Phosphine-palladium complex, polymerization catalyst, and method for producing aromatic polymer

Abstract

To provide a novel phosphine-palladium complex useful as a polymerization catalyst that functions effectively in catalyst-transfer chain-growth polycondensation, and a polymerization catalyst and a method for producing an aromatic polymer using the same.SOLUTION: The present invention is a phosphine-palladium complex represented by general formula (1). (In the formula, R1 represents a C1-4 alkyl group or a C1-4 alkoxy group; t represents an integer of 0-4; Ar represents a monovalent group containing an aromatic ring; X represents a halogeno group or a sulfonate group represented by the general formula: -SO3Z; Z represents a substituted or unsubstituted hydrocarbon group; and A represents a substituted or unsubstituted adamantyl group or an aryl group represented by general formula (2).)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a phosphine palladium complex, a polymerization catalyst using the same, and a method for producing an aromatic polymer.

Background Art

[0002] π-conjugated polymers exhibit conductivity comparable to that of metals from semiconductors by performing p-type or n-type doping such as oxidation and reduction. Therefore, research on applying their electrical and optical properties to capacitors, photoelectric conversion materials, organic EL materials, and field-effect organic transistors has been actively conducted. Among them, π-conjugated polymers having an aromatic ring are considered to be difficult to control the molecular weight of the resulting polymer and to quantitatively introduce terminal functional groups.

[0003] The present inventors have found that the Kumada-Tamao coupling polymerization of Grignard-type monomers using a nickel catalyst proceeds by a polymerization mechanism in which the catalyst migrates to the growing end within the molecule (catalyst migration type chain condensation polymerization) to give a polymer in which the molecular weight and molecular weight distribution are controlled, and have reported that π-conjugated polymers such as polythiophene, polyphenylene, polyfluorene, and polypyrrole can be precisely synthesized by this catalyst migration type chain condensation polymerization (see Non-Patent Documents 1 and 2, etc.).

[0004] In addition, the present inventors have reported that catalyst migration type chain condensation polymerization also proceeds in the polymerization using the Suzuki-Miyaura coupling reaction by a palladium catalyst, and that polyfluorene, polyphenylene, polythiophene, and their block copolymers can be synthesized under control (see Patent Document 1, Non-Patent Documents 3 to 5, etc.).

[0005] However, there is a problem that the types of palladium catalysts that function effectively in catalyst migration type chain condensation polymerization are few.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Non-Patent Document

[0007]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Non-Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0008] An object of the present invention is to provide a novel phosphine palladium complex useful as a polymerization catalyst that functions effectively in catalyst transfer type chain condensation polymerization, a polymerization catalyst using the same, and a method for producing an aromatic polymer.

Means for Solving the Problems

[0009] In the search for a palladium catalyst that functions effectively in catalyst transfer type chain condensation polymerization, the present inventors have found that a specific phosphine palladium complex having a novel adamantyl group is a polymerization catalyst that functions effectively in catalyst transfer type chain condensation polymerization, and have completed the present invention.

[0010] The first invention provided by the present invention is a phosphine palladium complex represented by the following general formula (1).

[0011]

Chemical Formula

[0012]

Chemical formula

[0013] Moreover, the second invention provided by the present invention is a polymerization catalyst containing the phosphine palladium complex of the first invention.)

[0014] Furthermore, the third invention provided by the present invention is a method for producing an aromatic polymer, which includes a polycondensation step of polycondensing an aromatic compound represented by the following general formula (3) in the presence of the polymerization catalyst of the second invention.)

[0015]

Chemical formula

Advantages of the Invention

[0016] According to the present invention, it is possible to provide a novel phosphine palladium complex useful as a polymerization catalyst that functions effectively in catalytic transfer chain condensation polymerization, a polymerization catalyst using the same, and a method for producing an aromatic polymer.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0018] Hereinafter, the present invention will be described based on preferred embodiments. Note that the phosphine palladium complex represented by the general formula (1) of the present invention may be simply referred to as "phosphine palladium complex".

[0019] Ad in the general formula (1) 1 represents an adamantyl group which may have t substituents R 1 . R 1 represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and t represents an integer of 0 to 4.

[0020] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0021] Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group.

[0022] In the general formula (1), t is preferably 0, that is, Ad 1 is preferably an unsubstituted adamantyl group.

[0023] In the general formula (1), Ar represents a monovalent group containing an aromatic ring. Examples of the aromatic ring include monocyclic aromatic rings such as a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, a furan ring, a pyrrole ring, a thiophene ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a thiadiazole ring, and an azadiazole ring; condensed polycyclic aromatic rings formed by condensing two or more selected independently from among the monocyclic aromatic rings; aromatic ring aggregates formed by connecting two or more rings selected independently from among the monocyclic aromatic rings and / or the condensed polycyclic aromatic rings with divalent atoms or groups such as a single bond, a methylene group, an ethylene group, an ethenylene group, an ethynylene group, an oxygen atom, a sulfur atom, an imino group, a carbonyl group, and a sulfonyl group; and bridged polycyclic aromatic rings having one or more bridges composed of divalent groups such as a methylene group, an ethylene group, a carbonyl group, and a sulfonyl group that connect two adjacent aromatic rings of the condensed polycyclic aromatic ring or the aromatic ring aggregate.

[0024] These aromatic rings may be substituted with the above-described alkyl group having 1 to 4 carbon atoms or alkoxy group having 1 to 4 carbon atoms.

[0025] In the present invention, Ar in the general formula (1) is preferably a substituted or unsubstituted phenyl group, and as the substituent in the substituted phenyl group, an alkyl group having 1 to 4 carbon atoms is preferable.

[0026] The substituted phenyl group is particularly preferably a group represented by the following general formula (4a) or (4b).

[0027] [Chemistry] (In the formula, R 11 represents an alkyl group having 1 to 4 carbon atoms.)

[0028] In general formula (1), X represents a halogeno group or a sulfonate group represented by the general formula: -SO3Z, and Z represents a substituted or unsubstituted hydrocarbon group.

[0029] Examples of the halogeno group include a chloro group, a bromo group, and an iodo group.

[0030] Examples of the unsubstituted hydrocarbon group include an alkyl group having 1 to 50 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a butyl group, and an isobutyl group; a cyclic saturated hydrocarbon group having 3 to 50 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; an alkenyl group having 2 to 50 carbon atoms such as an ethenyl group and a propenyl group; an aryl group having 6 to 50 carbon atoms such as a phenyl group and a 1-naphthyl group; and an aralkyl group having 7 to 50 carbon atoms such as a benzyl group, a 2-phenylethyl group, a 1-phenylpropyl group, a 2-phenylpropyl group, a 3-phenylpropyl group, a 1-phenylbutyl group, a 2-phenylbutyl group, a 3-phenylbutyl group, and a 4-phenylbutyl group. Among these, a hydrocarbon group having 1 to 8 carbon atoms is preferable.

[0031] Examples of the substituent in the substituted hydrocarbon group include the above-mentioned alkyl group having 1 to 4 carbon atoms and halogeno group.

[0032] In the present invention, X in general formula (1) is preferably a halogeno group, particularly preferably a bromo group.

[0033] In general formula (1), A represents a substituted or unsubstituted adamantyl group or an aryl group represented by general formula (2).

[0034] Examples of the substituent in the adamantyl group of the substitution include the above-described alkyl group having 1 to 4 carbon atoms and alkoxy group having 1 to 4 carbon atoms.

[0035] R in the general formula (2) 2 ~R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a general formula: -N(R 7 )(R 8 ), and R 7 ~R 8 each independently represents an alkyl group having 1 to 5 carbon atoms.

[0036] R 2 ~R 6 and R 7 ~R 8 Examples of the alkyl group having 1 to 5 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an n-pentyl group.

[0037] R 2 ~R 6 Examples of the alkoxy group having 1 to 5 carbon atoms represented by include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an n-pentyloxy group.

[0038] In the present invention, when A in the general formula (1) is an aryl group represented by the general formula (2), it is particularly preferable that it is an aryl group represented by the following general formula (2a) or (2b) from the viewpoint of high solubility and catalytic activity.

[0039]

Chemical formula

[0040] R 9Examples of the alkyl group having 1 to 5 carbon atoms represented by include the same groups as those described above.

[0041] As a method for producing the phosphine palladium complex of the present invention, 1) a palladium complex of a phosphine compound represented by the general formula: P(Ad 1 )2A (Ad 1 and A in the formula have the same meanings as in the general formula (1)), and an aromatic compound represented by the general formula: Ar-X (Ar and X in the formula have the same meanings as in the general formula (1)) are reacted (see J. Am. Chem. Soc., 126, 1184 (2004)). However, since it tends to be industrially difficult to isolate the obtained phosphine palladium complex, 2) it is preferably produced from (1,5-cyclooctadiene)bis(trimethylsilylpalladium(II))(5), a phosphine derivative (6), and an aryl halide compound (7) according to the following reaction scheme (1) (for example, see Organic Letters 2017, 19, 2853-2856).

[0042]

Chemical formula

[0043] When the phosphine palladium complex of the present invention is produced by the method of 1) above, after reacting a palladium complex of a phosphine compound represented by the general formula: P(Ad 1 )2A (Ad 1 and A in the formula have the same meanings as in the general formula (1)) with an aromatic compound represented by the general formula: Ar-X (wherein Ar and X have the same meanings as above), without isolating the phosphine palladium complex contained in the reaction solution, a reagent necessary for the polycondensation reaction can be added to the reaction solution to perform polycondensation.

[0044] In addition, the phosphine derivative (6) can be easily produced by a known method (see, for example, European Journal of Organic Chemistry, 2020, 1122-1128 and WO2017 / 075581 pamphlet, etc.).

[0045] The phosphine palladium complex of the present invention is suitable for polymerization using a transition metal complex as a catalyst, such as, for example, coupling polymerization, chain condensation polymerization, and catalytic transfer chain condensation polymerization.

[0046] The method for producing an aromatic polymer of the present invention uses the phosphine palladium complex of the present invention as a polymerization catalyst in catalytic transfer chain condensation polymerization and performs a Suzuki-Miyaura coupling reaction. The aromatic compound of the monomer used in the production method of the present invention is not particularly limited as long as it is a boron compound used in a conventional Suzuki-Miyaura coupling reaction, but is preferably an aromatic compound represented by the following general formula (3). That is, the method for producing an aromatic polymer of the present invention includes a polycondensation step of polycondensing an aromatic compound represented by the following general formula (3) in the presence of a polymerization catalyst containing the phosphine palladium complex of the present invention.

[0047] [Chemical formula] (In the formula, Ar 1 represents a divalent group containing an aromatic ring. X 1 represents a halogeno group, a nitro group, or a sulfonate group represented by -SO3Z 1 and Z 1 represents a substituted or unsubstituted hydrocarbon group. Q 1 each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and two Q 1 may be bonded to each other to form a ring.)

[0048] Ar in the general formula (3) above 1represents a divalent group containing an aromatic ring. Examples of the aromatic ring include monocyclic aromatic rings such as benzene ring, pyridine ring, 1,2-diazine ring, 1,3-diazine ring, 1,4-diazine ring, 1,3,5-triazine ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, oxadiazole ring, thiadiazole ring and azadiazole ring; condensed polycyclic aromatic rings formed by condensation of two or more selected independently from among the monocyclic aromatic rings; aromatic ring aggregates formed by linking two or more rings selected independently from among the monocyclic aromatic rings and / or the condensed polycyclic aromatic rings with divalent atoms or groups such as single bond, methylene group, ethylene group, ethenylene group, ethynylene group, oxygen atom, sulfur atom, imino group, carbonyl group and sulfonyl group; and bridged polycyclic aromatic rings having one or more bridges composed of divalent groups such as methylene group, ethylene group, carbonyl group and sulfonyl group that link two adjacent aromatic rings of the condensed polycyclic aromatic ring or the aromatic ring aggregate.

[0049] The hydrogen atom bonded to a carbon atom of the aromatic ring may be substituted with a substituent. Examples of the substituent include halogeno group, cyano group, hydrocarbon group and the like. When the aromatic ring contains a nitrogen atom, the hydrogen atom bonded to the nitrogen atom may be substituted with a hydrocarbon group. When two or more substituents are present on the carbon atom and / or the nitrogen atom, two substituents selected therefrom may combine to form a ring.

[0050] Examples of the hydrocarbon group of the substituent include alkyl groups having 1 to 50 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, nonyl group, dodecyl group, pentadecyl group, octadecyl group and docosyl group; cyclic saturated hydrocarbon groups having 3 to 50 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group and adamantyl group; alkenyl groups having 2 to 50 carbon atoms such as ethenyl group, propenyl group, 3-butenyl group, 2-butenyl group, 2-pentenyl group, 2-hexenyl group, 2-nonenyl group and 2-dodecenyl group; aryl groups having about 6 carbon atoms such as phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group and 4-phenylphenyl group; aralkyl groups having 7 to 50 carbon atoms such as phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group and 6-phenyl-1-hexyl group, etc.

[0051] The hydrocarbon group of the substituent may have a hetero atom such as O, N, S, etc., and may also have a group such as a carbonyl group, an oxycarbonyl group, an aminocarbonyl group, a sulfonyl group, an amino group, a mercapto group, a hydroxy group, a carboxyl group, a nitro group, a halogeno group and a cyano group.

[0052] X in the general formula (3) 1 represents a halogeno group, a nitro group, or a sulfonate group represented by -SO3Z 1 where Z 1 represents a substituted or unsubstituted hydrocarbon group.

[0053] Examples of the halogeno group include a chloro group, a bromo group, an iodine group, and the like.

[0054] Examples of the unsubstituted hydrocarbon group include alkyl groups having 1 to 50 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a butyl group, and an isobutyl group; cyclic saturated hydrocarbon groups having 3 to 50 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; alkenyl groups having 2 to 50 carbon atoms such as an ethenyl group and a propenyl group; aryl groups having 6 to 50 carbon atoms such as a phenyl group and a 1-naphthyl group; and aralkyl groups having 7 to 50 carbon atoms such as a benzyl group, a 2-phenylethyl group, a 1-phenylpropyl group, a 2-phenylpropyl group, a 3-phenylpropyl group, a 1-phenylbutyl group, a 2-phenylbutyl group, a 3-phenylbutyl group, and a 4-phenylbutyl group. Among these, hydrocarbon groups having 1 to 8 carbon atoms are preferable.

[0055] Examples of the substituent in the substituted hydrocarbon group include the above-described alkyl groups having 1 to 4 carbon atoms and halogeno groups.

[0056] In the present invention, X in the general formula (3) 1 is preferably a chloro group, a bromo group, or a trifluoromethylsulfonyl group.

[0057] Q in the general formula (3) 1 each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and two Qs 1 may be bonded to each other to form a ring.

[0058] Q 1Examples of the hydrocarbon group represented by include alkyl groups having 1 to 50 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, nonyl group, dodecyl group, pentadecyl group, octadecyl group and docosyl group; cyclic saturated hydrocarbon groups having 3 to 50 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group and adamantyl group; alkenyl groups having 2 to 50 carbon atoms such as ethenyl group, propenyl group, 3-butenyl group, 2-butenyl group, 2-pentenyl group, 2-hexenyl group, 2-nonenyl group and 2-dodecenyl group; aryl groups having 6 to 50 carbon atoms such as phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group and 4-phenylphenyl group; aralkyl groups having 7 to 50 carbon atoms such as phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group and 6-phenyl-1-hexyl group, etc.

[0059] Examples of the substituent of the hydrocarbon group include the above-mentioned alkyl groups having 1 to 4 carbon atoms and halogeno groups, etc.

[0060] In the present invention, Q in the general formula (3) 1 is preferably an alkyl group, preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group or nonyl group, and particularly preferably a methyl group, ethyl group, propyl group, butyl group, pentyl group or hexyl group. Further, two Qs 1Examples of the divalent hydrocarbon group that forms a ring by bonding to each other include a 1,2-ethylene group, a 1,1,2,2-tetramethyl-1,2-ethylene group, a 1,3-propylene group, a 2,2-dimethyl-1,3-propylene group, and a 1,2-phenylene group, etc. are preferable.

[0061] Examples of the aromatic compound represented by the general formula (3) include, for example, the boron-containing compounds described in paragraphs

[0058] to

[0059] of JP-A-2009-19186, the boron-containing compounds described in paragraph

[0028] of JP-A-2009-215538, etc.

[0062] In the polycondensation step in the method for producing the aromatic polymer of the present invention, it is preferable to use one or a combination of two or more aromatic compounds represented by the general formula (3) and carry out the reaction in a solvent in the presence of the polymerization catalyst and the base of the present invention.

[0063] In the method for producing the aromatic polymer of the present invention, the phosphine palladium complex of the present invention is used as the polymerization catalyst.

[0064] The addition amount of the polymerization catalyst is preferably 0.0001 to 10 mol%, more preferably 0.001 to 5 mol%, and particularly preferably 0.01 to 5 mol% based on the aromatic compound represented by the general formula (3).

[0065] Examples of the base used in the method for producing the aromatic polymer of the present invention include inorganic salts such as carbonates, phosphates, and acetates of alkali metals; organic salts such as hydroxides of alkali metals, cesium carbonate, cesium fluoride, triethylamine, pyridine, morpholine, quinoline, piperidine, DBU, anilines, and tetra-n-butylammonium acetate.

[0066] The addition amount of the base is preferably 0.01 to 1000 molar equivalents, more preferably 0.1 to 100 molar equivalents, and particularly preferably 1 to 50 molar equivalents based on the aromatic compound represented by the general formula (3).

[0067] In addition, in the polycondensation step, in order to perform the polycondensation reaction more efficiently, a phase transfer catalyst and / or a surfactant can be added as necessary to carry out the polycondensation reaction.

[0068] As the phase transfer catalyst, known ones such as phosphonium salts, ammonium salts, crown ethers, porphyrins, azacrowns, and thiocrowns can be used.

[0069] Examples of the phosphonium salt include phosphonium salts such as tributylmethylphosphonium bromide, tetrabutylphosphonium bromide, trioctylmethylphosphonium bromide, trioctylethylphosphonium bromide, tributyldodecylphosphonium bromide, tributylhexadecylphosphonium bromide, trioctylethylphosphonium bromide, tributylmethylphosphonium chloride, tetrabutylphosphonium chloride, trioctylmethylphosphonium chloride, trioctylethylphosphonium chloride, tributyldodecylphosphonium chloride, tributylhexadecylphosphonium chloride, and trioctylethylphosphonium chloride.

[0070] Examples of the ammonium salt include ammonium salts such as tributylmethylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, tributyldodecylammonium bromide, tributylhexadecylammonium bromide, trioctylethylammonium bromide, tributylmethylammonium chloride, tetrabutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, tributyldodecylammonium chloride, tributylhexadecylammonium chloride, and trioctylethylammonium chloride.

[0071] The addition amount of the phase-transfer catalyst is preferably 0.01 to 1000 molar times, more preferably 0.1 to 100 molar times, and particularly preferably 1 to 50 molar times, relative to the aromatic compound represented by the general formula (3).

[0072] Examples of the surfactant include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0073] Examples of the anionic surfactant include alkali metal salts of alkylbenzene sulfonic acid, fatty acids, and monoalkyl phosphoric acid. Examples of the cationic surfactant include tetraalkylammonium salts and alkylpyridinium salts. Examples of the amphoteric surfactant include long-chain alkyl amino acids. Examples of the nonionic surfactant include polyethylene glycol and polyvinyl alcohol.

[0074] The addition amount of the surfactant is preferably 0.01 to 1000 molar times, more preferably 0.1 to 100 molar times, and particularly preferably 1 to 50 molar times, relative to the aromatic compound represented by the general formula (3).

[0075] The solvent used in the polycondensation step is preferably appropriately selected according to the aromatic polymer to be produced. Generally, aromatic hydrocarbons such as benzene, toluene, and xylene; linear or cyclic aliphatic hydrocarbons such as heptane and cyclohexane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and dichloromethane; nitriles such as acetonitrile and benzonitrile; alcohols such as methanol, ethanol, n-propyl alcohol, and iso-propyl alcohol; ethers such as dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; amides such as N,N-dimethylformamide and N-methylpyrrolidone; and nitro compounds such as nitromethane and nitrobenzene can be mentioned. Among these, aromatic hydrocarbons, halogenated hydrocarbons, nitriles, ethers, and nitro compounds are preferred. Further, in the production method of the present invention, in addition to the above solvent, water such as distilled water may be used in combination.

[0076] The reaction temperature in the polycondensation step is preferably -100 to 200 °C, more preferably -50 to 150 °C, and particularly preferably -20 to 100 °C.

[0077] The reaction time in the polycondensation step is preferably 0.1 minute to 1000 hours, more preferably 1 minute to 500 hours, and particularly preferably 10 minutes to 200 hours.

[0078] The polycondensation reaction can be stopped by adding a polymerization terminator to the reaction system at the stage when the target polymer is produced. As the polymerization terminator, for example, common protonic compounds such as methanol, acetic acid, and a methanol solution of hydrochloric acid can be used.

[0079] After completion of the polycondensation reaction, the target aromatic polymer can be obtained by removing the reaction solvent by a conventional method and performing purification such as reprecipitation if necessary.

[0080] According to the method for producing an aromatic polymer of the present invention, since catalyst transfer type chain condensation polymerization proceeds by performing a Suzuki-Miyaura coupling reaction using the polymerization catalyst of the present invention (see Figure 1), living polymerization is possible despite the coupling polymerization, and an aromatic polymer having a high molecular weight and a narrower molecular weight distribution can be produced.

Examples

[0081] Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The number average molecular weight (Mn) and weight average molecular weight (Mw) in the examples were evaluated by gel permeation chromatography (Tosoh HLC-8320 GPC apparatus, eluent: chloroform, column: two TSK-gel columns (Multipore HZ-M) connected in series, polystyrene conversion). Also, PDI indicates the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

[0082] (Example 1) <Synthesis of Compound 4>

[0083]

Chemical formula

[0084] Under argon, 213 mg (0.489 mmol) of tri(1-adamantyl)phosphine (2) and 150 ml of deoxygenated pentane were placed in a 200 mL eggplant-shaped flask and stirred at room temperature for 5 minutes. Then, 0.13 mL (0.735 mmol) of 2-bromotoluene (3) and 191 mg (0.492 mmol) of (1,5-cyclooctadiene)bis(trimethylsilyl)palladium(II) (1) were added, and the mixture was stirred at room temperature for 16 hours. The supernatant was decanted and filtered, and the operation of adding 15 mL of deoxygenated pentane and decanting and filtering the supernatant was repeated 15 times. Finally, the supernatant was removed with a syringe and dried to obtain 337 mg (0.472 mmol) of a pale yellow solid compound 4. Yield: 96.5% 11H-NMR (C6D6): δ 7.53 (d, J = 5.5 Hz, 1H), 6.84 (m, 2H), 6.77 (d, J = 6.9 Hz, 1H), 3.27 (s, 3H), 2.29 (m, 18H), 1.74 (s, 10H), 1.50 (m, 18H 31 31P-NMR (C6D6): δ 47.6 IR (KBr) 2904, 2847, 1560, 1455, 1343, 1297, 1259, 1183, 1102, 1018, 971, 741, 420 cm -1

[0085] (Example 2) <Synthesis of Compound 6>

[0086] [Chemical Structure Diagram]

[0087] Under argon, 184 mg (0.436 mmol) of Compound 5 and 177 mg (0.455 mmol) of (1,5-cyclooctadiene)bis(trimethylsilyl)palladium(II) (1) were placed in a 30 mL eggplant-shaped flask and dissolved in 6.0 mL of THF. Then, 2.0 mL of a 0.50 mol / L THF solution of 4-tert-butylbromobenzene was added thereto. After stirring at room temperature for 16 hours, THF was distilled off under reduced pressure, 20 mL of deoxygenated hexane was added and stirred. It was allowed to stand, and the supernatant was removed with a syringe. Again, 20 mL of deoxygenated hexane was added, stirred, allowed to stand, and the supernatant was removed. This was repeated 8 times, and then dried under reduced pressure to obtain 107 mg (0.144 mmol) of Compound 6 as a pale yellow solid. Yield: 33.0% 1 1H-NMR (CDCl3): δ 7.67 (m, 2H), 7.33 (m, 2H), 6.66 (m, 2H), 6.12 (d, J = 8.0 Hz, 2H), 3.02 (s, 6H) 2.45 - 1.61 (m, 39H) 31 31P-NMR (C6D6): δ 42.1 IR (KBr): 2902, 2847, 1598, 1509, 1447, 1362, 1302, 1201, 1096, 809, 517, 456, 420 cm -1

[0088] (Example 3) (Synthesis of Compound 8)

[0089] [Chemical Structure Diagram]

[0090] Under argon, 124 mg (0.283 mmol) of Compound 7 and 110 mg (0.283 mmol) of (1,5-cyclooctadiene)bis(trimethylsilyl)palladium(II) (1) were added to a 20 mL eggplant-shaped flask, and 3.0 mL of a 0.20 mol / L THF solution of 2-bromotoluene was added thereto. After stirring at room temperature for 1 hour, 4.0 mL of deoxygenated hexane was added, and the mixture was stirred at room temperature overnight. The precipitate was filtered off and dried to obtain 179 mg (0.251 mmol) of Compound 8 as a pale yellow solid. Yield: 88.7% 1 1H-NMR (C6D6): δ 7.95 - 7.80 (m, 2H), 6.88 - 6.81 (m, 4H), 6.79 - 6.73 (m, 2H), 4.12 (sept, J = 6.0 Hz, 1H), 3.25 (s, 3H), 2.40 - 1.58 (m, 30H), 1.05 (d, J = 6.0 Hz, 6H) 31 31P-NMR (C6D6): δ 58.7 IR (KBr): 2905, 2847, 1592, 1498, 1454, 1282, 1247, 1185, 1105, 737, 499, 423 cm -1

[0091] (Example 4) (Measurement of Mobility) To confirm whether a part of the catalyst (the Pd-L part in Fig. 1) effectively moves on the π surface of the polymer and reductive elimination-oxidative addition proceeds quantitatively within the same polymer, evaluation was carried out according to Macromolecules, 2018, 51, 364-369.

[0092]

Chemical formula

[0093] (Test method) To 105 mg (0.241 mmol) of 1,4-dibromo-2,5-bis(hexyloxy)benzene (9), 22.4 mg (0.110 mmol) of phenylboronic acid pinacol ester (10), 349 mg of 18-crown-6-ether, 0.23 mL (0.460 mmol) of 2M K3PO4 solution, and 2.5 mL of dry THF, 0.00770 mmol of a polymerization catalyst (Compound 4, 6, or 8) was added, and the mixture was stirred at room temperature for 24 hours. 6M hydrochloric acid was added to stop the reaction, and the mixture was extracted with methylene chloride. The organic layer was dried over anhydrous magnesium sulfate. After filtration, naphthalene was added to the compound obtained by distilling off the solvent under reduced pressure, 1 The ratio of Compound 11 to Compound 12 was calculated using 1H-NMR. The results are shown in Table 1. Note that the higher the production ratio of Compound 11, the higher the mobility of Pd-L.

[0094]

Table 1

[0095] Table 1 shows that the formation of Compound 12 was not observed in the said test, and only the formation of Compound 11 was observed. Therefore, it was suggested that the phosphine palladium complex obtained in this example is a polymerization catalyst suitable for a catalyst migration type chain condensation polymerization reaction in which Pd-L effectively moves to the growth end and polymerization proceeds.

[0096] (Example 5) (Polymerization of thiophene monomer (13))

[0097] [Chemistry]

[0098] Under an argon atmosphere, 43.95 mg (0.105 mmol) of thiophene monomer (13), 71.2 mg (0.468 mmol) of cesium fluoride, 215 mg (0.814 mmol) of 18-crown-6-ether, 7.0 mL of deoxygenated THF, and 0.45 mL of deoxygenated distilled water were added to a 30 mL round-bottom flask and stirred for 10 minutes to prepare a monomer solution. Also, under an argon atmosphere, 7.21 mg (0.0101 mmol, 10 mol%) of polymerization catalyst (4) and 1.0 mL of deoxygenated THF were added to another eggplant-shaped flask and stirred for 10 minutes to prepare a catalyst solution. The above catalyst solution was added to the above monomer solution using a cannula, and after stirring at room temperature for 5 hours, 5 M hydrochloric acid was added to stop the reaction. It was extracted with 50 mL of chloroform, and the solvent was concentrated under reduced pressure to obtain a black crude product. Yield: 87% Mn(PDI): 3200 (1.15)

[0099] (Example 6) >[Polymerization of fluorene monomer (14)]

[0100] [Chemistry]

[0101] Under an argon atmosphere, 43.95 mg (0.105 mmol) of fluorene monomer (14), 71.2 mg (0.468 mmol) of cesium fluoride, 215 mg (0.814 mmol) of 18-crown-6-ether, 7.0 mL of deoxygenated THF, and 0.45 mL of deoxygenated distilled water were added to a 30 mL round-bottom flask and stirred for 10 minutes to prepare a monomer solution. Also, under an argon atmosphere, 7.21 mg (0.0101 mmol, 10 mol%) of polymerization catalyst (4) and 1.0 mL of deoxygenated THF were added to another eggplant-shaped flask and stirred for 10 minutes to prepare a catalyst solution. The above catalyst solution was added to the above monomer solution using a cannula, stirred at room temperature for 5 hours, and then 5 M hydrochloric acid was added to stop the reaction. It was extracted with 50 mL of chloroform, the solvent was concentrated under reduced pressure, and a black crude product was obtained. Yield: 98% Mn(PDI): 7800 (1.24)

[0102] (Example 7) <Block copolymerization>

[0103] [Chemical formula]

[0104] The copolymerization was carried out by a two-stage monomer charging method. Under an argon atmosphere, 14.55 mg (0.0244 mmol) of fluorene monomer (14), 54.3 mg (0.357 mmol) of cesium fluoride, 82.3 mg (0.312 mmol) of 18-crown-6-ether, 1.8 mL of deoxygenated THF, and 0.11 mL of deoxygenated distilled water were added to a 30 mL round-bottom flask and stirred for 10 minutes to prepare a monomer solution. Also, under an argon atmosphere, 2.21 mg (0.00310 mmol, 10%) of polymerization catalyst (4) and 1.0 mL of deoxygenated THF were added to another eggplant-shaped flask and stirred for 10 minutes to prepare a catalyst solution. The above catalyst solution was added to the above monomer solution using a cannula and stirred at room temperature for 5 hours (the first polymerization reaction). Then, a monomer solution in which 9.01 mg (0.0214 mmol) of thiophene monomer (13) was dissolved in 1.0 mL of deoxygenated THF was added to the reaction solution, and further stirred at room temperature for 24 hours (the second polymerization reaction). 5M hydrochloric acid was added to the reaction solution and extracted with 50 mL of chloroform, and the solvent was concentrated under reduced pressure to obtain a black crude product. Yield: 82% Mn(PDI): 7700 (1.22)

[0105] The dotted line in the GPC chart shown in Figure 2 is the elution curve of polyfluorene (14) obtained by the first polymerization reaction, and the solid line is the elution curve of the polymer obtained by the second polymerization reaction. By adding thiophene monomer (13) to the polymerization system containing polyfluorene (14) obtained by the first polymerization reaction, the elution curve is shifted to the high molecular weight side. This indicates that the polymer obtained by the second polymerization reaction is a polyfluorene (14)-polythiophene (13) block copolymer. Therefore, it can be seen that the polymerization catalyst of the present invention functions effectively in catalyst transfer type chain condensation polymerization.

Claims

1. A phosphine palladium complex represented by the following general formula (1). 【Chemical Formula 1】 (In the formula, R １ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and t represents an integer of 0 to 4. Ar represents a monovalent group containing an aromatic ring. X represents a halogeno group or a sulfonate group represented by the general formula: -SO ３ Z, where Z represents a substituted or unsubstituted hydrocarbon group. A represents a substituted or unsubstituted adamantyl group or an aryl group represented by the following general formula (2).) 【Chemical Formula 2】 (In the formula, R ２ to R ６ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or the general formula: -N(R ７ )(R ８ ), and R ７ to R ８ each independently represents an alkyl group having 1 to 5 carbon atoms.)

2. The phosphine palladium complex according to claim 1, wherein the aryl group represented by the general formula (2) is an aryl group represented by the following general formula (2a). 【Chemical Formula 3】 (R in the formula ７ and R ８ have the same meanings as in the general formula (2).)

3. The phosphine palladium complex according to claim 1, wherein the aryl group represented by the general formula (2) is an aryl group represented by the following general formula (2b). 【Chemical Formula 4】 (In the formula, R ９ represents an alkyl group having 1 to 5 carbon atoms.)

4. The phosphine palladium complex according to claim 1, wherein Ar in the general formula (1) is a substituted or unsubstituted phenyl group, and the substituent in the substituted phenyl group is an alkyl group having 1 to 4 carbon atoms.

5. The phosphine palladium complex according to claim 1, wherein X in the general formula (1) is a halogeno group.

6. A polymerization catalyst comprising the phosphine palladium complex according to claim 1.

7. The polymerization catalyst according to claim 6, which is used for polycondensation.

8. A method for producing an aromatic polymer, comprising a polycondensation step of polycondensing an aromatic compound represented by the following general formula (3) in the presence of the polymerization catalyst according to claim 6. 【Chemical formula 5】 (In the formula, Ar １ represents a divalent group containing an aromatic ring. X １ represents a halogeno group, a nitro group, or a sulfonate group represented by -SO ３ Z １ represents a sulfonate group, and Z １ represents a substituted or unsubstituted hydrocarbon group. Q １ each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and two Qs １ may be bonded to each other to form a ring.)

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