JP2014185086A - THIOPHENE MONOMER PRODUCTION METHOD, π-ELECTRON CONJUGATED POLYMER PRODUCTION METHOD, AND ELECTROCHROMIC SHEET - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thiophene monomer production method capable of easily and conveniently producing various thiophene monomers.SOLUTION: A method of producing a thiophene monomer represented by the general formula (2) comprises a process of mixing a halide with a titanacyclopentadiene derivative represented by the general formula (1). (R each independently represent hydrogen, halogen, alkyl, or the like, and Xrepresents divalent thiophene, selenophene, tellurophene, or the like.)

Description

The present invention relates to a method for producing a thiophene monomer capable of easily producing various thiophene monomers. The present invention also relates to a method for producing a π electron conjugated polymer including the method for producing the thiophene monomer, and an electrochromic sheet containing the π electron conjugated polymer obtained by the method for producing the π electron conjugated polymer.

A π-electron conjugated polymer formed from a thiophene monomer or a substituted thiophene monomer has a relatively low band gap (Eg), which is an energy difference between the conduction energy and the valence band, and is suitable for proper conduction. The electrochromism has a ratio and the light transmittance is changed by application of a voltage. By laminating an electrochromic sheet manufactured using a π-electron conjugated polymer and an electrolyte layer between a pair of conductive films, it is possible to manufacture a light adjuster whose light transmittance is changed by energization. .

Studies have been made for the purpose of applying the light control body to a display device such as a building or an electric light board. In recent years, a laminated glass using a dimmer as an interlayer film for laminated glass has been proposed in order to control the temperature inside a vehicle such as an automobile. It is considered that the light transmittance of the laminated glass can be controlled by using such an interlayer film for laminated glass.

Since the optical properties of the π-electron conjugated polymer vary depending on the structure of the π-electron conjugated polymer, various thiophene monomers or oligomers have been studied as materials for producing the π-electron conjugated polymer. For example, Patent Document 1 discloses a method for producing a thiophene-phenylene oligomer having a structure in which a phenylene group is sandwiched between two thiophenes. Patent Document 2 discloses a method for producing a thiophene oligomer capable of adjusting the number of thiophene monomer units in the range of 2 to 20.

JP 2005-225862 A Special table 2010-513613 gazette

As described above, the optical properties of the π-electron conjugated polymer change depending on the structure of the π-electron conjugated polymer. Therefore, in order to obtain the desired optical properties, a thiophene monomer or oligomer for producing the π-electron conjugated polymer is used. There is a need to consider a variety. In order to study such a variety of thiophene monomers or oligomers, a method for producing a variety of thiophene monomers by a simpler method is essential.
In particular, in conventional methods for producing thiophene monomers or oligomers as described in Patent Documents 1 and 2, π electrons having a unit structure in which a 5-membered ring structure or a conjugated diene structure is sandwiched between two thiophenes It was not possible to produce a conjugated polymer.

An object of this invention is to provide the manufacturing method of the thiophene monomer which can manufacture various thiophene monomers simply. The present invention also provides a method for producing a π-electron conjugated polymer including the method for producing the thiophene monomer, and an electrochromic sheet containing the π-electron conjugated polymer obtained by the method for producing the π-electron conjugated polymer. Objective.

The present invention provides a method for producing a thiophene monomer represented by the following general formula (2), which comprises a step of mixing a titanacyclopentadiene derivative represented by the following general formula (1) and a halide (of the present invention). It is also referred to as a first thiophene monomer production method).
(R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, halogen or an organic group having 1 to 20 carbon atoms, and R ₇ and R ₈ each independently represent carbon number. 1 to 6 linear or branched alkyl groups are shown.)
(R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent hydrogen, halogen or an organic group having 1 to 20 carbon atoms, X ₁ is a divalent thiophene which may have a substituent, substituted A thiophene oxide which may have a group, a selenophene which may have a substituent, a tellurophen which may have a substituent, a conjugated diene having 4 to 8 carbon atoms which may have a substituent or a substituent. (The phosphole which may have is shown.)

Further, the present invention provides a method for producing a thiophene monomer represented by the following general formula (4), which comprises a step of mixing a titanacyclopentadiene derivative represented by the following general formula (3) and a halide. It is also called the manufacturing method of the 2nd thiophene monomer of invention.
(R ₁₃ and R ₁₄ each independently represent hydrogen, halogen, or an organic group having 1 to 20 carbon atoms, and ring A ₁ and ring A ₂ each independently represent a 5-membered ring which may have a substituent or A 6-membered aromatic heterocyclic ring or a cycloalkene ring is shown, and R ₁₅ and R ₁₆ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.)
(Ring A ₃ and Ring A ₄ each independently represent a 5-membered or 6-membered aromatic heterocyclic ring or cycloalkene ring which may have a substituent, and X ₂ represents a divalent substituent. Thiophene which may have, thiophene oxide which may have a substituent, selenophene which may have a substituent, tellurophen which may have a substituent, carbon number which may have a substituent 4 to 4 8 conjugated dienes or phospholes optionally having substituents.)
The present invention is described in detail below.

The present inventor performs a process of mixing a titanacyclopentadiene derivative having a predetermined structure and a halide, and by changing the halide, a five-membered ring structure or a conjugate between two thiophenes. It has been found that various thiophene monomers having a structure in which a diene structure is sandwiched can be easily produced, and the present invention has been completed.
In addition, both the manufacturing method of the 1st thiophene monomer of this invention and the manufacturing method of the 2nd thiophene monomer of this invention perform thiophene by performing the process which mixes a titanacyclopentadiene derivative and a halide. A monomer is obtained. However, the production method of the first thiophene monomer of the present invention and the production method of the second thiophene monomer of the present invention differ in the structure of the raw material titanacyclopentadiene derivative. As a result, the resulting thiophene The monomer structure is also different.

In the manufacturing method of the 1st thiophene monomer of this invention, by performing the process of mixing the titanacyclopentadiene derivative represented by the said General formula (1), and a halide, the said General formula (2) The thiophene monomer represented is obtained.

The halogen in the general formulas (1) and (2) is not particularly limited, and a conventionally known halogen can be used.
The organic group having 1 to 20 carbon atoms in the general formulas (1) and (2) is preferably an organic group having a linear structure, an organic group having a branched structure, or an organic group having a cyclic structure. The organic group having a linear structure is preferably an alkyl group having a linear structure. The organic group having a branched structure is preferably an alkyl group having a branched structure. The organic group having a cyclic structure is preferably a phenyl group or a cycloalkyl group.

X ₁ in the general formula (2) is a divalent thiophene which may have a substituent, a thiophene oxide which may have a substituent, a selenophene which may have a substituent, or a substituent. The tellurophene which may have, the C4-C8 conjugated diene which may have a substituent, or the phosphole which may have a substituent are shown. Although a substituent is not specifically limited here, Halogen and the said C1-C20 organic group are preferable.
In addition, the thiophene which may have the above substituent, the thiophene oxide which may have a substituent, the selenophene which may have a substituent, the tellurophen which may have a substituent, the substituent A metal halide may be coordinated with the phosphole which may have a conjugated diene having 4 to 8 carbon atoms or a substituent. Examples of the metal halide include stannous chloride, bismuth chloride, bismuth bromide, indium chloride, indium iodide, zinc chloride, zinc bromide, cuprous chloride, cupric chloride, nickel chloride, palladium chloride, Examples thereof include gold chloride.

In the second method for producing a thiophene monomer of the present invention, the step of mixing the titanacyclopentadiene derivative represented by the above general formula (3) and a halide is performed to obtain the above formula (4). The thiophene monomer represented is obtained.

The halogen in the general formulas (3) and (4) is not particularly limited, and a conventionally known halogen can be used.
The organic group having 1 to 20 carbon atoms in the general formulas (3) and (4) is preferably an organic group having a linear structure, an organic group having a branched structure, or an organic group having a cyclic structure. The organic group having a linear structure is preferably an alkyl group having a linear structure. The organic group having a branched structure is preferably an alkyl group having a branched structure. The organic group having a cyclic structure is preferably a phenyl group or a cycloalkyl group.
Rings A ₁ to A ₄ in the general formulas (3) and (4) each independently represent a 5-membered or 6-membered aromatic heterocyclic ring or cycloalkene ring which may have a substituent. . Examples of the aromatic heterocycle include a pyrrole ring, a pyridine ring, a thiophene ring, a selenophene ring, a tellurophen ring, and a benzene ring. Examples of the cycloalkene ring include a cyclopentene ring and a cyclohexene ring.

X ₂ in the general formula (4) is a divalent thiophene which may have a substituent, a thiophene oxide which may have a substituent, a selenophene which may have a substituent, or a substituent. The tellurophene which may have, the C4-C8 conjugated diene which may have a substituent, or the phosphole which may have a substituent are shown. Although a substituent is not specifically limited here, Halogen and the said C1-C20 organic group are preferable.
In addition, the thiophene which may have the above substituent, the thiophene oxide which may have a substituent, the selenophene which may have a substituent, the tellurophen which may have a substituent, the substituent A metal halide may be coordinated with the phosphole which may have a conjugated diene having 4 to 8 carbon atoms or a substituent. Examples of the metal halide include stannous chloride, bismuth chloride, bismuth bromide, indium chloride, indium iodide, zinc chloride, zinc bromide, cuprous chloride, cupric chloride, nickel chloride, palladium chloride. And gold chloride.

In the method for producing the first thiophene monomer of the present invention and the method for producing the second thiophene monomer of the present invention, the halide is not particularly limited, but sulfur chloride, selenium chloride, tellurium tetrachloride, thionyl chloride, chloride At least one selected from the group consisting of hydrogen, phenylsulfenyl chloride, phenylchloroselenide and dichlorophenylphosphine is preferable. Moreover, phenyl selenyl chloride and iodine can also be used as the halide.
Although the compounding quantity of the said halide is not specifically limited, The preferable minimum with respect to 1 mol of said titanacyclopentadiene derivatives is 0.4 mol, and a preferable upper limit is 4 mol. When the blending amount of the halide is less than 0.4 mol, the unreacted titanacyclopentadiene derivative increases, which may lead to a reduction in yield. When the amount of the halide exceeds 4 mol, the amount of unreacted halogen increases, the number of purifications increases, and the yield may be reduced. As for the compounding quantity of the said halide, the more preferable minimum with respect to 1 mol of said titanacyclopentadiene derivatives is 1 mol, and a more preferable upper limit is 2 mol.

In the method for producing the first thiophene monomer of the present invention and the method for producing the second thiophene monomer of the present invention, the yield of the obtained thiophene monomer is improved. It is preferable to mix the clopentadiene derivative and the halide. The inert gas is not particularly limited, and a conventionally known inert gas such as nitrogen or argon can be used.
Moreover, since the yield of the obtained thiophene monomer improves, it is preferable to mix the said titanacyclopentadiene derivative and the said halide at -40 degrees C or less. From the viewpoint of further improving the yield, it is more preferably −50 ° C. or lower, and further preferably −78 ° C. or lower.
Moreover, since the yield of the thiophene monomer obtained improves, it is preferable to mix the said titanacyclopentadiene derivative and the said halide in presence of an organic solvent. Although the said organic solvent is not specifically limited, A conventionally well-known organic solvent can be used, However, Since the yield of the thiophene monomer obtained improves, ether, such as diethyl ether and cyclopentyl methyl ether (CPME), toluene, acetonitrile Is preferred.
Moreover, since the yield of the thiophene monomer obtained improves, it is preferable to mix the said titanacyclopentadiene derivative and the said halide in presence of a catalyst. As the catalyst, an organometallic compound containing an alkyl group and a halogen is preferable. As the alkyl group, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and an alkyl group having a cyclic structure having 3 to 6 carbon atoms are preferable. As the halogen, chlorine or iodine is preferable. The organometallic compound preferably further contains magnesium. Since the yield is further improved, the organometallic compound containing an alkyl group and a halogen is more preferably isopropylmagnesium chloride.

A step of obtaining a thiophene monomer by the method for producing the first thiophene monomer of the present invention or the method for producing the second thiophene monomer of the present invention, and polymerizing the thiophene monomer, the following general formula (5) or (6 A method for producing a π-electron conjugated polymer comprising a step of obtaining a π-electron conjugated polymer having a unit structure represented by () is also one aspect of the present invention.
(R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ each independently represent hydrogen, halogen or an organic group having 1 to 20 carbon atoms, and X ₃ is a divalent thiophene which may have a substituent, substituted A thiophene oxide which may have a group, a selenophene which may have a substituent, a tellurophen which may have a substituent, a conjugated diene having 4 to 8 carbon atoms which may have a substituent or a substituent. (The phosphole which may have is shown, and n shows an integer.)
(Ring A ₅ and Ring A ₆ each independently represent a 5-membered or 6-membered aromatic heterocyclic ring or cycloalkene ring which may have a substituent, and X ₄ represents a divalent substituent. Thiophene which may have, thiophene oxide which may have a substituent, selenophene which may have a substituent, tellurophen which may have a substituent, carbon number which may have a substituent 4 to 4 8 is a conjugated diene or a phosphole optionally having a substituent, and n is an integer.)

Although the upper limit and lower limit of n in the general formula (5) or (6) are not particularly limited, the upper limit is preferably 10,000, the lower limit is preferably 10, more preferably 50, and even more preferably 100. Moreover, the number average molecular weight of the π-electron conjugated polymer having the unit structure represented by the general formula (5) or (6) is not particularly limited, but is preferably 2000 to 5000000, and more preferably 10000 to 5000000.

The halogen in the general formula (5) is not particularly limited, and a conventionally known halogen can be used.
The organic group having 1 to 20 carbon atoms in the general formula (5) is preferably an organic group having a linear structure, an organic group having a branched structure, or an organic group having a cyclic structure. The organic group having a linear structure is preferably an alkyl group having a linear structure. The organic group having a branched structure is preferably an alkyl group having a branched structure. The organic group having a cyclic structure is preferably a phenyl group or a cycloalkyl group.
Ring A ₅ and ring A ₆ in the general formula (6) each independently represent a 5-membered or 6-membered aromatic heterocycle or cycloalkene ring which may have a substituent. Examples of the aromatic heterocycle include a pyrrole ring, a pyridine ring, a thiophene ring, a selenophene ring, a tellurophen ring, and a benzene ring. Examples of the cycloalkene ring include a cyclopentene ring and a cyclohexene ring.

X ₃ in the general formula (5) and X ₄ in the general formula (6) are divalent thiophene that may have a substituent, thiophene oxide that may have a substituent, Selenophene which may have a substituent, tellurophen which may have a substituent, conjugated diene having 4 to 8 carbon atoms which may have a substituent, or phosphole which may have a substituent are shown. Although a substituent is not specifically limited here, Halogen and the said C1-C20 organic group are preferable.
In addition, the thiophene which may have the above substituent, the thiophene oxide which may have a substituent, the selenophene which may have a substituent, the tellurophen which may have a substituent, the substituent A metal halide may be coordinated with the phosphole which may have a conjugated diene having 4 to 8 carbon atoms or a substituent. Examples of the metal halide include stannous chloride, bismuth chloride, bismuth bromide, indium chloride, indium iodide, zinc chloride, zinc bromide, cuprous chloride, cupric chloride, nickel chloride, palladium chloride. And gold chloride.

The method for polymerizing the thiophene monomer is not particularly limited, and examples thereof include a thermal polymerization method and an electrolytic polymerization method. Especially, since the yield of the obtained pi-electron conjugated polymer improves, it is preferable to polymerize the said thiophene monomer by an electrolytic polymerization method.

As the electrolytic polymerization method, by applying a voltage between the electrodes via a solution in which the monomer component containing the thiophene monomer is dissolved in an organic solvent, or an electrolytic solution in which a supporting electrolyte is further dissolved in this solution, A method of obtaining a π-electron conjugated polymer on the anode as an anodized polymer is preferable.
Examples of the organic solvent include propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, butylene carbonate, γ-butyl lactone, tetramethyl urea, sulfolane, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolide. Non, 2- (N-methyl) -2-pyrrolidinone, hexamethyl phosphortriamide, N-methylpropionamide, N, N-dimethylacetamide, N-methylacetamide, N, N dimethylformamide, N-methylformamide, butyronitrile , Propionitrile, acetonitrile, acetylacetone, 4-methyl-2-pentanone, 2-butanol, 1-butanol, 2-propanol, 1-propanol, acetic anhydride, ethyl acetate Ethyl propionate, dimethoxyethane, diethoxy furan, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol monobutyl ether, tricresyl phosphate, 2-ethylhexyl phosphate, dioctyl phthalate, dioctyl sebacate, and the like. Of these, carboxylic acid ester compounds such as propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, butylene carbonate, and γ-butyl lactone are preferred.

Examples of the supporting electrolyte in the electrolytic solution include ions of alkali metals such as lithium ions, potassium ions, and sodium ions, and cations such as quaternary ammonium ions, perchlorate ions, boron tetrafluoride ions, and phosphorus hexafluoride ions. And a supporting salt composed of a combination with anions such as halogen atom ions, arsenic hexafluoride ions, antimony hexafluoride ions, sulfate ions and hydrogen sulfate ions.
The content of the supporting electrolyte in the electrolytic solution is preferably 0.01 to 10 mol / L, more preferably 0.1 to 5 mol / L.

Examples of the electrolytic solution include ammonium ions such as imidazolium salts and pyridinium salts, cations such as phosphonium ions, inorganic ions, and halogen ions, and fluorine ions such as fluoride ions and triflate. It is also possible to use a solution in which a monomer component containing the thiophene monomer is dissolved in an ionic liquid in combination with the above anion.

Although the content rate of the monomer component containing the said thiophene monomer in the said solution or the said electrolyte solution is not specifically limited, Preferably it is 0.0001-10 mol / L, More preferably, it is 0.0001-0.5 mol / L.

The material of the electrode is not particularly limited. For example, metals such as platinum, gold, nickel, and silver, conductive polymers, ceramics, semiconductors, carbon, conductive carbides such as conductive diamond, and indium tin oxide (ITO) Further, metal oxides such as antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), and ZnO can be used.

Although the voltage at the time of the said voltage application is not specifically limited, -3-3V is preferable with respect to a silver / silver chloride reference electrode or a standard hydrogen electrode (SCE), and -2-2V is more preferable. Although the temperature at the time of applying the voltage is not particularly limited, 0 to 80 ° C is preferable, and 15 to 40 ° C is more preferable.

By such an electrolytic polymerization method, the π-electron conjugated polymer can be obtained in a sheet form or a layer form. Such a layer containing a π-electron conjugated polymer is suitably used as a material for constituting various electronic devices.
The layer containing the π electron conjugated polymer may contain other components as long as the performance as an electronic element is not hindered. As the other components, for example, chromic properties are obtained by redox such as single-walled carbon nanotubes, double-walled carbon nanotubes, π-electron conjugated carbides such as fullerene, viologen or derivatives thereof, Prussian blue or derivatives thereof, tungsten oxide or derivatives thereof, and the like. And the like.
However, the content of the π-electron conjugated polymer in the layer containing the π-electron conjugated polymer is preferably 50% by mass or more, and more preferably 80% by mass or more.

It is preferable that a dopant is added as an electrolytic component to the layer containing the π-electron conjugated polymer. The dopant is not particularly limited. For example, a halogenated anion of a Group 5B element such as PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ^−, a halogenated anion of a Group 3B element such as BF ₄ ⁻ , I ⁻ (I ₃ ⁻ ), Halogen anions such as Br ⁻ and Cl ⁻ , halogen acid anions such as ClO ₄ ⁻ , metal halide anions such as AlCl ₄ ⁻ , FeCl ₄ ⁻ and SnCl ₅ ⁻ , nitrate anions represented by NO ₃ ⁻ , SO ₄ sulfate anion represented ² by, p- toluenesulfonate anion, a naphthalenesulfonic acid ^{_{anion, CH 3 SO 3 -, CF}} 3 SO 3 - and the like organic sulfonic acid ^{_{anion, CF 3 COO -, C 6}} H 5 COO - , etc. Carboxylic acid anions, modified polymers having these anionic species in the main chain or side chain, and the like. These may be used alone or in combination of two or more.

The form of addition of the dopant is not particularly limited. For example, in an electronic device, an electrolyte layer containing the dopant is adjacent to the layer containing the π-electron conjugated polymer, and a dopant is applied by applying a voltage during operation of the electronic device. And a method in which a dopant is previously contained in the layer containing the π-electron conjugated polymer. The electrolyte layer may be solid, gel, or liquid.
In addition, when the layer containing the π-electron conjugated polymer formed on the anode by the electrolytic polymerization method as described above is used as a component of the electronic element together with the anode without being removed from the anode, it was used at the time of electrolytic polymerization. The anion derived from the supporting electrolyte can be used as it is as a dopant. When a π-electron conjugated polymer is obtained by chemical oxidative polymerization, the anion derived from the oxidizing agent used can be used as a dopant as it is.

The use of the π-electron conjugated polymer obtained by the method for producing a π-electron conjugated polymer of the present invention is not particularly limited. For example, the π-electron conjugated polymer is used as a π-electron conjugated polymer composition by mixing it with other components. be able to.

The π-electron conjugated polymer composition is mixed with water, a water-miscible organic solvent, an organic solvent or the like to obtain a dispersion containing the π-electron conjugated polymer composition, and this dispersion is used as a conventionally known coating method ( For example, inkjet printing, screen printing, roll baking, spin coating, meniscus and dip coating, spray coating, brush coating, doctor blade coating, curtain casting, etc.) and drying to remove the solvent, A desired sheet can be obtained.
The drying can be carried out at room temperature or any temperature that does not adversely affect the intended properties of the resulting sheet (more specifically, a temperature of room temperature to 200 ° C.). The thickness of the obtained sheet is usually about 50 nm to 25 μm.

The π-electron conjugated polymer composition may contain additives such as an antioxidant, a UV stabilizer, a surfactant, a viscosity modifier, and an associative thickener, depending on the application. By adding a surfactant, stability, surface tension and surface wettability can be controlled. The viscosity can be adjusted by adding a viscosity modifier or an associative thickener.

The conductivity of the π-electron conjugated polymer composition is adjusted by doping with an acidic dopant (p-dopant) and a basic dopant (n-dopant), if necessary, to suit a particular application. be able to.
Examples of the p-dopant include at least one mineral acid (eg, HCl, HNO ₃ , H ₂ SO ₄ , H ₃ PO ₄ , HBr, HI, etc.), an organic sulfonic acid (eg, dodecylbenzene sulfonic acid, lauryl sulfone). Acid, camphorsulfonic acid, methanesulfonic acid, toluenesulfonic acid, etc.), high molecular weight sulfonic acids (eg, poly (styrenesulfonic acid) and copolymers), organic acid dyes, carboxylic acids (eg, acetic acid, propionic acid, butyric acid) , Hexanoic acid, adipic acid, azelaic acid, oxalic acid, etc.), high molecular weight polycarboxylic acids (eg, poly (acrylic acid), poly (maleic acid), poly (methacrylic acid) and copolymers of these acids) preferable. These may be used alone or in combination of two or more. For example, mixed dopants (eg, mineral / organic acids, etc.) can be utilized.
Examples of the n-dopant include general basic dopants including Na, K, Li, and Ca, I ₂ , (PF ₆ ) ⁻ , (SbF ₆ ) ⁻ , FeCl _{3, and the} like.

The amount of the dopant is preferably about 1 to 98% by mass of the π-electron conjugated polymer composition, or an amount sufficient for doping at least 1%.

The application of the π-electron conjugated polymer composition is not particularly limited and may be used as a transparent conductive material or an opaque conductive material. Specifically, for example, an antistatic coating, a conductive coating, an electro Chromic element, photovoltaic element, light emitting diode (LED), flat panel display, photosensitive circuit, printed circuit, sheet transistor element, battery, electrical switch, capacitor coating, anticorrosion coating, electromagnetic shielding, sensor, LED lighting, other optoelectronics ( Electro-optical, or an optoelectronic element that operates as an opto-electric transducer).

By using the π-electron conjugated polymer composition (doping composition) as an aqueous or organic solvent-based dispersion, this dispersion can be used as an antistatic coating applied to a substrate. Such antistatic coatings can achieve a balance between conductivity and sheet properties such as adhesion to an appropriate substrate.

The electrochromic element permits or prevents light transmission through a transparent substrate by applying a voltage to both ends of a known general substrate.
An electrochromic sheet containing a π-electron conjugated polymer obtained by the method for producing a π-electron conjugated polymer of the present invention is also one aspect of the present invention.

The LED has, for example, many layers including a substrate, an indium tin oxide (ITO) anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode.
When the π-electron conjugated polymer composition is used in an LED, for example, the π-electron conjugated polymer composition (p-doped composition) is adapted to replace an indium tin oxide (ITO) anode. The π electron conjugated polymer composition (undoped composition) can be used for a hole transport layer, a light emitting layer and / or an electron transport layer.

In addition, using the π-electron conjugated polymer composition, for example, a light transmissive electrode, a transparent conductive adhesive, a stealth coating, a transparent electromagnetic solution (EMF) shielding material, a touch screen, a flat screen display, and mobile use An optically transparent conductive coating can be prepared for use in a flat antenna, a transparent power storage plate, and the like.
Moreover, an electrolyte capacitor can be produced using the π-electron conjugated polymer composition. The electrolyte capacitor includes a first layer formed of a foil of an oxidizable metal (for example, aluminum, niobium, tantalum, etc.), a second layer formed of a metal oxide on the metal foil, and the metal The third layer formed of the π-electron conjugated polymer composition on the oxide layer is a structure formed by laminating each.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the thiophene monomer which can manufacture various thiophene monomers easily can be provided. The present invention also provides a method for producing a π-electron conjugated polymer including the method for producing the thiophene monomer, and an electrochromic sheet containing the π-electron conjugated polymer obtained by the method for producing the π-electron conjugated polymer. be able to.

6 is a diagram showing a cyclic voltammogram of the electrochromic sheet obtained in Example 5. FIG. 6 is a diagram showing a cyclic voltammogram of the electrochromic sheet obtained in Example 6. FIG. 6 is a diagram showing a cyclic voltammogram of the electrochromic sheet obtained in Example 7. FIG. 10 is a diagram showing a cyclic voltammogram of the electrochromic sheet obtained in Example 8. FIG. 10 is a diagram showing a cyclic voltammogram of the electrochromic sheet obtained in Example 9. FIG. It is a figure which shows the cyclic voltammogram of the electrochromic sheet | seat obtained in Example 10. FIG. It is a figure which shows the ultraviolet visible absorption spectrum of the electrochromic sheet obtained in Example 5. FIG. It is a figure which shows the ultraviolet visible absorption spectrum of the electrochromic sheet | seat obtained in Example 6. FIG. It is a figure which shows the ultraviolet visible absorption spectrum of the electrochromic sheet obtained in Example 7. It is a figure which shows the ultraviolet visible absorption spectrum of the electrochromic sheet obtained in Example 8. It is a figure which shows the ultraviolet visible absorption spectrum of the electrochromic sheet | seat obtained in Example 9. FIG. It is a figure which shows the ultraviolet visible absorption spectrum of the electrochromic sheet obtained in Example 10. FIG.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

Example 1
(Synthesis of 2- (trimethylsilylethynyl) thiophene)
Under an argon atmosphere, 0.18 g of palladium chloride, 0.53 g of triphenylphosphine, 0.19 g of copper iodide and 6.7 g of 2-iodothiophene were added to the eggplant flask. Further, 70 mL of tetrahydrofuran (THF), 35 mL of diisopropylamine and 4.1 g of trimethylsilylacetylene were added, and the reaction and mixing were performed by stirring at 23 ° C. for 17 hours. An aqueous ammonium chloride solution was added to the obtained reaction mixture, and extraction was performed three times with diethyl ether. The obtained organic layer was dried using magnesium sulfate and purified by silica gel column chromatography using hexane as a developing solvent to obtain 5.8 g of 2- (trimethylsilylethynyl) thiophene.
When the obtained 2- (trimethylsilylethynyl) thiophene was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ0.25 (s, SiCH ₃ , 9H), 6.95 (dd, J = 3. 6 Hz, 4.5 Hz, aromatic, 1H), 7.23-7.25 (m, aromatic, 2H) ppm peaks were observed. When analyzed by ¹³ C-NMR (CDCl ₃ , 75 MHz), peaks of δ0.00, 97.7, 98.9, 123.4, 127.0, 127.4, 132.8 ppm were observed. It was.

(Synthesis of 2-ethynylthiophene)
50 mL of THF and 20 mL of 1 mol / L potassium hydroxide methanol solution were added to 1.2 g of 2- (trimethylsilylethynyl) thiophene in an eggplant flask, and the mixture was stirred at 23 ° C. for 4 hours. After completion of the reaction, an aqueous ammonium chloride solution was added, and extraction was performed 3 times with diethyl ether. The obtained organic layer was dried using magnesium sulfate and purified by silica gel column chromatography using ether as a developing solvent to obtain 0.50 g of 2-ethynylthiophene.
When the obtained 2-ethynylthiophene was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 3.33 (s, C≡C—H, 1H), 6.98 (dd, J = 3. 9 Hz, 4.8 Hz, aromatic, 1H), 7.12-7.29 (m, aromatic, 2H) ppm peaks were observed.

(Synthesis of thiophene monomer)
Under an argon atmosphere, 0.17 g of the obtained 2-ethynylthiophene and 0.31 g of tetraisopropoxytitanium were stirred at −78 ° C. using 20 mL of cyclopentylmethyl ether (CPME) as a solvent, and then 1.0 mol / L isopropyl magnesium. 2.2 mL of a diethyl ether solution of chloride was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours to obtain a titanacyclopentadiene derivative represented by the following formula (x).
Thereafter, 0.27 g of phenylsulfenyl chloride was added, and the mixture was gradually heated to 23 ° C. with stirring for 3 hours to be mixed. After completion of the reaction, 30 mL of a 1.0 mol / L hydrochloric acid aqueous solution was added, extraction was performed three times with methylene chloride, and the obtained organic layer was dried using magnesium sulfate. After completion of drying, the product is purified by silica gel column chromatography using methylene chloride as a developing solvent, and further recrystallized with a mixed solvent of methanol and methylene chloride, thereby obtaining a thiophene monomer represented by the following formula (a) 0. 20 g was obtained.
When the obtained thiophene monomer represented by the following formula (a) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 6.89 to 6.92 (m, aromatic, 2H), 7.12 Peaks of ˜7.30 (m, aromatic, 14H) and 7.80 (s, S—C═CH, 2H) ppm were observed. Further, analysis by ¹³ C-NMR (CDCl ₃ , 75 MHz) revealed that δ126.0, 126.4, 126.6, 127.8, 128.1, 129.0, 130.3, 131.7. , 136.0, and 145.7 ppm peaks.

(Example 2)
(Synthesis of thiophene monomer)
Under an argon atmosphere, using 20 mL of cyclopentyl methyl ether (CPME) as a solvent, 0.19 g of 2-ethynylthiophene and 0.34 g of tetraisopropoxytitanium obtained in Example 1 were stirred at −78 ° C., and then 1.0 mol. 2.4 mL of diethyl ether solution of / L isopropylmagnesium chloride was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours to obtain a titanacyclopentadiene derivative represented by the above formula (x).
Thereafter, 0.39 g of phenylselenyl chloride was added and mixed by gradually heating to 23 ° C. while stirring for 2 hours. After completion of the reaction, 30 mL of a 1.0 mol / L hydrochloric acid aqueous solution was added, extraction was performed three times with methylene chloride, and the obtained organic layer was dried using magnesium sulfate. After completion of drying, the product is purified by silica gel column chromatography using methylene chloride as a developing solvent, and further recrystallized with a mixed solvent of methanol and methylene chloride, thereby obtaining a thiophene monomer represented by the following formula (b) 0. 20 g was obtained.
When the obtained thiophene monomer represented by the following formula (b) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 6.92-6.95 (m, aromatic, 2H), 7.16. Peaks of −7.23 (m, aromatic, 8H), 7.32-7.39 (m, aromatic, 6H), 7.73 (s, Se—C═CH, 2H) ppm were observed. Further, analysis by ¹³ C-NMR (CDCl ₃ , 75 MHz) revealed that δ126.3, 126.6, 127.2, 127.7, 128.7, 129.3, 130.6, 131.8 , 133.9 and 146.9 ppm peaks were observed.

(Example 3)
(Synthesis of thiophene monomer)
Under an argon atmosphere, 0.26 g of 2-ethynylthiophene and 0.31 g of tetraisopropoxytitanium obtained in Example 1 were stirred at −78 ° C. using 12 mL of diethyl ether as a solvent, and then 1.0 mol / L isopropyl magnesium. 3.4 mL of a diethyl ether solution of chloride was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours to obtain a titanacyclopentadiene derivative represented by the above formula (x).
Thereafter, 0.30 g of dichlorophenylphosphine was added and mixed by gradually heating to 23 ° C. while stirring for 2 hours. After completion of the reaction, water was added, extraction was performed 3 times with methylene chloride, and the obtained organic layer was dried using magnesium sulfate. After completion of drying, the product is purified by alumina column chromatography using hexane as a developing solvent, and further recrystallized with a mixed solvent of methanol and methylene chloride, thereby obtaining 0.050 g of a thiophene monomer represented by the following formula (c). Got.
When the obtained thiophene monomer represented by the following formula (c) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 6.85-6.89 (m, aromatic, 2H), 6.96. (D, J = 10.8 Hz, P—C═CH, 2H), 7.06-7.11 (m, aromatic, 4H), 7.21-7.33 (m, aromatic, 3H) ppm peak Was recognized. Further, analysis by ¹³ C-NMR (CDCl ₃ , 75 MHz) revealed that δ124.2, 124.3, 127.8, 128.9 (d, J = 8.6 Hz), 130.1 (d, J = 1.1 Hz), 131.0 (d, J = 9.8 Hz), 131.6 (d, J = 7.4 Hz), 134.1 (d, J = 20.0 Hz), 140.2 ( d, J = 21.2 Hz) and 143.6 (d, J = 3.4 Hz) ppm peaks were observed. ^Furthermore, was analyzed by _{31 P-NMR (CDCl 3,} 121MHz), the peak of δ8.0ppm were observed.

Example 4
(Synthesis of thiophene monomer)
Under an argon atmosphere, 20 mL of cyclopentyl methyl ether (CPME) was used as a solvent, and 0.22 g of 2-ethynylthiophene and 0.40 g of tetraisopropoxytitanium obtained in Example 1 were stirred at −78 ° C., and then 1.0 mol. 2.8 mL of diethyl ether solution of / L isopropylmagnesium chloride was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours to obtain a titanacyclopentadiene derivative represented by the above formula (x).
Thereafter, 0.17 g of thionyl chloride was added, and the mixture was gradually heated to 23 ° C. while stirring for 3 hours, and mixed. 1 mol / L hydrochloric acid aqueous solution was added after completion | finish of reaction, the methylene chloride extracted 3 times, and the obtained organic layer was dried using magnesium sulfate. After completion of drying, the product was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 0.21 g of a thiophene monomer represented by the following formula (d).
When the obtained thiophene monomer represented by the following formula (d) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 6.73 (s, O = S—C═CH, 2H), 7 .11 (dd, J = 4.2 Hz, 4.2 Hz, aromatic, 2H), 7.37 (d, J = 5.4 Hz, aromatic, 2H), 7.59 (d, J = 3.9 Hz, aromatic) , 2H) ppm peak was observed.

(Example 5)
(Synthesis of thiophene monomer)
Under an argon atmosphere, 0.22 g of 2-ethynylthiophene and 0.40 g of tetraisopropoxytitanium obtained in Example 1 were stirred at −78 ° C. using 10 mL of cyclopentyl methyl ether (CPME) as a solvent, and then 1.0 mol. 2.8 mL of diethyl ether solution of / L isopropylmagnesium chloride was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours to obtain a titanacyclopentadiene derivative represented by the above formula (x).
Thereafter, 0.19 g of sulfur chloride was added and mixed by gradually heating to 23 ° C. while stirring for 2 hours. After completion of the reaction, water was added, extraction was performed 3 times with diethyl ether, and the obtained organic layer was dried using magnesium sulfate. After completion of drying, the product is purified by silica gel column chromatography using hexane as a developing solvent, and further recrystallized with a mixed solvent of hexane and methylene chloride, whereby 0.028 g of a thiophene monomer represented by the following formula (e) is obtained. Got.
When the obtained thiophene monomer represented by the following formula (e) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 7.02-7.04 (m, aromatic, 2H), 7.09 A peak of (s, S—C═CH, 2H), 7.17 (m, aromatic, 4H) ppm was observed. Moreover, when analyzed by ¹³ C-NMR (CDCl ₃ , 75 MHz), peaks at δ123.7, 124.3, 127.9, 136.2, and 137.1 ppm were observed.

(Production of electrochromic sheet)
2.5 mg of the thiophene monomer represented by the above formula (e) was mixed with 10 mL of acetonitrile solution containing tetra-n-butylammonium hexafluorophosphate (Bu ₄ NPF ₆ ) at a concentration of 0.1 mol / L as a supporting electrolyte. . Cyclic voltammetry (CV) using a 1 cm × 1 cm indium tin oxide (ITO) electrode as a working electrode, a 1 cm × 1 cm platinum electrode as a counter electrode, and a standard hydrogen electrode (SCE) as a reference electrode for the resulting solution. ) At a sweep rate of 100 mV / s for 5 cycles between 0 and 1.2 V, and a red electrochromic comprising a π-electron conjugated polymer having a unit structure represented by the following formula (e ′) on the ITO electrode A sheet was obtained.

(Example 6)
(Synthesis of thiophene monomer)
Under an argon atmosphere, 0.19 g of 2-ethynylthiophene and 0.37 g of tetraisopropoxytitanium obtained in Example 1 were stirred at −78 ° C. using 20 mL of diethyl ether as a solvent, and then 1.0 mol / L isopropyl magnesium. 2.6 mL of a diethyl ether solution of chloride was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours to obtain a titanacyclopentadiene derivative represented by the above formula (x).
Thereafter, 0.30 g of selenium chloride was added and mixed by gradually heating to 23 ° C. while stirring for 2 hours. After completion of the reaction, a 1.0 mol / L aqueous hydrochloric acid solution was added, extraction was performed 3 times with methylene chloride, and the obtained organic layer was dried using magnesium sulfate. After the completion of drying, the residue was purified by silica gel column chromatography using hexane as a developing solvent, and further recrystallized with hexane to obtain 0.051 g of a thiophene monomer represented by the following formula (f).
When the obtained thiophene monomer represented by the following formula (f) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 7.00 (dd, J = 3.6 Hz, 5.1 Hz, aromatic, 2H), 7.11 (dd, J = 1.2 Hz, 3.6 Hz, aromatic, 2H), 7.20-7.22 (m, aromatic, 4H) ppm. Further, when analysis was performed by ¹³ C-NMR (CDCl ₃ , 75 MHz), peaks at δ124.3, 124.7, 126.4, 127.9, 139.4, and 141.0 ppm were observed.

(Production of electrochromic sheet)
6.5 mg of the thiophene monomer represented by the above formula (f) was mixed with 10 mL of acetonitrile solution containing tetra-n-butylammonium hexafluorophosphate (Bu ₄ NPF ₆ ) at a concentration of 0.1 mol / L as a supporting electrolyte. . Cyclic voltammetry (CV) using a 1 cm × 1 cm indium tin oxide (ITO) electrode as a working electrode, a 1 cm × 1 cm platinum electrode as a counter electrode, and a standard hydrogen electrode (SCE) as a reference electrode for the resulting solution. ) At a sweep rate of 100 mV / s for 5 cycles between 0 and 1.3 V, and a red electrochromic comprising a π-electron conjugated polymer having a unit structure represented by the following formula (f ′) on the ITO electrode A sheet was obtained.

(Example 7)
(Synthesis of thiophene monomer)
Under an argon atmosphere, 20 mL of diethyl ether was used as a solvent, and 0.22 g of 2-ethynylthiophene and 0.40 g of tetraisopropoxytitanium obtained in Example 1 were stirred at −78 ° C., and then 1.0 mol / L isopropyl magnesium. 2.8 mL of a diethyl ether solution of chloride was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours to obtain a titanacyclopentadiene derivative represented by the above formula (x).
Thereafter, 0.38 g of tellurium tetrachloride was added, and the mixture was gradually heated to 23 ° C. with stirring for 3 hours to be mixed. After completion of the reaction, water was added, extraction was performed 3 times with methylene chloride, and the obtained organic layer was dried using magnesium sulfate. After completion of drying, the product is purified by silica gel column chromatography using a mixed solvent of hexane 33 vol% and methylene chloride 67 vol% as a developing solvent, and further recrystallized with a mixed solvent of methanol and ethylene to obtain the following formula (g) As a result, 0.11 g of a thiophene monomer represented by the following formula was obtained.
When the obtained thiophene monomer represented by the following formula (g) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 6.96-7.02 (m, aromatic, 4H), 7.19. Peaks of (dd, J = 1.2 Hz, 4.8 Hz, aromatic, 2H), 7.56 (s, Te—C═CH, 2H) ppm were observed. Moreover, when analyzed by ¹³ C-NMR (CDCl ₃ , 75 MHz), peaks at δ124.7, 125.6, 127.8, 133.6, 137.3, and 143.7 ppm were observed.

(Production of electrochromic sheet)
2.4 mg of the thiophene monomer represented by the above formula (g) was mixed with 10 mL of acetonitrile solution containing tetra-n-butylammonium hexafluorophosphate (Bu ₄ NPF ₆ ) at a concentration of 0.1 mol / L as a supporting electrolyte. . Cyclic voltammetry (CV) using a 1 cm × 1 cm indium tin oxide (ITO) electrode as a working electrode, a 1 cm × 1 cm platinum electrode as a counter electrode, and a standard hydrogen electrode (SCE) as a reference electrode for the resulting solution. ) At a sweep rate of 100 mV / s for 5 cycles between 0 and 1.2 V, and a red-purple electro-electron composed of a π-electron conjugated polymer having a unit structure represented by the following formula (g ′) on the ITO electrode. A chromic sheet was obtained.

(Example 8)
(Synthesis of thiophene monomer)
Under an argon atmosphere, 0.19 g of 2-ethynylthiophene and 0.34 g of tetraisopropoxytitanium obtained in Example 1 were stirred at −78 ° C. using 20 mL of diethyl ether as a solvent, and then 1.0 mol / L isopropyl magnesium. 2.4 mL of a diethyl ether solution of chloride was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours.
Thereafter, 2.4 mL of a 1.0 mol / L hydrochloric acid / methanol solution was added, and the mixture was gradually heated to 23 ° C. with stirring for 2 hours, and then mixed. After completion of the reaction, water was added, extraction was performed 3 times with methylene chloride, and the obtained organic layer was dried using magnesium sulfate. After completion of drying, the butadiene represented by the following formula (h) is purified by silica gel column chromatography using a mixed solvent of 50 vol% hexane and 50 vol% methylene chloride as a developing solvent, and further recrystallized with hexane. 0.048 g of a dithiophene monomer having a skeleton was obtained.
When the obtained dithiophene monomer having a butadiene skeleton represented by the following formula (h) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 6.64-6.80 (m, CH═CH -CH = CH, 4H), 6.96-6.97 (m, aromatic, 4H), 7.17 (dd, J = 1.5 Hz, 4.2 Hz, aromatic, 2H) ppm peaks were observed. . ^Furthermore, was analyzed by _{13 C-NMR (CDCl 3,} 75MHz), the peak of δ124.4,125.4,125.9,127.7,128.5,142.9ppm were observed.

(Production of electrochromic sheet)
Dithiophene monomer 4 having a butadiene skeleton represented by the above formula (h) in 10 mL of acetonitrile solution containing tetra-n-butylammonium hexafluorophosphate (Bu ₄ NPF ₆ ) at a concentration of 0.1 mol / L as a supporting electrolyte .2 mg was mixed. Cyclic voltammetry (CV) using a 1 cm × 1 cm indium tin oxide (ITO) electrode as a working electrode, a 1 cm × 1 cm platinum electrode as a counter electrode, and a standard hydrogen electrode (SCE) as a reference electrode for the resulting solution. ) At a sweep rate of 100 mV / s for 5 cycles between 0 and 1.2 V, and a red electrochromic comprising a π-electron conjugated polymer having a unit structure represented by the following formula (h ′) on the ITO electrode A sheet was obtained.

Example 9
(Synthesis of thiophene monomer)
Under argon atmosphere, 0.11 g of 2-ethynylthiophene and 0.20 g of tetraisopropoxytitanium obtained in Example 1 were stirred at −78 ° C. using 15 mL of cyclopentyl methyl ether (CPME) as a solvent, and then 1.0 mol. / L Isopropylmagnesium chloride in diethyl ether (1.4 mL) was added, the temperature was raised to −50 ° C., and the mixture was stirred for 12 hours to obtain a titanacyclopentadiene derivative represented by the above formula (x).
Thereafter, 0.18 g of iodine was added and mixed by gradually heating to 23 ° C. while stirring for 3 hours. After completion of the reaction, an aqueous sodium thiosulfate solution was added, extraction was performed 3 times with methylene chloride, and the obtained organic layer was dried using magnesium sulfate. After completion of the drying, the product is purified by silica gel column chromatography using a mixed solvent of 50 vol% hexane and 50 vol% methylene chloride as a developing solvent, and further recrystallized with a mixed solvent of hexane and methylene to obtain the following formula (i ) 0.13 g of a thiophene monomer represented by
When the obtained thiophene monomer represented by the following formula (i) was analyzed by ¹ H-NMR (CDCl ₃ , 300 MHz), δ 7.02-7.07 (m, aromatic, 4H), 7.37. A peak of −7.40 (m, aromatic, 4H) ppm was observed. Moreover, when analyzed by ¹³ C-NMR (CDCl ₃ , 75 MHz), peaks at δ 98.6, 126.8, 127.3, 130.3, 136.3, and 145.9 ppm were observed.

(Production of electrochromic sheet)
It is represented by the above formula (i) in 10 mL of a mixed solvent of 80 vol% acetonitrile and 20 vol% methylene chloride containing tetra-n-butylammonium hexafluorophosphate (Bu ₄ NPF ₆ ) as a supporting electrolyte at a concentration of 0.1 mol / L. 9.4 mg of the thiophene monomer to be mixed was mixed. Cyclic voltammetry (CV) using a 1 cm × 1 cm indium tin oxide (ITO) electrode as a working electrode, a 1 cm × 1 cm platinum electrode as a counter electrode, and a standard hydrogen electrode (SCE) as a reference electrode for the resulting solution. ) At a sweep rate of 100 mV / s for 5 cycles between 0 and 1.2 V, and an orange electrochromic composed of a π-electron conjugated polymer having a unit structure represented by the following formula (i ′) on the ITO electrode A sheet was obtained.

(Example 10)
(Conversion of thiophene monomer obtained in Example 3)
Under an argon atmosphere, 0.026 g of the thiophene monomer represented by the above formula (c) obtained in Example 3 was dissolved in methylene chloride, and 1.0 mL of a methylene chloride solution of 0.032 g of a gold chloride-tetrahydrothiophene complex was dissolved. In addition, the mixture was stirred at 23 ° C. for 1 hour. After completion of the reaction, washing with hexane was performed to obtain 0.045 g of a thiophene monomer represented by the following formula (j).
When the obtained thiophene monomer represented by the following formula (j) was analyzed by ¹ H-NMR (CDC ₁₃ , 300 MHz), δ 6.90-6.93 (m, aromatic, 2H), 7.09 Peaks of −7.26 (m, aromatic, 6H), 7.43-7.53 (m, aromatic, 3H), 7.75-7.82 (m, aromatic, 2H) ppm were observed. Further, analysis by ¹³ C-NMR (CDCl ₃ , 75 MHz) revealed that δ126.8, 127.0 (d, J = 5.7 Hz), 128.4, 129.9 (d, J = 12. 6 Hz), 133.2, 133.7 (d, J = 16.1 Hz), 134.1 (d, J = 14.9 Hz), 134.5, 135.2, 136.1 (d, J = A peak at 18.3 Hz) ppm was observed. Further, analysis by ³¹ P-NMR (CDCl ₃ , 121 MHz) revealed a peak at δ34.9 ppm.

(Production of electrochromic sheet)
It is represented by the above formula (j) in 10 mL of a mixed solvent of 80 vol% acetonitrile and 20 vol% methylene chloride containing tetra-n-butylammonium hexafluorophosphate (Bu ₄ NPF ₆ ) as a supporting electrolyte at a concentration of 0.1 mol / L. 11.1 mg of thiophene oligomer was mixed. Cyclic voltammetry (CV) using a 1 cm × 1 cm indium tin oxide (ITO) electrode as a working electrode, a 1 cm × 1 cm platinum electrode as a counter electrode, and a standard hydrogen electrode (SCE) as a reference electrode for the resulting solution. ) At a sweep rate of 100 mV / s for 5 cycles between 0 and 1.4 V, and a blue-violet electroluminescent polymer comprising a π-electron conjugated polymer having a unit structure represented by the following formula (j ′) on the ITO electrode. A chromic sheet was obtained.

<Evaluation>
(1) Evaluation of electrochemical properties An ITO electrode on which the electrochromic sheets obtained in Examples 5 to 10 were laminated as an anode, a platinum electrode as a cathode and SCE as a reference electrode, and a 0.1 mol / L tetra as an electrolyte. Cyclic voltammetry (CV) was performed using an acetonitrile solution of -n-butylammonium hexafluorophosphate (Bu ₄ NPF ₆ ). The results are shown in FIGS.

(2) Optical characteristics evaluation The ITO electrodes on which the electrochromic sheets obtained in Examples 5 to 10 were laminated as anodes, platinum electrodes as cathodes and SCEs as reference electrodes, and the voltages shown in FIGS. The UV-vis absorption spectrum was measured. The results are shown in FIGS.
The electrochromic sheet obtained in Example 5 was red, but turned blue when a voltage of 1.1 V was applied. The electrochromic sheet obtained in Example 6 was red, but turned blue when a voltage of 1.1 V was applied. The electrochromic sheet obtained in Example 7 was reddish purple, but changed to blue purple by applying a voltage of 1.1V. The electrochromic sheet obtained in Example 8 was red, but turned blue when a voltage of 1.1 V was applied. The electrochromic sheet obtained in Example 9 was orange, but turned blue-violet when a voltage of 1.2 V was applied. The electrochromic sheet obtained in Example 10 was bluish purple, but changed to a bluish purple that was nearly transparent by applying a voltage of 1.2 V.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the thiophene monomer which can manufacture various thiophene monomers easily can be provided. The present invention also provides a method for producing a π-electron conjugated polymer including the method for producing the thiophene monomer, and an electrochromic sheet containing the π-electron conjugated polymer obtained by the method for producing the π-electron conjugated polymer. be able to.

Claims (8)

A method for producing a thiophene monomer represented by the following general formula (2), comprising a step of mixing a titanacyclopentadiene derivative represented by the following general formula (1) and a halide.
(R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, halogen or an organic group having 1 to 20 carbon atoms, and R ₇ and R ₈ each independently represent carbon number. 1 to 6 linear or branched alkyl groups are shown.)
(R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent hydrogen, halogen or an organic group having 1 to 20 carbon atoms, X ₁ is a divalent thiophene which may have a substituent, substituted A thiophene oxide which may have a group, a selenophene which may have a substituent, a tellurophen which may have a substituent, a conjugated diene having 4 to 8 carbon atoms which may have a substituent or a substituent. (The phosphole which may have is shown.) A method for producing a thiophene monomer represented by the following general formula (4), comprising a step of mixing a titanacyclopentadiene derivative represented by the following general formula (3) and a halide.
(R ₁₃ and R ₁₄ each independently represent hydrogen, halogen, or an organic group having 1 to 20 carbon atoms, and ring A ₁ and ring A ₂ each independently represent a 5-membered ring which may have a substituent or A 6-membered aromatic heterocyclic ring or a cycloalkene ring is shown, and R ₁₅ and R ₁₆ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.)
(Ring A ₃ and Ring A ₄ each independently represent a 5-membered or 6-membered aromatic heterocyclic ring or cycloalkene ring which may have a substituent, and X ₂ represents a divalent substituent. Thiophene which may have, thiophene oxide which may have a substituent, selenophene which may have a substituent, tellurophen which may have a substituent, carbon number which may have a substituent 4 to 4 8 conjugated dienes or phospholes optionally having substituents.) The method for producing a thiophene monomer according to claim 1 or 2, further comprising a step of mixing a titanacyclopentadiene derivative and a halide under an inert gas atmosphere. The method for producing a thiophene monomer according to claim 1, 2 or 3, further comprising a step of mixing a titanacyclopentadiene derivative and a halide at -40 ° C or lower. The halide is at least one selected from the group consisting of sulfur chloride, selenium chloride, tellurium tetrachloride, thionyl chloride, hydrogen chloride, phenylsulfenyl chloride, phenylchloroselenide and dichlorophenylphosphine. The manufacturing method of the thiophene monomer of 1, 2, 3, or 4. Obtaining a thiophene monomer by the method for producing a thiophene monomer according to claim 1, 2, 3, 4 or 5,
And a step of obtaining a π-electron conjugated polymer having a unit structure represented by the following general formula (5) or (6) by polymerizing the thiophene monomer.
(R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ each independently represent hydrogen, halogen or an organic group having 1 to 20 carbon atoms, and X ₃ is a divalent thiophene which may have a substituent, substituted A thiophene oxide which may have a group, a selenophene which may have a substituent, a tellurophen which may have a substituent, a conjugated diene having 4 to 8 carbon atoms which may have a substituent or a substituent. (The phosphole which may have is shown, and n shows an integer.)
(Ring A ₅ and Ring A ₆ each independently represent a 5-membered or 6-membered aromatic heterocyclic ring or cycloalkene ring which may have a substituent, and X ₄ represents a divalent substituent. Thiophene which may have, thiophene oxide which may have a substituent, selenophene which may have a substituent, tellurophen which may have a substituent, carbon number which may have a substituent 4 to 4 8 is a conjugated diene or a phosphole optionally having a substituent, and n is an integer.) The π-electron conjugated polymer according to claim 6, wherein in the step of obtaining the thiophene monomer by the method for producing a thiophene monomer according to claim 1, the thiophene monomer is polymerized by an electrolytic polymerization method. Production method. An electrochromic sheet comprising a π-electron conjugated polymer obtained by the method for producing a π-electron conjugated polymer according to claim 6.