JP2000313739A - Polymer containing phenazacillin compound as main chain skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer extremely easily formable to a thin film, exhibiting electrochromism developing various colors, having heat-resistance, oxidation resistance and hole transportation property, etc., and useful as a constitution material for light-emitting element by using a phenazacillin compound as a main skeleton. SOLUTION: A phenazacillin compound of formula I (R is n-octyl or phenyl) or a phenazacillin compound of formula II (Ar is 1,3- or 1,4-phenylene) is used together with a diethynyl aromatic compound as main skeletons. The polymer can be produced by the polymerization of a halogenated phenazacillin compound in a solvent using a O-valent nickel complex [e.g. bis(1,5-cyclooctadiene)nickel(O)] or the coupling reaction of the above phenazacillin compound with diethynylbenzene using a O-valent palladium complex [e.g. tetrakis(triphenylphosphine)palladium(O)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer having a phenazacillin compound as a main chain skeleton, and a polymer having a phenazacillin compound and a diethynyl aromatic compound as a main chain skeleton. Prevention,
It can be used as a material having properties such as hole transportability.

[0002]

2. Description of the Related Art Phenazacillin compounds are known as compounds having a function of preventing oxidation and are known as Issled. Ob1. Fiz. Khim .. Kauc.
h. Rezin. 2, 14 (1973). Also, JP-A-8-302339 and JP-A-10-218884
The publication describes that this phenazacillin compound can be suitably used as a hole transport material of a light emitting device. Since this phenazacillin compound does not have a large absorption in the visible light region and has a high glass transition temperature (Tg), when used as a constituent material of a light-emitting element, a normal low-molecular compound crystallizes over time. In contrast, the phenazacillin compound is characterized in that the progress of crystallization is small due to a change with time, while there is a disadvantage that an electrical short circuit occurs because the interface becomes uneven and the interface becomes uneven.

[0003]

SUMMARY OF THE INVENTION The present invention provides a phenazacillin compound which has an antioxidant function, has a high glass transition temperature, and is also useful as a constituent material of a light emitting device.
An object of the present invention is to provide a low molecular weight compound which is difficult to use unless expensive equipment such as vacuum evaporation is used, instead of using a low molecular weight compound as a high molecular weight compound so that it can be used by simpler means.

[0004]

The present invention solves this problem by synthesizing a halogenated phenazacillin compound and polymerizing a single compound by a dehalogenation coupling reaction using a nickel zero-valent complex or the like. Alternatively, alternate copolymerization with another diethynyl aromatic compound is performed to convert the polymer into a polymer having phenazacillin as a main chain skeleton. Therefore, it is an object of the present invention to provide a material that can be formed into a thin film by a very simple method even in a molding process, such as spin coating, in applications that perform an antioxidant function or a hole transporting function. Also, by changing to a high molecular weight compound in this way, it is possible to provide a material which has an electrochromic property of exhibiting various colors by electrochemical oxidation / reduction reactions and is useful as a constituent material of a light emitting device. become.

That is, the present invention provides a polymer comprising a phenazacillin compound represented by the following formula (1) as a main chain skeleton:

[0006]

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(Wherein R represents an n-octyl group or a phenyl group) and a polymer having a main chain skeleton of a phenazacillin compound represented by the following formula (2) and a diethynyl aromatic compound:

[0008]

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Wherein R represents an n-octyl group or a phenyl group; Ar represents 1,3-phenylene or 1,4-phenylene.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the synthesis of a phenazacillin compound as a raw material used in the present invention, first, as shown in the following reaction formula, a 2,2 ′ position of N-methyldiphenylamine (a) is replaced with a halogen atom, particularly bromine. Bis (2,
Synthesizing 4-dibromophenyl) methylamine (b),
The halogen atom is replaced with lithium using n-butyllithium or the like, and then a silicon compound such as dichlorosilane is added, followed by delithiation and crosslinking / cyclization with silicon to obtain the desired phenazacillin compound (c). .

[0011]

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In order to synthesize a homopolymer using this raw material monomer, a zero-valent nickel complex, for example, bis (1,5-cyclooctadiene) nickel (0) [Ni (c
od) ₂ ] and the like, and homopolymerized in an appropriate solvent, whereby a homopolymer can be synthesized.

[0013]

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In the synthesis of the copolymer, a monomer represented by the formula (c) and diethynylbenzene are converted to a zero-valent palladium complex, for example, tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] to obtain the desired copolymer.

[0015]

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[0016]

EXAMPLES The present invention will be specifically described below with reference to examples.

Synthesis Example 1 [Synthesis of Monomer 1] 5.42 g (29.6 mmol) of N-methyldiphenylamine was mixed with a mixed solvent of carbon tetrachloride and chloroform (60).
25 g (140 mmol) after dissolving
l) N-bromosuccinimide was added. After stirring for 12 hours, the reaction was terminated by adding an aqueous solution. Further, after extraction with chloroform, recrystallization with a hexane-chloroform mixed solvent gave 9.02 g of bis (2,2).
4-Dibromophenyl) methylamine was isolated.

Next, 6.53 g (13 mmo) was placed in a water bath.
1) Bis (2,4-dibromophenyl) methylamine was suspended in 75 mL of ether, and then 17 mL of a hexane solution of n-butyllithium (1.6 M) was added. When the suspension became homogeneous, 4.49 g (14 mmol) of di-n-octyldichlorosilane was further added. After the precipitate formed, the water bath was removed and the mixture was stirred for 12 hours.
The reaction solution was added with water, extracted with ether, and purified by a silica gel column to obtain 4.51 g (7.6 mm).
ol) 2,8-dibromo-5,10-dihydro-1
0,10-Dioctyl-5-methylphenazacillin was isolated. The yield was 58%. The results of the elemental analysis are shown below. The result of NMR measurement is ¹³ C (N-CH ₃ ):
38.59, ^{2 9} Si: was -19.03ppm.

[0019]

[Table 1]

Synthesis Example 2 [Synthesis 2 of Monomer] Synthesis Example 1 was the same as Synthesis Example 1, except that 3.54 g (14 mmol) of diphenyldichlorosilane was used instead of 4.49 g (14 mmol) of di-n-octyldichlorosilane. 2,8-dibromo-5,10-dihydro-10,10-diphenyl-5-methylphenazacillin was isolated in the same manner as described above. The yield was 42%. The results of the elemental analysis are shown below. The result of the NMR measurement was ¹³ C (N-
^{_{CH 3): 38.65, 29 Si}} : was -29.32Ppm.

[0021]

[Table 2]

Example 1 [Synthesis of homopolymer 1] 0.45 g (1.6 m) of Ni (cod) ₂ under a nitrogen atmosphere
mol), 1 mL of 1,5-cyclooctadiene was added, and then 15 mL of toluene was added to suspend the mixture. Two more
0.26 g (1.6 mmol) of 2'-bipyridyl was added and the mixture was stirred. Furthermore, 2,8-dibromo-15,10-dihydro-10,10-dioctyl-5 obtained in Synthesis Example 1
0.80 g (1.3 mmol) of methylphenazacillin
Was added, and 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 in the order of 2M hydrochloric acid, water, methanol and hexane, then dissolved in THF and reprecipitated with methanol to obtain 0.54 g (1.2 mmol monom).
er unit) poly (5,10-dihydro-10,
10-dioctyl-5-methylphenazacillin) was isolated. Table 3 shows the results.

Example 2 [Synthesis 2 of homopolymer] A polymer was synthesized in the same manner as in Example 1 except that the reaction solvent was changed from toluene to N, N-dimethylformamide (DMF). Table 3 shows the results.

Example 3 [Synthesis 3 of homopolymer] The starting monomer was 2,8-dibromo-
A polymer was synthesized in the same manner as in Example 2 except that 5,10-dihydro-10,10-diphenyl-5-methylphenazacillin was used instead. Table 3 shows the results.

[0025]

[Table 3]

A) Gel permeation chromatography (GP
C method, CHCl ₃ , polystyrene standard)
Indicates w / Mn. b) Not measured due to low solubility in CHCl ₃ c) CDCl ₃ solution d) CP-MAS measurement

The difference in yield and molecular weight between the solvents in Examples 1 and 2 is considered to be due to the difference in solubility of the produced polymer in the solvent. ¹³ C- and ²⁹
As a result of Si-NMR measurement, peaks appeared at almost the same positions as the monomers of the raw materials, and it was confirmed that the polymerization reaction was proceeding while maintaining the phenazacillin skeleton.

Example 4 [Synthesis 1 of copolymer] 2,8-dibromo-5,10-dihydro-10,10-
Dioctyl-5-methylphenazacillin 301 mg
(0.51 mmol) and 1,3-diethynylbenzene 6
4 mg (0.51 mmol) was dissolved in 10 mL of toluene under a nitrogen atmosphere, and 1 mL of triethylamine was further added. Further, 5 mg of copper iodide and 29 mg of Pd (PPh ₃ ) ₄ were added, and 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 in the order of hexane and methanol to obtain 9
0 mg (0.16 mmol monomer uni)
The copolymer of t) was isolated. Table 4 shows the results.

Examples 5 to 8 Copolymers were synthesized in the same manner as in Example 4 except that the combinations of the starting monomers were changed as shown in Table 4. The results are shown in Table 4.

[0030]

[Table 4]

A) Gel permeation chromatography (GP
C method, CHCl ₃ , polystyrene standard)
Indicates w / Mn. b) Partial dissolution in CHCl ₃ c) CDCl ₃ solution d) CP-MAS measurement

As a result of ¹³ C- and ²⁹ Si-NMR measurements, a peak appears at almost the same position as the monomer of the raw material,
It was confirmed that the polymerization reaction was proceeding while maintaining the phenazacillin skeleton.

[Evaluation of Solubility] The homopolymer and copolymer obtained in the above Examples were evaluated for solubility in a solvent. Table 5 shows the results. The evaluation criteria were as follows: soluble (も の), partially soluble
△ (solubility: △> △) △, insoluble was rated as (×).

[0034]

[Table 5]

From the above results, it can be seen that the solubility in CHCl ₃ is improved by changing the substituent on silicon from a phenyl group to an octyl group. Furthermore, the introduction of a triple bond into the main chain reduces the solubility in trifluoroacetic acid.

[Optical Properties] Next, the optical properties of each polymer were evaluated. As the measurement items, the maximum absorption wavelength (UVλmax) in the ultraviolet region and the maximum wavelength (EMλmax) of the fluorescence spectrum by ultraviolet light irradiation were determined.
Table 6 shows the results.

[0037]

[Table 6]

A) In CHCl ₃ solution b) Partially soluble in CHCl ₃

In the case of the copolymer, it was confirmed that the absorption maximum changes depending on the difference in the bonding position to the benzene ring sandwiched by the ethynyl groups. It was also observed that the introduction of a triple bond into the polymer main chain enhanced the luminescence of the polymer in a CHCl ₃ solution.

[Electrochemical Measurement of Polymer] (a) To measure the electrochemical response of the polymer in the film state, 1 mg of the polymer was dissolved in 200 μL of dichloroethane or trifluoroacetic acid, and the polymer solution was placed on a glassy carbon electrode. Using a three-electrode electrochemical cell consisting of a platinum rod as a counter electrode, a silver / silver ion electrode as a reference electrode, tetrabutylammonium perchlorate (TBAP) as a supporting electrolyte, and dehydrated acetonitrile or dehydrated dichloromethane as a solvent. Use
Cyclic voltammetry (CV) was measured. (B) The electrochemical response of the polymer in the dissolved state was observed by dissolving the polymer in a dichloromethane solution containing a supporting electrolyte. (C) For the spectroelectrochemical response of the polymer, a polymer solution was cast on a commercially available transparent electrode (50 × 5 mm) and used as a working electrode. This was placed in a quartz cell together with a counter electrode (platinum plate) and a reference electrode, and a change in the color tone of the polymer due to a change in potential was detected by a spectroscope.

The above results are shown in the figure. The correspondence between the embodiments and the drawings is as shown in the table below.

[0042]

[Table 7]

1) Scanning speed: 50 mV / sec 2) 2 mg of polymer dissolved in 200 μl of dichloromethane, scanning speed: 50 mV 3) In FIG. 5, (a) is an oxidation potential, (b) is a reduction potential 4) FIG. Among 6 to 8, (a) is the absorbance due to the difference in applied voltage, and (b) is the change in the ABS intensity due to the potential. Also, the peaks of the oxidation and reduction potentials of the polymers of Examples 4, 6, 7, and 8 are shown below. .

[0044]

[Table 8]

From the above results, both the homopolymer and the copolymer of the present invention have reversible electrochemical responsiveness involving multi-stage oxidation-reduction, and this polymer has various color tones depending on the redox state. Was confirmed.

Reference Example FIG. 9 is a schematic sectional view of an electroluminescent element (EL element). As a transparent insulating substrate 1, a glass plate having a thickness of 1.1 mm was used.
A film of ITO having a thickness of nm was formed by a sputtering method to form an anode 2. The substrate on which the anode was formed was sufficiently washed with water, ozone, and plasma before use. Hole transport layer 3
As poly (5,10-dihydro-10,10-dioctyl-5-methylphenazacillin-2,8-diyl)
With an organic solvent (1,2-dichloroethane, toluene, etc.)
And a film was formed on the anode 2 by spin coating to a thickness of 40 nm.

Next, tris (8-quinolinol) aluminum is deposited to a thickness of 60 nm as the organic light emitting layer 4, and Mg and Al are deposited as the cathode 5 on the upper surface at a deposition rate ratio of 10: 1 to 150 nm.
nm. Finally, 1.6 as GeO is used as the sealing layer 6.
After the μm evaporation, the glass plate 7 was bonded with a photocurable resin 8 and sealed. In the figure, 9 is a power supply, 10 is a lead wire, 11
Indicates a cathode terminal.

This element emits green light at a DC voltage of 5 V or more, and has a luminance at 13 V of 5630 cd / m ² ,
The current density was 388 mA / cm ² .

[0049]

As described above, according to the present invention,
It is possible to provide a material that can be formed into a thin film by a very simple method even in the molding process, and it is possible to provide a material having an electrochromic property exhibiting various colors by an electrochemical oxidation / reduction reaction.

[Brief description of the drawings]

FIG. 1 is a CV curve showing an electrochemical response of a homopolymer obtained in Example 1, which was measured in a state of being formed into a film using trifluoroacetic acid.

FIG. 2 is a CV curve showing an electrochemical response of the homopolymer obtained in Example 1, which was measured in a state of forming a film using dichloroethane.

FIG. 3 is a CV curve showing an electrochemical response of the homopolymer obtained in Example 3, which was measured in a state of being formed into a film using trifluoroacetic acid.

FIG. 4 is a CV curve showing an electrochemical response of the homopolymer obtained in Example 1, which was measured in a state of being dissolved in dichloromethane.

FIG. 5 is a CV curve showing an electrochemical response of the copolymer obtained in Example 7.

FIG. 6 shows the spectroelectrochemical response of the homopolymer obtained in Example 1, which was measured in a state of being formed into a film using trifluoroacetic acid. ) Indicates a change in ABS intensity depending on the potential.

FIG. 7 shows the spectroelectrochemical response of the homopolymer obtained in Example 1, which was measured in a state of being formed into a film using dichloromethane, where (a) is the absorbance due to the difference in applied voltage, and (b) is the absorbance. 5 shows a change in ABS intensity depending on a potential.

FIG. 8 shows the spectroelectrochemical response of the homopolymer obtained in Example 3, which was measured in a state of being formed into a film using trifluoroacetic acid. ) Indicates a change in ABS intensity depending on the potential.

FIG. 9 is a schematic cross-sectional view of the EL element shown in the reference example.

[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 Adhesive material layer 8 Glass plate 9 Power supply 10 Lead wire 11 Cathode terminal

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koichi Okita 1-3-5 Kanda Jimbocho, Chiyoda-ku, Tokyo Inside the Chemical Technology Strategy Promotion Organization (72) Inventor Teruyuki Hayashi 1-1 Higashi 1-1, Tsukuba, Ibaraki Industrial Technology (72) Inventor: Masato Tanaka 1-1, Higashi, Tsukuba, Ibaraki Pref.

Claims (2)

[Claims] 1. A polymer having a phenazacillin compound represented by the following formula (1) as a main chain skeleton. Embedded image (In the formula, R represents an n-octyl group or a phenyl group.) 2. A polymer having a main chain skeleton of a phenazacillin compound represented by the following formula (2) and a diethynyl aromatic compound. Embedded image (Wherein, R represents an n-octyl group or a phenyl group.
r represents 1,3-phenylene or 1,4-phenylene. )