JPS6322067A - Lb film of pyrrole derivative and production thereof - Google Patents

Abstract

PURPOSE:To obtain LB film of a pyrrole derivative containing a hydrophilic substituent group and a hydrophobic substituent group capable of producing an ultrathin film of a polymer having electrical conductivity and electrochromic properties, by forming a single layer - plural layers of a monomolecular layer of the compound on the surface of solid. CONSTITUTION:A pyrrole derivative containing at least one hydrophilic substituent group (e.g. COOR, COR, CN, SH, SO3H, NH2 or OH; R is H or lower alkyl) and hydrophobic substituent group (e.g. 1-23C saturated or unsaturated aliphatic hydrocarbon group which may contain branched chain) at N-position, 3-position and 4-position of pyrrole ring is dissolved in an organic solvent, spread on water surface B' and the organic solvent is removed to form a monomolecular layer A'. Then the monomolecular film is transferred to the surface of a solid C at fixed surface pressure of 10-60dyne/cm and a single layer - plural layers of the monomolecular layer are formed on the surface of solid (especially electrode) to give a Langmuir Blodgett film (LB film) of pyrrole derivative to be expected as a functional material in electrical and electronic fields, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an ultra-thin film of an organic compound, and more particularly to a Langmuir-Blodgett film of a pyrrole derivative having a hydrophilic substituent and a hydrophobic substituent. The present invention relates to a film (hereinafter referred to as rLB film) and a method for manufacturing the same.

The LB film of the pyrrole derivative of the present invention can be made into an ultra-thin organic polymer film having conductivity and electrochromic properties by further electrolytic oxidative polymerization or chemical oxidative polymerization, and is a functional material in the fields of electricity, electronics, etc. It is expected that it will be used as a

[Conventional technology]

It is well known that pyrrole polymers have high conductivity and electrochromic properties, and in recent years, research on their application to the electrical and electronic fields has been actively conducted. (J.C. Niss Chemical Communications, J.
,C,S,Chem,Comm,.

p. 635 (1979), etc.) However, there are no known documents describing polymers of pyrrole derivatives having both hydrophilic substituents and hydrophobic substituents and their properties.

On the other hand, a monomolecular film of an organic compound having a hydrophilic substituent and a hydrophobic substituent is spread on the water surface, and then transferred to the substrate surface while being compressed.
It is well known as B film. (J+-/Kuss J, A
,C,S,, Vol 51. P 1007゜193
5) Furthermore, many LB films using compounds having heteroatoms such as N, S, and O in the main skeleton have been reported. (Refer to Japanese Unexamined Patent Publication No. 52-35.579, etc.) These LB films are made from a compound with a strong molecular structure such as anthracene.
As described in Japanese Patent No. 35579, it is said that it is difficult to manufacture an LB film of a mononuclear heterocyclic compound.

Therefore, there is no literature reporting on LB films of pyrrole BM conductors.

In addition, pyridine and tetracyanoquinodimethane (TCN
A LB film formed using a complex with Q) and given conductivity by doping with iodine in an iodine gas atmosphere was developed by Andre Barrault et al. (French Atomic Energy Research Institute, 198
4) was reported. In addition, a conductive organic thin film material that combines a pyridine derivative having an alkyl chain and an acceptor molecule was reported by Futan et al. (Agency of Industrial Science and Technology/Nihon Keizai Shimbun, dated 60.12.17).

[Problem that the invention seeks to solve]

In the conductive LB film reported by Andre Barrow et al., it is difficult to set conditions for quantitative iodine doping, and moreover, the iodine evaporates and the conductivity disappears several hours after doping.

On the other hand, the report on pressure end etc. is an improvement on the shortcomings of the technique of Andre Barraud et al., but the basic concept is based on CT1'i
They are common in that charge transfer between a donor and an acceptor placed in an i-body (charge transfer) is utilized, and the difficulty of setting doping conditions has not been improved.

Polymers of pyrrole derivatives are known as conductive polymers, but as described above, their LB films have not been obtained because they are difficult to manufacture.

The present invention describes the use of pyrrole derivatives that have the possibility of producing thin polymer films with conductivity and electrochromic properties.
The object of the present invention is to provide a B film and a method for manufacturing the same.

[Means for solving problems]

The present invention provides a method for applying a monolayer or multiple layers of a monolayer of a pyrrole derivative having at least one hydrophilic substituent and one hydrophobic substituent at the N-position, 3-position and 4-position of the pyrrole ring on a solid surface. The present invention provides a pyrrole derivative LB film formed and a method for producing the same.

In the present invention, the raw material pyrrole derivative has the following general formula (
1) In the formula, at least one of XI, XZ and x3 is a hydrophilic substituent and a hydrophobic substituent.

Examples of the hydrophilic substituent include -Coo)I.

-COOR, -COR (R represents hydrogen or a lower alkyl group here) CN, SH, SOJ, N
H□.

-Nl2. -OH etc., preferably -COO
H.

-C0OR is adopted. On the other hand, as a hydrophobic substituent,
An optionally branched saturated or unsaturated aliphatic hydrocarbon group having 1 to 23 carbon atoms, preferably 6 to 23 carbon atoms, is employed. 1 hydrophilic substituent and 1 hydrophobic substituent each
In cases where the substituents have both, there are no particular restrictions on the remaining substituents, but hydrogen or lower alkyl groups are preferably employed. More specifically, XI, X of the general formula +1)
When one of I and X3 is an optionally branched saturated or unsaturated aliphatic hydrocarbon group having 1 to 23 carbon atoms, the remaining 2 are -COON and/or -COOR derivatives , or the remaining 1 is -COOH or -C
OOR, and the others are hydrogen or lower alkyl groups, pyrrole derivatives are mentioned.

Furthermore, the pyrrole derivative referred to in the present invention may have a substituent having both hydrophilicity and hydrophobicity.

For example, 1 in XI, X2 and x3 is -GOO
In the case of R1-COR (R+ represents a higher alkyl group),
Examples include pyrrole derivatives in which the remaining 2 is hydrogen or a lower alkyl group.

Raw material pyrrole derivatives, such as pyrrole derivatives having a hydrophobic group at the N-position, are combined with a 3-substituted or 3.4-substituted pyrrole having a hydrophilic group at the 3- and/or 4-position and an alkali metal, e.g. By reacting with potassium,
After synthesizing an alkali metal salt, it can be synthesized by reacting this alkali metal salt with a monohalogenated aliphatic hydrocarbon.

A developing solution in which the pyrrole derivative is dissolved in an organic solvent is dripped onto the water surface, and the organic solvent is volatilized or removed by dissolving it in water, so that the hydrophilic groups are placed on the water side and the hydrophobic groups are placed on the air side. The fracture surface pressure was 30 d.
A monomolecular film of a pyrrole derivative of yne/cm or more can be formed on the water surface.

The LB film of pyrrole derivative has a molecular weight of 10 to 60
It is formed by transferring onto a solid surface while compressing and holding at a constant surface pressure in the range of dyne/cm.

Further, by repeating the transfer of this monomolecular film onto a solid surface, an LB film in which a plurality of monomolecular films are laminated can be obtained.

By subjecting the obtained pyrrole derivative LB film to electrolytic oxidative polymerization or chemical oxidative polymerization, it is possible to obtain an ultra-thin polymer film having conductivity and electrochromic properties.

When the purpose is electrolytic oxidation polymerization of an LB film of a pyrrole derivative, a conductive substrate that can be used as an electrode is used as the substrate for the LB film, and when focusing on its electrochromic property, a transparent electrode, for example, is used as the substrate for the LB film. A glass substrate with an ITO (tin-doped indium oxide) film and a NESA (antimony-doped tin oxide) film is used.

The developing solution is an organic solvent solution in which the concentration of the pyrrole derivative is 10-' to 10% by weight, preferably 10-4 to 10-1% by weight, more preferably 10-3 to io-''% by weight, The organic solvent is not particularly limited as long as it can dissolve the pyrrole derivative, and water-insoluble solvents, water-soluble solvents, or mixed solvents thereof can be used.As the organic solvent, hydrocarbons, halogenated solvents, etc. Hydrogen or a mixed solvent thereof is preferable, and benzene, chloroform, or a mixed solvent thereof is used more preferably.The developing solution may optionally contain a polymerization catalyst for the LB membrane,
Dopants and the like can be added.

The water that forms the water surface for developing the developing solution is usually clean water with a pH of 4 to 7 and a temperature of 5 to 20°C, or 2 to 3
Water to which valence metal ions, phosphoric acid, etc. are added is used.

As a method for transferring a monomolecular film of a pyrrole derivative onto a solid surface, the monomolecular film-forming surface of the solid is brought into contact with the monomolecular film perpendicularly, as shown in attached Figures 3 (a), (b) and (C). There are a method of contacting the monolayer in parallel with the monomolecular film, a method of contacting the monomolecular film at an angle, and any of these methods may be adopted.

[Effect]

The present invention is characterized in that the raw material compound of the LB film is a pyrrole derivative having a hydrophilic substituent and a hydrophobic substituent. Therefore, when a developing solution containing this pyrrole derivative is dropped and developed on a water surface, the hydrophilic substituents are aligned on the water surface side and a monomolecular film is easily formed. Furthermore, the pyrrole ring acts as a cushion, forming a monomolecular film with a high fracture surface pressure.

In particular, a good monomolecular film has a hydrophilic substituent of -C00H or -COOR (where R represents a lower alkyl group).

), obtained by a pyrrole derivative in which the hydrophobic substituent is a saturated or unsaturated aliphatic hydrocarbon which may have a branching of 6 to 23 carbon atoms.

〔Example〕

The present invention will be explained in more detail by way of examples.

However, the scope of the present invention is not limited to the same extent by the following examples.

(1) Synthesis of raw material pyrrole derivative (81 Invention sample 1) 5 g of 3-methylpyrrole-4-carboxylic acid (0,0
4n+ol) and metallic potassium 3.7g (0.09m
ol) was added to 50 ml of dry and purified THF and kept under stirring at room temperature. Hydrogen gas is generated immediately after the reaction starts,
Crystals of potassium salt precipitated and the potassium particles disappeared after 3 hours. To the reaction solution in which the obtained potassium salt crystals were suspended,
13.3g (0.04mol) of stearyl bromide in 10mj of THF! After the dropwise addition, the mixture was stirred and maintained at room temperature for 1 hour, and then for 30 minutes under reflux of THF to complete the reaction. The reaction product was purified by column chromatography to obtain N-stearyl-3-
Methylpyrrole-4-carboxylic acid was obtained. Synthesized compounds were identified by NMR.

ii) Crotonic acid chloride 2.32g (0,022m
ol) with 5 g (0,018 mol) of stearyl alcohol
) into 50mj7 of dry benzene. After 1 hour, warm water at 30 to 40°C was added, and the reaction was completed in 1 hour. The reaction solution was poured into water, and unreacted crotonic acid chloride was decomposed and extracted with benzene. The benzene was concentrated to give an oil. 4 g of this product and 2.3 g (0.01) mol) of tosylmethyl isocyanide were dissolved in 50 tnβ of dimethoxyethane with 0.0 g of sodium hydride.
A pyrrole ring synthesis reaction was carried out in the presence of 6 g (purity 60χ, 0.015 mol). The reaction product was purified by column chromatography, and 4-methylpyrrole-3=
Stearyl carboxylate was obtained. Synthesized compounds were identified by NMR.

(b) Comparative sample In the synthesis of the sample of the present invention, 5 g of pyrrole (0,
N-stearylpyrrole was synthesized under the same conditions as the present invention sample, except that the amount of stearyl bromide used was 25 g (0,075 mol). Synthesized compounds were identified by NMR.

(2) Preparation of developing solution N-stearyl-3-methylpyrrole-4-carboxylic acid (SMPC) synthesized in the above item (1), stearyl 4-methylpyrrole-3-carboxylate (MPCS)
Each of O and N-stearylpyrrole (SP) and n-octadecane were dissolved in benzene to prepare a developing solution having the following specifications.

(Production of 31LB membrane Fill tank 1 of the LB membrane manufacturing apparatus shown in attached Figure 2 with distilled water adjusted to pH 7 by adding phosphate buffer, and drop 100 μl of the developing solution prepared in the above item (2). It was developed and the benzene was evaporated to form a monomolecular film of the pyrrole derivative.

Next, the weight 4 is adjusted to move the float 3 to compress the monomolecular film of the pyrrole derivative, and the surface pressure Kerr surface area curve (
F-A curve) was measured.

In Examples 1, 2, and 3 using a developing solution of N-stearyl-3-methylpyrrole-4-carboxylic acid, good reversible F-A curves were obtained, and the respective fracture surface pressures were 45 dyne/cm, 35dyne/cI
1) and 55 dyne/mouth.

In Example 4, which used a developing solution of stearyl 4-methylpyrrole-3-carboxylate, a good reversible FA curve was obtained, and the fracture surface pressure was 55 dyne/cm.

On the other hand, in a comparative example using a developing solution of N-stearylpyrrole, the membrane was destroyed at a surface pressure of 15 dyne/cm.
It was not possible to obtain an FA curve.

FIG. 1 shows the FA curves of the systems using the developing solutions of Examples and Comparative Examples.

Furthermore, in the system using the developing solutions of Examples 1 and 4, the surface pressure of the monomolecular film of the pyrrole derivative was increased to 40
The monomolecular film was vertically moved up and down the glass substrate while maintaining the dyne/cm and 50 dyne/cm constant, and the monomolecular film was transferred onto the surface of the glass substrate to form an LB film.

Example 5 Using ITO vapor-deposited glass as the glass substrate, Example 1
200 layers of LB films were accumulated. LiCI O
, 0.1 mol/j! It turned reddish-brown by immersing it in an acetonitrile solution and undergoing electrolytic oxidation polymerization.

The conductivity of this polymerized LB film is 0.3X in the film surface direction.
10°Scm-' Approximately 10-'' Sc in the film thickness direction
It was m-'.

Example 6 The LB film of Example 4 was similarly subjected to electrolytic oxidation polymerization to obtain a reddish-brown polymerized LB film. The electrical conductivity is 0.9 in the film surface direction.
XIO''Scm-' Approximately 10-lScm in the film thickness direction
-' was.

FIG. 4 shows ATR-IR spectra before and after electrolytic oxidation. The spectrum of the LB film after electrolytic oxidation is 780 am-
The absorption of the out-of-plane bending vibration of hydrogen at the 2nd and 5th positions of pyrrole near '' disappeared, and from this it was confirmed that the LB film after electrolytic oxidation was a polymeric film.

〔Effect of the invention〕

In the present invention, as shown in the above examples, an LB film of a pyrrole derivative, which has conventionally been difficult to produce, can be obtained using a pyrrole derivative having a hydrophilic substituent and a hydrophobic substituent as a raw material.

Further, this LB film can be subjected to electrolytic oxidative polymerization or chemical oxidative polymerization to provide an organic ultra-thin film in which the pyrrole ring portion is conductive, the hydrophobic substituent portion is insulating, and has electrochromic properties. Moreover, its electrical conductivity, insulating properties, and electrochromic properties can be controlled by selecting hydrophilic substituents and hydrophobic substituents. Furthermore, the LB film polymer, which is composed of multiple monomolecular films of roll derivatives, has electrically sensitive layers and insulating layers alternately laminated, and can be used as a molecular electro device.

Therefore, the LB film of the pyrrole derivative of the present invention can be used as electrical and electronic materials such as insulating films, antistatic films, electronic devices, electrochromic devices, and various sensors, as well as highly functional materials such as externally controlled separation membranes. Its application is expected.

The present invention provides that the polymer has functionality such as high conductivity,
The present invention provides an LB film of a pyrrole derivative and a method for producing the same, which have been unknown due to their difficulty in production, although they have been attracting attention, and are of extremely great industrial significance.

[Brief explanation of drawings]

Figure 1 Implementation! FA curves of monomolecular films of pyrrole derivatives obtained in and comparative examples (a) Example 1, (b) Example 2, (C1 Example 3 (d) Example 4, (e) Comparative example 1 Figure 2
LB film manufacturing equipment used in the examples [Usage codes] l: water tank, 2: formwork, 3: float, 4: weight, 5: wire, 6: pulley, 7: drive device, B: water, B: water surface , C
: Solid, Fig. 3 (al, (bl and (C)) Transfer mode of monomolecular film [codes used] A: Monomolecular film, B: Water, B: Water surface, C: Solid, Fig. 4
Infrared absorption spectra before and after electrolytic oxidation of Example 6 Figure 19 Surface # per 1 m01 (Kyu 2)

Claims (6)

[Claims] (1) A single layer or multiple layers of a monomolecular film of a pyrrole derivative having at least one hydrophilic substituent and one hydrophobic substituent at the N-position, 3-position and 4-position of the pyrrole ring is applied to the solid surface. Langmuir, a pyrrole derivative formed by
Blodgett membrane (2) The hydrophilic substituent of the pyrrole derivative is -COOH,
-COOR, -COR (R represents hydrogen or a lower alkyl group) -CN, -SH, -SO_3H, -N
Langmuir-Blodgett membrane of the pyrrole derivative according to claim (1), which is H_2 or -OH (3) The hydrophobic substituent of the pyrrole derivative has 1 to 2 carbon atoms.
A Langmuir-Blodgett membrane of a pyrrole derivative according to claim (1), which is a saturated or unsaturated aliphatic hydrocarbon group optionally having 3 branches. (4) Langmuir-Blodgett membrane of the pyrrole derivative according to claim (1), wherein the hydrophilic substituent and the hydrophobic substituent of the pyrrole derivative are present in the same substituent group. (5) A Langmuir-Blodgett film of a pyrrole derivative according to claim (1), wherein the solid to be formed into a film is an electrode. (6) A developing solution in which a pyrrole derivative having at least one hydrophilic substituent and a hydrophobic substituent at the N-position, 3-position and 4-position of the pyrrole ring is dissolved in an organic solvent is developed on the water surface. A run of pyrrole derivatives, which is characterized in that a monomolecular film is formed by removing the organic solvent, and this monomolecular film is compressed and held at a constant surface pressure in the range of 10 to 60 dyne/cm to be transferred to a solid surface. Method for manufacturing Muir-Blodgett membrane