JPS62109819A - Organic semiconductor - Google Patents

Abstract

PURPOSE:The titled novel substance which is stable in air, not oxidized, has improved molded properties and readily producible, obtained by polymerizing a pyrrole compound or an aniline compound in the presence of a high polymer containing a specific structural unit. CONSTITUTION:A pyrrole compound shown by the formula III (R<5> and R<6> are H, halogen, etc.; R<7> is H, aryl, etc.,) or an aniline compound shown by the formula IV (R<8> and R<9> are H, allyloxy, etc.; R<10> and R<11> are R<7>) is polymerized in the presence of a high polymer having a constituent unit shown by the formula I (R<1> and R<2> are H, alkyl, etc.,) such as polyvinyl carbazole, etc., or of a high polymer having a constituent unit shown by the formula II (R<3> and R<4> are R<1>) such as polyacenaphthaylene, etc., preferably at 0-80 deg.C for 1-50hr, to give the aimed substance. The polymerization reaction is preferably carried out in the presence of an organic solvent such as THF, etc., to dissolve the polmer shown by the formula I or formula II.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a novel organic semiconductor obtained by polymerizing a specific nitrogen-containing compound in the presence of a polymer having a specific structural unit. It is.

<Prior Art> In 1977, it was reported that when polyacetylene is brought into contact with halogen atoms, its electrical conductivity is significantly improved, providing a highly conductive polymer.

Subsequently, various polymers with conjugated double bonds in the main chain of the polymer, such as polyparaphenylene, polythenylene, polypyrrole, polyparaphenylenevinylene, etc., were saved, and arsenic pentafluoride, antimony pentafluoride, iodine, bromine, When treated with various P-type or H-type doping agents such as sulfur trioxide, nitrogen oxide, n-butyllidium, and naphthalesina di- or helium, the electrical conductivity is significantly improved, changing from an insulator to a semiconductor to a rough conductor. It has been reported that the body

These conductive polymers are obtained in the form of powder, particles, blocks, or films, and are used as they are or after processing and molding depending on the purpose, and are used as antistatic materials, electromagnetic shielding materials, electro-optical functional devices, Optical memory (holographic memory) and various sensors.

Display elements (electrocrocism), switches.

It is applied to a wide range of fields such as various hybrid materials (transparent conductive films, etc.), various terminal devices, and electrode materials for secondary batteries.

<Problems to be solved by the invention> However, these conductive polymers are not stable in air, are easily oxidized and deteriorate, and have insufficient moldability. They have had various problems such as dryness, complicated manufacturing methods, and poor reproducibility.

Means for Solving the Problems> The present inventor conducted research on modern conductive polymers that do not have the problems of the conventional conductive polymers mentioned above, and found that
By polymerizing at least one of a pyrrole-based compound monomer or an aniline-based compound monomer in the presence of at least one of a vinylcarbazole-based polymer or an acenaphthylene-based polymer, it becomes stable in air. The present invention was completed by discovering that it is possible to provide an organic semiconductor that not only has good moldability but also is easy to manufacture.

However, the gist of the present invention is at least a general formula %formula% or general formula (In the formula, R1 to R4 are hydrogen atoms and alkyl groups.

Alkoxy group, aryl group, allyloxy group.

Thioether group, amine group, halogen atom.

In the presence of at least one of the polymers having the structural unit represented by the general formula (wherein R5 and R6 are a hydrogen atom or an alkyl group).

Arcogysyl group, aryl group, allyloxy group.

a thioether group, a halogen atom, and R7 represents a hydrogen atom, an argyl group, or an aryl group) or a pyrrole compound represented by the general formula (wherein R8 and R9 are a hydrogen atom or an alkyl group).

Represents Alfuki 9th base, aryl group, allyloxy group, R
10 and R11 represent a hydrogen atom, an alkyl group, or an aryl group).

In the vinylcarbazole polymer represented by the general formula (1) and the acenaphthylene polymer represented by the general formula (2), in the formula, R1-R4 are hydrogen atoms, methyl groups,
Ethyl group, n-propyl group, 1so-propyl group, n-
Ethyl group, 1so-butyl group, 5ec-butyl group, t
Alkyl groups such as ert-butyl groups, methoxy groups, ethoxy groups, n-propoxy groups, 1so-propoxy groups,
Alkoxy groups such as n-butoxy groups, aryl groups such as phenyl groups, tolyl groups, naphthyl groups, phenoxy groups,
Allyloxy groups such as methylphenoxy groups and naphthoxy groups, thioether groups such as methylthioether groups and ethylthioether groups, amino groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, aldehyde groups, cyano groups, and nitro groups. represents.

Specifically, vinylcarbazole-based polymers include polyvinylcarbazolevinylcarbazole, 4,7-dimethylborivinylcarbazole, 4-methoxypolyvinylcarbazole, 4-ethoxybo-1novinylcarbazolenylpolyvinylcarbazole, and 4,7-diphenyl. Examples include polyvinylcarbazole, 4-naphdylpolyvinylcarbazole, 4-phenoxyborivinylcarbazole, 4-methylthiopolyvinylcarbazole, polyvinylcarbazole, 4-cyanopolyvinylcarbazole, and anopolyvinylcarbazole.

In addition, examples of the acepphrene-based polymers include borialepphthylene, 5-medylbo-1 noacenaphthylene, 5-ethylpolyacenaphthylene, 5-methoxypolyacenaphthylene,
5-ethoxypolyacenaphthylene, 5,6-dime-1-xypolyacenaphthylene, 5-phenylpolyacenaphthylene, 5-1-ruylboreacenaphthylene, 5-naphthylpolyacenaphthylene, 5-phenylpolyacenaphthylene Enoxyboriacenaphthylene, 5-methylthioboriacenaphthylene, 5-aminopolyacenaphthylene, 5-bromopolyacenaphthylene, 5
, 6-dibromopolyacenaphthylene, boriacenaphthylene 5-aldehyde, 5-cyanopolyacenaphthylene, 5
, 6 dinitro polyacenaphthylene, and the like.

The molecule 1 of the vinyl carbazole polymer and acenaphthylene polymer used is 5000 to 800000,
Preferably it is 10,000 to 500,000.

Further, as the pyrrole compound represented by the general formula (3), R5. r:<6 is a hydrogen atom, methyl group, ethyl group,
Alkyl groups such as n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, methoxy group, ethoxy group, n-propoxy group, is
Alkoxy groups such as o-propoxy group and n-butoxy group, 7-aryl group such as phenyl group, 1-helyl group, and naphthyl group, allyloxy group such as phenoxy group, methylphenoxy group, and naphthoxy group, methylthioether group, and ethylthioether group. R7 is a halogen atom such as a thioether group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and R7 is a hydrogen atom, an alkyl λ(, phenyl represents an aryl group such as a tolyl group, a tolyl group, or a naphkyl group.

Specifically, pyrrole, N-methylpyrrole, N-ethylpyrrole, N-n-propylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-methyl-N-methylpyrrole, 3-edy-N-methylpyrrole, 3-me 1
~Gicipyrrole, 3-ethoxypyrrole, 3-methoxy-N-methylpyrrole, 3-ethoxy-N-ethylpyrrole, 3-phenylpyrrole, 3-phenyl-N-methylpyrrole, 3-phenoxypyrrole, 3-naphthoxypyrrole , 3-methylthiopyrrole, 3-ethylthiopyrrole, 3-bromopyrrole, 3,4-dibromopyrrole, 3,4-dimethylpyrrole, 3,4-diethyl-N
-Methylpyrrole and the like.

Further, as the aniline compound represented by the general formula (4), R8 and R9 are hydrogen atoms, methyl groups, ethyl groups, n
-propyl group, 1so-propyl group, n-butyl group,
Alkyl groups such as 1so-butyl group, 5ec-butyl group, tert-butyl group, methoxyly, 1hexyl group, n
-propoxy group, 1so-propoxy group, alkoxy group such as n-butoxy group, phenyl group, 1-ruyl group,
It represents an aryl group such as a naphthyl group, an allyloxy group such as a phenoxy group, a methylphenoloxy group, a bufthoxy group, and R10 and R11 are a hydrogen atom, a methyl group, an ethyl group,
It does not represent alkyl groups such as n-propyl group, 1so-propyl group, n-butyl group, or aryl groups such as phenyl group, tolyl group, naphthyl group.

Specifically, aniline, 3-methylaniline, 3.5-
Dimethylaniline, 3-ethylaniline, 3-n-propylaniline, 3-methoxyaniline, 3,5-dimethoxyaniline, 3-ethoxyaniline, 3,5-jethoxyaniline, 3-phenylaniline, 3,5-diphenyl Aniline, 3-naphthylanione, 3-tolylaniline, 2,5-dimethylaniline, 3-phenoxyaniline, 3-pufthoxyanilon, N,N-dimethylaniline, N,N-dimethylaniline, 3-methylN.

N-dimethylaniline, 3,5-dimethylN, N-diethylaniline, 3-ethylN. N-dimethylaniline,
3-Me1hexyN.

N-dimethyl)aniline, 3,5-dimethoxyN.

N-dimethylaniline, 3-phenoxyN, N=nidimethylaniline, etc.).

The amount of the pyrrole compound or aniline compound to be used is 0.01 to 100 times the mole of the vinylcarbazole polymer or acenaphthylene polymer, preferably 0.01 to 100 times the molar amount.
05-.50 times the mole.

The polymerization reaction of the heptamer compound represented by the general formula (3) or (4) in the presence of the polymer represented by the general formula (1) or (2) can be carried out in any phase of the same phase, liquid phase, or gas phase. or the polymer represented by the general formula (3) in the presence of an organic solvent in which the polymer represented by the general formula (1) or (2) is uniformly dissolved.
It is preferable to carry out a polymerization reaction of a heptamer compound represented by (/1). In particular, in a homogeneous solution containing a polymer represented by general formula (1) or (2), general formula (3) or (4) is added.
By carrying out the reaction in a completely homogeneous solution system in which the heptamine compound represented by is uniformly dissolved, the polymer represented by (1) or (2) and the heptamine represented by (3) or (4) can be reacted.
The polymer of the compound is homogeneously dispersed.

In the polymerization reaction of the heptamer compound represented by formula (3) or (4), metal salts, peroxides, and nitrogen oxides having strong acid residues, halogen, and cyan are usually used. Specifically, Fe(C104)3, Fe(BF4)3
, Fe2 (s i F6 )3, Cu (CCC4
)2, Cu (BF4)2, CuS i F6,
FeCn3, CuC,g2, K (Fe(CN)6
), RuCf! ,3,Mocz5,WCβ,(NH4
) 28208, 2320B, N 82820B,
\a B O3, 1-1202, N0BF4, No28
F4, N0CJ20/l, N0RsF6, N0PF
6 etc.

The amount of ml used is 0.01 to 100 times, preferably 0.05 to 50 times, the mole of the heptamer compound.

In addition, as the battering machine solvent to be used, the general formula (1) or (2
) Any solvent can be used as long as it can uniformly dissolve the polymer shown in the formula, such as tetrahydrofuran, dioxane, chloroform, dichloroethane, dichloromethane,
Dichlorobenzene and the like can be used as good solvents.

The amount of the polymer represented by general formula (1) or (2) relative to the solvent used is 0.1 to 60% by weight, preferably 1 to 50% by weight.
The amount is %. The reaction temperature is -20 to 100°C, preferably 0 to 80'C, and the reaction time is related to the reaction temperature, but is usually 0.5 to 100 hours, preferably 1 to 50 hours.

The reaction product is necessarily a dark brown to black solid substance; in the case of a reaction in the presence of a solvent, after the reaction is complete, the solvent is removed in the usual way, or it is transferred to water or alcohol, and the product is filtered and washed. It can be easily separated and purified by

Effect> By using the above-described means, it is possible to obtain a conductive polymer (organic semiconductor) that is stable in the air, is not oxidized, has good moldability, and is easy to manufacture.

<Example> The present invention will be specifically explained below with reference to Examples.

Example 1 Polyvinyl carbazole (
6.0 g (molecular weight: 210,000) was taken, and 70 mβ of tetrahydrofuran was added and dissolved to prepare a uniform viscous liquid.

Add 2.0 g of pyrrole to this viscous liquid to prepare a homogeneous mixture of polyvinylcarbazole and pyrrole, and while stirring this mixture at room temperature under a nitrogen stream, FeCβ34.8
7g dissolved in 30ml of tetrahydrofuran, 10ml
It was added dropwise over a period of minutes. At this time, the reaction solution was initially colorless, but turned black over time, and a black viscous solution was obtained after 3 hours. After leaving this solution overnight, pour it into a large amount of methanol, and dissolve the residue in 200 mg of methanol.
After washing twice and drying at 60° C. under reduced pressure, 7.18 g of a uniform black powder was obtained.

In addition, polyvinylcarbazole was quantitatively recovered when the treatment was performed in exactly the same manner except that pyrrole was not used.

The above results indicate that the above treatment produced a polymer consisting of polypyrrole in which pyrrole was combined and uniformly dispersed in polyvinylcarbazole.

In addition, from the increase in ff1l, the polymer increased by 1 is polyvinylcarbazole 6.0 (polypyrrole 1.18 in 1).
It shows that it is made of polymer containing ( ).

The electrical conductivity of this polymer was measured using the two-terminal method, and the result was 3.3 x 10"63 cm-', which was
It has been found that organic semiconductors with conductivity in the semiconductor region are necessary. And polyvinylcarbazole alone has 10
It is known to be a -10-158C insulator.

Therefore, the electrical conductivity of the polymer obtained above is significantly improved.

The electrical conductivity was measured as follows. First, the black powder obtained by the above treatment was ground sufficiently finely with milk, and then pressure-molded (5 tons/C1!!2) into a disk shape with a diameter of 1 Qmm. Next, stainless steel disks of the same size were sandwiched between both sides of this disk sample, placed between Teflon bolts and nuts, and the disks were sufficiently crimped and fixed by tightening, then stored in a dry box and electrolyzed. Meter (Takeda Risen T)
The electrical conductivity of the disk samples was measured using R-8651>.

In addition, 0.95 g of the polymer obtained above and Polyte 1~
Lafluoroethylene powder (Polyflon Fine Powder F 103 manufactured by Daikin) 0.05 (J) was weighed into milk, pre-kneaded until it became flaky, then kneaded with a roll and formed into a sheet, resulting in a black uniform powder. I was able to remove 1 q of flexible sheet (thickness: 200 μm). Visually inspecting this flexible sheet, I found that the entire sheet was a slightly wide black color with no uneven parts observed. It was found that the dispersibility of polypyrrole (white) and polypyrrole (black when used alone) was extremely good.

Comparative Example 300 mΩ in a round bottom flask
, polycarbonate 1~(molecule ff 1.2 million) 6. O
A viscous liquid was prepared by uniformly dissolving 2.51 g of barley and pyrrole (2.51 g of barley and pyrrole were added and stirred to mix uniformly. Next, this mixed liquid was stirred at room temperature under a nitrogen stream, 100 mfJ of dioxane in which Fe (439,73 (l) was dissolved was added little by little to the mixed solution. At this time, the reaction solution turned black and separation of black particulate solids was observed. Stirred for 2 hours. However, when left overnight at room temperature, a black substance precipitated in the lower layer of the reaction solution was observed.The reaction solution and the entire amount of black precipitate were placed in a large amount of methanol, and the filtrate was dissolved in 200 mN methanol. After washing four times and drying under reduced pressure at 60°C, 7.21 g of a fluffy gray and black non-uniform solid was obtained. 51~n/c
m2), the surface was clearly separated into black and gray areas, indicating that the uniform dispersibility of both polymers was extremely poor.

Example 2 Polyacenaphthylene 6 instead of polyvinylcarbazole
．． 0g (molecular weight: 150,000), and FeC, C39,74
A reaction of pyrrole was carried out in the same manner as in Example 1, except that G was used in the presence of homogeneously dissolved polyacenaphthylene. At this time, the color of the reaction solution is FeCJ? When 3-tetrahydrofuran was added, the reaction was reddish at the initial stage, but the blackening progressed over time, and the entire reaction solution after 2 hours of contact became a viscous black liquid.

After leaving this black liquid overnight, it was transferred to methanol in a large pot, and the residue was washed four times with 200 mfJ of methanol, and then heated at 60°C.
When dried under reduced pressure, 6.68 Cl of a homogeneous black solid becomes 1
I was pissed.

In addition, f was prepared in exactly the same way except without using pyrrole.
When f1Ll was carried out, polyacenaphthylene was quantitatively recovered.

The above results indicate that pyrrole was polymerized by the above treatment and a polymer consisting of polypyrrole uniformly dispersed in polyacenaphthylene was produced. Furthermore, the increase in weight d indicates that the obtained polymer contains 0.68 g of polygorol in 6.0 g of polyacenaphthylene. The electrical conductivity of this polymer was 4.2 x 10'5 cm-1 TeSV), indicating that it was an organic semiconductor with conductivity in the semiconductor region.

Examples 3 to 11 Polymerization of a pyrrole compound or aniline compound was carried out in the same manner as in Example 1 in the presence of various vinyl carbazole polymers or acenaphthylene polymers, and jq
The results for the black solids obtained are shown in Table 1.

<Effects of the Invention> The organic semiconductor of the present invention configured as described above is stable in air and does not oxidize, has good moldability and is easy to manufacture, and has extremely great practical value. . Thus, the organic semiconductor of the present invention can be applied to a wide range of fields such as antistatic materials, N magnetic wave blocking materials, electronic/optical functional devices, optical memories, various sensors, display devices, switches, various terminal devices, and storage batteries. .

Claims (1)

[Claims] 1. At least a general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) Or a general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (R in the formula ^1 to R^4 are hydrogen atoms, alkyl groups, alkoxy groups, aryl groups, allyloxy groups, thioether groups,
At least a general formula ▲ mathematical formula, chemical formula, table, etc. exists in the presence of one of the polymers having a constitutional unit represented by amino group, halogen atom, aldehyde group, cyano group, nitro group ▼... (3) (In the formula, R^5 and R^6 are hydrogen atoms, alkyl groups, alkoxy groups, aryl groups, allyloxy groups, thioether groups,
(represents a halogen atom, and R^7 represents a hydrogen atom, an alkyl group, or an aryl group) or general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼...(4) (In the formula R^ 8, R^9 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an allyloxy group, and R^1^0 and R^1^1 represent a hydrogen atom, an alkyl group, or an aryl group) An organic semiconductor obtained by polymerizing either one of the system compounds.