JPH0363970B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel organic conductive material. BACKGROUND ART In recent years, with the remarkable technological development in the electrical and electronic industries, there is a demand for new materials with excellent electrical functions. Materials with various electrical properties have also been discovered in the field of polymer chemistry.
Many polymer materials have already been put into practical use, but
The search for materials with even better electrical properties is actively underway. In particular, polymeric materials having 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 on polymeric materials with electrical conductivity is being conducted in various places.
Many polymeric materials with electrical conductivity have also been developed. However, currently known polymeric materials with high conductivity have problems with stability, moldability, etc., and their application to electrical and electronic materials is currently limited. 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 10 ³ Ω ^-1 cm ^-1 or more, and is useful as an electronics material. A major practical drawback is that the polyacetylene of the matrix is unstable to air oxygen and heat. Furthermore, since high molecular weight polyacetylene is insoluble and infusible, melt processing or solution processing is impossible, and it is difficult to mold it into a specific shape. On the other hand, poly(p-phenylene), in contrast to polyacetylene, is a polymeric material with very high thermal stability and oxidative stability. It is possible to obtain electrical conductivity close to . 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, as described in Polymer Journal Vol. 11 (10) P819, substituted polyacetylenes synthesized by polymerizing substituted acetylenes such as phenylacetylene and butylacetylene are soluble in organic solvents and can be formed into films by the casting method. . However, although the moldability of substituted polyacetylene was significantly improved, the conductivity was only 1/10 ¹¹ to 1/10 ⁹ of that of unsubstituted polyacetylene. Based on this background, the present inventors conducted intensive research to find a conductive polymer material with excellent moldability. As a result, the present inventors developed a specific substituted polyphenylene having at least one alkoxy group in the phenylene nucleus. A modified polymer substance produced by reacting with a halide in a gas phase and performing reduced pressure and/or heat treatment after the reaction has high conductivity;
By selecting the substituted polyphenylene, it is possible to mold the substituted polyphenylene by an appropriate method such as a casting method or melt molding method using a solvent. Therefore, by subjecting the substituted polyphenylene that has been previously molded into a membrane, film, etc. to the reaction treatment, it can be formed into any shape. The present invention was completed by discovering that a modified polymeric substance can be obtained. To briefly describe the present invention, the present invention is produced by reacting a substituted polyphenylene having at least one alkoxy group in the phenylene nucleus with a specific halide in a gas phase, and performing reduced pressure and/or heat treatment after the reaction. The present invention relates to a method for producing a modified polymeric substance characterized by: The substituted polyphenylene used in the present invention is a substantially linear poly(alkoxyphenylene) in which a substituted phenylene group having at least one alkoxy group in the phenylene nucleus is a substantial repeating unit, and the average number of the repeating units is 8 or more. It is a nylene)-based polymer compound. Here, the average repeating unit is 8 or more.
For example, polymers can be mixed with tetrahydrofuran (hereinafter referred to as
Gel permeation chromatography (hereinafter abbreviated as GPC)
Judging from the weight average molecular weight (w) measured based on polystyrene, the repeating unit is 8.
The meaning corresponds to the above. For reference, looking at the intrinsic viscosity, the intrinsic viscosity in sulfuric acid is approximately
It is 0.02 or more, and the measured value will be included 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 -OR, and when this R is a general alkyl group, it may be long chain, cyclic, or branched. Further, it may be an alkyl group or other group containing ether oxygen, an aromatic ring, a heterocycle, etc. 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. The number of alkoxy groups may be one or more per phenylene nucleus. 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. The phenylene nucleus may have other substituents other than alkoxy groups, as long as they are electron-donating groups, such as alkyl groups. abbreviated). The substituted polyphenylene used in the present invention can be produced using known methods such as a method of polymerizing alkoxybenzenes in the presence of a Lewis acid and an oxidizing agent, a method of polymerizing dihaloalkoxybenzenes in the presence of magnesium, copper, etc. All methods of producing polyphenylene are possible. 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 the substituted phenylene group is 8 or more. Lewis acids used include anhydrous aluminum chloride,
Anhydrous ferric chloride, anhydrous titanium chloride (), anhydrous tin chloride, anhydrous molybdenum chloride, anhydrous tungsten chloride, anhydrous antimony chloride (), boron fluoride and boron fluoride etherate, etc. are used, but anhydrous aluminum chloride , anhydrous ferric chloride is particularly preferred. It is also effective to use other halides such as metal bromides corresponding to the metal chlorides. The inert solvent is the one used in normal Friedel-Crafts reactions, and any organic solvent that is inert to the Lewis acid aryl cation can be used.
Particularly suitable are nitroalkanes. Although the polymerization reaction can be carried out under normal pressure, increased pressure, or reduced pressure, it is possible to achieve excellent heat resistance and moldability by reducing the pressure to 10 to 40 mmHg to remove the generated hydrogen chloride. A polymer is obtained. In addition to the oxidative cationic polymerization method using a Lewis acid and an oxidizing agent, a method in which a dihalogen compound is polymerized via a Grignard intermediate and after a carbon-carbon coupling reaction can also be applied. In this case, for example, using dihaloalkoxybenzenes as a raw material (here, a suitable halogen is chlorine or bromine), metallic magnesium is By reacting with
The raw material halide can be the corresponding Grignard reagent. The generated Grignard reagent uses a salt or complex of a first transition metal such as nickel, palladium, or chromium iron as a catalyst to eliminate magnesium halide from the Grignard moiety and the halogen moiety, thereby generating a carbon-carbon bond. By carrying out this reaction continuously, the desired substituted polyphenylene can be produced. Catalysts that promote this dehalogenated magnesium include nickel,
Examples include anhydrides of halides such as iron, chromium, and palladium, salts such as acetates, sulfates, and nitrates, and divalent and zero-valent complexes of nickel and palladium. The present invention provides a method for producing a modified poly(alkoxyphenylene), characterized in that the substituted polyphenylene is produced by reacting the substituted polyphenylene with a specific halide in a gas phase, and then subjecting it to reduced pressure and/or heat treatment. It is related to. The specific halides used here refer to halides of group B elements or halides of group B elements.
Generally refers to high-valent halides of elements that can take on more than one valence state. Typical examples of applicable halides of group B elements include BF ₃ , BCl ₃ , AlCl ₃ , GaCl ₃ and ether complexes thereof. Typical examples of high-valent halides include halides of group B elements such as SnCl ₄ and GeCl ₄ , PF ₅ , AsF ₅ ,
Halides of Group B elements such as SbF ₅ and SbCl ₅ ; Group B halides such as SF ₅ and SF ₆ ;
Examples include transition metal halides such as TiCl ₄ , VF ₅ , VOCl ₃ , FeCl ₃ , MoF ₆ , and WF ₆ . Among these, high-valent halides have higher reactivity than halides of group B elements. Based on this, the present invention combines high-valent halides with oxidizing power and alkoxy groups. It is thought that the chemical reaction of substituted polyphenylene chemically activated by the method is utilized. Therefore, the reason why halides of Group B elements are effective is not necessarily clear, but low-valent halides that do not have oxidizing power, such as AgCl, Hg ₂ Cl ₂ , CaCl ₂ and the like, are not effective. The present inventors have invented a method for obtaining a similar object by reacting the substituted polyphenylene of the present invention with a halide in a liquid phase, and a separate patent application has been filed for this invention as well. Although this method has a high reaction effect and is preferable as a reaction operation, sufficient care must be taken to maintain the shape of the substituted phenylene during the reaction and to make the desired modified product in a favorable shape. It takes. Since the present invention involves reacting a substituted polyphenylene with a halogen compound in a gas phase, it is easy to maintain the original shape of the substituted polyphenylene, and the present invention was made with this point in mind. However, simply carrying out the reaction in the gas phase poses some problems in terms of reaction efficiency, and as a solution to this problem, in the present invention, reduced pressure and/or heat treatment is performed after the reaction treatment. That is, the reaction between a substituted polyphenylene and a halide is generally carried out by placing the solid substituted polyphenylene in a gaseous halide and bringing the substance into contact with it. In this case, the reaction rate depends on the surface area of the substituted polyphenylene, Depends on halide concentration, vapor pressure, etc. In general, the larger the surface area per unit volume of substituted polyphenylene, the smoother the reaction proceeds, and in this sense, substituted polyphenylene is
It is desirable that the material be shaped into a thin film, a film, or a porous shape. However, this is not an essential condition, and the shape of the substituted polyphenylene can be selected depending on necessity and purpose, such as, for example, manufacturing a molded product having conductivity only in the surface layer. In addition, when reacting a halide alone in the gas phase, the higher the vapor pressure, the higher the reaction rate, but quality control by controlling the reaction and making it uniform is also important, so the vapor pressure should be adjusted depending on the purpose. selected. Generally 0.1mm
It is preferable to carry out the reaction at a vapor pressure of Hg or higher. Furthermore, even if the reaction is carried out in a mixed gas of two or more halides, it may also be carried out in a gas inert to the reaction system, such as N ₂ ,
It may also be carried out in a system diluted with Ar or the like. Although the reaction temperature can be selected depending on the purpose, it is not preferable to carry out the reaction at a low temperature that lowers the vapor pressure of the halide more than necessary. As mentioned above, after the reaction with the halide, reduced pressure and/or heat treatment is performed. Decompression treatment is usually
Perform at 300mmHg or less, preferably 100mmHg or less,
Heat treatment is usually from 30℃ to 300℃, preferably from 50℃
Perform at 200℃. Both processes can be performed at the same time or in combination one after the other, if necessary. The depressurization and/or heat treatment step may be performed consecutively to the previous step, or after a certain period of time has elapsed, or the two steps of reaction treatment and post-treatment may be repeated two or more times. In this case, different halides may be used for the first and subsequent times. Although the same effect as the production method of the present invention can be obtained by leaving the product in a stream of inert gas such as N ₂ or Ar for a long time after the reaction treatment, the process becomes extremely long, which is not preferred in practice. Such reduced pressure treatment or heat treatment is thought to have effects such as promoting the reaction, removing residual unreacted substances, and completing the reaction, and can be said to be a complementary treatment that forms a part of the reaction treatment. In the modified product produced by the method of the present invention, a substituted polyphenylene having a phenylene nucleus chemically activated by an alkoxy group is chemically reacted with a specific halide having the above-mentioned activity. It is what was done. 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 caused by the change. It is presumed that the original substituted polyphenylene can be said to be newly crosslinked intramolecularly, intermolecularly, or both. Therefore, the method of the present invention is similar to the 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. Doping techniques are effective in improving conductivity, but
On the other hand, stability, strength, durability, etc. are reduced, which poses a practical problem. In the case of reaction treatment with a halide of the present invention,
If the reaction conditions are selected, the doping technique can reverse the strength, strength,
There are also secondary effects such as improved durability. 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 electrical conductivity of the modified product of the present invention varies depending on the type of the original substituted polyphenylene and the reaction treatment conditions, it is at least 10 ^{-4 Ω} -1 and generally 10 ^-3 to ^{10 -1} Ω ^-1
reaching cm ^-1 . Since the conductivity of the original substituted polyphenylene is generally around 10 ^-14 Ω ^-1 cm ^-1 , this value is extremely high for a polymer substance itself, and moreover, when a dopant is added to the substituted polyphenylene, 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 Semiconductors" by Iguchi, Nakata, and Hatano (Kyoritsu Publishing, published in 1966), p. 53. On the other hand, the modified product produced by the method of the present invention is
As described above, it has sufficiently high conductivity by itself, but in order to further improve the conductivity, an electron-accepting dopant and an electron-donating dopant can be added to form a charge transfer complex. Typical examples of applicable dopants include lithium,
Electron donors such as Group IA metals such as sodium and potassium, Group IA metals such as sodium naphthalene, potassium naphthalene, sodium biphenyl and potassium biphenyl, Group A metals such as calcium, and halogens such as iodine and bromine.
Brønsted acid, _SO3 , including _HClO4 , _HSO3F
and non-metal oxides containing N ₂ O ₅ , sulfides of group elements containing Sb ₂ S ₅ , B, transition metals, B,
Halides of A and group A elements, BCl ₃ , AsF ₅ ,
_SbF5 , _PF5 , _BF5 , _BCl5 , _SbBr3 , _CuCl2 , _NiCl2
and electron acceptors such as halides such as MoCl ₅ , WCl ₆ , VOCl ₃ , SnCl ₄ and fluorine-containing peroxides including FSO ₂ OOSO ₂ F or mixtures thereof, silver and alkali metals, alkaline earth metals. and quaternary ammonium tetrafluoroborates, phosphonium hexafluoride salts, perchlorates, hexafluoroantimonates, hexafluoroarsenates, and the like. 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. Examples of methods for adding a conductive dopant to the modified polymeric substance of the present invention to form a charge transfer complex include adding the dopant from the gas phase, adding the dopant from the solution phase,
Various methods are possible, such as addition in the molten phase or by intimate mixing of solid materials, or using electrochemical reactions to change the oxidation state and form a charge transfer complex with the dopant. A modified polymer material produced by reaction treatment according to the method of the present invention is further formed with a dopant to form a charge transfer complex, and a substituted polyphenylene which has not been subjected to reaction treatment is prepared by forming a charge transfer complex with the same dopant. Compared to conventional products, the conductivity can be 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, ie, molded articles, made of materials having the above composition. Therefore, it is possible to use such compositions in n-type and p-type materials, rectifier diodes and transistors, conductors such as P-n junctions, semiconductor devices, solar cells, and the like. In obtaining such various molded products, the advantage of the modified material of the present invention as a raw material compared to other conductive polymer materials such as polyacetylene, (SN)x, etc. is that it is easy to obtain the desired shape. This is an easy point. This is due to the good moldability of the substituted polyphenylene used as a raw material. Furthermore, the highly electrically conductive modified product of the present invention is
It has 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. Examples 1, 2 Nitromethane 50 in which 40 g of anhydrous ferric chloride was dissolved
ml of paradibutoxybenzene dissolved in 120 ml of nitromethane at room temperature under a vacuum of 20 mmHg.
19.8 g was carefully added so that the internal temperature did not exceed 40°C, and after completion, the mixture was stirred at room temperature under a reduced pressure of 20 mmHg for 2 hours. Pour the reaction mixture into 300 ml of methanol at room temperature.
and stir for 1 hour to remove insoluble matter.
After thoroughly washing the insoluble matter repeatedly with 2N hydrochloric acid water,
Dry under vacuum at 100°C overnight. Yield 12.7g (65%)
A substituted polyphenylene was obtained. Substituted polyphenylene was formed into a film from a toluene solution by a casting method to prepare two films measuring 10 cm x 10 cm x 20 μm.
This film was heated under AlCl ₃ or SnCl ₄ atmosphere, respectively.
It was left at 100°C or 60°C for 24 hours. After a predetermined period of time, each film was taken out from the reaction vessel and treated under a reduced pressure of 0.1 mmHg at 60°C for 8 hours or 40°C for 3 hours to obtain a black film of a modified polymer substance insoluble in toluene. These two films are stable in air, and their electrical conductivity in argon is
It was 1.4×10 ^-3 or 5.0×10 ^-3 Ω ^-1 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 3200 to 3600 cm ^-1 . Elemental analysis also revealed that the repeating unit of the polymer is C ₆ H ₂ (OC ₄ H ₉ ) ₂
The calculated value (C; 76.32
%, H; 9.15%) and actual value (C; 76.28%, H;
9.12%) showed good agreement, and no chlorine atoms were detected. The obtained polymer was dissolved in concentrated sulfuric acid,
The intrinsic viscosity [η] obtained by extrapolating the n(η/ηo)/C curve obtained when C (g/100ml) is in the range of 1.0 to 0.1 to C=0 was 0.30 at 37°C. This polymer is soluble in organic solvents and was completely extracted into toluene using a Soxhlet extractor. In addition, the results of thermogravimetric analysis (TGA) of this polymer in air showed that the temperature of 5% weight loss was 320℃,
The same 50% temperature is 500℃. Also polymer
When the molecular weight was measured by GPC after dissolving it in THF, the weight average molecular weight (
w) showed 140000. Examples 3 and 4 Two black films of a modified polymer substance insoluble in toluene were obtained in the same manner as in Example 1 except that BBr ₃ or SbF ₅ was used instead of AlCl ₃ . Both films are stable in air, with electrical conductivities of 8.6×10 ^-4 and 4.1× in argon, respectively.
It was 10 ^-1 Ω ^-1 cm ^-1 . Examples 5 and 6 BF ₃ using BF ₃ or VOCl ₃ instead of AlCl ₃
Two black films of a toluene-insoluble modified polymer substance were obtained by the same method as in Example 1, except that VOCl 3 was treated at room temperature and VOCl ₃ was treated at 40°C. Both films are stable in air;
The electrical conductivity in argon was 5.2×10 ⁻⁴ or 1.9×10 ⁻³ Ω ⁻¹ cm ⁻¹ , respectively. Examples 7 and 8 A substituted polyphenylene film formed from a toluene solution by a casting method is immersed in a mixed solvent of acetone/methanol (10/90) and left overnight. When the film was taken up and thoroughly dried under reduced pressure, it was observed that the surface of the film became slightly whitish and porous. This porous film 2
under an atmosphere of AlCl ₃ in the same manner as in Example 1.
It was left at 60° C. for 4 hours or at room temperature under an atmosphere of SnCl ₄ for 24 hours. Remove from reaction vessel after specified time.
When the mixture was treated under reduced pressure of 0.1 mmHg at 60° C. for 3 hours, two black films of a modified polymer substance insoluble in toluene were obtained. This modified porous polymer film is
Stable in air, electrical conductivity in argon is
It was 10 ^-3 or 6.6×10 ^-3 Ω ^-1 cm ^-1 . Examples 9 and 10 7.036 g of 1,4-dibromo-2,5-diisoproboxybenzene and 0.4864 g of magnesium are mixed in 25 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere and reacted under reflux. 10 mg when metallic magnesium disappears and Grignard reagent generation is completed.
dichloro(2,2'-pyridyl)nickel()
(NiCl ₂ (bpy); bpy = 2,2'-pyridine) and refluxed for 5 hours. After once cooling the reaction solution to room temperature, 30 ml of methanol is added, and the resulting precipitate is collected using a rocker. Wash repeatedly with water, methanol, and 1N hydrochloric acid, and dry under vacuum. Yield 1.27g
Substituted polyphenylene was obtained (yield 33%). Two films of 10 cm x 10 cm x 20 μm were prepared by melting substituted polyphenylene at 200° C. and forming a film. The films were each heated in a _BBr3 atmosphere at room temperature.
Leave for 12 hours or 8 hours at 80°C under SbCl ₃ atmosphere. After a predetermined time, they were taken out from the reaction vessel and subjected to vacuum treatment for 16 hours at room temperature under a vacuum of 1 mmHg for the former, and for 10 hours at room temperature under a vacuum of 0.01 mmHg for the latter, to obtain two black films that were infusible even at 200°C. The electrical conductivity of this film is 7.0×10 ^-4
or 1.2×10 ^-1 Ω ^-1 cm ^-1 . Note that the original substituted polyphenylene is soluble in hot THF, and slightly dissolves at room temperature. When the molecular weight of this THF solution was measured by GPC, w was
It was 6800. Examples 11 and 12 Two films that were infusible even at 200°C were obtained in the same manner as in Example 9 except that BF ₃ or FeCl ₃ was used instead of BBr ₃ . The electrical conductivity of this film was 1.0×10 ⁻³ or 1.4×10 ⁻³ Ω ⁻¹ cm ⁻¹ , respectively. Examples 13 and 14 Example 1 except that 11.0 g of p-methoxymethylbenzene was used instead of paradibutoxybenzene.
Substituted polyphenylene was synthesized in the same manner as above, yielding 5.3 g (49%) of substituted polyphenylene. Substituted polyphenylene at room temperature, 200Kg/
Diameter 13mm thickness by pressure molding with a pressure of cm ²
A 0.1 mm disc-shaped pellet was prepared. The pellets were heated at 150°C for 12 hours in an atmosphere of AlCl ₃ or
It was left for 24 hours at room temperature under an atmosphere of VoCl ₃ . After a predetermined time, the pellets were taken out from the reaction vessel and dried at 100° C. under a reduced pressure of 10 mmHg for 8 hours to obtain two black disc-shaped pellets. The respective electrical conductivity is 2.1×10 ^-3 or 8.7×
It was 10 ^-4 Ω ^-1 cm ^-1 . Examples 15, 16 Powders of substituted polyphenylene were heated at 150 °C under an atmosphere of AlCl ₃ for 12 hours or at 50 °C under an atmosphere of SbCl ₅ .
It was left for 24 hours. After a predetermined time, it was taken out from the reaction vessel and heated at 100°C for 3 hours to produce a black powder.
Two disc-shaped pellets each having a diameter of 13 mm and a thickness of 0.1 mm were prepared by press-molding each black powder at a pressure of 200 kg/cm ² at room temperature. The electrical conductivity of each is 7.7×10 ^-4
or 7.8×10 ^-2 Ω ^-1 cm ^-1 . Example 17 The modified polymer film prepared in Example 1 was left at 20° C. for 3 hours in an anhydrous sulfuric acid atmosphere. (The vapor pressure of anhydrous sulfuric acid is approximately 200 mmHg) After a predetermined period of time, the film was taken out and its electrical conductivity was measured in an argon atmosphere and found to be 1.8×10 ^-1 Ω ^-1 cm ^-1 . Comparative Example The substituted polyphenylene film 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 approximately 200 mmHg) After a predetermined period of time, the film was taken out and its electrical conductivity was measured in an argon atmosphere and found to be 8.2×10 ^-5 Ω ^-1 cm ^-1 . Example 18 4.1 g (0.01 mole) of 1,4-dibromo-2,5-bis(tetrahydrofuryloxy)benzene was dissolved in 50 ml of anhydrous tetrahydrofuran and heated to -78°C.
Cool to While stirring well, add a hexane solution of n-butyl lithium (15% 6.2 ml), and slowly bring the temperature inside the reactor to -10°C over 1 hour.
Raise the temperature to ℃. Here is anhydrous zinc chloride (1.43g)
Add anhydrous tetrahydrofuran solution (20ml) of
Continue stirring for 1 hour at 0°C. Next, the temperature inside the reactor was raised to 10°C, and 10 mg of anhydrous nickel chloride-pipyridine complex ([Ni(bip)Cl ₂ ]) was added thereto, the temperature was raised, and the reaction was carried out for 5 hours at the reflux temperature of tetrahydrofuran. . Pour the reaction solution into 200 ml of methanol, and collect the insoluble matter formed using a locator. Insoluble matter was washed repeatedly with methanol, water, and 1/2N hydrochloric acid to obtain 1.66 g of substituted polyphenylene (yield: 67%). This substituted polyphenylene was heated at room temperature.
Diameter 13 by pressure forming at a pressure of 400Kg/ ^cm2
Disk-shaped pellets with a thickness of 0.05 mm were prepared. The pellet was left for 48 hours at room temperature in an atmosphere of SbF ₅ . After the specified time, remove from the reaction container and 0.2mmHg.
The mixture was treated at room temperature under reduced pressure for 4 hours. When the electrical conductivity of this modified molded product was measured in an argon atmosphere, it was found to be 1.5×10 ^-1 Ω ^-1 cm ^-1 . In addition, the original substituted polyphenylene is
When dissolved in THF and the molecular weight was measured, w was 3800 in terms of polystyrene. Example 19 3.84 g (10 mmole) of 1,4-dibromo-2,5-bis(ethoxymethoxy)benzene is dissolved in 50 ml of anhydrous tetrahydrofuran and cooled to -78°C.
After stirring well, a hexane solution of n-butyl lisium (15% 6.2 ml) was slowly added, the temperature inside the reactor was raised to 0°C, and 1.84 g of anhydrous magnesium bromide was added thereto. 10 in a row
The anhydrous nickel chloride-bipyridine complex was heated to ℃.
Add 10 mg and 50 ml of anhydrous n-butyl ether, raise the temperature, and react under reflux for 6 hours. Pour the reaction solution into 200 ml of methanol, collect the insoluble matter produced, wash repeatedly with methanol, water, and diluted hydrochloric acid, and then dry under vacuum. Substituted polyphenylene was obtained in a yield of 1.17 g (yield 52%). This was molded in the same manner as in Example 18 to obtain disc-shaped pellets with a diameter of 13 mm and a thickness of 0.05 mm. By performing a reaction treatment in the same manner as in Example 18 except using SnCl ₄ instead of SbF ₅ , the electrical conductivity in argon was 3.5×10 ^-3 Ω ^-1 cm ^-1
A modified molded product was obtained. In addition, the original substituted polyphenylene is
When it was dissolved in THF and the molecular weight was measured by GPC, w was 4500 in terms of polystyrene. Example 20 4.44 g (10 mmole) of 1,4-dibromo-2,5-bis(trimethylsiloxy)benzene is dissolved in 50 ml of anhydrous tetrahydrofuran and cooled to -78°C. After stirring well, a hexane solution (15% 62 ml) of n-butyl lithium was slowly added thereto, the temperature inside the reactor was raised to 0°C, and 1.43 g of anhydrous zinc chloride was added thereto. Subsequently, the temperature was raised to 10℃, and anhydrous nickel () acetylacetonate was added.
10 mg and 50 ml of anhydrous n-butyl ether were added and reacted under reflux for 6 hours. After cooling, pour the reaction solution into 200 ml of methanol, and collect the formed insoluble matter in a locator. The product was washed repeatedly with cold methanol and cold water and dried under vacuum to yield 1.56 g of substituted polyphenylene (55% yield). By melting and molding this at 150℃, 10cm×
A sheet-like molded product of 10 cm x 100 μm was obtained. this
Example 18 except using VOCl ₃ instead of SbF ₅
When the reaction treatment was carried out in the same manner as above, a modified product was obtained as a sheet-like molded product. The electrical conductivity of this modified product in argon was 1.6×10 ^-2 Ω ^-1 cm ^-1 . In addition, the original substituted polyphenylene is
When it was dissolved in THF and its molecular weight was measured by GPC, w was 3400 in terms of polystyrene.
The infrared absorption spectrum of this polymer is 3300cm
Strong and wide absorption near ^-1 , 2800cm ^-1 and 3000cm ^-1
When the polymer is washed with methanol, some of the trimethylsilyl groups show multiple sharp absorptions.
It is possible that it has been disassembled.

Claims (1)

[Scope of Claims] 1. Substantially linear poly(alkoxyphenylene) in which a substituted phenylene group having at least one alkoxy group in the phenylene nucleus is a substantial repeating unit, and the average number of the repeating units is 8 or more. ) system polymer compound in the gas phase of a halide of a group B element or a high valence halide of an element other than a group B element that can take two or more valence states, or containing the halide. The polymer compound is intramolecularly or intermolecularly crosslinked by reacting with the halide in a gas phase, and then the reaction system is reduced in pressure or heated, or reduced pressure and heating are carried out simultaneously or alternately. Characteristic method for producing modified poly(alkoxyphenylene). 2. The manufacturing method according to claim 1, wherein the halide has a vapor pressure of 0.1 mmHg or more. 3. The manufacturing method according to claim 1 or 2, wherein the reduced pressure treatment is performed at a pressure of 300 mmHg or less. 4. The manufacturing method according to claim 1, 2 or 3, wherein the heat treatment is performed at a temperature of 50°C or higher. 5 Claims 1, 2, and 3, wherein the electrical conductivity of the obtained modified poly(alkoxyphenylene) is 10 ^-4 Ω ^-1 cm ^-1 or more when measured by the four-terminal method in argon. Or the manufacturing method described in Section 4.