JPH0333726B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel polymer comprising a 4,4',4''-triphenylamine structure as a repeating unit.

Disclosure of the Invention The present invention was achieved by confirming that triphenylamine forms a stable complex with an electron acceptor, and was obtained as a result of numerous studies. This is a novel polymer (poly(4,4',4"-triphenylamine)) consisting of a repeating unit having a ',4'-triphenylamine structure.

The novel polymer of the present invention has the following formula: (n in the formula represents 10 to 15) 4,
The 4′,4″-triphenylamine structure is used as a repeating unit, and the oxidation potential is relative to Ag/AgCl.
It is a high molecular compound with a voltage range of 0.8 to 1.1V.

The polymer of the present invention having the above structure as a repeating unit is a novel polymer compound hitherto unknown, and can be produced by the chemical reaction formula shown below.

2K＋MgCl ₂ →Mg＋2KCl (1) The above reaction formula (1) is a generally known reaction for producing active magnesium, and the above reaction formula
(2) and (3) can be carried out by a polymerization reaction using a Grignard reagent in an intermediate state (Mr. Yamamoto et al. "Bull.Chem.Soc.JaPan" 51, 2091 (1978) and Japanese Patent Publication No. 58-46268) ). These reactions are known as polymerization reactions that produce bonds at halogen substitution positions. Although the right side of the above reaction formula (2) describes an intermediate state in which only one side is a Grignard reagent, other intermediate states can be created as long as the equivalence with magnesium is maintained.

The monomers used to obtain the novel polymers of the present invention include, for example, 4,4′,4″-tribromotophenylamine, 4,4′,4″-trichlorotriphenylamine, etc. Mention may be made of ',4''-trihalogentriphenylamine.

Examples of the solvent used in the above reaction include ether solvents such as tetrahydrofuran, diethyl ether, and dibutyl ether,
Examples of the catalyst include dichloro(2,2'-bipyridine)nickel, dichloronickel, dibromonnickel, dibromobis(triphenylphosphine)nickel, and 1,5-cyclooctadienebis(triphenylphosphine)nickel. be able to.

By doping the above-mentioned novel polymer with a dopant, the nitrogen atoms become positively charged and become stable, and the conductivity is increased. Especially when used as an electrode material, it is resistant to repeated redox reactions. It is possible to create polymeric materials that are stable and can prevent deterioration of electrode performance.

When the polymer of the present invention is used as a polymer conductive material, dopants used for doping include, for example, halogen compounds such as iodine, bromine, and bromine iodide; arsenic pentafluoride, phosphorus pentachloride,
Metal halides such as phosphorus pentafluoride, antimony pentafluoride, silicon tetrafluoride, aluminum chloride, aluminum bromide, aluminum fluoride, and ferric chloride; protonic acids such as sulfuric acid, nitric acid, and fluorosulfuric acid; sulfur trioxide , nitrogen dioxide, difluorosulfonyl peroxide; and organic substances such as tetracyanoquinodimethane and tetracyanoethylene. When used as an electrode material, for example, lithium perchlorate, lithium borofluoride, etc. Solutes used in organic electrolytes such as

In addition, examples of dopants to be electrochemically doped include Va, such as PF ^- ₆ , SbF ^- ₃ and ASF ^- _6.
Halide anions of group elements; a such as BF ^- ₄
Halide anions of group elements; I ^- (I ^- ₃ ), Br ^- ,
Mention may be made of halogen anions such as Cl ^- ; and anions such as perchlorate anions such as ClO ^- ₄ .

The polymers of the present invention also include those in which some of the hydrogen atoms in the terminal groups are replaced with halogens. This is the above
In formula (3), for example, some of the bromine that did not participate in the reaction of 4,4',4''-tribromotriphenylamine may remain as it is. In this way, some of the bromine may be replaced by hydrogen. Structures such as these are also included in the present invention.

Next, the present invention will be explained with reference to examples.

Example 1 0.8 g (0.02 gram atomic weight) of potassium metal, 0.95 g (0.01 mol) of magnesium chloride, and 50 ml of tetrahydrofuran were heated to reflux and reacted in a 100 ml flask with stirring under a nitrogen atmosphere. Approximately 1
After a period of time, a black powder was produced, confirming the production of metallic magnesium.

Next, 3.2 g (0.067 mol) of 4,4',4''-tribromotriphenylamine was added to this reaction product, and the mixture was heated to reflux with stirring. After about 1 hour,
It was confirmed that metallic magnesium was completely consumed.

Next, 10 mg of dichlorobis(2,2'-bipyridine)nickel was added to this reaction product as a catalyst,
The polymerization reaction started smoothly by stirring and heating under reflux, and a yellowish brown polymer was precipitated. The polymerization reaction was carried out for about 2 hours, and the resulting precipitate was poured into hydrochloric acid-acidic ethanol, stirred for 1 hour, and then filtered. After thoroughly washing with ethanol on the filter, it was extracted with hot ethanol for 12 hours using a Soxhlet extractor to remove impurities, and the desired polymer poly(4,4′,4″-trifluoride) was obtained, yielding 1.9 g after drying. enylamine) was obtained.

The thus obtained polymer was a yellow powder and remained extremely stable without any change even after being left in the air for two months. Additionally, this polymer was subjected to thermogravimetric analysis, and the results are shown in Figures 1 and 2.
From these figures, it can be seen that the polymer has extremely high thermal stability without losing weight up to 300°C, and shows approximately 70% residual weight even at a high temperature of 700°C in a nitrogen atmosphere.

Further, the obtained polymer was subjected to infrared spectrum analysis, and the measured infrared absorption spectrum is shown in FIG. From this figure 3, 1270cm ^-1 and 1310cm
^-1 , with strong peaks based on the triphenylamine structure at 1480 cm ^-1 and 1590 cm ^-1 , and at 820 cm ^-1
It can be seen that there is an absorption of para-substituted benzene in the vicinity. This proves that the polymer is composed of regular repeating units and has the structure of the above formula.

In addition, elemental analysis of the polymer was performed and the results are as follows: Elemental analysis values of the polymer: Carbon 71.5%, Hydrogen 4.3%, Nitrogen 4.4%, Halogen 15.7% From this analysis value, C:H:N: Br=18:12.9:095:0.59, which was close to the theoretical value C ₁₈ H ₁₂ N. The extra 0.9 for H and 0.59 for Br seem to be due to unterminated groups. The molecular weight could not be measured because the polymer of the present invention was not soluble in ordinary solvents. However, reactions of other similar substances and H and Br
Judging from the number of , it seems that 10 to 15 triphenylamines have been polymerized.

Example 2 (Measurement of electrical conductivity in the absence of air) The polymer obtained in Example 1 was compression-molded at a pressure of 8 t cm ^-2 using a tablet molding machine for infrared spectrophotometer, and then cut out. Platinum wires were attached to both ends using a conductive adhesive (trade name: ``Electrodak'', manufactured by Mattison, USA) to prepare a test piece for measuring conductivity.

The electrical conductivity of this test piece at room temperature is 1.3×
It was an insulator of 10 ^-9 S cm ^-1 . When this test piece was exposed to iodine-saturated steam at room temperature in the absence of air, it showed a value of 0.2S cm ^-1 after one day and a value of 0.8S cm after one week.
It showed a high conductivity of cm ^-1 . Also, the color changed to black.

Example 3 (Measurement of electrical conductivity in air) After measuring the electrical conductivity in Example 2, when the test piece was taken out into the air and dedoped with iodine at room temperature, immediately after taking it out into the air,
It showed an electrical conductivity of 0.8S cm ^-1 .

The conductivity decreased as iodine was desorbed, but it maintained a high conductivity of 0.2 S·cm ^-1 after one week and 0.06 S·cm ^-1 after 40 days.

Furthermore, when the test piece was doped again in the presence of air at iodine saturated vapor pressure, after 24 hours
The conductivity becomes 0.6S・cm ^-1 and 0.8S・cm after 48 hours.
The conductivity was restored to ^-1 . This shows that high conductivity is stably maintained in the air and that there is no irreversible decrease in conductivity.

Conventional conductive polymer materials, such as polyacetylene, have high conductivity, but they have had the problem of using toxic ASF ₅ as a dopant, or of being oxidized when in contact with air, resulting in a significant decrease in conductivity. Polyparaphenylene and the like also exhibit good conductivity, but they also have the problem that when exposed to the atmosphere, hydrogen is added to them by moisture in the atmosphere, resulting in a significant decrease in conductivity. Moreover,
These substances have the disadvantage that they do not easily return to their original state when oxidized or hydrogen is added to them. However, the novel polymer of the present invention exhibited good properties such as being stable in air and having high electrical conductivity.

Example 4 A very small amount of conductive adhesive (trade name "Electrodak" manufactured by Mattison, USA) was applied to the tip of the platinum wire, and a very small amount of the poly(4,
Measurement electrodes were fabricated by bonding 4′,4″-triphenylamine) polymer powder.

Next, a 1 mol/mol electrolyte was prepared using propylene carbonate as a solvent and lithium perchlorate as a solute, and a platinum wire was used as a counter electrode.
The redox potential of the measurement electrode was measured in a nitrogen atmosphere using the Ag/AgCl electrode as a reference electrode. The voltage sweep rate was 20 mV/sec. This result is the fourth
As shown in the figure. The redox potential of the polymers of the present invention is approximately
It was 0.98V.

From Figure 4, it can be seen that there is almost no change in the results even if the measurement of redox potential is repeated over 200 times, indicating that the electrode made from the polymer of the present invention is extremely stable against repeated redox reactions. .

Furthermore, a molded article formed into an arbitrary shape by pressure molding or using an adhesive using the polymer of the present invention as a main component could be used as an electrode. In this case, other than the above-mentioned adhesive, for example, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc. could be similarly used. In addition to the electrolytic solution described above, an organic electrolyte dissolved in an organic solvent such as tetrahydrofuran or γ-butyllactone as a solvent and lithium borofluoride as a solute could be used.

Example 5 After measuring in a nitrogen atmosphere in Example 4,
The redox potential was subsequently measured using the electrode taken out into the air. The voltage sweep speed is
The voltage was set to 20mV/sec. The results are shown in FIG.

In this measurement, even if oxygen and moisture dissolve in the electrolyte after being exposed to air for several hours, the 5th
As is clear from the figure, it is extremely stable against repeated redox reactions.

The polymer of the present invention has a molecular weight per repeating unit.
242, by doping with iodine, the amount of reaction per repeating unit amount becomes 200%, and the amount of electricity per g is 96500 ÷ 1 (g) / 242 / 200 = 798 [c/g], which has been well studied in the past. The amount of reaction electricity per gram was 1.8 times that of the polyacetylene electrode.

Effects of the Invention As described above, in the present invention, by obtaining a new polymer having the 4,4',4''-triphenylamine structure of the above formula as a repeating unit and a new material doped with the same, We were able to obtain an electrode material with excellent polymer conductivity that can maintain stable conductivity and whose performance does not change even after repeated oxidation-reduction.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the results of thermogravimetric analysis of the novel polymer of the present invention in air, FIG. 2 is a graph showing the results of thermogravimetric analysis of the polymer of the present invention in a nitrogen atmosphere, and FIG. FIG. 4 is a graph showing the infrared absorption spectrum of the polymer of the present invention, FIG. It is a graph showing the results of oxidation-reduction in

Claims (1)

[Claims] Primary formula: (n in the formula represents 10 to 15) 4,
The 4′,4″-triphenylamine structure is used as a repeating unit, and the oxidation potential is relative to Ag/AgCl.
A polymer characterized in that it has a voltage in the range of 0.8 to 1.1V.