Classifications

• • 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

Definitions

• the present invention relates to a method for producing a polymer compound.
• a polymer compound containing a thiophene ring is useful as a material for a functional layer provided in an electronic element such as an organic electroluminescence element (organic EL element), a photoelectric conversion element, or an organic thin film transistor, various studies have been promoted. Yes.
• Patent Documents 1 and 2 Non-Patent Documents 1 and 2.
• the length of the ⁇ -conjugated system of a polymer compound containing a thiophene ring can affect electrical characteristics when such a polymer compound is used as a functional layer material for an electronic device. Accordingly, there is a demand for a production method that can provide a high molecular weight compound having a long ⁇ -conjugated system and a large molecular weight.
• An object of the present invention is to provide a production method for obtaining a polymer compound containing a thiophene ring and having a large weight average molecular weight.
• the present inventors have found that the above problems can be solved by performing the coupling reaction under predetermined conditions, and have completed the present invention. That is, the present invention provides the following [1] to [15].
• a method for producing a polymer compound containing a repeating unit represented by the following formula (1) A step of reacting a compound represented by the following formula (2) and a compound represented by the following formula (3) in a reaction solvent containing a palladium catalyst and a base,
• the reaction solvent is A first solvent that is at least one hydrocarbon solvent;
• a second solvent which is at least one organic solvent consisting only of at least one carbon atom, at least one hydrogen atom, and at least one oxygen atom, and water,
• the manufacturing method of the high molecular compound whose volume ratio of the water with respect to the sum total of the volume of the said 1st solvent, the volume of the said 2nd solvent, and the volume of the said water exceeds 10 volume%, and is less than 100 volume%.
• Ar A represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group
• Ar B represents a divalent aromatic heterocyclic group containing at least one thiophene ring.
• X 1 and X 2 represent each independently a chlorine atom, a bromine atom, or iodine atom
• Ar A represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group.
• Y 1 and Y 2 each independently represent a monovalent group containing one boron atom and at least two oxygen atoms
• Ar B represents a divalent aromatic heterocyclic group containing at least one thiophene ring.
• the volume ratio of the water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of the water is more than 35% by volume and less than 100% by volume.
• the volume ratio of the water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of the water is 50% by volume or more and less than 100% by volume.
• the volume ratio of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is more than 50% by volume and less than 100% by volume.
• Ar B is a divalent group represented by the following formula (B-1) or a divalent group represented by the following formula (B-2), [1] to [8] and [8] [10] The method for producing a polymer compound according to any one of [10].
• Z is a group represented by any one of the following formulas (Z-1) to (Z-8).
• each R independently represents a hydrogen atom or a substituent.
• Each R independently represents a hydrogen atom or a substituent; p represents 0 or 1, W 1 and W 2 each independently represent a carbon atom or a sulfur atom.
• the base is at least one selected from the group consisting of alkali metal carbonates, sulfates, and phosphates, and alkaline earth metal carbonates, sulfates, and phosphates.
• Y 1 and Y 2 are each independently formula: -B (-O-R B) 2, a group represented by (wherein two R B each independently a hydroxy group represents a monovalent hydrocarbon group which may have, two R B are mutually connected to may form a divalent group.), one of the [1] to [14] The manufacturing method of the high molecular compound as described in any one.
• the present invention may include the following aspects [2-1] to [2-2].
• chloromethyl (tri-tert-butylphosphine) palladium (II) as a palladium catalyst and potassium phosphate as a base.
• the reaction solvent is Mesitylene as the first solvent, Containing tetrahydrofuran and water as the second solvent, Except when the volume ratio of mesitylene, tetrahydrofuran, and water to the sum of mesitylene volume, tetrahydrofuran volume, and water volume is 15%, 35%, and 50% by volume, respectively [1]-[ [15] The method for producing a polymer compound according to any one of [15].
• the present invention can provide a production method for obtaining a polymer compound containing a thiophene ring and having a large weight average molecular weight.
• polymer compound means a polymer having a molecular weight distribution and a polystyrene-equivalent number average molecular weight (Mn) of 1000 or more.
• aromatic hydrocarbon is selected from the group consisting of monocyclic aromatic hydrocarbons, condensed ring aromatic hydrocarbons, and monocyclic aromatic hydrocarbons and condensed ring aromatic hydrocarbons Or a compound formed by two or more of them being directly bonded or indirectly bonded via a hetero atom or a carbonyl group (—CO—).
• the hetero atom to which the aromatic hydrocarbon is indirectly bonded has a remaining bond
• the hetero atom is, for example, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Is combined with.
• Examples of monocyclic aromatic hydrocarbons include benzene.
• Examples of the aromatic hydrocarbon having a condensed ring structure include naphthalene, anthracene, and fluorene.
• Two or more selected from the group consisting of monocyclic aromatic hydrocarbons and condensed ring aromatic hydrocarbons are directly bonded or via a heteroatom or carbonyl group (—CO—)
• Examples of the compound formed by being indirectly bonded include biphenyl.
• the number of carbon atoms in the aromatic hydrocarbon is usually 6 to 60.
• the aromatic hydrocarbon may have a substituent.
• substituents that the aromatic hydrocarbon may have include a halogen atom, an alkyl group, an alkyloxy group, and an alkylthio group. These substituents may further have a substituent.
• heterocyclic compound means that, among organic compounds having a cyclic structure, the atoms constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. A compound containing a heteroatom is meant.
• the heterocyclic compound is selected from the group consisting of a heterocyclic compound having a monocyclic structure, a heterocyclic compound having a condensed ring structure, and a heterocyclic compound having a monocyclic structure and a heterocyclic compound having a condensed ring structure. It includes compounds formed by one or more being linked directly or indirectly through a heteroatom or carbonyl group. When the hetero atom to which the heterocyclic compound is indirectly bonded has a remaining bond, the hetero atom is, for example, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Is combined with.
• the ring included in the heterocyclic compound having a condensed ring structure may be a condensed ring of two or more heterocyclic rings, or a condensed ring of one or more heterocyclic rings and one or more carbocycles. Also good.
• the number of carbon atoms in the heterocyclic compound is usually 4-20.
• heterocyclic compound examples include furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, triazole, thiadiazole, oxadi Azole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene, chroman, isochroman , Benzopyran, quinoline, isoquinoline, quinolidine, benzimi
• the heterocyclic compound may have a substituent.
• substituents that the heterocyclic compound may have include a halogen atom, an alkyl group, an alkyloxy group, and an alkylthio group. These substituents may further have a substituent.
• aromatic heterocyclic compound means a heterocyclic compound containing an aromatic ring.
• Aromatic heterocyclic compounds include aromatic heterocyclic compounds having a monocyclic structure, aromatic heterocyclic compounds having a condensed ring structure, aromatic heterocyclic compounds having a monocyclic structure, and aromatic heterocyclic compounds having a condensed ring structure.
• An aromatic heterocyclic compound having a structure and / or a condensed ring structure and one or more monocyclic structures and / or an aromatic hydrocarbon having a condensed ring structure are directly bonded to each other, or a hetero atom or a carbonyl group Including compounds formed by being indirectly bound via a.
• the hetero atom to which the aromatic heterocyclic compound is indirectly bonded has a remaining bond
• the hetero atom may have, for example, an alkyl group which may have a substituent or a substituent. Bonded to an aryl group.
• the ring included in the aromatic heterocyclic compound having a condensed ring structure may be a condensed ring of two or more aromatic heterocycles, or one or more heterocycles and one or more aromatic carbocycles.
• the condensed ring may be used.
• the number of carbon atoms in the aromatic heterocyclic compound is usually 4-20.
• the aromatic heterocyclic compound may have a substituent.
• substituents that the aromatic heterocyclic compound may have include a halogen atom, an alkyl group, an alkyloxy group, and an alkylthio group. These substituents may further have a substituent.
• substituted means a monovalent group and includes a halogen atom.
• substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkyloxy group, a cycloalkyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, and an arylcycloalkyl group.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the halogen atom as a substituent is preferably a fluorine atom.
• the alkyl group may be linear or branched.
• the alkyl group usually has 1 to 30 carbon atoms.
• Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and 2,2-dimethylpropyl.
• cyclopentyl group n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 3,7-dimethyloctyl group, 2-ethylhexyl group, n-nonyl group, n-decyl Group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n- An icosyl group is mentioned.
• the alkyl group may further have a substituent.
• the alkyl group may be, for example, an alkyl group substituted with a fluorine atom that is a substituent.
• Examples of the alkyl group substituted with a fluorine atom include 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 5,5,5, 5-trifluoropentyl group, 6,6,6-trifluorohexyl group, 7,7,7-trifluoroheptyl group, 8,8,8-trifluorooctyl group, 9,9,9-trifluorononyl group And a 10,10,10-trifluorodecyl group.
• the cycloalkyl group may be monocyclic or polycyclic.
• the number of carbon atoms in the cycloalkyl group is usually 3-30.
• Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group.
• the cycloalkyl group may further have a substituent.
• the alkyloxy group may be linear or branched.
• the alkyloxy group usually has 1 to 30 carbon atoms. Examples of the alkyl group that the alkyloxy group has are the same as the examples given as the alkyl group.
• alkyloxy group examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-dimethyl group.
• the alkyloxy group may further have a substituent.
• the alkyloxy group which may have a substituent includes an alkyloxy group in which a part of a methylene group is replaced with an oxygen atom.
• Specific examples of the alkyloxy group having a substituent include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and 2-methoxyethyl.
• An oxy group is mentioned.
• the cycloalkyloxy group usually has 3 to 30 carbon atoms.
• Examples of the cycloalkyl group that the cycloalkyloxy group has are the same as the examples given as the cycloalkyl group.
• cycloalkyloxy group examples include a cyclopropyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
• the cycloalkyloxy group may further have a substituent.
• the alkylthio group usually has 1 to 30 carbon atoms.
• Examples of the alkyl group possessed by the alkylthio group are the same as the examples given as the alkyl group.
• alkylthio group examples include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, n-hexylthio group.
• n-heptylthio group n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio group, and n-dodecylthio group.
• the alkylthio group may further have a substituent.
• Specific examples of the alkylthio group having a substituent include a trifluoromethylthio group.
• the cycloalkylthio group usually has 3 to 30 carbon atoms.
• Examples of the cycloalkyl group that the cycloalkylthio group has are the same as the examples of the cycloalkyl group.
• cycloalkylthio group examples include a cyclopropylthio group, a cyclopentylthio group, a cyclohexylthio group, a cycloheptylthio group, and a cyclooctylthio group.
• the cycloalkylthio group may further have a substituent.
• aryl group means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.
• the number of carbon atoms in the aryl group is usually 6-60.
• Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-phenanthryl group, and a 2-anthryl group.
• the aryl group may further have a substituent.
• substituents that the aryl group may have include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, and a halogen atom.
• aryl group having a substituent examples include a C1-C12 alkyloxyphenyl group, a C1-C12 alkylphenyl group (eg, 4-methylphenyl group, 2-methylphenyl group, 2,6-dimethylphenyl group), And a pentafluorophenyl group.
• C1 to C12 alkyl means an alkyl group having 1 to 12 carbon atoms.
• C1-C12 alkyl is preferably C1-C8 alkyl, more preferably C1-C6 alkyl.
• C1-C8 alkyl means an alkyl group of 1-8 carbon atoms.
• C1-C6 alkyl means an alkyl group of 1-6 carbon atoms. Specific examples of C1-C12 alkyl, C1-C8 alkyl, and C1-C6 alkyl include the groups described and exemplified as the alkyl group. The same applies to the following description.
• heteroaryl group means an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic heterocyclic compound.
• the number of carbon atoms in the heteroaryl group is usually 4-20.
• heteroaryl group examples include 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-pyridyl group, 3-pyridyl group, 3 -Pyridazinyl group, 4-pyridazinyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-pyrazinyl group, 2-triazinyl group, 2-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, and A 3-isoquinolyl group can be mentioned.
• the heteroaryl group may further have a substituent.
• substituents that the heteroaryl group may have include an alkyl group, an alkyloxy group, and a halogen atom.
• aryloxy group means a group in which an aryl group is bonded to an oxy group.
• the aryloxy group usually has 6 to 60 carbon atoms.
• Examples of the aryl group that the aryloxy group has are the same as the examples given as the aryl group.
• Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a phenanthryloxy group, and an anthryloxy group.
• the aryloxy group may further have a substituent.
• substituents that the aryloxy group may have include an alkyl group, an alkyloxy group, and a halogen atom.
• Specific examples of the aryloxy group having a substituent include a C1-C12 alkyloxyphenoxy group, a C1-C12 alkylphenoxy group, and a pentafluorophenyloxy group.
• the arylthio group usually has 6 to 60 carbon atoms.
• Examples of the aryl group that the arylthio group has are the same as the examples given as the aryl group.
• arylthio group examples include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.
• the arylthio group may further have a substituent.
• substituents that the arylthio group may have include an alkyl group, an alkyloxy group, and a halogen atom.
• arylthio group having a substituent examples include a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, and a pentafluorophenylthio group.
• arylalkyl group means an alkyl group having an aryl group as a substituent.
• the number of carbon atoms in the arylalkyl group is usually 7-60.
• Examples of the aryl group that the arylalkyl group has are the same as the examples given as the aryl group, and examples of the alkyl group that the arylalkyl group has are the same as the examples given as the alkyl group.
• arylalkyl group examples include a phenyl-C1 to C12 alkyl group, a 1-naphthyl-C1 to C12 alkyl group, and a 2-naphthyl-C1 to C12 alkyl group.
• the arylalkyl group may further have a substituent.
• substituents that the arylalkyl group may have include an alkyl group, an alkyloxy group, and a halogen atom.
• Specific examples of the arylalkyl group having a substituent include a C1-C12 alkyloxyphenyl-C1-C12 alkyl group and a C1-C12 alkylphenyl-C1-C12 alkyl group.
• arylcycloalkyl group means a cycloalkyl group having an aryl group as a substituent.
• the arylcycloalkyl group usually has 9 to 60 carbon atoms.
• Examples of the aryl group that the arylcycloalkyl group has are the same as the examples given as the aryl group, and examples of the cycloalkyl group that the arylcycloalkyl group has are the same as the examples given as the cycloalkyl group.
• the arylcycloalkyl group may further have a substituent.
• arylalkyloxy group means an oxy group to which an arylalkyl group is bonded.
• the number of carbon atoms in the arylalkyloxy group is usually 7-60.
• Examples of the aryl group possessed by the arylalkyloxy group are the same as the examples given as the aryl group.
• Examples of the alkyl group that the arylalkyloxy group has are the same as the examples given as the alkyl group.
• arylalkyloxy group examples include a phenyl-C1 to C12 alkyloxy group, a 1-naphthyl-C1 to C12 alkyloxy group, and a 2-naphthyl-C1 to C12 alkyloxy group.
• the arylalkyloxy group may further have a substituent.
• substituents that the arylalkyloxy group may have include an alkyl group, an alkyloxy group, and a halogen atom.
• arylalkyloxy group having a substituent examples include a C1-C12 alkyloxyphenyl-C1-C12 alkyloxy group and a C1-C12 alkylphenyl-C1-C12 alkyloxy group.
• arylcycloalkyloxy group means an oxy group to which an arylcycloalkyl group is bonded.
• the arylcycloalkyloxy group usually has 9 to 60 carbon atoms.
• Examples of the aryl group that the arylcycloalkyloxy group has are the same as the examples given as the aryl group.
• Examples of the cycloalkyl group that the arylcycloalkyloxy group has are the same as the examples given as the cycloalkyl group.
• the arylcycloalkyloxy group may further have a substituent.
• substituents that the arylcycloalkyloxy group may have include an alkyl group, an alkyloxy group, and a halogen atom.
• the number of carbon atoms of the arylalkylthio group is usually 7-60.
• Examples of the aryl group that the arylalkylthio group has are the same as the examples given as the aryl group.
• the example of the alkyl group which an arylalkylthio group has is the same as the example given as the alkyl group.
• arylalkylthio group examples include a phenyl-C1 to C12 alkylthio group, a 1-naphthyl-C1 to C12 alkylthio group, and a 2-naphthyl-C1 to C12 alkylthio group.
• the arylalkylthio group may further have a substituent.
• substituent that the arylalkylthio group may have include an alkyl group, an alkyloxy group, and a halogen atom.
• Specific examples of the arylalkylthio group having a substituent include a C1-C12 alkyloxyphenyl-C1-C12 alkylthio group and a C1-C12 alkylphenyl-C1-C12 alkylthio group.
• the arylcycloalkylthio group usually has 9 to 60 carbon atoms.
• Examples of the aryl group that the arylcycloalkylthio group has are the same as the examples given as the aryl group.
• Examples of the cycloalkyl group included in the arylcycloalkylthio group are the same as the examples given as the cycloalkyl group.
• the arylcycloalkylthio group may further have a substituent.
• substituents that the arylcycloalkylthio group may have include an alkyl group, an alkyloxy group, and a halogen atom.
• acyl group means a group represented by R a CO—.
• R a represents a hydrogen atom, a monovalent hydrocarbon group, or a monovalent heterocyclic group which may have an alkyl group.
• the number of carbon atoms of the monovalent hydrocarbon group is preferably 1-20.
• the acyl group usually has 2 to 20 carbon atoms.
• acyl group examples include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group, and isobutyryl group, and aromatic acyl groups such as benzoyl group and naphthoyl group.
• the acyl group may further have a substituent.
• substituents that the acyl group may have include a halogen atom.
• Specific examples of the acyl group having a substituent include a trifluoroacetyl group and a pentafluorobenzoyl group.
• the acyloxy group usually has 2 to 20 carbon atoms.
• the example of the acyl group which an acyloxy group has is the same as the example given as the acyl group.
• acyloxy group examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.
• the acyloxy group may further have a substituent.
• substituents that the acyloxy group may have include a halogen atom.
• Specific examples of the acyloxy group having a substituent include a trifluoroacetyloxy group and a pentafluorobenzoyloxy group.
• amide group means a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an amide.
• the amide group usually has 1 to 20 carbon atoms.
• Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a diformamide group, a diacetamido group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group.
• the amide group may further have a substituent.
• substituents that the amide group may have include a halogen atom.
• amide group having a substituent examples include a trifluoroacetamide group, a pentafluorobenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.
• acid imide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid imide.
• the acid imide group usually has 2 to 20 carbon atoms.
• Specific examples of the acid imide group include the following groups.
• the acid imide group may further have a substituent.
• substituents that the acid imide group may have include a halogen atom.
• the substituted amino group usually has 1 to 40 carbon atoms.
• a substituent which a substituted amino group has an alkyl group and an aryl group are mentioned, for example.
• Examples of the alkyl group that the substituted amino group may have are the same as the examples given as the alkyl group.
• Examples of the aryl group that the substituted amino group may have are the same as the examples given as the aryl group.
• the alkyl group and aryl group that the substituted amino group may have may further have a substituent.
• substituted amino group examples include methylamino group, dimethylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, diisopropylamino group, n-butylamino.
• group having a carbon atom-nitrogen atom double bond refers to the remaining atom after removing one hydrogen atom directly bonded to the carbon atom or nitrogen atom constituting the carbon atom-nitrogen atom double bond from the imine compound. Means a group.
• an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group is bonded to a nitrogen atom constituting a carbon atom-nitrogen atom double bond in aldimine, ketimine, and aldimine.
• the group having a carbon atom-nitrogen atom double bond includes a group represented by —CR ′′ ⁇ N—R ′ ′′ and a group represented by —N ⁇ C (R ′ ′′) 2 (in the formula, , R ′′ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group or an arylalkynyl group, and one or two R ′ ′′ each independently represents an alkyl group, cycloalkyl A group, an aryl group, an arylalkyl group, an arylcycloalkyl group, an arylalkenyl group, an arylalkynyl group, wherein two R ′ in the group represented by —N ⁇ C (R ′ ′′) 2 '' Are bonded to each other to form a divalent group (specifically, an alkylene group having 2 to 18 carbon atoms such as ethylene group, trimethylene group,
• the number of carbon atoms in the group having a carbon atom-nitrogen atom double bond is usually 2 to 20, preferably 2 to 18, and more preferably 2 to 16.
• group having a carbon atom-nitrogen atom double bond include the following groups.
• substituted silyl group means a silyl group having a substituent.
• the substituted silyl group usually has 3 to 40 carbon atoms.
• substituent that the substituted silyl group has include an alkyl group and an aryl group, and examples of the alkyl group that the substituted silyl group may have are the same as the examples given as the above alkyl group.
• examples of the aryl group that the silyl group may have are the same as the examples given as the aryl group.
• substituted silyl group examples include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, Examples thereof include a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.
• the substituted silyloxy group usually has 3 to 40 carbon atoms.
• Examples of the substituted silyl group that the substituted silyloxy group has are the same as the examples given above as the substituted silyl group.
• substituted silyloxy group examples include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylyl group.
• examples thereof include a silyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.
• the number of carbon atoms in the substituted silylthio group is usually 3 to 40.
• Examples of the substituted silyl group that the substituted silylthio group has are the same as the examples given above as the substituted silyl group.
• substituted silylthio group examples include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, triisopropylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, tri-p-xylyl group.
• examples thereof include a silylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.
• the number of carbon atoms of the substituted silylamino group is usually 3 to 80, preferably 6 to 60.
• Examples of the substituted silyl group that the substituted silylamino group has are the same as the examples given above as the substituted silyl group.
• substituted silylamino group examples include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, triisopropylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylyl group.
• the term “monovalent heterocyclic group” means a remaining atomic group obtained by removing one hydrogen atom directly bonded to an atom constituting a ring from an optionally substituted heterocyclic compound. .
• the number of carbon atoms in the monovalent heterocyclic group is usually 3-20.
• the monovalent heterocyclic group examples include pyrrolidyl group, piperidyl group, thienyl group, C1-C12 alkylthienyl group, pyrrolyl group, furyl group, pyridyl group, C1-C12 alkylpyridyl group, imidazolyl group, pyrazolyl group, Examples include a triazolyl group, an oxazolyl group, a thiazolyl group, and a thiadiazolyl group.
• a monovalent aromatic heterocyclic group is preferable.
• heterocyclic oxy group means an oxy group to which a monovalent heterocyclic group is bonded.
• heterocyclic oxy group examples include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group.
• examples include a ruoxy group, an oxazolyloxy group, a thiazolyloxy group, and a thiadiazolyloxy group.
• heterocyclic thio group means a thio group to which a monovalent heterocyclic group is bonded.
• heterocyclic thio group examples include thienylthio group, C1-C12 alkylthienylthio group, pyrrolylthio group, furylthio group, pyridylthio group, C1-C12 alkylpyridylthio group, imidazolylthio group, pyrazolylthio group, triazolylthio group, oxazolylthio group Groups, thiazolylthio groups, and thiadiazolylthio groups.
• the number of carbon atoms of the arylalkenyl group is usually 8-20.
• Examples of the aryl group that the arylalkenyl group has are the same as the examples given as the aryl group.
• Specific examples of the arylalkenyl group include a styryl group.
• the arylalkynyl group usually has 8 to 20 carbon atoms.
• Examples of the aryl group that the arylalkynyl group has are the same as the examples given as the aryl group.
• Examples of the arylalkynyl group include a phenylethynyl group.
• alkyloxycarbonyl group means a group in which an alkyloxy group is bonded to a carbonyl group.
• alkyloxy group possessed by the alkyloxycarbonyl group are the same as the examples given as the alkyloxy group.
• alkyloxycarbonyl group examples include, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert- Butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxy Examples include a carbonyl group, 3,7-dimethyloctyloxycarbonyl group, and n-dodecyloxycarbonyl group.
• the alkyloxycarbonyl group may further have a substituent.
• substituents include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, and a perfluorooctyloxycarbonyl group.
• cycloalkyloxycarbonyl group means a group in which a cycloalkyloxy group is bonded to a carbonyl group.
• Examples of the cycloalkyl group that the cycloalkyloxycarbonyl group has are the same as the above-described examples of the cycloalkyloxy group.
• cycloalkyloxycarbonyl group examples include a cyclohexyloxycarbonyl group.
• aryloxycarbonyl group means a group in which an aryloxy group is bonded to a carbonyl group.
• Examples of the aryloxy group possessed by the aryloxycarbonyl group are the same as the examples of the aryloxy group.
• aryloxycarbonyl group examples include a phenoxycarbonyl group, a naphthoxycarbonyl group, and a pyridyloxycarbonyl group.
• divalent aromatic hydrocarbon group refers to the remaining atomic group obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an optionally substituted aromatic hydrocarbon. means.
• the divalent aromatic hydrocarbon group may have a substituent.
• substituents that the divalent aromatic hydrocarbon group may have include a halogen atom, an alkyl group, an alkyloxy group, and an alkylthio group. These substituents may further have a substituent.
• divalent aromatic heterocyclic group means an atomic group obtained by removing two hydrogen atoms directly bonded to atoms constituting a ring from an aromatic heterocyclic compound which may have a substituent. Means.
• the divalent aromatic heterocyclic group may have a substituent.
• substituents that the divalent aromatic heterocyclic group may have include a halogen atom, an alkyl group, an alkyloxy group, and an alkylthio group. These substituents may further have a substituent.
• the term “monovalent hydrocarbon group” means the remaining atomic group obtained by removing one hydrogen atom from a hydrocarbon.
• the monovalent hydrocarbon group may further have a substituent. Examples of the substituent that the monovalent hydrocarbon group may have include a hydroxy group.
• the production method of the present invention is a production method of a polymer compound containing a repeating unit represented by the formula (1), wherein the compound represented by the formula (2) and the compound represented by the formula (3) Reacting in a reaction solvent comprising a palladium catalyst and a base, wherein the reaction solvent is a first solvent that is at least one hydrocarbon solvent, at least one carbon atom, at least one hydrogen atom, and A second solvent, which is at least one organic solvent consisting only of at least one oxygen atom, and water, the sum of the volume of the first solvent, the volume of the second solvent, and the volume of the water
• the reaction solvent is a first solvent that is at least one hydrocarbon solvent, at least one carbon atom, at least one hydrogen atom, and A second solvent, which is at least one organic solvent consisting only of at least one oxygen atom, and water, the sum of the volume of the first solvent, the volume of the second solvent, and the volume of the water
• a polymer compound having a large weight average molecular weight can be produced.
• the weight average molecular weight of the polymer compound obtained by the production method of the present invention is not particularly limited depending on the kind of the polymer compound obtained.
• the weight average molecular weight of the polymer compound obtained by the production method of the present invention can be measured by gel permeation chromatography (hereinafter referred to as GPC) in terms of polystyrene using tetrahydrofuran or o-dichlorobenzene as a mobile phase.
• the production method includes a step of reacting a compound represented by the formula (2) and a compound represented by the following formula (3) in a reaction solvent containing a palladium catalyst and a base,
• the reaction solvent is A first solvent that is at least one hydrocarbon solvent;
• a second solvent which is at least one organic solvent consisting only of at least one carbon atom, at least one hydrogen atom, and at least one oxygen atom, and water,
• the method for producing a polymer compound wherein a volume ratio of water to a total of the volume of the first solvent, the volume of the second solvent, and the volume of the water is more than 10% by volume and less than 100% by volume.
• the compound represented by the formula (2) is “4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole” and the compound represented by the formula (3) is “2,2 ′-( 5,5-bis (3,7-dimethyloctyl) -5H-dithieno [3,2-b: 2 ′, 3′-d] pyran-2,7-diyl) bis (5-methyl-1,3 2-dioxaborinane-5-methanol) "in a reaction solvent containing" chloromethyl (tri-tert-butylphosphine) palladium (II) "as a palladium catalyst and potassium phosphate as a base,
• the reaction solvent is Mesitylene as the first solvent, Tetrahydrofuran as the second solvent, Including water, A production method, except that the volume ratio of mesitylene, tetrahydrofuran, and water to the sum of the volume of mesitylene, the volume of t
• the production method includes a step of reacting a compound represented by the formula (2) and a compound represented by the following formula (3) in a reaction solvent containing a palladium catalyst and a base,
• the reaction solvent is A first solvent that is at least one hydrocarbon solvent;
• a second solvent which is at least one organic solvent consisting only of at least one carbon atom, at least one hydrogen atom, and at least one oxygen atom, and water,
• the method for producing a polymer compound wherein a volume ratio of water to a total of the volume of the first solvent, the volume of the second solvent, and the volume of the water is more than 10% by volume and less than 100% by volume.
• the manufacturing method which is another embodiment of this invention is as follows.
• the compound represented by the formula (2) is “4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole” and the compound represented by the formula (3) is “2,2 ′-( 5,5-bis (3,7-dimethyloctyl) -5H-dithieno [3,2-b: 2 ′, 3′-d] pyran-2,7-diyl) bis (5-methyl-1,3 2-dioxaborinane-5-methanol) "in a reaction solvent containing" chloromethyl (tri-tert-butylphosphine) palladium (II) "as a palladium catalyst and potassium phosphate as a base,
• the reaction solvent is Mesitylene as the first solvent, Containing tetrahydrofuran and water as the second solvent,
• the production method may be such that the volume ratio of mesitylene, tetrahydrofur
• the manufacturing method which is another embodiment of this invention is as follows.
• a compound represented by the formula (2) “4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole 3.0 mmol” and as a compound represented by the formula (3) “2,2 '-(5,5-bis (3,7-dimethyloctyl) -5H-dithieno [3,2-b: 2', 3'-d] pyran-2,7-diyl) bis (5-methyl-1 , 3,2-dioxaborinane-5-methanol) 3.0 mmol ”,“ chloromethyl (tri-tert-butylphosphine) palladium (II) 9.0 ⁇ mol ”as the palladium catalyst and“ 3M aqueous potassium phosphate solution 10 mL ”as the base Reacting in a reaction solvent comprising
• the reaction solvent is 30 mL of mesitylene as the first solvent, 70 mL of
• the manufacturing method of this invention is a manufacturing method of the high molecular compound containing the repeating unit represented by following formula (1).
• Ar A represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group
• Ar B represents a divalent aromatic heterocyclic group containing at least one thiophene ring.
• divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group represented by Ar A groups represented by the following formulas (Cy-1) to (Cy-5) are preferable.
• each R independently represents a hydrogen atom or a substituent.
• R 1 and R 2 each independently represents a hydrogen atom or a substituent.
• R 1 and R 2 may be connected to each other to form a cyclic structure together with the carbon atom to which they are bonded.
• Ring Cy is the same or different, and represents the aromatic ring which may have a substituent.
• R 3 represents a divalent group.
• R 1 and R 2 may be connected to each other to form a cyclic structure together with the carbon atom to which they are bonded.
• Specific examples of the cyclic structure include structures represented by the following formulas (D-1) to (D-5). In formulas (D-1) to (D-5), R has the same meaning as described above.
• the aromatic ring represented by ring Cy may be a single ring or a condensed ring.
• Examples of the aromatic ring that is a single ring include a benzene ring, a pyrrole ring, a furan ring, a thiophene ring, an oxazole ring, a thiazole ring, a thiadiazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, an imidazole ring, a triazole ring, and an isoxazole ring.
• Isothiazole ring, pyrimidine ring, pyridazine ring and triazine ring are examples of the aromatic ring that is a single ring.
• Examples of the aromatic ring that is a condensed ring include an aromatic ring in which an arbitrary ring is condensed to the above-mentioned single ring.
• Examples of the ring condensed with a single ring include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, thiadiazole ring, imidazole ring, imidazoline ring, and imidazole.
• divalent group represented by R 3 include groups represented by the following formulas (b-1) to (b-8).
• R has the same meaning as described above.
• Specific examples of the substituent represented by R in formulas (b-1) to (b-8) include an alkyl group.
• each R is independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms. .
• Examples of the groups represented by formula (Cy-1) to formula (Cy-5) include groups represented by the following formula (C-1) to formula (C-31).
• R has the same meaning as described above.
• the divalent aromatic heterocyclic group represented by Ar A is selected from the group consisting of a divalent aromatic heterocyclic group having a monocyclic structure and a divalent aromatic heterocyclic group having a condensed ring structure. Two or more of them may be directly bonded, or may be a divalent group formed by bonding indirectly through a hetero atom or a carbonyl group, and one or more monocyclic structures and A divalent aromatic heterocyclic group having a condensed ring structure and one or more monocyclic structures and / or a divalent aromatic hydrocarbon group having a condensed ring structure are directly bonded to each other or a hetero atom Or the bivalent group formed by couple
• Examples of such a divalent group include a divalent group represented by the following formula (RA-1).
• R has the same meaning as described above.
• the “divalent aromatic heterocyclic group containing at least one thiophene ring” represented by Ar B is an aromatic heterocyclic compound containing at least one thiophene ring as a ring structure from a carbon atom constituting the ring. It means the remaining atomic group excluding two hydrogen atoms directly bonded.
• An aromatic heterocyclic compound containing at least one thiophene ring as a ring structure includes thiophene, a compound in which any ring structure is condensed to at least one thiophene ring, and any ring structure in thiophene and at least one thiophene ring
• Two or more selected from the group consisting of compounds in which are condensed include compounds formed by being directly bonded or indirectly bonded via a hetero atom or a carbonyl group.
• the divalent aromatic heterocyclic group containing at least one thiophene ring may have a substituent.
• the divalent aromatic heterocyclic group containing at least one thiophene ring may have a substituent on at least one thiophene ring, for example.
• the ring Cy is A group representing a thiophene ring, a group represented by the following formula (B-1), the following formula (B-2) or the following formula (B-3), and the above formulas (C-16), (C-17), (C-18), (C-19), (C-21), (C-25), (C-26), (C-27), (C-28), or (RA-1) Group to be used.
• the group represented by formula (B-1), formula (B-2) or formula (B-3) will be described later.
• the divalent aromatic heterocyclic group containing at least one thiophene ring represented by Ar B may be a divalent heterocyclic group containing only one thiophene ring.
• a group represented by the following formula (B-3) is preferable.
• the divalent aromatic heterocyclic group containing at least one thiophene ring represented by Ar B may be a divalent aromatic heterocyclic group containing at least two thiophene rings.
• As the divalent aromatic heterocyclic group containing at least two thiophene rings represented by Ar B two hydrogen atoms directly bonded to the carbon atom constituting the thiophene ring from a compound containing two thiophene rings are used.
• the remaining atomic group is more preferably a group represented by the following formula (B-1), a group represented by the following formula (B-2), or a group represented by the above formula (RA-1). And more preferably a group represented by the following formula (B-1).
• Z is a group represented by any one of the following formulas (Z-1) to (Z-8).
• R has the same meaning as described above.
• Specific examples of the substituent represented by R in the formulas (Z-1) to (Z-8) include an alkyl group.
• each R is independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms. .
• R each independently represents a hydrogen atom or a substituent. p represents 0 or 1.
• W 1 and W 2 each independently represent a carbon atom or a sulfur atom. However, when W 1 is a carbon atom, W 2 is a sulfur atom, and when W 1 is a sulfur atom, W 2 is a carbon atom.
• each R is independently preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. .
• Z ′ is a group represented by any one of the following formulas (Z′-1) to (Z′-3).
• R each independently represents a hydrogen atom or a substituent.
• X 1 and X 2 each independently represent a chlorine atom, a bromine atom, or an iodine atom.
• Ar A has the same meaning as described above.
• X 1 and X 2 are preferably each independently a bromine atom or an iodine atom, more preferably a bromine atom.
• X 1 and X 2 are preferably the same as each other, more preferably both are bromine atoms.
• the compound represented by the formula (2) includes all combinations of the example of Ar A , the example of X 1 and the example of X 2 described above.
• the amount of the compound represented by the formula (2) is usually 0.5 to 1.5 mol with respect to 1 mol of the compound represented by the formula (3) described later.
• the amount is preferably 0.8 to 1.2 mol.
• the compound represented by Formula (2) can be manufactured by a well-known method. For example, it can be produced by treating a compound in which X 1 and X 2 are hydrogen atoms in formula (2) with a halogenating agent such as N-bromosuccinimide by a known method.
• a halogenating agent such as N-bromosuccinimide
• Y 1 and Y 2 each independently represents a monovalent group containing one boron atom and at least two oxygen atoms.
• Ar B has the same meaning as described above.
• Examples of the monovalent group containing one boron atom represented by Y 1 and Y 2 and at least two oxygen atoms include —B (OH) 2 and —B (—O—R B ) 2 .
• the two R B each independently, represent a monovalent hydrocarbon group which may have a hydroxy group, two R B is to form a divalent group linked together May be.
• M represents a group 1 element.
• M is preferably a lithium atom, a sodium atom, or a potassium atom.
• Me represents a methyl group.
• the compound represented by the formula (3) includes all combinations of the example of Ar B described above, the example of Y 1 described above, and the example of Y 2 described above.
• the groups represented by Y 1 and Y 2 may be the same as or different from each other. Since the compounds represented by formula (3) can be easily synthesized, they are preferably identical to each other.
• Specific examples of the compound represented by the formula (3) include compounds represented by the following formulas (501) to (516).
• R has the same meaning as described above.
• the compound represented by Formula (3) can be manufactured by a well-known method.
• the compound represented by the formula (3) in which Y 1 and Y 2 are groups represented by —B (—O—R B ) 2 is, for example, (HO) 2 B—Ar, which is diboronic acid.
• the alcohol is HO—R 2B —OH (where R 2B is a bond between the two R B And a compound represented by (2) formed by dehydration reaction.
• the compound represented by (HO) 2 B—Ar B —B (OH) 2 (wherein Ar B is as defined above) is, for example, Hal—Ar B —Hal (where Hal is Independently represents a hydrogen atom, a bromine atom or an iodine atom) and a metallizing agent are reacted with each other to give Mtl-Ar B -Mtl (where Mtl represents a metal atom).
• Mtl-Ar B -Mtl where Mtl represents a metal atom.
• the reaction solvent used in the production method of the present invention consists of a first solvent which is at least one hydrocarbon solvent, at least one carbon atom, at least one hydrogen atom, and at least one oxygen atom.
• a second solvent which is at least one organic solvent, and water.
• the reaction solvent may contain any solvent other than the first solvent, the second solvent, and water.
• the optional solvent include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, monochlorobenzene, dichlorobenzene, and trichlorobenzene.
• the volume ratio of the arbitrary solvent is preferably 50% by volume or less, more preferably 25% by volume or less, with respect to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water. Even more preferably, it is 10 volume% or less.
• the reaction solvent preferably consists essentially of the first solvent, the second solvent, and water.
• Examples of the first solvent include an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, and an aromatic hydrocarbon solvent.
• Examples of the aliphatic hydrocarbon solvent include hexane, heptane, octane, nonane, decane, undecane, and dodecane.
• Examples of the alicyclic hydrocarbon solvent include cyclohexane and decalin.
• Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, trimethylbenzene (eg, mesitylene), tetralin, indane, naphthalene, and methylnaphthalene.
• the first solvent may be a single hydrocarbon solvent or a combination of two or more hydrocarbon solvents.
• the first solvent is preferably at least one selected from the group consisting of toluene, xylene, trimethylbenzene, decalin, tetralin, indane, naphthalene, and methylnaphthalene, and more preferably from toluene, mesitylene, and tetralin. It is 1 or more types selected from the group which consists of, More preferably, they are toluene, mesitylene, or tetralin.
• the organic solvent as the second solvent includes a hydroxy group, an oxo group, an oxycarbonyl group (a group represented by — (C ⁇ O) —O—), an ether bond (a group represented by —O—), and the like. , May have only one group containing an oxygen atom, or may have two or more groups. In addition, the organic solvent as the second solvent may have only one type of group containing an oxygen atom, or may have two or more types.
• Examples of the second solvent include alcohol solvents, ether solvents, ketone solvents, phenol solvents, and carboxylic acid ester solvents.
• the alcohol solvent examples include primary alcohols (eg, methanol, ethanol, 2-phenylethanol, n-propyl alcohol, n-butyl alcohol, 3-methyl-1-butanol, 1-pentanol, 1-hexanol, 2-ethyl-1-hexanol, 1-octanol, benzyl alcohol), secondary alcohol (eg, isopropyl alcohol, sec-butyl alcohol, 2-octanol, 3-pentanol, cyclohexanol), tertiary alcohol (eg, Tert-butyl alcohol, 1-methylcyclohexanol, 1-ethylcyclohexanol, 1-methylcyclopentanol, tert-amyl alcohol, 2-phenyl-2-propanol, 2-methyl-1-phenyl-2-propanol, 2-methyl 2-pentanol, 3-ethyl-3-pentanol), and the like.
• primary alcohols eg,
• ether solvents include anisole, cyclopentyl methyl ether, tert-butyl methyl ether, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane.
• ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
• phenol solvents examples include phenol, o-cresol, m-cresol, and p-cresol.
• carboxylic acid ester solvent examples include ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, ⁇ -butyl lactone is mentioned.
• the second solvent may be a single type or a combination of two or more types.
• the second solvent is preferably at least one selected from the group consisting of an alcohol solvent, an ether solvent, and a ketone solvent, more preferably a tertiary alcohol solvent, and even more preferably 1-methylcyclopentanol. 1 or more selected from the group consisting of 1-methylcyclohexanol, 1-ethylcyclohexanol and 2-phenyl-2-propanol.
• the second solvent may be a solvent immiscible with water.
• a certain solvent is “immiscible with water” means a liquid obtained by adding 5% by mass or more of water to the solvent and 5% by mass or more of the solvent to water. It means that the liquid obtained by adding to the above does not form a transparent one-phase solution.
• Examples of the solvent that is immiscible with water that can be used as the second solvent include 2-phenylethanol, 3-methyl-1-butanol, 1-pentanol, 1-hexanol, 2-ethyl-1-hexanol, 1 -Octanol, benzyl alcohol, 2-octanol, cyclohexanol, 1-methylcyclohexanol, 1-ethylcyclohexanol, 1-methylcyclopentanol, 2-phenyl-2-propanol, 2-methyl-1-phenyl-2- Propanol, 2-methyl-2-pentanol, 3-ethyl-3-pentanol, anisole, cyclopentyl methyl ether, tert-butyl methyl ether, diisopropyl ether, methyl isobutyl ketone, o-cresol, m-cresol, p-cresol , Acetic acid pro Butyl acetate,
• a solvent is “miscible with water” means a liquid obtained by adding 5% by mass or more of water to the solvent and 5% by mass or more of the solvent to water. It means that the liquid obtained by adding to 1 forms a transparent one-phase solution.
• the second solvent may be a solvent miscible with water.
• the solvent miscible with water that can be used as the second solvent include methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isopropyl alcohol, sec-butyl alcohol, 3-pentanol, and tert-butyl alcohol.
• One or more selected from the group consisting of drofuran, 2-methyltetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, and cyclohexanone is preferable, and includes tert-butyl alcohol, tert-amyl alcohol, ethylene glycol dimethyl ether, tetrahydrofuran, and 2-
• Examples of the combination of the first solvent and the second solvent include all combinations of the above example mentioned as the first solvent and the above example mentioned as the second solvent.
• the combination of a 1st solvent and a 2nd solvent is not specifically limited, For example, the combination shown by following Table 1 is mentioned.
• the second solvent is a solvent that is not miscible with water
• the combinations shown in Table 2 below are preferable, and the combinations shown in Table 3 below are more preferable.
• the combinations shown in Table 4 below are preferable.
• the first solvent, the second solvent, and water are mixed at a volume ratio of a: b: c.
• a + b + c 100
• c is more than 10 and less than 100. That is, the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is more than 10 volume% and less than 100 volume%.
• the volume ratio of water is determined based on the volume of the first solvent, the volume of the second solvent, and the volume of water used to prepare the reaction solvent.
• the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is more than 10% by volume, preferably 25% by volume or more, more preferably more than 25% by volume, still more preferably 35% by volume or more, still more preferably more than 35% by volume, still more preferably 45% by volume or more, still more preferably 45% by volume. %, More preferably 50% by volume or more, and particularly preferably more than 50% by volume.
• the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is less than 100% by volume, preferably Is 90% by volume or less, more preferably less than 90% by volume, still more preferably 80% by volume or less, still more preferably less than 80% by volume, still more preferably 70% by volume or less, and further preferably Is less than 70% by volume, more preferably 65% by volume or less, and particularly preferably less than 65% by volume.
• the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is more than 10% by volume and 100% by volume. Less than, preferably 25 volume% or more and 90 volume% or less, more preferably more than 25 volume% and less than 90 volume%, still more preferably 35 volume% or more and 80 volume% or less, still more preferably 35 More than 45 volume% and less than 80 volume%, More preferably, it is 45 volume% or more and 70 volume% or less, More preferably, it exceeds 45 volume% and less than 70 volume%, More preferably, it is 50 volume% or more and 65 volume% Or less, particularly preferably more than 50% by volume and less than 65% by volume.
• the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is greater than 10% by volume, preferably 20% by volume or more, more preferably more than 20% by volume, still more preferably 25% by volume or more, still more preferably more than 25% by volume, still more preferably 35% by volume or more, still more preferably 35% by volume. %, More preferably 45% by volume or more, more preferably more than 45% by volume, still more preferably 50% by volume or more, and particularly preferably more than 50% by volume.
• the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is less than 100% by volume, preferably Is 90% by volume or less, more preferably less than 90% by volume, still more preferably 80% by volume or less, still more preferably less than 80% by volume, still more preferably 70% by volume or less, and further preferably Is less than 70% by volume, more preferably 65% by volume or less, and particularly preferably less than 65% by volume.
• the volume ratio c (%) of water to the sum of the volume of the first solvent, the volume of the second solvent, and the volume of water is more than 10% by volume and 100% by volume. Less than, preferably 20% by volume or more and 90% by volume or less, more preferably more than 20% by volume and less than 90% by volume, still more preferably 25% by volume or more and 90% by volume or less, and further preferably 25% by volume. More than 35% by volume and less than 90% by volume, more preferably 35% by volume or more and 80% by volume or less, more preferably more than 35% by volume and less than 80% by volume, more preferably 45% by volume or more and 70% by volume or less. Or less, more preferably more than 45 volume% and less than 70 volume%, further preferably 50 volume% or more and 65 volume% or less, particularly preferably more than 50 volume% and more than 65 volume%. It is less than.
• the mixing volume ratio a: b of the first solvent and the second solvent is preferably in the range of 1: 9 to 9: 1, more preferably in the range of 3: 7 to 7: 3.
• Examples of the palladium catalyst used in the production method of the present invention include a Pd (0) catalyst and a Pd (II) catalyst.
• Specific examples of the palladium catalyst include palladium [tetrakis (triphenylphosphine)], dichlorobis (triphenylphosphine) palladium, palladium (II) acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, bis (Tri-tert-butylphosphine) palladium (0), a palladium complex represented by the following formula (C), and a palladium complex represented by the following formula (C ′).
• the palladium catalyst may be used alone or in combination of two or more.
• X represents a chlorine atom, a bromine atom or an iodine atom.
• A represents an alkyl group having 1 to 3 carbon atoms.
• R 4 represents an alkyl group having 1 to 20 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms which may have a cycloalkyl group having 5 to 10 carbon atoms, and R 5 and R 6 are each independently And an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms.
• the number of carbon atoms of the aryl group and heteroaryl group does not include the number of carbon atoms of the substituent.
• the substituent that the aryl group and heteroaryl group may have is selected from the following group 1.
• X, A, R 4 , R 5 and R 6 are as defined above.
• a plurality of X, A, R 4 , R 5 and R 6 may be the same or different.
• Group 1 Fluorine atom, alkyl group, cycloalkyl group, alkyloxy group, cycloalkyloxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylcycloalkyl group, arylalkenyl group, arylalkynyl group, an alkyl group or a monovalent optionally having heterocyclic group, -N (R ') a group represented by (two R 2' independently represent a hydrogen atom, a carbon atom A monovalent hydrocarbon group of 1 to 20 or a monovalent heterocyclic group optionally having an alkyl group), a group represented by —Si (R ′) 3 (R ′ is And the three R's may be the same or different from each other.), An acyl group, a group having a carbon atom-nitrogen atom double bond, an acid imide group, an alky
• the palladium complex represented by the formula (C) or the formula (C ′) include (tri- (tert-butyl) phosphine) chloromethylpalladium, (di- (tert-butyl) (4-fluorophenyl) Phosphine) chloromethylpalladium, (di- (tert-butyl) (3-fluorophenyl) phosphine) chloromethylpalladium, (di- (tert-butyl) (4-methylphenyl) phosphine) chloromethylpalladium, (di- ( tert-butyl) (3-methylphenyl) phosphine) chloromethylpalladium, (di- (tert-butyl) (4-ethylphenyl) phosphine) chloromethylpalladium, (di- (tert-butyl) (3-ethylphenyl) Phosphine) chloromethylpalladium, ((di- (tert
• the palladium complex represented by the formula (C) is organic metallics. 2006, 25, 4588-4595. It can synthesize
• the addition amount of the palladium catalyst is not particularly limited, but is usually 0.00001 mol to 0.8 mol, preferably 0.00005 to 0.5 mol, relative to 1 mol of the compound represented by the formula (3). More preferably, it is 0.0001 mol to 0.2 mol.
• a compound that becomes a ligand of the palladium catalyst may be added to the reaction solvent in the production method of the present invention.
• a trialkyl phosphine, a dialkyl aryl phosphine, an alkyl diaryl phosphine, and a triaryl phosphine are mentioned.
• Further examples include triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, and tri-tert-butylphosphine.
• the phosphorus compound serving as a ligand for the palladium catalyst may be obtained by reacting a phosphonium salt with a base.
• a phosphonium salt examples include phosphorus compounds such as tri-tert-butylphosphonium tetrafluoroborate.
• the base used in the production method of the present invention may be an inorganic base or an organic base.
• Examples of the inorganic base include alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carboxylate, alkaline earth metal carboxylate, alkali metal carbonate, alkaline earth metal carbonate, and alkali metal carbonate.
• Examples include hydrogen salt, alkaline earth metal hydrogen carbonate, alkali metal sulfate, alkaline earth metal sulfate, alkali metal phosphate, and alkaline earth metal phosphate, alkali metal carbonate, alkali metal phosphate It is preferably at least one selected from the group consisting of a salt, an alkaline earth metal carbonate, an alkali metal sulfate, an alkaline earth metal sulfate, and an alkaline earth metal phosphate.
• the inorganic base includes an alkali metal sulfate and an alkaline earth metal sulfate.
• the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, sodium formate, potassium formate, calcium formate, sodium acetate, potassium acetate, sodium carbonate, Examples include potassium carbonate, cesium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, and potassium dihydrogen phosphate. .
• sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate or potassium phosphate is preferable.
• organic base examples include alkali metal alkoxides such as potassium tert-butoxide; alkaline earth metal alkoxides such as sodium tert-butoxide; alkylammonium hydroxides; alkylammonium carbonates; alkylammonium bicarbonates; alkylammonium boronic acids 1,5-diazabicyclo [4.3.0] non-5-ene (DBN); 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU); 1,4-diazabicyclo [ 2.2.2] Octane (DABCO); Dimethylaminopyridine (DMAP); Pyridine; Trialkylamine; Alkylammonium fluoride such as tetraalkylammonium fluoride.
• alkali metal alkoxides such as potassium tert-butoxide
• alkaline earth metal alkoxides such as sodium tert-butoxide
• alkylammonium hydroxides alkylammoni
• tetraalkylammonium hydroxides such as potassium tert-butoxide, sodium tert-butoxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetra-n-propylammonium hydroxide are preferable.
• the amount of base used is usually 0.5 equivalents to 20 equivalents, preferably 2 equivalents to 10 equivalents.
• the equivalent represents the ratio of the theoretical amount of hydrogen ions that can be neutralized by the base to the total amount of X 1 and X 2 contained in the compound represented by the formula (2).
• the base may be used as it is or in the form of an aqueous solution.
• the volume of water used to prepare the aqueous solution of the base is included in the volume of water used to prepare the reaction solvent.
• two or more bases may be used in combination.
• phase transfer catalyst When an inorganic base is used as the base, a phase transfer catalyst may be used in combination.
• the phase transfer catalyst include tetraalkyl ammonium halide, tetraalkyl ammonium hydrogen sulfate, and tetraalkyl ammonium hydroxide.
• the inorganic base is preferably a tetraalkylammonium halide such as tricaprylmethyl ammonium chloride (available as Aliquat® 336 from Sigma-Aldrich).
• the production method of the present invention includes a step of reacting the compound represented by formula (2) and the compound represented by formula (3) in a reaction solvent containing a palladium catalyst and a base (reaction step).
• a polymer containing a repeating unit represented by formula (1) by reacting a compound represented by formula (2) and a compound represented by formula (3) in a reaction solvent containing a palladium catalyst and a base.
• a compound is obtained.
• the compound represented by formula (2) and the compound represented by formula (3) are mixed with the compound represented by formula (2), the compound represented by formula (3), the palladium catalyst, the base, and the reaction solvent.
• the compound represented by these is made to react.
• the order of mixing is not particularly limited.
• the compound represented by the formula (2), the compound represented by the formula (3), the palladium catalyst, the base, and the reaction solvent may be mixed at the same time. After mixing the compound represented by (2), the compound represented by formula (3), the base, and a part of the reaction solvent, the resulting mixture, the remaining reaction solvent and the palladium catalyst may be mixed. Good.
• the resulting mixture may be mixed with a base.
• the reaction temperature of the production method of the present invention is usually in the range of ⁇ 20 ° C. to 180 ° C., preferably in the range of ⁇ 20 ° C. to 100 ° C., more preferably in the range of ⁇ 20 ° C. to 80 ° C.
• the reaction time of the production method of the present invention is usually in the range of 30 minutes to 96 hours, preferably in the range of 30 minutes to 48 hours.
• the production method of the present invention may include an optional step other than the step of reacting the compound represented by the formula (2) and the compound represented by the formula (3).
• an optional step for example, after the step of reacting the compound represented by the formula (2) and the compound represented by the formula (3), the high unit containing the repeating unit represented by the formula (1) obtained is obtained.
• a step of separating the molecular compound from the reaction mixture may be mentioned.
• a reaction mixture and a poor solvent are added.
• a step of mixing and precipitating the target polymer compound and collecting the polymer compound by filtration may be included.
• the obtained aromatic compound was analyzed by GPC under the following analysis conditions, and the weight average molecular weight (Mw) in terms of polystyrene was calculated from the analysis result.
• GPC measuring device CTO-10AC (Shimadzu Corporation column oven), SPD-10A (Shimadzu Corporation detector) Column: Shodex KD-806 8.0 mm (diameter) x 30 cm (manufactured by Showa Denko KK) -Column temperature: 60 ° C ⁇ Mobile phase: o-dichlorobenzene ⁇ Flow rate: 1 mL / min ⁇ Detection: Visible light detection (wavelength 600 nm)
• Example 1 As shown in the following scheme, polymer A was synthesized from compound 2 and compound 3.
• Compound 3 was synthesized by the method described in Synthesis Example 1 of International Publication Number (WO2014 / 112656). To a glass reaction vessel equipped with a cooling device at room temperature, 0.58 mL of water was added. The reaction vessel was filled with nitrogen gas, and 75 ⁇ mol of compound 2, 75 ⁇ mol of compound 3, and 3.0 ⁇ mol of bis (tri-tert-butylphosphine) palladium (0) were added to 1.25 mL of 1-methylcyclohexanol and 1.25 mL of toluene. The solution dissolved in the mixed solvent was added and mixed, and then 0.25 mL of 3M aqueous potassium phosphate solution was added and mixed. The obtained mixture was stirred at 65 ° C.
• Example 2 A polymer was obtained in the same manner as in Example 1 except that the amount of water added was changed from 0.58 mL to 1.10 mL.
• the volume percentages of toluene, 1-methylcyclohexanol, and water relative to the total volume of toluene, 1-methylcyclohexanol, and water are 32.5%, 32.5%, and 35%, respectively. % By volume.
• the obtained polymer had Mw of 8.8 ⁇ 10 4 .
• Example 3 A polymer was obtained in the same manner as in Example 6 except that the amount of water added was changed from 0.58 mL to 2.25 mL.
• the volume percentages of toluene, 1-methylcyclohexanol, and water relative to the total volume of toluene, 1-methylcyclohexanol, and water are 25%, 25%, and 50% by volume, respectively.
• the obtained polymer had Mw of 9.0 ⁇ 10 4 .
• Example 4 A polymer was obtained in the same manner as in Example 6 except that the amount of water added was changed from 0.58 mL to 4.39 mL.
• the volume percentages of toluene, 1-methylcyclohexanol, and water relative to the sum of the volume of toluene, the volume of 1-methylcyclohexanol, and the volume of water are 17.5%, 17.5%, and 65%, respectively. % By volume.
• the obtained polymer had Mw of 8.2 ⁇ 10 4 .
• Comparative Example 1 A polymer was obtained in the same manner as in Example 1 except that water was not added.
• the volume percentages of toluene, 1-methylcyclohexanol, and water relative to the sum of the volume of toluene, the volume of 1-methylcyclohexanol, and the volume of water are 45.5%, 45.5%, and 9%, respectively. % By volume.
• the obtained polymer had Mw of 6.7 ⁇ 10 4 .
• Table 5 shows the results of Examples 1 to 4 and Comparative Example 1.
• Example 5 A polymer was obtained in the same manner as in Example 1 except that the second solvent was changed from 1-methylcyclohexanol to anisole.
• the volume percentages of toluene, anisole, and water relative to the sum of the volume of toluene, the volume of anisole, and water are 40%, 40%, and 20% by volume, respectively.
• the obtained polymer had Mw of 8.4 ⁇ 10 4 .
• Example 6 A polymer was obtained in the same manner as in Example 5 except that the amount of water added was changed from 0.58 mL to 1.10 mL.
• the volume percentages of toluene, anisole, and water relative to the sum of the volume of toluene, the volume of anisole, and the water are 32.5%, 32.5%, and 35% by volume, respectively.
• the obtained polymer had Mw of 1.2 ⁇ 10 5 .
• Example 7 A polymer was obtained in the same manner as in Example 5 except that the amount of water added was changed from 0.58 mL to 2.25 mL.
• the volume percentages of toluene, anisole, and water relative to the total volume of toluene, anisole, and water are 25%, 25%, and 50% by volume, respectively. According to GPC analysis, the obtained polymer had Mw of 1.2 ⁇ 10 5 .
• Example 8 A polymer was obtained in the same manner as in Example 5 except that the amount of water added was changed from 0.58 mL to 4.39 mL.
• the volume percentages of toluene, anisole, and water relative to the sum of the volume of toluene, the volume of anisole, and water are 17.5%, 17.5%, and 65% by volume, respectively.
• the obtained polymer had Mw of 1.2 ⁇ 10 5 .
• Comparative Example 2 A polymer was obtained in the same manner as in Example 5 except that water was not added.
• the volume percentages of toluene, anisole, and water relative to the sum of the volume of toluene, the volume of anisole, and water are 45.5%, 45.5%, and 9% by volume, respectively.
• the obtained polymer had Mw of 2.2 ⁇ 10 4 .
• Table 6 shows the results of Examples 5 to 8 and Comparative Example 2.
• Example 9 A polymer was obtained in the same manner as in Example 1 except that the second solvent was changed from 1-methylcyclohexanol to tert-butanol.
• the volume percentages of toluene, tert-butanol, and water relative to the sum of the volume of toluene, the volume of tert-butanol, and the volume of water are 40%, 40%, and 20% by volume, respectively.
• the obtained polymer had Mw of 6.5 ⁇ 10 4 .
• Example 10 A polymer was obtained in the same manner as in Example 9 except that the amount of water added was changed from 0.58 mL to 2.25 mL.
• the volume percentages of toluene, tert-butanol, and water relative to the sum of the volume of toluene, the volume of tert-butanol, and the volume of water are 25%, 25%, and 50% by volume, respectively.
• the obtained polymer had Mw of 8.6 ⁇ 10 4 .
• Example 11 A polymer was obtained in the same manner as in Example 9 except that the amount of water added was changed from 0.58 mL to 4.39 mL.
• the volume percentages of toluene, tert-butanol, and water relative to the total volume of toluene, tert-butanol, and water are 17.5%, 17.5%, and 65% by volume, respectively.
• the obtained polymer had Mw of 1.0 ⁇ 10 5 .
• Comparative Example 3 A polymer was obtained in the same manner as in Example 9 except that water was not added.
• the volume percentages of toluene, tert-butanol, and water relative to the total volume of toluene, tert-butanol, and water are 45.5%, 45.5%, and 9% by volume, respectively.
• the obtained polymer had Mw of 5.0 ⁇ 10 4 .
• Table 7 shows the results of Examples 9 to 11 and Comparative Example 3.
• Example 12 A polymer was obtained in the same manner as in Example 2 except that 1-methylcyclohexanol was changed to tetrahydrofuran.
• the volume percentages of toluene, tetrahydrofuran, and water relative to the sum of the volume of toluene, the volume of tetrahydrofuran, and the volume of water are 32.5%, 32.5%, and 35% by volume, respectively.
• the obtained polymer had Mw of 1.4 ⁇ 10 5 .
• Example 13 A polymer was obtained in the same manner as in Example 12 except that the amount of water added was changed from 1.10 mL to 2.25 mL.
• the volume percentages of toluene, tetrahydrofuran, and water relative to the sum of the volume of toluene, the volume of tetrahydrofuran, and the volume of water are 25%, 25%, and 50% by volume, respectively.
• the obtained polymer had Mw of 1.7 ⁇ 10 5 .
• Example 14 A polymer was obtained in the same manner as in Example 12 except that the amount of water added was changed from 1.10 mL to 4.39 mL.
• the volume percentages of toluene, tetrahydrofuran, and water relative to the sum of the volume of toluene, the volume of tetrahydrofuran, and the volume of water are 17.5%, 17.5%, and 65% by volume, respectively.
• the obtained polymer had Mw of 1.4 ⁇ 10 5 .
• Comparative Example 4 A polymer was obtained in the same manner as in Example 12 except that water was not added.
• the volume percentages of toluene, tetrahydrofuran, and water relative to the sum of the volume of toluene, the volume of tetrahydrofuran, and the volume of water are 45.5%, 45.5%, and 9% by volume, respectively.
• the obtained polymer had Mw of 1.3 ⁇ 10 5 .
• Table 8 shows the results of Examples 12 to 14 and Comparative Example 4.
• Example 15 Polymer B was synthesized from compound 3 and compound 4 as shown in the following scheme.
• Compound 4 was synthesized by the method described in Example 2 of International Publication Number (WO2014 / 112656). To a glass reaction vessel equipped with a cooling device at room temperature, 0.38 mL of water was added. The reaction vessel was filled with nitrogen gas, and 75 ⁇ mol of compound 4, 75 ⁇ mol of compound 3, and 3.0 ⁇ mol of bis (tri-tert-butylphosphine) palladium (0) were added to 1.25 mL of 1-methylcyclohexanol and 1.25 mL of toluene. The solution dissolved in the mixed solvent was added and mixed, and then 0.25 mL of 3M aqueous potassium phosphate solution was added and mixed. The obtained mixture was stirred at 65 ° C.
• Example 16 A polymer was obtained in the same manner as in Example 15 except that the amount of water added was changed from 0.58 mL to 1.10 mL.
• the volume percentages of toluene, 1-methylcyclohexanol, and water relative to the total volume of toluene, 1-methylcyclohexanol, and water are 32.5%, 32.5%, and 35%, respectively. % By volume. According to GPC analysis, the obtained polymer had Mw of 6.8 ⁇ 10 4 .
• Example 17 A polymer was obtained in the same manner as in Example 15 except that the amount of water to be added was changed from 0.58 mL to 2.25 mL.
• the volume percentages of toluene, 1-methylcyclohexanol, and water relative to the total volume of toluene, 1-methylcyclohexanol, and water are 25%, 25%, and 50% by volume, respectively.
• the obtained polymer had Mw of 7.4 ⁇ 10 4 .
• Example 18 A polymer was obtained in the same manner as in Example 15 except that the amount of water added was changed from 0.58 mL to 4.39 mL.
• the volume percentages of toluene, 1-methylcyclohexanol, and water relative to the sum of the volume of toluene, the volume of 1-methylcyclohexanol, and the volume of water are 17.5%, 17.5%, and 65%, respectively. % By volume.
• the obtained polymer had Mw of 7.5 ⁇ 10 4 .
• Comparative Example 5 A polymer was obtained in the same manner as in Example 15 except that water was not added.
• the volume percentages of toluene, 1-methylcyclohexanol, and water relative to the sum of the volume of toluene, the volume of 1-methylcyclohexanol, and the volume of water are 45.5%, 45.5%, and 9%, respectively. % By volume.
• the obtained polymer had Mw of 2.6 ⁇ 10 4 .
• Table 9 shows the results of Examples 15 to 18 and Comparative Example 5.
• Example 19 A polymer was obtained in the same manner as in Example 15 except that 1-methylcyclohexanol was changed to anisole.
• the volume percentages of toluene, anisole, and water relative to the sum of the volume of toluene, the volume of anisole, and water are 40%, 40%, and 20% by volume, respectively.
• the obtained polymer had Mw of 2.0 ⁇ 10 4 .
• Example 20 A polymer was obtained in the same manner as in Example 19 except that the amount of water added was changed from 0.58 mL to 1.10 mL.
• the volume percentages of toluene, anisole, and water relative to the sum of the volume of toluene, the volume of anisole, and the water are 32.5%, 32.5%, and 35% by volume, respectively.
• the obtained polymer had Mw of 3.8 ⁇ 10 4 .
• Example 21 A polymer was obtained in the same manner as in Example 19 except that the amount of water added was changed from 0.58 mL to 2.25 mL.
• the volume percentages of toluene, anisole, and water relative to the total volume of toluene, anisole, and water are 25%, 25%, and 50% by volume, respectively. According to GPC analysis, the obtained polymer had Mw of 5.0 ⁇ 10 4 .
• Example 22 A polymer was obtained in the same manner as in Example 19 except that the amount of water added was changed from 0.58 mL to 4.39 mL.
• the volume percentages of toluene, anisole, and water relative to the sum of the volume of toluene, the volume of anisole, and water are 17.5%, 17.5%, and 65% by volume, respectively.
• the obtained polymer had Mw of 1.8 ⁇ 10 4 .
• Comparative Example 6 A polymer was obtained in the same manner as in Example 19 except that water was not added.
• the volume percentages of toluene, anisole, and water relative to the sum of the volume of toluene, the volume of anisole, and water are 45.5%, 45.5%, and 9% by volume, respectively.
• the obtained polymer had Mw of 1.1 ⁇ 10 4 .
• Table 10 shows the results of Examples 19 to 22 and Comparative Example 6.
• Example 23 A polymer was obtained in the same manner as in Example 15 except that 1-methylcyclohexanol was changed to tert-butanol.
• the volume percentages of toluene, tert-butanol, and water relative to the sum of the volume of toluene, the volume of tert-butanol, and the volume of water are 40%, 40%, and 20% by volume, respectively.
• the obtained polymer had Mw of 1.7 ⁇ 10 4 .
• Example 24 A polymer was obtained in the same manner as in Example 23 except that the amount of water to be added was changed from 0.58 mL to 1.10 mL.
• the volume percentages of toluene, tert-butanol, and water relative to the total volume of toluene, tert-butanol, and water are 32.5%, 32.5%, and 35% by volume, respectively.
• the obtained polymer had Mw of 2.1 ⁇ 10 4 .
• Example 25 A polymer was obtained in the same manner as in Example 23 except that the amount of water to be added was changed from 0.58 mL to 2.25 mL.
• the volume percentages of toluene, tert-butanol, and water relative to the sum of the volume of toluene, the volume of tert-butanol, and the volume of water are 25%, 25%, and 50% by volume, respectively.
• the obtained polymer had Mw of 3.1 ⁇ 10 4 .
• Example 26 A polymer was obtained in the same manner as in Example 23 except that the amount of water added was changed from 0.58 mL to 4.39 mL.
• the volume percentages of toluene, tert-butanol, and water relative to the total volume of toluene, tert-butanol, and water are 17.5%, 17.5%, and 65% by volume, respectively.
• the obtained polymer had Mw of 4.1 ⁇ 10 4 .
• Comparative Example 7 A polymer was obtained in the same manner as in Example 24 except that water was not added.
• the volume percentages of toluene, tert-butanol, and water relative to the total volume of toluene, tert-butanol, and water are 45.5%, 45.5%, and 9% by volume, respectively.
• the obtained polymer had Mw of 1.1 ⁇ 10 4 .
• Table 11 shows the results of Examples 23 to 26 and Comparative Example 7.
• Example 27 A polymer was obtained in the same manner as in Example 16 except that 1-methylcyclohexanol was changed to tetrahydrofuran.
• the volume percentages of toluene, tetrahydrofuran, and water relative to the sum of the volume of toluene, the volume of tetrahydrofuran, and the volume of water are 32.5%, 32.5%, and 35% by volume, respectively.
• the obtained polymer had Mw of 8.6 ⁇ 10 4 .
• Example 28 A polymer was obtained in the same manner as in Example 27 except that the amount of water to be added was changed from 1.10 mL to 2.25 mL.
• the volume percentages of toluene, tetrahydrofuran, and water relative to the sum of the volume of toluene, the volume of tetrahydrofuran, and the volume of water are 25%, 25%, and 50% by volume, respectively.
• the obtained polymer had Mw of 1.3 ⁇ 10 5 .
• Example 29 A polymer was obtained in the same manner as in Example 27 except that the amount of water added was changed from 1.10 mL to 4.39 mL.
• the volume percentages of toluene, tetrahydrofuran, and water relative to the sum of the volume of toluene, the volume of tetrahydrofuran, and the volume of water are 17.5%, 17.5%, and 65% by volume, respectively.
• the obtained polymer had Mw of 1.1 ⁇ 10 5 .
• Comparative Example 8 A polymer was obtained in the same manner as in Example 27 except that water was not added.
• the volume percentages of toluene, tetrahydrofuran, and water relative to the sum of the volume of toluene, the volume of tetrahydrofuran, and the volume of water are 45.5%, 45.5%, and 9% by volume, respectively.
• the obtained polymer had Mw of 6.3 ⁇ 10 4 .
• Table 12 shows the results of Examples 27 to 29 and Comparative Example 8.
• Example 30 After making the inside of the glass reaction vessel equipped with a cooling apparatus into a nitrogen gas atmosphere, 3,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole 3.0 mmol, 2,2 ′-(5 5-bis (3,7-dimethyloctyl) -5H-dithieno [3,2-b: 2 ′, 3′-d] pyran-2,7-diyl) bis (5-methyl-1,3,2- Dioxaborinane-5-methanol (3.0 mmol), chloromethyl (tri-tert-butylphosphine) palladium (II) 9 ⁇ mol, water 90 mL, tetrahydrofuran 70 mL and mesitylene 30 mL were added to the reaction vessel.
• the resulting mixture was heated to 45 ° C. with stirring. 10 mL of 3M aqueous potassium phosphate solution was added to the resulting mixture. While stirring the obtained mixture, it was heated to 45 ° C. and reacted for 4 hours to obtain a reaction mixture containing an aromatic compound composed of a repeating unit represented by the following formula. After the obtained reaction mixture was dissolved in 1-chloronaphthalene, the molecular weight was analyzed by GPC. As a result, the molecular weight (Mw) was 3.6 ⁇ 10 4 .

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