WO2016111277A1 - Composé contenant un hétérocycle, polymère utilisant le composé, et leur utilisation - Google Patents

Composé contenant un hétérocycle, polymère utilisant le composé, et leur utilisation Download PDF

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WO2016111277A1
WO2016111277A1 PCT/JP2016/050078 JP2016050078W WO2016111277A1 WO 2016111277 A1 WO2016111277 A1 WO 2016111277A1 JP 2016050078 W JP2016050078 W JP 2016050078W WO 2016111277 A1 WO2016111277 A1 WO 2016111277A1
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group
substituent
carbon atoms
polymer
optionally substituted
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Japanese (ja)
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岡本　秀二
文明 小林
智弘 宮崎
真理子 上村
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綜研化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints

Definitions

  • the conductive polymer has a conjugated structure and a combination of a main skeleton capable of electron transfer and a dopant for imparting electron or hole carriers in the expanded conjugate to the main skeleton.
  • a skeleton having a chemical structure in which a ⁇ -electron conjugated system is developed such as a polymer such as 3,4-ethylenedioxythiophene (EDOT), pyrrole, and aniline, is generally used.
  • EDOT 3,4-ethylenedioxythiophene
  • pyrrole pyrrole
  • aniline is generally used as various dopants such as inorganic Lewis acids and organic proton acids. Of these, sulfonic acid compounds are generally used as organic protonic acids.
  • the main skeleton is a conductive polymer in which polyaniline is doped with bis-2-ethylhexylsulfosuccinic acid (for example, Patent Document 1) or polyethylenedioxythiophene (PEDOT).
  • PEDOT / PSS doped with polystyrene sulfonic acid (PSS).
  • Patent Document 2 there are many related techniques for PEDOT / PSS (for example, Patent Document 2), which is a material that is often used.
  • PEDOT / PSS has a very small particle size in the order of nanometers by adjusting the main conductive PEDOT, the molecular weight of the PSS used as a dopant, the amount of doping, the concentration of undoped sulfonic acid, etc. Has been imparted with excellent processability such that a uniform film can be easily dispersed in water and a uniform film can be easily produced by coating.
  • the conductive polymer alone is often insufficient in physical strength, solvent resistance and the like of the coating film, and is used as a water-based paint in which a water-based emulsion binder and various additives are mixed.
  • Patent 3426637 Patent 2636968 WO2010 / 095648
  • PEDOT / PSS is characterized by the fact that gel particles are dispersed and stabilized in water by the residual sulfo group derived from PSS. Therefore, due to the metal corrosivity due to low acidity and the occurrence of sulfo group elimination over time, etc.
  • there are various problems such as inherently poor water resistance of the coating film, and physical properties of the coating film have been improved as a composite paint with various materials. I came.
  • binders and various additives being limited to water-based systems and limitations on miscibility with the materials.
  • the sulfo group of PEDOT / PSS is modified with an amine compound
  • the use of water is unavoidable although it is possible to reduce metal corrosivity and improve the miscibility with the binder.
  • the miscibility improvement by changing the dopant composition although it is possible to improve the miscibility with an organic solvent or the like, it is difficult to balance the electrical conductivity and the uniformity of the coating film.
  • thiophene when thiophene is used as a heterocycle, there is a problem that the activity with aldehyde is weak and the synthesis does not proceed sufficiently.
  • the inventors have synthesized thienoporphyrin under normal porphyrin synthesis conditions when thiophene having an electron donating group at the 3,4-position, particularly 3,4-ethylenedioxythiophene (EDOT) is used. I found out that it is possible.
  • EDOT 3,4-ethylenedioxythiophene
  • the present invention has been made in view of such circumstances, and provides a heterocycle-containing compound represented by the following chemical formula (1).
  • one of X1 and X2 is an alkoxy group that may have a substituent, an alkylene oxide group that may have a substituent, a thiocyano group that may have a substituent, or a substituent.
  • R represents alkyl having 1 to 12 carbon atoms
  • the compound represented by the chemical formula (1) is obtained by condensing a heterocyclic compound of the chemical formula (3) and an aldehyde derivative of the chemical formula (4).
  • X1 and X2 in formula (3) and R in formula (4) are the same as in chemical formula (1).
  • X1 and X2 each have an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, a thiocyano group which may have a substituent, or a substituent.
  • X1 and X2 each represents an alkoxy group having 1 to 12 carbon atoms which may have a substituent, an alkylene oxide group having 1 to 12 carbon atoms which may have a substituent, or
  • X1 And X2 is an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent.
  • R is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an optionally substituted phenyl group.
  • X1, X2 and R are the same as those in the chemical formula (1), and n is 2 to 100.
  • a polymer composition comprising the polymer and a polymerization solvent.
  • FIG. 3 (b) shows the result of measuring the IR of polymer 8 synthesized by synthesis method 11 of the present invention.
  • FIG. 4 (c) shows the result of measuring the IR of monomer 3 synthesized by the synthesis method 3 of the present invention
  • FIG. 4 (d) shows the result of measuring the IR of monomer 4 synthesized by the synthesis method 4 of the present invention.
  • FIG. 5 (e) shows the result of measuring IR of the polymer 5 synthesized by the synthesis method 9 of the present invention
  • FIG. 5 (f) shows the result of measuring IR of the polymer 11 synthesized in Comparative Example 1.
  • FIG. 6 shows the results of LC-MS measurement of the polymer 8 synthesized by the synthesis method 11 of the present invention.
  • FIG. 7 (a) shows the results of measuring the UV of the monomer 1 synthesized by the synthesis method 1, the monomer 3 synthesized by the synthesis method 3, and the monomer 4 synthesized by the synthesis method 4, and FIG.
  • FIG. 8A shows the result of measuring the decomposition start temperature of the polymer 4 synthesized by the synthesis method 8 of the present invention
  • FIG. 8B shows the start of decomposition of the polymer 5 synthesized by the synthesis method 9 of the present invention. The result of measuring the temperature is shown.
  • FIG. 9C shows the result of measuring the decomposition start temperature of the polymer 11 synthesized in Comparative Example 1.
  • the present invention relates to a heterocycle-containing compound having a novel structure represented by the following chemical formula (1).
  • this heterocyclic compound is not limited, as an example, it can be used as an organic conductor material (more specifically, a conductive polymer and a monomer of a main chain of a semiconductor polymer).
  • the constitution and synthesis method of the heterocycle-containing compound will be described, and then, a method for synthesizing a polymer that can be used as a conductive polymer using this compound as a monomer will be described.
  • heterocycle-containing compound of the present invention is represented by the following chemical formula (1).
  • one of X1 and X2 is an alkoxy group that may have a substituent, an alkylene oxide group that may have a substituent, a thiocyano group that may have a substituent, or a substituent.
  • At least one of X1 and X2 has an electron donating group directly bonded to the heterocycle.
  • An alkoxy group which may have a substituent of X1 and X2, an alkylene oxide group, a thiocyano group, an amino group, a thioalkyl group, an alkylenedioxy group in which X1 and X2 are linked, an alkylenedithio group, an alkyl group having 1 to 12 carbon atoms;
  • the substituent of the alkyl group is not limited, but a substituent that does not inhibit the electron donating property relative to the heterocycle is preferable, and specifically, a linear, branched, or cyclic alkyl group, sulfo group , Hydroxyl group, carboxyl group, amino group, amide group, ester group, and straight or branched alkyl group, alkoxyalkyl group, alkylene substituted with sulfo group, hydroxyl group, carboxyl group, amino group, halogen group It may be an oxide group and may have a plurality of substituents.
  • One of X1 and X2 may be hydrogen or an alkyl group having 1 to 12 carbon atoms, but it is better to exclude a combination in which both are alkyl groups, both are hydrogen, one is hydrogen and the other is an alkyl group.
  • the alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent of X1 and X2 and the alkylenedithio group having 1 to 12 carbon atoms which may have a substituent may be an ethylene structure in the alkylene main chain. Instead of, it may have an oxygen analog, nitrogen analog, or sulfur analog structure.
  • an alkoxy group having 1 to 12 carbon atoms an alkylene oxide group having 1 to 50 carbon atoms having 1 to 50 repeating units, a phenyl group, a heterocyclic group, a condensed ring group, a hydroxy group, an aldehyde group, a carboxy group, and a halogen group
  • it may have a plurality of alkali metal salts thereof, sulfo groups or alkali metal salts thereof, phosphoric acid groups or alkali metal salts thereof, amino groups, and cyano groups.
  • the group, phenyl group, heterocyclic group, condensed ring group and amino group may have an arbitrary substituent at an arbitrary position.
  • the R alkyl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, and the alkylene oxide group having 1 to 50 carbon atoms and having 1 to 50 carbon atoms have an arbitrary substituent at an arbitrary position. May be.
  • heterocyclic group examples include silole ring, furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole.
  • Examples of the condensed ring include naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, pentacene ring, perylene ring. , Pentaphen ring, picene ring, pyranthrene ring, and the like.
  • the W can be synthesized by selecting a hydroxy group or a heterocyclic residue represented by the chemical formula (2) depending on the reaction conditions. Under basic conditions it becomes a hydroxy group, and under acidic conditions it becomes a heterocyclic residue.
  • the heterocyclic compound represented by the chemical formula (1) is obtained by condensing a heterocyclic compound of the chemical formula (3) and an aldehyde derivative of the chemical formula (4).
  • one of X3 and X4 is an optionally substituted alkoxy group having 1 to 12 carbon atoms and an optionally substituted alkylene oxide group having 1 to 12 carbon atoms.
  • the substituent of the amino group that may have a substituent, the thioalkyl group that may have a substituent, and the alkyl group having 1 to 12 carbon atoms that may have a substituent is not limited. Substituents similar to the substituents for X1 and X2 can be used.
  • Y 1 and Y 2 represent an oxygen atom, a sulfur atom, and a selenium atom
  • X 5 is an alkylene group having 1 to 12 carbon atoms that may have a substituent. And may have an oxygen analog, nitrogen analog, or sulfur analog structure in place of the ethylene structure in the alkylene main chain.
  • the substituent of the alkylene group having 1 to 12 carbon atoms which may have the substituent of X5 is not limited, but the same substituents as the substituents of X1 and X2 can be used.
  • the chemical formula (4) aldehyde derivatives can be mainly divided into the following chemical formulas (4-A) and (4-B).
  • R2 to R6 are alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, alkylene oxide groups having 1 to 50 carbon atoms and 1 to 50 carbon atoms, and phenyl groups. , Heterocyclic group, condensed ring group, hydroxy group, aldehyde group, carboxy group, halogen group or alkali metal salt thereof, sulfo group or alkali metal salt thereof, phosphoric acid group or alkali metal salt thereof, amino group, cyano You may have two or more groups.
  • ⁇ Basic conditions> A heterocyclic compound is weighed in a reaction vessel, and a base and a solvent are added and stirred while an inert gas is sealed. Add the aldehyde derivative with stirring and react with stirring. After completion of the reaction, ion exchange water is added, and acid is added little by little while stirring to neutralize to pH about 6-8. Through the purification step, a heterocyclic-containing compound having a hydroxyl group in the side chain is obtained.
  • the reaction vessel is not particularly limited, but glass or Teflon (registered trademark) can be used.
  • a volatile component removal step of removing volatile components may be used.
  • the volatile component may be removed using a vacuum pump or the like under reduced pressure conditions or heating conditions by heating, or the reduced pressure conditions and heating conditions may be combined.
  • the volatile component include water, organic solvents, unreacted substrates, and the like, which are compounds that could not be removed when the heterocyclic compound was synthesized.
  • the inert gas includes nitrogen, argon, helium and the like.
  • the stirring method is not particularly limited, but a stirrer or a shaker may be used.
  • the stirring temperature during synthesis of the intermediate reaction product of the heterocyclic compound under basic conditions is ⁇ 40 to 50 ° C., preferably ⁇ 10 to 30 ° C. Specifically, this temperature is, for example, ⁇ 40, ⁇ 30, ⁇ 20, ⁇ 10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 ° C., and is exemplified here. It may be within a range between any two of the numerical values. Further, the stirring temperature during the condensation reaction with the aldehyde derivative is 25 ° C. to 100 ° C., preferably 40 ° C. to 80 ° C.
  • this temperature is, for example, 25, 30, 40, 50, 60, 70, 80, 90, or 100 ° C., and may be within a range between any two of the numerical values exemplified here. .
  • the temperature at the time of synthesizing the intermediate reactant of the heterocyclic compound is too high, the production of by-products is increased, so the reaction at a low temperature is preferable.
  • the stirring time under basic conditions is not particularly limited, but is, for example, 1 to 12 hours, preferably 2 to 6 hours. This time is specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 hours, and is a range between any two of the numerical values exemplified here. It may be within.
  • the base under basic conditions is not particularly limited as long as the condensation reaction of the heterocyclic compound and the aldehyde derivative proceeds.
  • TMP base MAGNESIUMCHLOROTRATRAMETHYLPIPERIDIDIPLITHIUMCHLORID COMPLEX
  • lithium diisopropylamide n-butyllithium, and sec-butyllithium, tert-butyllithium, sodium ethoxide and the like.
  • the solvent under basic conditions is not particularly limited as long as the condensation reaction of the heterocyclic compound and the aldehyde derivative proceeds, and examples thereof include tetrahydrofuran and tert-butyl methyl ether.
  • the acid under basic conditions is not particularly limited as long as the acid can be neutralized after completion of the condensation reaction of the heterocyclic compound and the aldehyde derivative, such as hydrochloric acid, nitric acid, sulfuric acid, or 0.1N. Examples thereof include an aqueous solution.
  • the purification process is a process for performing an extraction process, a fractionation process, and the like.
  • the extraction step is not limited as long as the oil layer containing the target product can be recovered, and examples include separation extraction.
  • As the fractionation step it is sufficient if the target product can be isolated, and examples thereof include column chromatography and distillation.
  • a heterocyclic compound and an acid are weighed in a reaction vessel, substituted with an inert gas, an aldehyde derivative and a solvent are dropped, and the reaction is conducted with stirring. After the reaction is complete, base and solvent are added. By the purification step, a heterocyclic-containing compound having a heterocyclic residue in the side chain is obtained.
  • reaction vessel, inert gas, stirring method, and purification step are not particularly limited, and the same conditions as basic conditions can be used.
  • the temperature at the time of stirring under acidic conditions is 0 to 100 ° C., preferably 50 to 90 ° C. Specifically, this temperature is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 ° C., and the numerical value exemplified here It may be within the range between any two.
  • the stirring time under acidic conditions is not particularly limited, but is, for example, 1 to 12 hours, preferably 2 to 6 hours. This time is specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 hours, and is a range between any two of the numerical values exemplified here. It may be within.
  • the acid under acidic conditions is not particularly limited as long as the condensation reaction of the heterocyclic compound and the aldehyde derivative proceeds.
  • Perchloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, p-toluenesulfone Examples include acids.
  • the solvent under acidic conditions is not particularly limited, and may be any solvent in which the condensation reaction of the heterocyclic compound and the aldehyde derivative proceeds, and examples thereof include toluene, benzene, methyl ethyl ketone, and heptane.
  • the base under acidic conditions is not particularly limited, and may be any base that can complete the condensation reaction of the heterocyclic compound and the aldehyde derivative, and examples thereof include dimethylaminoethanol, triethylamine, and pyridine.
  • heterocyclic ring-containing compound when synthesizing a polymer using a plurality of types of heterocyclic ring-containing compounds described later, a preferred combination of functional groups can be synthesized side by side, and more effective. It is possible to increase the number of heterocyclic compounds and aldehyde derivatives to directly synthesize the polymer, and the functional group combination that occurs when the polymer is directly randomized is prevented from being lost or reduced. Can do.
  • the reaction time can be shortened when the polymer is synthesized from a heterocyclic compound, and the occurrence of side reactions is reduced, thereby generating impurities. It is possible to suppress the above, and the purity of the polymer can be increased because it can be purified at the stage of the heterocycle-containing compound.
  • a polymer can be obtained by adding a heterocycle-containing compound to a reaction vessel and stirring with heating.
  • a dopant sulfonic acid compound anion or a salt thereof
  • a polymerization solvent are weighed, stirred, and then oxidized. Add and stir. After completion of the reaction, the ion content is removed to obtain a polymer composition.
  • the stirring time during the synthesis of the polymer is not particularly limited, but is 1 to 12 hours, preferably 2 to 6 hours. This time is specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 hours, and is a range between any two of the numerical values exemplified here. It may be within.
  • the polymerization solvent is not particularly limited, but alcohol solvents such as water, methanol, ethanol, isopropyl alcohol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether And glycol solvents such as propylene glycol ethyl ether, lactic acid solvents such as methyl lactate and ethyl lactate, toluene, and ethyl acetate.
  • alcohol solvents such as water, methanol, ethanol, isopropyl alcohol and butanol
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • methyl cellosolve ethyl cellosolve
  • glycol solvents such as propylene glycol
  • the oxidizing agent is not particularly limited, and may be any oxidizing agent that allows a polymerization reaction to proceed.
  • the dopant and the oxidizing agent may be used alone or in a plurality of kinds.
  • the ion content removal method is not particularly limited, and any method that can remove the ion content may be used. Examples include a method of passing an excess ion exchange resin, ultrafiltration, solvent washing by polymer precipitation, and the like.
  • the polymer composition can form a uniform film by coating, and can impart necessary physical strength, solvent resistance, and the like depending on the application depending on the type of functional group to be introduced.
  • the coating method is not particularly limited, but a known coating method can be used.
  • the heterocycle-containing compound In the synthesis of the polymer, only one kind of the heterocycle-containing compound may be used, or a plurality of kinds may be used as a copolymer.
  • the repeating unit of the polymer is not particularly limited, but is 2 to 100, preferably 2 to 20. Specifically, for example, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100, even if it is within the range between any two of the numerical values exemplified here Good.
  • an alkyl group as a functional group, it is possible to impart an effect of being easily soluble in an organic solvent or the like. By being easily dissolved in a solvent, it can be easily applied to a device application in which mixing of water becomes a problem, and a uniform film can be formed at a low temperature when a coating film is formed.
  • a crosslinking reaction occurs by adding a crosslinking agent such as epoxy or carbodiimide, and a film stability effect can be imparted.
  • a crosslinking agent such as epoxy or carbodiimide
  • the heterocycle-containing compound of the present invention is used as a conductive polymer material, various functional groups can be easily introduced into the side chain, so that a polymer having the function introduced above is synthesized. be able to. Furthermore, the ionization potential can be easily adjusted by changing the composition and blending ratio of the heterocycle-containing compound.
  • the use of the polymer, polymer composition and coating film of the present invention is not limited, but antistatic agents for various uses, antistatic films using the same, p-type organic semiconductors, n-type organic semiconductors, solid electrolytic capacitors Solid electrolytes and additives thereof, electrochromic elements, transparent electrodes of organic thin film solar cells, counter electrodes of dye-sensitized solar cells and auxiliary agents thereof, organic electroluminescence, chemical sensors, fuel cells, electronic devices such as touch panels and liquid crystal displays It can be suitably used as an additive for adhesives, carbon and the like.
  • Synthesis method 1 Synthesis of monomer 1 (basic conditions) In a 300 ml reaction vessel, 14.2 g of 3,4-ethylenedioxythiophene (EDOT) was weighed and evacuated using a vacuum pump at 40 ° C. for 1 hour to remove volatile components. While adding dry nitrogen, 100 ml of a TMP base / THF solution (1 mol / L) was added, and the mixture was reacted at room temperature for 2 hours while stirring. 10 g of benzaldehyde was added with stirring, the temperature was raised to 50 ° C., the reaction was performed for 6 hours, and then cooled to room temperature.
  • EDOT 3,4-ethylenedioxythiophene
  • Synthesis method 2 Synthesis of monomer 2 (basic conditions) Synthesis was performed in the same manner as in Synthesis Method 1 except that benzaldehyde was changed to 2-ethylhexyl aldehyde to obtain a light yellow liquid monomer 2.
  • Synthesis method 4 Synthesis of monomer 4 (acidic conditions) Synthesis was performed in the same manner as in Synthesis Method 3 except that 6 g of benzaldehyde was changed to 11 g of syringaldehyde and toluene was changed to methyl ethyl ketone, to obtain monomer 4 of pale red crystals.
  • Fig. 2c shows the NMR results
  • Fig. 4d shows the IR results.
  • Synthesis method 5 Synthesis of monomer 5 (acidic conditions) Synthesis was carried out in the same manner as in Synthesis Method 3 except that 6 g of benzaldehyde was changed to 7.3 g of 2-ethylhexyl aldehyde to obtain a light yellow liquid monomer 5.
  • Synthesis of monomer 6 (acidic conditions) Synthesis was performed in the same manner as in Synthesis Method 3 except that 6 g of benzaldehyde was changed to 7.5 g of 2-deoxy-D-ribose, and 100 g of toluene was changed to 50 g of methyl ethyl ketone and 50 g of ethanol to obtain monomer 6 as a pale yellow solid. It was.
  • Synthesis Method 8 Synthesis of Polymer 4 Polymerization was conducted in the same manner as in Synthesis Method 7 except that 0.37 g of monomer 3 in Synthesis method 7 was changed to 0.2 g of monomer 3 and 0.1 g of EDOT (monomer molar ratio 50:50). A polymer 4 of a deep blue polymer dispersion was obtained.
  • FIG. 8a shows the result of the decomposition start temperature measurement.
  • Synthesis Method 9 Synthesis of Polymer 5 Polymerization 5 was performed in the same manner as in Synthesis Method 7 except that 0.37 g of monomer 3 in Synthesis method 7 was changed to 0.45 g of monomer 4, and polymer 5 in a deep blue-violet polymer dispersion. Got. FIG. 5e shows the IR, and FIG. 8b shows the result of the decomposition start temperature measurement.
  • the polymer 7 was synthesized by the same method as the synthesis method 7 except that the synthetic monomer 3 of the polymer 7 was changed to the monomer 5 to obtain a polymer 7 of a polymer dispersion.
  • Synthesis Method 11 Synthesis of Polymer 8 1 g of monomer 1, 50 g of toluene, and 0.2 g of tetrafluoroacetic acid were weighed into a 300 ml reaction vessel, and heated and stirred at 50 ° C. while purging with nitrogen. After reacting for 7 hours, the mixture was cooled, and the precipitate was collected by filtration, washed with isopropyl alcohol, and dried to obtain orange crystalline polymer 8. The identification of the polymer 8 was confirmed by LC-MS, NMR and IR. Fig. 2d shows NMR results, and Fig. 3b shows IR results.
  • FIG. 6 shows the result of LC-MS measurement of polymer 8. From the measurement results by LC-MS, it was found that the number of repeating units was about 2 to 20.
  • Comparative Example 1 Synthesis of polymer 11
  • the polymer 3 was synthesized in the same manner as in the synthesis method 7 except that the monomer 3 was changed to EDOT 0.15 g to obtain a polymer 11 of a dark blue polymer dispersion.
  • FIG. 5f shows the IR
  • FIG. 9c shows the result of the decomposition start temperature measurement.
  • Comparative Example 2 Synthesis of Polymer 12 1 g of monomer 1, 1.14 g of 3-hexylthiophene, 50 g of toluene and 0.2 g of tetrafluoroacetic acid were weighed and stirred at 50 ° C. with nitrogen substitution. After the reaction for 7 hours, the reaction state was confirmed by thin layer chromatography, but it was not reacted only by light emission derived from the raw material.
  • Table 1 shows a summary of the molar ratios of polymers 1 to 9 and 11.
  • ⁇ Conductivity measurement sample adjustment method 6 g of the polymer 1 was weighed into a sample bottle and crushed by a probe type ultrasonic crusher. The polymer 1 after pulverization was used as the measurement sample 1 as it was. Similarly, 1 g of the polymer 1 after pulverization was weighed, 0.08 g of dimethyl sulfoxide was added, and the mixture was well stirred to obtain a measurement sample 2. Measurement samples 1 and 2 were similarly prepared for the polymers 2 to 8, 10 and 11.
  • IPA isopropyl alcohol
  • ⁇ Decomposition start temperature measurement sample adjustment method> The polymer 1 was put in a vacuum dryer in a sample bottle, and the water was dried by reducing the pressure to 10 Pa or less at 30 ° C. to obtain a polymer 1 powder.
  • Table 3 shows the results of evaluating the film solvent resistance under the following conditions.
  • Table 5 shows the results of evaluation of self-doping under the following conditions.
  • the polymer 9 was dissolved in ion exchange water so as to be 1.5%, and a solution as it was and a solution from which Na was removed with a cation exchange resin were prepared. The appearance and conductivity of the coating film after drying at 105 ° C. for 30 minutes were measured.
  • Reference Example 1 Thienoporphyrin synthesis 355 mg of 3,4-ethylenedioxythiophene, 255 mg of benzaldehyde, and 250 mL of dichloromethane were weighed in a 500 mL reaction vessel and stirred in a dry nitrogen atmosphere. Further, 60 mg of Lewis acid (BF 3 .O (Et) 2 ) was added and reacted at room temperature for 3 hours. Thereafter, 603 mg of dichlorodicyanobenzoquinone was added and stirred for 1 hour.
  • Lewis acid BF 3 .O (Et) 2

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

L'invention concerne un composé contenant un hétérocycle permettant, lorsqu'un composé de matière première présentant divers groupes fonctionnels est choisi comme étant celui qui doit être utilisé, d'introduire facilement un groupe fonctionnel dans une composition produite. L'invention concerne un composé contenant un hétérocycle représenté par la formule chimique (1). (Dans la formule (1), l'un de X1 et X2 représente un groupe alcoxy éventuellement substitué, un groupe oxyde d'alkylène éventuellement substitué, un groupe thiocyano éventuellement substitué, un groupe amino éventuellement substitué ou un groupe thioalkyle éventuellement substitué, et l'autre représente hydrogène, un groupe alkyle éventuellement substitué comprenant 1 à 12 atomes de carbone, un groupe alcoxy éventuellement substitué, un groupe oxyde d'alkylène éventuellement substitué, un groupe thiocyano éventuellement substitué, un groupe amino éventuellement substitué, ou un groupe thioalkyle éventuellement substitué; ou X1 et X2 sont liés l'un à l'autre et représentent un groupe alkylènedioxy éventuellement substitué comprenant 1 à 12 atomes de carbone ou un groupe alkylènedithio éventuellement substitué comprenant 1 à 12 atomes de carbone, R représente un groupe alkyle comprenant 1 à 12 atomes de carbone, un groupe alcoxy comprenant 1 à 12 atomes de carbone, 1 à 50 unités de répétition d'un groupe oxyde d'alkylène comprenant 1 à 12 atomes de carbone, un groupe phényle éventuellement substitué, un groupe hétérocyclique éventuellement substitué ou un groupe cyclique condensé éventuellement substitué, et W représente un groupe hydroxyle ou la formule chimique (2).) (Dans la formule (2), X1 et X2 sont identiques à ceux de la formule chimique (1).)
PCT/JP2016/050078 2015-01-05 2016-01-05 Composé contenant un hétérocycle, polymère utilisant le composé, et leur utilisation WO2016111277A1 (fr)

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