JP3321604B2 - Diphenylamine compound fused with siloxane, polymer having the compound as a main chain skeleton, and organic thin film element - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a 5,7-disila-
The present invention relates to a polymer having 6-oxa-5,6,7,12-tetrahydrodibenzo [b, g] azocin (hereinafter, dibenzodisilaazosin) as a main chain skeleton and a method for producing the same. This polymer has heat resistance and can be used as a material having the hole transport property of the organic thin film light emitting device. The present invention also relates to a novel dibenzodisilaazosin compound which is a monomer of the polymer material.

[0002]

2. Description of the Related Art Phenazacillin compounds fused with silicon have been disclosed in JP-A-8-302339 and JP-A-1-302339.
Japanese Patent Application Laid-Open No. 0-218884 describes that it is suitably used as a hole transporting material for a light emitting device. In addition, since this phenazasiline compound has a high glass transition temperature Tg, when used as a constituent material of a light-emitting element,
The conventional low molecular compound crystallizes with the passage of time, and the interface becomes uneven, thereby causing an electric short circuit. On the other hand, the characteristic is that the crystallization progresses little with time.

On the other hand, aromatic amine-type polymers such as polyaniline have high electric activity, but have low solubility in general organic solvents, so that they have a problem that they are difficult to form a film and are difficult to make into an element. .

Further, when a low molecular compound is used as a constituent material of an electronic device such as a light emitting device, expensive equipment such as a vacuum evaporation device must be used, and it is required that the device can be used by simple means. I have.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer having good film-forming properties useful as a material for a light-emitting device or an electrochromic device, a method for producing the same, and a monomer compound thereof.

[0006]

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 dibenzodisilaazosin compound represented by the following general formula (1) as a skeleton of a main chain.

Embedded image (Wherein, R _{1 to} R ₅ 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)

Further, according to the present invention, the following general formula (2)
5,7-disila-6-oxa-5,6,7,
A 12-tetrahydrodibenzo [b, g] azocine compound is provided.

Embedded image (Wherein, R _{1 to} R ₅ have the same meaning as described above, and X ₁ and X ₂ each independently represent a halogen atom, an alkyl group, an aryl group, an aryloxy group or an alkoxy group)

Further, according to the present invention, in order to produce the polymer, 5,7-disila-6-oxa-5,6,7,12-tetrahydrodibenzo represented by the following general formula (3): The method is provided, wherein the [b, g] azocin compound is polymerized under a dehalogenation coupling reaction using a nickel complex.

Embedded image (Wherein, R _{1 to} R ₅ have the same meaning as described above, and X represents a halogen atom)

Further, according to the present invention, in order to produce the polymer, a polymer having polydibenzodisilazepine represented by the following general formula (4) as a main chain skeleton is used by using an oxidizing agent. There is provided a method as described above, characterized by oxidizing.

Embedded image (Wherein, R _{1 to} R ₅ and n have the same meaning as described above)

Furthermore, according to the present invention, there is provided an organic thin-film electrochromic device using the polymer as a constituent element.

Further, according to the present invention, there is provided an organic thin-film light-emitting device using the polymer for a hole transport layer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), R ₁
To R ₅ represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group. In this case, the alkyl group
Linear, branched and cyclic ones are included, and the carbon number is 1 to 10, preferably 1 to 8. Specific examples thereof include methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, n-, i
Examples include so- or neo-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl and the like.

The aryl group includes those having 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms. Specific examples thereof include phenyl, tolyl, naphthyl, anthryl and the like.

The alkoxy group includes linear, branched and cyclic ones, and has 1 to 10, preferably 1 to 8 carbon atoms. Specific examples thereof include methoxy, ethoxy, n- or iso-propoxy, n-, iso-
Or tert-butoxy, n-, iso- or ne
o-pentoxy, n-hexoxy, cyclohexoxy,
n-Heptoxy, n-octoxy and the like.

The aryloxy group includes those having 6 to 30, preferably 6 to 15 carbon atoms. Specific examples include phenoxy, toloxy, naphthoxy, anthroxy and the like.

A preferred method for producing the polymer represented by the general formula (1) is a method for preparing the polymer represented by the general formula (3), such as 5,7-disila-6-oxa-5,6,7, This is a method of polymerizing a 12-tetrahydrodibenzo [b, g] azocin compound under a dehalogenation coupling reaction using a nickel complex. In the general formula (3), R ₁
To R ₅ have the same meaning as described above. X represents a halogen atom, and specific examples thereof include fluorine, chlorine, bromine and iodine, with bromine being particularly preferred.

The dibenzodisilaazocine compound of the general formula (2) is prepared by dissolving a dibenzodisilaazepine compound of the following general formula (5) in a solvent, and then oxidizing 1 to 20 equivalents to the dibenzodisilaazepine unit. It can be produced by performing an oxidation reaction using an agent.

[0018]

Embedded image In the above formula, R _{1 to} R ₅ have the same meaning as described above. X ₁ ,
X ₂ each independently represents a halogen atom, an alkyl group, an aryl group, an aryloxy group or an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a bromine atom is particularly preferable. In addition, the alkyl group, the aryl group, the alkoxy group, and the aryloxy group can be those described above.

As the oxidizing agent, perbenzoic acid derivatives such as perbenzoic acid and m-chloroperbenzoic acid are used in addition to ozone and amine oxide, and amine oxide is particularly preferable. As the amine oxide, trimethylamine oxide, pyridine-N-oxide, 3-methylpyridine-N-oxide, 4-dimethylaminopyridine-
Examples include N-oxide, 3-cyanopyridine-N-oxide, quinoline-N-oxide, and isoquinoline-N-oxide.

In the oxidation reaction, various solvents commonly used in this reaction can be used. Examples include dioxane, toluene, benzene, tetrahydrofuran, dichloromethane and the like.

The oxidation reaction can be carried out at various temperatures from the melting point of the solvent to the boiling point of the solvent, and particularly preferably from 60 ° C. to the boiling point of the solvent. After the reaction, it can be purified by reprecipitation or the like.

The polymer represented by the general formula (1) is prepared by dissolving the halogenated dibenzodisilaazosin compound of the general formula (3) in a solvent,
It can be produced by performing polymerization under a dehalogenation coupling reaction using 0 equivalent of a nickel complex. The reaction in this case is represented by the following equation (6).

[0023]

Embedded image (Wherein, R _{1 to} R ₅ each independently represent an alkyl group, an aryl group, an alkoxy group, or an aryloxy group;
Represents a halogen atom, and n represents an average degree of polymerization of 3 to 3000.
Indicates the number of 0)

In the dehalogenation polycondensation using a nickel complex, various solvents usually used in this reaction can be used. To illustrate this, N, N-
Dimethylformamide, toluene, benzene, tetrahydrofuran and the like.

Examples of the nickel complex include tetracarbonylnickel (0), dicarbonylbis (triphenylphosphine) nickel (0), bis (1,5-cyclooctadiene) nickel (0), and tetrakistriphenylphosphinenickel (0). ), (Η2-ethylene) bistriphenylphosphine nickel (0), tetrakis (t-butyl isocyanide) nickel (0), [(1,2,5,
6,8,10-η) -trans, trans, tra
ns-1,5,9-cyclododecatriene] nickel (0), and the like.

The nickel complex has 0.1 to 10 equivalents of 2,2'-bipyridyl or 1,10-equivalent as a supporting ligand.
Ligands such as phenanthroline and tertiary phosphines such as triphenylphosphine may be added. 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, but in particular at 40 ° C.
Approximately -80 ° C is desirable. After the reaction, it can be purified by reprecipitation or the like.

The average degree of polymerization of the polymer obtained by the above reaction is 3 to 30,000, preferably 5 to 1
0000.

The polymer represented by the general formula (1) is prepared by dissolving the polydibenzodisilazepine represented by the general formula (4) in a solvent and oxidizing the polymer by using 1 to 20 equivalents of an oxidizing agent. It can also be produced by performing a reaction. The reaction in this case is represented by the following equation (7).

[0030]

Embedded image (Wherein, R _{1 to} R ₅ each independently represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and n is an average degree of polymerization of 3 to 30,000, preferably 5 to 100,000.
00 indicates the number)

As the oxidizing agent, perbenzoic acid derivatives such as perbenzoic acid and m-chloroperbenzoic acid are used in addition to ozone and amine oxide, and amine oxide is particularly preferable. As the amine oxide, trimethylamine oxide, pyridine-N-oxide, 3-methylpyridine-N-oxide, 4-dimethylaminopyridine-N-oxide, 3-cyanopyridine-N-oxide, quinoline-N-oxide, isoquinoline- N-oxide.

In the oxidation reaction, various solvents usually used in this reaction can be used. Examples include dioxane, toluene, benzene, tetrahydrofuran, dichloromethane and the like.

The oxidation reaction can be carried out at various temperatures from the melting point of the solvent to the boiling point of the solvent. After the reaction, it can be purified by reprecipitation or the like.

The average degree of polymerization n of this polymer is from 3 to 300.
00, preferably 5 to 10,000.

The polydibenzodisilaazepine represented by the above general formula (4) is obtained by converting a dibenzodisilaazepine represented by the following general formula (8), which is a monomer thereof, from Japanese Patent Application Laid-Open No. H10-163,878.
It can be produced by polymerizing according to the method described in 1-63412 (JP-A-2000-256445) .

Embedded image (In the formula, R _{1 to} R ₅ and X have the same meaning as described above.) The polymerization reaction can be carried out in the same manner as in the case of the polymerization reaction shown in the above formula (6).

The polymer obtained by the above method can be easily formed into a thin film by a simple molding method such as spin coating. The polymer of the present invention can be made into an organic thin film electrochromic device by thinning the polymer. Further, by using the polymer of the present invention for the hole transport layer, an organic thin film light emitting device can be obtained.

[0037]

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 [3,9-Dibromo-5,7-disila-6-oxa-
5,5,7,7,12-pentamethyl-5,6,7,1
Synthesis of ₂ -tetrahydrodibenzo [b, g] azocine (general formula 2, R _{1 to} R ₅ = methyl, X ₁ = X ₂ = Br)]
38 g (3.0 mmol) of 2,8-dibromo-10,
11-Dihydro-5,10,10,11,11-pentamethyl-5H-dibenzodisilaazepine was dissolved in 20 mL of benzene. Further, 0.38 g of trimethylamine oxide dihydrate was added, and the mixture was heated to 85 ° C. and stirred for 24 hours. The reaction solution was purified by a silica gel column and recrystallized with a mixed solvent of dichloromethane-methanol to obtain 1.14 g (2.4 mmol) of 3,9.
-Dibromo-5,7-disila-6-oxa-5,5,
7,7,12-pentamethyl-5,6,7,12-tetrahydrodibenzo [b, g] azocine was isolated. The obtained compound is a novel compound not described in the literature, and has a melting point of 1
19-119.5 ° C.

The elemental analysis values are as follows. Elemental analysis: C ₁₇ H ₂₁ Br ₂ NOSi ₂ Calculated: C, 43.32; H, 4.49; N, 2.9
7; Br, 33.91 Found: C, 43.40; H, 4.54; N, 2.9
7; Br, 34.25

The NMR spectrum data is as follows. ¹ H-NMR (CDCl ₃ ): δ 7.2-7.6 (m, 6
H), 3.11 (s, 3H), 0.49 (s, 6H),
0.17 (s, 6H) ¹³ C-NMR (CDCl ₃ ): δ 156.53, 14
0.61, 137.35, 133.66, 125.3
5,118.73, 45.77, 1.81, 0.41 ²⁹ Si-NMR (CDCl ₃ ): δ-0.45

Example 2 [3,9-diphenyl-5,7-disila-6-oxa-
5,5,7,7,12-pentamethyl-5,6,7,1
Synthesis of ₂ -tetrahydrodibenzo [b, g] azocin (general formula 2, R _{1 to} R ₅ = methyl, X ₁ = X ₂ = phenyl)]
10,11-dihydro-2,8-diphenyl-5,10,10,11,11-pentamethyl-5 as starting material
Reaction with trimethylamine oxide dihydrate using H-dibenzodisilaazepine as in Example 1 gives 3,9-diphenyl-5,7 in 93% yield.
-Disila-6-oxa-5,5,7,7,12-pentamethyl-5,6,7,12-tetrahydrodibenzo [b, g] azocine was obtained. The obtained compound was a novel compound not described in the literature, and had a melting point of 172 to 174 ° C.

The results of the elemental analysis are as follows. Elemental analysis: C ₂₉ H ₃₁ NOSi ₂ .0.6H ₂ O Calculated: C, 73.09; H, 6.81; N, 2.94 Found: C, 72.81; H, 6 .74; N, 2.83

The NMR spectrum data is as follows. ¹ H-NMR (CDCl ₃ ): δ 7.1-7.7 (m, 1
6H), 3.25 (s, 3H), 0.53 (s, 6
H), 0.17 (s, 6H) ¹³ C-NMR (CDCl ₃ ): δ 157.52, 14
1.00, 137.97, 137.20, 133.6
5,129.65,128,71,127.04,12
7.01, 123.74, 45.83, 2.06, 0.
60 ²⁹ Si-NMR (CDCl ₃ ): δ-0.31

Example 3 [Poly (5,7-
Disila-6-oxa-5,5,7,7,12-pentamethyl-5,6,7,12-tetrahydrodibenzo [b,
g] Azocin-3,9-diyl) (general formula 1, R _{1 to} R ₅
Synthesis of bis (1,5-cyclooctadiene) nickel (0) 0.37 g (1.3 m) under a nitrogen atmosphere.
mol) was added to 1 mL of 1,5-cyclooctadiene, and then 10 mL of toluene was added to suspend the mixture. Two more
0.21 g (1.3 mmol) of 2'-bipyridyl was added and the mixture was stirred. Further, 0.52 g (1.1 mmol) of 3,9-dibromo-5,7-disila-6-oxa-5,
5,7,7,12-pentamethyl-5,6,7,12-
After adding tetrahydrodibenzo [b, g] azocine, 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, then dissolved in dichloromethane and reprecipitated with methanol to give 318 mg.
(1.0 mmol as a monomer unit) of poly (dibenzodisilaazosin) was isolated. The resulting polymer is T
It was soluble in common organic solvents such as HF and chloroform. The polymer obtained is a novel compound not described in the literature.

Example 4 [Poly (5,7-disila-6-oxa-5,5,7,7,12-pentamethyl-5,6,7,
12-tetrahydrodibenzo [b, g] azocin-3,
Synthesis of 9-diyl) (general formula 1, R _{1 to} R ₅ = methyl)] 115 mg (0.38 mmol as monomer unit)
l) Polydibenzodihydrodisilaazepine was dissolved in 5 mL of benzene. Further, 59 mg of trimethylamine oxide dihydrate was added, and the mixture was heated to 85 ° C. and stirred for 24 hours. The reaction solution was poured into methanol, and the obtained powder was filtered to isolate 103 mg of poly (dibenzodisilaazosin). Table 2 shows the elemental analysis values. The polymer obtained is a novel compound not described in the literature.

The elemental analysis values are as follows. Elemental analysis: C ₁₇ H ₂₁ NOSi ₂ Calculated: C, 65.54; H, 6.79; N, 4.50 Found: C, 65.22; H, 6.70; N, 4 .21

The NMR spectrum data is as follows. ¹ H-NMR (CDCl ₃ ): δ 7.2-7.6 (m, 6
H), 3.20 (s, 3H), 0.46 (s, 6H),
0.11 (s, 6H) ¹³ C-NMR (CDCl ₃ ): δ 157.42, 13
8.04, 137.16, 133.62, 129.6
1,123.82, 45.91, 2.07, 0.54 ²⁹ Si-NMR (CDCl ₃ ): δ-0.85

Example 5 [Electrochromic Device Using Polymer] The electrochromic properties of the polymer obtained in Example 3 or 4 were evaluated as follows. 200mg of polymer 1mg
The polymer solution was dissolved in 1 l of dichloroethane, and the polymer solution was cast on a commercially available transparent electrode (50 × 5 mm), 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.

At neutral, the color of the polymer was colorless, but it changed from colorless to red, magenta and purple by increasing the potential applied to the cast film.

Embodiment 6 [Organic Light Emitting Device Using Polymer] FIG. 1 is a schematic sectional view of an electroluminescent device (light emitting device). 1.1 mm thick transparent insulating substrate 1
The above glass plate was used, and 120 nm of ITO was coated thereon by a sputtering method to form an anode 2. Before use, the transparent conductive substrate was sufficiently washed with water, ozone, and plasma. As the hole transport layer 3, the poly (dibenzodisilaazosin) obtained in Example 3 was mixed with an organic solvent (1,2-
Dissolved in dichloroethane, toluene, etc.), and formed into a film having a thickness of 40 nm 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 the 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.

The device emitted green light at a DC voltage of 5 V or more, had a luminance of 616 cd / m ^{2 at} 13 V, and a current density of 73.2 mA / cm ² .

[0053]

According to the present invention, there is provided a novel dibenzodisilaazosin compound, and by converting the compound into a polymer, a material which can be formed into a thin film by a very simple method even in molding processing. Can be provided, and 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 sectional view of a light emitting element.

[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 Continuation of the front page (51) Int.Cl. ⁷ Identification code FI H05B 33/22 H05B 33/22 D (72) Inventor Teru Adachi 1-3-5 Kanda Jimbocho, Chiyoda-ku, Tokyo Toyama Fusa Building 3F Foundation Within the Chemical Technology Strategy Promotion Organization (72) Koichi Okita 1-3-5 Kanda Jimbocho, Chiyoda-ku, Tokyo Toyama Fusa Building 3F Inside the Chemical Technology Strategy Promotion Organization (72) Inventor Teruyuki Hayashi 1-chome Higashi, Tsukuba City, Ibaraki Prefecture No. 1 Industrial Technology Institute, Institute of Materials Science and Technology (72) Inventor Masato Tanaka 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Institute of Industrial Science and Technology, Materials Science and Technology Institute (56) References JP-A-2000-256445 (JP, A) JP-A-2000-313739 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/12 CA (STN) REGISTRY (ST N)

Claims (6)

(57) [Claims] 1. A polymer having a main chain skeleton of a 5,7-disila-6-oxa-5,6,7,12-tetrahydrodibenzo [b, g] azocin compound represented by the following general formula (1): . Embedded image (Wherein, R _{1 to} R ₅ 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 5,7-disila-6-oxa-5,6,7,12-tetrahydrodibenzo [b, g] azocin compound represented by the following general formula (2). Embedded image (Wherein, R _{1 to} R ₅ each independently represent an alkyl group, an aryl group, an alkoxy group, or an aryloxy group;
₁ and X ₂ each independently represent a halogen atom, an alkyl group, an aryl group, an aryloxy group or an alkoxy group) 3. A method of removing a 5,7-disila-6-oxa-5,6,7,12-tetrahydrodibenzo [b, g] azocin compound represented by the following general formula (3) using a nickel complex. The polymerization is carried out under a halogenated coupling reaction. The 5,7-disila-6-oxa-5,6,7,12-tetrahydrodibenzo [1] represented by the general formula (1) according to claim 1, wherein b, g] A method for producing a polymer having an azocin compound as a main chain skeleton. Embedded image (Wherein, R _{1 to} R ₅ each independently represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and X represents a halogen atom) 4. The general formula according to claim 1, wherein a polymer having polydibenzodisilazepine represented by the following general formula (4) and having a main chain skeleton is oxidized using an oxidizing agent. 5,7-disila-6-oxa- represented by (1)
A method for producing a polymer having a 5,6,7,12-tetrahydrodibenzo [b, g] azocin compound as a main chain skeleton. Embedded image (Wherein, R _{1 to} R ₅ 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) 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 for a hole transport layer.