JP5120787B2 - Production method of supramolecular free-standing film by aromatic ring formation of polyphenylacetylene film - Google Patents
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Description
本発明は、ポリフェニルアセチレン膜の芳香環形成による超分子自立膜の製造方法に関する。 The present invention relates to a method for producing a supramolecular free-standing film by forming an aromatic ring of a polyphenylacetylene film.
ポリフェニルアセチレンは、高温での加熱でわずかに環化三量化を起こし、１，３，５−置換の芳香環が生成することが知られている（非特許文献１）。一方、発明者らは、側鎖間の分子内水素結合によって片巻きらせん構造が保持されているポリ（４−ドデシルオキシ−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）（ポリ（ＤｏＤＨＰＡ））（非特許文献２）が、膜状態において水中への浸漬やＵＶ照射を行うことにより、他のポリフェニルアセチレンには見られない選択的な芳香環形成反応でｃ−トリ（４−ドデシルオキシ−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）（ｃ−トリ（ＤｏＤＨＰＡ））を与えることを見出した。しかも、この際、膜状態が維持された超分子自立膜を与えた（非特許文献３、４）。 It is known that polyphenylacetylene causes slight cyclization and trimerization by heating at a high temperature to produce a 1,3,5-substituted aromatic ring (Non-patent Document 1). On the other hand, the inventors have disclosed poly (4-dodecyloxy-3,5-bis (hydroxymethyl) phenylacetylene) (poly (DoDHPA)) in which a single-wound helical structure is maintained by intramolecular hydrogen bonding between side chains. (Non-Patent Document 2) is a selective aromatic ring formation reaction not found in other polyphenylacetylenes by performing immersion in water or UV irradiation in a film state, and c-tri (4-dodecyloxy- It was found to give 3,5-bis (hydroxymethyl) phenylacetylene) (c-tri (DoDHPA)). In addition, at this time, a supramolecular free-standing film in which the film state was maintained was provided (Non-Patent Documents 3 and 4).
しかし、これまでに、水への浸漬では反応速度が遅く完全に芳香環生成物のみを得られていない。また、ＵＶ照射では反応速度は早いものの芳香環とは異なる有機溶媒に不溶な生成物が１０〜２０％程度生成するといった問題点があった。 However, so far, the immersion rate in water has slow reaction rate, and it has not been possible to obtain only aromatic ring products. Further, although the reaction rate is high by UV irradiation, there is a problem that about 10 to 20% of a product insoluble in an organic solvent different from the aromatic ring is generated.
そこで、本発明は、反応速度が速く、完全に芳香環生成物のみからなる超分子自立膜を製造することのできる、ポリフェニルアセチレン膜の芳香環形成による超分子自立膜の製造方法を提供することを目的とする。 Accordingly, the present invention provides a method for producing a supramolecular free-standing film by forming an aromatic ring of a polyphenylacetylene film, which can produce a supramolecular free-standing film consisting only of an aromatic ring product and having a high reaction rate. For the purpose.
本発明者らは、上記のような特徴的な反応性を示す片巻らせんポリ（ＤｏＤＨＰＡ）膜の芳香環形成反応を用いて、環化三量体のみからなる超分子自立膜の製造を試みるため、反応条件の検討及び置換基の異なるポリ（４−［４−（フェニルエチニル）ベンジルオキシ］−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜（ポリ（ＰＥＢＤＨＰＡ）膜）、及びポリ（４−［４−（ドデシルオキシ）ベンジルオキシ］−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜（ポリ（ＤｏＢＤＨＰＡ）膜）との芳香環形成反応の選択性の比較を行なった。そして、その結果、本発明に想到した。 The present inventors tried to produce a supramolecular self-supporting film composed only of a cyclized trimer by using an aromatic ring formation reaction of a single-wound helical poly (DoDHPA) film exhibiting the characteristic reactivity as described above. Therefore, poly (4- [4- (phenylethynyl) benzyloxy] -3,5-bis (hydroxymethyl) phenylacetylene) film (poly (PEBDHPA) film) and poly (PE The selectivity of the aromatic ring formation reaction with a 4- [4- (dodecyloxy) benzyloxy] -3,5-bis (hydroxymethyl) phenylacetylene) membrane (poly (DoBDHPA) membrane) was compared. As a result, the present invention has been conceived.
すなわち、本発明のポリフェニルアセチレン膜の芳香環形成による超分子自立膜の製造方法は、ポリフェニルアセチレン膜に蛍光灯による可視光を照射することを特徴とする。 That is, the method for producing a supramolecular free-standing film by forming an aromatic ring of a polyphenylacetylene film according to the present invention is characterized in that visible light from a fluorescent lamp is irradiated onto the polyphenylacetylene film.
また、前記ポリフェニルアセチレン膜は、ポリ（４−ドデシルオキシ−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜、ポリ（４−［４−（フェニルエチニル）ベンジルオキシ］−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜、ポリ（４−［４−（ドデシルオキシ）ベンジルオキシ］−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜のいずれかであることを特徴とする。 The polyphenylacetylene film includes a poly (4-dodecyloxy-3,5-bis (hydroxymethyl) phenylacetylene) film and a poly (4- [4- (phenylethynyl) benzyloxy] -3,5-bis. It is a (hydroxymethyl) phenylacetylene) film or a poly (4- [4- (dodecyloxy) benzyloxy] -3,5-bis (hydroxymethyl) phenylacetylene) film.
さらに、前記ポリフェニルアセチレン膜は、ポリ（４−ドデシルオキシ−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜であることを特徴とする。 Further, the polyphenylacetylene film is a poly (4-dodecyloxy-3,5-bis (hydroxymethyl) phenylacetylene) film.
本発明によれば、ポリフェニルアセチレン膜に蛍光灯による可視光を照射することにより、ポリフェニルアセチレン膜の芳香環形成反応の選択性を向上して、芳香環生成物からなる超分子自立膜を製造することができる。 According to the present invention, by irradiating the polyphenylacetylene film with visible light from a fluorescent lamp, the selectivity of the aromatic ring formation reaction of the polyphenylacetylene film is improved, and a supramolecular free-standing film made of an aromatic ring product is formed. Can be manufactured.
本発明のポリフェニルアセチレン膜の芳香環形成による超分子自立膜の製造方法は、ポリフェニルアセチレン膜に蛍光灯による可視光を照射するものである。 The method for producing a supramolecular free-standing film by forming an aromatic ring of a polyphenylacetylene film according to the present invention irradiates the polyphenylacetylene film with visible light from a fluorescent lamp.
ここで使用されるポリフェニルアセチレン膜は、フェニルアセチレンを重合、製膜して得られる。また、片巻きらせん構造を有しているポリフェニルアセチレンからなるものが好適に用いられる。このようなポリフェニルアセチレン膜としては、これらに限定されるものではないが、例えば、ポリ（４−ドデシルオキシ−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜（ポリ（ＤｏＤＨＰＡ）膜）、ポリ（４−［４−（フェニルエチニル）ベンジルオキシ］−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜（ポリ（ＰＥＢＤＨＰＡ）膜）、ポリ（４−［４−（ドデシルオキシ）ベンジルオキシ］−３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜（ポリ（ＤｏＢＤＨＰＡ）膜）のいずれかを用いることができる。 The polyphenylacetylene film used here is obtained by polymerizing and forming phenylacetylene. Moreover, what consists of polyphenyl acetylene which has a single-winding helical structure is used suitably. Examples of such polyphenylacetylene films include, but are not limited to, poly (4-dodecyloxy-3,5-bis (hydroxymethyl) phenylacetylene) films (poly (DoDHPA) films), Poly (4- [4- (phenylethynyl) benzyloxy] -3,5-bis (hydroxymethyl) phenylacetylene) membrane (poly (PEBDHPA) membrane), poly (4- [4- (dodecyloxy) benzyloxy] Any of −3,5-bis (hydroxymethyl) phenylacetylene) film (poly (DoBDHPA) film) can be used.
ポリフェニルアセチレン膜への蛍光灯による可視光の照射は、不活性ガス雰囲気下、例えば、窒素雰囲気下において行うのが望ましい。なお、蛍光灯による可視光を照射する時間は、適宜調節すればよい。 Irradiation of visible light with a fluorescent lamp to the polyphenylacetylene film is preferably performed in an inert gas atmosphere, for example, in a nitrogen atmosphere. In addition, what is necessary is just to adjust suitably the time which irradiates visible light with a fluorescent lamp.
また、ここで使用される蛍光灯は、特定のものに限られない。例えば、色温度の種類として、昼光色（5700〜7100K）、昼白色（4600〜5400K）、白色（3900〜4500K）、温白色（3200〜3700K）、電球色（2600〜3150K）のもの、演色性の種類として、三波長発光形蛍光灯、高演色形蛍光灯、一般型（普及型）蛍光灯のいずれであっても用いることができる。 Moreover, the fluorescent lamp used here is not restricted to a specific thing. For example, daylight color (5700-7100K), day white (4600-5400K), white (3900-4500K), warm white (3200-3700K), light bulb color (2600-3150K), color rendering As the type, any of a three-wavelength light-emitting fluorescent lamp, a high color rendering fluorescent lamp, and a general type (spread type) fluorescent lamp can be used.
そして、ポリフェニルアセチレン膜へ可視光を照射することによって、化１に示すように、膜状態を維持したままポリマー主鎖が選択的に芳香環を形成して、環化三量体からなる超分子自立膜が合成される。なお、化１は、ポリ（３，５−ビス（ヒドロキシメチル）フェニルアセチレン）膜（ポリ（ＤＨＰＡ）膜）を用いた場合の反応式を示している。 Then, by irradiating the polyphenylacetylene film with visible light, as shown in Chemical Formula 1, the polymer main chain selectively forms an aromatic ring while maintaining the film state, and the superstructure consisting of the cyclized trimer is formed. A molecular free-standing film is synthesized. Chemical formula 1 shows a reaction formula when a poly (3,5-bis (hydroxymethyl) phenylacetylene) film (poly (DHPA) film) is used.
このようにして得られた超分子自立膜は、工業用、医薬品用として、幅広い利用が可能である。 The supramolecular free-standing film thus obtained can be widely used for industrial use and pharmaceutical use.
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、本発明のポリフェニルアセチレン膜の芳香環形成による超分子自立膜の製造方法について説明する。 Hereinafter, a method for producing a supramolecular free-standing film by forming an aromatic ring of the polyphenylacetylene film of the present invention will be described more specifically.
［ポリフェニルアセチレンの合成］
フェニルアセチレンとして、４−ドデシルオキシ−３，５−ビス（ヒドロキシメチル）フェニルアセチレン（ＤｏＤＨＰＡ）、４−［４−（フェニルエチニル）ベンジルオキシ］−３，５−ビス（ヒドロキシメチル）フェニルアセチレン（ＰＥＢＤＨＰＡ）、４−［４−（ドデシルオキシ）ベンジルオキシ］−３，５−ビス（ヒドロキシメチル）フェニルアセチレン（ＤｏＢＤＨＰＡ）を用いて、下記の反応条件１〜３にて、片巻きらせん構造を有するポリフェニルアセチレンを合成した。
[Synthesis of polyphenylacetylene]
As phenylacetylene, 4-dodecyloxy-3,5-bis (hydroxymethyl) phenylacetylene (DoDHPA), 4- [4- (phenylethynyl) benzyloxy] -3,5-bis (hydroxymethyl) phenylacetylene (PEBDHPA) ), 4- [4- (dodecyloxy) benzyloxy] -3,5-bis (hydroxymethyl) phenylacetylene (DoBDHPA), and the reaction conditions 1 to 3 below, Phenylacetylene was synthesized.
三方コックを取り付けた試験管に３００ｍｇのフェニルアセチレンを入れて窒素置換した。そこへ無水トルエンを下記の濃度になるように加え、均一溶液としてモノマー溶液を得た。また、［Ｒｈ（ｎｂｄ）Ｃｌ］２（ｎｂｄ：ノルボルナジエン）を秤取り無水トルエンに溶かして均一系としたロジウム触媒溶液を別途用意し、そこに（Ｒ）−ＰＥＡ（フェニルエチルアミン）又は（Ｓ）−ＰＥＡを下記の共触媒比になるように加えた。その後、下記の触媒比になるように触媒溶液を秤取り、モノマー溶液にすばやく加えて室温で撹拌した。下記の時間の反応後、大量のメタノール中に滴下し、沈殿したポリマーをＧ４ガラスフィルターで吸引ろ過し、デシケータ内で一晩乾燥させた。
（反応条件１）［ＤｏＤＨＰＡ］＝０．１０ｍｏｌ／Ｌ，［ＤｏＤＨＰＡ］／［［Ｒｈ（ｎｂｄ）Ｃｌ］２］＝５０，［（Ｒ）−ＰＥＡ］／［［Ｒｈ（ｎｂｄ）Ｃｌ］２］＝２５０，３ｈ
（反応条件２）［ＰＥＢＤＨＰＡ］＝０．１５ｍｏｌ／Ｌ，［ＰＥＢＤＨＰＡ］／［Ｒｈ（ｎｂｄ）Ｃｌ］２］＝５０，［（Ｒ）−ＰＥＡ］／［Ｒｈ（ｎｂｄ）Ｃｌ］２］＝２５０，２４ｈ
（反応条件３）［ＤｏＢＤＨＰＡ］＝０．１０ ｍｏｌ／Ｌ，［ＤｏＢＤＨＰＡ］／［［Ｒｈ（ｎｂｄ）Ｃｌ］２］＝１００，［（Ｒ）−ＰＥＡ］／［［Ｒｈ（ｎｂｄ）Ｃｌ］２］＝１００），６ｈ
［ポリフェニルアセチレン膜の調製］
得られたポリマー３０ｍｇをトルエン１６ｍＬ、クロロホルム４ｍＬ、又はテトラヒドロフラン４ｍＬに溶解させ、キャスト法により膜厚１５〜３０μｍの膜を製膜し、１日減圧乾燥した。
A test tube equipped with a three-way cock was charged with 300 mg of phenylacetylene and purged with nitrogen. Anhydrous toluene was added to the following concentration to obtain a monomer solution as a uniform solution. Further, a rhodium catalyst solution prepared by weighing [Rh (nbd) Cl] 2 (nbd: norbornadiene) and dissolving it in anhydrous toluene to prepare a homogeneous system is prepared separately, and (R) -PEA (phenylethylamine) or (S) is prepared there. -PEA was added to give the following cocatalyst ratio. Thereafter, the catalyst solution was weighed so as to have the following catalyst ratio, quickly added to the monomer solution, and stirred at room temperature. After the reaction for the following time, the solution was dropped into a large amount of methanol, and the precipitated polymer was suction filtered through a G4 glass filter and dried overnight in a desiccator.
(Reaction condition 1) [DoDHPA] = 0.10 mol / L, [DoDHPA] / [[Rh (nbd) Cl] 2 ] = 50, [(R) -PEA] / [[Rh (nbd) Cl] 2 ] = 250,3h
(Reaction condition 2) [PEBDHPA] = 0.15 mol / L, [PEBDHPA] / [Rh (nbd) Cl] 2 ] = 50, [(R) -PEA] / [Rh (nbd) Cl] 2 ] = 250 , 24h
(Reaction condition 3) [DoBDHPA] = 0.10 mol / L, [DoBDHPA] / [[Rh (nbd) Cl] 2 ] = 100, [(R) -PEA] / [[Rh (nbd) Cl] 2 ] = 100), 6h
[Preparation of polyphenylacetylene film]
30 mg of the resulting polymer was dissolved in 16 mL of toluene, 4 mL of chloroform, or 4 mL of tetrahydrofuran, a film having a film thickness of 15 to 30 μm was formed by a casting method, and dried under reduced pressure for 1 day.
［超分子自立膜の調製］
調製されたポリマー膜をガラス瓶に入れ、Ｎ２雰囲気下で蛍光灯（昼白色、２７Ｗ）による光照射を行うことで、選択的な芳香環形成反応を行った。
[Preparation of supramolecular free-standing film]
The prepared polymer film was put into a glass bottle, and a selective aromatic ring formation reaction was performed by irradiating light with a fluorescent lamp (day white, 27 W) under an N 2 atmosphere.
反応後、１Ｈ ＮＭＲ、１３Ｃ ＮＭＲ、ＭＡＬＤＩ−ＴＯＦ−ＭＳ及びＧＰＣ測定により、構造、分子量を決定した。生成物の１Ｈ ＮＭＲ、１３Ｃ ＮＭＲから、生成物が環状構造であることが同定された。さらに、ポリ（ＤｏＤＨＰＡ）の光照射により得られた生成物のＭＡＬＤＩ−ＴＯＦ−ＭＳ測定の結果、質量はＭ／Ｚ＝１０６１（Ｍ＋Ｎａ＋)であり、化１に示す環化三量体であることが確認された（図１）。反応後の膜のＧＰＣは、図１、２に示すように、高分子量のピークが消失して新たに低分子量体のピークが現れ、反応の進行が確認された。また、ＧＰＣより求めた光照射による環化三量化の選択性は、ポリ（ＤｏＤＨＰＡ）は９８％、ポリ（ＤｏＢＤＨＰＡ）は７４％であった。 After the reaction, the structure and molecular weight were determined by 1 H NMR, 13 C NMR, MALDI-TOF-MS and GPC measurement. From the 1 H NMR and 13 C NMR of the product, it was identified that the product had a cyclic structure. Furthermore, as a result of MALDI-TOF-MS measurement of the product obtained by light irradiation of poly (DoDHPA), the mass was M / Z = 1061 (M + Na + ), which is a cyclized trimer shown in Chemical formula 1. (Fig. 1). As shown in FIGS. 1 and 2, the GPC of the membrane after the reaction disappeared from the high molecular weight peak and a new low molecular weight peak appeared, confirming the progress of the reaction. Moreover, the selectivity of the cyclization trimerization by light irradiation calculated | required from GPC was 98% for poly (DoDHPA), and 74% for poly (DoBDHPA).
図３に示すように、片巻きらせんポリ（ＤｏＤＨＰＡ）の光照射により、環化三量体からなる超分子自立膜が合成された。なお、光照射前の膜は濃い赤色であった（図３左）が、光照射後は薄い橙色になった（図３右）。 As shown in FIG. 3, a supramolecular free-standing film composed of a cyclized trimer was synthesized by light irradiation of a single-wound spiral poly (DoDHPA). In addition, the film before light irradiation was dark red (FIG. 3 left), but became light orange after light irradiation (FIG. 3 right).
［ＵＶ照射との比較］
光照射に、高圧水銀ランプ（ＵＶ光照射、２５３．７〜５７９．１ｎｍ）、蛍光灯（可視光照射、３波長形昼白色２７Ｗ、（４５０、５４０、６１０ｎｍ））をそれぞれ用いた。片巻きらせんポリマーの芳香環形成反応は、ＵＶ及びＣＤ検出器を備えたＧＰＣ測定（ポリスチレン標準）で評価した。また、生成物の同定は１Ｈ ＮＭＲ、１３Ｃ ＮＭＲ及びＭＡＬＤＩ−ＴＯＦ−ＭＳによって行った。
[Comparison with UV irradiation]
For light irradiation, a high-pressure mercury lamp (UV light irradiation, 253.7 to 579.1 nm) and a fluorescent lamp (visible light irradiation, three-wavelength daylight white 27 W, (450, 540, 610 nm)) were used. The aromatic ring formation reaction of the single-wound helical polymer was evaluated by GPC measurement (polystyrene standard) equipped with UV and CD detectors. The product was identified by 1 H NMR, 13 C NMR and MALDI-TOF-MS.
ポリ（ＤｏＤＨＰＡ）膜の蛍光灯による可視光照射を行った結果、水銀ランプによるＵＶ光照射よりも反応は遅かったものの、４週間で高分子量体のピークが消失し、わずかにオリゴマーを含むものの、新たに低分子量域に単峰性の環化三量体のピークが観測された。また、反応後の膜は、ＵＶ照射により得られた不溶部は生成せず、ＴＨＦに全て可溶であった。このように、可視光照射を行うことで、芳香環形成反応の選択性は９４％となり、高い選択性を示した。 As a result of performing visible light irradiation with a fluorescent lamp of a poly (DoDHPA) film, although the reaction was slower than UV light irradiation with a mercury lamp, the peak of the high molecular weight disappeared in 4 weeks, and a slight oligomer was included. A new peak of unicyclic cyclized trimer was observed in the low molecular weight region. Moreover, the insoluble part obtained by UV irradiation did not produce | generate the film | membrane after reaction, but it was all soluble in THF. Thus, by performing visible light irradiation, the selectivity of the aromatic ring formation reaction was 94%, indicating high selectivity.
一方、高圧水銀ランプによるＵＶ光照射では、わずか１８時間でＧＰＣによる高分子領域のピークが完全に消失し、オリゴマーを含むものの、新たに低分子量域に単峰性の環化三量体のピークが観測された。しかし、ＵＶ光照射では、ＴＨＦなどの有機溶媒に不溶な生成物が１７％生成し、芳香環形成反応の選択性は７４％と低かった。 On the other hand, in the UV light irradiation with a high-pressure mercury lamp, the peak of the polymer region due to GPC disappears completely in 18 hours and contains oligomers, but the peak of a new monocyclic cyclized trimer in the low molecular weight region. Was observed. However, irradiation with UV light produced 17% of a product insoluble in organic solvents such as THF, and the selectivity of the aromatic ring formation reaction was as low as 74%.
［置換基による芳香環形成反応の選択性への影響］
置換基Ｒの異なるポリ（ＰＥＢＤＨＰＡ）及びポリ（ＤｏＢＤＨＰＡ）の自立膜へ高圧水銀ランプによる光照射を行い、置換基による芳香環形成反応の選択性について検討した。
[Influence on selectivity of aromatic ring formation reaction by substituents]
The poly (PEBDHPA) and poly (DoBDHPA) free-standing films having different substituents R were irradiated with light using a high-pressure mercury lamp, and the selectivity of the aromatic ring formation reaction by the substituents was examined.
いずれも高分子量体のピークが消失し、新たに低分子量域に環化三量体のピークが観測されたものの、オリゴマーの量が多く、さらにポリ（ＤｏＤＨＰＡ）膜と同様に、ＴＨＦ不溶部が生成した。ポリ（ＰＥＢＤＨＰＡ）及びポリ（ＤｏＢＤＨＰＡ）では、ＴＨＦ不溶部の生成量がポリ（ＤｏＤＨＰＡ）より多く、ＴＨＦ不溶部の生成物がそれぞれ２５％、４１％生成した。また、芳香環形成反応の選択性は、それぞれ６４％、４２％であった。これにより、置換基により選択性が大きく異なり、ポリ（ＤｏＤＨＰＡ）膜が最も高い選択性を有することがわかった。 In both cases, the peak of the high molecular weight disappeared, and the peak of the cyclized trimer was newly observed in the low molecular weight region, but the amount of oligomer was large and, like the poly (DoDHPA) film, the THF insoluble part was present. Generated. In poly (PEBDHPA) and poly (DoBDHPA), the amount of THF-insoluble part produced was larger than that of poly (DoDHPA), and the product of THF-insoluble part was produced by 25% and 41%, respectively. The selectivity of the aromatic ring formation reaction was 64% and 42%, respectively. Thereby, it was found that the selectivity varies greatly depending on the substituent, and the poly (DoDHPA) membrane has the highest selectivity.
［製膜法の比較］
上記の可視光照射又はＵＶ光照射により得られたいずれの膜も、芳香環形成反応後に膜の状態を保っており、ポリ（ＤｏＤＨＰＡ）膜の可視光照射により得られた膜の組成が９４％環状化合物（ｃ−トリ（ＤｏＤＨＰＡ））からなる膜でさえ自立性を示した。一方、精製したｃ−トリ（ＤｏＤＨＰＡ）をＴＨＦ溶液からキャスト法により製膜しても自立膜は得られなかった。
[Comparison of film forming methods]
Any of the films obtained by the above visible light irradiation or UV light irradiation maintains the film state after the aromatic ring formation reaction, and the composition of the film obtained by the visible light irradiation of the poly (DoDHPA) film is 94%. Even membranes made of cyclic compounds (c-tri (DoDHPA)) showed self-supporting properties. On the other hand, even when purified c-tri (DoDHHPA) was formed from a THF solution by a casting method, a self-supporting film was not obtained.
これらのことから、ポリ（ＤｏＤＨＰＡ）鎖の選択的な芳香環形成反応は、膜状態と水素結合を保ちながら環化三量化を起こし、超分子的に自立膜の状態が維持されたと考えられた。 From these, it was considered that the selective aromatic ring formation reaction of the poly (DoDHPA) chain caused cyclization and trimerization while maintaining the membrane state and hydrogen bond, and the state of the self-supporting membrane was supramolecularly maintained. .
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