JPS6011528A - Substituted polyphenylenevinylene and highly electroconductive composition - Google Patents

Abstract

PURPOSE:To obtain a substituted polyphenylenevinylene which can be processed into any desired shape and give a high electric conductivity by doping, by eliminating a sulfonium salt group from a specified polymeric sulfonium salt. CONSTITUTION:Poly(nucleus-alkoxy substituted p-phenylenevinylene) is obtained by eliminating a sulfonium salt group from a polymeric sulfonium salt of the formula (wherein R is a 1-6C alkyl, R2 and R3 are each a 1-10C hydrocarbon group, X is a counter ion, n is an integer >=2, and m is 1-2). The obtained polymer can be doped with an electron acceptor or donor to acquire a markedly high electric conductivity. The polymeric sulfonium salt can be obtained by, for example, polycondensing a nucleus-alkoxy substituted p-xylylenedisulfonium salt, obtained by reacting a nucleus-alkoxy substituted p-xylene dihalide with a dialkyl sulfide, in the presence or absence of water or a water-soluble organic solvent with the aid of an alkali.

Description

Detailed Description of the Invention The present invention provides poly-nuclear alkoxy-substituted p-phenylene vinylene and poly-nuclear alkoxy-substituted p-phenylene vinylene and electron acceptors or electron donors ( The present invention relates to a highly conductive composition containing a dopant (hereinafter referred to as a dopant) as an essential component.

In general, conjugated polymers are insulators or semiconductors as they are, and high conductivity cannot be obtained.However, in recent years, starting from the discovery that doping polyacetylene to develop metal conductivity, various conjugated polymers have been developed. By doping a polymer compound with an appropriate electron acceptor or electron donor,
Attempts have been made to improve conductivity. However, many of these conjugated polymers are generally infusible and insoluble as they are, making them difficult to mold and process, which poses a major obstacle to their practical application.

Polynuclear alkoxy-substituted -p-phenylenevinylene is known as a linear conjugated polymer, and its production method involves the reaction of a disulnium salt with a dialdehyde.
It is known that it can be synthesized by a reaction method or a dehydrohalogenation method using an alkali of a nuclear alkoxy-substituted xylylene civalide.

However, it is virtually impossible to imagine that any of the polymers obtained by these synthesis methods would have a degree of polymerization of less than 10, and even if special powder compaction methods were used, no useful molded products could be obtained. .

The present inventors have intensively investigated the possibility of obtaining a conjugated polymer that can be processed into any desired shape and that can be doped to provide high conductivity. The inventors have discovered that this object can be achieved by the following methods, and have arrived at the present invention.

That is, we have determined that polynuclear alkoxy substituted -p
- As a result of examining various production methods for obtaining phenylene vinylene, a polymer sulfonium salt was produced by condensation polymerization of a disulfonium salt of a nuclear alkoxy-substituted -p-xylylene civalide using an alkali, and this polymer intermediate We have found a method for producing polynuclear alkoxy-substituted -p-phenylenevinylene by shaping the product and then treating it with a desulfonium salt.

Furthermore, the polynuclear alkoxy i-substituted-p-phenylene vinylene produced in this way can be produced with a much higher molecular weight than those produced by the Wittig method or the dehydrohalogenation method. It has also been found that by doping it, significantly high conductivity can be imparted.

The fact that a polyphenylene vinylene structure can be created by the sulfonium salt decomposition method is reported in J. PolymerS.
, A-1, 6, 1058 (1968), etc., but there is no information regarding polynuclear alkoxy-substituted p-phenylenevinylene in which the phenyl group contains an alkoxy substituent, its production method, and its conductivity. It wasn't known.

That is, the present invention has the general formula (I) (5) R: an alkyl group having 1 to 6 carbon atoms Rz, Ra: a hydrocarbon group having 1 to 10 carbon atoms X: counter ion n: an integer of 2 or more mal~2 It is an object of the present invention to provide a highly conductive composition containing as essential components a polynuclear alkoxy-substituted p-phenylene vinylene obtained by desulfonium salt treatment of a polymeric sulfonium salt having the present invention and a dopant.

One OR in the general formula (Il) indicates that the benzene nucleus is substituted with an alkoxy group.

Examples of alkoxy groups include hydrocarbon groups having 1 to 6 carbon atoms, such as alkyl groups such as methyl, ethyl, isopropyl, 1-butyl, cyclopentyl, and 2-ethyl-hexyl groups, phenyl groups, and derivatives thereof, but methyl basis,
An ethyl group, (6) particularly a methyl group is preferred.

R2 and R3 are hydrocarbon groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, 2-
ethylhexyl, dodecyl, octadecyl, phenyl,
Examples include cyclohexyl and benzyl groups, but hydrocarbon groups having 1 to 6 carbon atoms, particularly methyl and ethyl groups, are preferred.

Any counter ion of the sulfonium salt or a conventional method can be used. For example, halogen, hydroxyl group, 4
Obtained by boron fluoride, perchlorate ion method, but for example, nuclear alkoxy! A nuclear alkoxy-substituted -p-xylylene disulfonium salt obtained by the reaction of a substituted-p-xylylene civalide and a dialkyl sulfide is prepared alone in water or a water-soluble organic solvent such as a mixed solvent of alcohols, It can be obtained by condensation polymerization using an alkali. In addition, by making another type of p-xylylene disulfonium salt coexist and similarly performing condensation copolymerization with alkali, phenylene vinylene substituted with nuclear alkoxy can be prepared.

(-, 1:"!-:=+,.

The title of the book refers to polymeric sulfonium salts containing structural units.

The alkaline solution used for condensation polymerization can be water or an organic solvent that does not react with the sulfonium salt, such as rHl 1 or more: fat (OH type) in a mixed solvent of alcohols and water, but sodium hydroxide can be used. Potassium hydroxide, and strongly basic ion exchange resins can be suitably used. In order to obtain a highly conductive molded product, it is preferable that the molecular weight is sufficiently large, and n is at least 2 or more, preferably 5 to 5.
For example, those having a molecular weight of 8,500 and which cannot be dialyzed by a dialysis membrane with a molecular weight fraction of 8,500 are effectively used.

It is possible.

The sulfonium salt used in the present invention is sensitive to heat, light, ultraviolet rays, strong basic conditions, etc., and desulfonium salts gradually occur and tend to become polymeric sulfonium salts with a partially conjugated structure, which may result in heterogeneity. be. Therefore, at relatively low temperatures, i.e. at least 650 CJu, especially at 25
It is preferable to process quickly at a temperature of 1° C. or lower and to use a homogeneous polymeric sulfonium salt during processing.

Any method can be used to obtain a polymer molded article from a polymer sulfonium salt. Regarding the form, 2 is, for example, a film, a thread, a coated material, and 9) is a method of casting or solution spinning from a solution in another medium. At this time, it is preferable to use a polymer sulfonium salt solution that has been desalted or unreacted substances removed by dialysis treatment or the like.

The desulfonium salt treatment of the sulfonium salt can be carried out by applying conditions such as heat, light, ultraviolet rays, strong base treatment, etc., but heat treatment is preferable. In order to obtain a highly conductive composition, it is essential to carry out the desulfonium salt treatment of the polymeric sulfonium salt in an inert atmosphere. The inert atmosphere here refers to an atmosphere that does not cause deterioration of the polymer film during processing, and in particular it is necessary to prevent oxidation reactions due to oxygen and air.

This is generally carried out using an inert gas such as nitrogen, argon, helium, etc., but it may also be carried out under vacuum or in an inert medium.

(10) is suitable at 50°C to 250°C. More preferably, it can be carried out before or simultaneously with the lamb salt treatment. Orientation can be achieved by devising a molding method, such as extrusion using high shear force, but high orientation can be imparted by stretching a molded product made from a sulfonium salt solution.

This stretching orientation is an extremely important operation in order to obtain high conductivity.

Next, a highly conductive conjugated polymer composition comprising a polymer obtained by the desulfonium salt treatment of the present invention and an electron acceptor or electron donor that provides conductivity will be described. As the electron acceptor or electron donor, conventional conductive polymer compounds such as polyacetylene doped or compounds that have been found to have an effect of improving conductivity by forming an intercalation compound of graphite can be effectively used. used.

Doping by methods such as oxidation, iodine chloride, iodine trichloride, iodine bromide, iodine pentafluoride Lewis acids: phosphorus pentafluoride, arsenic pentafluoride, antimony pentafluoride, fluoride trifluoride 1. Trichloride, boron trichloride, boron tribromide, sulfur trioxide Protonic acids: hydrogen fluoride, hydrogen chloride, nitric acid, sulfuric acid, perchloric acid, fluorosulfonic acid, chlorinated sulfonic acid, metallesulfonic acid trifluoride Transition metal chloride Materials: Titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, niobium pentachloride, tantalum pentachloride, molybdenum pentachloride, macrotungsten chloride, iron trichloride Organic compounds: tetracyanoethylene, tetracyanoquinodimethane, chloranil, Dichlorodicyanobenzoquinone electron donors can be arbitrarily changed depending on the reagent concentration, etc. Ru.

~0.8 mol, and if the number of moles is small, high conductivity will not be achieved, and if the number of moles is large, the electric conductivity tends to be saturated, which is not economical. Among these doping agents, dopants that do not react with the conjugated bond formed and the dialkoxy substituent are preferred because they provide a highly conductive composition. Particularly effective doping agents include anhydrous or fuming sulfuric acid and iodine.

In the composition of the present invention, when iodine is used as a dopant having a particularly weak oxidizing power, it is possible to achieve a ratio of 1008/C11 or more.

What should be noted here is that the polynuclear alkoxy-substituted -p-phenylenevinylene obtained in this way or the co-association body mainly composed of this structural unit has do, p,
Burning, more substituents. Furthermore, the polynuclear alkoxy-substituted p-phenylene vinylene obtained in the present invention has surprisingly good oxidation stability and is extremely preferred as a conductive material.

The composition of the doping agent and conjugated polymer according to the present invention can be applied to various electrical and electronic materials utilizing conductivity, and its uses are not particularly limited.

The present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 - 8.6 p of 2.5-dimethoxy-P-xylylene (dimethylsulfonium bromide) was added dropwise to a specified NaOH aqueous solution 50°C over 15 minutes at 0 to 5°C, and after the dropwise addition Stirring was continued for 30 minutes at ~5°C. 0.7 after reaction
It was neutralized using a 7N HBr aqueous solution, and 0.77N HBr was further added to the amount equivalent to NaOH.

This reaction solution was filtered through a dialysis membrane (Cellotube, molecular weight fraction 80).
Dialysis treatment was performed using 00) for one day.

This liquid was cast and dried under reduced pressure at 40℃ or less to a thickness of 3.
A polymeric sulfonium salt film having a pale red sulfonium salt of μ in the side chain was obtained.

This film (length: 5 Cl, width: 30 I) was heated in a horizontal tube furnace at 200°C for 80 minutes in a nitrogen atmosphere to form a poly-2,5-dimethoxyphenylene vinyl film. When doping was performed as an electron acceptor compound, 1.
It showed an electrical conductivity of 55 s/-. (Measurement of electrical conductivity i was carried out using a four-probe method.) After doping, the electrical conductivity of the material left in the air for 4 days was 11 S/scratch.

When doping was performed, the conductivity was 10.88/m.

・(Example 8 The film obtained by heating at 200°C for 30 minutes was electrolytically doped using a 0.5 N LiClO4-propylene carbonate solution as the electrolyte. The resulting film became glossy black and had a high conductivity. is 5887a
(17) After dissolving 1.5 g of ethylsulfonium bromide in 50% of a mixed solvent of distilled water and ethanol (weight ratio 1:2), it is cooled to 0°C.

Next, a strongly basic ion exchange resin (Am
berlite IRA-401) was gradually added over 10 minutes and stirring was continued for 100 minutes at 0 to 5°C.

After the reaction, the ion exchange resin was removed by filtration, and then the filtrate was subjected to dialysis treatment at θ°C to 5°C using a dialysis membrane (Cellotube molecular weight fraction 8500). This liquid was cast and dried under reduced pressure at 80°C for 24 hours.

The obtained polymer sulfonium salt film was heated under nitrogen flow.
A stretched poly-2,5-jetoxy-p-phenylene vinylene film was synthesized by heating and stretching the film to 200° C. and stretching the film twice.

Next, doping with iodine was carried out using a conventional method (18).The conductive dust was measured to be 718 for the 2x stretched film.
/cs.

(19 completed) 206-

Claims (2)

[Claims] (1) General formula IIL: Alkyl group having 1 to 6 carbon atoms Rz, Ra: Hydrocarbon group having 1 to 10 carbon atoms Polynuclear alkoxy-substituted -p-phenylenevinylene obtained by carrying out a desulfonium salt treatment. (2) General formula: Alkyl group having 1 to 6 carbon atoms Rz, Ra: Hydrocarbon group having 1 to 10 carbon atoms A highly conductive composition containing as essential components a polynuclear alkoxy-substituted p-phenylene vinylene obtained by a polynuclear alkoxy salt treatment obtained by a desulfonium salt treatment, a polynuclear alkoxysubstituted p-phenylene vinylene, and a dopant.