JPH08269174A - Poly(isoquinolindiyl) polymer, its production and its use - Google Patents

Abstract

PURPOSE: To obtain a polymer excellent in heat resistance, soluble to organic solvents and controllable in depolarization degree and electrochemical oxidation- reduction potential, useful for films, etc., by reaction of a specific isoquinoline dihalide with a zero-valent nickel compound. CONSTITUTION: An isoquinoline dihalide of formula I (X is a halogen) formed by halogen substitution of any two H atoms in quinoline is reacted with a zero-valent nickel compound, or preferably, the dihalide compound is electrolytically reduced in the presence of the nickel compound to obtain the objective polymer of formula II having a polymerization degree (n) of >=5 made up of recurring constitutive unit i.e. a divalent group derived from the isoquinoline as a condensed heterocyclic compound by eliminating any two H atoms from the isoquinoline.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention comprises a repeating heterocyclic unit composed of a divalent residue obtained by removing two hydrogen atoms from isoquinoline which is a fused heterocyclic compound, exhibits solubility, and has excellent heat resistance and electrochemical properties. TECHNICAL FIELD The present invention relates to a poly (isoquinolinediyl) polymer having active activity, a method for producing the same, and use thereof.

[0002]

Poly (arylene) having a structure in which aromatic rings are continuously bonded [eg, poly (p-phenylene), poly (2,5-thienylene), poly (1,4-naphthylene)] are generally used. Has excellent heat resistance. Further, the adduct of such poly (arylene) with an electron acceptor (AsF ₅ etc.) or an electron donor (lithium, sodium etc.) has conductivity and is used as an active material for a primary battery or a secondary battery. Known to have available properties [eg,
"Polymer" 34, 848 (1985)]. Also, a conductive material produced by reducing a polymer having a continuous 6-conjugated system along the main chain and comprising a group consisting of a 6-membered heterocyclic unit, for example, a 2,5-pyridinediyl group as a repeating constitutional unit. The substance is JP 1-
Proposed in No. 210420.

[0003]

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

Under these circumstances, the present invention has been completed as a result of earnest 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 the electrochemical redox potential, particularly poly (isoquinolinediyl). 3.) Providing a polymer.

Another object of the present invention is to use such a novel poly (isoquinolinediyl) polymer as a molded product such as a fiber or a film, an electrochromic device, an active material or electrode of a battery, an n-type semiconductor, etc. There is.

[0007]

The above object is to provide a divalent group derived from isoquinoline, which is a condensed heterocyclic compound, by removing hydrogen atoms at any two positions as repeating constitutional units, and

Embedded image And a degree of polymerization (n) of 5 or more is achieved by a poly (isoquinolinediyl) polymer. Here, if the degree of polymerization (n) is less than 5, a sufficient function as a polymer cannot be exhibited. The inventors of the present invention have experimentally confirmed that the polymer of the present invention having a degree of polymerization (n) of up to about 200 and its excellent properties and usefulness are experimentally confirmed by the production method described below. It is of course technically expected to prepare and use a polymer having a degree of polymerization exceeding the limit.

The above polymer has the following chemical formula 4 in which hydrogen atoms at any two positions of isoquinoline are substituted with halogens.

[Chemical 4] It is produced by reacting an isoquinoline dihalide represented by the formula (wherein X represents halogen) with a zero-valent nickel compound.

Further, such a polymer can also be produced by electrolytically reducing the isoquinoline dihalide compound represented by Chemical formula 4 in the presence of a nickel compound.

The novel poly (isoquinolinediyl) polymer of the present invention is applied to a fiber or film, an electrochromic device, an active material or an electrode of a battery by utilizing its excellent properties, and the polymer is used as a reducing agent. Alternatively, it can be reduced by electrochemical doping and used as an n-type semiconductor.

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), and 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 according to the present invention is obtained by reacting an isoquinoline dihalide represented by Chemical formula 4, for example, isoquinoline dichloride or dibromide, with an equimolar or more zero-valent nickel compound in an organic solvent, Obtained by dehalogenation. Suitable 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 halogen from a halogenated aromatic compound and causes a coupling reaction between aromatic groups [for example, "Synthesis"].
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' are aromatic groups, X is a halogen atom, and L is a neutral ligand). , And thus NiLm represents a zero-valent nickel compound.)

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

[0016]

[Chemical 6] 2.X-Ar "-X + NiLm → X-Ar" -Ar "-X + NiX ₂ Lm

[Chemical 7] [Here, X-Ar "-X represents isoquinoline dihalide (X is halogen).]

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

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

[0019]

[Chemical formula 8] [Ni ¹¹ Lm] ²⁺ + 2e → Ni ⁰ Lm

Therefore, when an aromatic compound having two halogens in the molecule, that is, isoquinoline dihalide, is electrolytically reduced in the presence of a divalent nickel compound, the reaction of Chemical formula 8 and the Ni ⁰ Lm generated subsequently in the reaction system are involved. Conversion 9 to 11
The polymer of Chemical formula 3 is obtained by the reaction shown in. 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 prepare an electrolytic solution, and a platinum electrode, an ITO transparent electrode, or Use graphite electrodes. The isoquinoline dihalide and divalent nickel complex are dissolved in the electrolytic solution, and the reduction potential of the divalent nickel compound [for example, tris (2,2-bipyridine) nickel salt is -1.7V.
(Against Ag / Ag ⁺ )].

[0021]

[Chemical 9] Ni ⁰ Lm + X-Ar "-X → X-Ni ¹¹ Lm-Ar" -X

[0022]

[Of 10] ^{2 · X-Ni 11 Lm- Ar} "-X + 2e → X- Ar" - Ar "-X + Ni 0 Lm + 2X -

[0023]

[Chemical 11]

[Here, X-Ar "-X represents isoquinoline dihalide (X is halogen).]

As the above nickel compound, those synthesized and isolated in advance before carrying out the polymerization reaction may be used, or those synthesized directly from nickel or a nickel compound in an electrolytic cell may be used as they are. Examples of such nickel compounds include 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) is dissolved in 100 ml of toluene to obtain 65.6 mm
40 ml of a toluene solution of triethylaluminum of ol was added dropwise to the reaction to react with bis (1,5-
Cyclooctadiene) nickel [abbreviated as 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 another 4
mmol of 1,4-dibromoisoquinoline was added and the reaction was carried out 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. The powdery polymer was taken out by filtration, and then, in order to remove impurities such as nickel compounds, the powdery polymer was washed several times in the following order using the substances (a) to (f) below.

(A) Ammonia water (29%), (b) methanol, (c) warm aqueous solution of sodium ethylenediaminetetraacetate (pH adjusted 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 values of this polymer were as follows: carbon 84.8%, hydrogen 4.0%, nitrogen 11.1%, chlorine 0.0%.

[Chemical 12] It was almost in agreement with the calculated values (85.0% of carbon, 3.9% of hydrogen, 11.6% of nitrogen) of the polymer having a repeating unit of. The difference between the observed and calculated values in elemental analysis is believed to be primarily due to the high thermal stability of this polymer and the difficulty of complete combustion in elemental analysis. The bromine obtained by the observation is the unreacted terminal as shown in Chemical formula 13 of the polymer.

[Chemical 13] 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 solution and formic acid solution was measured by GPC and light scattering method.The GPC result showed that the number average molecular weight was 2,600.
(Polymerization degree: about 21), weight average molecular weight by light scattering method
It was found to be a polymer with 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, 629 s, 461 w, 429 w. (The numbers indicate the absorption position indicating the cm ^-1 number. W, m, s, and vs indicate weak absorption, medium absorption, strong absorption, and extremely strong absorption.) All of the above measurement results In KBr pellets.

Further, the formic acid solution of the above-mentioned polymer showed an absorption maximum showing a relatively sharp and clear chevron shape in the vicinity of about 370 and 260 nm in ultraviolet and visible spectra.

Furthermore, the above polymers showed high thermal stability. As a result of thermogravimetric analysis, a slight weight loss was first observed at about 300 ° C. The rate of weight loss was about 17% when heated to 900 ° C under nitrogen.

Example 2 0.3 mmol of 1,4-dibromoisoquinoline and 0.15 mmol of tris (2,2'-bipyridine) nickel salt in 15 cm ³ of N, N-dimethylformamide [Ni (bpy) ₃ Br ₂ ]. , 3.75 mmol tetraethylammonium perchlorate [(C ₂ H ₅ ) ₄ NClO ₄ )] was dissolved to prepare an electrolytic solution. Platinum plates (1 x 2 cm = 2c) were used as the anode and 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 with respect to Ag / Ag ⁺ , the same applies below). A yellow film polymer [poly (isoquinoline-1,4-diyl)] was obtained on the cathode. After taking out the film-shaped polymer, the film-shaped 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) warm 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 polymer was dried using a vacuum line. The infrared absorption spectrum of this polymer showed the following absorption.

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, 629 s, 462 w, 425 w. (The numbers indicate the absorption position indicating the cm ^-1 number. W, m, s, and vs indicate weak absorption, medium absorption, strong absorption, and extremely strong absorption.) All of the above measurement results In KBr pellets.

Further, the formic acid solution of the above-mentioned polymer showed an absorption maximum showing a relatively sharp and clear chevron in the vicinity of about 370 and 260 nm in the ultraviolet and visible spectra.

These spectral data show that the obtained yellow film polymer was the same as the polymer having the repeating structural unit of Chemical formula 12 obtained in Example 4.

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. About 0.1 mol / l (C ₂ H ₅ ) of this polymer film
Cyclic voltammograms were measured in 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 with respect to g ^{+ and} dedoped at about −2.0 V (potential for Ag / Ag ⁺ ) in the reverse sweep. The color of the polymer changed from pale yellow to magenta upon doping, and the opposite color was observed upon 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.

Further, the poly (isoquinoline-1,
The doping and dedoping potentials obtained with the 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 n-type doped at this potential, and the polymer of the present invention is poly (pyridine).
-2,5-diyl) has a π-conjugated system basically similar to that of the above, it is considered that n-type doping occurs in the above electrochemical doping. In addition, the poly (isoquinoline-1,4-diyl) polymer of the present invention can be used as sodium naphthalide (a reaction product of naphthalene and sodium).
When it was dipped in a solution containing Pt, the color changed from pale yellow to purple or magenta, and the same color change as in electrochemical doping was observed. Produced poly (isoquinoline- 1, 4
-Diyl) polymer and sodium ion addition product under pressure, the solid product obtained by compression molding is 1.8
It was found that the semiconductor had a conductivity of × 10 ^-3 Scm ^-1 (Siemens / centimeter). Sodium naphthalide is a typical compound for n-type doping of a π-conjugated polymer, and n-type is similar to the electrochemical doping described above.
It is considered that type doping is occurring.

[0044]

Since the poly (isoquinolinediyl) polymer of the present invention has heat resistance and is soluble in an organic solvent, a fiber obtained by dissolving it in an appropriate organic solvent is used.
It can be dry-molded into films. In addition, it has excellent properties that conventional polyarylene does not have, such as the degree of depolarization and the electrochemical redox potential that can be controlled by its structure.

Further, according to the method of the present invention, the bonding position of the monomer can be accurately determined by the bonding position of the halogen group which is the leaving group, and various polyisoquinolines having different bonding positions can be optionally synthesized. be able to. That is, 1,
The IR spectra of the polymers (a) and (b) obtained from 4-dibromoisoquinoline and 5,8-dibromoisoquinoline according to the method of Example 1 above are shown in FIG. In each case, absorption characteristic of the fused heterocyclic ring, isoquinoline, is observed, but the absorption peaks due to C—H 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.
Further, all the obtained polymers were soluble in formic acid, chloroform and the like, and the peak of the isoquinoline ring proton was observed at 7-10 ppm in the ¹ H-NMR spectrum of each polymer. Also in ¹³ C-NMR, a peak of isoquinoline ring carbon was observed at 120-160 ppm. From these results,
It can be seen that polyisoquinolines having controlled binding positions are obtained.

[Brief description of drawings]

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

[Explanation of symbols] a poly (isoquinoline-1,4-diyl) b poly (isoquinoline-5,8-diyl)

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Claims (7)

[Claims] 1. A divalent group derived from isoquinoline, which is a condensed heterocyclic compound, by removing hydrogen atoms at any two positions is used as a repeating constitutional unit. And a degree of polymerization (n) of at least 5, a poly (isoquinolinediyl) polymer. 2. The following chemical formula 2, in which any two hydrogen atoms of isoquinoline are substituted with halogen, (Wherein, X represents halogen), the isoquinoline dihalide is reacted with a zero-valent nickel compound, wherein the chemical formula 1 (wherein n is an integer of 5 or more)
A method for producing a poly (isoquinolinediyl) polymer represented by: 3. An isoquinoline dihalide compound represented by the above chemical formula 2 (in the formula, X represents halogen) in which hydrogen is substituted at any two hydrogen atoms of isoquinoline, is electrolytically reduced in the presence of a nickel compound. The method for producing a poly (isoquinolinediyl) polymer represented by the above chemical formula 1 (wherein n is an integer of 5 or more). 4. The polymerization degree (n) represented by the chemical formula 1 is 5
A fiber or film comprising the above poly (isoquinolinediyl) polymer. 5. The polymerization degree (n) represented by the chemical formula 1 is 5
An electrochromic device comprising the above poly (isoquinolinediyl) polymer. 6. The polymerization degree (n) represented by the chemical formula 1 is 5
A battery active material or electrode comprising the above poly (isoquinolinediyl) polymer. 7. The polymerization degree (n) represented by the chemical formula 1 is 5
An n-type semiconductor obtained by reducing the above poly (isoquinolinediyl) polymer with a reducing agent or electrochemical doping.