 is cited as a material that most satisfies such performance.

【0004】0004

【化2】[Case 2]

【0005】この素材は特定の有機溶剤に可溶で、溶液
からキャスト法によって容易に薄膜化できる。このよう
にして作られた膜は、通常の高分子フィルム(たとえば
ポリジメチルシロキサン)に比較して気体透過性が格段
に優れており、気体透過係数にすると、1桁以上も大き
い。
[0005] This material is soluble in a specific organic solvent, and can be easily formed into a thin film from a solution by a casting method. The membrane produced in this manner has much better gas permeability than ordinary polymer films (eg, polydimethylsiloxane), and its gas permeability coefficient is more than an order of magnitude higher.

【0006】しかしこの高分子膜は、気体透過性が経時
的に低下する性質があり、長時間が経過したときの気体
透過性は、通常の高分子フィルムと同等あるいはそれ以
下にまで低下してしまう。
However, the gas permeability of this polymer film decreases over time, and after a long period of time, the gas permeability decreases to the same level or lower than that of a normal polymer film. Put it away.

【0007】これを改善するために、ポリ置換アセチレ
ンからなる薄膜に放射線を照射する方法が、本発明者に
よって別途提案された(特願平2−223391号)。 このように放射線を照射することによって、この種高分
子膜の経時性能低下はかなり抑制される。
In order to improve this problem, the present inventor separately proposed a method of irradiating a thin film made of polysubstituted acetylene with radiation (Japanese Patent Application No. 2-223391). By irradiating with radiation in this manner, deterioration in the performance of this type of polymer film over time is considerably suppressed.

【0008】しかしこの放射線反応の場合、架橋反応と
分解反応が競争して起こるため、所要の効果を得るため
の照射線量域の巾が狭く、制御が極めて困難となる。効
果的な線量よりも低線量では未反応となり、高線量では
分解反応が優先となり、期待される効果は簡単には得ら
れない。
However, in the case of this radiation reaction, since the crosslinking reaction and the decomposition reaction occur in competition with each other, the width of the irradiation dose range for obtaining the desired effect is narrow, making control extremely difficult. At doses lower than the effective dose, no reaction occurs, and at higher doses, the decomposition reaction takes priority, making it difficult to obtain the expected effects.

【0009】[0009]

【発明が解決しようとする課題】本発明は、ポリ置換ア
セチレンからなる高分子膜を用いる気体透過性膜におい
て、初期の気体透過性が極力損なうことなく、かつ経時
的な性能の低下が抑制できる気体透過性膜を製造するこ
とを目的とする。
[Problems to be Solved by the Invention] The present invention provides a gas permeable membrane using a polymer membrane made of polysubstituted acetylene, which can suppress the deterioration of performance over time without impairing the initial gas permeability as much as possible. The purpose is to produce gas permeable membranes.

【0010】0010

【課題を解決するための手段】本発明は、ポリ置換アセ
チレンと、反応性モノマー又はそのオリゴマーを混合さ
せてなる薄膜に、放射線を照射して高分子を架橋化する
ことを特徴とする。
[Means for Solving the Problems] The present invention is characterized in that a thin film made of a mixture of polysubstituted acetylene and a reactive monomer or an oligomer thereof is irradiated with radiation to crosslink the polymer.

【0011】[0011]

【作用】ポリ置換アセチレンの構造式は下記の化2で表
される。ポリ置換アセチレンは下記の化3で表される二
置換アセチレンを重合したものである。
[Operation] The structural formula of polysubstituted acetylene is represented by the following chemical formula 2. Polysubstituted acetylene is obtained by polymerizing disubstituted acetylene represented by the following chemical formula 3.

【0012】0012

【化2】[Case 2]

【0013】[0013]

【化3】[Chemical formula 3]

【0014】重合体は、TaCl5,NbCl5,Ta
Br5,NbBr5などのV族遷移金属触媒と、芳香族
炭化水素(ベンゼン、トルエン、キシレンなど)、脂環
式炭化水素(シクロヘキサンなど)、ハロゲン系炭化水
素(四塩化炭素、トリクロロエチレンなど)などの溶剤
を用い、不活性気体中で30〜100℃で加熱すること
によって得られる。
[0014] The polymer is TaCl5, NbCl5, Ta
Group V transition metal catalysts such as Br5 and NbBr5 and solvents such as aromatic hydrocarbons (benzene, toluene, xylene, etc.), alicyclic hydrocarbons (cyclohexane, etc.), halogenated hydrocarbons (carbon tetrachloride, trichloroethylene, etc.) is obtained by heating at 30 to 100°C in an inert gas.

【0015】得られた重合体と、反応性モノマーあるい
はそのオリゴマーの適当量を混合して、その混合物を、
芳香族炭化水素(ベンゼン、トルエン、キシレンなど)
、脂環式炭化水素(シクロヘキサンなど)、ハロゲン系
炭化水素(四塩化炭素、トリクロロエチレンなど)など
の溶剤に溶解させ、この溶液をキャストすることによつ
て薄膜化できる。
[0015] The obtained polymer is mixed with an appropriate amount of a reactive monomer or its oligomer, and the mixture is
Aromatic hydrocarbons (benzene, toluene, xylene, etc.)
, alicyclic hydrocarbons (cyclohexane, etc.), halogenated hydrocarbons (carbon tetrachloride, trichloroethylene, etc.), and cast the solution to form a thin film.

【0016】本発明で使用する反応性モノマーまたはそ
のオリゴマーとしては、例えば、■スチレン、N−ビニ
ルピロリドンなどのビニル基を含有する反応性モノマー
またはそのオリゴマー、■トリメチロールプロパントリ
アクリレートなどのアクリル基を含有する反応性モノマ
ーまたはそのオリゴマー、■トリメチロールプロパント
リメタクリレートなどのメタクリル基を含有する反応性
モノマーまたはそのオリゴマー、などのうちの1種また
は複数種が利用できる。
Examples of the reactive monomer or oligomer thereof used in the present invention include: (1) a reactive monomer containing a vinyl group such as styrene or N-vinylpyrrolidone or an oligomer thereof; (2) an acrylic group such as trimethylolpropane triacrylate; (2) reactive monomers containing methacrylic groups such as trimethylolpropane trimethacrylate or oligomers thereof, and the like can be used.

【0017】キャストする下地としては、表面が平滑な
ガラス板、金属板、溶剤に不溶な高分子板(テフロンな
ど)または液体平面(水、適当な水溶液、溶剤かつ重合
体が不溶である有機液体など)などが用いられる。その
下地の上に溶液を延展し、蒸発させた後、形成したフィ
ルムを剥離することによって、この種重合体膜が得られ
る。
The substrate for casting is a glass plate with a smooth surface, a metal plate, a polymer plate insoluble in solvents (such as Teflon), or a liquid surface (water, an appropriate aqueous solution, an organic liquid in which the solvent and polymer are insoluble). etc.) are used. This type of polymer film is obtained by spreading the solution on the substrate, evaporating it, and then peeling off the formed film.

【0018】この場合使用される下地の種類、溶液の濃
度、或は積層(重ね塗り)の回数によって、膜厚を調整
することができる。また機械的強度の補強のため、既製
の多孔質フィルムを支持体として使用することもできる
In this case, the film thickness can be adjusted by the type of base used, the concentration of the solution, or the number of times of lamination (overcoating). In addition, ready-made porous films can also be used as supports for mechanical strength reinforcement.

【0019】このようにして形成された重合体フィルム
は、続いて放射線処理される。放射線としては、たとえ
ば電子線、ガンマ線などが利用できる。これらの放射線
は通常の方法で照射すればよい。
The polymer film thus formed is subsequently treated with radiation. As the radiation, for example, electron beams, gamma rays, etc. can be used. These radiations may be irradiated using a normal method.

【0020】一般には電子線を利用するとよい。その理
由は操作が簡単であり、短時間で処理できるからである
。この場合電子線の加速電圧は50kV以上、好ましく
は100kV以上であり、吸収線量としては、0.1〜
100メガラドが好ましく、より好ましいのは、1〜3
0メガラドである。また場合によっては数メガラドある
いは数十メガラドを数回繰り返して照射するようにして
もよい。
Generally, it is preferable to use an electron beam. The reason for this is that it is easy to operate and can be processed in a short time. In this case, the accelerating voltage of the electron beam is 50 kV or more, preferably 100 kV or more, and the absorbed dose is 0.1 to
100 megarads is preferable, more preferably 1 to 3
It is 0 megarad. In some cases, irradiation of several megarads or tens of megarads may be repeated several times.

【0021】またガンマ線を用いる場合も、同程度の吸
収線量が好ましいが、あまり高線量になると照射時間が
長くなり、効率上良くない。より好ましいのは1〜30
メガラドである。
When gamma rays are used, it is preferable to use a similar absorbed dose, but if the dose is too high, the irradiation time becomes long, which is not good in terms of efficiency. More preferably 1 to 30
It's Megarad.

【0022】[0022]

【実施例】実施例  1−(トリメチルシリル)−1−
プロピン(アルドリッチ)1g、TaCl5  0.0
6g、トルエン10ccを用い、80℃にて24時間、
窒素雰囲気中で反応させることにより、粘調な重合体ゲ
ルを得た。この重合体ゲルをトルエンにて希釈した後、
多量のメタノール中に滴下して重合体を析出沈殿させた
。 得られた重合体を濾過および乾燥した。
[Example] Example 1-(trimethylsilyl)-1-
Propyne (Aldrich) 1g, TaCl5 0.0
6 g and 10 cc of toluene at 80°C for 24 hours.
A viscous polymer gel was obtained by reacting in a nitrogen atmosphere. After diluting this polymer gel with toluene,
The polymer was dropped into a large amount of methanol to precipitate the polymer. The resulting polymer was filtered and dried.

【0023】得られた重合体1gとトリメチロールプロ
パントリアクリレート0.1gをトルエン100ccに
溶解し、重合体溶液とした。この重合体溶液をテフロン
板上に延展し、室温で溶剤を蒸発させた後、テフロン板
より剥離し、厚さ20μmの重合体膜を得た。続いてこ
の重合体膜を、エリアビーム型の電子線照射装置により
、加速電圧200kV、吸収線量30メガラドの条件で
電子線を照射して架橋した。
1 g of the obtained polymer and 0.1 g of trimethylolpropane triacrylate were dissolved in 100 cc of toluene to prepare a polymer solution. This polymer solution was spread on a Teflon plate, and after evaporating the solvent at room temperature, it was peeled off from the Teflon plate to obtain a 20 μm thick polymer film. Subsequently, this polymer film was crosslinked by irradiating it with an electron beam using an area beam type electron beam irradiation device under conditions of an acceleration voltage of 200 kV and an absorbed dose of 30 megarads.

【0024】比較例  重合体溶液として、ポリ(−1
−トリメチルシリル)−1−プロピン重合体1gを、ト
ルエン100ccに溶解させたものを用いた以外は、実
施例と全く同じ条件で膜形成を行った。
Comparative Example Poly(-1
Film formation was carried out under exactly the same conditions as in the example except that 1 g of the -trimethylsilyl)-1-propyne polymer was dissolved in 100 cc of toluene.

【0025】以上の各例の膜について、ガス透過率測定
器を用いて、真空法、35℃において酸素および窒素の
透過量を測定した。その際、電子線照射直後の性能を初
期値とし、それぞれのその後の経過時間特性を評価した
。それぞれの酸素透過係数(Po2),および酸素/窒
素透過係数比(分離性能α)の初期値と、100日経過
後の値を下記の表1に、また経過時間特性を図1に示す
[0025] For each of the membranes of the above examples, the permeation amount of oxygen and nitrogen was measured using a gas permeability measuring device using a vacuum method at 35°C. At that time, the performance immediately after electron beam irradiation was used as the initial value, and the subsequent elapsed time characteristics were evaluated. The initial values of each oxygen permeability coefficient (Po2) and oxygen/nitrogen permeability coefficient ratio (separation performance α) and the values after 100 days are shown in Table 1 below, and the elapsed time characteristics are shown in FIG. 1.

【0026】なお酸素透過係数(Po2)の単位は、c
m3(STP)・cm/cm2・sec・cmHgであ
る。
[0026] The unit of oxygen permeability coefficient (Po2) is c
m3(STP)・cm/cm2・sec・cmHg.

【0027】[0027]

【表1】[Table 1]

【0028】表1および図1に示す結果から明らかなよ
うに、実施例による高分子膜は、分解要因を受けていな
いため、初期の気体透過性の低下巾を、比較例であるポ
リ置換アセチレン単体膜に電子線を照射したものよりも
小さく抑えることができ、長期安定性にも優れているこ
とが判明する。また比較例の場合よりも架橋性に優れる
ため、低線量で良好な架橋構造が得られる。
As is clear from the results shown in Table 1 and FIG. 1, the polymer membrane according to the example was not subjected to decomposition factors, so the initial decrease in gas permeability was lower than that of the polysubstituted acetylene membrane used in the comparative example. It has been found that the size can be kept smaller than that of a single film irradiated with electron beams, and that it has excellent long-term stability. In addition, since the crosslinkability is superior to that of the comparative example, a good crosslinked structure can be obtained at a low dose.

【0029】なお実施例以外の他の反応性モノマーおよ
びそのオリゴマーを使用した場合でも、同等の効果が得
られることが判明している。
It has been found that similar effects can be obtained even when using other reactive monomers and oligomers thereof than those in the examples.

【0030】[0030]

【発明の効果】以上詳述したように本発明によれば、ポ
リ置換アセチレンを素材として気体透過性膜を得るにあ
たり、従来法によるものよりも長期にわたって安定した
気体透過性能を呈するこの種気体透過性膜を製造するこ
とができる効果を奏する。
Effects of the Invention As detailed above, according to the present invention, in obtaining a gas permeable membrane using polysubstituted acetylene as a material, this type of gas permeable membrane exhibits a more stable gas permeation performance over a long period of time than that obtained by conventional methods. This has the effect of making it possible to produce a sexual membrane.

【図面の簡単な説明】[Brief explanation of the drawing]

【図1】本発明方法によって得られた膜の、経過日数に
対する酸素透過係数の変化を示す特性図である。
FIG. 1 is a characteristic diagram showing changes in oxygen permeability coefficient with respect to elapsed days of a membrane obtained by the method of the present invention.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】  構造式が 【化1】 で表されるポリ置換アセチレンと、反応性モノマー又は
そのオリゴマーを混合させてなる薄膜に、放射線を照射
して高分子を架橋化することを特徴とする気体透過性膜
の製造方法。
[Claim 1] A thin film made of a mixture of a polysubstituted acetylene represented by the structural formula [Chemical formula 1] and a reactive monomer or an oligomer thereof is irradiated with radiation to crosslink the polymer. A method for producing a gas permeable membrane.
JP15420491A 1991-04-03 1991-04-03 Production of gas diffusible membrane Pending JPH04310224A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP15420491A JPH04310224A (en) 1991-04-03 1991-04-03 Production of gas diffusible membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP15420491A JPH04310224A (en) 1991-04-03 1991-04-03 Production of gas diffusible membrane

Publications (1)

Publication Number Publication Date
JPH04310224A true JPH04310224A (en) 1992-11-02

Family

ID=15579123

Family Applications (1)

Application Number Title Priority Date Filing Date
JP15420491A Pending JPH04310224A (en) 1991-04-03 1991-04-03 Production of gas diffusible membrane

Country Status (1)

Country Link
JP (1) JPH04310224A (en)

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