JP3108755B2 - Use of poly (isoquinolinediyl) polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fused heterocyclic compound, isoquinoline, in which divalent residues obtained by removing two hydrogen atoms are used as repetitive constitutional units, exhibit solubility, excellent heat resistance and excellent electrochemical properties. The present invention relates to a method of using a poly (isoquinolinediyl) polymer having an activity.

[0002]

2. Description of the Related Art Poly (arylene) having a structure in which aromatic rings are continuously bonded [for example, poly (p-phenylene), poly (2,5-thienylene), poly (1,4-naphthylene)] is generally used. Has excellent heat resistance. Further, of those poly (arylene) and electron acceptor (AsF ₅ and the like) and an electron donor (lithium, sodium, etc.) with the adduct is electrically conductive and as an active material for primary and secondary batteries It is known to have available properties [for example,
"Polymer", 34, 848 (1985)]. Also, a conductive polymer formed by reducing a polymer having a continuous π-conjugated system along the main chain and comprising a heterocyclic six-membered ring unit, for example, a 2,5-pyridinediyl group as a repeating constitutional unit, is used. If the substance is
It is proposed in 210420.

[0003]

However, most of the conventionally proposed poly (arylene) s have low solubility in organic solvents and are often infusible, so that their use is limited, and their characteristic functions are limited. This is a problem in withdrawing. Also, with respect to the above-mentioned poly (arylene), it is desired to develop a substance having physical properties not found in conventional poly (arylene) by devising a molecular structure. For example, if a poly (arylene) having an oxidation / reduction potential different from that of a conventional poly (arylene) can be obtained, it can be used as an active material or an electrode material for a conventional polymer battery [eg, “electrochemical and industrial physical chemistry”. 54, p. 306 (1986)].

[0004] Under these circumstances, the present invention has been completed as a result of intensive research to search for poly (arylene) having a new molecular structure.

An object of the present invention is to provide a novel poly (arylene) which has excellent heat resistance, is soluble in an organic solvent, and can control the degree of depolarization and electrochemical redox potential, especially poly (isoquinolinediyl). ) The polymer is used as an electrochromic device or the like.

[0006]

The object of the present invention is to provide a divalent group derived from isoquinoline, which is a condensed heterocyclic compound by removing any two hydrogen atoms, as a repeating constitutional unit.

Embedded image And a poly (isoquinolinediyl) polymer having a degree of polymerization (n) of 5 or more. Here, if the degree of polymerization (n) is less than 5, a sufficient function as a polymer cannot be exhibited.

Further, the present inventors have experimentally confirmed the polymer of the present invention having a degree of polymerization (n) of up to about 200 and its excellent properties and usefulness by the following production method. The preparation and utilization of those having a degree of polymerization exceeding about 200 are technically expected.

The above polymer is obtained by substituting any two hydrogen atoms of isoquinoline with a halogen.

Embedded image (Wherein, X represents a halogen), which is produced by reacting an isoquinoline dihalide with a zero-valent nickel compound.

[0009] Such a polymer can also be produced by electrolytic reduction of an isoquinoline dihalide compound represented by the formula (4) in the presence of a nickel compound.

The poly (isoquinolinediyl) polymer used in the present invention can be used as a fiber, film or electrochromic device by utilizing its excellent properties.

In the present specification, "poly (arylene)" means a polymer having an aromatic ring as a repeating constitutional unit, such as poly (p-phenylene) or poly (1,4-naphthylene). The “aromatic ring” includes, for example, a heterocyclic ring such as pyridine and thiophene in addition to an aromatic hydrocarbon ring such as a benzene ring.

The poly (isoquinolinediyl) polymer used in the present invention is reacted with an isoquinoline dihalide represented by the formula (4), for example, isoquinoline dichloride or dibromide by adding an equimolar or more zero-valent nickel compound in an organic solvent, Obtained by dehalogenation. Preferred reaction temperatures are between room temperature and about 80 ° C,
The reaction is completed in about 24 hours. As the organic solvent, for example, N, N-dimethylformamide, acetonitrile, toluene, tetrahydrofuran and the like can be applied.

A zero-valent nickel compound takes a halogen from a halogenated aromatic compound and causes a coupling reaction between aromatic groups [for example, “Synthesis” (Synthesi).
s), p. 736 (1984)]. This reaction is represented by the following chemical formula 5.

[0014]

Embedded image Ar-X + Ar'-X + NiLm → Ar-Ar '+ NiX 2 Lm ( where, Ar and Ar' an aromatic group, X is a halogen atom, L is a neutral ligand And thus NiLm represents a zero-valent nickel compound.)

Therefore, when an aromatic compound having two halogens in a molecule, for example, isoquinoline dihalide is reacted with an equimolar or more zero-valent nickel compound,
And a polymer is obtained by the dehalogenation reaction shown in Chemical formula 7.

[0016]

Embedded image 2.X-Ar ″ -X + NiLm → X-Ar ″ -Ar ″ -X + NiX ₂ Lm

Embedded image [Where X-Ar ″ -X represents isoquinoline dihalide (X is a halogen)]

In the above reaction, the zero-valent nickel compound is added to the reaction system (so-called insi
The compound synthesized by tu) can be used as it is, or a compound previously synthesized and isolated can be used. Such a zero-valent nickel compound is, for example, a nickel complex generated by a reduction reaction or a ligand exchange reaction in the presence of a neutral ligand, and the neutral ligand includes 1,5-cyclooctadiene, Examples thereof include 2,2'-bipyridine and triphenylphosphine.

As another method, when the isoquinoline dihalide of the above formula (4) is subjected to an electrolytic reduction reaction in the presence of a divalent nickel compound, an isoquinoline diyl polymer represented by the following formula (3) can be obtained by a dehalogenation reaction. it can. That is, if the divalent nickel compound is electrolytically reduced in an electrolytic cell, a zero-valent nickel compound is generated by the reaction of Chemical formula 8.

[0019]

Embedded image [Ni ¹¹ Lm] ²⁺ + 2e → Ni ⁰ Lm

Therefore, when an aromatic compound having two halogens in the molecule, ie, isoquinoline dihalide, is electrolytically reduced in the presence of a divalent nickel compound, the reaction of Chemical Formula 8 and Ni ⁰ Lm subsequently generated in the reaction system are involved. 9 to 11
Is obtained by the reaction shown in the above. The electrolysis can be usually performed under the following conditions. That is, for example, N, N-dimethylformamide or acetonitrile is used as a solvent, tetraethylammonium perchlorate or tetraethylammonium tetrafluoroborate is dissolved as a supporting electrolyte to form an electrolytic solution, and the electrode is a platinum electrode, an ITO transparent electrode, or Use graphite electrodes. Isoquinoline dihalide and a divalent nickel complex are dissolved in an electrolytic solution, and the reduction potential of a divalent nickel compound [for example, tris (2,2-bipyridine) nickel salt is -1.7 V
(Relative to Ag / Ag ⁺ )].

[0021]

Embedded image Ni ⁰ Lm + X-Ar ″ -X → X-Ni ¹¹ Lm-Ar ″ -X

[0022]

Embedded image 2.X-Ni ¹¹ Lm-Ar ″ -X + 2e → X-Ar ″ -Ar ″ -X + Ni ⁰ Lm + 2X ⁻

[0023]

Embedded image

[Where X-Ar ″ -X represents isoquinoline dihalide (X is a halogen)]

As the nickel compound, a compound synthesized and isolated in advance before the polymerization reaction may be used, or a compound synthesized directly from nickel or a nickel compound in an electrolytic bath may be used as it is. Such nickel compounds, such as tris (2, 2'-bipyridine) nickel bromide _{[Ni (bpy) 3 Br 2} ], dibromobis (triphenylphosphine) nickel [NiBr ₂ (PPh _{3) 2],} and the like.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically and in detail with reference to examples.

Example 1 Anhydrous bis (acetylacetonato) nickel [Ni (acac)
Abbreviated as ₂ ] 44 mmol, 1,5-cyclooctadiene (114.8 mmol) was dissolved in 100 ml of toluene, and 65.6 mm
ol of a toluene solution of triethylaluminum (40 ml) was added dropwise and allowed to react to form a zero-valent nickel complex, bis (1,5-
Cyclooctadiene) nickel [Ni (cod) ₂ ]
Was synthesized. This Ni (cod) ₂ was recrystallized from toluene.

4 mmol of this Ni (cod) ₂ was dissolved in 30 ml of N, N-dimethylformamide, 4 mmol of 1,5-cyclooctadiene and 2,2′-bipyridine were added, and 4 mmol was added.
1 mmol of 1,4-dibromoisoquinoline was added and reacted at a reaction temperature of 60 ° C. for 24 hours. By this reaction, a pale yellow powdery polymer of poly (isoquinoline-1,4-diyl) was obtained. After removing the powdery polymer by filtration, the powdery polymer was washed several times in the following order using the following substances (a) to (f) in order to remove impurities such as nickel compounds.

(A) ammonia water (29%), (b) methanol, (c) a hot aqueous solution of sodium ethylenediaminetetraacetate (adjusting the pH to 3), (d) ammonia water, (e)
Warm water, (f) methanol

After the above washing was completed, the powdery polymer was dried using a vacuum line. The elemental analysis value of this polymer was 84.8% for carbon, 4.0% for hydrogen, 11.1% for nitrogen, and 0.0% for chlorine.

Embedded image Was almost the same as the calculated value (85.0% of carbon, 3.9% of hydrogen, 11.6% of nitrogen) of a polymer having as a repeating constitutional unit. The difference between the observed and calculated values in elemental analysis appears to be primarily due to the high thermal stability of the polymer and the difficulty of complete combustion in elemental analysis. The bromine obtained from the observed value is the unreacted terminal as shown in Chemical formula 13 of the polymer.

Embedded image It is thought to be due to. The yield of the polymer in this example was 95%.

The above polymer was soluble in formic acid and chloroform. Therefore, the molecular weight of this polymer in chloroform and formic acid solutions was measured by GPC and light scattering, and as a result of GPC, the number average molecular weight was 2,600.
(Degree of polymerization approx. 21), weight-average molecular weight according to light scattering method
The polymer was found to have 2,000 (degree of polymerization about 16).

The infrared absorption spectrum of the above polymer showed the following absorption.

3042 m, 1613 s, 1570 m, 1539 s, 1501
vs, 1450 w, 1368 m, 1333 m, 1287 m, 1253 m, 1161
m, 1143 m, 1022 w, 965 vs, 915 m, 870 w, 796
m, 761vs, 629s, 461w, 429w. (The numbers indicate the absorption positions in cm ^-1. W, m, s, and vs indicate weak, medium, strong, and very strong absorptions, respectively.) In KBr pellets.

Further, the formic acid solution of the above polymer showed an absorption maximum showing a relatively sharp and distinct peak at around 370 and 260 nm in the ultraviolet and visible spectra.

Further, the above polymer showed high thermal stability. As a result of thermogravimetric analysis, a slight weight loss was first observed at about 300 ° C. Upon heating to 900 ° C. under nitrogen, the rate of weight loss was about 17%.

Example 2 0.3 mmol of 1,4-dibromoisoquinoline and 0.15 mmol of tris (2,2'-bipyridine) nickel salt [Ni (bpy) ₃ Br ₂ ] in 15 cm ³ of N, N-dimethylformamide And 3.75 mmol of tetraethylammonium perchlorate [(C ₂ H ₅ ) ₄ NClO ₄ ) were dissolved to prepare an electrolytic solution. A platinum plate (1 × 2 cm = 2 c) is used as an anode and a cathode.
m ² ), placed in an electrolytic cell equipped with a silver electrode as a reference electrode, and subjected to electrolytic polymerization for 16 hours at a polymerization temperature of 60 ° C. and an electrolytic potential of −1.7 V (potential for Ag / Ag ⁺ , the same applies hereinafter) A yellow film polymer [poly (isoquinoline-1,4-diyl)] was obtained on the cathode. After taking out the film-like polymer, the film-like polymer was washed several times in the following order using the following substances (a) to (f) in order to remove impurities such as nickel compounds.

(A) ammonia water (29%), (b) methanol, (c) a hot aqueous solution of sodium ethylenediaminetetraacetate (pH adjusted to 3), (d) ammonia water, (e)
Warm water, (f) methanol

After the above washing was completed, the film-form polymer was dried using a vacuum line. The infrared absorption spectrum of this polymer showed the following absorptions.

3048 m, 1614 s, 1571 m, 1543 s, 1504
vs, 1449 w, 1372 m, 1333 m, 1283 m, 1254 m, 1161
m, 1144 m, 1024 w, 965 vs, 914 m, 870 w, 796
m, 763vs, 629s, 462w, 425w. (The numbers indicate the absorption positions in cm ^-1. W, m, s, and vs indicate weak, medium, strong, and very strong absorptions, respectively.) In KBr pellets.

Further, the formic acid solution of the above polymer showed an absorption maximum showing a relatively sharp and distinct peak at around 370 and 260 nm in the ultraviolet and visible spectra.

These spectral data indicate that the yellow film polymer obtained was the same as the polymer obtained in Example 4 and having the repeating unit represented by Chemical formula 12.

Example 3 Poly (isoquinoline-1,4-diyl) obtained in Example 1
A chloroform solution of the polymer was spread on a platinum plate, and chloroform was removed by an evaporation method to obtain a polymer film. 0.1 mol / l (C ₂ H ₅ ) of this polymer film
_The cyclic voltammogram was measured in an acetonitrile solution containing ₄ NClO ₄ . As a result, the polymer is Ag / A
It was found to be doped at about -2.1 V for g ⁺ and undoped at about -2.0 V (potential for Ag / Ag ⁺ ) in the reverse sweep. Upon doping, the color of the polymer changed from pale yellow to reddish purple, and the opposite discoloration was observed with dedoping. Such electrochemical behavior and discoloration phenomenon indicate that the polymer of the present invention is electrochemically active and can be used as a battery electrode and a material exhibiting electrochromism.

The poly (isoquinoline) used in the present invention
The doping and undoping potentials obtained with the (1,4-diyl) polymer were almost the same as those obtained with poly (pyridine-2,5-diyl). Poly (pyridine-
2,5-diyl) is a typical compound that is doped n-type at this potential, and the polymer used in the present invention is a π-conjugated system basically similar to poly (pyridine-2,5-diyl). Therefore, it is considered that the n-type doping also occurs in the electrochemical doping.
Further, when the poly (isoquinoline-1,4-diyl) polymer used in the present invention is immersed in a solution containing sodium naphthalide (a reaction product of naphthalene and sodium), the color changes from pale yellow to purple or magenta. A similar color change was observed as in the electrochemical doping. The solid obtained by compression molding the resulting poly (isoquinoline-1,4-diyl) polymer and adduct of sodium ion under pressure is as follows:
The semiconductor was found to have a conductivity of 1.8 × 10 ⁻³ Scm ⁻¹ (Siemens / cm) at room temperature. Sodium naphthalide is a typical compound for doping a π-conjugated polymer into n-type, and it is considered that n-type doping has occurred in the same manner as the electrochemical doping.

[0044]

Since the poly (isoquinolinediyl) polymer used in the present invention has heat resistance and is soluble in an organic solvent, it can be used as a fiber or film by using a solution obtained by dissolving in an appropriate organic solvent. Dry molding to etc. is possible,
The structure has excellent properties not found in conventional polyarylenes, such as the degree of depolarization and the control of the electrochemical oxidation-reduction potential, and can be effectively used as an electrochromic device.

In preparing the polymer used in the present invention, the bonding position of the monomer can be accurately determined by the bonding position of the halogen group which is a leaving group, and various polyisoquinolines having different bonding positions can be prepared. It can be synthesized at will. That is, the IR spectra of the polymers (a) and (b) obtained from 1,4-dibromoisoquinoline and 5,8-dibromoisoquinoline according to the method of Example 1 are shown in FIG. In each case, absorption specific to the isoquinoline ring which is a condensed heterocyclic ring is observed, but absorption peaks based on CH out-of-plane bending vibration and ring stretching vibration are slightly different. These absorption peaks showed good agreement with the spectra of the respective monomers. In addition, all of the obtained polymers are soluble in formic acid, chloroform, etc.
^{In the 1} H-NMR spectrum, an isoquinoline ring proton peak was observed at 7 to 10 ppm. Also, ¹³ C-NMR shows that
An isoquinoline ring carbon peak was observed at 0-160 ppm. These results indicate that polyisoquinolines with controlled binding positions can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing an IR spectrum of each polymer used in the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 61/12 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A divalent group derived from isoquinoline which is a condensed heterocyclic compound by removing any two hydrogen atoms as a repeating constitutional unit, represented by the following general formula: And an electrochromic device comprising a poly (isoquinolinediyl) polymer having a degree of polymerization (n) of at least 5.