JP2009046653A - Method for producing polymer of aromatic compound and heterocyclic aromatic compound by using hypervalent iodine reagent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing polymers of an aromatic compound and a heterocyclic aromatic compound with reduced metal ion content. <P>SOLUTION: The method for producing the polymers of aromatic compound and the heterocyclic aromatic compound comprises an oxidation polymerization step wherein the aromatic compound and the heterocyclic aromatic compound are polymerized by using the hypervalent iodine reagent. The hypervalent iodine reagent can be recovered and reused when the reagent has an adamantane structure and/or tetraphenylmethane structure. A catalytic amount of the hypervalent iodine reagent can be used in the oxidation polymerization step when another oxidizing reagent containing no metal is used and the polymerization is carried out in the existence of such co-oxidizing agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer of an aromatic compound and a heterocyclic aromatic compound having a low content of metal ions as impurities.

  The polymer of an aromatic compound and a heterocyclic aromatic compound is usually produced by a chemical oxidative polymerization method or an electrolytic oxidative polymerization method. In particular, the chemical oxidative polymerization method is simple and can be mass-produced. Such polymers of aromatic compounds and heterocyclic aromatic compounds are used as, for example, antistatic agents for electronic parts, hole injection materials for organic electroluminescent elements, light emitting materials, and the like.

Patent Document 1 describes a method for producing polypyrroles using an oxidizing agent having a sulfonic acid compound as an anion and an expensive transition metal as a cation. Examples of expensive transition metal ions constituting this oxidant include Ag ⁺ , Cu ²⁺ , Fe ³⁺ , Al ³⁺ , Ce ⁴⁺ , W ⁶⁺ , Mo ⁶⁺ , Cr ⁶⁺ , Mn ⁷⁺ , and Sn ⁴⁺ . Fe ³⁺ and Cu ²⁺ are described as preferred. It is described that this method is simple and can be applied to mass synthesis.

Patent Document 2 describes poly (3,4-dialkoxythiophene), and FeCl ₃ , Fe (ClO ₄ ) ₃ , H ₂ O ₂ are used as catalysts in the oxidative polymerization of 3,4-dialkoxythiophene. , K ₂ CrO ₇ , alkali or ammonium persulfate, alkali perborate, potassium permanganate, and copper tetrafluoroborate. Furthermore, it is described that air and oxygen can be advantageously used in the presence of catalytic amounts of metal ions (iron, cobalt, nickel, molybdenum and vanadium ions) as oxidants.

  As described in Patent Documents 1 and 2, metal ions are used in ordinary chemical oxidative polymerization methods. Therefore, the polypyrroles and polythiophenes obtained by these methods retain a considerable amount of metal ions even after purification such as reprecipitation.

The method described in Patent Document 2 also describes an oxidizing agent that does not contain metal ions, such as H ₂ O ₂ and ammonium persulfate. However, even with such an oxidizing agent, it is preferable to use a catalytic amount of metal ions in combination for the purpose of shortening the reaction time. As a result, the poly (3,4-dialkoxythiophene) obtained has a considerable amount of metal ions. Remains.

When an aromatic compound containing a metal ion and a polymer of a heterocyclic aromatic compound are used as an antistatic agent for an electronic component, there is a risk that the metal ion may contaminate the electronic component. When used as a hole injection material or a light emitting material of an organic electroluminescence device, metal ions cause a reduction in light emission characteristics and device lifetime.
JP-A-7-70294 Japanese Patent No. 2636968

  An object of the present invention is to provide a method for producing a polymer of an aromatic compound and a heterocyclic aromatic compound having a low metal ion content.

  As a result of intensive studies on the above problems, the present inventors have found that aromatic compounds and heterocyclic aromatic compounds containing almost no metal ions as impurities can be obtained by using a hypervalent iodine reactant as a chemical oxidation polymerization catalyst. The present invention was completed by finding that a polymer was obtained.

  The method for producing a polymer of an aromatic compound of the present invention includes a step of oxidatively polymerizing an aromatic compound using a hypervalent iodine reactant.

  Furthermore, the method for producing a polymer of a heterocyclic aromatic compound of the present invention includes a step of oxidatively polymerizing the heterocyclic aromatic compound using a hypervalent iodine reactant.

  In one embodiment, the hypervalent iodine reactant has an adamantane structure.

  In one embodiment, the hypervalent iodine reactant has a tetraphenylmethane structure.

  In one embodiment, a metal-free oxidizing agent is further used in the oxidative polymerization step.

  Furthermore, in one embodiment, the usage-amount of the said hypervalent iodine reactant is 0.001-0.3 mol with respect to 1 mol of an aromatic compound or a heterocyclic aromatic compound, and does not contain the said metal. The usage-amount of an oxidizing agent is 1-4 molar equivalent with respect to 1 mol of an aromatic compound or a heterocyclic aromatic compound.

  ADVANTAGE OF THE INVENTION According to this invention, (1) The manufacturing method of the polymer of an aromatic compound and a heterocyclic aromatic compound with little metal ion content can be provided. (2) When hypervalent iodine reactants having an adamantane structure are used, these hypervalent iodine reactants can be recovered and reused. (3) When hypervalent iodine reactants having a tetraphenylmethane structure are used, these hypervalent iodine reactants can be recovered and reused.

  A hypervalent iodine reactant refers to a reactant containing an iodine atom in a trivalent or pentavalent hypervalent state. Since the hypervalent iodine reactant has the property of returning to a more stable octet state (monovalent iodine), a heavy metal oxidizing agent such as lead (IV), thallium (III), mercury (II), etc. And similar reactivity. Furthermore, the hypervalent iodine reactant is less toxic than such a heavy metal oxidant and is excellent in safety.

  The hypervalent iodine reactant that can be used in the production method of the present invention is not particularly limited. Examples of the trivalent hypervalent iodine reactant include phenyliodine bis (trifluoroacetate) (bis (trifluoroacetoxy) iodobenzene (hereinafter sometimes referred to as PIFA)), phenyliodine diacetate ( Examples thereof include iodosobenzene diacetate (hereinafter sometimes referred to as PIDA), hydroxy (tosyloxy) iodobenzene, iodosylbenzene and the like. The structural formulas of these reactants are shown below.

  Examples of the pentavalent hypervalent iodine reactant include Dess-Martin periodinane (DMP), o-iodoxybenzoic acid (IBX), and the like. The structural formulas of these reactants are shown below.

  Among these hypervalent iodine reactants, trivalent hypervalent iodine reactants are preferred, and PIFA is more preferred because it is stable and easy to handle and has a sufficiently high oxidizing ability.

  Further, among the hypervalent iodine reactants, it is preferable to select a hypervalent iodine reactant having an adamantane structure and a hypervalent iodine reactant having a tetraphenylmethane structure because they can be recovered and reused. More specifically, 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis-((4- (hydroxy) tosyloxyiodo) phenyl ) Hypervalent iodine reactants having a trivalent adamantane structure such as adamantane, 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, and tetrakis-4- (diacetoxy) A hypervalent iodine reactant having a trivalent tetraphenylmethane structure such as iodo) phenylmethane and tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane is stable and easy to handle and has a sufficiently high oxidizing ability. Further, it is more preferable because it has high fat solubility and can be recovered and reused. When a pentavalent hypervalent iodine reactant is used, desmartin periodinane (DMP) is preferred.

As such a hypervalent iodine reactant, one obtained by synthesis may be used, or a commercially available product may be used. For example, PIFA can be obtained by adding trifluoroacetic acid to PIDA and reacting, so that PIFA is precipitated as a reaction product (see J. Chem. Soc. Perkin Trans. 1, 1985, 757). ). PIDA is obtained by oxidizing iodobenzene with sodium peroxoborate (tetrahydrate) (NaBO ₃ .4H ₂ O) in acetic acid (Tetrahedron, 1989, 45, 3299 and Chem. Rev., 1996, 96, 1123). In addition, PIDA is obtained from iodobenzene using m-chloroperbenzoic acid (mCPBA) as an oxidizing agent (see Angew. Chem. Int. Ed., 2004, 43, 3595). 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis-((4- (hydroxy) tosyloxyiodo) phenyl) adamantane, 1,3 , 5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane and tetrakis-4- (diacetoxyiodo) phenylmethane, tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane are for example It can be synthesized by the method described in Kaikai 2005-220122.

  Aromatic compounds that can be used in the production method of the present invention include benzene-based aromatic compounds such as benzene, toluene, p-dimethoxybenzene, and cresol, polycyclic aromatic compounds such as biphenyl and triphenylmethane, naphthalene, and anthracene. Aromatic fused ring compounds and the like can be used. Of these, benzene-based aromatic compounds are preferable, and benzene or 1,4-substituted benzene is particularly preferable.

  The heterocyclic compound that can be used in the production method of the present invention is preferably one in which the heteroatom is any one of nitrogen, sulfur, and oxygen. For example, pyrroles, thiophenes, and furans, and these two amounts Bodies and trimers can be used.

  Examples of pyrroles that can be used in the production method of the present invention include pyrrole, 3-substituted pyrrole, 3,4-substituted pyrrole, N-substituted pyrrole, bipyrrole, and bipyrrole derivatives. Specifically, pyrrole, 3-methylpyrrole, 3-hexylpyrrole, 3-phenylpyrrole, N-ethylsulfonate pyrrole, bipyrrole, 3,4-cyclohexylpyrrole and the like can be mentioned. Among these, when using substituted pyrroles, the kind of substituent and its substitution position are not particularly limited, but it is preferable to use substituted pyrroles having an alkyl group or an aryl group at the 3-position.

  Examples of thiophenes that can be used in the production method of the present invention include thiophene, 3-substituted thiophene, 3,4-substituted thiophene, bithiophene, and bithiophene derivatives. Specific examples include thiophene, 3-methylthiophene, 3-hexylthiophene, 3-phenylthiophene, 3,4-ethylenedioxythiophene, bithiophene, 3-methoxythiophene, and 3-butoxythiophene. Among these, when using substituted thiophenes, the kind of substituent and its substitution position are not particularly limited, but it is preferable to use substituted thiophenes having an alkyl group or an alkoxy group at the 3-position.

  Examples of furans that can be used in the production method of the present invention include furan, 3-substituted furan, 3,4-substituted furan, bifuran, and bifuran derivatives. Specific examples include furan, 3-methylfuran, 3-hexylfuran, 3-phenylfuran, 3,4-ethylenedioxyfuran, bifuran, 3-methoxyfuran, and 3-butoxyfuran. Among these, when substituted thiophenes are used, the type of substituent and the substitution position thereof are not particularly limited, but it is preferable to use a substituted furan having an alkyl group or an alkoxy group at the 3-position.

  In the production method of the present invention, the amount of the hypervalent iodine reactant used is not particularly limited, and is preferably 1 to 4 mol, more preferably 1. mol per 1 mol of the aromatic compound or heterocyclic aromatic compound. It is used in a proportion of 5 to 4 mol, more preferably in a proportion of 2 to 2.5 mol.

  When the amount of the hypervalent iodine reactant is small, the oxidative polymerization reaction may be difficult to proceed. On the other hand, if the amount of the hypervalent iodine reactant is large, excessive oxidation may occur and a product completely insoluble in the solvent may be obtained, resulting in a decrease in the yield of polymers of aromatic compounds and heterocyclic aromatic compounds. There are things to do.

  In the production method of the present invention, a hypervalent iodine reactant and a metal-free oxidizing agent may be used in combination. The combined use of a hypervalent iodine reactant and an oxidizing agent that does not contain a metal can reduce the amount of hypervalent iodine reactant used. Examples of the oxidizing agent not containing metal include peroxodisulfuric acid, ammonium peroxodisulfate, hydrogen peroxide, and metachloroperbenzoic acid.

  In the production method of the present invention, when a hypervalent iodine reactant and a metal-free oxidizing agent are used in combination, the hypervalent iodine reactant acts as an oxidation catalyst, and an aromatic compound or a heterocyclic aromatic compound 1 Preferably it is used in a proportion of 0.001 to 0.3 mol, more preferably 0.01 to 0.1 mol, relative to mol. On the other hand, the metal-free oxidizing agent is preferably used in a proportion of 1 to 4 molar equivalents, more preferably 1.5 to 2.5 molar equivalents, per 1 mol of the aromatic compound or heterocyclic aromatic compound. It is done.

  When the oxidizing agent not containing a metal and the hypervalent iodine reactant are used in combination, the polymerization reaction may not sufficiently proceed if the amount of the hypervalent iodine reactant is too small. On the other hand, if the amount of the hypervalent iodine reactant is too large, the degree of polymerization will not be greater than a certain degree of polymerization, and the hypervalent iodine reactant will be wasted.

  In the case where a hypervalent iodine reactant and an oxidizing agent not containing a metal are used in combination, a precursor of the hypervalent iodine reactant may be used when starting the polymerization reaction. For example, 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane precursor 1,3,5,7-tetrakis- (4-iodophenyl) adamantane is used in catalytic amounts and chemistry. A stoichiometric amount of a reaction substrate such as metachloroperbenzoic acid, acetic acid and pyrroles or thiophenes may be added.

  The aromatic compound or the heterocyclic aromatic compound polymer obtained by the production method of the present invention may be doped with a dopant. By doping with a dopant, conductivity can be imparted to the resulting polymer of an aromatic compound or heterocyclic aromatic compound. The dopant may be charged as a raw material before the reaction, may be added during the polymerization reaction, or may be added to the aromatic compound or heterocyclic aromatic compound polymer obtained after the reaction.

The dopant is not particularly _{limited, Cl 2, Br 2, I} 2, halogen such as _ICl; PF 5, BF _3, Lewis acids such as trimethylsilyl _{trifluoromethanesulfonate; HF, HCl, HNO 3,} H 2 SO 4 And proton acids such as p-toluenesulfonic acid and polystyrenesulfonic acid.

  The dopant used for the purpose of imparting conductivity is preferably used in a proportion of 5 to 600 mol, more preferably in a proportion of 20 to 400 mol, relative to 100 mol of the aromatic compound or heterocyclic aromatic compound. Used.

  When the amount of the dopant is less than 5 mol, there is a possibility that sufficient conductivity cannot be imparted to the polymer of the obtained aromatic compound or heterocyclic aromatic compound. On the other hand, when the amount of the dopant is more than 600 moles, all the dopants added to the resulting polymer of the aromatic compound or heterocyclic aromatic compound are not doped, and an effect proportional to the added amount cannot be expected. Also, excess dopant is wasted.

  The Lewis acid not only acts as a dopant, but also has an effect of promoting an oxidative polymerization reaction. When a Lewis acid is used for the purpose of promoting the oxidative polymerization reaction, trimethylsilyl trifluoromethanesulfonate is particularly preferably used.

  The solvent used in the production method of the present invention may be any solvent that dissolves or disperses the aromatic compound or heterocyclic aromatic compound, hypervalent iodine reactant, and dopant. Examples of such solvents include water, organic solvents (alcohols such as methanol, ethanol, 2-propanol, 1-propanol, and n-butanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; Propylene glycol , Propylene glycols such as dipropylene glycol and tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl Propylene glycol ethers such as ether and dipropylene glycol diethyl ether; propylene glycol such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate Ether acetates: N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, acetone, acetonitrile, and toluene, xylene (o-, m-, or p-xylene), benzene, acetic acid Ethyl, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t-butyl ether, hexane, heptane, chloromethane (methyl chloride), dichloromethane (methylene chloride), trichloromethane (chloroform), tetrachloromethane ( Carbon tetrachloride)), a mixed solvent of water and these organic solvents (hydrous organic solvent), and a mixed solvent of two or more organic solvents.

  The temperature of the oxidative polymerization reaction using the hypervalent iodine reactant is preferably -100 ° C to 100 ° C. The reaction temperature of the oxidative polymerization reaction of the present invention is more preferably 0 ° C. to 40 ° C. in both cases of using an organic solvent as a solvent and water.

  In the oxidative polymerization reaction of the present invention, when the reaction temperature is lower than −100 ° C., the reaction rate becomes slow or depending on the solvent, the yield of the polymer of the aromatic compound or the heterocyclic aromatic compound is increased. May decrease. On the other hand, when the reaction temperature is higher than 100 ° C., side reaction or excessive oxidation may occur, and the yield of the polymer of the aromatic compound or the heterocyclic aromatic compound may be reduced.

  In the production method of the present invention, the reaction time for the oxidation polymerization reaction is not particularly limited. When a Lewis acid is used to promote the oxidative polymerization reaction, about 12 hours are preferable, and when a Lewis acid is not used, about 20 hours are preferable.

  The polymer of the aromatic compound or heterocyclic aromatic compound thus obtained is further purified. The purification method (purification step) is not particularly limited. For example, after the reaction, the solvent is filtered through a glass filter, and the resulting polymer is methanol, ethanol, 2-propanol, n-hexane, diethyl ether, acetonitrile, ethyl acetate. And a method of washing with toluene or the like. Other purification methods include purification by Soxhlet extraction or the like.

  After washing, the obtained aromatic compound or heterocyclic aromatic compound polymer is dried by a usual means as necessary (drying step). The drying method can be appropriately determined depending on the degree of polymerization of polypyrroles and polythiophenes, substituents, and contained dopants. For example, drying at room temperature (about 25 ° C.) under reduced pressure (about 0.5 mmHg), heating under normal pressure Air blowing (about 60 ° C.) drying and the like can be mentioned. The drying temperature is preferably 100 ° C. or lower, and if it exceeds 200 ° C., the risk of decomposition of the polymer of the aromatic compound or the heterocyclic aromatic compound increases.

  Further, when a hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure is used, it is recovered by the following method. For example, the solution after completion of the reaction is concentrated under reduced pressure, and methanol is added to the residue (polymer, a hypervalent iodine reagent having an adamantane structure or tetraphenylmethane structure, an oxidizing agent not containing a metal, an unreacted monomer) and mixed. By filtering using a glass filter, the metal-free oxidizing agent and unreacted monomer can be removed as a methanol solution. The polymer remaining as a residue and a hypervalent iodine reagent having an adamantane structure or a tetraphenylmethane structure are mixed with diethyl ether, mixed and filtered through a glass filter, and then the residue polymer and the adamantane structure and the tetraether of the diethyl ether solution are mixed. It can be separated into a hypervalent iodine reactant having a phenylmethane structure. By concentrating the diethyl ether, a hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure can be recovered. The method for recovering a hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure is not limited to the above example, but a polymer, a hypervalent iodine reactant having an adamantane structure or a tetraphenylmethane structure, and a metal-free oxidizing agent. Each component can be separated by selecting an appropriate solvent using the difference in solubility of the unreacted monomer depending on the solvent species.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to this Example.

Example 1
To a 50 mL eggplant flask, 168 mg (1 mmol) of 3-hexylthiophene and 10 mL of methylene chloride were added and cooled to −78 ° C. under a nitrogen atmosphere (using dry ice and methanol as a cryogen). 889 mg of trimethylsilyl trifluoromethanesulfonate was then added, followed by 860 mg (2 mmol) of PIFA.

  Eight hours after the addition of PIFA, the cryogen was removed and the reaction temperature was gradually raised to room temperature. Furthermore, stirring was performed for 4 hours, and the reaction time after addition of PIFA was set to 12 hours in total.

  This reaction solution was dropped into 50 mL of methanol. Subsequently, the black insoluble matter was collected by a glass filter. Next, the insoluble material was washed with n-hexane to obtain 60 mg of poly (3-hexylthiophene). When the molecular weight of the obtained poly (3-hexylthiophene) was measured, the weight average molecular weight (Mw) was 13930, the number average molecular weight (Mn) was 6930, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 2 .010.

  The obtained poly (3-hexylthiophene) is incinerated, and iron contained by inductively coupled plasma mass spectrometry (ICP-MS method) (using ICP mass spectrometer (SPQ9500) manufactured by SII Nanotechnology, Inc.) The element ratio was measured and found to be 23 ppm. The detected iron element is considered to be an iron element derived from impurities contained in the raw material, solvent and the like.

(Comparative Example 1)
90 mg of poly (3-hexylthiophene) was prepared in the same manner as in Example 1 except that 324 mg (2 mmol) of iron (III) chloride was used instead of 860 mg of PIFA used in Example 1 above. Got. When the molecular weight of the obtained poly (3-hexylthiophene) was measured, the weight average molecular weight (Mw) was 25984, the number average molecular weight (Mn) was 17632, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 474.

  The obtained poly (3-hexylthiophene) was incinerated, and the ratio of iron element contained by the ICP-MS method was measured to be 3600 ppm.

(Comparative Example 2)
To a 50 mL eggplant flask, 168 mg (1 mmol) of 3-hexylthiophene and 10 mL of chloroform were added and cooled to 0 ° C. using an ice bath under a nitrogen atmosphere. Then 648 mg (4 mmol) of iron (III) chloride was added.

  The ice bath was removed 5 hours after the addition of iron (III) chloride. Subsequently, the reaction temperature was gradually raised, and iron (III) chloride was added to reach room temperature after 6 hours. The mixture was further stirred for 18 hours, and the reaction time after addition of iron (III) chloride was 24 hours.

  This reaction solution was dropped into 50 mL of methanol. Subsequently, the black insoluble matter was collected by a glass filter. Next, the insoluble material was washed with n-hexane and further washed with ion-exchanged water to obtain 103 mg of poly (3-hexylthiophene).

  The obtained poly (3-hexylthiophene) was incinerated, and the ratio of the iron element contained by the ICP-MS method was measured to be 8600 ppm. The weight average molecular weight (Mw) was 8502, the number average molecular weight (Mn) was 3955, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 2.128.

  As is clear from the results of Example 1, Comparative Example 1, and Comparative Example 2, the ratio of iron element contained in the polythiophenes obtained by the production method of the present invention is contained in the polythiophenes produced using the metal catalyst. It was found to be much lower than the proportion of iron element.

(Example 2)
To a 50 mL eggplant flask, 143 mg (1 mmol) of 3-phenylpyrrole and 10 mL of methylene chloride were added and cooled to 0 ° C. using an ice bath under a nitrogen atmosphere. 889 mg of trimethylsilyl trifluoromethanesulfonate was then added, followed by 860 mg (2 mmol) of PIFA.

  After 8 hours of PIFA addition, the ice bath was removed and the reaction temperature was gradually raised to room temperature. Furthermore, stirring was performed for 4 hours, and the reaction time after addition of PIFA was set to 12 hours in total.

  The reaction solution was concentrated, and the residue was collected by a glass filter. Subsequently, the residue was washed with methanol, and further washed with n-hexane to obtain 50 mg of poly (3-phenylpyrrole). When the molecular weight of the obtained poly (3-phenylpyrrole) was measured, the weight average molecular weight (Mw) was 609, the number average molecular weight (Mn) was 419, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 .453.

  The obtained poly (3-phenylpyrrole) was incinerated and the ratio of the iron element contained by the ICP-MS method was measured to be 34 ppm. The detected iron element is considered to be an iron element derived from impurities contained in the raw material, solvent and the like.

  Furthermore, a thin film was formed by the following procedure using the obtained poly (3-phenylpyrrole). First, 20 mg of poly (3-phenylpyrrole) was dissolved in 1 mL of chloroform to prepare a coating material. Then, the prepared paint was No. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.25 μm.

  Subsequently, the surface resistivity of the obtained thin film was measured according to JIS K6911 using Hiresta UP (MCP-HT450) (Mitsubishi Chemical Corporation). As a result of measuring the surface resistivity of the obtained thin film, it was 5.6E + 11Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

(Comparative Example 3)
80 mg poly (3-phenylpyrrole) in the same procedure as in Example 2 except that 324 mg (2 mmol) of iron (III) chloride was used instead of 860 mg of PIFA used in Example 2 above. Got. When the molecular weight of the obtained poly (3-phenylpyrrole) was measured, the weight average molecular weight (Mw) was 362, the number average molecular weight (Mn) was 357, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 .014.

  The obtained poly (3-phenylpyrrole) was incinerated, and the ratio of the iron element contained by the ICP-MS method was measured and found to be 900 ppm.

  As is clear from the results of Example 2 and Comparative Example 3, the ratio of the iron element contained in the polypyrrole obtained by the production method of the present invention is the ratio of the iron element contained in the polypyrrole produced using the metal catalyst. Was found to be much lower.

  Furthermore, the procedure similar to the said Example 2 except having used the poly (3-phenylpyrrole) obtained by the comparative example 3 instead of the poly (3-phenylpyrrole) obtained by the said Example 2. A thin film was formed, and the surface resistivity of this thin film was measured. As a result of measuring the surface resistivity of the obtained thin film, it was 2.0E + 10Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

(Example 3)
To a 50 mL eggplant flask, 143 mg (1 mmol) of 3-phenylpyrrole and 10 mL of water were added. Then, 860 mg (2 mmol) of PIFA was added and stirred at room temperature for 20 hours.

  The insoluble matter in the reaction solution was collected by a glass filter. Next, the insoluble material was washed with methanol and further washed with n-hexane to obtain 120 mg of poly (3-phenylpyrrole). When the molecular weight of the obtained poly (3-phenylpyrrole) was measured, the weight average molecular weight (Mw) was 1192, the number average molecular weight (Mn) was 789, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 .511.

  The obtained poly (3-phenylpyrrole) was incinerated, and the ratio of the copper element contained by the ICP-MS method was measured to be 28 ppm. The detected copper element is considered to be a copper element derived from impurities contained in the raw material, the solvent and the like.

  Further, the same procedure as in Example 2 except that the poly (3-phenylpyrrole) obtained in Example 3 was used instead of the poly (3-phenylpyrrole) obtained in Example 2 above. Was used to form a thin film (film thickness: 0.21 μm), and the surface resistivity of this thin film was measured. As a result of measuring the surface resistivity of the obtained thin film, it was 6.7E + 9Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

Example 4
To a 50 mL eggplant flask, 143 mg (1 mmol) of 3-phenylpyrrole and 10 mL of water were added. Then, 644 mg (2 mmol) of PIDA was added and stirred at room temperature for 20 hours.

  The insoluble matter in the reaction solution was collected by a glass filter. Next, the insoluble material was washed with methanol and further washed with n-hexane to obtain 140 mg of poly (3-phenylpyrrole). When the molecular weight of the obtained poly (3-phenylpyrrole) was measured, the weight average molecular weight (Mw) was 1697, the number average molecular weight (Mn) was 1163, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 459.

  The obtained poly (3-phenylpyrrole) was incinerated and the ratio of the copper element contained by the ICP-MS method was measured to be 2 ppm. The detected copper element is considered to be a copper element derived from impurities contained in the raw material, the solvent and the like.

  Furthermore, the procedure similar to the said Example 2 except having used the poly (3-phenylpyrrole) obtained in Example 4 instead of the poly (3-phenylpyrrole) obtained in the said Example 2. Then, a thin film (film thickness: 0.14 μm) was formed, and the surface resistivity of this thin film was measured. As a result of measuring the surface resistivity of the obtained thin film, it was 2.9E + 12Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

(Example 5)
To a 50 mL eggplant flask, 143 mg (1 mmol) of 3-phenylpyrrole and 10 mL of acetonitrile were added. Next, 860 mg (2 mmol) of PIFA was added, and the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere.

  The insoluble matter in the reaction solution was collected by a glass filter. Subsequently, the insoluble material was washed with methanol, and further washed with n-hexane to obtain 68 mg of poly (3-phenylpyrrole). When the molecular weight of the obtained poly (3-phenylpyrrole) was measured, the weight average molecular weight (Mw) was 346, the number average molecular weight (Mn) was 226, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 531.

  The obtained poly (3-phenylpyrrole) was incinerated, and the ratio of the copper element contained by the ICP-MS method was measured to be 3 ppm. The detected copper element is considered to be a copper element derived from impurities contained in the raw material, the solvent and the like.

  Further, the same procedure as in the above Example 2 except that the poly (3-phenylpyrrole) obtained in Example 5 was used instead of the poly (3-phenylpyrrole) obtained in Example 2 above. Then, a thin film (film thickness: 0.14 μm) was formed, and the surface resistivity of this thin film was measured. As a result of measuring the surface resistivity of the obtained thin film, it was 1.2E + 12Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

(Comparative Example 4)
To a 50 mL eggplant flask, 143 mg (1 mmol) of 3-phenylpyrrole and 10 mL of water were added. Next, 474 mg (3.3 mmol) of copper bromide was added, and the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere.

  The insoluble matter in the reaction solution was collected by a glass filter. Next, the insoluble material was washed with methanol and then with n-hexane to obtain 70 mg of poly (3-phenylpyrrole). When the molecular weight of the obtained poly (3-phenylpyrrole) was measured, the weight average molecular weight (Mw) was 397, the number average molecular weight (Mn) was 374, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 0.061.

  The obtained poly (3-phenylpyrrole) was incinerated, and the ratio of the copper element contained by the ICP-MS method was measured to be 53400 ppm.

  Furthermore, the procedure similar to the said Example 2 except having used the poly (3-phenylpyrrole) obtained by the comparative example 4 instead of the poly (3-phenylpyrrole) obtained by the said Example 2. Then, a thin film (film thickness: 0.18 μm) was formed, and the surface resistivity of this thin film was measured. As a result of measuring the surface resistivity of the obtained thin film, it was 9.0E + 9Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

  As is clear from the results of Examples 3 to 5 and Comparative Example 4, the ratio of the copper element contained in the polypyrroles obtained by the production method of the present invention is the copper element contained in the polypyrroles produced using the metal catalyst. It was found to be much lower than the percentage of.

  Next, polypyrroles and polythiophenes were produced by using a hypervalent iodine reactant in combination with an oxidizing agent not containing metal.

(Example 6)
In a 200 mL eggplant flask, 82 g of ion-exchanged water, 8.2 g of 17.6% by mass polystyrenesulfonic acid aqueous solution, 200 mg (2.9 mmol) pyrrole, and 5.77 g of 10.9% by mass peroxodisulfuric acid aqueous solution ( 3.23 mmol) was added. Next, 21.5 mg (0.05 mmol) of PIFA was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (5 ml) and added. Then, it stirred at 18 degreeC for 6 hours, and obtained the polypyrrole water dispersion of polystyrene sulfonic acid dope.

  It was 2 ppm when the ratio of the iron element contained in the obtained polystyrene sulfonic acid dope polypyrrole aqueous dispersion was measured by an atomic absorption photometer.

  Further, the obtained polystyrene sulfonic acid-doped polypyrrole aqueous dispersion was used as it was. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.25 μm.

  Next, in place of the poly (3-phenylpyrrole) thin film obtained in Example 2 above, the polystyrene sulfonate-doped polypyrrole thin film obtained in Example 6 was used, except for the above Example 2. The surface resistivity was measured by the same method. As a result of measuring the surface resistivity of the obtained thin film, it was 1.4E + 8Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

(Comparative Example 5)
In a 200 mL eggplant flask, 82 g of ion-exchanged water, 8.2 g of 17.6% by mass polystyrenesulfonic acid aqueous solution, 200 mg (2.9 mmol) pyrrole, and 5.77 g of 10.9% by mass peroxodisulfuric acid aqueous solution ( 3.23 mmol) was added. Then, 2.0 g of 1 mass% iron (III) sulfate aqueous solution (0.05 mmol) was added. Then, it stirred at 18 degreeC under nitrogen atmosphere for 6 hours, and obtained the polystyrene sulfonic acid dope polypyrrole water dispersion.

  About the obtained polystyrene sulfonic acid dope polypyrrole aqueous dispersion, the ratio of the iron element contained by an atomic absorption photometer was 55 ppm.

  Further, in place of the polystyrenesulfonic acid-doped polypyrrole aqueous dispersion obtained in Example 6 above, the above-mentioned Example 6 was used except that the polystyrenesulfonic acid-doped polypyrrole aqueous dispersion obtained in Comparative Example 5 was used. A thin film (film thickness: 0.27 μm) was formed by the same procedure as above, and the surface resistivity of this thin film was measured. As a result of measuring the surface resistivity of the obtained thin film, it was 4.7E + 7Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

(Example 7)
In a 300 mL eggplant flask, 182 g of ion exchange water, 27.9 g of 17.6 wt% polystyrene sulfonic acid aqueous solution, 0.8 g (5.63 mmol) of 3,4-ethylenedioxythiophene, and 11.5 g of 10 A 9 mass% aqueous peroxodisulfate solution (6.46 mmol) was added. Then 0.044 g (0.10 mmol) of PIFA was added. Thereafter, the mixture was stirred at 18 ° C. for 24 hours to obtain a polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion.

  About the obtained polystyrene sulfonic acid dope poly (3,4-ethylenedioxythiophene) aqueous dispersion, the ratio of the iron element contained by an atomic absorption photometer was 1 ppm.

  Furthermore, 3 g of N-methyl-2-pyrrolidone was added to and mixed with 100 g of the polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion obtained in Example 7 above. Then, No. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.12 μm.

  Next, instead of the poly (3-phenylpyrrole) thin film obtained in Example 2 above, the polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) thin film obtained in Example 7 was used. Except for the above, the surface resistivity was measured in the same manner as in Example 2 above. The surface resistivity of the obtained thin film was measured and found to be 3.6E + 4Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

(Comparative Example 6)
In a 300 mL eggplant flask, 178 g of ion exchange water, 27.9 g of 17.6 wt% polystyrene sulfonic acid aqueous solution, 0.8 g (5.63 mmol) of 3,4-ethylenedioxythiophene, and 11.5 g of 10 A 9 mass% aqueous peroxodisulfate solution (6.46 mmol) was added. Then, 4.0 g of 1 mass% iron (III) sulfate aqueous solution (0.10 mmol) was added. Thereafter, the mixture was stirred at 18 ° C. for 24 hours to obtain a polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion.

  About the obtained polystyrene sulfonic acid dope poly (3,4-ethylenedioxythiophene) aqueous dispersion, the ratio of the iron element contained by an atomic absorption photometer was 63 ppm.

  Furthermore, instead of the polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion obtained in Example 7, the polystyrenesulfonic acid-doped poly (3,4) obtained in Comparative Example 6 was used. -Ethylenedioxythiophene) A thin film (film thickness: 0.12 µm) was formed in the same procedure as in Example 7 except that an aqueous dispersion was used, and the surface resistivity of this thin film was measured. As a result of measuring the surface resistivity of the obtained thin film, it was 4.9E + 3Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

  As is clear from the results of Examples 6 and 7 and Comparative Examples 5 and 6, the ratio of iron element contained in the polypyrroles and polythiophenes obtained by the production method of the present invention was determined using polypyrroles produced using a metal catalyst. It was found that it was much lower than the ratio of iron element contained in polythiophenes.

(Example 8)
To a 50 mL eggplant flask, add 154 mg (1 mmol) of 3-butoxythiophene and 10 mL of methylene chloride, stir at room temperature (about 25 ° C.) under a nitrogen atmosphere, and then add 889 mg of trimethylsilyl trifluoromethanesulfonate. 46 mg (0.025 mmol) 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, 516 mg (3 mmol) metachloroperbenzoic acid, and 0.15 ml trifluoroacetic acid (2 mmol) was added.

After addition of 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, the mixture was further stirred for 20 hours. Thereafter, the reaction solution was concentrated under reduced pressure, and 20 mL of methanol was added to the residue. Subsequently, the black insoluble matter was collected by filtration with a glass filter and washed with 30 ml of methanol. Further, the insoluble matter was washed with 30 ml of diethyl ether to obtain 45 mg of purified poly (3-butoxythiophene). On the other hand, the reactant (16 mg, recovery rate: 67%) of 1,3,5,7-tetrakis- (4-iodophenyl) adamantane was recovered by concentrating the washed diethyl ether.
When the molecular weight of the obtained poly (3-butoxythiophene) was measured, the weight average molecular weight (Mw) was 2313, the number average molecular weight (Mn) was 1812, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 .28.

  The obtained poly (3-butoxythiophene) was incinerated, and the ratio of the iron element contained by the ICP-MS method was measured to be 6 ppm. The detected iron element is considered to be an iron element derived from impurities contained in the raw material, solvent and the like.

  Furthermore, a thin film was formed by the following procedure using the obtained poly (3-butoxythiophene). First, 20 mg of poly (3-butoxythiophene) was dissolved in 1 mL of chloroform to prepare a paint. Then, the prepared paint was No. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.10 μm.

Example 9
To a 50 mL eggplant flask, add 154 mg (1 mmol) of 3-butoxythiophene and 10 mL of methylene chloride, stir at room temperature (about 25 ° C.) under a nitrogen atmosphere, and then add 889 mg of trimethylsilyl trifluoromethanesulfonate. 44 mg (0.025 mmol) of tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane, 516 mg (3 mmol) of metachloroperbenzoic acid, and 0.15 ml (2 mmol) of trifluoroacetic acid were then added.

  After addition of tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane, the mixture was further stirred for 20 hours. Thereafter, the reaction solution was concentrated under reduced pressure, and 20 mL of methanol was added to the residue. Subsequently, the black insoluble matter was collected by filtration with a glass filter and washed with 30 ml of methanol. Further, 30 mg of acetone was used to dissolve poly (butoxythiophene), and the resulting solution was concentrated to obtain 43 mg of poly (3-butoxythiophene). Further, a tetrakis- (4-iodophenyl) methane reactant remains on the glass filter, which is dissolved in 20 ml of methylene chloride, and the resulting methylene chloride solution is again concentrated under reduced pressure, and tetrakis- ( Recovery of 4-iodophenyl) methane reactant (9 mg, recovery; 43%) was performed.

  When the molecular weight of the obtained poly (3-butoxythiophene) was measured, the weight average molecular weight (Mw) was 1545, the number average molecular weight (Mn) was 1498, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 0.03.

  The obtained poly (3-butoxythiophene) was incinerated, and the ratio of the iron element contained by the ICP-MS method was measured and found to be 7 ppm. The detected iron element is considered to be an iron element derived from impurities contained in the raw material, solvent and the like.

  Furthermore, a thin film was formed by the following procedure using the obtained poly (3-butoxythiophene). First, 20 mg of poly (3-butoxythiophene) was dissolved in 1 mL of chloroform to prepare a paint. Then, the prepared paint was No. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.08 μm.

(Example 10)
To a 50 mL eggplant flask, add 143 mg (1 mmol) of 3-phenylpyrrole and 10 mL of methylene chloride, stir at room temperature (about 25 ° C.) under a nitrogen atmosphere, and then add 889 mg of trimethylsilyl trifluoromethanesulfonate. 46 mg (0.025 mmol) 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, 516 mg (3 mmol) metachloroperbenzoic acid, and 0.15 ml trifluoroacetic acid (2 mmol) was added.

After addition of 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, the mixture was further stirred for 20 hours. Thereafter, the reaction solution was concentrated under reduced pressure, and 20 mL of methanol was added to the residue. Subsequently, the black insoluble matter was collected by filtration with a glass filter and washed with 30 ml of methanol. The insoluble material was further washed with 30 ml of diethyl ether to obtain 68 mg of purified poly (3-phenylpyrrole). On the other hand, the reactant (11 mg, recovery rate: 47%) of 1,3,5,7-tetrakis- (4-iodophenyl) adamantane was recovered by concentrating the washed diethyl ether.
When the molecular weight of the obtained poly (3-phenylpyrrole) was measured, the weight average molecular weight (Mw) was 1355, the number average molecular weight (Mn) was 1338, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 .01.

  The obtained poly (3-phenylpyrrole) was incinerated, and the ratio of the iron element contained by the ICP-MS method was measured and found to be 12 ppm. The detected iron element is considered to be an iron element derived from impurities contained in the raw material, solvent and the like.

  Furthermore, a thin film was formed by the following procedure using the obtained poly (3-phenylpyrrole). First, 20 mg of poly (3-phenylpyrrole) was dissolved in 1 mL of chloroform to prepare a coating material. Then, the prepared paint was No. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.12 μm.

  Next, in place of the poly (3-phenylpyrrole) thin film obtained in Example 2 above, the poly (3-phenylpyrrole) thin film obtained in Example 10 was used, except that the above Example 2 was used. The surface resistivity was measured by the same method. As a result of measuring the surface resistivity of the obtained thin film, it was 4.7E + 9Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

(Example 11)
To a 50 mL eggplant flask, add 143 mg (1 mmol) of 3-phenylpyrrole and 10 mL of methylene chloride, stir at room temperature (about 25 ° C.) under a nitrogen atmosphere, and then add 889 mg of trimethylsilyl trifluoromethanesulfonate. 44 mg (0.025 mmol) of tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane, 516 mg (3 mmol) of metachloroperbenzoic acid, and 0.15 ml (2 mmol) of trifluoroacetic acid were then added.

  After addition of tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane, the mixture was further stirred for 20 hours. Thereafter, the reaction solution was concentrated under reduced pressure, and 20 mL of methanol was added to the residue. Subsequently, the black insoluble matter was collected by filtration with a glass filter and washed with 30 ml of methanol. Furthermore, 30 mg of acetone was used to dissolve poly (butoxythiophene), and the resulting solution was concentrated to obtain 60 mg of poly (3-phenylpyrrole). Further, a tetrakis- (4-iodophenyl) methane reactant remains on the glass filter, which is dissolved in 20 ml of methylene chloride, and the resulting methylene chloride solution is again concentrated under reduced pressure, and tetrakis- ( Recovery of the 4-iodophenyl) methane reactant (10 mg, recovery; 48%) was performed.

  When the molecular weight of the obtained poly (3-phenylpyrrole) was measured, the weight average molecular weight (Mw) was 1337, the number average molecular weight (Mn) was 1315, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 .02.

  The obtained poly (3-phenylpyrrole) was incinerated, and the ratio of the iron element contained by the ICP-MS method was measured and found to be 8 ppm. The detected iron element is considered to be an iron element derived from impurities contained in the raw material, solvent and the like.

  Furthermore, a thin film was formed by the following procedure using the obtained poly (3-phenylpyrrole). First, 20 mg of poly (3-phenylpyrrole) was dissolved in 1 mL of chloroform to prepare a coating material. Then, the prepared paint was No. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.15 μm.

  Next, in place of the poly (3-phenylpyrrole) thin film obtained in Example 2 above, the poly (3-phenylpyrrole) thin film obtained in Example 11 was used except that the above Example 2 was used. The surface resistivity was measured by the same method. As a result of measuring the surface resistivity of the obtained thin film, it was 1.0E + 9Ω / □. From this result, it was found that the obtained thin film had antistatic performance.

Example 12
To a 50 mL eggplant flask, 78 mg (0.5 mmol) of 3-butoxythiophene and 10 mL of methylene chloride are added and stirred at room temperature (about 25 ° C.) under a nitrogen atmosphere, and then 666 mg of trimethylsilyl trifluoromethanesulfonate. And then 346 mg (0.187 mmol) of 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane was added.

After addition of 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, the mixture was further stirred for 10 hours. Thereafter, the reaction solution was concentrated under reduced pressure, and 20 mL of methanol was added to the residue. Subsequently, it filtered using the glass filter and 53 mg of poly (3-butoxythiophene) was obtained by concentrating the methanol solution of a filtrate. Also, the residue remaining on the glass filter was dissolved in 40 ml of methylene chloride and concentrated again under reduced pressure to recover 1,3,5,7-tetrakis- (4-iodophenyl) adamantane (112 mg, recovery rate: 63%). did.
When the molecular weight of the obtained poly (3-butoxythiophene) was measured, the weight average molecular weight (Mw) was 1867, the number average molecular weight (Mn) was 1322, and the ratio Mw / Mn between the weight average molecular weight and the number average molecular weight was 1 .41.

  The obtained poly (3-butoxythiophene) was incinerated, and the ratio of the iron element contained by the ICP-MS method was measured and found to be 5 ppm. The detected iron element is considered to be an iron element derived from impurities contained in the raw material, solvent and the like.

  Furthermore, a thin film was formed by the following procedure using the obtained poly (3-butoxythiophene). First, 20 mg of poly (3-butoxythiophene) was dissolved in 1 mL of chloroform to prepare a paint. Then, the prepared paint was No. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.07 μm.

(Example 13)
To a 50 mL eggplant flask, 522 mg (4 mmol) of 1,4-dimethoxybenzene and 20 mL of methylene chloride were added and cooled to −78 ° C. under a nitrogen atmosphere (using dry ice and methanol as a cryogen). Then 3.2 g (16 mmol) of boron trifluoride-ethyl ether complex was added followed by 3.44 g (8 mmol) of PIFA.

  Eight hours after the addition of PIFA, the cryogen was removed and the reaction temperature was gradually raised to room temperature. Furthermore, stirring was performed for 8 hours, and the reaction time after the addition of PIFA was 16 hours in total.

  The reaction solution was concentrated, 50 ml of methanol was added, and insoluble matters of the reaction solution were collected by filtration with a glass filter. Subsequently, the insoluble material was washed with methanol, and further washed with n-hexane to obtain 415 mg of poly (2,5-dimethoxy-p-phenylene).

  When the molecular weight of the obtained poly (2,5-dimethoxy-p-phenylene) was measured, the weight average molecular weight (Mw) was 15213, the number average molecular weight (Mn) was 10865, and the ratio of the weight average molecular weight to the number average molecular weight. Mw / Mn was 1.40.

  The obtained poly (2,5-dimethoxy-p-phenylene) was incinerated, and the ratio of iron element contained by the ICP-MS method was measured to be 4 ppm. The detected iron element is considered to be an iron element derived from impurities contained in the raw material, solvent and the like.

  Furthermore, a thin film was formed by the following procedure using the obtained poly (2,5-dimethoxy-p-phenylene). First, 20 mg of poly (2,5-dimethoxy-p-phenylene) was dissolved in 1 mL of chloroform to prepare a paint. Then, the prepared paint was No. It applied to the glass plate (JIS R3202) using the wire bar of 8 (application quantity: thickness of 18 micrometers in the wet state). Next, the film was blown and dried at 100 ° C. for 2 minutes to obtain a thin film. The thickness of the obtained thin film was 0.15 μm.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the polymer of an aromatic compound and a heterocyclic aromatic compound with little metal ion content can be provided. Therefore, the polymer of the aromatic compound and the heterocyclic aromatic compound obtained by the production method of the present invention is an antistatic agent for electronic films, sheets, molded articles, parts, etc., hole injection material for organic electroluminescence , Luminescent material, surface electrode of electroluminescence panel, pixel electrode of liquid crystal display, capacitor electrode, transparent electrode of touch panel, transparent electrode of membrane switch, transparent electrode of electronic paper, etc., electromagnetic shielding of cathode ray tube display, liquid crystal It can be used as an electromagnetic wave shield for noise reduction, such as a display and a pachinko machine, a light control glass, and an electrode of an organic TFT.

Claims (11)

  A method for producing a polymer, comprising a step of oxidative polymerization of an aromatic compound using a hypervalent iodine reactant.   A method for producing a polymer, comprising a step of oxidatively polymerizing a heterocyclic aromatic compound using a hypervalent iodine reactant.   The production method according to claim 1, wherein the aromatic compound is a benzene-based aromatic compound.   The production method according to claim 2, wherein the heteroatom of the heterocyclic aromatic compound is any one of nitrogen, sulfur, and oxygen.   The production method according to claim 3, wherein the benzene-based aromatic compound is benzene or 1,4-substituted benzene.   The production method according to claim 2, wherein the heterocyclic aromatic compound is a pyrrole, and the polymer is a polypyrrole.   The production method according to claim 2, wherein the heterocyclic aromatic compound is a thiophene, and the polymer is a polythiophene.   The method according to any one of claims 1 to 7, wherein the hypervalent iodine reactant has an adamantane structure.   The production method according to any one of claims 1 to 7, wherein the hypervalent iodine reactant has a tetraphenylmethane structure.   The manufacturing method according to any one of claims 1 to 9, wherein an oxidizing agent not containing a metal is further used in the oxidative polymerization step.   The amount of the hypervalent iodine reactant used is 0.001 to 0.3 mol with respect to 1 mol of the aromatic compound or heterocyclic aromatic compound, and the amount of the oxidizing agent not containing the metal is aromatic. The manufacturing method of Claim 10 which is 1-4 molar equivalent with respect to 1 mol of an aromatic compound or a heterocyclic aromatic compound.