JPH0761427B2 - Permselective membrane and method for producing the same - Google Patents
Permselective membrane and method for producing the sameInfo
- Publication number
- JPH0761427B2 JPH0761427B2 JP63137820A JP13782088A JPH0761427B2 JP H0761427 B2 JPH0761427 B2 JP H0761427B2 JP 63137820 A JP63137820 A JP 63137820A JP 13782088 A JP13782088 A JP 13782088A JP H0761427 B2 JPH0761427 B2 JP H0761427B2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Engineering & Computer Science (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、産業材料に関するものである。更に詳しく
は、ガスや液体の選択透過性膜に関するものである。TECHNICAL FIELD OF THE INVENTION The present invention relates to industrial materials. More specifically, it relates to a gas or liquid selectively permeable membrane.
従来の技術 従来選択透過性膜は大きく分けて気体用と液体用があ
る。気体用ではガスや石油燃料の燃焼性向上の目的で酸
素富化膜が検討されている。また、液体用ではアルコー
ル−水の分離膜や油−水の分離膜が検討されている。2. Description of the Related Art Conventional permselective membranes are roughly classified into those for gas and those for liquid. For gases, oxygen-enriched membranes are being studied for the purpose of improving the combustibility of gas and petroleum fuels. For liquids, alcohol-water separation membranes and oil-water separation membranes have been investigated.
発明が解決しようとする課題 ところが、現在知られている選択性透過膜は、主にポリ
マーを多孔性基板にコーティングする方法が採られてい
るため選択透過効率が悪い。そこで、現在も効率向上の
為数々の方法が検討されているが、未だに選択透過性の
よい膜は得られてないのが実状である。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, currently known permselective membranes have a poor permselective efficiency because they mainly adopt a method of coating a polymer on a porous substrate. Therefore, various methods are being studied to improve the efficiency at present, but the reality is that a membrane with good selective permeability has not been obtained yet.
課題を解決するための手段 一端に を持つ直鎖上の炭化水素誘導体を用いれば、有機溶媒中
で化学吸着により親水性基板表面に単分子膜を形成で
き、さらに前記累積された単分子膜表面を酸素を含むガ
ス中で高エネルギー線照射して表面を親水性化すること
により単分子膜を累積膜を形成することが出来ることが
知られている。Means to solve the problem By using a straight chain hydrocarbon derivative having, it is possible to form a monomolecular film on the surface of a hydrophilic substrate by chemisorption in an organic solvent, and further, the accumulated monomolecular film surface has high energy in a gas containing oxygen. It is known that a monomolecular film can be formed into a cumulative film by irradiating with rays to make the surface hydrophilic.
従って、直鎖状炭化水素の一部に重合性基（例えば、ビ
ニル基やアセチレン基、ジアセチレン基等）を含むよう
な物質を用い化学吸着により単分子膜を作成し重合を行
えば、数十オングストロームオーダの単分子膜ポリマー
を形成でる。さらに、上述の方法で単分子膜を複数層累
積された膜も容易に得ることが出来る。Therefore, if a substance that contains a polymerizable group (for example, vinyl group, acetylene group, diacetylene group, etc.) in a part of linear hydrocarbon is used for chemical adsorption to form a monomolecular film and polymerization is carried out, It can form a monolayer polymer of the order of 10 Å. Further, a film in which a plurality of monomolecular films are accumulated can be easily obtained by the above method.
この方法により、多孔性基板上に形成された単分子膜
を、ハロゲン化金属触媒を含む有機溶媒中に浸漬したり
放射線で、前記単分子膜の重合性基の部分を重合させる
と、酸素を含む雰囲気中でも安定な超薄膜のポリマーが
形成でき、選択透過効率の優れた選択透過性膜を製造で
きることを見いだした。By this method, when the monomolecular film formed on the porous substrate is immersed in an organic solvent containing a metal halide catalyst or irradiated with radiation to polymerize the polymerizable group portion of the monomolecular film, oxygen is generated. It has been found that a stable ultra-thin film polymer can be formed even in an atmosphere containing the selective permeation film having excellent selective permeation efficiency.
つまり、一定の配向性を保った状態で分子を重合するこ
とにより、選択透過効率の優れた選択透過性膜を製造で
きる。That is, by polymerizing molecules in a state where a certain orientation is maintained, it is possible to manufacture a selectively permeable membrane having excellent selective permeation efficiency.
さらに、透過性も単分子膜の層数を制御することで任意
に選べる効果もある。Furthermore, the permeability can be arbitrarily selected by controlling the number of monolayer layers.
また、本発明では、有機溶媒に溶解させた重合性基を含
む物質を水面上に展開し前記有機溶媒を蒸発させた後、
水面上に残った前記物質の分子を水面上で水面方向にバ
リヤでかき集め、所定の表面圧を加えながら基板を上下
させてアセチレン誘導体の単分子膜を基板上に累積（こ
の累積法をラングミュアー・ブロジェット（LB）法と言
い、この方法により累積された単分子膜をLB膜という）
した後、ハロゲン化金属触媒を含む有機溶媒中に前記単
分子膜の累積された基板を浸漬したり、あるいは放射線
照射により前記単分子膜の重合性基の部分を重合させる
と、超薄膜のポリマーを形成出来ることを見いだした。Further, in the present invention, after the substance containing a polymerizable group dissolved in an organic solvent is spread on the water surface and the organic solvent is evaporated,
The molecules of the substance remaining on the water surface are scraped on the water surface in the direction of the water surface with a barrier, and the substrate is moved up and down while applying a predetermined surface pressure to accumulate a monomolecular film of the acetylene derivative on the substrate.・ It is called the Blodgett (LB) method, and the monomolecular film accumulated by this method is called the LB film)
After that, by immersing the substrate on which the monomolecular film has been accumulated in an organic solvent containing a metal halide catalyst, or by polymerizing a part of the polymerizable group of the monomolecular film by irradiation with radiation, an ultrathin film polymer is obtained. I found that I can form.
つまり、この場合も一定の配向性を保った状態で分子を
重合することにより、選択透過効率の優れた選択透過性
膜を製造できる。That is, in this case as well, by polymerizing the molecules in a state where a certain orientation is maintained, a permselective membrane having excellent permselectivity can be produced.
さらに、透過性も単分子膜の層数を制御することで任意
に選べる効果もある。Furthermore, the permeability can be arbitrarily selected by controlling the number of monolayer layers.
さらにまた、此の方法の場合、前記LB膜の累積時に面方
向に直流バイアスを印加しておくと、より配向性の優れ
た選択透過膜を作れることを見いだした。Furthermore, in the case of this method, it was found that by applying a DC bias in the surface direction during the accumulation of the LB film, it is possible to form a selective permeation film having more excellent orientation.
作用 例えば、重合性基としてアセチレン（Ｃ≡Ｃ）基および
他の官能基としてクロルシラン基 を含む物質を溶解させた非水系有機溶媒中に表面が親水
性の多孔性基板を浸漬し、前記基板表面に前記アセチレ
ン（Ｃ≡Ｃ）基およびクロルシラン基 を含む物質を化学吸着させることにより多孔性基板上に
アセチレン（Ｃ≡Ｃ）基およびクロルシラン基 を含む物質の単分子膜を分子状態が並んだ状態で作成す
ることが出来、さらに所定の基板上に形成したアセチレ
ン誘導体の化学吸着膜を金属触媒を用いて重合すること
により、重合時の分子配向性を保った状態で、超高分子
量のポリマーを作ることができる。また、重合反応に
は、ハロゲン化金属触媒たとえばMoCl5やWCl6、NbCl5、
TaCl5、Mo(CO)5、W(CO)6、あるいはNb(CO)5、やTa(CO)5
等が利用できる。なお、有機溶媒はトルエン、ジオキサ
ン、アニソール等が利用できる。Action For example, an acetylene (C≡C) group as a polymerizable group and a chlorosilane group as another functional group. A porous substrate having a hydrophilic surface is immersed in a non-aqueous organic solvent in which a substance containing is dissolved, and the acetylene (C≡C) group and chlorosilane group are added to the substrate surface. By chemically adsorbing a substance containing acetylene (C≡C) group and chlorosilane group on the porous substrate It is possible to create a monomolecular film of a substance containing a substance in a state in which the molecular states are lined up, and by further polymerizing the chemically adsorbed film of the acetylene derivative formed on a predetermined substrate using a metal catalyst, An ultra high molecular weight polymer can be produced while maintaining the orientation. Further, in the polymerization reaction, a metal halide catalyst such as MoCl 5 , WCl 6 , NbCl 5 ,
TaCl 5 , Mo (CO) 5 , W (CO) 6 , or Nb (CO) 5 , Ta (CO) 5
Etc. are available. The organic solvent may be toluene, dioxane, anisole, or the like.
或は、前述の重合方法の代わりに放射線（紫外線、Ｘ
線、電子線、ガンマ線等）照射方法を用いることも出来
る。Alternatively, instead of the above-mentioned polymerization method, radiation (ultraviolet rays, X
Radiation method, electron beam, gamma ray, etc.) can also be used.
更にまた、ある一定の表面圧の基で所定の多孔性基板上
に累積した重合性基として、例えばアセチレン基を含む
誘導体のLB膜を金属触媒を用いて重合する方法でも、重
合時の分子配向性を保った状態で重合すれば超高分子量
のポリマーを作ることができる。Furthermore, as a polymerizable group accumulated on a predetermined porous substrate with a certain surface pressure group, for example, a method of polymerizing an LB film of a derivative containing an acetylene group by using a metal catalyst, molecular orientation at the time of polymerization If the polymerization is carried out while maintaining the property, an ultrahigh molecular weight polymer can be produced.
また、前記アセチレン誘導体分子を水面上で面方向にバ
リヤでかき集め累積する際、面方向に直流バイアスを印
加しておくと、更にモノマ分子の累積時の配向性がよい
ポリマーを作ることが可能となる。Further, when the acetylene derivative molecules are scratched and accumulated in the plane direction on the water surface by a barrier and a direct current bias is applied in the plane direction, it is possible to further produce a polymer having a good orientation when the monomer molecules are accumulated. Become.
なお、この方法においても前述の触媒を用いた重合方法
の代わりに、放射線照射方法を用いることも出来る。Incidentally, also in this method, a radiation irradiation method can be used instead of the above-mentioned polymerization method using a catalyst.
これらのポリマーは、透過性も単分子膜の層数を制御す
ることで任意に選べるので、選択透過性膜として効率の
高い膜が得られる。Since the permeability of these polymers can be arbitrarily selected by controlling the number of layers of the monomolecular film, a highly efficient membrane can be obtained as a selectively permeable membrane.
実施例 以下、実施例を用いて本発明の詳細を説明する。Examples Hereinafter, the details of the present invention will be described using examples.
（実施例１） 使用したサンプルは、数々あるが、アセチレン誘導体の
一種であり末端にアセチレン基を１個含むω−ノナデシ
ルイノイックトリクロルシラン（NCS;CH≡Ｃ−（CH2）
ｎ−SiCl3、ここでｎは17であるが、14から24の範囲で
良好な結果が得られた）の場合を用いて説明する。(Example 1) There are many samples used, but one of the acetylene derivatives and ω-nonadecylinoic trichlorosilane (NCS; CH≡C- (CH 2 )) containing one acetylene group at the terminal is used.
n-SiCl 3 , where n is 17, but good results were obtained in the range of 14 to 24).
例えば、親水性の多孔性基板１（セルロースフィルタ
ー、ガラスフィルター、多孔性金属膜等）上にシラン系
界面活性剤（NCS:CH≡Ｃ−（CH2）17−SiCl3）を用いて
基板表面に単分子膜を化学吸着して形成する。この時、
−SiCl基と基板表面に形成されている−OH基が反応して
脱塩酸して、基板表面に の単分子膜２が形成できる。例えば2.0X10-3〜5.0X10-3
mol/lの濃度で前記シラン系界面活性剤を溶かした80％
ｎ−ヘキサン、12％四塩化炭素、８％クロロホルム溶液
中に、室温で数分間親水性の多孔性基板を浸漬すると、
基板表面で の結合を形成できる。（第１図（ａ）） ここで、多孔性基板表面に の単分子膜２が形成できていることは、FTIRにて確認さ
れた。For example, using a silane-based surfactant (NCS: CH≡C- (CH 2 ) 17 -SiCl 3 ) on the hydrophilic porous substrate 1 (cellulose filter, glass filter, porous metal film, etc.), the substrate surface It is formed by chemically adsorbing a monomolecular film on. At this time,
-SiCl group reacts with the -OH group formed on the substrate surface to dehydrochlorinate, leaving the substrate surface The monomolecular film 2 can be formed. For example, 2.0X10 -3 to 5.0X10 -3
80% of the above silane-based surfactant dissolved at a concentration of mol / l
When a hydrophilic porous substrate is immersed in a solution of n-hexane, 12% carbon tetrachloride and 8% chloroform for several minutes at room temperature,
On the board surface Can form a bond. (Fig. 1 (a)) Here, on the surface of the porous substrate It was confirmed by FTIR that the monomolecular film 2 of 1 was formed.
なお、このとき化学吸着膜の形成は、湿気を含まないN2
雰囲気中で行った。At this time, the chemisorption film is formed by N 2 containing no moisture.
I went in the atmosphere.
次に金属触媒としてMoCl5を溶かしたトルエン中にNCS吸
着膜が１層形成された基板を浸漬し30〜70℃程度に溶媒
を昇温すると第１図（ｂ）に示すような反応、即ちTran
s−ポリアセチレン結合３が製造されたことがFTIRによ
り明かとなった。なお、触媒としてはWCl6やNbCl5、TaC
l5を用いても分子量は異なるが同様の重合膜が得られ
た。さらにまた、触媒としてMo(CO)6あるいはW(CO)6をC
Cl4溶媒に溶かした溶液に基板を浸漬し紫外線を照射し
ても分子量は異なるが赤褐色の重合膜が得られた。Next, when the substrate on which one layer of NCS adsorption film is formed is immersed in toluene in which MoCl 5 is dissolved as a metal catalyst and the temperature of the solvent is raised to about 30 to 70 ° C., the reaction as shown in FIG. Tran
FTIR revealed that the s-polyacetylene bond 3 was produced. The catalyst used was WCl 6 , NbCl 5 , TaC.
The same polymerized film was obtained even when l 5 was used, although the molecular weight was different. Furthermore, Mo (CO) 6 or W (CO) 6 as C is used as a catalyst.
Even when the substrate was immersed in a solution of Cl 4 solvent and irradiated with ultraviolet rays, a reddish brown polymer film with different molecular weights was obtained.
さらに前記親水性の多孔性基板上に１−（トリメチルシ
リル）−ω−ノナデシルイノイックトリクロロシラン
（TMS−NCS:SiMe3−Ｃ≡Ｃ（CH2）ｎ−SiCl3、ここでｎ
は17であるが、14から24の範囲で良好な結果が得られ
た）吸着膜を１層累積した基板を（第２図（ａ））、金
属触媒としてWCl6と共触媒としてBu4Sn（1:1）を溶かし
たトルエン中に浸漬し30〜70℃程度に溶媒を昇温すると
第２図（ｂ）に示すような反応、即ち−SiMe3基を含ん
だTrans−ポリアセチレン結合３が製造されたことが明
かとなった。Furthermore, 1- (trimethylsilyl) -ω-nonadecylinoic trichlorosilane (TMS-NCS: SiMe 3 -C≡C (CH 2 ) n-SiCl 3 , where n is formed on the hydrophilic porous substrate.
Is 17, but good results were obtained in the range of 14 to 24). A substrate with one layer of adsorbed film accumulated (Fig. 2 (a)) was used with WCl 6 as a metal catalyst and Bu 4 Sn as a cocatalyst. When it is immersed in toluene in which (1: 1) is dissolved and the temperature of the solvent is raised to about 30 to 70 ° C, a reaction as shown in Fig. 2 (b), that is, a Trans-polyacetylene bond 3 containing a -SiMe 3 group is formed. It was revealed that it was manufactured.
また多孔性基板１上にNCS吸着膜を１層累積した基板を
（第３図（ａ））、金属触媒としてMoCl6を溶かした含
酸素有機溶媒であるアニソール中に浸漬し30〜70℃程度
に溶媒を昇温すると第３図（ｂ）に示すような反応、即
ちCis−ポリアセチレン４が製造されたことが明かとな
った。Also, a substrate in which one layer of NCS adsorption film was accumulated on the porous substrate 1 (Fig. 3 (a)) was immersed in anisole, which is an oxygen-containing organic solvent in which MoCl 6 was dissolved as a metal catalyst, at about 30 to 70 ° C. It was revealed that the reaction as shown in FIG. 3 (b), that is, the production of Cis-polyacetylene 4 was produced when the temperature of the solvent was raised.
さらにまた多孔性基板１上にTMS−NCS吸着膜を１層累積
した基板を（第４図（ａ））、金属触媒としてMoCl6と
共触媒としてPh3Bi（1:1）を溶かした含酸素有機溶媒で
あるアニソール中に浸漬し30〜70℃程度に溶媒を昇温す
ると第４図（ｂ）に示すような反応、即ち−SiMe3基を
含んだCis−ポリアセチレン４が製造されたことが明か
となった。Furthermore, a substrate in which one layer of TMS-NCS adsorption film was accumulated on the porous substrate 1 (Fig. 4 (a)) was prepared by dissolving MoCl 6 as a metal catalyst and Ph 3 Bi (1: 1) as a cocatalyst. By immersing in anisole, which is an oxygen organic solvent, and raising the temperature of the solvent to about 30 to 70 ° C., the reaction as shown in FIG. 4 (b), that is, Cis-polyacetylene 4 containing —SiMe 3 group was produced. Became clear.
一方、上述の方法で累積されたLB膜はアルコール溶媒に
は不溶性であるることが確認された。On the other hand, it was confirmed that the LB film accumulated by the above method was insoluble in alcohol solvent.
以上の結果より、本発明の重合方法を用いればCis型あ
るいはTrans型ポリアセチレンを基板上に容易に形成で
きることが確認された。From the above results, it was confirmed that Cis-type or Trans-type polyacetylene can be easily formed on the substrate by using the polymerization method of the present invention.
なお、上述の実施例では、金属触媒を用いて吸着膜を重
合する方法に付いて述べたが、放射線、例えば電子線Ｘ
線或はガンマー線照射法を用いても、Cis型あるいはTra
ns型の制御はできないがポリアセチレンポリマーを容易
に製造できることが確認できた。In addition, in the above-mentioned embodiment, although the method of polymerizing the adsorption film by using the metal catalyst is described, radiation such as electron beam X is used.
Ray or gamma ray irradiation method
It was confirmed that the polyacetylene polymer could be easily produced although the ns type could not be controlled.
また、この様にして製造されたポリアセチレンは、従来
チグラーナッタ系触媒法で製造されていたポリアセチレ
ン誘導体に比べ、酸素を含む雰囲気中でも、熱や圧力あ
るいは紫外線などにたいして著しく安定であった。Further, the polyacetylene produced in this manner was significantly more stable to heat, pressure, ultraviolet rays, etc. in an atmosphere containing oxygen than the polyacetylene derivative conventionally produced by the Ziegler-Natta catalyst method.
以上の、実施例では、NCSやTMS−NCSについてのみ示し
たが、分子内にアセチレン（Ｃ≡Ｃ）基を含み吸着膜形
成が可能なものであれば、累積条件は異なっても同様の
方法が利用出来ることは明らかであろう。なお、ジアセ
チレン基を１個もつトリコサジイノイックトリクロロシ
ラン（Ｈ−Ｃ≡Ｃ−Ｃ≡Ｃ−(CH2)19−SiCl3）を用いた
場合には、ポリジアセチレンが得られた。In the above examples, only NCS and TMS-NCS are shown. However, as long as the molecule contains an acetylene (C≡C) group and an adsorbed film can be formed, the same method can be used even if the accumulation conditions are different. Will be available. In addition, when tricosadiinoic trichlorosilane having one diacetylene group (H—C≡C—C≡C— (CH 2 ) 19 —SiCl 3 ) was used, polydiacetylene was obtained.
また、前述の実施例では１層化学吸着膜を形成し重合を
行う方法について述べたが吸着膜を多層積層した後で重
合反応を行っても良いし、あるいは吸着膜の形成−重合
反応を交互に行ってもポリアセチレンの多層分子膜の作
製が可能なことは明らかであろう。Further, in the above-mentioned embodiment, the method of forming a one-layered chemisorption film and carrying out the polymerization was described, but the polymerization reaction may be carried out after laminating the adsorption films in multiple layers, or the formation of the adsorption film and the polymerization reaction are alternately conducted. It will be apparent that a polyacetylene multi-layered molecular film can be prepared even if the above procedure is performed.
（実施例２） さらにまた、アセチレン誘導体の一種であるオメガトリ
コシノイック酸（TCA:CH≡Ｃ−(CH2)n−COOH、ここでｎ
は20であるが14から23の誘導体でも良好な結果が得られ
た）の場合を用いて説明する。(Example 2) Furthermore, omega tricosinoic acid (TCA: CH≡C- (CH 2 ) n- COOH, which is one of the acetylene derivatives, where n
Is 20 but good results were obtained with the derivatives of 14 to 23).
LB膜の累積には、ジョイスレーベル社のトラフIV（Joic
e−LoeblTroughIV）を用い、500nm以下の光をカットし
たイエロー光照明のクラス100のクリーンルーム内で行
った。このときクリーンルーム内は、室温23±１℃、湿
度40±５％に調節されている。LB膜の累積に使用した基
板は、親水性の多孔性基板（セルロースフィルター、ガ
ラスフィルター、多孔性金属膜等）である。重合反応に
使用したハロゲン化金属触媒はMoCl5、またはWCl6、ま
たはNbCl5、またはTaCl5、またはMo(CO)5、またはW(CO)
6、またはNb(CO)5、またはTa(CO)5等か利用できた。ま
た、有機溶媒はトルエン、ジオキサン、アニソール等が
利用できる。Trough IV (Joic Label) of Joyce Label Co.
e-LoeblTroughIV) was used in a clean room of yellow light illumination class 100 where light of 500 nm or less was cut. At this time, the room temperature in the clean room is adjusted to 23 ± 1 ° C and the humidity is adjusted to 40 ± 5%. The substrate used for accumulating the LB film is a hydrophilic porous substrate (cellulose filter, glass filter, porous metal film, etc.). The metal halide catalyst used for the polymerization reaction is MoCl 5 , or WCl 6 , or NbCl 5 , or TaCl 5 , or Mo (CO) 5 , or W (CO)
6 , or Nb (CO) 5 , or Ta (CO) 5 etc. were available. Further, as the organic solvent, toluene, dioxane, anisole or the like can be used.
例えば、親水性の多孔質基板１上にオメガトリコシノイ
ック酸（TCA）LB膜を累積すると第５図（ａ）に示すよ
うな分子配列状態の単分子膜５が得られる。さらに金属
触媒としてMoCl5を溶かしたトルエン中にオメガトリコ
シノイック酸LB膜が１層累積された基板を浸漬し30〜70
℃程度に溶媒を昇温すると第１図（ｂ）に示すような反
応、即ち、Trans−ポリアセチレン結合３が製造された
ことが明かとなった。なお、触媒としてはWCl6やNbC
l5、TaCl5を用いても分子量は異なるが同様の重合膜が
得られた。さらにまた、触媒としてMo(CO)6あるいはW(C
O)6をCCl4溶媒に溶かした溶液に基板を浸漬し紫外線を
照射しても分子量は異なるが赤褐色の重合膜が得られ
た。For example, when an omega tricosinoic acid (TCA) LB film is accumulated on the hydrophilic porous substrate 1, a monomolecular film 5 having a molecular arrangement as shown in FIG. 5 (a) is obtained. Further, the substrate on which one layer of the omega tricosinoic acid LB film was accumulated was immersed in toluene containing MoCl 5 dissolved as a metal catalyst for 30 to 70
When the temperature of the solvent was raised to about 0 ° C., it became clear that the reaction shown in FIG. 1 (b), that is, the Trans-polyacetylene bond 3 was produced. The catalyst is WCl 6 or NbC.
Similar polymers with different molecular weights were obtained using l 5 and TaCl 5 . Furthermore, Mo (CO) 6 or W (C
Even when the substrate was immersed in a solution of O) 6 in a CCl 4 solvent and irradiated with ultraviolet rays, a reddish brown polymer film with different molecular weights was obtained.
さらに基板１上に１−（トリメチルシリル）−ω−トリ
コシノイック酸（TMS−TCA:SiMe3−Ｃ≡Ｃ−（CH2）ｎ
−COOH、ここでｎは20であるが14から23の誘導体でも良
好な結果が得られた）LB膜を１層累積した基板を（第６
図（ａ））、金属触媒としてWCl6と共触媒としてBu4Sn
（1:1）を溶かしたトルエン中に浸漬し30〜70℃程度に
溶媒を昇温すると第６図（ｂ）に示すような反応、すな
わち−SiMe3基を含んだTrans−ポリアセチレン結合３が
製造されたことが明かとなった。Furthermore, 1- (trimethylsilyl) -ω-tricosinoic acid (TMS-TCA: SiMe 3 -C≡C- (CH 2 ) n was formed on the substrate 1.
-COOH, where n is 20, but good results were obtained with derivatives of 14 to 23).
Figure (a)), WCl 6 as metal catalyst and Bu 4 Sn as cocatalyst
When it is immersed in toluene in which (1: 1) is dissolved and the temperature of the solvent is raised to about 30 to 70 ° C., a reaction as shown in FIG. 6 (b), that is, a Trans-polyacetylene bond 3 containing a —SiMe 3 group is formed. It was revealed that it was manufactured.
また多孔性基板上にオメガトリコシノイック酸LB膜を１
層累積した基板を（第７図（ａ））、金属触媒としてMo
Cl6を溶かした含酸素有機溶媒であるアニソール中に浸
漬し30〜70℃程度に溶媒を昇温すると第７図（ｂ）に示
すような反応、即ちCis−ポリアセチレン４が製造され
たことが明かとなった。In addition, 1 omega trichocinoic acid LB film on the porous substrate
The layer-accumulated substrate (Fig. 7 (a)) was used as a metal catalyst for Mo.
When it was immersed in anisole, which is an oxygen-containing organic solvent in which Cl 6 was dissolved, and the temperature of the solvent was raised to about 30 to 70 ° C., the reaction as shown in FIG. 7 (b), that is, Cis-polyacetylene 4 was produced. It became clear.
さらにまた多孔性基板１上にTMS−TCA・LB膜を１層累積
した基板を（第８図（ａ））、金属触媒としてMoCl6と
共触媒としてPh3Bi（1:1）を溶かした含酸素有機溶媒で
あるアニソール中に浸漬し30〜70℃程度に溶媒を昇温す
ると第８図（ｂ）に示すような反応、即ち−SiMe3基を
含んだCis−ポリアセチレン４が製造されたことが明か
となった。Furthermore, a substrate in which one layer of TMS-TCA / LB film was accumulated on the porous substrate 1 (Fig. 8 (a)) was prepared by dissolving MoCl 6 as a metal catalyst and Ph 3 Bi (1: 1) as a cocatalyst. By immersing in anisole, which is an oxygen-containing organic solvent, and raising the temperature of the solvent to about 30 to 70 ° C., a reaction as shown in FIG. 8 (b), that is, Cis-polyacetylene 4 containing —SiMe 3 group was produced. It became clear.
一方、上述の方法で累積された吸着膜はアルコール溶媒
には不溶性であるることが確認された。On the other hand, it was confirmed that the adsorption film accumulated by the above method was insoluble in the alcohol solvent.
以上の結果より、本発明の方法を用いればCis型あるい
はTrans型ポリアセチレンを容易に製造できることが確
認された。From the above results, it was confirmed that Cis-type or Trans-type polyacetylene can be easily produced by using the method of the present invention.
なお、上述の実施例では、金属触媒を用いて吸着膜を重
合する方法に付いて述べたが、放射線、例えば電子線Ｘ
線或はガンマー線照射法を用いても、Cis型あるいはTra
ns型の制御はできないがポリアセチレンポリマーを容易
に製造できることが確認できた。In addition, in the above-mentioned embodiment, although the method of polymerizing the adsorption film by using the metal catalyst is described, radiation such as electron beam X is used.
Ray or gamma ray irradiation method
It was confirmed that the polyacetylene polymer could be easily produced although the ns type could not be controlled.
また、この様にして製造されたポリアセチレンは、従来
チグラーナッタ系触媒法で製造されていたポリアセチレ
ン誘導体に比べ、酸素を含む雰囲気中でも、熱や圧力あ
るいは紫外線などにたいして著しく安定であった。Further, the polyacetylene produced in this manner was significantly more stable to heat, pressure, ultraviolet rays, etc. in an oxygen-containing atmosphere than the polyacetylene derivative conventionally produced by the Ziegler-Natta catalyst method.
また、ジアセチレン誘導体分子を水面上で面方向にバリ
ヤでかき集めたり、累積を行う際、面方向に数十ボルト
の直流バイアスを印加しておくと更にモノマ分子の配向
性がよくなることが確認された。It was also confirmed that when the diacetylene derivative molecules are scratched in the plane direction on the water surface by a barrier or accumulated, a direct current bias of several tens of volts is applied in the plane direction to further improve the orientation of the monomer molecules. It was
以上の、実施例では、ω−トリコシノイック酸やTMS−T
CAについてのみ示したが、分子内にジアセチレン基、ア
セチレン基あるいはビニル基等を含みLB膜形成が可能な
ものであれば、累積条件は異なっても同様の方法が利用
出来ることは明らかであろう。なお、ジアセチレン基を
１個もつペンタコサジイノイック酸を用いた場合には、
ポリジアセチレンが得られた。In the above examples, ω-tricosinoic acid and TMS-T
Although only CA is shown, it is clear that the same method can be used even if the accumulating conditions are different, as long as the LB film can be formed by containing a diacetylene group, an acetylene group, a vinyl group or the like in the molecule. Let's do it. If pentacosadiinoic acid having one diacetylene group is used,
Polydiacetylene was obtained.
また、実施例では１層LB膜を累積した後に重合する方法
を示したが、LB膜を多層累積した後重合反応を行っても
良いし、あるいは累積−重合反応の工程を交互に行って
も多分子層のポリアセチレン膜を作ることも可能なこと
が確認された。Further, in the examples, the method of polymerizing after accumulating the one-layer LB film was shown, but the polymerization reaction may be carried out after accumulating the LB films in multiple layers, or the steps of accumulating-polymerizing reaction may be alternately performed. It was confirmed that it is possible to make a polyacetylene film having a multi-layer structure.
発明の効果 本発明の方法を用いることにより、分子配向性の非常に
優れ安定な超薄膜のポリマーを高能率に製造できる。従
って、ガスや液体の選択透過性の良い膜が得られ選択透
過膜ととして極めて有効である。例えば、TMS−NCSある
いはTMS−TCAを用いた膜では空気より酸素を分離する特
性が極めて高い選択ガス透過膜が得られる。また、今後
さらに原料となるアセチレンやジアセチレン誘導体モノ
マーの種類や製造条件を適正化することにより、透過率
を段階的に制御した選択透過膜の製造も可能になると思
われる。EFFECTS OF THE INVENTION By using the method of the present invention, it is possible to highly efficiently produce a stable ultrathin polymer having excellent molecular orientation. Therefore, a film having good selective permeability of gas or liquid is obtained, which is extremely effective as a selective permeable film. For example, a membrane using TMS-NCS or TMS-TCA can provide a selective gas permeable membrane having extremely high characteristics of separating oxygen from air. In addition, by optimizing the types of acetylene and diacetylene derivative monomers, which are raw materials, and manufacturing conditions, it is possible to manufacture a permselective film with the transmittance controlled stepwise.
第１図（ａ）はNCS吸着膜を１層形成した基板の分子オ
ーダーの拡大断面概念図、第１図（ｂ）は重合後のTran
s型ポリアセチレンの形成された基板の分子オーダーの
拡大断面概念図、第２図（ａ）はTMS−NCS吸着膜を１層
形成した基板の分子オーダーの拡大断面概念図、第２図
（ｂ）は重合後のTrans型ポリアセチレンの形成された
基板の分子オーダーの拡大断面概念図、第３図（ａ）は
NCS膜を１層形成した基板の分子オーダーの拡大断面概
念図、第３図（ｂ）は重合後のCis型ポリアセチレンの
形成された基板の分子オーダーの拡大断面概念図、第４
図（ａ）はTMS−NCS吸着膜を１層形成した基板の分子オ
ーダーの拡大断面概念図、第４図（ｂ）は重合後のCis
型ポリアセチレンの形成された基板の分子オーダーの拡
大断面概念図、第５図（ａ）はTCA・LB膜を１層累積し
た基板の分子オーダーの拡大断面概念図、第５図（ｂ）
は重合後のTrans型ポリアセチレンの形成された基板の
分子オーダーの拡大断面概念図、第６図（ａ）は１−
（トリメチルシリル）−１−トリコサン酸・LB膜を１層
累積した基板の分子オーダーの拡大断面概念図、第６図
（ｂ）は重合後のTrans型ポリアセチレンの形成された
基板の分子オーダーの拡大断面概念図、第７図（ａ）は
TCA・LB膜を１層累積した基板の分子オーダーの拡大断
面概念図、第７図（ｂ）は重合後のCis型ポリアセチレ
ンの形成された基板の分子オーダーの拡大断面概念図、
第８図（ａ）は１−（トリメチルシリル）−１−トリコ
サン酸・LB膜を１層累積した基板の分子オーダーの拡大
断面概念図、第８図（ｂ）は重合後のCis型ポリアセチ
レンの形成された基板の分子オーダーの拡大断面概念図
である。 １……多孔性基板、２……単分子吸着膜、５……単分子
累積膜（LB膜）。Fig. 1 (a) is an enlarged cross-sectional conceptual diagram of the molecular order of a substrate on which one NCS adsorption film is formed, and Fig. 1 (b) is Tran after polymerization.
A molecular-order enlarged cross-sectional conceptual view of a substrate on which s-type polyacetylene is formed, FIG. 2 (a) is a molecular-order enlarged cross-sectional conceptual diagram of a substrate on which one layer of TMS-NCS adsorption film is formed, FIG. 2 (b) Is an enlarged cross-sectional conceptual view of the molecular order of the substrate on which the trans-type polyacetylene is formed after polymerization, and FIG.
FIG. 4B is an enlarged cross-sectional conceptual view of the molecular order of the substrate on which the Cis-type polyacetylene after polymerization is formed, and FIG.
Figure (a) is an enlarged cross-sectional conceptual diagram of the molecular order of the substrate on which one layer of TMS-NCS adsorption film is formed, and Figure 4 (b) is Cis after polymerization.
5 is an enlarged cross-sectional conceptual view of the molecular order of the substrate on which the polyacetylene is formed. FIG. 5 (a) is an enlarged conceptual cross-sectional view of the molecular order of the substrate in which one layer of TCA / LB film is accumulated.
Is an enlarged cross-sectional conceptual view of the molecular order of the substrate on which the trans-type polyacetylene is formed after polymerization, and FIG.
A molecular-scale enlarged cross-sectional conceptual view of a substrate in which one layer of (trimethylsilyl) -1-tricosanoic acid / LB film is accumulated, and FIG. 6 (b) is a molecular-order enlarged cross-sectional view of a substrate on which Trans-type polyacetylene after polymerization is formed. Conceptual diagram, Fig. 7 (a)
A molecular-order enlarged cross-sectional conceptual view of a substrate in which one layer of TCA / LB film is accumulated, and FIG. 7 (b) is a molecular-order enlarged cross-sectional conceptual diagram of a substrate on which Cis-type polyacetylene after polymerization is formed,
FIG. 8 (a) is an enlarged cross-sectional conceptual diagram of the molecular order of a substrate in which 1- (trimethylsilyl) -1-tricosanoic acid / LB film is accumulated, and FIG. 8 (b) is the formation of Cis-type polyacetylene after polymerization. FIG. 6 is an enlarged cross-sectional conceptual view of the molecular order of the prepared substrate. 1 ... Porous substrate, 2 ... Monomolecular adsorption film, 5 ... Monomolecular cumulative film (LB film).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｄ 71/82 ５００ 9153−4Ｄ Ｃ０８Ｆ 2/46 ＭＤＨ Ｃ０８Ｊ 5/18 9267−4Ｆ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location B01D 71/82 500 9153-4D C08F 2/46 MDH C08J 5/18 9267-4F
Claims (19)
単分子膜または単分子膜累積膜が多孔性の基板表面に形
成され、触媒または放射線照射を用いて重合されている
ことを特徴とする選択透過性膜。1. A monomolecular film or a monomolecular film cumulative film of a substance containing a polymerizable group and another functional group is formed on the surface of a porous substrate and polymerized by using a catalyst or radiation irradiation. A permselective membrane characterized by:
たはジアセチレン基であることを特徴とした特許請求の
範囲第１項記載の選択透過性膜。2. The selectively permeable membrane according to claim 1, wherein the polymerizable group is a vinyl group, an acetylene group or a diacetylene group.
ことを特徴とした特許請求の範囲第２項記載の選択透過
性膜。3. The permselective membrane according to claim 2, wherein a --SiMe 3 group is bonded to the acetylene group.
選択透過性膜。4. Another functional group is --COOH or The permselective membrane according to claim 1, which contains Cl.
またはセラミックまたは金属であることを特徴とした特
許請求の範囲第１項記載の選択透過性膜。5. The permselective membrane according to claim 1, wherein the porous substrate is a hydrophilic polymer, glass, ceramic or metal.
イノイックトリクロロシラン又は１−（トリメチルシリ
ル）−ω−ノナデシルイノイックトリクロロシランであ
ることを特徴とした特許請求の範囲第２項記載の選択透
過性膜。6. The method according to claim 2, wherein the substance containing an acetylene group is ω-nonadecylinoic trichlorosilane or 1- (trimethylsilyl) -ω-nonadecylinoic trichlorosilane. Permselective membrane.
単分子膜または単分子累積膜を親水性の多孔性の基板表
面に形成する工程と、前記重合性基を触媒または放射線
照射を用いて重合することを特徴とする選択透過性膜の
製造方法。7. A step of forming a monomolecular film or a monomolecular cumulative film of a substance containing a polymerizable group and another functional group on the surface of a hydrophilic porous substrate, and the step of forming the polymerizable group with a catalyst or radiation. A method for producing a selectively permeable membrane, which comprises polymerizing using irradiation.
おいて、化学吸着法又はLB法を用いたことを特徴とする
特許請求の範囲第７項記載の選択透過膜の製造方法。8. The method of producing a permselective membrane according to claim 7, wherein a chemisorption method or an LB method is used in the step of forming the monomolecular film or the monomolecular cumulative film.
チレン基（−CqC−）またはジアセチレン基（−CqC−Cq
C−）基と−Si−Cl基を含む化合物であることを特徴と
する特許請求の範囲第７項記載の選択透過性膜の製造方
法。9. The substance is a vinyl group (-C = C-) or an acetylene group (-CqC-) or a diacetylene group (-CqC-Cq).
The method for producing a selectively permeable membrane according to claim 7, which is a compound containing a C-) group and a -Si-Cl group.
ることを特徴とした特許請求の範囲第９項記載の選択透
過性膜の製造方法。10. The method for producing a selectively permeable membrane according to claim 9, wherein the --SiMe 3 group is bonded to the acetylene group.
Ta又は、ハロゲン化金属触媒と共触媒である有機Snある
いは有機Bi化合物を含むことを特徴とした特許請求の範
囲第７項又は第８項記載の選択透過性膜の製造方法。11. The catalyst is Mo, or W, or Nb, or
9. The method for producing a permselective membrane according to claim 7, which contains Ta or a metal halide catalyst and an organic Sn or organic Bi compound that is a cocatalyst.
チルシリル）−ω−ノナデシルイノイックトリクロロシ
ランであることを特徴とした特許請求の範囲第10項記載
の選択透過性膜の製造方法。12. The method for producing a selectively permeable membrane according to claim 10, wherein the substance containing an acetylene group is 1- (trimethylsilyl) -ω-nonadecylinoic trichlorosilane.
ルイノイックトリクロロシラン又は、１−（トリメチル
シリル）−ω−ノナデシルイノイックトリクロロシラン
であることを特徴とした特許請求の範囲第９項記載の選
択透過性膜の製造方法。13. The method according to claim 9, wherein the substance containing an acetylene group is ω-nonadecylinoic trichlorosilane or 1- (trimethylsilyl) -ω-nonadecylinoic trichlorosilane. Of the permselective membrane of.
セチレン基（−CqC−）またはジアセチレン基（−CqC−
CqC−）基と−COOH基を含む化合物であることを特徴と
する特許請求の範囲第７項又は第８項記載の選択透過性
膜の製造方法。14. The substance is a vinyl group (—C═C—) or an acetylene group (—CqC—) or a diacetylene group (—CqC—).
9. The method for producing a selectively permeable membrane according to claim 7, which is a compound containing a CqC-) group and a -COOH group.
ることを特徴とした特許請求の範囲第14項記載の選択透
過性膜の製造方法。15. The method for producing a selectively permeable membrane according to claim 14, wherein the —SiMe 3 group is bonded to the acetylene group.
Ta又は、ハロゲン化金属触媒と共触媒である有機Snある
いは有機Bi化合物を含むことを特徴とした特許請求の範
囲第７項又は第８項記載の選択透過性膜の製造方法。16. The catalyst is Mo, or W, or Nb, or
9. The method for producing a permselective membrane according to claim 7, which contains Ta or a metal halide catalyst and an organic Sn or organic Bi compound that is a cocatalyst.
ノイック酸又は、１−（トリメチルシリル）−ω−トリ
コシノイック酸であることを特徴とした特許請求の範囲
第14項記載の選択透過性膜の製造方法。17. The selective permeability according to claim 14, wherein the substance containing an acetylene group is ω-tricosinoic acid or 1- (trimethylsilyl) -ω-tricosinoic acid. Membrane manufacturing method.
ンマ線であることを特徴とした特許請求の範囲第１項又
は第７項記載の選択透過性膜の製造方法。18. The method for producing a selectively permeable membrane according to claim 1 or 7, wherein the radiation is an electron beam, an X-ray, or a gamma ray.
膜の形成工程において、水面の面方向に直流電圧を印加
しておくことを特徴とする特許請求の範囲第８項記載の
選択透過性膜の製造方法。19. The selection according to claim 8, wherein a DC voltage is applied in the surface direction of the water surface in the step of forming the monomolecular film or the monomolecular cumulative film using the LB method. Method for manufacturing a permeable membrane.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63137820A JPH0761427B2 (en) | 1988-06-03 | 1988-06-03 | Permselective membrane and method for producing the same |
| EP89110030A EP0344799B1 (en) | 1988-06-03 | 1989-06-02 | Selectively permeable film and process for producing the same |
| DE89110030T DE68909840T2 (en) | 1988-06-03 | 1989-06-02 | Selective permeable film and process for its manufacture. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63137820A JPH0761427B2 (en) | 1988-06-03 | 1988-06-03 | Permselective membrane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01307405A JPH01307405A (en) | 1989-12-12 |
| JPH0761427B2 true JPH0761427B2 (en) | 1995-07-05 |
Family
ID=15207612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63137820A Expired - Fee Related JPH0761427B2 (en) | 1988-06-03 | 1988-06-03 | Permselective membrane and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761427B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0761428B2 (en) * | 1989-03-09 | 1995-07-05 | 松下電器産業株式会社 | Permselective membrane and method for producing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62180777A (en) * | 1986-02-04 | 1987-08-08 | Kanegafuchi Chem Ind Co Ltd | Method for film formation |
-
1988
- 1988-06-03 JP JP63137820A patent/JPH0761427B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01307405A (en) | 1989-12-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |