JPH0667982B2 - Method for producing highly oriented conjugated polymer - Google Patents
Method for producing highly oriented conjugated polymerInfo
- Publication number
- JPH0667982B2 JPH0667982B2 JP2541590A JP2541590A JPH0667982B2 JP H0667982 B2 JPH0667982 B2 JP H0667982B2 JP 2541590 A JP2541590 A JP 2541590A JP 2541590 A JP2541590 A JP 2541590A JP H0667982 B2 JPH0667982 B2 JP H0667982B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- substrate
- conjugated polymer
- highly oriented
- type highly
- 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.)
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Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、電気材料に関するものである。更に詳しく
は、導電性や非線形光学効果を示すポリアセチレン結合
たはポリアセン結合を有する有機物質に関するものであ
る。TECHNICAL FIELD OF THE INVENTION The present invention relates to electrical materials. More specifically, the present invention relates to an organic substance having a polyacetylene bond or a polyacene bond that exhibits conductivity and a non-linear optical effect.
従来の技術 アセチレン誘導体のポリマーは、パイ電子共役系を持つ
一次元の主鎖を分子内に保有していることで、導電性や
非線形光学効果を持つことから光、電子機能材料として
広く研究されている。2. Description of the Related Art Polymers of acetylene derivatives have a one-dimensional main chain with a pi-electron conjugated system in the molecule, and have conductivity and nonlinear optical effects. ing.
また、ポリアセチレンの製造方法としては、チグラーナ
ッタ触媒を用いた白川らの重合方法がよく知られてい
る。As a method for producing polyacetylene, the polymerization method of Shirakawa et al. Using a Ziegler-Natta catalyst is well known.
発明が解決しようとする課題 ところが、現在知られているポリアセチレン誘導体は、
酸素を含む雰囲気中では、熱や圧力あるいは紫外線など
にたいして不安定であるため、安定化させる研究が進め
られている。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, currently known polyacetylene derivatives are
In an atmosphere containing oxygen, it is unstable with respect to heat, pressure, ultraviolet rays, and the like, so studies for stabilizing it are underway.
しかしながら、未だにアセチレン誘導体ポリマを安定化
する方法は見いだされていない。However, a method for stabilizing an acetylene derivative polymer has not been found yet.
また、配向性を制御する技術も開発されていない。Moreover, a technique for controlling the orientation has not been developed.
課題を解決するための手段 一端に−Si−Cl基を持つ直鎖状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、さらに前記吸着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 for Solving the Problems By using a linear hydrocarbon derivative having a --Si--Cl group at one end, a monomolecular film can be formed on the surface of a hydrophilic substrate by chemisorption in an organic solvent. It is known that a monomolecular film can be formed into a cumulative film by irradiating the surface of the monomolecular film with a high energy ray in a gas containing oxygen to make the surface hydrophilic.
従って、直鎖状炭化水素の一部にアセチレン基やジアセ
チレン基及び酸素（−Ｏ−）を含む物質を用い化学吸着
法を行えば、数十オングストロームオーダのアセチレン
誘導体の単分子膜を形成でき、さらに多層の累積膜も容
易に得ることができる。また、このとき、重合前にあら
かじめ前記単分子膜を特定の方向に選択的に失活させて
おき、金属化合物触媒を含む第２の有機溶媒中に前記基
板を浸漬して、前記単分子膜の残存したアセチレン基や
ジアセチレン基の部分を重合させたり、あるいはラビン
グにより吸着単分子膜中の分子を再配向させておいたの
ち重合させると、配向性が極めて高く、比較的高分子量
（分子量数百以上）で共役系が非常に長くしかも酸素を
含む雰囲気中でも安定で非線形光学効果や導電性の大き
なポリアセチレン系ポリマーが形成されることを発見し
た。また、触媒を用いてジアセチレン基の一部分を重合
させた後、さらに電子線やＸ線、ガンマ線等の放射線を
照射すれば、ポリアセン系ポリマーが形成された。Therefore, if a chemical adsorption method is performed using a substance containing an acetylene group, a diacetylene group, and oxygen (-O-) as a part of a linear hydrocarbon, a monomolecular film of an acetylene derivative of the order of tens of angstroms can be formed. Further, a multilayer cumulative film can be easily obtained. Further, at this time, the monomolecular film is selectively deactivated in a specific direction in advance before polymerization, and the substrate is immersed in a second organic solvent containing a metal compound catalyst to form the monomolecular film. When the remaining acetylene group or diacetylene group is polymerized, or the molecules in the adsorbed monolayer are reoriented by rubbing and then polymerized, the orientation is extremely high and the relative molecular weight (molecular weight It was discovered that a polyacetylene-based polymer having a very long conjugated system and a stable nonlinear optical effect and large conductivity is formed even in an atmosphere containing oxygen. Further, a part of the diacetylene group was polymerized using a catalyst, and then radiation of electron beam, X-ray, gamma ray or the like was further irradiated to form a polyacene polymer.
つまり、一定の方向性を保った状態でエネルギービーム
を用いてアセチレン誘導体の分子を重合することによ
り、共役系が連続した直鎖状のポリマー（共役ポリマ
ー）を作れることを見いだした。That is, it was found that a linear polymer (conjugated polymer) having a continuous conjugated system can be produced by polymerizing molecules of an acetylene derivative using an energy beam while maintaining a certain directionality.
作用 即ち、アセチレン（−Ｃ≡Ｃ−）基あるいはジアセチレ
ン基（−Ｃ≡Ｃ−Ｃ≡Ｃ−）、およびクロルシラン基
（−SiCl）、さらに炭化水素鎖の間に酸素（−Ｏ−）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
の基板を浸漬し、前記基板表面に前記アセチレン基ある
いはジアセチレン基、酸素およびクロルシラン基（−Si
Cl）を含む物質（すなわち直鎖状分子）を化学吸着さ
せ、さらに重合前にあらかじめ前記単分子膜を選択的に
線状に失活させ、さらに金属化合物触媒を含む第２の有
機溶媒中に前記基板を浸漬して重合させると、基板上に
形成されたアセチレン基あるいはジアセチレン基および
クロルシラン基（−SiCl）を含む物質の単分子膜は分子
の重合方向がきれいに並んだ状態で線状に保持されて、
しかも予め失活されていなかった部分のアセチレン誘導
体の化学吸着膜は触媒により線状方向に重合されるの
で、重合方向を制御した状態で共役系が連続した直鎖状
のポリアセチレン系系ポリマーを作ることができる。ま
た、基板表面にジアセチレン基、酸素およびクロルシラ
ン基（−SiCl）を含む物質を化学吸着させた後、重合前
にあらかじめ前記単分子膜を選択的に線状に失活させて
おいてから、金属化合物触媒を含む第２の有機溶媒中に
前記基板を浸漬して重合し、さらに放射線を照射して残
存しているアセチレン基を重合すると、ジアセチレン
基、酸素およびクロルシラン基（−SiCl）を含む物質の
単分子膜は分子の重合方向がきれいに並んだ状態で基板
上に線状に保持されて、しかも予め失活されていなかっ
た部分のジアセチレン誘導体の化学吸着膜はジアセチレ
ン基の一部のアセチレン基が線状方向に重合され、さら
に放射線により残りのアセチレン基が重合されるので、
重合方向を制御した状態で共役系が連続した直鎖状のポ
リアセン系ポリマーを作ることも可能である。Action: That is, an acetylene (-C≡C-) group or a diacetylene group (-C≡C-C≡C-), a chlorosilane group (-SiCl), and oxygen (-O-) between hydrocarbon chains. A hydrophilic substrate is immersed in a non-aqueous organic solvent in which a substance containing is dissolved, and the acetylene group or diacetylene group, oxygen and chlorosilane group (-Si
Cl) -containing substance (that is, linear molecule) is chemisorbed, and the monomolecular film is selectively and linearly deactivated in advance before polymerization, and further, in a second organic solvent containing a metal compound catalyst. When the substrate is immersed and polymerized, a monomolecular film of a substance containing an acetylene group or a diacetylene group and a chlorosilane group (-SiCl) formed on the substrate becomes linear in a state in which the polymerization directions of the molecules are neatly arranged. Held
Moreover, since the chemisorption film of the acetylene derivative that has not been deactivated in advance is polymerized in the linear direction by the catalyst, a linear polyacetylene polymer in which the conjugated system is continuous is formed in the state where the polymerization direction is controlled. be able to. In addition, after chemically adsorbing a substance containing a diacetylene group, oxygen and a chlorosilane group (-SiCl) on the surface of the substrate, the monomolecular film is selectively deactivated linearly in advance before polymerization, When the substrate is immersed in a second organic solvent containing a metal compound catalyst for polymerization, and the remaining acetylene group is polymerized by irradiation with radiation, diacetylene group, oxygen and chlorosilane group (—SiCl) are generated. The monomolecular film of the substance contained is linearly held on the substrate in a state where the polymerization directions of the molecules are aligned neatly, and the chemisorption film of the diacetylene derivative in the part which has not been deactivated in advance has a diacetylene group. Part of the acetylene group is polymerized in a linear direction, and the remaining acetylene group is polymerized by radiation,
It is also possible to prepare a linear polyacene polymer in which conjugated systems are continuous while controlling the polymerization direction.
一方、前記基板表面に前記アセチレン基あるいはジアセ
チレン基、酸素およびクロルシラン基（−SiCl）を含む
物質を化学吸着させてから、ラビングを行なうと、ラビ
ングにより単分子膜内の分子がきれいに並んだ状態で吸
着膜を再配向させることができるので、その状態で金属
化合物触媒を含む第２の有機溶媒中に前記基板を浸漬し
て重合すると、同様に重合方向を制御した状態で共役系
が連続した直鎖状の超高分子量のポリアセチレン系ポリ
マーを作ることができる。また、前記基板表面にジアセ
チレン基、酸素およびクロルシラン基（−SiCl）を含む
物質を化学吸着させてから、ラビングを行なうと、ラビ
ングにより単分子膜内の分子がきれいに並んだ状態で吸
着膜を再配向させることができるので、その状態で金属
化合物触媒を含む第２の有機溶媒中に前記基板を浸漬し
てジアセチレン誘導体の一部のアセチレン基を重合し、
さらに残ったアセチレン基を放射線照射することで重合
すると、放射線によりさらに残りのアセチレン基が重合
され、重合方向を制御した状態で共役系が連続した直鎖
状のポリアセン系ポリマーを作ることができる。On the other hand, when a substance containing the acetylene group or the diacetylene group, oxygen and a chlorosilane group (-SiCl) is chemically adsorbed on the surface of the substrate and then rubbed, the molecules in the monolayer are neatly arranged by rubbing. Since the adsorption film can be reoriented with, the substrate is immersed in a second organic solvent containing a metal compound catalyst in that state to polymerize, and the conjugated system continues in a state in which the polymerization direction is similarly controlled. A linear ultra high molecular weight polyacetylene-based polymer can be prepared. In addition, when a substance containing a diacetylene group, oxygen and a chlorosilane group (-SiCl) is chemically adsorbed on the surface of the substrate and then rubbed, the adsorbed film is formed in a state where the molecules in the monomolecular film are neatly arranged by rubbing. Since it can be reoriented, the substrate is immersed in a second organic solvent containing a metal compound catalyst in that state to polymerize a part of the acetylene group of the diacetylene derivative,
Further, when the remaining acetylene group is polymerized by irradiation with radiation, the remaining acetylene group is further polymerized by the radiation, and a linear polyacene polymer having a continuous conjugated system in a state where the polymerization direction is controlled can be produced.
なお、ここで直鎖状の炭化水素鎖の途中に−Ｏ−基を含
ませて置くことは、吸着単分子膜内の分子の自由度を増
加せしめ、重合時のひずみを減少させ収率を大幅に改善
できる効果がある。また、アセチレン基の重合反応に
は、ハロゲン化金属触媒たとえばMocl５やWCl６、NbCl
５、TaCl５、Mo（CO）５、Ｗ（CO）６、あるいはNb（C
O）５、やTa（CO）５等が利用できる。また、このとき
の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。さらに、ジアセチレン基の重合の場合には、
触媒重合に引続き、Ｘ線または電子線、ガンマ線、イオ
ンビーム等の放射線照射を行なうとホリアセンを作成で
きた。The inclusion of an —O— group in the middle of the linear hydrocarbon chain here increases the degree of freedom of molecules in the adsorption monolayer, reduces the strain during polymerization, and reduces the yield. There is an effect that can be greatly improved. In addition, for the polymerization reaction of the acetylene group, a metal halide catalyst such as Mocl 5 , WCl 6 , or NbCl is used.
5 , TaCl 5 , Mo (CO) 5 , W (CO) 6 , or Nb (C
O) 5 , Ta (CO) 5, etc. can be used. The organic solvent used at this time may be toluene, dioxane, anisole, or the like. Further, in the case of polymerization of diacetylene group,
Subsequent to the catalyst polymerization, irradiation with X-rays, electron beams, gamma rays, ion beams, or other radiation was carried out, whereby horiacene could be prepared.
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.
使用した直鎖状のシラン系界面活性剤サンプルは種々あ
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CH≡Ｃ−（CH２）ｍ−Ｏ−（CH２）ｎ−Si
Cl３（AOS系、ここでｍ、ｎは整数であるが、合計５か
ら25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。There are various kinds of linear silane-based surfactant samples used, but CH≡C- (CH 2 ) m- O- (CH 2 ) n- Si, which is a kind of acetylene derivative and contains one acetylene group at the end.
A case of Cl 3 (AOS system, where m and n are integers, but good results were obtained in a total range of 5 to 25) will be described.
例えばSiO２の形成されたSi基板１上にシラン系界面活
性剤（CH≡Ｃ−（CH２）４−Ｏ−（CH２）２−SiCl３:6
−AOS）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基と基板表面のSiO２とともに
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。For example silane on the Si substrate 1 formed of SiO 2 based surfactant (CH≡C- (CH 2) 4 -O- (CH 2) 2 -SiCl 3: 6
-AOS) is used to form a monomolecular film by chemisorption on the substrate surface. At this time, the --SiCl group reacts with the --OH group formed with the SiO 2 on the substrate surface to dehydrochlorine, and The monomolecular film 2 can be formed.
例えば1.0X10−３〜4.0X10−３mol／ｌの濃度で前記シ
ラン系界面活性剤を溶かした85％ｎ−ヘキサン、８％四
塩化炭素、７％クロロホルム溶液中に、室温で30分間Si
O２の形成されたSi基板浸漬すると、SiO２表面で−Si−
Ｏ−の結合を形成できる。（第１図（ａ）） ここで、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, in a solution of 85% n-hexane, 8% carbon tetrachloride and 7% chloroform in which the silane-based surfactant is dissolved at a concentration of 1.0X10 -3 to 4.0X10 -3 mol / l, Si at room temperature for 30 minutes.
When Si substrate immersed formed of O 2, with SiO 2 surface -Si-
O-bonds can be formed. (Fig. 1 (a)) Here, on the substrate surface 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Ｎ
２雰囲気中で行った。化学吸着膜の形成に使用した基板
は、直径３インチの酸化膜（SiO２）を形成したSi基板
である。At this time, the chemical adsorption film is formed by N
2 I went in an atmosphere. The substrate used for forming the chemisorption film is a Si substrate on which an oxide film (SiO 2 ) having a diameter of 3 inches is formed.
次に、第１図（ｂ）に示したように、重合前にあらかじ
め前記単分子膜の不飽和基をSTM（走査トンネル顕微
鏡）による描画（ライティング）または電子ビーム露光
またはＸ−ray露光（何れも、露光量は5mJ／cm２程度で
よい）により線状に失活し、特定の方向に線状に不飽和
基を残存させた後、金属触媒としてMoCl５を溶かしたト
ルエン中に６−AOS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（ｃ）に示す
ような反応、即ち失活されないで残存していた不飽和の
アセチレン基が線状に重合してTrans−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。Next, as shown in FIG. 1 (b), before polymerization, the unsaturated groups of the monomolecular film are drawn (writing) by STM (scanning tunneling microscope), electron beam exposure or X-ray exposure (any one). However, the exposure dose may be about 5 mJ / cm 2 ), and linearly deactivates to leave linear unsaturated groups in a specific direction, and then 6-in toluene in which MoCl 5 is dissolved as a metal catalyst. When the substrate on which one layer of AOS adsorption film is formed is immersed and the temperature of the solvent is raised to about 30 to 70 ° C, the reaction as shown in Fig. 1 (c), that is, the unsaturated acetylene group which remains without being deactivated It was revealed by FTIR that the polymer was linearly polymerized to produce Trans-polyacetylene bond 3.
なお、触媒としてはWCl６やNbCl５、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（CO）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。Even if WCl 6 , NbCl 5 , or TaCl 5 was used as the catalyst, the same polymer film was obtained although the molecular weight was different. Furthermore, Mo (CO) 6 or W (CO) 6 is used as a catalyst in CCl 4
Even when the substrate was immersed in a solution dissolved in a solvent and irradiated with ultraviolet rays, a reddish brown polymer film having different molecular weights was obtained.
一方、前記Si基板上にシラン系活性剤として （DMS−６−AOS、ここでｍ、ｎはそれぞれ４と２である
が、合計で５から25の範囲で良好な結果が得られた。ま
た以後CH３はMeで表わす）を用いた場合にも、吸着膜を
１層累積した基板を（第２図（ａ））選択的に失活後、
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−SiMe２Ｈ
基を含んだ線状で配向性の高い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。On the other hand, as a silane-based activator on the Si substrate (DMS-6-AOS, where m and n are 4 and 2, respectively, but good results were obtained within a total range of 5 to 25. Also, CH 3 is represented by Me hereinafter) Also, after selectively deactivating the substrate on which one layer of the adsorption film has been accumulated (FIG. 2 (a)),
When the solvent is heated to about 30 to 70 ° C by immersing it in toluene in which WCl 6 as a metal catalyst and Bu 4 Sn (1: 1) as a cocatalyst are dissolved, the reaction as shown in Fig. 2 (b), -SiMe 2 H
It was revealed that a linear and highly oriented Trans-polyacetylene bond 3 containing a group was produced.
従って、吸着単分子膜の層数を増やす必要がある場合に
は、この膜のように、アセチレン基を含む分子の末端に
−SiMe２Ｈ基を導入して置けば、アルカリ水処理のみで
−Si（CH３）２−OHに変換できるので、前述と同様の反
応液を用いて化学吸着工程およびOH付加工程を繰り返す
ことにより単分子膜を必要な膜厚で累積形成できる。す
なわち、単分子膜表面のOH基が反応して単分子膜上に、
アセチレン基を有する単分子吸着膜を積層できる。Therefore, when it is necessary to increase the number of layers of the adsorbed monolayer, if a -SiMe 2 H group is introduced at the end of a molecule containing an acetylene group as in this membrane, it can be treated with alkaline water only- Since it can be converted to Si (CH 3 ) 2 —OH, a monomolecular film can be cumulatively formed in a required film thickness by repeating the chemisorption step and the OH addition step using the same reaction solution as described above. That is, the OH groups on the surface of the monolayer react to react on the monolayer,
A monomolecular adsorption film having an acetylene group can be laminated.
また、分子の末端のSiMe２Ｈ基の代わりにビニル基を導
入して置けば、単分子膜を１層形成した後、単分子膜の
形成された基板を室温でジボラン1mol／ｌのTHF溶液に
浸漬し、さらにNaOH0.1mol／ｌの30％Ｈ２Ｏ２水溶液に
浸漬することにより、単分子膜の表面に水酸基（OH）を
付加した単分子膜を形成することができるので、前述と
同様の反応液を用いた化学吸着工程およびOH付加工程を
繰り返すことにより単分子膜を必要な膜厚で累積形成で
きる。すなわち、単分子膜のOH基が反応した単分子膜上
に、アセチレン基を有する単分子吸着膜を積層できる。
また、積層数も任意である。Also, if a vinyl group is introduced instead of the SiMe 2 H group at the terminal of the molecule, a monomolecular film is formed and then the substrate with the monomolecular film is formed at room temperature on a diborane 1 mol / l THF solution. Since it can be formed into a monomolecular film in which a hydroxyl group (OH) is added to the surface of the monomolecular film, it can be formed by immersing it in an aqueous solution of 0.1 mol / l of a 30% H 2 O 2 aqueous solution. By repeating the chemisorption step and the OH addition step using the same reaction solution, a monomolecular film having a required film thickness can be cumulatively formed. That is, the monomolecular adsorption film having an acetylene group can be laminated on the monomolecular film obtained by reacting the OH group of the monomolecular film.
Further, the number of stacked layers is also arbitrary.
なお、ビニル基を−CH２−CH２−OHに変換する他の方法
として、Ｏ２を含む雰囲気中でＸ線、電子線、ガンマ線
照射しても同様の効果がえられる。また、Ｎ２を含む雰
囲気中でＸ線、電子線、ガンマ線照射した場合には分子
末端に−NH２基を導入でき、この官能基の場合にも同様
の効果がえられ、吸着単分子の累積がより行いやすくな
る。As another method of converting a vinyl group into —CH 2 —CH 2 —OH, the same effect can be obtained by irradiating X-rays, electron beams or gamma rays in an atmosphere containing O 2 . Further, when irradiated with X-rays, electron beams or gamma rays in an atmosphere containing N 2 , a —NH 2 group can be introduced at the terminal of the molecule, and in the case of this functional group, the same effect can be obtained and the adsorption monomolecule Accumulation becomes easier.
なお、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も確認された。It was also confirmed that the adsorption film accumulated by the above method was insoluble in the alcohol solvent.
以上の結果より、本発明の重合方法を用いればTrans型
高配向共役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 the trans-type highly oriented conjugated polyacetylene can be easily produced by using the polymerization method of the present invention.
また、Si基板上に６−AOS吸着膜を１層累積した基板を
（第３図（ａ））選択的に失活させた後、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、即ち線状の配向性の高いCis−ポリ
アセチレン４が製造されたことが明かとなった。Further, after the substrate obtained by accumulating one layer 6-AOS adsorbed film on the Si substrate is (FIG. 3 (a)) selectively deactivated, an oxygen-containing organic solvent dissolved MoCl 6 metal catalyst anisole Fig. 3 (b), when it is immersed in water and the temperature of the solvent is raised to about 30-70 ℃
It was revealed that the reaction as shown in Fig. 1, that is, the production of Cis-polyacetylene 4 having a high linear orientation was produced.
さらにまたSi基板上にDMS−６−AOS吸着膜を１層累積し
た基板を（第４図（ａ））、線状に失活後、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−SiMe２Ｈ基を含んだ高い配向性の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 obtained by accumulating one layer of a DMS-6-AOS adsorption film on a Si substrate (Fig. 4 (a)) was linearly deactivated, and then MoCl 6 as a metal catalyst and ph 3 Bi (1 as a cocatalyst. 1) is immersed in anisole, which is an oxygen-containing organic solvent in which 1) is dissolved, and the temperature of the solvent is raised to about 30 to 70 ° C, a reaction as shown in Fig. 4 (b), that is, a high-SiMe 2 H group-containing group is included. It was revealed that oriented Cis-polyacetylene 4 was produced.
以上の２つの実施例より明らかなように、本発明の重合
方法を用いればCis型あるいはTrans型高配向長共役ポリ
アセチレンを容易に製造できることが確認された。As is clear from the above two examples, it was confirmed that Cis type or Trans type highly oriented long conjugated polyacetylene can be easily produced by using the polymerization method of the present invention.
なお、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。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、６−AOSやDMS−６−AOS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、吸着条件は異なって
も同様の方法が利用出来ることは明らかであろう。In the above examples, only 6-AOS and DMS-6-AOS are shown, but the adsorption conditions are different as long as the molecule contains an acetylene (C≡C) group and an adsorbed film can be formed. It will be clear that a similar method can be used.
さらに、ジアセチレン基を１個もつ :13−DASを用いた場合にも、第５図に示すように、化学
吸着膜作成後選択的に線状に失活させた後、金属化合物
触媒を含む第２の有機溶媒中に前記基板を浸漬して重合
すると、単分子膜状でかつ線状のTransポリアセチレン
結合３を有するポリアセチレン型共役ポリマー（第５図
（ｄ））が得られる。Furthermore, it has one diacetylene group Also in the case of using: 13-DAS, as shown in FIG. 5, after the chemisorption film was formed, it was selectively deactivated linearly, and then the substrate was placed in a second organic solvent containing a metal compound catalyst. By dipping and polymerizing, a polyacetylene-type conjugated polymer having a linear poly-acetylene bond 3 in a monolayer form (FIG. 5 (d)) is obtained.
さらに、ポリジアセチレンにより得られたポリアセチレ
ン型共役ポリマーに電子線（Ｘ線やガンマ線等の放射線
でもよい）を5mJ／cm２程度全面に照射すると線状の高
配向ポリアセン結合５を有するポリアセン型共役ポリマ
ー（第５図（ｅ））が得られる。Furthermore, when a polyacetylene-type conjugated polymer obtained from polydiacetylene is irradiated with an electron beam (which may be radiation such as X-rays and gamma rays) at about 5 mJ / cm 2, the polyacene-type conjugated polymer having a linear highly oriented polyacene bond 5 (FIG. 5 (e)) is obtained.
この場合も同様に、吸着単分子膜の層数を増やす必要が
ある場合には、ジアセチレン基を含む分子の末端に−Si
Me２Ｈ基を導入して置けば、アルカリ水処理のみで−Si
（CH３）２−OHに変換できるので、前述と同様の反応液
を用いて化学吸着工程およびOH付加工程を繰り返すこと
により単分子膜を必要な膜厚で累積形成できる。すなわ
ち、単分子膜のOH基が反応した単分子膜上に、ジアセチ
レン基を有する単分子吸着膜を積層できる。積層数は任
意である。Also in this case, when it is necessary to increase the number of layers of the adsorbed monolayer, --Si is added to the end of the molecule containing the diacetylene group.
If a Me 2 H group is introduced and placed, it can be treated with alkaline water only
Since it can be converted to (CH 3 ) 2- OH, a monomolecular film can be cumulatively formed in a required film thickness by repeating the chemisorption step and the OH addition step using the same reaction solution as described above. That is, a monomolecular adsorption film having a diacetylene group can be laminated on the monomolecular film obtained by reacting the OH group of the monomolecular film. The number of layers is arbitrary.
また、分子の末端の−SiMe２Ｈ基の代わりにビニル基を
導入して置けば、単分子膜を１層形成した後、単分子膜
の形成された基板を室温でジボラン1mol／ｌのTHF溶液
に浸漬し、さらにNaOH0.1mol／１、30％Ｈ２Ｏ２水溶液
に浸漬することにより、単分子膜の表面に水酸基（OH）
を付加した単分子膜を形成することができる。従って、
前述と同様の反応液を用いて化学吸着工程およびOH付加
工程を繰り返すことにより単分子膜を必要な膜厚で累積
形成できる。また、積層数も任意である。If a vinyl group is introduced instead of the -SiMe 2 H group at the end of the molecule, a monomolecular film is formed, and then the substrate on which the monomolecular film is formed is subjected to diborane 1 mol / l THF at room temperature. By immersing in the solution, and further by immersing in NaOH 0.1mol / 1, 30% H 2 O 2 aqueous solution, hydroxyl groups (OH) are formed on the surface of the monomolecular film.
Can be added to form a monomolecular film. Therefore,
By repeating the chemisorption step and the OH addition step using the same reaction solution as described above, a monomolecular film having a required film thickness can be cumulatively formed. Further, the number of stacked layers is also arbitrary.
なお、ビニル基を−CH２−CH２−OHに変換する他の方法
として、Ｏ２を含む雰囲気中でＸ線、電子線、ガンマ線
照射しても同様の効果がえられる。また、Ｎ２を含む雰
囲気中でＸ線、電子線、ガンマ線照射した場合には分子
末端に−NH２基を導入でき、この官能基の場合にも同様
の効果がえられ、吸着単分子の累積がより行いやすくな
る。As another method of converting a vinyl group into —CH 2 —CH 2 —OH, the same effect can be obtained by irradiating X-rays, electron beams or gamma rays in an atmosphere containing O 2 . Further, when irradiated with X-rays, electron beams or gamma rays in an atmosphere containing N 2 , a —NH 2 group can be introduced at the terminal of the molecule, and in the case of this functional group, the same effect can be obtained and the adsorption monomolecule Accumulation becomes easier.
さらにまた、前述の２つの実施例では１層化学吸着膜を
形成した後、不飽和基を選択的に線状に失活させ、重合
を行う方法について述べたが、吸着後選択的に線状に失
活させる代わりにラビングを行なって吸着膜を再配向さ
せた後、金属触媒を用いて重合を行なっても高配向ポリ
アセチレンが得られた。また、吸着後ラビングを行なっ
て吸着膜を再配向させた後、金属触媒を用いて重合しさ
らに放射線を用いて重合を行なうと高配向ポリアセンが
得られた。Furthermore, in the above-mentioned two examples, the method of carrying out the polymerization by selectively deactivating the unsaturated group linearly after forming the one-layer chemisorption film was described. Highly oriented polyacetylene was obtained even when the adsorption film was reoriented by rubbing instead of deactivating it and polymerized with a metal catalyst. Further, after the adsorption, rubbing was performed to reorientate the adsorbed film, followed by polymerization using a metal catalyst and further polymerization using radiation, whereby highly oriented polyacene was obtained.
なお、吸着膜を多層積層した後で不飽和基を選択的に線
状に失活した後触媒重合反応を行っても良いし、あるい
は吸着膜の形成−線状失活−触媒重合反応を交互に行っ
ても高配向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。さらに、吸着膜を多層積層した
後で不飽和基を選択的に線状に失活した後、触媒重合と
放射線重合を続けて行っても良いし、あるいは吸着膜の
形成−線状失活−触媒重合−放射線照射を順番に繰り返
し行っても高配向ポリアセンの多層分子膜の作製が可能
なことは明らかであろう。The catalyst polymerization reaction may be carried out after the unsaturated groups are selectively linearly deactivated after the adsorption films are laminated in multiple layers, or the formation of the adsorption film-the linear deactivation-the catalytic polymerization reaction may be alternately performed. It will be clear that even if it is carried out, it is possible to prepare a multilayer molecular film of highly oriented polyacetylene. Further, after the adsorption film is laminated in multiple layers, the unsaturated groups may be selectively deactivated linearly, and then catalytic polymerization and radiation polymerization may be continuously performed, or formation of an adsorption film-linear deactivation- It will be apparent that a highly oriented polyacene multilayer molecular film can be prepared by sequentially repeating catalytic polymerization and irradiation.
なお、上記実施例以外に、本願発明にしよう出来る界面
活性剤としては、 CH３−（CH２）１−Ｃ≡Ｃ−（CH２）ｍ−Ｏ−（CH２）
ｎ−SiCl３ （ここでl,m,nは０、または整数、ただし合計で５〜25
が良い。但し、この場合は、累積膜を作成することはで
きない。）で表わされるシラン系界面活性剤、たとえば CH３−（CH２）８−Ｃ≡Ｃ−（CH２）３−Ｏ−（CH２）
３−SiCl３ あるいは （CH３）２HSi−（CH２）１−Ｃ≡Ｃ−（CH２）ｍ−Ｏ
−（CH２）ｎ−SiCl３ （ここで1,m,nは０、または整数、ただし合計で５〜25
が良い。）で表わされるシラン系界面活性剤、たとえ
ば、 （CH３）２HSi−（CH２）９−Ｃ≡Ｃ− （CH２）３−Ｏ−（CH２）３−SiCl３、 あるいは CH２＝CH−（CH２）１−Ｃ≡Ｃ−（CH２）ｍ−Ｏ−（CH
２）ｎ−SiCl３ （ここで1,m,nは０、または整数、ただし合計で５〜25
が良い。）で表わされるシラン系界面活性剤、たとえ
ば、 CH２＝CH−（CH２）６−Ｃ≡Ｃ−（CH２）５−Ｏ−（CH
２）３−SiCl３ あるいは CH３−（CH２）１−Ｃ≡Ｃ−Ｃ≡Ｃ−（CH２）ｍ−Ｏ−
（CH２）ｎ−SiCl３ （ここで1,m,nは０、または整数、ただし合計で５〜25
が良い。但し、この場合は、累積膜を作成することはで
きない。）で表わされるシラン系界面活性剤たとえば、 CH３−（CH２）２−Ｃ≡Ｃ−Ｃ≡Ｃ−（CH２）６−Ｏ−
（CH２）３−SiCl３、 や CH３−CH２−Ｃ≡Ｃ−Ｃ≡Ｃ−（CH２）６−Ｏ−（C
H２）３−SiCl３、 あるいは （CH３）２HSi−（CH２）１−Ｃ≡Ｃ−Ｃ≡Ｃ−（C
H２）ｍ−Ｏ−（CH２）ｎ−SiCl３ （ここで1,m,nは０、または整数、ただし合計で５〜25
が良い。）で表わされるシラン系界面活性剤、たとえ
ば、 （CH３）２HSi−（CH２）３−Ｃ≡Ｃ−Ｃ≡Ｃ−（C
H２）３−Ｏ−（CH２）２−SiCl３、 あるいは CH２＝CH−（CH２）１−Ｃ≡Ｃ−Ｃ≡Ｃ−（CH２）ｍ−
Ｏ−（CH２）ｎ−SiCl３ （ここで1,m,nは０、または整数、ただし合計で５〜25
が良い。）で表わされるシラン系界面活性剤、たとえ
ば、 CH２＝CH−CH２−Ｃ≡Ｃ−Ｃ≡Ｃ−（CH２）７−Ｏ−
（CH２）３−SiCl３、 などがある。In addition to the above-mentioned examples, as a surfactant that can be used in the present invention, CH 3 — (CH 2 ) 1 —C≡C— (CH 2 ) m —O— (CH 2 )
n- SiCl 3 (where l, m, n are 0 or integers, but 5 to 25 in total)
Is good. However, in this case, a cumulative film cannot be created. Silane-based surfactant represented by), for example, CH 3 - (CH 2) 8 -C≡C- (CH 2) 3 -O- (CH 2)
3 -SiCl 3 or (CH 3) 2 HSi- (CH 2) 1 -C≡C- (CH 2) m -O
- (CH 2) n -SiCl 3 ( where 1, m, n is 0 or an integer, with the proviso total 5-25
Is good. Silane-based surfactant represented by), for example, (CH 3) 2 HSi- ( CH 2) 9 -C≡C- (CH 2) 3 -O- (CH 2) 3 -SiCl 3 or CH 2, = CH- (CH 2) 1 -C≡C- ( CH 2) m -O- (CH
2 ) n- SiCl 3 (where 1, m, n are 0 or integers, but 5 to 25 in total)
Is good. Silane-based surfactant represented by), for example, CH 2 = CH- (CH 2 ) 6 -C≡C- (CH 2) 5 -O- (CH
2) 3 -SiCl 3 or CH 3 - (CH 2) 1 -C≡C-C≡C- (CH 2) m -O-
(CH 2 ) n -SiCl 3 (where 1, m, n are 0 or integers, but 5 to 25 in total)
Is good. However, in this case, a cumulative film cannot be created. Silane-based surface active agents such as represented by), CH 3 - (CH 2 ) 2 -C≡C-C≡C- (CH 2) 6 -O-
(CH 2) 3 -SiCl 3, and CH 3 -CH 2 -C≡C-C≡C- ( CH 2) 6 -O- (C
H 2) 3 -SiCl 3, or (CH 3) 2 HSi- (CH 2) 1 -C≡C-C≡C- (C
H 2) m -O- (CH 2 ) n -SiCl 3 ( where 1, m, n is 0 or an integer, with the proviso total 5-25
Is good. ) A silane-based surfactant represented by, for example, (CH 3 ) 2 HSi— (CH 2 ) 3 —C≡C—C≡C— (C
H 2) 3 -O- (CH 2 ) 2 -SiCl 3 or CH 2 = CH- (CH 2) 1 -C≡C-C≡C- (CH 2,) m -
O- (CH 2) n -SiCl 3 ( where 1, m, n are 0 5-25 or an integer, provided that in total,
Is good. Silane-based surfactant represented by), for example, CH 2 = CH-CH 2 -C≡C-C≡C- (CH 2) 7 -O-
(CH 2) 3 -SiCl 3, and the like.
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、こ
の方法を用いて電導性のすぐれた物質の製造が可能とな
る。In the future, by optimizing the types of acetylene and diacetylene derivative monomers as raw materials and the production conditions, it becomes possible to produce a substance having excellent conductivity using this method.
発明の効果 本発明の方法を用いることにより、導電性や非線形光学
効果の非常に優れ安定な高配向性超長共役ポリアセチレ
ンやポリアセンの超薄膜ポリマーを高能率に製造できる
ので、非線形光学効果を利用したデバイスの製作には極
めて有効である。なお、ここで、直鎖状の炭化水素鎖の
途中に−Ｏ−基を含ませて置くことは、吸着単分子膜内
の分子の自由度を増加せしめ重合時のひずみを減少させ
収率を大幅に改善できる効果がある。EFFECTS OF THE INVENTION By using the method of the present invention, it is possible to highly efficiently produce a highly oriented ultralong conjugated polyacetylene or ultrathin film polymer of polyacene, which is extremely excellent in conductivity and nonlinear optical effect, and thus the nonlinear optical effect is utilized. It is extremely effective for manufacturing the device. In addition, here, placing an -O- group in the middle of the linear hydrocarbon chain increases the degree of freedom of molecules in the adsorbed monolayer, reduces strain during polymerization, and decreases yield. There is an effect that can be greatly improved.
第１図（ａ）は６−AOS吸着膜を１層形成した後の基板
の分子オーダーの拡大断面概念図、第１図（ｂ）は、電
子線露光（EB照射）を用いて不飽和基を選択的に線状に
失活させる工程の概念図、第１図（ｃ）は、線状に触媒
重合された後の高配向超長共役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
２図（ａ）はDMS−６−AOS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）は触媒重
合後の高配向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、６
−AOS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３図（ｂ）は触媒重合後の高配向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DMS−６−AOS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）は触媒重合後の高配向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
は、13−DASを用いたジアセチレン単分子膜の分子オー
ダーでのポリジアセチレン型超長共役ポリマー作成にお
ける工程を示し、同（ａ）は13−DAS分子の構造式を示
す図、同（ｂ）は13−DAS分子の略式図、同（ｃ）は13
−DASを用いたジアセチレン単分子膜の分子オーダーの
拡大概念図、同（ｄ）はTransポリアセチレンの分子オ
ーダーの拡大概念図、同（ｅ）はポリアセンの分子オー
ダーの拡大概念図を示す。 １…SiO２／Si基板、２…単分子吸着膜、 ３…高配向Trans−ポリアセチレン結合、 ４…高配向Cis−ポリアセチレン結合、 ５…ポリアセン結合。FIG. 1 (a) is an enlarged cross-sectional conceptual view of the molecular order of the substrate after one layer of 6-AOS adsorption film is formed, and FIG. 1 (b) is an unsaturated group using electron beam exposure (EB irradiation). Fig. 1 (c) is a conceptual diagram of the step of selectively linearly deactivating cis., And Fig. 1 (c) shows a molecular-order expansion of a substrate on which highly oriented ultralong conjugated Trans-type polyacetylene is formed after linearly catalytic polymerization. FIG. 2 (a) is a conceptual cross-sectional view of an enlarged cross-section of a substrate on which one layer of DMS-6-AOS adsorption film is formed, and FIG. 2 (b) is a highly oriented Trans-type polyacetylene after catalytic polymerization. An enlarged cross-sectional conceptual view of the formed substrate in the molecular order is shown in FIG.
-A molecular-order enlarged cross-sectional conceptual view of a substrate on which one layer of AOS adsorption film is formed, and FIG. 3 (b) is a molecular-order enlarged cross-sectional conceptual diagram of a substrate on which highly oriented Cis-type polyacetylene is formed after catalytic polymerization. FIG. 4 (a) is an enlarged cross-sectional conceptual view of the molecular order of a substrate on which one layer of DMS-6-AOS adsorption film is formed, and FIG. 4 (b) is a substrate on which highly oriented Cis-type polyacetylene is formed after catalytic polymerization. Fig. 5 is an enlarged cross-sectional conceptual diagram of the molecular order. Fig. 5 shows the steps in the production of a polydiacetylene-type ultralong conjugated polymer in the molecular order of a diacetylene monomolecular film using 13-DAS. A diagram showing the structural formula of the molecule, the same (b) is a schematic diagram of the 13-DAS molecule, and the same (c) is 13
An enlarged conceptual diagram of the molecular order of a diacetylene monomolecular film using -DAS is shown, (d) is an enlarged conceptual diagram of the molecular order of Trans polyacetylene, and (e) is an enlarged conceptual diagram of the molecular order of polyacene. 1 ... SiO 2 / Si substrate, 2 ... monomolecular adsorption film, 3 ... highly oriented Trans- polyacetylene bonds, 4 ... highly oriented Cis- polyacetylene bonds, 5 ... polyacene bond.
Claims (33)
ン基（−Ｃ≡Ｃ−Ｃ≡Ｃ−）と酸素（−Ｏ−）と−Si−
Cl基を含む直鎖状分子を溶解させた非水系の第１の有機
溶媒中に表面が親水性の基板を浸漬し、化学吸着法によ
り前記基板上に前記物質の単分子膜を吸着形成する工程
と、金属化合物触媒を含む第２の有機溶媒中に前記基板
を浸漬して前記アセチレン基又はジアセチレン基の部分
を重合させる工程を含むことを特徴とするポリアセチレ
ン型高配向性共役ポリマーの製造方法。1. An acetylene (—C≡C—) or diacetylene group (—C≡C—C≡C—), oxygen (—O—), and —Si—.
A hydrophilic substrate having a surface is immersed in a non-aqueous first organic solvent in which a linear molecule containing a Cl group is dissolved, and a monomolecular film of the substance is adsorbed and formed on the substrate by a chemical adsorption method. And a step of dipping the substrate in a second organic solvent containing a metal compound catalyst to polymerize a portion of the acetylene group or diacetylene group. Method.
−（CH２）ｍ−Ｏ−（CH２）ｎ−SiCl３（ここで1,m,n
は０、または整数、ただし合計で５〜25が良い。）で表
わされるシラン系界面活性剤であることを特徴とする請
求項１記載のポリアセチレン型高配向性共役ポリマーの
製造方法。2. The linear molecule is CH 3- (CH 2 ) 1 --C≡C
- (CH 2) m -O- ( CH 2) n -SiCl 3 ( where 1, m, n
Is 0 or an integer, but 5 to 25 in total is preferable. The method for producing a polyacetylene type highly oriented conjugated polymer according to claim 1, which is a silane-based surfactant represented by the formula (1).
と−Si−Cl基を含む直鎖状分子を溶解させた非水系の第
１の有機溶媒中に表面が親水性の基板を浸漬し化学吸着
法により前記基板上に前記物質の単分子膜を吸着形成す
る工程と、電子ビーム露光またはSTMライティングまた
はＸ線露光より前記分子膜を選択的に線状に失活させる
工程と、金属化合物触媒を含む第２の有機溶媒中に前記
基板を浸漬して、前記単分子膜の失活されないで残った
前記アセチレン又はジアセチレン基の部分を重合させる
工程を含むことを特徴とするポリアセチレン型高配向性
共役ポリマーの製造方法。3. An acetylene group or a diacetylene group and -O-
And a -Si-Cl group-containing linear molecule is dissolved in a non-aqueous first organic solvent in which a hydrophilic substrate is immersed and a monomolecular film of the substance is formed on the substrate by a chemical adsorption method. A step of forming by adsorption, a step of selectively deactivating the molecular film linearly by electron beam exposure, STM writing or X-ray exposure, and immersing the substrate in a second organic solvent containing a metal compound catalyst. And a step of polymerizing a portion of the acetylene or diacetylene group remaining in the monomolecular film without being deactivated, the method for producing a polyacetylene-type highly oriented conjugated polymer.
と−Si−Cl基を含む直鎖状分子を溶解させた非水系の第
１の有機溶媒中に表面が親水性の基板を浸漬し、化学吸
着法により前記基板上に前記物質の単分子膜を吸着形成
する工程と、ラビングにより前記吸着膜を再配向させる
工程と、金属化合物触媒を含む第２の有機溶媒中に前記
基板を浸漬して前記基板に不活性ガス雰囲気中で全面に
エネルギービームを照射し前記アセチレン又はジアセチ
レン基の部分を重合させる工程を含むことを特徴とする
ポリアセチレン型高配向性共役ポリマーの製造方法。4. An acetylene group or a diacetylene group and --O--
And a -Si-Cl group-containing linear molecule is dissolved in a non-aqueous first organic solvent, the substrate having a hydrophilic surface is immersed in the monomolecular film of the substance on the substrate by a chemical adsorption method. A step of re-orienting the adsorption film by rubbing, a step of immersing the substrate in a second organic solvent containing a metal compound catalyst, and an energy beam over the entire surface of the substrate in an inert gas atmosphere. And a step of polymerizing the portion of the acetylene or diacetylene group by irradiating the acetylene or diacetylene group.
基が結合していることを特徴とする請求項１、３または
４記載のポリアセチレン型高配向性共役ポリマーの製造
方法。5. A --Si (CH 3 ) 2 H at the molecular end of a linear molecule.
The method for producing a polyacetylene-type highly oriented conjugated polymer according to claim 1, wherein the groups are bonded.
を特徴とする請求項５記載のポリアセチレン型高配向性
共役ポリマーの製造方法。6. A linear molecule The method for producing a polyacetylene-type highly oriented conjugated polymer according to claim 5, wherein (l, m, n are 0 or integers and a total of 5 to 25).
合していることを特徴とする請求項１、３または４記載
のポリアセチレン型高配向性共役ポリマーの製造方法。7. A process according to claim 1, 3 or 4 polyacetylene type highly oriented conjugated polymer, wherein the -CH = CH 2 group at the molecular end of the linear molecule is attached.
Ｏ−（CH２）ｎ−SiCl３ （l,m,nは、０または整数で合計５から25）であること
を特徴とする特許請求の範囲第７項記載のポリアセチレ
ン型高配向性共役ポリマーの製造方法。8. linear molecule CH = CH 2 - (CH 2 ) 1 -C≡C-C≡C- (CH 2) m -
O- (CH 2) n -SiCl 3 (l, m, n is 0 or a total 5 integer 25) polyacetylene type highly oriented conjugated polymer ranges seventh claim of claims, which is a Manufacturing method.
たはNb、またはTa化合物であることを特徴とする請求項
１から８のいずれかに記載のポリアセチレン型高配向性
共役ポリマーの製造方法。9. The method for producing a polyacetylene type highly oriented conjugated polymer according to claim 1, wherein the metal of the metal compound catalyst is Mo, W, Nb, or Ta compound. .
に共触媒として有機Snあるいは有機Bi化合物を含むこと
を特徴とする請求項１から８のいずれかに記載のポリア
セチレン型高配向性共役ポリマーの製造方法。10. The polyacetylene-type highly oriented conjugated polymer according to claim 1, wherein the organic compound further contains an organic Sn or organic Bi compound as a cocatalyst in the organic solvent. Production method.
物触媒がMoCl５であることを特徴とする請求項１から８
のいずれかに記載のCis型のポリアセチレン型高配向性
共役ポリマーの製造方法。In 11. organic solvent is an oxygen-containing organic solvent, claim 1 in which the metal compound catalyst is characterized in that it is a MoCl 5 8
5. The method for producing a Cis-type polyacetylene-type highly oriented conjugated polymer according to any one of 1.
（CH２）ｎ−SiCl３ （ここでl,m,nは０、または整数、ただし合計で５〜25
が良い。）で表わされるシラン系界面活性剤であること
を特徴とする請求項１記載のポリアセチレン型高配向性
共役ポリマーの製造方法。12. The linear molecule is CH 3 — (CH 2 ) 1 —C≡C—C≡C— (CH 2 ) m —O—.
(CH 2) n -SiCl 3 (where l, m, n is 0 or an integer, with the proviso total 5-25
Is good. The method for producing a polyacetylene type highly oriented conjugated polymer according to claim 1, which is a silane-based surfactant represented by the formula (1).
（CH２）３−SiCl３、 または、 CH３−CH２−Ｃ≡Ｃ−Ｃ≡Ｃ−（CH２）６−Ｏ−（C
H２）３−SiCl３ で表わされるシラン系界面活性剤であることを特徴とす
る請求項１記載のポリアセチレン型高配向性共役ポリマ
ーの製造方法。13. The linear molecule is CH 3 — (CH 2 ) 2 —C≡C—C≡C— (CH 2 ) 6 —O—.
(CH 2) 3 -SiCl 3, or, CH 3 -CH 2 -C≡C-C≡C- (CH 2) 6 -O- (C
H 2) 3 method for producing a polyacetylene type highly oriented conjugated polymer according to claim 1 characterized in that the silane-based surfactant represented by -SiCl 3.
と−Ｏ−と−Si−Cl基を含む直鎖状分子を溶解させた非
水系の第１の有機溶媒中に表面が親水性の基板を浸漬し
化学吸着法により前記基板上に前記物質の単分子膜を吸
着形成する工程と、電子ビーム露光またはSTMライティ
ングまたはＸ線露光より前記分子膜を選択的に線状に失
活させる工程と、金属化合物触媒を含む第２の有機溶媒
中に前記基板を浸漬して、前記単分子膜の失活されない
で残ったジアセチレン基の部分を重合させる工程を含む
ことを特徴とするポリアセチレン型高配向性共役ポリマ
ーの製造方法。14. A surface in a non-aqueous first organic solvent in which a linear molecule containing a diacetylene (—C≡C—C≡C—) group and —O— and —Si—Cl groups is dissolved. A step of immersing a hydrophilic substrate into the substrate to form a monomolecular film of the substance on the substrate by a chemical adsorption method, and selectively linearizing the molecular film by electron beam exposure, STM writing, or X-ray exposure. A step of deactivating, and a step of immersing the substrate in a second organic solvent containing a metal compound catalyst to polymerize a portion of the diacetylene group remaining in the monomolecular film without being deactivated. A method for producing a polyacetylene-type highly oriented conjugated polymer having
と−Ｏ−と−Si−Cl基を含む直鎖状分子を溶解させた非
水系の第１の有機溶媒中に表面が親水性の基板を浸漬
し、化学吸着法により前記基板上に前記物質の単分子膜
を吸着形成する工程と、ラビングにより前記吸着膜を再
配向させる工程と、金属化合物触媒を含む第２の有機溶
媒中に前記基板を浸漬して前記基板に不活性ガス雰囲気
中で全面にエネルギービームを照射し前記ジアセチレン
基の部分を重合させる工程を含むことを特徴とするポリ
アセチレン型高配向性共役ポリマーの製造方法。15. The surface of a non-aqueous first organic solvent in which a linear molecule containing a diacetylene (—C≡C—C≡C—) group and a —O— and —Si—Cl group is dissolved. Is immersed in a hydrophilic substrate, and a monomolecular film of the substance is adsorbed and formed on the substrate by a chemisorption method; a step of reorienting the adsorbed film by rubbing; and a second step including a metal compound catalyst. A polyacetylene-type highly-oriented conjugated polymer characterized by including a step of immersing the substrate in an organic solvent and irradiating the substrate with an energy beam over the entire surface in an inert gas atmosphere to polymerize a portion of the diacetylene group. Manufacturing method.
Ｈ基が結合していることを特徴とする請求項1,14または
15記載のポリアセチレン型高配向性共役ポリマーの製造
方法。16. A —Si (CH 3 ) 2 at the molecular end of a linear molecule.
15. The H group is bound to claim 1, 14 or
15. The method for producing a polyacetylene type highly oriented conjugated polymer according to 15.
を特徴とする請求項16記載のポリアセチレン型高配向性
共役ポリマーの製造方法。17. The linear molecule is 17. The method for producing a polyacetylene type highly oriented conjugated polymer according to claim 16, wherein (l, m, n are 0 or integers and a total of 5 to 25).
が結合していることを特徴とする請求項1,14または15記
載のポリアセチレン型高配向性共役ポリマーの製造方
法。18. The method for producing a polyacetylene-type highly oriented conjugated polymer according to claim 1, 14 or 15, wherein a —CH═CH 2 group is bonded to the molecular end of the linear molecule.
Ｏ−（CH２）ｎ−SiCl３ （l,m,nは、０または整数で合計５から25）であること
を特徴とする請求項18記載のポリアセチレン型高配向性
共役ポリマーの製造方法。19. The straight-chain molecule has CH═CH 2 — (CH 2 ) 1 —C≡C—C≡C— (CH 2 ) m −.
O- (CH 2) n -SiCl 3 (l, m, n is a total 5 0 or an integer 25) The process according to claim 18 polyacetylene type highly oriented conjugated polymer, wherein the a.
またはNb、またはTa化合物であることを特徴とする請求
項14または15に記載のポリアセチレン型高配向性共役ポ
リマーの製造方法。20. The metal of the metal compound catalyst is Mo or W,
16. The method for producing a polyacetylene type highly oriented conjugated polymer according to claim 14, which is a Nb or Ta compound.
に共触媒として有機Snあるいは有機Bi化合物を含むこと
を特徴とする請求項14または15に記載のポリアセチレン
型高配向性共役ポリマーの製造方法。21. The method for producing a polyacetylene type highly oriented conjugated polymer according to claim 14 or 15, wherein the organic compound further contains an organic Sn or organic Bi compound as a cocatalyst in the organic solvent.
物触媒がMoCl５であることを特徴とする請求項14または
15に記載のCis型のポリアセチレン型高配向性共役ポリ
マーの製造方法。In 22. organic solvent is an oxygen-containing organic solvents, according to claim 14 metal compound catalyst is characterized in that it is a MoCl 5 or
15. The method for producing a Cis-type polyacetylene-type highly oriented conjugated polymer according to 15.
と−Ｏ−と−Si−Cl基を含む直鎖状分子を溶解させた非
水系の第１の有機溶媒中に表面が親水性の基板を浸漬
し、化学吸着法により前記基板上に前記物質の単分子膜
を吸着形成する工程と、金属化合物触媒を含む第２の有
機溶媒中に前記基板を浸漬して重合する工程と、さらに
不活性ガス雰囲気中で全面に放射線照射を行い、前記単
分子膜の残存したアセチレン基の部分を重合させる工程
とを含むことを特徴とするポリアセン型高配向性共役ポ
リマーの製造方法。23. The surface of a non-aqueous first organic solvent in which a linear molecule containing a diacetylene (—C≡C—C≡C—) group and —O— and —Si—Cl groups is dissolved. Is immersed in a hydrophilic substrate, and a monomolecular film of the substance is adsorbed and formed on the substrate by a chemical adsorption method; and the substrate is immersed in a second organic solvent containing a metal compound catalyst for polymerization. A method for producing a polyacene-type highly oriented conjugated polymer, which comprises a step, and further irradiating the entire surface in an inert gas atmosphere to polymerize a portion of the remaining acetylene group of the monomolecular film. .
（CH２）ｎ−SiCl３ （ここでl,m,nは０、または整数、ただし合計で５〜25
が良い。）で表わされるシラン系界面活性剤であること
を特徴とする請求項23記載のポリアセン型高配向性共役
ポリマーの製造方法。24. The linear molecule is CH 3- (CH 2 ) 1 -C≡C—C≡C— (CH 2 ) m —O—.
(CH 2) n -SiCl 3 (where l, m, n is 0 or an integer, with the proviso total 5-25
Is good. 24. The method for producing a polyacene-type highly oriented conjugated polymer according to claim 23, which is a silane-based surfactant represented by
（CH２）３−SiCl３、 または、 CH３−CH２−Ｃ≡Ｃ−Ｃ≡Ｃ−（CH２）６−Ｏ−（C
H２）３−SiCl３ で表わされるシラン系界面活性剤であることを特徴とす
る請求項24記載のポリアセン型高配向性共役ポリマーの
製造方法。25. The linear molecule is CH 3 — (CH 2 ) 2 —C≡C—C≡C— (CH 2 ) 6 —O—.
(CH 2) 3 -SiCl 3, or, CH 3 -CH 2 -C≡C-C≡C- (CH 2) 6 -O- (C
H 2) 3 The process of claim 24 polyacene type highly oriented conjugated polymer, wherein it is a silane-based surfactant represented by -SiCl 3.
と−Ｏ−と−Si−Cl基を含む直鎖状分子を溶解させた非
水系の第１の有機溶媒中に表面が親水性の基板を浸漬し
化学吸着法により前記基板上に前記物質の単分子膜を吸
着形成する工程と、電子ビーム露光またはSTMライティ
ングまたはＸ線露光より前記分子膜を選択的に線状に失
活させる工程と、金属化合物触媒を含む第２の有機溶媒
中に前記基板を浸漬して重合する工程と、さらに不活性
ガス雰囲気中で全面に放射線照射を行い、前記単分子膜
の残存したアセチレン基の部分を重合させる工程とを含
むことを特徴とするポリアセン型高配向性役ポリマーの
製造方法。26. The surface of a non-aqueous first organic solvent in which a linear molecule containing a diacetylene (—C≡C—C≡C—) group, —O— and —Si—Cl group is dissolved. A step of immersing a hydrophilic substrate into the substrate to form a monomolecular film of the substance on the substrate by a chemical adsorption method, and selectively linearizing the molecular film by electron beam exposure, STM writing, or X-ray exposure. The step of deactivating, the step of immersing the substrate in a second organic solvent containing a metal compound catalyst for polymerization, and further irradiating the entire surface with radiation in an inert gas atmosphere to leave the monomolecular film remaining. And a step of polymerizing a portion of an acetylene group, the method for producing a polyacene-type highly orienting role polymer.
と−Ｏ−と−Si−Cl基を含む直鎖状分子を溶解させた非
水系の第１の有機溶媒中に表面が親水性の基板を浸漬
し、化学吸着法により前記基板上に前記物質の単分子膜
を吸着形成する工程と、ラビングにより前記吸着膜を再
配向させる工程と、金属化合物触媒を含む第２の有機溶
媒中に前記基板を浸漬して重合する工程と、さらに不活
性ガス雰囲気中で全面に放射線照射を行い、前記単分子
膜の残存したアセチレン基の部分を重合させる工程とを
含むことを特徴とするポリアセン型高配向性共役ポリマ
ーの製造方法。27. A surface is immersed in a non-aqueous first organic solvent in which a linear molecule containing a diacetylene (-C≡C-C≡C-) group and -O- and -Si-Cl groups is dissolved. Is immersed in a hydrophilic substrate, and a monomolecular film of the substance is adsorbed and formed on the substrate by a chemisorption method; a step of reorienting the adsorbed film by rubbing; and a second step including a metal compound catalyst. And a step of polymerizing the substrate by immersing it in an organic solvent, and further irradiating the entire surface with radiation in an inert gas atmosphere to polymerize the remaining acetylene group portion of the monolayer. A method for producing a polyacene type highly oriented conjugated polymer.
２Ｈ基が結合していることを特徴とする請求項23、26ま
たは27記載のポリアセン型高配向性共役ポリマーの製造
方法。28. -Si (CH 3 ) is attached to the molecular end of a linear molecule.
28. The method for producing a polyacene type highly oriented conjugated polymer according to claim 23, 26 or 27, wherein 2 H groups are bonded.
を特徴とする請求項28記載のポリアセン型高配向性共役
ポリマーの製造方法。29. The linear molecule is 29. The method for producing a polyacene type highly oriented conjugated polymer according to claim 28, wherein (l, m, n are 0 or integers and a total of 5 to 25).
が結合していることを特徴とする請求項23、26または27
記載のポリアセン型高配向性共役ポリマーの製造方法。30. The —CH═CH 2 group is bonded to the molecular end of the linear molecule, 23, 26 or 27.
A method for producing the polyacene-type highly oriented conjugated polymer as described above.
Ｏ−（CH２）ｎ−SiCl３ （l,m,nは、０または整数で合計５から25）であること
を特徴とする請求項30記載のポリアセン型高配向性共役
ポリマーの製造方法。31. A linear molecule having CH═CH 2 — (CH 2 ) 1 —C≡C—C≡C— (CH 2 ) m —.
O- (CH 2) n -SiCl 3 (l, m, n is 0 or a total 5 integer 25) The process according to claim 30 polyacene type highly oriented conjugated polymer, wherein the a.
またはNb、またはTa化合物であることを特徴とする請求
項23から31のいずれかに記載のポリアセン型高配向性共
役ポリマーの製造方法。32. The metal of the metal compound catalyst is Mo or W,
32. A method for producing a polyacene type highly oriented conjugated polymer according to claim 23, which is a Nb or Ta compound.
に共触媒として有機Snあるいは有機Bi化合物を含むこと
を特徴とする請求項23から31のいずれかに記載のポリア
セン型高配向性共役ポリマーの製造方法。33. The polyacene-type highly-oriented conjugated polymer according to claim 23, wherein the organic compound further contains an organic Sn or organic Bi compound as a cocatalyst in the organic solvent. Production method.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2541590A JPH0667982B2 (en) | 1990-02-05 | 1990-02-05 | Method for producing highly oriented conjugated polymer |
| US07/651,069 US5114737A (en) | 1990-02-05 | 1991-02-05 | Process for preparing an organic monomolecular film |
| DE69128160T DE69128160T2 (en) | 1990-02-05 | 1991-02-05 | Process for the production of an organic monomolecular coating |
| EP91101532A EP0445534B1 (en) | 1990-02-05 | 1991-02-05 | A process for preparing an organic monomolecular film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2541590A JPH0667982B2 (en) | 1990-02-05 | 1990-02-05 | Method for producing highly oriented conjugated polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03229710A JPH03229710A (en) | 1991-10-11 |
| JPH0667982B2 true JPH0667982B2 (en) | 1994-08-31 |
Family
ID=12165312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2541590A Expired - Fee Related JPH0667982B2 (en) | 1990-02-05 | 1990-02-05 | Method for producing highly oriented conjugated polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0667982B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08846B2 (en) * | 1992-01-14 | 1996-01-10 | 松下電器産業株式会社 | Method for producing polyacetylene type conjugated polymer |
| TW555790B (en) | 2000-12-26 | 2003-10-01 | Matsushita Electric Ind Co Ltd | Conductive organic thin film, process for producing the same, and organic photoelectronic device, electric wire, and electrode aech employing the same |
| CN100585751C (en) * | 2001-04-17 | 2010-01-27 | 松下电器产业株式会社 | Conductivity organic film, its manufacture method and electrode and cable using such film |
| WO2009041365A1 (en) * | 2007-09-27 | 2009-04-02 | Sharp Kabushiki Kaisha | Organic transistor and process for producing the same |
-
1990
- 1990-02-05 JP JP2541590A patent/JPH0667982B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03229710A (en) | 1991-10-11 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |