JPH06166743A - Linear poly@(3754/24)arylene-ethynylene-arylene-ethynylene) polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having excellent heat-resistance, chemical stability, electrical conductivity, optical response and moldability and useful as a light-emitting material, color-developing display material, etc., by reacting a specific diethynylaryl compound with a specific dihalogenated aryl compound under specific conditions. CONSTITUTION:The objective polymer of formula III ((n) is 10-1000) can be produced by the dehydrohalogenative coupling reaction of a diethynylaryl compound of formula I (Ar is bivalent group obtained by eliminating 2 hydrogen groups from a ring of an aromatic compound including heterocyclic compound) with a dihalogenated aryl compound of formula II (X is halogen; Ar' is Ar; at least one of Ar and Ar' is 2,5-pyridinediyl or alkylsubstituted aromatic compound residue) in the presence of a palladium-copper catalyst and an amine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a linear poly (arylene-ethynylene-arylene-ethynylene) polymer used as a heat-resistant functional material having photo-electrical response, a process for producing the same, and a luminescent material using the polymer. And a color display material.

[0002]

2. Description of the Related Art Generally, as an example of a polymer having a π-conjugated bond in its main chain, polyacetylene and other poly (p-
Polyarylene such as phenylene), poly (thiophene-2,5-diyl) or poly (1,4-naphthalenediyl), or polyarylene such as poly (p-phenylene vinylene) or poly (2,5-phenylene vinylene). Examples thereof include arylene vinylene and the like, and all of these have a single skeleton-double bond as a basic skeleton. The above-mentioned polyarylene, in which aromatic rings are continuously bonded and has a π-conjugated bond, is chemically stable and has excellent heat resistance.

With respect to these electrical responsiveness, it is known that polyacetylene having the simplest structure exhibits conductivity comparable to that of metal by doping under special conditions.

Further, π-conjugated polymers having a triple bond in the main chain have high crystallinity, and various polydiacetylenes have been studied as nonlinear optical materials, but research reports on other compounds are extremely high. Few. Examples of the synthesis of a π-conjugated polymer having an arylene-acetylene bond in the main chain include poly (1,4-phenylene-ethynylene) or poly (1,4-phenylene-ethynylene-).
2,5-Chenylene-ethynylene) and the like.

[0005]

However, the above-mentioned conventional conductive polyacetylene has a problem that it has poor moldability and is chemically unstable. Similarly, most of the other polyarylene compounds, which are also expected to be electrically conductive, have low solubility in organic solvents and are infusible, so that they can be sufficiently used as functional materials utilizing their respective characteristics. I couldn't. In particular, polyarylene vinylene, which has an intermediate structure between polyacetylene and polyarylene, is considered to be useful as an intended material because it passes through a solvent-soluble precursor in the synthetic method, but conversion from the precursor Is difficult to do completely,
It has a defect that a defect occurs in the conjugated chain.

Further, even in a π-conjugated polymer having an arylene-acetylene bond in the main chain, these are difficult to dissolve in an organic solvent (Bull. Chem. Soc. Jpn.,
57, page 752, (1984)), it has been difficult to form it into a thin film or thread form and form it into a shape that can take advantage of functions such as conductivity.

Accordingly, the present invention solves the above-mentioned problems and devises the structure of the polymer molecule having a π-conjugated bond in the main chain to maintain the excellent heat resistance and chemical stability of the polymer. At the same time, conductivity and photoresponsiveness due to electric excitation are to be exhibited, and further, the solubility in an organic solvent is increased to improve the usability such as molding as a general-purpose functional material. .

[0008]

In order to solve the above problems, in the present invention, a linear poly (arylene-ethynylene-arylene-ethynylene) polymer represented by the following formula 5 is used.

[0009]

[Chemical 5]

This polymer comprises a diethynyl aryl represented by the following formula 6 and a dihalogenated aryl represented by the following formula 7 (provided that at least one of Ar and Ar 'in both formulas is 2,5 A pyridinediyl group, or a divalent group obtained by removing two hydrogen atoms from an aromatic ring of an aromatic compound having an alkyl substituent) in the presence of a palladium-copper catalyst and an amine, for dehydrohalogenation coupling reaction. Can be manufactured by.

[0011]

[Chemical 6]

[0012]

[Chemical 7]

Alternatively, the above polymer may be produced by subjecting an ethynyl aryl halide represented by the following chemical formula 8 to a dehydrohalogenation coupling reaction in the presence of a palladium-copper catalyst and an amine.

[0014]

[Chemical 8]

Further, a light emitting material made of the above-mentioned linear poly (arylene-ethynylene-arylene-ethynylene) polymer or a color display material made of the same polymer can be used.

The details will be described below.

Specific examples of Ar or Ar 'shown in the above formulas 5-8 in the present invention include those shown in the following formulas.

[0018]

[Chemical 9]

The principle of the method for producing the linear poly (arylene-ethynylene-arylene-ethynylene) polymer shown in Chemical Formula 5 will be described below.

First, as shown in the reaction formula below,
Aryl halide (Ar-X) and terminal acetylene palladium phosphine complex catalyst _{(Pd (PPh 3) 4)} ,
When reacted in the presence of an amine (NR ₃ ), acetylene hydrogen is replaced with an aryl group (for example, J. Orga).
nomet. Chem. , 93, 253, (197
5)). In this case, the palladium catalyst Pd (PP
Instead of h ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , PdC
l ₂ (DPPE) ₂ (wherein DPPE represents diphenylphosphinoethane), Pd (0Ac) ₂ + 2PPh ₃
It is also possible to use a catalyst composed of a palladium compound such as In addition to triethylamine, the amine may be a strongly basic alkylamine such as diethylamine or piperidine, and the compounding amount thereof is not particularly limited, and may be slightly excessive with respect to the reaction substrate.

[0021]

[Chemical 10]

Particularly, when copper iodide is added, the reaction proceeds smoothly. This is because it is considered that copper acetylide is produced and the reaction proceeds by transmetallation with palladium (Pd) and reductive desorption, as shown in the reaction formula of Chemical Formula 11 below. (Tetrahedron Lett., 4407
P., 1975). In this case, the copper iodide is particularly preferable from the viewpoint of easy handling, but it is needless to say that the same effect can be expected with copper chloride or copper bromide instead.

[0023]

[Chemical 11]

Therefore, as shown in the reaction formula below, an aromatic compound having two halogens (X) in the molecule and an aromatic compound also having two ethynyl groups are used together with a solvent in palladium- When reacted in the presence of a copper catalyst and an amine, a polymer is obtained by dehydrohalogenation coupling.

[0025]

[Chemical 12]

Further, as shown in the reaction formula of the following chemical formula 13,
Even when an aromatic compound having one halogen (X) and one ethynyl group in the molecule is reacted with a solvent in the presence of a palladium-copper catalyst and an amine, dehydrohalogenation coupling results in A compound corresponding to the formula where Ar = Ar ′ is obtained.

[0027]

[Chemical 13]

The proportion of the palladium catalyst used in the above production method is 0.1 to 10 mol% with respect to the reaction substrate.
Is preferable, and 1 to 4 mol% is particularly preferable. A suitable blending ratio of copper iodide is about 0.1 to 10 mol%. As the reaction solvent, benzene, dimethylformamide (hereinafter abbreviated as DHF), tetrahydrofuran (hereinafter abbreviated as THF), pyridine, and the like can be adopted as a reaction solvent without particular limitation. The concentration of the reaction substrate in the reaction solvent is not particularly limited, and is preferably 0.01 to 1 mol.
/ Liter, particularly preferably 0.05 to 0.2 mol /
It may be liter. Furthermore, the reaction temperature may be room temperature to a solvent reflux temperature (for example, 40 to 100 ° C.), and the reaction time is about 5 minutes to 100 hours, and particularly 1 to
If it is about 24 hours, it is preferable in terms of production efficiency.

[0029]

【Example】

[Example 1] 1 mmol of dibromopyridine, 1 mmol of diethynylpyridine, and tetrakistriphenylphosphine palladium: Pd (P
Ph ₃ ) ₄ 0.04 mmol, copper iodide 0.08 mm
3 ml of triethylamine was added to ol, and the mixture was stirred in 20 ml of toluene at 70 ° C. for 1 hour for reaction. When a powdery polymer was obtained in this reaction system, the reaction system was added to a large amount of methanol, stirred, thoroughly washed, filtered, and dried using a vacuum line. The yield of the obtained polymer was 100%.

When the obtained polymer was analyzed for its constituent elements by thermal decomposition according to a conventional method, the percentage of carbon, hydrogen and nitrogen as constituent constituent elements was 83.9 for carbon.
It was 9%, hydrogen 3.54%, and nitrogen 12.57%.

On the other hand, the calculated value of the elemental composition of a polymer having a compound represented by the following chemical formula 14 as a repeating unit is 8
The percentages were 3.17%, 2.97% hydrogen, and 13.86% nitrogen, which were almost in agreement with the above percentages. The obtained polymer had high thermal stability, and it was not easy to completely burn it in the elemental analysis, so it was presumed that a slight error occurred between the observed value and the converted value. .

[0032]

[Chemical 14]

[Examples 2 to 7] Compounds shown in Table 1 were used as the aryl halide and diethynyl aryl, except that the polymerization reaction was carried out at the temperature (° C), time (h) and solvent shown in the table. A polymer was obtained in the same manner as in Example 1. The yield and the formula of the polymer produced are also shown in Table 1. The elemental analysis values of each example (polymer) were measured in exactly the same manner as in Example 1. The converted value was
The calculated values of the constituent elements of the product shown in Table 1 were almost the same.

[0034]

[Table 1]

Example 8 2-Bromo-2-ethynylpyridine (2 mmol), a zero-valent palladium compound, P
d (PPh ₃ ) ₄ 0.02 mmol, copper iodide 0.04
Triethylamine (3 ml) was added to the mmol, and the mixture was reacted in 7 ml of toluene by stirring at 70 ° C. for 3 hours. After that, a polymer was obtained in exactly the same manner as in Example 1.

When the constituent elements of the obtained polymer were analyzed, the percentages of carbon, hydrogen and nitrogen as constituent elements were 82.83% carbon, 3.40% hydrogen and 13.78% nitrogen. As described above, the calculated values of the elemental composition of the polymer having the compound represented by the formula 14 as a repeating unit are 83.17% carbon, 2.97% hydrogen, 13.2% nitrogen.
It was 86%, and these values and the above percentages were in good agreement.

[Experimental Example 1] The infrared absorption spectra of Examples 1 to 8 showed the following absorptions (cm ^-1 ).

Example 1 (same for Example 8): 3
040, 2208, 1575, 1558, 1540, 1
532, 1436, 1363, 1088, 1002, 8
38, Example 2: 3040, 2214, 1575, 1539,
1472, 1366, 1224, 1288, 1019,
1003, 840, Example 3: 3036, 2216, 1575, 1559,
1506, 1454, 1403, 1362, 1311
1277, 1211, 1087, 1015, 1002
835, Example 4: 2200, 1573, 1555, 1537,
1458, 1360, 1261, 1099, 1010,
838, 799, Example 5: 2920, 2850, 2198, 1574,
1539, 1456, 1357, 1261, 1281,
1075, 1014, 926, 835, 747, Example 6: 2910, 2850, 2192, 1538,
1487, 1417, 1397, 1259, 1099,
1014, 832, 718, 539, Example 7: 3288, 2192, 1617, 1576,
1539, 1464, 1435, 1362, 1257,
1025, 905, 839, 756, 638, 620, thus, the infrared absorption spectra of Examples 1 to 8 are 2
Absorption characteristic of stretching vibration of the acetylene bond was shown near 200 cm ^-1 (2214 to 2192), and four absorptions peculiar to the pyridine ring were observed near 1575 to 1440 cm ^-1 except for Example 6. The absorption at 840 cm ⁻¹ is characteristic of the C—H out-of-plane bending vibration of the aromatic ring.
In Nos. 5 and 6, absorptions characteristic of the out-of-plane bending vibration of the thiophene ring were observed at 799, 747 and 718 cm ^-1 , respectively.

[Experimental Example 2] The absorption spectrum (H'-NMR) by the nuclear magnetic resonance method of Example 6 was examined by using tetramethylsilane as a standard substance, and its chemical shift σ value (ppm). Is 0.89, 1.25, 1.6
8, 2.52, 2.73, 6.92, 7.08, 7.4
It was at 7, 7.48.

In this case, the assignment of the σ value of Example 6 (the chemical formula is shown in Table 1) is as follows.

0.89 ppm is the CH ₃ group proton at the terminal of the thiophene ring alkyl chain shown in Chemical formula 15 below, 1.25, 1.68 ppm is the proton at the 2-5 position of the thiophene ring alkyl chain shown in Chemical formula 15 below, 2 0.52, 2.73 ppm is the proton at the 6-position of the thiophene ring alkyl chain shown in Chemical formula 15, 6.92, 7.08 ppm is the thiophene ring proton, 7.47 and 7.48 ppm is the benzene ring proton,

[0042]

[Chemical 15]

The integral ratio of each of the above protons is
Both chart and calculated value :::: = 3:
8: 2: 1: 4 and the compound of Example 6 was identified as the compounds shown in Table 1.

[Experimental Example 3] The polymers of Examples 1 to 8 were subjected to thermogravimetric analysis. The thermal decomposition temperature was about 30.
The temperature was 0 ° C., and all showed high thermal stability.

The relationship between the temperature (° C.) and the weight loss rate (%) for Examples 1, 2, 5, and 6 is shown in FIG. 1 or 2.

As is clear from these graphs, both Example 1 and Example 2 were stable until the heating temperature reached 310 ° C., but they were 315 ° C. and 319 ° C., respectively.
With the above, it begins to decompose slowly, and 40% to 45 at 600 ° C.
% Weight loss was shown. Example 5 and Example 6 are 27
Stable up to 5 ℃, but 311 ℃ or 28 respectively
It started to decompose at 9 ° C or higher and showed a weight loss rate of 25% at 600 ° C.

[Experimental Example 4] With respect to the polymers of Examples 1 to 8, the UV-visible spectrum was measured in a formic acid or chloroform solution. As a result, an absorption maximum showing a relatively sharp and clear chevron shape at about 350 to 460 nm was exhibited. . The position of the absorption maximum obtained for each polymer (λmax: n
m) is as follows.

Example 1 352 〃 2 382 〃 3 398 〃 4 399 〃 5 426 〃 6 403 〃 7 461 〃 8 340 [Experimental Example 5] The light scattering method or G. P. The weight average molecular weight Mw was determined according to the C method.

First, the polymers obtained in Examples 5 and 6 were prepared according to G.I. P. It was soluble in THF and chloroform suitable for C determination. Then, G.I. P. According to the C measurement, the Mw of the polymer compound of Example 5 was 19000, and the Mw of the polymer compound of Example 6 was 3
It was found to be 6000 and the degree of polymerization was calculated to be 65 and 124, respectively.

It should be noted that, in the embodiments other than the above, G.
P. An attempt was made to measure the molecular weight by the C method. For example,
Example 1 containing the compound represented by the formula (4) as a repeating unit shows a high solubility in a formic acid solution.
P. Since it is not suitable for C. P. For C, THF was used as a solvent. In this case, the polymer compound of Example 1 was
It was soluble in about 10% THF, the average molecular weight of the THF-soluble portion was confirmed to be about 1000, and the molecular weight distribution was confirmed to be about 4000. It was estimated that the THF-insoluble portion was 1000 or more and tens of thousands.

Experimental Example 6 For the polymers of Examples 1 to 8, a solution of formic acid or chloroform was prepared at a concentration of 1 mg / ml at about 25 ° C., spread on a petri dish, and then the solvent was removed by an evaporation method. Thus, a film-like substance was obtained. When the infrared absorption spectrum of this substance was examined, it was in agreement with the infrared absorption spectrum of the polymer before the addition of the solvent, and the polymer of the Example was easily formed into a film or a thread by a known injection method. It turned out that it can be molded into.

[Experimental Example 7] Regarding the polymers of Examples 1 to 8 in which a thin film was formed on a metal substrate by a vacuum vapor deposition method, semiconductivity with an applied voltage was observed and light emission was observed although it was weak. A material which can be used as a material or an electro-optical material is obtained.

Experimental Example 8 In Example 5, cyclic voltammetry was measured in order to further confirm the chemiluminescent state by electric excitation. That is, the chloroform solution of Example 5 was film-cast on a platinum electrode to produce an electrode, which was prepared in a concentration of 0.1 mol [NEt ₄ ].
[ClO _4] was immersed in an acetonitrile solution that a supporting electrolyte, flowing through the potential of the electrode to the electrode when varying the range of -2.2～1 bolts 50 mV / s current (m
The change in A) was examined, and the results are shown in the chart of FIG.

As a result, Example 5 is electrochemically active and exhibits n-type characteristics, and 2.6 due to the semiconducting property with applied voltage.
The current value changed in the mA range. This is also considered to be the influence of the electron-withdrawing group such as the pyridinediyl group and the ethynylene group of Example 5. In addition, the color of the film changed from blue purple to red with n-doping and dedoping. From these, it was confirmed that this material has preferable physical properties as a color display material that can be a constituent element of a display panel of various colors.

[0055]

As described above, the present invention is a linear poly (arylene-ethynylene-arylene-ethynylene) polymer represented by a predetermined formula. Therefore, the aryl group such as the 2,5-pyridinediyl group is high. It forms a compound with highly controlled orientation by forming a continuous π-conjugated system along the main chain of the molecule, maintaining excellent heat resistance and chemical stability, as well as coloring state due to conductivity and electric excitation. The above-mentioned photosensitivity is changed, and since it has high solubility in an organic solvent, it is easy to mold and process, and there is an advantage that a highly versatile functional material can be provided.

[Brief description of drawings]

FIG. 1 is a chart showing the relationship between heating temperature and weight loss rate for Examples 1 and 2.

FIG. 2 is a chart showing the relationship between the heating temperature and the weight loss rate for Examples 5 and 6.

FIG. 3 is a diagram showing the relationship between potential and current for explaining cyclic voltammetry in Example 5.

Claims (5)

[Claims] 1. A linear poly (arylene-ethynylene-arylene-ethynylene) polymer represented by the following formula. [Chemical 1] 2. A diethynyl aryl represented by the following formula 2 and a dihalogenated aryl represented by the following formula 3 (provided that at least one of Ar and Ar 'in both formulas is 2,5-pyridine). And a diyl group, or a divalent group obtained by removing two hydrogen atoms from an aromatic ring of an aromatic compound having an alkyl substituent) in the presence of a palladium-copper catalyst and an amine, for dehydrohalogenation coupling reaction. The method for producing a linear poly (arylene-ethynylene-arylene-ethynylene) polymer according to claim 1, which comprises [Chemical 2] [Chemical 3] 3. An ethynyl aryl halide represented by the following formula 4 is added in the presence of a palladium-copper catalyst and an amine.
The method for producing a linear poly (arylene-ethynylene-arylene-ethynylene) polymer according to claim 1, which comprises a dehydrohalogenation coupling reaction. [Chemical 4] 4. The linear poly (arylene-) according to claim 1.
A light emitting material comprising an ethynylene-arylene-ethynylene) polymer. 5. The linear poly (arylene-) according to claim 1.
A color display material comprising an ethynylene-arylene-ethynylene) polymer.