JPS60212421A - Copolymer having structural unit of triphenylamine - Google Patents

Abstract

PURPOSE:The titled copolymer that has alternated bonds of 4,4',4''-triphenylamine and benzene represented by specific formulas as recurring units, thus being suitably used as a high-polymeric electroconductive material and electrode material, because it maintains high electroconductivity and causes no changes in performances. CONSTITUTION:Metallic potassium and magnesium chloride are added to a solvent such as tetrahydrofuran) and allowed to react with each other in a nitrogen atmosphere for about 1hr to form a black powder of metallic magnesium. The reaction product is combined with 4,4',4''-tribromotriphenylamine and they are refluxed with heat. After the metallic magnesium is consumed out, the reaction product is combined with 4,4'-dibromobenzene and they are refluxed with heat. Then, a catalyst such as dichlorobis(2,2'-bipyridine)nickel is added to effect polymerization to obtain the objective copolymer having, as recurring units, the alternate bonds of compounds of formula I and II. EFFECT:The product is excellent in thermal stability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a copolymer having a 4,4',4'-triphenylamine structural unit.

・Disclosure of the invention Focusing on the conventional problems as mentioned above, the present invention was obtained as a result of numerous studies, confirming that triphenylamine forms a stable complex with an electron acceptor. Excellent as polymeric conductive material and t1# material 4,
It is a novel copolymer having a 4',4'-triphenylamine structural unit. Furthermore, by doping this copolymer with an electron acceptor, the conductivity can be further enhanced and stably maintained. It is a polymer compound having repeating units consisting of alternating bonds with benzene structural units.

The copolymer of the present invention having the above-mentioned structural unit is a novel polymer compound not previously known, and can be prepared by a generally known reaction, for example, by the chemical reaction formula shown below.

The above reaction formula (1) is a reaction generally known for producing active magnesium, and the above reaction formulas (2) and (8) can be carried out by a polymerization reaction using the Grignard test as an intermediate method (Yamamoto Mr. Bull+Oh
em, Soc, Japan J 51, 2091 (
19781, and Special Publication No. 58-461168)
. These reactions are known as polymerization reactions that form bonds at halogen substitution positions.

One of the monomers used to obtain the novel copolymers of the present invention may be, for example, 4.4',4'-)lipmotriphenylamine, 4.4',4'-)lichloro/liphenylamine, Examples of the other monomer include 4,4',4'-trihalogentriphenylamine such as 4,4'-dibromobenzene, 4,4'-dibromobenzene,
, 4,4'-dihalogenobenzene such as 4'-dichlorobenzene.

Examples of the solvent used in the above reaction include ether solvents such as tetrahydrofuran, diethyl ether, and dibutyl ether, and examples of the catalyst include dichloro+2,2'-bipyridine]nickel, dictffpnickel, and dibromonickel. , Jibshi Mobis (
Examples include triphenylphosphine)nickel, 1,5-cyclooctadienebis(triphenylphosphine)nickel, and the like.

By doping the above-mentioned novel copolymer with a dopant, the nitrogen atoms become positively charged and become stable, and the conductivity increases, especially 1! When used as an electrode material, a polymer material can be made that is stable against repeated redox reactions and can prevent deterioration in electrode performance.

Examples of dopants used for doping when the copolymer of the present invention is used as a polymer conductive material include halogen compounds such as iodine, bromine, and bromine iodide;
Arsenic pentafluoride, phosphorus pentafluoride.

Metal halides such as phosphorus pentafluoride, antimony pentafluoride, silicon tetrafluoride, aluminum chloride, aluminum bromide, aluminum fluoride, ferric chloride, 5-sulfuric acid, nitric acid,
Examples include protic acids such as fluorosulfuric acid; oxidizing agents such as sulfur nitride, nitrogen dioxide, difluorosulfonyl peroxide; and organic substances such as tetracyanoquinodimethane and tetracyanoethylene. , for example, oversalt! El! Examples include substances that serve as solutes in bound electrolytes, such as lithium and lithium borofluoride.

In addition, as a dopant to be electrochemically doped, for example, a halide anion of a ttla group element' I-(Ii
l e Br-.

Kihalogen anions such as at-); and anions such as perchlorate anions such as ato4 can be mentioned.

The copolymers of the present invention also include those in which some of the hydrogen atoms in the terminal groups are replaced with halogens. This is because in the above-mentioned formula (8), for example, a part of bromine that did not participate in the reaction of 4,4',4'-)rib pmotriphenylamine may remain as it is.

Structures in which halogen is partially substituted with hydrogen are also included in the present invention.

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

Example 1 Metallic potassium 0.8 g (0.0g gram atomic weight), magnesium chloride 0.959 (0.01 mol), and tetrahydrofuran 501a/ were reacted by heating to reflux with stirring under a nitrogen atmosphere in a 1001 volume flask. After about 1 hour, black powder was produced, confirming the production of metallic magnesium.

Next, 1.69 (0,088 mol) of 4.4'',4'-cribromotriphenylamine was added to this product, and the mixture was heated to reflux with stirring.◇After about 1 hour, the metallic magnesium was almost consumed. 〇Next, 1.4'-dibromobenzene was added to this reaction product.
8 mol (o, o Is mol) was added and the mixture was heated to reflux with stirring. Next, dichlorohis (2
, 2'-bipyridine) nickel 10■ (0,08mi!J
The polymerization reaction was started smoothly by heating and refluxing with stirring, and a yellow-brown polymer was precipitated.

This bundling reaction 'f: was carried out for 2 hours, and the resulting precipitate was poured into hydrochloric acid acidic ethanol, stirred for about 1 hour, and then separated. The precipitate was thoroughly washed with ethanol on the filter, and then extracted with hot ethanol using a Soxhlet extractor for 12 hours to remove impurities and obtain the desired copolymer with a yield of 1.4 g after drying. The copolymer thus obtained was a yellow powder, and was extremely stable with no change observed even after being left in the air for 2 tons. We also conducted thermogravimetric analysis of this copolymer,
The results are shown in Figures 1 and 2. From these figures, it can be seen that the copolymer does not lose weight up to 800''C, has very high thermal stability, and shows 80% residual weight even at high temperatures of 700°C in a nitrogen atmosphere.

In addition, the obtained polymer was subjected to infrared spectrum analysis, and the measured infrared absorption spectrum is shown in FIG. This sv! 1270 crA-” from J.

1810 cm, 1480 am and 159G
It can be seen that CI11-1□ has a strong peak based on the triphenylamine structure and also has an absorption of rose-substituted benzene around 820 cm-''. This indicates that the copolymer is composed of regular repeating units. , which proves that it has the structure of Formula 1 above.

In addition, the obtained copolymer was subjected to elemental atmosphere analysis, and the results are shown below: Source analysis values: Carbon 75.7% Hydrogen 4.8% Nitrogen 8.1% Halogen 7.2% This analysis value From 0:H:N:Br -97: 20.1 + 0.9
6 = 0.88, which was a value close to the theoretical value of 01H18N. extra 2.1 for H, 0.8 for halogen
8 seems to be for the terminal group. The molecular weight could not be measured because the copolymer of the present invention was not soluble in ordinary solvents. However, judging from the reaction of other similar substances and the number of H and halogens, triphenylamine is 10-15
It seems that it is polymerized.

Example 2 (Measurement of electrical conductivity in the absence of air) The copolymer obtained in Example 1 was compression-molded at a pressure of 8 t-cm using a tablet molding machine for infrared spectrophotometer and cut out. , conductive adhesive (product name: ``Elect0 Duck J'') on both ends.
A platinum wire was attached using a wire (manufactured by Mattison, USA) to prepare a test piece for measuring conductivity.

The electrical conductivity of this test piece at room temperature is 7.8 x 10-
x.

It was a B-crm insulator. When this test piece was exposed to iodine-saturated vapor at room temperature in the absence of air, 1
0.028mcm after 1 day, 0.048<m after 3 days
The lightning was so high that it showed good conductivity. Also, the color changes to black,
5. 'Example 8C Measurement of electrical conductivity in air) After measuring the electrical conductivity in Example S, when this test piece was taken out into the air and subjected to fatigue doping with iodine at room temperature, immediately after it was taken out into the air, it became 0. 048-Cm
It showed a conductivity of . As iodine is desorbed, the conductivity decreases, but after one week it reaches 0.08 Ill cm, 4
After 2008, it maintained good electrical conductivity.

Furthermore, when the test piece was doped again in the presence of air at iodine saturated vapor pressure, the rWIe at 24 hours was 0,88-
The conductivity recovered to 0.41 cm-1 after 48 hours.
It recovered to 3-cs+-1. This indicates that high conductivity is stably maintained in air and that irreversible conductivity decrease does not occur.

Polyacetylene is a conventional polymeric conductive material with high conductivity, but it uses toxic ASF as a dopant, or oxidizes when it comes into contact with air, resulting in a significant decrease in conductivity and then returning to its original state. The problem was that it could not be done. Polyparaphenylene and the like also show good conductivity, but when exposed to the atmosphere, the moisture in the atmosphere creates a water field, reducing the conductivity, and furthermore, there is the problem that it cannot be restored to its original state. However, it was difficult to handle. However, the novel copolymer of the present invention exhibited good properties such as stability in air and high torpor conductivity.

Example 4 A trace amount of conductive monovalent adhesive (trade name "Electrodac" manufactured by Mattison, USA) was applied to the tip of the platinum wire, and a very small amount of the copolymer powder obtained in Example 1 was adhered. We manufactured measurement electrodes.

Next, an electrolytic solution of 1 mol/l was prepared using bicine carbonate as a solvent and lithium perchlorate as a solute, and a platinum wire was used as a counter electrode, and the Ag/Ago/electrode was used as a reference for the above measurement [l]. The redox potential of # was measured in a nitrogen atmosphere. The voltage sweep rate was BOmV/sec.

The results are shown in FIG.

The redox potential of the above copolymer of the present invention was about 0.97V.

From FIG. 4, even if the measurement of redox potential was repeated more than 200 times, there was almost no change in the results, and 1! It can be seen that the electrode is extremely stable against repeated redox reactions.

Furthermore, a molded article formed into an arbitrary shape by pressure molding or using an adhesive containing the copolymer of the present invention as a main component could be used as an electrode. In this case, in addition to the above-mentioned adhesive, for example, Polyethylene fluoride, 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 r-butyl lactone as a solvent and lithium fluoroborate as a solute could be used.

- Example 5 After the measurement in the nitrogen atmosphere in Example 4, the oxidation-reduction potential was subsequently measured using the electrode taken out into the air. The voltage sweep rate was 20 mV/sec. The results are shown in FIG.

In this measurement, it can be seen that even if the electrolyte is not exposed to air for several hours and oxygen and moisture are dissolved in the electrolyte, it is extremely stable against repeated redox reactions, as is clear from FIG.

The novel copolymer of the present invention has a molecular cap of 866 per repeating unit of triphenylamine and benzene, and the reaction amount per repeating unit is 200% due to iodine doping.
The amount of electricity per Q is 00. The polyacetylene electrode, which has not undergone much research so far, has a molecular weight per repeating unit of 18, and the amount of reaction per repeating unit is less than 6% (if it exceeds 6%, side reactions may occur). Therefore, the copolymer of the present invention has a polyacetylene electrode of 1.06.
It shows good performance of twice as much.

Effects of the Invention As mentioned above, in the present invention, 4, 4 of the formula I
', 4'-) By obtaining a new copolymer having a liphenylamine structural unit and a new material doped with it, it is possible to maintain high conductivity in a stable state, and the performance does not change even after repeated oxidation-reduction. Excellent polymer conductivity and 1. I was able to obtain the bar material.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the results of thermogravimetric analysis of the novel copolymer of the present invention in air; FIG. 2 is a graph showing the results of thermogravimetric analysis of the copolymer of the present invention in a nitrogen atmosphere; Figure 8 is a graph showing the infrared absorption spectrum of the copolymer of the present invention, Figure 4 is a graph showing the redox results of the copolymer of the present invention in a nitrogen atmosphere, and Figure 5 is a graph showing the results of the present invention. 1 is a graph showing the results of acid reduction of the copolymer of the invention in air. Patent applicant: Nissan Motor Co., Ltd.

Claims (1)

[Claims] A copolymer having, as a repeating unit, alternating bonds between 4,4',4'-)liphenylamine Ill structural units represented by the following formula and benzene structural units represented by the following formula (■): Combined.