JPS6366224A - Polymer and electrically conductive high polymer having diphenylamine structural unit - Google Patents

Abstract

PURPOSE:To obtain the titled thermoplastic polymer, having specific repeating units as well as improved processability and capable of exhibiting high electric conductivity by doping, by reacting a dihalodiphenyl with metallic magnesium and carrying out polymerization in the presence of a catalyst. CONSTITUTION:A polymer, obtained by dissolving (A) a 4,4'-dihalodiphenyl in an unreactive solvent, e.g. diethyl ether, etc., adding (B) metallic magnesium to form a compound expressed by formula I (R is 1-6C alkyl; X is halogen), adding (C) a catalyst, e.g. dichloronickel, etc., and carrying out polymerization and having repeating units expressed by formula II. The polymer is thermoplastic, moldable into films, sheets, etc., and capable of reversibly doping an electron receptor, e.g. iodine, etc.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel polymer having a 4,4'-diphenylamine structure represented by the following formula (1) as a repeating unit; This invention relates to a conductive polymer obtained by doping a polymer with an electrolyte acceptor.

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms.) <Prior art and problems to be solved by the invention> As polymers used to form conductive polymer materials, polyacetylene, poly Paraphenylene, polythiophene, polypyrrole, etc. are known. These polymers can be used as conductive polymer materials by doping them with certain compound powders, but they are easily degraded in the air and their electrical properties change. Furthermore, there are problems such as poor meltability and solubility, and extremely poor processability, which is a major obstacle in practical use.

As a method to solve these problems, JP-A-59-102
No. 928 proposes various heterodiazole-based electroactive polymers, and for example, polyoxadiazole-based polymers represented by the following general formula are considered to be effective.

However, the synthesis method for the polymers listed in "--" is complicated, and the resulting polymers have many problems, such as high moisture absorption f1 and poor chemical stability. However, when used as an electroactive polymer, its performance was unsatisfactory, and further improvements are desired.

Furthermore, in JP-A No. 61-28524, various triphenylamine-based electrolytically low active polymers have been proposed.
For example, it has been shown that a triphenylamine-based polymer represented by the general formula shown below is effective.

However, in triphenylamine-based polymers described above, it is difficult to synthesize triphenylamine, which is the starting material, and 4,4'-dihalo-1-rifhenylamine, which is its dihalide. Not only does it have the disadvantage that it cannot be obtained with good selectivity, but it also has the disadvantage that it is difficult to obtain a linear polymer.

Furthermore, when triphenylamine-based polymers are used as battery electrode materials, the large amount per polymer unit causes the disadvantage that the batteries become heavier and larger in terms of the amount of electricity held per unit. be.

<Means for solving the problems> The present invention relates to a new polymer, and by using the polymer of the present invention, a conductive polymer that solves the conventional problems can be obtained. It is.

That is, according to the present invention, 4 expressed by the following formula (f)
, 4'-diphenylamine transversely as a repeating unit (wherein R represents an alkyl group having 1 to 6 carbon atoms) is provided.

Further, according to the present invention, 4, 4' represented by the following formula
- A conductive polymer obtained by doping a polymer having diphenylamine la'IN repeatedly at the il1 position with an electron acceptor is provided (wherein R represents an alkyl group having 1 to 6 carbon atoms) .

The polymer of the present invention is represented by the following formula (11), 4.4
'-Dihalodiphenyl C In the formula, R represents an alkyl group having 6 to 6 carbon atoms, and X represents a halogen. ) with metallic magnesium to obtain a compound represented by the following formula (m),
It is then obtained by polymerizing compound (III) using a catalyst.

Preferably, the reaction is carried out in a non-reactive solvent.

The reaction temperature is -208C to 200'C1, preferably 0
It can be selected within the range of ~150°C.

(n) (m) The polymer of the present invention can also be obtained by the following method.

Examples of the non-reactive solvent used in the above reaction include diethyl ether, tetrahydrofuran, and dibutyl ether.

In addition, as a catalyst, dibromonickel, dibromonickel, dichloro(2,2'-bipyridine)nickel, dibromobis(triphenylphosphine)nickel, 1,5
- Nickel compounds such as cyclooctadienebis(1-rifenylphosphine)nickel are used.

Incidentally, as a method for synthesizing the polymer of the present invention, oxidative polymerization method and electrolytic polymerization method can also be preferably used.

Since the polymer of the present invention is substantially linear, it has excellent processability and can be made into various molded products as a thermoplastic polymer.

In addition, it can be dissolved in electron-accepting organic solvents such as nitrobenzene, 2,4-dinitrochlorobenzene, and 2,4-dinitrofluorobenzene, or in strong acid solvents such as sulfuric acid, formic acid, and polyphosphoric acid to form films, sheets, etc. It can also be molded.

The polymer of the present invention can solve at once the drawback that conventional conductive polymers have extremely poor processability due to poor solubility, meltability, etc.

The polymer of the present invention can exhibit high conductivity by doping with an electron acceptor as a dopant, and the doping is reversible, making it excellent as a conductive polymer.

When the conductive polymer obtained by the present invention is used, for example, as an electrode material for a battery, reversible charging and discharging is possible, and the amount per polymer unit is small, so the energy density per unit weight can be reduced. It can be made higher.

In this case, halogen compounds such as iodine, bromine, and bromine iodide, arsenic pentafluoride, phosphorus pentachloride, phosphorus pentafluoride, antimony pentafluoride, silicon tetrafluoride, aluminum chloride, Metal halogen compounds such as aluminum bromide, aluminum fluoride, ferric chloride, protic acids such as sulfuric acid, nitric acid, fluorosulfuric acid, oxidizing agents such as sulfur dioxide, nitrogen dioxide, difluorosulfonyl peroxide.

Examples include organic substances such as Te1-lacyanoquinodimethane and Te1-lacyanoethylene.

In addition, dopants to be doped electrochemically include P F6''-, S b F [, -, As ]?6- force 11 V + halide anion of group i element, 1
Halide anions of elements of III a jlA, such as -, 1-(i[ll-).

Halogen anions such as Br-, CQ-, (': Q,
Examples include anions such as perchlorate anions such as 04-.

Furthermore, when the polymer of this invention is doped with anions, the nitrogen atoms in the polymer have a positive charge and become stable, so they are stable against repeated redox reactions and have good processability. It is used to construct electrodes by taking advantage of its good properties. That is, the electrode may be formed by dissolving the polymer of the present invention in a solvent, by pressure molding the polymer as a main component, or by molding it into an arbitrary shape using a binder. Can be done. Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but are not necessarily limited to these.

<Effects of the Invention> Since the polymer of the present invention is linear, it has excellent processability and can be easily produced into various molded products.

Further, by doping the polymer of the present invention with an electron acceptor, high conductivity can be exhibited, and the doping is reversible, making it excellent as a conductive polymer.

<Examples> The present invention will be specifically explained below using Examples and Reference Examples, but the present invention is not limited thereto.

□P U (Example) -- Metallic potassium 4.613g (0,1,I80 gram atomic weight), potassium iodide (K I ) 9.7!'I
g (0,054)0 mol), magnesium chloride (anhydrous) 5.62 g (0,0590 mol) and dry tetrahydrofuran (T' Hl?) L OOmQ
The mixture was heated to reflux and reacted in a 300 mfl flask under a nitrogen atmosphere with stirring. After approximately [hours], a black powder was produced, and it was recognized that metallic magnesium had been produced.

Then 10.4,4'-dibromo-N-methyldiphenylamine. (lf'ig ((1,0205 mol)) was dissolved in 50 mfl of dry THF and added from the dropping funnel. After the addition was completed, the mixture was heated to reflux while stirring for 1 hour. Furthermore, 4,4'-dibromo-N-methyldiphenylamine 1
0.06 g (0,0205 mol) and N i B r2
Approximately 0.03 g of (PPh3)z (ph “phenyl) was dissolved in 50 mM dry THF and added via addition funnel. After 1 day of preheating under reflux under stirring, the product was poured into hydrochloric acidic ethanol and incubated for 1 hour. After stirring, the mixture was filtered and washed thoroughly with ethanol using a filter, and then extracted with ethanol overnight using a Soxhlet extractor to remove impurities. The yield of the resulting polymer after drying was 8.55 g.

The polymer thus obtained is a pale-colored powder that is
Even after being left alone for several months, no changes were observed and it was extremely stable. Further, thermogravimetric analysis of this polymer was conducted in a nitrogen atmosphere. The results are shown in FIG. This figure shows that the polymer is stable without weight loss up to 350°C, and up to 700°C.
It can be seen that even at high temperatures of C, the residual weight remains about 70%.

In addition, elemental analysis yielded the following results.

Elemental analysis value of polymer: Carbon (C) 84. ]7% Hydrogen (H) 5.86%
Nitrogen (N) 7.67% Atomic ratio is C: IT: N=12.8: 10.7:
1, which was close to the theoretical value (C031-10, N).

Next, the polymer was subjected to infrared spectrum analysis, and the measured infrared spectrum is shown in FIG. Figure 11 River 590■-1,1
The absorption near 4,90 an-' and 1-320 on-' is due to the diphenylamine structure, and the absorption around 800
The absorption near -1 is due to the para-substituted benzene structure.

These results show that the produced polymer is poly(/1.4'-N-
It was confirmed that the product was methyl-diphenylamine).

Reference Example 1 The polymer obtained in Example 1 was crimped onto a platinum plate to produce a measurement electrode.

Next, a 1 mol/Q electrolyte was prepared using acetonitrile as the solvent and tetrabutylammonium perchlorate as the solute, and a platinum plate was used as the counter electrode, and an Ag/AgN○3 electrode was used as the reference electrode, in N2. The redox potential of the electrode described above was measured. The obtained results are shown in Figure 3. Poly(4,4'-
The redox potential of N-methyldiphenylamine is approximately 0.
It was 37V. .

Example 2 Metallic potassium 4.613g (0,1180 grams 11
atomic mouse), =12- Magnesium chloride (anhydrous) 5.62g (0,05
90 mol) and 10% tetrahydrofuran (THF)
0 mρ was heated to reflux while stirring in a 300 mΩ flask under a nitrogen atmosphere to cause a reaction. After about 1 hour, black powder was produced, and it was recognized that metallic magnesium had been produced. Then, 20.12 g (0,0590 mol) of 4,4'-dibromo-N-methyldiphenylamine was added to the TIT
It was dissolved in F 100+nQ, added through a dropping funnel, and heated to reflux with stirring to react. After about 1 hour, it was observed that the metallic magnesium was completely consumed. Next, this reaction product was treated with N1(d 1p)2C as a catalyst.
Qz (d jp: 2+2'-bipyridine) about 0. I
When Og was added and the mixture was heated and refluxed while stirring, the polymerization reaction started smoothly. The reaction was carried out for 2 hours, and after the reaction, the product was poured into ethanol acidified with hydrochloric acid, stirred for 11 hours, and then filtered. After thoroughly washing the filter with ethanol, it was extracted with ethanol using a Soxhlet extractor for 5 hours to remove impurities. The yield of the resulting polymer after drying was 7.12 g.

When the infrared spectrum of this polymer was measured, it was the same as that of Example 1.

= 11mm - Similarly to Reference Example 1, in the electrolytic solution of te-1-butylammonium perchlorate/acetonyl-1-lyl, the polymer pressed onto the platinum plate was used as the working electrode, the platinum plate was used as the counter electrode, and Ag/AgN0 was used as the working electrode. ．． Using the electrode as a reference electrode, the redox potential of the electrode described in 112 was measured in N2. The results obtained are shown in FIG. The redox potential is approximately 0. /IV.

□ Setting up the tip □ In Example 1, 4,4'-dibromo-N-n was used instead of 4,4'-dibromo-N-methyldiphenylamine.
-Butyldiphenylamine in total 22.60g (0,
The reaction was carried out in the same manner as in Example 1, except that 0590 mol) was used. After purification, IO, 52 g of polymer was obtained. When the elemental analysis was carried out, the following 5-order results were obtained.

Elemental analysis values of the polymer: Carbon (C) 85.7% Hydrogen (H) 8.0% Nitrogen (
N) 6°3% Atomic ratio is C: I-I: N-15,9: 17.8
: 1, which was close to the theoretical value (C□GII, -1N).

Moreover, it was found from the infrared spectrum that it was poly-N-n-butyldiphenylamine.

[Brief explanation of the drawing]

FIG. 1 shows the results of thermogravimetric analysis of the polymer obtained in Example 1. FIG. 2 is an infrared absorption spectrum diagram of the same polymer. The horizontal axis is the wave number (wavenumber I Cm-')
, the vertical axis indicates transmittance (%). FIG. 3 is a cyclic portammogram of Reference Example 1. The horizontal axis is the Ag/AgNO3 reference electrode (0,799V
vs H+/Hz) reference voltage, and the vertical axis is current (mA
) is shown. FIG. 4 shows the cyclic portamole 11 of Reference Example 2, and the horizontal and vertical axes are the same as in FIG. 3.

Claims (1)

[Scope of Claims] 1) A polymer having a 4,4'-diphenylamine structure represented by the following formula as a repeating unit. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents an alkyl group having 1 to 6 carbon atoms) 2) A polymer having a 4,4'-diphenylamine structure represented by the following formula as a repeating unit is electronically A conductive polymer obtained by doping with a receptor. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents an alkyl group having 1 to 6 carbon atoms)