JP2001316457A - Silicon-closed polydiphenylamine compound and organic thin-film device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material usable for the construction of electronic devices such as a light emitting diode. SOLUTION: The material is a polymer in which the phenazasiline compound described by formula (1) or (2) constitutes the principal chain structure. (In the formulas, R1 and R2 independently denote an alkyl group, an aryl group, an alkoxy group, or an aryloxy group; R3 denotes an aryl group; and n is a 3-30,000 number denoting the means degree of polymerization).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymer having a 5,10-dihydro-5H-phenazacillin (hereinafter referred to as phenazacillin) compound as a main chain skeleton. This polymer has heat resistance and an organic thin film. It can be used as a material having a hole transporting property of a light emitting element.

[0002]

2. Description of the Related Art The synthesis of a polymer represented by the following formula having diphenylamine in the main chain skeleton is described in Macrom.
olecules 1998, 31, 988-993
Has been reported. It is reported that an NMP (N-methyl-2-pyrrolidone) solution of this polymer exhibits a high fluorescence quantum yield.

[0003]

Embedded image

A phenazacillin compound which is a diphenylamine derivative condensed with silicon is disclosed in JP-A-8-3023.
No. 39 and Japanese Patent Application Laid-Open No. 10-218884 describe that it is suitably used as a hole transport material of a light emitting device. In addition, when used as a constituent material of a light-emitting element, a normal low-molecular compound crystallizes with the passage of time, and the interface becomes uneven, thereby causing an electric short circuit. Since it has a transition temperature Tg, it has been characterized in that crystallization progresses little with time.

Aromatic amine-type polymers such as polyaniline exhibit high electric activity, but have low solubility in general organic solvents, so that there is a problem that film formation is difficult and device formation is difficult.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a phenazacillin compound having excellent film-forming properties, a method for producing the same, and an organic thin-film device comprising the phenazacillin compound.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided a polymer having a main chain skeleton of a 5,10-dihydro-5H-phenazasiline compound represented by the following general formula (1).

Embedded image (In the formula, R ₁ and R ₂ each independently represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and n represents a number of 3 to 30,000 in terms of an average degree of polymerization.) 5 represented by the general formula (2)
A polymer having -methylaryl-5,10-dihydro-5H-phenazasiline compound as a main chain skeleton is provided.

Embedded image (Wherein, R ₁ and R ₂ are each independently an alkyl group, an aryl group, an alkoxy group or an aryloxy group, R ₃
Represents an aryl group, and n represents an average degree of polymerization of 3 to 30,000.
Further, according to the present invention, a polymer having a main chain skeleton of the 5-methylaryl-5,10-dihydro-5H-phenazacillin compound of the general formula (2) is dearylmethylated. 5,10- in the general formula (1)
A method for producing a polymer having a dihydro-5H-phenazacillin compound as a main chain skeleton is provided. Furthermore, according to the present invention, 5,10- represented by the following general formula (3):
A method for synthesizing the polyphenazacillin compound represented by the general formula (2), wherein the dihydro-5H-phenazacillin compound is subjected to a dehalogenation condensation reaction using a nickel complex and polymerized.

Embedded image (Wherein, R ₁ and R ₂ are each independently an alkyl group, an aryl group, an alkoxy group or an aryloxy group, R ₃
Represents an arylmethyl group, and X represents a halogen atom. Further, according to the present invention, there is provided an organic thin-film electrochromic device using the polymer of the general formula (1) or (2) as a constituent element. You. Furthermore, according to the present invention, there is provided an organic thin-film light emitting device using the polymer of the general formula (1) or (2) as a constituent element.

In the above general formulas (1) to (3), R ₁
And the alkyl group represented by R ₂ include methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, n-, iso- or neo-pentyl, n-hexyl, cyclohexyl, n- Straight-chain, branched, and cyclic carbon atoms having 1 to 2 carbon atoms such as heptyl and n-octyl;
0, preferably 1 to 12 alkyl groups. Alkoxy groups include methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-
Butoxy, n-, iso- or neo-pentoxy,
n-hexoxy, cyclohexoxy, n-heptoxy,
straight-chain, branched, and cyclic carbon atoms of 1-2 such as n-octoxy
0, preferably 1 to 12 alkoxy groups.
Examples of the aryl group include aryl groups having 6 to 20, preferably 6 to 14 carbon atoms, such as a phenyl group, an o-, m-, p-tolyl group, a 1- and 2-naphthyl group, and an anthryl group. The aryloxy group includes a phenoxy group, o
Examples thereof include aryloxy groups having 6 to 20, preferably 6 to 14 carbon atoms, such as-, m-, p-tolyloxy, 1- and 2-naphthoxy, and anthroxy groups.

In the above general formulas (2) and (3), R
_{As the} aryl group represented by ₃ , a phenyl group, o-,
An aryl group having 6 to 20, preferably 6 to 14 carbon atoms, such as m-, p-tolyl, 1- and 2-naphthyl, and anthryl is mentioned.

In the general formula (3), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a bromine atom is particularly preferred.

[0011] The polymer of the general formula (2) according to the present invention is represented by the general formula (3).
It can be produced by subjecting a 5H-phenazacillin compound to a dehalogenation condensation reaction using a nickel complex and polymerizing the compound.

In the dehalogenation polycondensation using a nickel complex, various organic solvents usually used in this type of reaction can be used. To illustrate this,
N, N-dimethylformamide, toluene, benzene,
And tetrahydrofuran.

The nickel complex includes tetracarbonylnickel (0), dicarbonylbis (triphenylphosphine) nickel (0), bis (1,5-cyclooctadiene) nickel (0), tetrakis (triphenylphosphine) Nickel (0), (η2-ethylene) bis (triphenylphosphine) nickel (0), tetrakis (t-butyl isocyanate) nickel (0),
[(1,2,5,6,8,10-η) -trans, t
rans, trans-1,5,9-cyclododecatriene] nickel (0), and the like. The nickel complex is used in an amount of 0.1 per equivalent of the compound (3).
It is used at a ratio of ２０20 equivalents, preferably 1-5 equivalents.

The nickel complex may contain 0.1 to 10 equivalents of a ligand such as 2,2'-bipyridyl or triphenylphosphine as a supporting ligand. For example, bis (1,5-cyclooctadiene) nickel (0) is used after adding one equivalent of 2,2′-bipyridyl.
For example, bis (1,5-cyclooctadiene) nickel (0) is used after adding 2 equivalents of triphenylphosphine.

The dehalogenation polycondensation reaction is carried out at a temperature between the melting point of the solvent and
It can be carried out at various temperatures up to the boiling point of the solvent, especially
About 100 ° C. is desirable. After the reaction, it can be purified by reprecipitation or the like.

The average degree of polymerization n of the polymer is from 3 to 300.
00, preferably 5 to 10,000. 5,10-dihydro-5H represented by the above general formula (1) according to the present invention
The polymer having a phenazacillin compound as a main chain skeleton is obtained by dearylmethylating the N-substituent —CH ₂ —R ₃ in the polyphenazacillin compound of the general formula (2) to obtain an NH-type polyphenazacillin compound And can be manufactured. In this case, various conventionally known reactions are used as the dearylmethylation reaction. Such a reaction includes a chemical reduction reaction, an electrochemical reduction reaction, and the like. In the chemical reduction reaction, a method generally used for a dearylmethylation reaction of an amine protected with a benzylamine derivative, for example, a hydrogen reduction method using palladium-carbon, Raney nickel, sodium or the like as a catalyst, Can be mentioned. On the other hand, as the electrochemical reduction reaction, a conventionally known method can be employed. The dearylmethylation reaction of polyphenazaline of the general formula (2) can be performed in various forms, for example, in the form of a film or a solution.

When the polyphenazacillin film represented by the general formula (2) is converted into NH-type polyphenazacillin by an electrochemical reduction reaction, the supporting electrolyte used in the electrolysis reaction is a general electrolytic reaction. The electrolyte used can be used. As such an electrolyte, for example, tetrabutylammonium perchlorate, sodium perchlorate, tetrabutylammonium tetrafluoroborate, or the like is used. The temperature of the electrolytic reaction can be carried out at various temperatures from the melting point of the solvent to the boiling point of the solvent. As the solvent used for the electrolytic reaction, a solvent generally used for the electrolytic reaction can be used, and acetonitrile is particularly desirable.
Reduction potential can be carried out electrolytic reduction at a potential which appears reduction peak at the CV measurement of the compound in the electrolytic reaction, in particular, the range of -4V from -2V with respect to Ag / Ag ⁺ is desirable.

The polymer of the present invention represented by the general formulas (1) and (2) is soluble in an organic solvent, and can be formed into a thin film by a simple molding method such as spin coating.

The polymer of the present invention functions as an electrochromic element and a light emitting element by forming a film on an electrode such as ITO by a method such as a vacuum evaporation method, a spin coating method, and a casting method.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to only these examples.

Example 1 [2,8-dibromo-10,10
-Di-n-butyl-5- (2-naphthylmethyl) -5,
Synthesis of 10-dihydrophenazacillin (general formula 3,
R ₁ , R ₂ = n-butyl, R ₃ = 2-naphthyl, X = B
Synthesis of r)] 4.94 g of bis (2,4-dibromophenyl) amine, 2.25 g of 2-naphthylbromomethane and 1.03 g
Of tetrabutylammonium bromide and 0.68 g of sodium hydroxide were dissolved in 100 mL of tetrahydrofuran and heated under reflux for 24 hours. Water was added to the reaction mixture to terminate the reaction, followed by extraction, followed by purification on a silica gel column to obtain 3.40 g of bis (2,4-dibromophenyl)-(2-naphthylmethyl) amine. Subsequently, after suspending in 20 mL of ether in 1.29 g (2.1 mmol) of bis (2,4-dibromophenyl)-(2-naphthylmethyl) amine in an ice bath, 3
mL of hexane solution of n-butyllithium (1.6 M)
Was added. When the suspension became homogeneous,
0.44 g (2.1 mm) of n-butyldichlorosilane
ol) added. After the precipitate had formed, the ice bath was removed and the mixture was stirred for 12 hours. The reaction solution was added with water, extracted with ether, and then purified with a silica gel column to give 0.1.
51 g (0.84 mmol) of 2,8-dibromo-1
0,10-di-n-butyl-5- (2-naphthylmethyl) -5,10-dihydrophenazacillin was isolated.
The obtained compound was a novel compound not described in the literature.

The elemental analysis values are as follows. Elemental analysis: Calculated for C ₃₁ H ₃₃ Br ₂ NSi: C, 61.29; H, 5.48; N, 2.31 Found: C, 61.11; H, 5.40; 2.09

The NMR spectrum data is as follows. ¹ H-NMR (CDCl ₃ ): δ 6.8-8.0 (m,
13H), 5.41 (s, 2H), 1.0-2.0
(M, 18H) ¹³ C-NMR (CDCl ₃ ): δ148.81, 13
5.77, 134.40, 133.45, 132.9
9, 132.63, 128.90, 127.70, 12
6.40, 125.93, 124.76, 123.9
2,122.64,118.21,113.69,5
6.65, 26.38, 25.78, 13.76, 1
3.65 ²⁹ Si-NMR (CDCl ₃ ): δ-20.10

Example 2 [Poly (10,10-di-n-butyl-5- (2-
Synthesis of naphthylmethyl) -5,10-dihydrophenazacillin-2,8-diyl (general formula 2, R ₁ , R ₂ = n-butyl, R ₃ = 2-naphthyl) under a nitrogen atmosphere To 0.28 g (1.0 mmol) of 1,5-cyclooctadiene) nickel (0),
After adding 1 mL of 1,5-cyclooctadiene, 5 mL of toluene was added and suspended. Further, 0.16 g (1.0 mmol) of 2,2′-bipyridyl was added and the mixture was stirred. 0.42 g (0.7 mmol) of 2,
8-Dibromo-10,10-di-n-butyl-5- (2
After adding (-naphthylmethyl) -5,10-dihydrophenazacillin, the mixture was heated to 60 ° C and stirred for 48 hours. The reaction solution was poured into methanol, and the obtained powder was filtered. This powder was washed with water and methanol in that order, dissolved in dichloromethane and reprecipitated with methanol to give 0.27 g (0.60 mmo as a monomer unit).
The polymer of l) was isolated. The resulting polymer is TH
It was soluble in common organic solvents such as F and chloroform.
The obtained polymer is a novel compound not described in the literature, and has a number average molecular weight of 10,000 and a weight average molecular weight of 24,000.
Met.

The elemental analysis values are as follows. Elemental analysis: Calculated as C ₃₁ H ₃₃ NSi · H ₂ O: C, 79.96; H, 7.58; N, 3.00 Found: C, 79.59; H, 7.29; N, 2.79

The NMR spectrum data is as follows. ¹ H-NMR (CDCl ₃ ): δ 6.8-8.0 (m,
13H), 5.4 (s, 2H), 1.0-2.0
(M, 18H) ¹³ C-NMR (CDCl ₃ ): δ149.15, 13
5.60, 133.61, 132.65, 132.3
2,131.82,128.76,126.29,12
5.77, 124.91, 120.47, 116.4
7, 56.79, 26.55, 26.09, 14.2
0,13.76 ²⁹ Si-NMR (CDCl ₃ ): δ-21.18

The data of the IR spectrum is as follows. IR (KBr pellet) 3050, 3008, 295
2,2919,2867,1633,1590,154
0, 1508, 1452, 1407, 1373, 131
5,1269,1214,1076,1004,96
0,890,868,810,741,474 cm ^-1

Example 3 [Poly (10,
10-di-n-butyl-5,10-dihydrophenazacillin-2,8-diyl (general formula 1, R ₁ = R ₂ = n-
Synthesis of butyl)] 33.5 mg of poly (10,10-di-n-butyl-5)
-(2-Naphthylmethyl) -5,10-dihydrophenazacillin-2,8-diyl) was dissolved in 10 mL of tetrahydrofuran, 0.2 g of sodium was added, and the mixture was stirred. After stirring for 24 hours, the sodium was quenched by adding 2-propanol. After distilling off the solvent, methanol was added and the mixture was filtered to obtain 22.7.
mg of poly (10,10-di-n-butyl-5,10-
Dihydrophenazacillin-2,8-diyl) was obtained. The obtained polymer was a novel compound not described in any literature, and had a number average molecular weight of 18,000 and a weight average molecular weight of 32,000. CDCl ^{2 9} Si-NMR at ₃ in the [delta]-20.
It was 38 ppm, and it was confirmed that the reaction was progressing while leaving the skeleton of the raw material polymer.

Example 4 [Poly (10,1
Synthesis of 0-di-n-butyl-5,10-dihydrophenazacillin-2,8-diyl (general formula 1, R ₁ = R ₂ = n-butyl) 1 mg of the polymer was dissolved in 200 μl of dichloroethane, The polymer solution was cast on the electrode surface and used as a working electrode. This was placed in an electrolytic cell together with a counter electrode (platinum plate) and a reference electrode, and electrolytic reduction was performed at -3 V (vs. Ag / Ag ⁺ ) using sodium perchlorate as a supporting electrolyte and dehydrated acetonitrile as a solvent. As a result, the poly (10,10-di-n-
Butyl-5,10-dihydrophenazacillin-2,8-
Diyl) was obtained.

The data of the IR spectrum is as follows. IR (KBr pellet) 3419, 3050, 300
8,2952,2919,2867,2854,159
2, 1454, 1407, 1373, 1315, 126
9,1215,1146,1111,1088,100
7,881,866,810,741,627,474
cm ^-1

Example 5 [Electrochromic device using polymer] The evaluation of the electrochromic properties of the polymer was performed as follows. 200mg of polymer 1mg
1) in dichloroethane, and the polymer solution was cast on the electrode surface, and this was used as a working electrode. This was placed in a quartz cell together with a counter electrode (platinum plate) and a reference electrode. Using tetrabutylammonium perchlorate as a supporting electrolyte and dehydrated acetonitrile as a solvent, changes in the color tone of the polymer due to potential changes were observed.

Poly (10,10-di-n-butyl-5-
(2-naphthylmethyl) -5,10-dihydrophenazacillin-2,8-diyl) (general formula 2, R ₁ = R ₂ = n-
Butyl, R ₃ = 2-naphthyl) for the working electrode,
In neutral, the color of the polymer was colorless, but by increasing the potential applied to the cast film, the color was changed from colorless to yellow,
Brown, black and changed.

Poly (10,10-di-n-butyl-5,5)
When 10-dihydrophenazacillin-2,8-diyl) (general formula 1, R ₁ = R ₂ = n-butyl) was used for the working electrode, the color of the polymer was colorless when neutral, but the cast film was used. The color changed from colorless to red, magenta, and purple by increasing the potential applied to.

Example 6 [Organic Light Emitting Device Using Polymer] FIG. 1 is a schematic sectional view of an electroluminescent device (light emitting device). As a transparent insulating substrate 1, a glass plate having a thickness of 1.1 mm was used.
A film of ITO with a thickness of nm was formed by a sputtering method to form an anode 2. Before using this transparent conductive substrate, wash it with water, wash with ozone,
It was sufficiently cleaned by plasma cleaning. As the hole transport layer 3, a polymer was dissolved in an organic solvent (1,2-dichloroethane, toluene, or the like), and a film having a thickness of 40 nm was formed on the anode 2 by spin coating.

Next, tris (8-quinolinol) aluminum is deposited to a thickness of 60 nm as the organic light emitting layer 4, and Mg and Ag are deposited as a cathode 5 on the upper surface at a deposition rate ratio of 10: 1.
0 nm was deposited. Finally, GeO is used as the sealing layer 6.
After vapor deposition of 6 μm, the glass plate 7 was bonded and sealed with a photo-curable resin 8. In the drawing, reference numeral 9 denotes a power source, 10 denotes a lead wire, and 11 denotes a cathode terminal.

As the polymer, (10,10-di-n-butyl-5- (2-naphthylmethyl) -5,10-dihydrophenazacillin-2,8-diyl) (general formula 2, R ₁
= R ₂ = n-butyl, R ₃ = 2-naphthyl), this device emits green light at a DC voltage of 5 V or more, has a luminance at 14.5 V of 1450 cd / m ² , and a current density of 280 mA / cm ² .

[0037]

According to the present invention, a novel phenazacillin compound is provided, and furthermore, by converting the compound into a polymer, it is possible to provide a material which can be formed into a thin film by a very simple method even in molding. Thus, a material useful as a constituent material of a light emitting element and an electrochromic element can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a light emitting device shown in Example 6.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection / transport layer 4 Organic light emitting layer 5 Cathode 6 Sealing layer 7 Glass plate 8 Adhesive material layer 9 Power supply 10 Lead wire 11 Cathode terminal

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koichi Okita 1-3-5 Kanda Jimbocho, Chiyoda-ku, Tokyo Within the Chemical Technology Strategy Promotion Organization (72) Inventor Teruyuki Hayashi 1-1-1, Higashi, Tsukuba, Ibaraki, Industry (72) Inventor Masato Tanaka 1-1-1 Higashi, Tsukuba City, Ibaraki Pref. VR24 VR41 VR42 VU20 VU29 VW02 4J032 BA12 BA18 BB01 BC03 BD05 CG03

Claims (6)

[Claims] 1. The method according to claim 1, wherein the compound represented by the following general formula (1) is:
A polymer having a dihydro-5H-phenazacillin compound as a main chain skeleton. Embedded image (In the formula, R ₁ and R ₂ each independently represent an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and n represents a number of 3 to 30,000 in terms of average degree of polymerization.) 2. A polymer having a main chain skeleton of a 5-methylaryl-5,10-dihydro-5H-phenazacillin compound represented by the following general formula (2). Embedded image (Wherein, R ₁ and R ₂ are each independently an alkyl group, an aryl group, an alkoxy group or an aryloxy group, R ₃
Represents an aryl group, and n represents an average degree of polymerization of 3 to 30,000.
Indicates the number of 3. The 5-methylaryl-5,1 of claim 2
The polymer having the main chain skeleton of 0-dihydro-5H-phenazasiline compound is dearylmethylated, and the 5,10-dihydro-5H-phenazacillin compound according to claim 1 is used as the main chain skeleton. A method for producing a polymer. 4. A 5,10-formula represented by the following general formula (3):
The method for synthesizing a polyphenazacillin compound according to claim 2, wherein the dihydro-5H-phenazacillin compound is polymerized by a dehalogenation condensation reaction using a nickel complex. Embedded image (Wherein, R ₁ and R ₂ are each independently an alkyl group, an aryl group, an alkoxy group or an aryloxy group, R ₃
Represents an arylmethyl group, and X represents a halogen atom. 5. An organic thin-film electrochromic device using the polymer according to claim 1 as a constituent element. 6. An organic thin-film light-emitting device using the polymer according to claim 1 as a constituent element.