JP2010163561A - Substituted polyacetylene, production method thereof, self-supporting substituted polyacetylene film, production method thereof, carbon dioxide separation membrane, and film which reversibly changes color thereof upon elongation or contraction - Google Patents
Substituted polyacetylene, production method thereof, self-supporting substituted polyacetylene film, production method thereof, carbon dioxide separation membrane, and film which reversibly changes color thereof upon elongation or contraction Download PDFInfo
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- 0 C*C=C(*(C)C)c1ccc(CN2C(CC3)N(*)CC2C3ClC)cc1 Chemical compound C*C=C(*(C)C)c1ccc(CN2C(CC3)N(*)CC2C3ClC)cc1 0.000 description 2
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Abstract
Description
本発明は、イオン液体構造を有する、新規の置換ポリアセチレン及びその製造方法、置換ポリアセチレン自立膜及びその製造方法、気体分離膜、伸縮により可逆的に色変化を呈する膜に関する。 The present invention relates to a novel substituted polyacetylene having an ionic liquid structure and a method for producing the same, a substituted polyacetylene free-standing membrane and a method for producing the same, a gas separation membrane, and a membrane that reversibly changes color by stretching.
イオン液体は、イオンのみからなる液体であり、難揮発性や高い熱安定性などの特徴を持つ。このため、電解質、溶媒、分離・抽出などのさまざまな分野への応用が研究されている。 An ionic liquid is a liquid composed only of ions and has characteristics such as low volatility and high thermal stability. For this reason, applications to various fields such as electrolytes, solvents, separation and extraction have been studied.
近年、二酸化炭素がイオン液体中に溶解することが見出された（非特許文献１）。また、イオン液体にアミノ基を導入することにより二酸化炭素を溶解する性能が向上された（非特許文献２）。このような性質を有するイオン液体は、二酸化炭素分離膜に有望な材料として期待される。イオン液体を高分子化し、丈夫な自己支持膜を得ることができれば気体分離などさまざまな機能が期待できる。しかし、従来の技術では丈夫な膜ができていない。 In recent years, it has been found that carbon dioxide dissolves in an ionic liquid (Non-Patent Document 1). Moreover, the performance which melt | dissolves a carbon dioxide was improved by introduce | transducing an amino group into an ionic liquid (nonpatent literature 2). An ionic liquid having such properties is expected as a promising material for a carbon dioxide separation membrane. If an ionic liquid is polymerized and a strong self-supporting membrane can be obtained, various functions such as gas separation can be expected. However, the conventional technology has not produced a strong film.
一方、置換ポリアセチレンは、優れた自己支持膜性を持ち、大きな気体透過性を示すことが知られている（非特許文献３）。 On the other hand, substituted polyacetylene is known to have excellent self-supporting membrane properties and large gas permeability (Non-patent Document 3).
そこで、本発明は、自己支持膜性を有し、二酸化炭素分離膜をはじめさまざまな利用が可能な、新規の置換ポリアセチレン及びその製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a novel substituted polyacetylene having a self-supporting membrane property and capable of various uses including a carbon dioxide separation membrane and a method for producing the same.
本発明の請求項１記載の置換ポリアセチレンは、一般式（１）〜（３） The substituted polyacetylene according to claim 1 of the present invention has the general formulas (1) to (3).
（式中、Ｒは炭化水素基、ｎは自然数）のいずれかで表される。 (Wherein R is a hydrocarbon group and n is a natural number).
本発明の請求項２に記載の置換ポリアセチレンは、請求項１において、Ｒがメチル基、エチル基、プロピル基、ブチル基、アリル基、ベンジル基のいずれかである。 In the substituted polyacetylene according to claim 2 of the present invention, in claim 1, R is any one of a methyl group, an ethyl group, a propyl group, a butyl group, an allyl group, and a benzyl group.
本発明の請求項３に記載の置換ポリアセチレン自立膜は、請求項１又は２に記載の置換ポリアセチレンからなる。 A substituted polyacetylene self-supporting film according to a third aspect of the present invention comprises the substituted polyacetylene according to the first or second aspect.
本発明の請求項４に記載の二酸化炭素分離膜は、請求項１又は２に記載の置換ポリアセチレンからなる。 A carbon dioxide separation membrane according to a fourth aspect of the present invention comprises the substituted polyacetylene according to the first or second aspect.
本発明の請求項５に記載の伸縮により可逆的に色変化を呈する膜は、請求項１又は２に記載の置換ポリアセチレンからなる。 The film which reversibly changes color by expansion and contraction according to claim 5 of the present invention is composed of the substituted polyacetylene according to claim 1 or 2.
本発明の請求項６に記載の置換ポリアセチレンの製造方法は、一般式（４） The method for producing a substituted polyacetylene according to claim 6 of the present invention is represented by the general formula (4).
（式中、Ｒは炭化水素基）で表される置換アセチレンを重合して一般式（５） (Wherein R is a hydrocarbon group) and the substituted acetylene represented by general formula (5)
（式中、Ｒは炭化水素基、ｎは自然数）で表される置換ポリアセチレンを得る重合工程と、この置換ポリアセチレンをアニオン交換して一般式（１）〜（３） (Wherein R is a hydrocarbon group, n is a natural number) and a polymerization step for obtaining a substituted polyacetylene, and the substituted polyacetylene is anion-exchanged to perform the general formulas (1) to (3)
（式中、Ｒは炭化水素基、ｎは自然数）のいずれかで表される置換ポリアセチレンを得るアニオン交換工程と、を備えたことを特徴とする。 (Wherein R is a hydrocarbon group, and n is a natural number), and an anion exchange step for obtaining a substituted polyacetylene.
本発明の請求項７に記載の置換ポリアセチレン製造方法は、請求項６において、Ｒがメチル基、エチル基、プロピル基、ブチル基、アリル基、ベンジル基のいずれかである。 According to a seventh aspect of the present invention, in the method for producing a substituted polyacetylene according to the sixth aspect, R is any one of a methyl group, an ethyl group, a propyl group, a butyl group, an allyl group, and a benzyl group.
本発明の請求項８に記載の置換ポリアセチレンの製造方法は、請求項６又は７において、前記重合工程において、触媒として［Ｒｕ（ｎｂｄ）Ｃｌ］２とトリエチルアミンを用い、溶媒としてＮ，Ｎ−ジメチルホルムアミドを用いる。 The method for producing a substituted polyacetylene according to claim 8 of the present invention is the method according to claim 6 or 7, wherein in the polymerization step, [Ru (nbd) Cl] 2 and triethylamine are used as a catalyst and N, N-dimethyl is used as a solvent. Formamide is used.
本発明の請求項９に記載の置換ポリアセチレンの製造方法は、請求項６〜８のいずれかにおいて、前記アニオン交換工程において、溶媒として水あるいはメタノールを用いる。 The method for producing a substituted polyacetylene according to claim 9 of the present invention uses water or methanol as a solvent in any one of claims 6 to 8 in the anion exchange step.
本発明の請求項１０に記載の置換ポリアセチレン自立膜の製造方法は、請求項１又は２に記載の置換ポリアセチレンを製膜して自立膜を得る製膜工程を備えたことを特徴とする。 According to a tenth aspect of the present invention, there is provided a method for producing a substituted polyacetylene self-supporting film, comprising a film forming step of forming a self-supporting film by forming the substituted polyacetylene according to the first or second aspect.
本発明の請求項１１に記載の置換ポリアセチレン自立膜の製造方法は、請求項１０において、前記製膜工程において、溶媒としてメタノール、アセトン、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミドのいずれかを用いる。 A method for producing a substituted polyacetylene self-supporting film according to an eleventh aspect of the present invention uses the methanol, acetone, acetonitrile, or N, N-dimethylformamide as a solvent in the film forming step according to the tenth aspect.
本発明によれば、自己支持膜性を有し、二酸化炭素分離膜の材料として利用可能な、新規の置換ポリアセチレン及びその製造方法を提供することができる。さらに、本発明の置換ポリアセチレンにより、新規の置換ポリアセチレン自立膜及びその製造方法、気体分離膜、伸縮により可逆的に色変化を呈する膜を提供することができる。 The present invention can provide a novel substituted polyacetylene having a self-supporting membrane property and usable as a material for a carbon dioxide separation membrane, and a method for producing the same. Furthermore, the substituted polyacetylene of the present invention can provide a novel substituted polyacetylene self-supporting membrane, a method for producing the same, a gas separation membrane, and a membrane that reversibly changes color due to expansion and contraction.
本発明の請求項１記載の置換ポリアセチレンは、イミダゾリル基とイオン液体構造を有し、一般式（１）〜（３） The substituted polyacetylene according to claim 1 of the present invention has an imidazolyl group and an ionic liquid structure, and is represented by the general formulas (1) to (3).
（式中、Ｒは炭化水素基、ｎは自然数）のいずれかで表される。ここで、Ｒは、任意の炭化水素基であって特定のものに限定されないが、製造の容易さを考慮すると、メチル基、エチル基、プロピル基、ブチル基、アリル基、ベンジル基のいずれかが好ましい。また、ｎは、任意の自然数であって特定のものに限定されないが、本発明の置換ポリアセチレンからなる自立膜の強度等を考慮すると、１０以上が好ましく、さらには１５以上が好ましい。なお、Ｒ及びｎについては、以下の記載においても同様である。 (Wherein R is a hydrocarbon group and n is a natural number). Here, R is an arbitrary hydrocarbon group and is not limited to a specific group, but considering the ease of production, R is any one of a methyl group, an ethyl group, a propyl group, a butyl group, an allyl group, and a benzyl group. Is preferred. Further, n is an arbitrary natural number and is not limited to a specific one, but is preferably 10 or more, and more preferably 15 or more in consideration of the strength of the free-standing film made of the substituted polyacetylene of the present invention. The same applies to R and n in the following description.
本発明の置換ポリアセチレンを製造するには、はじめの重合工程において、一般式（４） In order to produce the substituted polyacetylene of the present invention, in the first polymerization step, the general formula (4)
（式中、Ｒは炭化水素基）で表される置換アセチレンを重合して一般式（５） (Wherein R is a hydrocarbon group) and the substituted acetylene represented by general formula (5)
（式中、Ｒは炭化水素基、ｎは自然数）で表される置換ポリアセチレンを得る。この重合工程において用いられる触媒と溶媒は、置換アセチレンを重合することのできるものであれば特定のものに限定されないが、反応効率等を考慮すると、触媒として［Ｒｕ（ｎｂｄ）Ｃｌ］２（ｎｂｄ＝ノルボルナジエン）とトリエチルアミン、溶媒としてＮ，Ｎ−ジメチルホルムアミドが好適に用いられる。 A substituted polyacetylene represented by the formula (wherein R is a hydrocarbon group and n is a natural number) is obtained. The catalyst and the solvent used in this polymerization step are not limited to specific ones as long as they can polymerize substituted acetylene. However, in consideration of reaction efficiency and the like, [Ru (nbd) Cl] 2 (nbd = Norbornadiene) and triethylamine, and N, N-dimethylformamide is preferably used as a solvent.
つぎのアニオン交換工程において、重合工程で得られた置換ポリアセチレンをアニオン交換して一般式（１）〜（３） In the next anion exchange step, the substituted polyacetylene obtained in the polymerization step is subjected to anion exchange to obtain general formulas (1) to (3).
（式中、Ｒは炭化水素基、ｎは自然数）のいずれかで表される置換ポリアセチレンを得る。すなわち、ＢｒアニオンをＢＦ４アニオン、ＰＦ６アニオン、又は（ＣＦ３ＳＯ２）２Ｎアニオン（Ｔｆ２Ｎアニオン）に交換する。ここでの溶媒は水が好適に用いられ、アニオン交換が終了した置換ポリアセチレンは沈殿物として得られる。 A substituted polyacetylene represented by any one of the formulas (wherein R is a hydrocarbon group and n is a natural number) is obtained. That is, the Br anion is exchanged for a BF 4 anion, a PF 6 anion, or a (CF 3 SO 2 ) 2 N anion (Tf 2 N anion). As the solvent here, water is preferably used, and the substituted polyacetylene after anion exchange is obtained as a precipitate.
本発明の置換ポリアセチレン自立膜は、本発明の置換ポリアセチレンからなる。そして、本発明の置換ポリアセチレン自立膜を製造するには、製膜工程において、本発明の置換ポリアセチレンを溶媒に溶解して、キャスト法などにより製膜する。溶媒は、置換ポリアセチレンを溶解できるものであればよく、置換ポリアセチレンの種類に応じて、例えば、メタノール、アセトン、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミドを用いることができる。 The substituted polyacetylene self-supporting film of the present invention is composed of the substituted polyacetylene of the present invention. And in order to manufacture the substituted polyacetylene self-supporting film of the present invention, the substituted polyacetylene of the present invention is dissolved in a solvent and formed into a film by a casting method or the like in the film forming step. Any solvent can be used as long as it can dissolve the substituted polyacetylene. For example, methanol, acetone, acetonitrile, or N, N-dimethylformamide can be used depending on the type of the substituted polyacetylene.
本発明の置換ポリアセチレン自立膜は、高い疎水性を有するフレキシブルな自立膜であり、イオン液体と同様に極めて高い熱安定性を示す。また、本発明の置換ポリアセチレン自立膜は、二酸化炭素に対する高い溶解選択性を示し、高性能な二酸化炭素分離膜として作用する。 The substituted polyacetylene self-supporting film of the present invention is a flexible self-supporting film having high hydrophobicity and exhibits extremely high thermal stability like an ionic liquid. Moreover, the substituted polyacetylene self-supporting membrane of the present invention exhibits high solubility selectivity with respect to carbon dioxide and acts as a high-performance carbon dioxide separation membrane.
さらに、本発明の置換ポリアセチレン自立膜は、伸縮により可逆的に色変化を呈する。この色変化は瞬間的である。このように、本発明の置換ポリアセチレン自立膜は、印加した張力に応じて色が瞬間的・可逆的に変化するため、力学的な力を色の変化で見えるようにすることができ、釣り糸や梱包、建築物などの構造体のストレスを検知するセンサーとしての応用が期待される。 Furthermore, the substituted polyacetylene self-supporting film of the present invention reversibly changes color by expansion and contraction. This color change is instantaneous. As described above, the substituted polyacetylene self-supporting film of the present invention changes its color instantaneously and reversibly according to the applied tension, so that the mechanical force can be seen by the color change, and the fishing line and It is expected to be applied as a sensor for detecting stress in structures such as packaging and buildings.
このほか、本発明の置換ポリアセチレン自立膜は、気体分離膜、有機化合物分離膜、異性体分離膜、印刷工程での帯電防止コーティング剤としての応用が期待される。また、リチウム電池、太陽電池、アクチュエータなどに用いられるポリマー電解質としての用途が考えられる。 In addition, the substituted polyacetylene self-supporting membrane of the present invention is expected to be applied as a gas separation membrane, an organic compound separation membrane, an isomer separation membrane, and an antistatic coating agent in a printing process. Moreover, the use as a polymer electrolyte used for a lithium battery, a solar cell, an actuator, etc. can be considered.
なお、本発明は上記実施形態に限定されるものではなく、本発明の思想を逸脱しない範囲で種々の変形実施が可能である。 The present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.
以下、より具体的に、本発明の置換ポリアセチレン及びその製造方法、置換ポリアセチレン自立膜及びその製造方法、二酸化炭素分離膜、伸縮により可逆的に色変化を呈する膜について説明する。 Hereinafter, the substituted polyacetylene of the present invention and the production method thereof, the substituted polyacetylene self-supporting membrane and the production method thereof, the carbon dioxide separation membrane, and the membrane that reversibly changes color by stretching will be described.
ＥＢＢｕＩｍＢｒモノマーの合成 Synthesis of EBBuImBr monomer
上記のスキーム１にしたがって合成を行った。三方コックフラスコに入れたＮａＨ（０．１３ｍｏｌ，オイル含有）をヘキサンにより洗浄し、窒素置換後、０℃でイミダゾール（７ｇ，０．１ｍｏｌ）のＤＭＦ溶液（５０ｍｌ）をシリンジでゆっくり入れ、生成したＨ２を開放した。１時間反応させた後、ブロモベンジルブロマイド（２５ｇ，０．１ｍｏｌ）のＤＭＦ溶液（４０ｍｌ）を入れ、６０℃で一晩反応させた。反応溶液を濃縮し、ＤＭＦを除去した後ジクロロメタンを加えた。塩をろ別した後、水により洗浄した。硫酸マグネシウムで乾燥し、濃縮した後、シリカカラムクロマトグラフィ及びジクロロメタン／酢酸エチル混合溶媒中での再結晶化により生成した。生成物として、Ｎ−（４−ブロモベンジル）イミダゾール（化合物１）を得た。
化合物１：
外観：白色固体
Ｒｆ：０．３８（クロロホルム：ＭｅＯＨ＝８：１）
収量：１８．３ｇ，収率：７６％
１Ｈ ＮＭＲ（ＣＤＣｌ３，２７０ＭＨｚ，ｐｐｍ）：７．５３（ｓ，１Ｈ，Ｎ−ＣＨ＝Ｎ），７．４９−７．４６（ｄ，２Ｈ，Ａｒ−Ｈ），７．０９（ｓ，１Ｈ，Ｎ−ＣＨ＝ＣＨ−Ｎ），６．８７（ｓ，１Ｈ，Ｎ−ＣＨ＝ＣＨ−Ｎ），７．０３−７．００（ｄ，２Ｈ，Ａｒ−Ｈ）
Synthesis was performed according to Scheme 1 above. NaH (0.13 mol, containing oil) placed in a three-way cock flask was washed with hexane, and after substitution with nitrogen, a DMF solution (50 ml) of imidazole (7 g, 0.1 mol) was slowly added with a syringe at 0 ° C. It opened the H 2. After reacting for 1 hour, a DMF solution (40 ml) of bromobenzyl bromide (25 g, 0.1 mol) was added and reacted at 60 ° C. overnight. The reaction solution was concentrated, DMF was removed, and dichloromethane was added. The salt was filtered off and washed with water. After drying with magnesium sulfate and concentrating, it was produced by silica column chromatography and recrystallization in a mixed solvent of dichloromethane / ethyl acetate. As a product, N- (4-bromobenzyl) imidazole (Compound 1) was obtained.
Compound 1:
Appearance: White solid Rf: 0.38 (chloroform: MeOH = 8: 1)
Yield: 18.3 g, Yield: 76%
1 H NMR (CDCl 3 , 270 MHz, ppm): 7.53 (s, 1H, N—CH═N), 7.49-7.46 (d, 2H, Ar—H), 7.09 (s, 1H, N—CH═CH—N), 6.87 (s, 1H, N—CH═CH—N), 7.03-7.00 (d, 2H, Ar—H)
つぎに、上記のスキーム２にしたがって合成を行った。Ｎ−（４−ブロモベンジル）イミダゾール（化合物１）（１８ｇ，０．０８ｍｏｌ）と触媒（Ｐｄ（ＰＰｈ３）２Ｃｌ２ ０．１ｍｏｌ％，ＰＰｈ３ ０．４ｍｏｌ％，ＣｕＩ ０．３ｍｏｌ％）を２方コックフラスコに入れ、窒素置換後、トリエチルアミン（５０ｍｌ）を入れた。原料が完全に溶解するまでＤＭＦを加え、１時間攪拌してからトリメチルシリルフェニルアセチレン（１３．２ｍｌ，０．０９ｍｏｌ）を入れて６０℃で２４時間反応させた。溶媒を除去した後、酢酸エチルを加えて溶解させた。不溶物をろ別した後、飽和食塩水溶液で洗浄し、硫酸マグネシウムにより水分を取り除いた。乾燥後、シリカゲルカラムクロマトグラフィにより精製し、Ｎ−（４−トリメチルシリルエチニルベンジル）イミダゾール（化合物２）を白色固体として得た（収率６８％）。得られた化合物２とＫ２ＣＯ３（５倍モル）をメタノールに溶解させ、室温で一晩反応させた。溶媒を除去した後、酢酸エチルを加えて溶解させた。不溶物（塩）をろ別してから飽和食塩水溶液により洗浄し、硫酸マグネシウムで水分を除去した後、濃縮した。得られたＮ−（４−エチニルベンジル)イミダゾール（化合物３）をシリカゲルクロマトグラフィにより精製し、さらにメタノール中で再結晶化を行い、結晶を得た。
化合物３：
収率９３％，収量８．２ｇ
Ｒｆ：０．５（クロロホルム：メタノール＝８：１）
１Ｈ ＮＭＲ（ＣＤＣｌ３，２７０ＭＨｚ，ｐｐｍ）：７．５５（ｓ，１Ｈ，Ｎ−ＣＨ＝Ｎ），７．４９−７．４６（ｄ，２Ｈ，Ａｒ−Ｈ），７．１１（ｓ，１Ｈ，Ｎ−ＣＨ＝ＣＨ−Ｎ），７．０８−７．１０（ｄ，２Ｈ，Ａｒ−Ｈ），６．８９（ｓ，１Ｈ，Ｎ−ＣＨ＝ＣＨ−Ｎ），５．１２（ｓ，２Ｈ，Ｃ−ＣＨ２−Ｎ），３．０９（ｓ，１Ｈ，Ｃ≡Ｈ）
Next, the synthesis was performed according to Scheme 2 above. N- (4-Bromobenzyl) imidazole (Compound 1) (18 g, 0.08 mol) and catalyst (Pd (PPh 3 ) 2 Cl 2 0.1 mol%, PPh 3 0.4 mol%, CuI 0.3 mol%) After putting into a two-way cock flask and nitrogen substitution, triethylamine (50 ml) was added. DMF was added until the raw materials were completely dissolved, and the mixture was stirred for 1 hour, and then trimethylsilylphenylacetylene (13.2 ml, 0.09 mol) was added and reacted at 60 ° C. for 24 hours. After removing the solvent, ethyl acetate was added and dissolved. The insoluble material was filtered off, washed with a saturated saline solution, and water was removed with magnesium sulfate. After drying, the residue was purified by silica gel column chromatography to obtain N- (4-trimethylsilylethynylbenzyl) imidazole (Compound 2) as a white solid (yield 68%). The obtained compound 2 and K 2 CO 3 (5-fold mol) were dissolved in methanol and reacted at room temperature overnight. After removing the solvent, ethyl acetate was added and dissolved. Insoluble matter (salt) was filtered off, washed with a saturated aqueous sodium chloride solution, water was removed with magnesium sulfate, and the mixture was concentrated. The obtained N- (4-ethynylbenzyl) imidazole (compound 3) was purified by silica gel chromatography, and further recrystallized in methanol to obtain crystals.
Compound 3:
Yield 93%, Yield 8.2g
Rf: 0.5 (chloroform: methanol = 8: 1)
1 H NMR (CDCl 3 , 270 MHz, ppm): 7.55 (s, 1H, N—CH═N), 7.49-7.46 (d, 2H, Ar—H), 7.11 (s, 1H, N—CH═CH—N), 7.08-7.10 (d, 2H, Ar—H), 6.89 (s, 1H, N—CH═CH—N), 5.12 (s , 2H, C—CH 2 —N), 3.09 (s, 1H, C≡H)
つぎに、上記のスキーム３にしたがって合成を行った。反応後の溶媒を濃縮した後、過剰のエーテルに滴下し、沈殿を得た。沈殿物を再びエーテルで２回洗い、遠心分離により回収した。１−（４−エチニルベンジル)−３−ブチルイミダゾリウムブロミド（ＥＢＢｕＩｍＢｒ）モノマー（化合物４）は白色固体として得られた。
化合物４：
収率：６２％
１Ｈ ＮＭＲ（ＣＤＣｌ３，２７０ＭＨｚ，ｐｐｍ）：１０．７５（ｓ，１Ｈ，Ｎ−ＣＨ＝Ｎ），７．４９（ｓ，４Ｈ，Ａｒ−Ｈ），７．３５（ｓ，１Ｈ，Ｎ−ＣＨ＝ＣＨ−Ｎ），７．２９（ｓ，１Ｈ，Ｎ−ＣＨ＝ＣＨ−Ｎ），５．６９（ｓ，２Ｈ，Ｃ−ＣＨ２−Ｎ），４．３１−４．２５（ｔ，Ｎ−ＣＨ２−ＣＨ２−），３．１３（ｓ，１Ｈ，Ｃ≡Ｈ），１．９５−１．８４（ｍ，２Ｈ，Ｎ−ＣＨ２−ＣＨ２−），１．４４−１．３０（ｍ，２Ｈ，ＣＨ２−ＣＨ２−ＣＨ３），０．９８−０．９２（ｔ，３Ｈ，ＣＨ２−ＣＨ２−ＣＨ３）
Next, the synthesis was performed according to Scheme 3 above. The solvent after the reaction was concentrated and then added dropwise to excess ether to obtain a precipitate. The precipitate was again washed twice with ether and collected by centrifugation. 1- (4-Ethynylbenzyl) -3-butylimidazolium bromide (EBBuImBr) monomer (Compound 4) was obtained as a white solid.
Compound 4:
Yield: 62%
1 H NMR (CDCl 3 , 270 MHz, ppm): 10.75 (s, 1 H, N—CH═N), 7.49 (s, 4 H, Ar—H), 7.35 (s, 1 H, N—) CH = CH-N), 7.29 (s, 1H, N-CH = CH-N), 5.69 (s, 2H, C-CH 2 -N), 4.31-4.25 (t, N-CH 2 -CH 2 -) , 3.13 (s, 1H, C≡H), 1.95-1.84 (m, 2H, N-CH 2 -CH 2 -), 1.44-1 .30 (m, 2H, CH 2 -CH 2 -CH 3), 0.98-0.92 (t, 3H, CH 2 -CH 2 -CH 3)
ＥＢＢｕＩｍＢｒモノマーの重合 Polymerization of EBBuImBr monomer
上記のスキーム４にしたがってＥＢＢｕＩｍＢｒモノマー（化合物４）の重合を行った。触媒として［Ｒｕ（ｎｂｄ）Ｃｌ］２（ｎｂｄ＝ノルボルナジエン）とトリエチルアミン（ＴＥＡ）を用いた。２４時間反応させた後反応溶液を過剰のアセトンに滴下し、沈澱させた。遠心分離によりポリマーを回収し、乾燥させた。ポリ（１−（４−エチニルベンジル)−３−ブチルイミダゾリウムブロミド）（ポリ（ＥＢＢｕＩｍＢｒ））は黄色ポリマーとして得られた。 The EBBuImBr monomer (compound 4) was polymerized according to the above scheme 4. [Ru (nbd) Cl] 2 (nbd = norbornadiene) and triethylamine (TEA) were used as catalysts. After reacting for 24 hours, the reaction solution was added dropwise to excess acetone to cause precipitation. The polymer was recovered by centrifugation and dried. Poly (1- (4-ethynylbenzyl) -3-butylimidazolium bromide) (poly (EBBuImBr)) was obtained as a yellow polymer.
ポリ（ＥＢＢｕＩｍＢｒ）のアニオン交換反応
下記のスキーム５にしたがって、一晩、ポリマーのアニオン交換を行った。すなわち、ＢｒアニオンをＢＦ４アニオン又は（ＣＦ３ＳＯ２）２Ｎアニオン（Ｔｆ２Ｎアニオン）に交換した。時間の経過に伴い沈澱が観測され、アニオン交換が進行していると考えられた。沈殿は、すべて黄色のものであった。アニオン交換反応前とアニオン交換反応後の重量変化により、アニオン交換率が９５以上であることがわかった。
Anion exchange reaction of poly (EBBuImBr) According to the following scheme 5, the anion exchange of the polymer was performed overnight. That is, the Br anion was exchanged for a BF 4 anion or a (CF 3 SO 2 ) 2 N anion (Tf 2 N anion). Precipitation was observed over time, and anion exchange was considered to be in progress. The precipitate was all yellow. It was found that the anion exchange rate was 95 or more due to the change in weight before and after the anion exchange reaction.
ポリ（ＥＢＢｕＩｍＢｒ）とアニオン交換反応による得られたポリ（ＥＢＢｕＩｍＴｆ２Ｎ）の１Ｈ−ＮＭＲ測定を行った（図１）。最も低磁のピークはイミダゾリウム環の−Ｎ−ＣＨ−Ｎ−のプロトンに由来し、このピークがシフトしたことからアニオンが交換されたことが示唆された。この結果と生成したポリマーの量の変化から、アニオンがほぼ完全に交換されたと考えられた。 1 H-NMR measurement of poly (EBBuImBr) and poly (EBBuImTf 2 N) obtained by anion exchange reaction was performed (FIG. 1). The lowest magnetic peak was derived from the —N—CH—N— proton of the imidazolium ring, and this peak shifted, suggesting that the anion was exchanged. From this result and the change in the amount of polymer produced, it was considered that the anion was almost completely exchanged.
ポリ（ＥＢＢｕＩｍＢｒ）については、イミダゾリウム環のＮ−ＣＨ−Ｎに基づくピークが９．３０から１０．００にシフトし、またアセチレンのプロトンに基づくピーク（４．２７）が消えたことから重合が進行したことが確認された。
ポリ（ＥＢＢｕＩｍＢｒ）：
１Ｈ−ＮＭＲ（ＤＭＳＯ，２７０ＭＨｚ）：１０．００（１Ｈ），７．８５（２Ｈ），７．４７（４Ｈ），５．５０（３Ｈ），４．２０（２Ｈ），１．７７（２Ｈ），１．２３（２Ｈ），０．８６（３Ｈ）
ポリ（ＥＢＢｕＩｍＢＦ４）については、イミダゾリウム環のプロトンが（特にＮ−ＣＨ−Ｎに基づくピークが１０．００から９．１５に）完全にシフトしたことからほぼ完全にアニオン交換されたと考えられた。
ポリ（ＥＢＢｕＩｍＢＦ４）：
１Ｈ−ＮＭＲ（ＤＭＳＯ，２７０ＭＨｚ）：９．１５（１Ｈ），７．６８（１Ｈ），７．２０（２Ｈ），７．０５（２Ｈ），６．６８（１Ｈ），５．５０（１Ｈ），５．０２（１Ｈ），４．１３（２Ｈ），１．８０（２Ｈ），１．２３（２Ｈ），０．８４（３Ｈ）
ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）については、イミダゾリウム環のプロトンが（特にＮ−ＣＨ−Ｎに基づくピークが１０．００から９．１５に）完全にシフトしたことからほぼ完全にアニオン交換されたと考えられた。
ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）：
１Ｈ−ＮＭＲ（ＤＭＳＯ，２７０ＭＨｚ）：９．１５（１Ｈ），７．６８（１Ｈ），７．１４（２Ｈ），７．００（２Ｈ），６．７０（１Ｈ），５．５０（１Ｈ），５．０２（１Ｈ），４．１３（２Ｈ），１．８０（２Ｈ），１．２３（２Ｈ），０．８４（３Ｈ）
For poly (EBBuImBr), the peak due to N—CH—N of the imidazolium ring shifted from 9.30 to 10.00, and the peak due to acetylene proton (4.27) disappeared. It was confirmed that it had progressed.
Poly (EBBuImBr):
1 H-NMR (DMSO, 270 MHz): 10.00 (1H), 7.85 (2H), 7.47 (4H), 5.50 (3H), 4.20 (2H), 1.77 (2H) ), 1.23 (2H), 0.86 (3H)
For poly (EBBuImBF 4 ), it was considered that the proton of the imidazolium ring was almost completely anion-exchanged, especially because the peak based on N—CH—N was completely shifted from 10.00 to 9.15. .
Poly (EBBuImBF 4 ):
1 H-NMR (DMSO, 270 MHz): 9.15 (1H), 7.68 (1H), 7.20 (2H), 7.05 (2H), 6.68 (1H), 5.50 (1H ), 5.02 (1H), 4.13 (2H), 1.80 (2H), 1.23 (2H), 0.84 (3H)
For poly (EBBuImTf 2 N), the proton of the imidazolium ring is considered to be almost completely anion-exchanged, especially because the peak based on N—CH—N was completely shifted from 10.00 to 9.15. It was.
Poly (EBBuImTf 2 N):
1 H-NMR (DMSO, 270 MHz): 9.15 (1H), 7.68 (1H), 7.14 (2H), 7.00 (2H), 6.70 (1H), 5.50 (1H ), 5.02 (1H), 4.13 (2H), 1.80 (2H), 1.23 (2H), 0.84 (3H)
ポリマーの溶解性
ポリマーの溶解性を以下の表２に示す。ポリ（ＥＢＢｕＩｍＢＦ４）とポリ（ＥＢＢｕＩｍＴｆ２Ｎ）は水に不溶であった。これは、ＢＦ４アニオンとＴｆ２Ｎアニオンが水に不溶であるためと考えられる。また、ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）はアセトンとＴＨＦに溶解した。この結果から、アニオン交換により溶解性の制御が可能となることが分かった。
Polymer Solubility Polymer solubility is shown in Table 2 below. Poly (EBBuImBF 4 ) and poly (EBBuImTf 2 N) were insoluble in water. This is considered because BF 4 anion and Tf 2 N anion are insoluble in water. Poly (EBBuImTf 2 N) was dissolved in acetone and THF. From this result, it was found that the solubility can be controlled by anion exchange.
ポリ（ＥＢＢｕＩｍＢｒ）、ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）とポリ（ＥＢＢｕＩｍＢＦ４）の製膜 Poly (EBBuImBr), poly (EBBuImTf 2 N) and poly (EBBuImBF 4 ) film formation
ポリ（ＥＢＢｕＩｍＢｒ）、ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）はメタノールに、ポリ（ＥＢＢｕＩｍＢＦ４）はアセトニトリルに溶解してから濾過し、テフロン（登録商標）シート上にキャスト法で製膜し、ゆっくり乾燥させた後、真空乾燥した。ポリ（ＥＢＢｕＩｍＢｒ）は製膜性が悪く、膜を得ることができなかったが、ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）とポリ（ＥＢＢｕＩｍＢＦ４）はフレキシブルな自立膜として得られた。特にポリ（ＥＢＢｕＩｍＴｆ２Ｎ）は最も優れた強度とフレキシビリティを示した。このことから大きなアニオンに交換することで製膜性が向上することがわかった。 Poly (EBBuImBr), poly (EBBuImTf 2 N) are dissolved in methanol, and poly (EBBuImBF 4 ) is dissolved in acetonitrile, filtered, cast onto a Teflon (registered trademark) sheet, and slowly dried. And vacuum dried. Poly (EBBuImBr) had poor film-forming properties, and a film could not be obtained, but poly (EBBuImTf 2 N) and poly (EBBuImBF 4 ) were obtained as flexible free-standing films. In particular, poly (EBBuImTf 2 N) showed the best strength and flexibility. From this, it was found that the film forming property was improved by exchanging with a large anion.
膜の熱安定性 Thermal stability of membrane
イオン液体構造を有する置換ポリアセチレンであるポリ（ＥＢＢｕＩｍＢＦ４）とポリ（ＥＢＢｕＩｍＴｆ２Ｎ）膜の熱安定性（熱重量測定（ＴＧＡ測定））を検討した。その結果、イオン液体と同様に高い熱安定性を示し、ポリ（ＥＢＢｕＩｍＢＦ４）の場合は３００℃まで、ポリ（ＥＢＢｕＩｍＴｆ２Ｎ)の場合は３５０℃まで、熱分解による重量の減少はほとんど見られなかった。図２は、ＴＧＡ測定結果を示している。 The thermal stability (thermogravimetry (TGA measurement)) of poly (EBBuImBF 4 ) and poly (EBBuImTf 2 N) films, which are substituted polyacetylenes having an ionic liquid structure, was examined. As a result, it shows high thermal stability as in the case of the ionic liquid, with poly (EBBuImBF 4 ) up to 300 ° C. and poly (EBBuImTf 2 N) up to 350 ° C., almost no decrease in weight due to thermal decomposition is seen. There wasn't. FIG. 2 shows the TGA measurement results.
ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）の気体透過性 Gas permeability of poly (EBBuImTf 2 N)
ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）膜に対し、ＣＯ２／Ｎ２気体透過性を検討した。ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）膜の気体透過を測定し（膜厚θ８０μｍ、２５℃における）、その結果を表３に示す。α（ＰＣＯ２／ＰＮ２）は２４．８と高い値であり、二酸化炭素分離膜として作用することが分かった。溶解選択性も非常に高かった。これまでの気体透過性ポリマーで最も高い溶解選択性であった。イオン液体構造はポリマーとＣＯ２の親和性の向上に有効であることがわかった。 The CO 2 / N 2 gas permeability was examined for a poly (EBBuImTf 2 N) membrane. The gas permeation of the poly (EBBuImTf 2 N) membrane was measured (film thickness θ80 μm at 25 ° C.), and the results are shown in Table 3. α (P CO2 / P N2 ) is a high value of 24.8, and it was found that it acts as a carbon dioxide separation membrane. The dissolution selectivity was also very high. The highest gas-permeable polymer so far has the highest dissolution selectivity. It was found that the ionic liquid structure is effective in improving the affinity between the polymer and CO 2 .
ポリ（ＥＢＢｕＩｍＢｒ）のアニオン交換反応（２）
下記のスキーム６にしたがってポリ（ＥＢＢｕＩｍＢｒ）とＫＰＦ６の反応によるアニオン交換を行った。反応に伴いポリマーの沈澱が観測され、アニオン交換が進行したと考えられた。
Anion exchange reaction of poly (EBBuImBr) (2)
Anion exchange by reaction of poly (EBBuImBr) and KPF 6 was performed according to the following scheme 6. Polymer precipitation was observed with the reaction, and anion exchange was considered to have proceeded.
膜の伸び、伸縮と色の変化
ポリ（ＥＢＢｕＩｍＴｆ２Ｎ）にメタノールを少しずつ加え、粘性溶液になるまで溶解させた後、テフロン（登録商標）シート上でキャスト法により製膜し、ゆっくり乾燥させた。その後、真空乾燥により完全に溶媒を除去した。得られた膜を用い、破断伸び率、伸縮と色の変化を検討した。その結果、膜の破断伸び率が２００％（２倍伸びることができる）であった。また、両手で膜を軽く伸ばすと、図３に示すように、膜の色が黄色から赤色に瞬間的に変化した。収縮すると色は黄色に戻り、伸縮を繰り返しても可逆的に色変化を呈することが確認された。
Elongation, expansion and contraction of film and change in color Methanol is added to poly (EBBuImTf 2 N) little by little and dissolved until it becomes a viscous solution. It was. Thereafter, the solvent was completely removed by vacuum drying. Using the obtained film, breaking elongation, expansion and contraction and color change were examined. As a result, the elongation at break of the film was 200% (can be doubled). When the film was lightly stretched with both hands, the film color changed instantaneously from yellow to red as shown in FIG. When contracted, the color returned to yellow, and it was confirmed that the color changes reversibly even after repeated expansion and contraction.
Claims (11)
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| WO2013118776A1 (en) * | 2012-02-06 | 2013-08-15 | 株式会社ルネッサンス・エナジー・リサーチ | Selectively co2-permeable membrane, method for separating co2 from mixed gas, and membrane separation equipment |
| KR20140130469A (en) * | 2012-02-06 | 2014-11-10 | 가부시키가이샤 르네상스 에너지 리서치 | Selectively co2-permeable membrane, method for separating co2 from mixed gas, and membrane separation equipment |
| US9597632B2 (en) | 2012-02-06 | 2017-03-21 | Renaissance Energy Research Corporation | Selectively CO 2-permeable membrane, method for separating CO2 from mixed gas, and membrane separation equipment |
| KR101942135B1 (en) | 2012-02-06 | 2019-01-24 | 가부시키가이샤 르네상스 에너지 리서치 | Selectively co2-permeable membrane, method for separating co2 from mixed gas, and membrane separation equipment |
| JP2017024376A (en) * | 2015-07-28 | 2017-02-02 | 大日本印刷株式会社 | Laminate |
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| JP5131643B2 (en) | 2013-01-30 |
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