JPS6058427A - Production of modified poly(alkoxyphenylene) article - Google Patents

Abstract

PURPOSE:To obtain the titled modified high polymer of any shape having improved electric electric conductivity, by reacting a molded article of a linear poly(alkoxyphenylene) based high polymer in the liquid phase containing a specific halogen compound. CONSTITUTION:(A) A molded article of a poly(alkoxyphenylene) based high polymer having substituent groups having one or more alkoxyl groups in the phenylene nucleus as repeating units and 8 or more average number of the repeating units is reacted with (B) (i) a halide of an element of Group IIIB or (ii) a halide in a high valence state of an element capable of assuming the two or more valence state other than the element of Group IIIB in the vapor phase thereof or liquid phase containing the component (B) under the conditions of retained shape of the molded article to crosslink the high polymer in the component (A) in or between the molecules and afford the aimed modified article.

Description

[Detailed description of the invention] The present invention relates to a novel organic conductive material.

BACKGROUND ART In recent years, with remarkable technological development in the electrical and electronic industries, new materials with excellent electrical functions are being sought.

In the field of polymer chemistry, materials with various electrical properties have been discovered, and many polymer substances have already been put into practical use, but the search for materials with even better electrical properties is actively underway. In particular, polymeric materials with electrical conductivity can be used as materials for, for example, wiring materials, electrode materials, sensors, photoelectric conversion elements, and the development of such polymeric materials is highly anticipated.

Against the background of such social demands, research into electrically conductive polymeric materials is being conducted in various places, and many electrically conductive polymeric materials have also been developed. However, the polymer materials with high conductivity known to date are stable,
Currently, there are problems with moldability, etc., which limits its application to electrical and electronic materials.

For example, a complex of unsubstituted polyacetylene and a specific electron donor or electron acceptor is a polymeric material with extremely high electrical conductivity of 108Ω-'cIIL-' or more, and is useful as an electronics material, but A major practical drawback is that polyacetylene is unstable to oxygen in the air and heat.

Further, since high molecular weight polyacetylene is insoluble and infusible, it cannot be melt-processed or solution-processed, and it is difficult to mold it into a specific shape.

On the other hand, BoIJ (p-phenylene), in contrast to polyacetylene, is a polymeric material with very high thermal and oxidative stability, and can be further doped with an electron donor or an electron acceptor. It is possible to obtain electrical conductivity close to that of polyacetylene. However, like polyacetylene, unsubstituted poly(p-phenylene) is insoluble and infusible and difficult to mold.

In order to improve such moldability, polyacetylenes with substituents introduced have also been studied.

For example, Polymer Publications I Vol 11 (
10) As described in P. 819, substituted polyacetylene synthesized by polymerizing substituted acetylenes such as phenylacetylene and butylacetylene is soluble in organic solvents and can be formed into a film by the cast method.

However, although the moldability of these substituted polyacetylenes was significantly improved, the conductivity was only i/10" to 1/109 of that of unsubstituted polyacetylene.

Based on this background, the present inventors conducted intensive research in order to find a conductive polymer material with excellent moldability. The modified polymer material produced by reaction treatment with a compound under liquid phase reaction conditions has high conductivity, and the selection of substituted polyphenylene as a raw material makes it possible to use solvent casting and melt molding. Because molding can be done by appropriate means such as the law,
By subjecting the substituted polyphenylene that has been previously molded into a membrane, film, etc. to the reaction treatment under conditions that substantially maintain the shape of the molded product, a modified polymeric substance of any shape can be obtained. To summarize the present invention, which was discovered and completed, the present invention is based on a process in which a substituted polyphenylene having at least one alkoxy group in the phenylene nucleus is reacted with a specific halide in a liquid phase.
The present invention relates to a method for producing a modified polymeric substance, characterized in that the production is carried out under conditions in which the shape of the molded product is substantially maintained.

The substituted polyphenylene/ used in the present invention is a substantially linear poly(alkoxy phenylene)-based polymer compound. Here, the average repeating unit is 8 or more, for example, the weight average measured by dissolving the polymer in tetrahydrofuran (hereinafter abbreviated as THF) and using gel permeation chromatography (hereinafter abbreviated as GPC) with respect to polystyrene. Molecular weight (eel)
Judging from this, it means that the repeating unit is 8 or more.

As a reference, when looking at the intrinsic viscosity, the intrinsic viscosity in sulfuric acid is approximately 0.02 or more, and the measured values are also listed as reference data in the Examples below.

The alkoxy group in this substituted polyphenylene is a general term for a functional group represented by the general formula -〇-R, and when this R is an alkyl group in general, it may be long chain, cyclic, or branched. It may also be an alkyl group containing oxygen, an aromatic ring, a heterocycle, or other groups. As the number of carbon atoms in this alkoxy group increases, the moldability of the modified product of the present invention improves, but the conductivity decreases, so the number of carbon atoms is selected depending on the purpose.

When both electrical conductivity and moldability are important, a carbon number of 1 to 8 is appropriate.

There may be one alkoxy group per phenylene nucleus,
Even more than that is a good fish. When there are two or more alkoxy groups, the alkoxy groups may be the same or different, and can be selected depending on the purpose.

Even if the phenylene nucleus is a group other than an alkoxy group,
As long as it is an electron-donating group, other substituents such as an alkyl group may be present (such groups are also simply referred to as substituted polyphenylene).

As methods for producing the substituted polyphenylene used in the present invention, there are known methods such as a method of polymerizing alkoxybenzenes in the presence of a Lewis acid and an oxidizing agent, and a method of polymerizing dihaloalkoxybenzenes in the presence of magnesium, copper, etc. All methods for producing polyphenylene are applicable.

Those synthesized by a method of polymerizing alkoxybenzenes in an inert solvent in the presence of a Lewis acid and an oxidizing agent generally give a high degree of polymerization. In the present invention, the average number of repeats of substituted phenylene groups is 8 or more. The Lewis acids used include anhydrous aluminum chloride, anhydrous ferric chloride, anhydrous titanium chloride (CM), anhydrous stannic chloride, anhydrous molybdenum chloride, anhydrous chloride/gesten, anhydrous antimony (v) chloride, boron fluoride, and Boron fluoride etherate and the like are used, but anhydrous aluminum chloride and anhydrous ferric chloride are particularly preferred, and halides such as -i and metal bromides corresponding to the metal chlorides are also effective.

The inert solvent is one used in ordinary Friedel-Crafts reactions, and any organic solvent inert to the Lewis acid aryl cation can be used, but nitroalka/s are particularly preferred.

The polymerization reaction can be carried out under normal pressure, increased pressure, or reduced pressure, but the pressure is 10 to 40°C to remove the generated hydrogen chloride.
A polymer with excellent heat resistance, moldability, etc. can be obtained by applying a reduced pressure such as mHl.

In addition to the oxidative cationic polymerization method using Lewis acids and oxidizing agents,
A method in which a J dihalogen compound is polymerized via a Grignard intermediate, followed by a carbon-carbon coupling reaction can also be applied.

In this case, for example, dihaloalkoxybenzenes are used as raw materials (here, a suitable halogen is chlorine or bromine).
The raw material halide can be converted into the corresponding Grignard reagent by reacting it with metallic magnesium in the presence of a solvent such as an anhydrous alkyl ether or tetrahydrofuran in a nitrogen stream as an inert gas stream. The generated Grignard reagent uses salts or complexes of first transition metals such as nickel, palladium, and chromium iron as catalysts to eliminate magnesium halides from the Grignard layer portion and halogen portion, thereby forming carbon-carbon bonds. By continuously carrying out this reaction, the desired substituted polyphenylene can be produced. Catalysts that promote this deno-logogenation of magnesium include halides such as nickel, iron chromium, and palladium, anhydrides of salts such as acetates, sulfates, and nitrates, or divalent and zero-valent complexes of nickel and palladium. is exemplified.

The present invention relates to a method for producing a modified poly(alkoxyphenylene), which comprises reacting the substituted polyphenylene with a specific compound in a liquid phase.

The specific halides used herein refer to halides of DIB group elements or high-valent halides of elements other than IFB group elements that have two or more valence states. Typical applicable halides of Group IIB elements include BF3. B.C.J.
, AIcI3. GaCA! 3 and their ether complexes. Typical examples of high-valent halides include SnF, , 8nC4, halides of group B elements, PCI, , AsF, , SbF5.5b
Norohide of group VB elements such as C1, SF
6. halides of group VIB elements such as TeCl4,
TiCl2, VO(J3-FeC1l3, CuCl2
+MoCl1! I, HgCjl! There are transition metals such as 2/'% halides. Among these, high-valent halogenides have higher reactivity than halogenides of mB group elements. Based on this, the present invention can be applied to high-valent halogenides with oxidizing power. It is believed that a chemical reaction between a halogenide and a substituted polyphenylene chemically activated (by an alkoxy group) is mainly utilized. Therefore, it cannot be said that the reason why 7-halides of TffB group elements are effective is not necessarily clear, but low-valent halogenides that do not have oxidizing power, such as AgC6, Hgt C12
, CaC4, etc. are not effective.

Poly(alkoxyphenylene) produced by the method of the present invention
Modified polyphenylene generally has lower molding processability than substituted polyphenylene before modification, so in order to obtain a modified polyphenylene in the desired molded state, it is necessary to use substituted polyphenylene that has been molded in advance into the desired molded state, such as a thin film or porous film. It is necessary to use a polyphenylene molding. Therefore, the reaction treatment must be carried out under reaction conditions that substantially maintain the shape of the substituted polyphenylene and its modified product. These conditions include: reaction solvent chloride, solvent a), halide concentration,
It can be set by selecting the reaction temperature and the like.゛The selection of these conditions is determined by the solubility of the substituted polyphenylene. For example, when using a substituted polyphenylene having two butoxy groups in the phenylene nucleus, the substituted polyphenylene is easily soluble in toluene, acetone, tetrahydrofuran, etc. Solvents that do not dissolve
For example, the reaction may be carried out in n-hexane or acetonitrile.

Similarly, when reacting in a liquid phase containing only a halide without using a solvent, the substituted polyphenylene may be immersed in the liquid halide as long as this condition is satisfied. Furthermore, when a solvent is used, it is preferable that the solvent be compatible with the substituted polyphenylene to the extent that it does not dissolve it, rather than one that is not compatible with the substituted polyphenylene at all, when the reaction needs to proceed to the inside of the substituted polyphenylene. In this case, for example, polymer films swell.

Although dimensional changes such as shrinkage and thickness changes occur, it is sufficient for the present invention that a substantially acceptable shape is maintained, and these dimensional changes do not impede the purpose of the present invention.

The amount of reaction solvent, concentration of halide, reaction temperature, etc. can also be selected within this range, but as a general condition, the halide is phenylene of substituted polyphenylene; 1JjL0.01
~4.0 equivalents, the total weight of the reaction solvent and halide is 0.5 times or more the weight of the substituted polyphenylene, the reaction temperature is O
It is appropriate to carry out the reaction at a temperature of .degree. C. to 200.degree.

The modified product thus obtained may be subjected to drying under normal pressure or reduced pressure, reduced pressure or pressure treatment, heat treatment, stretching treatment, etc., as necessary. In particular, reduced pressure treatment and heat treatment are effective for removing residual unreacted substances, completing the reaction, etc., and if carried out under selected conditions, further improvement in conductivity can be seen.

The modified product produced by the method of the present invention is obtained by chemically reacting a substituted polyphenylene having a phenylene nucleus chemically activated by an alkoxy group with a specific halide having the above-mentioned activity. It is something. Therefore, compared to the original substituted polyphenylene, the modified polyphenylene of the present invention has a new chemical bond, a change in the chemical structure due to removal of a functional group, and a change in the steric configuration due to this. It is presumed that the substituted polyphenylene can be said to be newly crosslinked intramolecularly, intermolecularly, or both.

Therefore, the method of the present invention can be applied to conventional J, Chem, Phys,
71.

1506 (1979), which is essentially a doping technique aimed at forming a charge transfer complex with an electron-accepting or electron-donating doping agent. When a doping method is used, it is effective in improving conductivity, but on the other hand, stability, strength, durability, etc. are reduced, which poses a practical problem.

In the case of the reaction treatment using a halide of the present invention, if the reaction conditions are selected, there is also the secondary effect of improving strength, durability, etc., compared to the substituted polyphenylene before treatment, contrary to the doping method. Furthermore, the modified product of the present invention is generally stable in air, and these points are extremely advantageous when the modified product of the present invention is applied to electrical and electronic devices and electrode materials.

Although the conductivity of the modified product of the present invention varies depending on the type of the original substituted polyphenylene and the conditions of the reaction treatment, the conductivity is at least io-', and generally -1 of 10-3 to 10-1 Ω-1.
reach. Since the conductivity of the original substituted polyphenylene is generally around 1o-+4Ω-'[J7&-1, this value is extremely high for the polymer substance itself, and moreover, the conductivity of the substituted polyphenylene is extremely high when the dopant is This is a value that cannot be reached by adding it.

In this specification, electrical conductivity, which specifically indicates electrical conductivity, was measured using a four-probe method in argon as usual. The four-terminal method is shown in "Organic Semiconductor" (Kyoritsu Publishing Co., Ltd., published in 1968) Pb0 by Ime, Kabira, and Kano.

On the other hand, the modified product produced by the method of the present invention has sufficiently high conductivity by itself, but in order to further improve the conductivity, an electron-accepting dopant and an electron-donating dopant are added. Transfer complexes can also be formed.

Typical examples of applicable dopants include Group IA metals such as lithium, sodium, potassium, sodium naphthalene,
Group IA metal arylenes such as potassium naphthalene, sodium biphenyl and potassium biphenyl, electron donors such as group IA metals such as calcium, rhodanes such as iodine and bromine, HCl0. , H8O, Brønsted acid containing F, SO5 and N20. non-metallic oxides containing, 5b2s, sulfides of group elements including B, ■transition metals, IB, UIA and VA group elements 5bBr3, C
uCl2, N1CA'2 and MoC65, WCls
, VOCls, halides such as 5nC14 and F
Electron acceptors such as fluorine-containing peroxides or mixtures thereof including So, 00802F, tetrafluoroborates of silver and alkali metals, alkaline earth metals and quaternary ammonium, phosphonium hexafluoride salts, perchloric acid salt, hexa70roantimonate, hexafluoroarsenate, etc. The type of dopant selected depends on what electrical properties are desired in the resulting composition.

Electron-donating dopants such as group IA metals and group IA metal arylenes provide n-type conductive materials, and electron-accepting dopants provide p-type materials, which can be selected depending on the application and purpose.

Methods for adding the conductive dopant to the modified polymeric material of the present invention to form a charge transfer complex include, for example, adding the dopant from the gas phase, adding the dopant from the solution phase, adding it in the molten phase, or adding the dopant into a solid material. Various methods are possible, such as addition by mixing and electrochemical reaction to change the oxidation state to form a charge transfer complex with the dopant. The modified polymer material produced by reaction treatment according to the method of the present invention was further formed with a dopant to form a charge transfer complex, and the substituted polyphenylene which had not been subjected to the reaction treatment was made to form a charge transfer complex with the same dopant. A comparison shows that the conductivity is more than 100,000 times higher depending on the reaction treatment conditions and dopant selection.

By selecting the structure and number of alkoxy groups, the substituted polyphenylene used in the present invention can be formed into membranes, films, fibers, and fillers using ordinary polymer processing techniques such as solvent casting, melt molding, and pressure sintering. It can be molded into a desired shape such as a composite. Therefore, it is possible to obtain a modified product of any shape by subjecting a substituted polyphenylene that has been previously processed to a desired shape to a reaction treatment with a specific halide.

Applications of the modified product according to the present invention also include specific tangible articles or molded products made of materials having the above composition.

Therefore, n-type and p-type materials applying such compositions,
Examples include rectifying diodes and transistors, electrical conductors such as P-n junctions, semiconductor devices, solar cells, and the like. In order to obtain such various molded products, the advantage of the modified material of the present invention as a material compared to other conductive polymer materials such as polyacetylene, (SN)X, etc. is that it is possible to obtain the desired shape. This is an easy point. This is a good product for substituted polyphenylene as a raw material.

It comes from form. Furthermore, the highly electrically conductive modified product of the present invention has selective high absorption ability over a wide spectral range in the infrared region. Such materials can therefore be used as filter materials, for example infrared absorbers for solar energy.

Also, because the compositions of the invention are electrically conductive, they can be used as antistatic materials or devices, such as internal gaskets in solvent container lids.

EXAMPLES The present invention will be specifically explained in more detail with reference to Examples below.

Example 1.2 50 g of nitromethane in which 40.9 g of anhydrous ferric chloride was dissolved was placed under a reduced pressure of 20 malt DI, and 198 g of nitromethane 120+l/VC-dissolved at room temperature was heated to an internal temperature of 40 μC. Add carefully so as not to overcoat, and after finishing, add for 2 hours, 20
Stir at room temperature under a vacuum of +iHg. The reaction mixture was added to 600 d of methanol at room temperature, stirred for 1 hour, and the insoluble material was filtered. After thoroughly washing the insoluble matter repeatedly with 2N hydrochloric acid water, it was dried overnight under vacuum at 100°C.
Substituted polyphenylene was obtained at a ratio of 2.7/1 (65%).

Two films of 10 tm x 1 QOi x 20 μ were formed by casting substituted polyphenylene I from a toluene solution.
I created one. Spread each of these films over AlCl3.
8 in a 10% by weight solution of n C14 in acetonitrile at room temperature.
Soaked for an hour. After soaking for a specified time, remove from the solution.
(, 9 was dried under reduced pressure for 3 hours to obtain a black film of a modified polymer substance insoluble in toluene. Both films were stable in air, and the electrical conductivity in argon was 1.0X10'-3 or 4.2X10-"
It was Ω-'cm-1.

As a result of examining the infrared absorption spectrum of the original substituted polyphenylene, no absorption based on hydroxyl groups was observed at 320[] to 3600Cm-'. In addition, as a result of elemental analysis, the calculated value (C; 76.32%, assuming that the repeating unit of the polymer is C, H2 (QC, H,)2,
H; 9.15%) and actual value (C; 76.28%, H;
9.12%) showed good agreement, and no chlorine atom was detected. The obtained polymer was dissolved in concentrated sulfuric acid, and C(#
/100 mA') is obtained in the range of 1.0 to i, oo. . This polymer is soluble in organic solvents and was extracted into toluene using a Nuxle extractor. The results of thermogravimetric analysis (TGA) of the polymer in air showed that the 5% weight loss temperature was 320°C, and the 50% weight loss temperature was 50°C.
00"C.

In addition, when the polymer was dissolved in THFK and the molecular weight was measured using GPCK, the weight average molecular weight i (in terms of polystyrene) was determined.
MW) showed 140.000.

Example 6.4 B F, -E t20 or S on SnC4,O
By carrying out the same method as in Example 1 except for using bF, two films of a black toluene-insoluble modified polymer substance were obtained. Konofi/I and Mu are both stable in air, with electrical conductivity in argon of 1.6, 0-4 or 1.0, respectively.
It was 8×10 −1 Ω −1 bias −1.

Example 5.6 A black toluene-insoluble denatured polymer was obtained by using the same method as in Example 1 except that BBr or MoC1a was used as a substitute for SnC13 and carbon tetrachloride was used instead of acetonitrile in the case of SnC13. Two films of molecular substances were obtained. Both films are stable in air and have electrical conductivities of 2.7X10-' and 8.0X10-' in argon, respectively.
-'Ω-1 was -1.

Example 7.8 A film of substituted polyphenylene I, which was formed by a casting method from a toluene solution, was mixed with acetone/methanol (10
/90) and left overnight. By pulling it out and drying it thoroughly under reduced pressure, the surface of the film becomes
A slight whitish color and formation of pores were observed. Using these two porous films, AIC was prepared in the same manner as in Example 1.
II, or 10' of 5bC4! It was immersed in i% acetonitrile solution for 8 hours at room temperature.

After immersing for a predetermined time, take it out from the liquid and soak it for 1mmH,! After drying for 6 hours under a reduced pressure of 7°C, two black films of a modified polymer substance insoluble in toluene were obtained. This modified porous polymer film is stable in air and has an electrical conductivity of 4.8X10-3 or 1.8X10-2Ω-I in argon, respectively.
It was wet -1.

Example 9.10 1,4-dibromo-2,5-diynepropoxybenzene 7,03611 and magnesium 0.486411 are mixed in anhydrous tetrahydrofuran 25d under nitrogen atmosphere,
React under reflux. When the metallic magnesium disappears and the Grignard reagent generation is completed, add 10 Da of dichloro(2
, 2'-pyridyl)nickel(II) (NiC4(b
py); bpy=2.2'-pyridine) and reflux for 5 hours. After once cooling the reaction solution to room temperature, methanol 3
Add 0.0 g and collect the resulting precipitate by filtration. Wash by cycling with water, methanol, and 1N hydrochloric acid, and dry under vacuum. Substituted polyphenylene (2) was obtained in a yield of 1.271 (yield 33%). Substituted polyphenylene■ at 150℃
910 (7MX10eX2)
Two films of 0 μm were prepared. This film is AlC
l, or in a 10 wt% acetonitrile solution of WCJ,
The sample was immersed in a 0.05% by weight acetonitol solution at room temperature for 8 hours.

1mmH,! After vacuum drying for 1 hour under a reduced pressure of 9, two black films which were infusible even at 200° C. were obtained. The electrical conductivity of this film is 1.2X1
0-3 or 8. <SX 10-'Q-' arb-
' There was.

In addition, the original substituted polyphenylene ■ is soluble in hot THF,
Slightly soluble at room temperature. When the molecular weight of this THF solution was measured by GPCK, it was found to be 6.800.

Example 11.12 BF3-Et20 or IVIo instead of klc13
By carrying out the same method as in Example 9 except for using C15, two films which were infusible even at 200"C were obtained.The electrical conductivity of these films was 4.9XID"" or 6.5X, respectively.
1D-'Ω--Door-1.

Example 13.14 Substituted polyphenylene was synthesized in the same manner as in Example 1 except that 11.0 g of p-methoxymethylbenzene was used as a substitute for paradibutoxybenzene. The yield was 5.1
Substituted polyphenylene (49%) was obtained. Substituted polyphenylene III was press-molded at room temperature and under a pressure of 200 ky/LMl to produce disc-shaped pellets with a diameter of 13 mm and a thickness of 01 plate. This beret is kllcl, no.1
0 wt% carbon tetrachloride solution or 60 wt% of vOC13
It was immersed in an n-hexane solution at 50°C for 24 hours.

Remove the liquid from the immersion drain for a specified period of time under a vacuum of 10 mmHg at 60°C.
After drying at ℃ for 1 hour, two black disc-shaped pellets were obtained. The electrical conductivity of each is 1.6X10-' or 9.4X
10-'Ω-'fJ! -' was.

Example 15.16 Substituted polyphenylene powder was mixed with BF, 1 IEt20
It was immersed in a 0 wt% acetonitrile solution or a 50 wt% FeC4 acetonitrile solution at 50°C for 24 hours. After being immersed for a predetermined time, it was taken out from the liquid and heated at 100° C. for 3 hours to produce two types of black powder. Add each black powder to room temperature 200
By pressure forming at a pressure of kgrollf, the diameter is 1.
Two disc-shaped pellets measuring 3 m x 0.1 mm in thickness were prepared. The electrical conductivity of each is 6.2X10" or 2.2
XID-”Ω-1 bias-1.

Example 17 The film of the modified polymer material prepared in Example 1 was left at 20° C. for 6 hours in an anhydrous sulfuric acid atmosphere. (The vapor pressure of sulfuric anhydride is approximately 200 ramH1) After a predetermined period of time, the film was taken out and the electrical conductivity was measured under an argon atmosphere, and it was found to be 1.8.
It was X10-1Ω-1 bias-1.

Comparative Example The film of substituted polyphenylene (1) prepared in Example 1 was left for 3 hours at 20° C. in an anhydrous sulfuric acid atmosphere. (The vapor pressure of anhydrous sulfuric acid is about 200 m, iHg) After a predetermined time, the film was taken out and its electrical conductivity was measured in an argon atmosphere and found to be 8.2 x 10-50-1 儂-1.

Example 18 4.561 (10 mmole) of 1,4-dibromo-2,5-bis(tetrahydropyranyloxy)benzene are suspended in 50 g of anhydrous tetrahydrone and cooled to -78<0>C. After stirring well, a hexane solution (15% 62%) of n-butyllithium was slowly added to the mixture, and the temperature inside the reactor was slowly raised to 10°C over 1 hour. Subsequently, 1.90 g of anhydrous stannous chloride was added, and stirring was continued at that temperature for 1 hour to form anhydrous nickel chloride-bipyridine complex ([N1(bip)C4
)) 10 ml was added, then the temperature was raised and the reaction was carried out under reflux for 6 hours. Pour the reaction solution into 200ffl/methanol,
The resulting insoluble matter was collected by mouth filtration, washed repeatedly with methanol, water, and diluted hydrochloric acid, and then dried in vacuo to obtain 1.74 g of pale yellow substituted polyphenylene (2). (Yield 63%) This substituted polyphenylene ■ was melt-molded at 100°C, and 103X
A film-like molded product of 10CMX 10μ was obtained. This was immersed in a 10% acetonitrile solution of 5bC1 for 1 hour and then dried for 30 minutes under a reduced pressure of 1+++ mHg.
A film-like molded product which did not melt at 50°C was obtained. The electrical conductivity of this molded product in argon is 1.4X10'''3Ω-
It was -1 of 1.

When the original substituted polyunisine was dissolved in THF and the molecular weight was measured by GPC, the molecular weight was 3,800 in terms of polystyrene.

Example 19 1,4-dibromo-2,5-bis(methoxymethoxy)
3.569 (I Dm mole) of benzene is dissolved in 50 - of anhydrous tetrahydrofuran and cooled to -78<0>C. After stirring well and slowly adding a hexane solution of n-butylrhydium (15 g, 2 m),
The temperature inside the reactor is raised to D''C, and 1.8411 l of anhydrous magnesium bromide is added thereto.

Subsequently, the temperature was raised to 10 DEG C., 10 ml of anhydrous nickel chloride-bipyridine complex and 50 ml of anhydrous n-butyl ether were added, the temperature was raised, and the mixture was allowed to react under reflux for 6 hours. The reaction solution was poured into 200 d of methanol, the insoluble matter produced was collected, refluxed with methanol, water and diluted hydrochloric acid, washed, and dried under vacuum to yield substituted polyphenylene V in a yield of 1.15 g (yield 5B, 7%). Obtained. This powder was mixed with 3 F e CIs.
Immersed in 0% nitromethane and dried at 600 ky/r
When pressure molded at xl 8oC, the diameter is 13 mm and the thickness is 0.5 mm.
A disk-shaped pellet of mm was obtained. The electrical conductivity of this molded modified product in an argon atmosphere is 4.4X10-3Ω-'
It was tm-'.

In addition, when the original substituted polyphenylene V was dissolved in TI(F) and the molecular weight was measured by GPC, it was found that 6 was 4,500 in terms of polystyrene.

Example 20 4.44 g (10 mmole) of 1,4-dibromo-2,5-bis(trimethylsiloxy)benzene is dissolved in 50 WLl of anhydrous tetrahydrofuran and cooled to -78°C. After stirring well, slowly add a hexane solution of n-butylrhydium (15%, 62d), raise the temperature inside the reactor to 0°C, and add 1.43 g of anhydrous zinc chloride. . Subsequently, the temperature was raised to 10°C, 1 liter of anhydrous nickel (II) acetylacetonate (Uy) and 50 rnl of anhydrous n-butyl ether were added, and the reaction was allowed to proceed under reflux for 6 hours. After cooling, the reaction solution was poured into 200 ml of methanol.
Pour into the container and collect the formed insoluble matter by mouth. The product was washed repeatedly with cold methanol and cold water, and dried under vacuum to obtain substituted polyphenylene (yield: 1.s6 g,
yield 55%).

By using this substituted polyphenylene (■) and molding it in the same manner as in Example 18, 1ocyix 1Ωcmx
A film-like molded product having a thickness of 1 μm was prepared. Example 1
A molded modified product was obtained by carrying out a reaction treatment in the same manner as in 8. The electrical conductivity of this material was similarly measured and found to be 2.5 o-2Ω-'cyi-'.

The original substituted polyphenylene ■ was dissolved in TI (FK), and its molecular weight was measured by GPC and found to be 3,400 in terms of polystyrene.The infrared absorption spectrum of this polymer was 3,400. , 3QQ (strong and broad absorption near 7M-', 2.800Ωm'''1 and 3,0
It shows multiple sharp absorptions between -1 and 00, and it is thought that part of the citrimethylsilyl group is decomposed by washing the polymer with methanol or the like.

Agent: Patent attorney Katsutoshi Takahashi

Claims (1)

[Scope of Claims] 1. A substantially linear poly(alkoxyphenylene) in which a substituted phenylene group having at least one alkoxy group in the phenylene nucleus is used as a substantial repeating unit, and the average number of the repeating units is 8 or more. A molded product of a system polymer compound is placed in a liquid phase of a halide of an mB group element or a high valence halide of an element other than a IIIB group element that can take two or more valence states, or containing the halide. The poly(( A method for producing a modified alkoxyphenylene. 2. The manufacturing method according to claim 1, wherein the amount of the halide is 0.01 to 4.0 equivalents relative to the phenylene nucleus of the polymer compound. 5. The manufacturing method according to claim 1 or 2, wherein the reaction is carried out at a temperature of 0 to 200°C. 4 The electrical conductivity of the obtained poly(alkoxyphenylene) modified product was 1 when measured by the four-terminal method using Alnig.
0-4Ω-'1711" or more Claim 1
．． The manufacturing method according to item 2 or 3.