JP2018127572A - Manufacturing method and purification method of conjugated polymer, and manufacturing method of trimer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a conjugated polymer for manufacturing an alignment-based conjugated polymer larger in molecular weight by polymerization with a coupling reaction between a monomer and a trimer.SOLUTION: There are provided a manufacturing method of a conjugated polymer by polymerizing a trimer which may have a substituent having a halogen atoms at 2, 6 positions of cyclopenta-dithiophene represented by Formula (1), and a monomer having trialkyl tin at the 2, 6 positions of the cyclopenta-dithiophene in co-presence of two or more kinds of transition metal complex catalysts by a coupling reaction, and a manufacturing method of a trimer by conducting a coupling reaction on the latter trialkyl tin-containing monomer and a monomer having an aromatic hydrocarbon group which may have a substituent group having 2 halogen atoms or an aromatic heterocyclic group which may have a substituent group in co-presence of two or more kinds of the transition metal complex catalysts.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing and purifying a conjugated polymer such as a locally regular conjugated polymer. The present invention also relates to a method for producing a trimer as a raw material for producing the conjugated polymer. The aligned conjugated polymer produced in the present invention is also referred to as “regioselective (regioselective) conjugated polymer”, and is synthesized with a specific regioselectivity by reaction.

  Conjugated polymers are used as semiconductor materials for devices such as organic EL, organic thin film transistors, and organic light-emitting sensors. Among these, aligned conjugated polymers are attracting attention for application to organic thin film transistors.

  Conventionally, a method of coupling monomers using a transition metal catalyst is known as a method for synthesizing an alignment conjugated polymer and a trimer that is a raw material for the production. For example, in Patent Documents 1 and 2 and Non-Patent Documents 1 and 2, a trimer-monomer coupling reaction is performed at 200 ° C. for 2 hours under microwave using a homogeneous catalyst of tetrakistriphenylphosphine palladium (0). By aligning a trimer unit of a cyclopentadithiophene skeleton and a condensed aromatic ring skeleton and a monomer unit of a cyclopentadithiophene skeleton, and including an aligning conjugated polymer in the main chain, including a low molecular weight body and an oligomer A method for producing a reaction product and a method for producing a trimer by reaction at 90 ° C. for 72 hours under normal conditions are disclosed.

US Pat. No. 9,293,708 Chinese Patent Application No. 105131258

Chem. Commun. 2016, 52, 3207-3210. J. Am. Chem. Soc. 2011, 133, 18538-18541.

In order to develop a device with higher performance by applying the aligned conjugated polymer, it is required to obtain an aligned conjugated polymer having a higher molecular weight distribution. However, the conventional transition metal-catalyzed coupling reaction cannot produce an aligned conjugated polymer having a large molecular weight. There are two reasons for this.
(1) The purity of the ditin derivative of cyclopentadithiophene, which is a raw material for polymerization, varies.
(2) During the coupling reaction, the unstable carbon-tin bond of the ditin derivative of the above (1) is broken, and as a result, a low molecular weight body and an oligomer remain.
Furthermore, there is a problem in that the polymer or oligomer on the low molecular weight side remains on the purified polymer side when the polymer is purified by the Soxhlet extraction method or the like in the purification process of the obtained crude polymer. .

  The present invention relates to a method for producing and purifying a conjugated polymer for producing an aligned conjugated polymer having a higher molecular weight by polymerization by a coupling reaction between a monomer and a trimer, and a trimer as a raw material for the conjugated polymer. It aims at providing the manufacturing method of the trimer obtained in a high yield in a short time by the coupling reaction of monomers.

As a result of intensive studies to solve the above-mentioned problems, the present inventors conducted a monomer coupling reaction in the presence of two or more kinds of transition metal complex catalysts, so that the trimer can be obtained in a high yield in a short time. In addition, by polymerizing the obtained trimer and monomer by a coupling reaction in the presence of two or more transition metal complex catalysts, the obtained polymer can be further obtained by a specific method. It has been found that a conjugated polymer having a higher molecular weight can be obtained by purification, and the present invention has been completed.
That is, the gist of the present invention is as follows.

[1] The method includes polymerizing a trimer represented by the following formula (1) and a monomer represented by the following formula (2) by a coupling reaction in the presence of two or more transition metal complex catalysts. A process for producing a conjugated polymer characterized by

(In the above formula (1), R ¹ and R ² each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. A represents an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, and X represents a halogen atom.

(In the above formula (2), R ³ and R ⁴ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. And R represents an aliphatic hydrocarbon group.)

[2] The method for producing a conjugated polymer according to [1], wherein at least one of the two or more transition metal complex catalysts is a heterogeneous transition metal complex catalyst.

[3] At least one of the two or more transition metal complex catalysts is a heterogeneous transition metal complex catalyst, and at least one is a homogeneous transition metal complex catalyst, [2] A method for producing a conjugated polymer as described in 1.

[4] A reaction solution containing the trimer represented by the formula (1) and the monomer represented by the formula (2) is mixed with the homogeneous transition metal complex catalyst and the heterogeneous transition metal complex catalyst. The method for producing a conjugated polymer according to [3], comprising a step.

[5] The method for producing a conjugated polymer according to any one of [1] to [4], wherein each of the transition metals constituting the two or more transition metal complex catalysts is palladium.

[6] The method for producing a conjugated polymer according to any one of [1] to [5], wherein the conjugated polymer is an aligned conjugated polymer.

[7] The conjugated polymer obtained by the method for producing a conjugated polymer according to any one of [1] to [6] is dissolved in a halogen-based solvent, and then contacted with basic silica gel and acidic silica gel. A method for purifying a conjugated polymer characterized by the following.

[8] The conjugated polymer obtained by the method for producing a conjugated polymer according to any one of [1] to [6] is dissolved in a halogen-based solvent, and then the alcohol-based solvent is added to the obtained conjugated polymer solution. Alternatively, a method for purifying a conjugated polymer, comprising adding an ester solvent to precipitate the conjugated polymer.

[9] including a step of coupling a monomer represented by the following formula (2) and a monomer represented by the following formula (3) in the presence of two or more transition metal complex catalysts. A method for producing a trimmer.

(In the above formula (2), R ³ and R ⁴ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. And R represents an aliphatic hydrocarbon group.)

(In said formula (3), A represents the aromatic hydrocarbon group which may have a substituent, or the aromatic heterocyclic group which may have a substituent, X represents a halogen atom. .)

[10] The method for producing a trimer according to [9], wherein at least one of the two or more transition metal complex catalysts is a heterogeneous transition metal complex catalyst.

[11] Of the two or more transition metal complex catalysts, at least one is a heterogeneous transition metal complex catalyst and at least one is a homogeneous transition metal complex catalyst, [10] A method for producing a trimmer according to 1.

[12] A reaction solution containing the monomer represented by the formula (2) and the monomer represented by the formula (3) is mixed with the homogeneous transition metal complex catalyst and the heterogeneous transition metal complex catalyst. The method for producing a trimer according to [11], comprising a step.

[13] The method for producing a trimer according to any one of [9] to [12], wherein each of the transition metals constituting the two or more transition metal complex catalysts is palladium.

According to the method for producing a conjugated polymer of the present invention, a conjugated polymer having a higher molecular weight is produced by performing polymerization by a monomer-trimer coupling reaction in the presence of two or more transition metal complex catalysts. By purifying the produced conjugated polymer according to the method for purifying conjugated polymer of the present invention, it can be recovered as a high molecular weight conjugated polymer having a small amount of low molecular weight components.
In addition, according to the method for producing a trimer of the present invention, a specific monomer is subjected to a coupling reaction in the presence of two or more transition metal complex catalysts, thereby shortening the trimer that is a raw material for polymerizing the conjugated polymer. It can be obtained in high yield over time.

  Hereinafter, embodiments of the present invention will be described in detail. The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist.

The method for producing a conjugated polymer of the present invention includes a step of polymerizing a specific trimer and a monomer by a coupling reaction in the presence of two or more transition metal complex catalysts. And a step of coupling a specific two kinds of monomers in the presence of two or more kinds of transition metal complex catalysts.
In the present invention, the “trimer” has an aromatic hydrocarbon group (which includes a condensed ring as described later) and / or a substituent which may have a substituent described later. It refers to a compound in which two aromatic bonds (as described below, these include a condensed ring) are connected by two single bonds, and the “monomer” may have a substituent. This refers to a compound having only one aromatic heterocyclic group which may have an aromatic hydrocarbon group or a substituent (as described below, these include a condensed ring).

[Method for producing conjugated polymer]
[Transition metal complex catalyst]
First, the transition metal complex catalyst used in the coupling reaction in the present invention will be described.

  There are no particular restrictions on the two or more transition metal complex catalysts used in the coupling reaction in the present invention, but at least one of the two or more transition metal complex catalysts is a heterogeneous transition metal complex catalyst, and at least It is preferable that one type is a homogeneous transition metal complex catalyst. Thus, by using a heterogeneous transition metal complex catalyst and a homogeneous transition metal complex catalyst in combination, efficient coupling can be achieved from the following effects. The reaction can be performed.

  That is, in the coupling reaction of the present invention, when at least one kind is a heterogeneous metal complex catalyst, a monomer unstable under coupling reaction conditions can be quickly converted into an oligomer having a relatively stable carbon-tin bond. Can do. In addition, although the polymerization reaction rate due to the heterogeneous metal catalyst tends to decrease when it becomes an oligomer, a polymer having a higher molecular weight can be obtained by conducting the induction from the oligomer to the polymer with at least one homogeneous metal catalyst. Will be able to.

  Conventionally, it has been common to use only a homogeneous transition metal complex catalyst or only a heterogeneous transition metal complex catalyst as a catalyst in the coupling reaction. As an advantage of using the homogeneous transition metal complex catalyst, first, since the catalyst is dissolved in the solution, the contact frequency with the monomer is high and the reactivity is generally high. Moreover, since a ligand can be freely selected according to the reactivity, it is advantageous in terms of design of the catalyst compound. On the other hand, the homogeneous transition metal complex catalyst has problems such as being difficult to recover from the reaction solution.

  However, by using a homogeneous transition metal complex catalyst and a heterogeneous transition metal complex catalyst together, especially by allowing a homogeneous transition metal complex catalyst and a heterogeneous transition metal complex catalyst to coexist in the reaction system, The synthesis reaction rate of the trimer and polymer is improved and the reproducibility is improved, and an aligned conjugated polymer having a large molecular weight can be obtained. This effect is particularly effective when the raw material monomer is a thermally and / or chemically unstable monomer.

  The reason why the coupling reaction speed is improved by the combined use of the homogeneous transition metal complex catalyst and the heterogeneous transition metal complex catalyst is not clear. For example, the homogeneous transition metal complex catalyst and the heterogeneous transition metal complex catalyst to be used are used. It is considered that the synthesis reaction of trimer and polymer is promoted and the reaction rate is improved due to the difference in TOF (turnover frequency) and TON (turnover number).

  For example, by converting a monomer into an oligomer in a short time with a heterogeneous transition metal complex catalyst having a large TOF, and then proceeding with a reaction with a homogeneous transition metal complex catalyst having a large TON, as a result, the reactivity of polymer synthesis Can be improved. A transition metal complex catalyst having a large TOF may be a homogeneous transition metal complex catalyst, and a transition metal complex having a large TON may be a heterogeneous transition metal catalyst.

When one or more homogeneous transition metal complex catalysts and one or more heterogeneous transition metal complex catalysts are used in combination, one or more homogeneous transition metal complex catalysts and one or more heterogeneous transition metal complex catalysts are contained in the reaction system. A homogeneous transition metal complex catalyst may be added at the same time, or after one of the homogeneous transition metal complex catalyst and the heterogeneous transition metal complex catalyst is added to the reaction system, the other may be added.
However, in order to improve the reaction rate and the convenience of the reaction operation, one or more homogeneous transition metal complex catalysts and one or more heterogeneous transition metal complex catalysts are mixed in the reaction system at the same time to carry out a coupling reaction. Preferably it is done.

  In this specification, the transition metal complex catalyst refers to a catalyst obtained by combining a transition metal salt and an organic ligand that forms a transition metal complex with the transition metal salt. On the other hand, transition metal salts having no organic ligand are not included in the transition metal complex catalyst in the present invention.

Examples of transition metal salts without organic ligands include transitions used as promoters in Stille couplings such as Cu ₂ O, CuO, CuI, CuBr, CuCl, CuCl ₂ , CuBr ₂ , or CuI ₂ A metal inorganic salt is mentioned.

  In order to more reliably obtain the effect of improving the reaction rate, it is preferable that one or more homogeneous transition metal complex catalysts and one or more heterogeneous transition metal complex catalysts can each independently catalyze a coupling reaction. Here, as an example of using one or more kinds of homogeneous transition metal complex catalysts and one or more kinds of heterogeneous transition metal complex catalysts, there is a case where transition metal complex catalysts having different structures are used in combination.

  In the case where one or more homogeneous transition metal complex catalysts and one or more heterogeneous transition metal complex catalysts are used in combination, by reacting each transition metal catalyst active species with a transition metal salt and a ligand. After the formation, each may be introduced into a coupling reaction system, or a transition metal salt and a ligand may be reacted in the reaction system to form a transition metal catalytically active species.

  Two or more homogeneous transition metal complexes may be used, or two or more heterogeneous transition metal complexes may be used.

  Examples of different types of homogeneous transition metal complexes include, for example, those having different types of transition metals, those having different types and numbers of ligands, and those having different points. In addition, different types of heterogeneous transition metal complexes include, for example, those with different types of transition metals, those with different types and numbers of ligands, those with different types of carriers, and those with different points. Is mentioned.

<Homogeneous transition metal complex catalyst>
The homogeneous transition metal complex catalyst that can be used in the coupling reaction of the present invention will be described below. In order to make the coupling reaction proceed smoothly, it is preferable to use a transition metal complex for coupling as the homogeneous transition metal complex, and it is particularly preferable to use a late transition metal as the transition metal.

In the present specification, the term “periodic transition metal” refers to a Group 8 to Group 11 element in the periodic table. Among the late transition metals, it is particularly preferable to use a homogeneous transition metal complex containing palladium (Pd), nickel (Ni), iron (Fe), or copper (Cu) in order to improve the reactivity. More preferred is palladium (Pd), which has good reactivity and does not select a reaction substrate.
In this specification, the periodic table refers to the IUPAC 2006 recommended version (Recommendations of IUPAC 2006).

  In particular, palladium is preferable because it can be widely used in various cross-coupling reactions and has high reactivity.

  Examples of the organic ligand possessed by the homogeneous transition metal complex catalyst include those formed from typical elements of Groups 13 to 16 of the periodic table, and those having carbon atoms.

  Further, a part of the transition metal complex catalyst may have a halogen atom or a hydrogen atom. Such an organic ligand is preferable in terms of improving the function of the transition metal complex catalyst. As a specific example, J. Org. Organic ligands described in Hartwig, “Organotransition Metal Chemistry”, University Science Books (2010) and references cited therein, Strem, “Metal Catalysts for Organics 11” A child. An organic ligand suitable for each transition metal may be appropriately selected.

Below, the most suitable palladium complex as a homogeneous transition metal complex catalyst is demonstrated.
In the palladium complex, palladium (0) is an important catalyst species, but in general, it is unstable and easily decomposed in air. On the other hand, palladium (II) is stable and easily converted to palladium (0) by coexistence with a ligand to generate active species in the system. In addition, when producing an active palladium (0) complex from a palladium (II) complex and a ligand in the system, two types of complexes of a palladium (II) complex and a palladium (0) complex are used. It is considered that one kind of palladium complex is used instead.

Specific examples of the palladium reagent include Pd (PPh ₃ ) ₄ , Pd (P (o-tol) ₃ ) ₄ , Pd (P (t-Bu) ₃ ) ₄ , Pd ₂ (dba) ₃ , Pd ₂ (Dba) ₃ CHCl ₃ , Pd (dba) ₂ , Pd (MeCN) ₄ (BF ₄ ) ₂ , PdCl ₂ , PdBr ₂ , Pd (acac) ₂ , Pd (TFA) ₂ , Pd (allyl) Cl ₂ , [ Pd (allyl) Cl] ₂ , Pd (PCy ₃ ) ₂ Cl ₂ , Pd (P (o-tol) ₃ ) ₂ Cl ₂ , Pd (OAc) ₂ , PdCl ₂ (dppf), PdCl ₂ (dppf) CH ₂ Examples thereof include zero-valent or divalent compounds such as Cl ₂ , Pd (MeCN) ₂ Cl ₂ , Pd (amPhos) Cl ₂ , PdCl ₂ (dtbpf), or PdCl ₂ (PPh ₃ ) ₂ .

A divalent palladium complex and dibenzylideneacetone palladium can form an active Pd (0) complex by mixing with various ligands. Specific examples of the ligand include PPh ₃ , dppf, dba, P (t-Bu) ₃ , P (Cy) ₃ , AsPh ₃ , P (o-tol) _{3 and the} like.

  Other examples of the ligand include Buchwald-type biphenyl type (biphenylphosphine derivative) (for example, Acc. Chem. Res., 41, 1461-1473, 2008, Chem. Sci., 2, 27-50, 2011). Nolan type carbene type (for example, those listed in Chem. Rev., 109, 3612-3676, Acc. Chem. Res., 41, 1440-1449), Fu type aliphatic Phosphine type (for example, those listed in Acc. Chem. Res., 41, 1555-1564), Organ et al., PEPPSI type, Beller type, palladacycle type (for example, Dupont et al., Chem. Rev., 105, 2527). -2571 (2005), Nolan et al., A c.Chem.Res., 41,1440-1449 (2008) to those listed), and the like. From the viewpoint of improving the reactivity, a phosphine ligand is preferably used as the ligand.

<Heterogeneous transition metal complex catalyst>
The heterogeneous transition metal complex catalyst that can be used in the coupling reaction of the present invention will be described below. In order to facilitate the coupling reaction, it is preferable to use a transition metal complex for coupling as the heterogeneous transition metal complex, and it is particularly preferable to use a late transition metal as the transition metal. Among the late transition metals, it is particularly preferable to use a heterogeneous transition metal complex containing palladium (Pd) or nickel (Ni) in order to improve the reactivity. More preferably, a heterogeneous transition metal complex containing palladium (Pd) is used.

  As an organic ligand which a heterogeneous transition metal complex catalyst has, the same thing as what was mentioned about the homogeneous transition metal complex catalyst can be used. In addition, organic ligands described in known literature (Strem, “Heterogeneous Catalysts” (2011)) can also be used.

  From the viewpoint of ease of operation, the heterogeneous transition metal complex catalyst is preferably supported on a carrier. Examples of carriers include metals, nanocolloids, nanoparticles, magnetic compounds, metal oxides, glasses, microporous materials, mesoporous materials, zeolites, polymers, and the like.

  Among these, it is more preferable to use a heterogeneous transition metal complex catalyst supported on zeolite, a polymer, or the like because the heterogeneous transition metal complex catalyst can be easily recovered.

  Moreover, it is more preferable that the support of the heterogeneous transition metal complex catalyst is a porous support in terms of promoting the reaction. Examples of the porous carrier include porous glass, zeolite, and porous polymer. Among these, the support for the heterogeneous transition metal complex catalyst is preferably porous glass or a porous polymer.

  Examples of the porous glass include glass wool. Examples of the porous polymer include polystyrene, polyethylene, and urea resin. Specifically, publicly known literature, Recoverable and Recyclable Catalysts, Benaqlia, M., et al. Author, Wiley, 2009, Chemical Reviews, 107, 133-173 (2007), Chemical Reviews, 111, 251-2320 (2011), Chemical Reviews, 109, 594-642 (2009), Chemical Rev. 109 -838 (2009).

  Specific examples of heterogeneous transition metal complex catalysts include Liebscher et al., Chem. Rev. 107, 133-173 (2007), Molnar, Chem. Rev. 111, 2251-2320 (2011), Polshettiwar et al., Chem. Rev. 111, 3036-3075 (2011), Adv. Synth. Catal. , 346, 1553-1582 (2006), Adv. Synth. Catal. 348, 609-679 (2008), Alonso et al., Tetrahedron, 64, 3047-3101 (2008), Tetrahedron, 61, 11771-11835 (2005), Polshettiwar et al., Tetrahedron, 63, 6949-6976 (2007), Coord. . Chem. Rev. 253, 2599-2626 (2009), Kobayashi et al., Chem. Rev. 109, 594-642 (2009), and the like.

More specific examples of the heterogeneous transition metal complex catalyst include FibreCat 1001, FibreCat 1007, FibreCat 1026, Pl Palladium, Palladium-Nanocage, Palladium (II) -Hydroitalite (m), Palladium (ro) , Manufactured by Wako Pure Chemical Industries, Ltd.), Pd EnCat series (registered trademark), PS-TPP ₂ PdCl ₂ , PS-TPP ₂ Pd (OAc) ₂ , PS-TPP ₂ PdTPP ₂ , Pd-containing ChemDose tablet (above, Aldrich) SiriCat S-Pd, SiliaCat DPP-Pd (manufactured by SiliCycle).

  Some commercially available heterogeneous transition metal complex catalysts do not contain a ligand in advance. When no ligand is contained, a ligand may be added.

  The addition of the ligand may be performed in advance or may be performed in the reaction system of the coupling reaction. As the ligand, the same ligands as those described for the homogeneous transition metal complex catalyst can be used. In order to facilitate the reaction operation, it is preferable to use, as a catalyst, a porous carrier in which a transition metal complex and a ligand are kneaded in advance.

<Amount of catalyst used>
In the present invention, when a homogeneous transition metal complex catalyst and a heterogeneous transition metal complex catalyst are used in combination as two or more kinds of transition metal complex catalysts, in order to effectively obtain the above-described effects by using both, a homogeneous system The transition metal complex catalyst and the heterogeneous transition metal complex catalyst are used in an amount ratio (mol ratio) in terms of active metal, and the homogeneous transition metal complex catalyst: heterogeneous transition metal complex catalyst = 1: 0.1. It is preferable to use it in a ratio of ˜5, particularly 1: 0.5 to 1.5. Since the heterogeneous transition metal complex catalyst is used from a low molecule to an oligomer, and the homogeneous transition metal complex catalyst is used from an oligomer to a polymer, the functions of the catalyst are separately used.

  There is no restriction | limiting in particular about the total usage-amount of 2 or more types of transition metal complex catalysts, According to the reaction form, reaction conditions, etc., it can set suitably within the range of the catalyst usage-amount in a normal coupling reaction.

[Trimmer (1)]
Next, a trimer represented by the following formula (1) (hereinafter sometimes referred to as “trimer (1)”), which is one of the polymerized raw materials of the method for producing a conjugated polymer of the present invention, will be described.

In the present specification, the aromatic hydrocarbon group is a group having a bond in the aromatic hydrocarbon ring, and further to this aromatic hydrocarbon ring, an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, The aromatic hydrocarbon group also includes a condensed ring group in which about 1 to 5 rings of one or two or more kinds selected from an aromatic heterocyclic ring and an aliphatic heterocyclic ring (non-aromatic heterocyclic ring) are condensed.
Similarly, the aromatic heterocyclic group is a group having a bond to the aromatic heterocyclic ring, and further includes an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, an aromatic heterocyclic ring, and A condensed heterocyclic group obtained by condensing about 1 to 5 rings of one or two or more selected from an aliphatic heterocyclic ring (non-aromatic heterocyclic ring) is also included in the aromatic heterocyclic group.

(In the above formula (1), R ¹ and R ² each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. A represents an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, and X represents a halogen atom.

Examples of the aliphatic hydrocarbon group of the aliphatic hydrocarbon group that may have a substituent of R ¹ and R ² in the above formula (1) include an aliphatic hydrocarbon group having 1 to 30 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group or an alkenyl group.

  The carbon number of the alkyl group is usually 1 or more, preferably 3 or more, more preferably 4 or more, and usually 30 or less, preferably 25 or less, more preferably 20 or less. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a cyclopropyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, a 3-methylbutyl group, and a cyclobutyl group. Group, pentyl group, cyclopentyl group, hexyl group, 2-ethylhexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, decyl group, cyclodecyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, or eicosyl group. Among them, 2-ethylhexyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, or eicosyl group is preferable.

  The carbon number of the alkenyl group is usually 1 or more, preferably 3 or more, more preferably 4 or more, and usually 30 or less, preferably 25 or less, more preferably 20 or less. Examples of such alkenyl groups include ethene, propene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and the like. Group, hexadecene group, heptadecene group, octadecene group, nonadecene group, icocene group or geranyl group.

The aromatic hydrocarbon group of the aromatic hydrocarbon group which may have a substituent for R ¹ and R ² is an aromatic hydrocarbon group having 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms. Examples of the hydrocarbon group include a phenyl group, a naphthyl group, an indanyl group, an indenyl group, a fluorenyl group, an anthracenyl group, and an azuleninyl group, and a phenyl group and a naphthyl group are preferable.

  The substituent that these aliphatic hydrocarbon groups and aromatic hydrocarbon groups may have is not particularly limited, but is preferably a halogen atom, a hydroxyl group, a cyano group, an amino group, an ester group, an alkylcarbonyl group, An acetyl group, a sulfonyl group, a silyl group, a boryl group, a nitrile group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aromatic hydrocarbon group, or an aromatic heterocyclic group. These may be connected with adjacent substituents to form a ring. In particular, the substituent which the aromatic group may have includes an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, A fluorine atom is especially preferable.

R ¹ and R ² may be the same or different, but are preferably the same in terms of synthesis.

R ¹ and R ² are preferably alkyl groups having 3 to 30 carbon atoms, particularly 6 to 25 carbon atoms, especially 10 to 20 carbon atoms, which have no substituent. It is preferable that R ¹ and R ² are alkyl groups having the above carbon number in that a high-performance device can be efficiently produced from the produced ordered conjugated polymer.

  A is an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent.

Examples of the aromatic hydrocarbon group of the aromatic hydrocarbon group which may have a substituent for A include those exemplified as the aromatic hydrocarbon groups for R ¹ and R ² , and the condensed ring groups described below. .

  The aromatic heterocyclic group of the aromatic heterocyclic group which may have a substituent of A is a C3-C12, preferably 5-membered or 6-membered aromatic heterocyclic group, Examples include a thienyl group, a furyl group, a pyridyl group, a pyrimidyl group, a thiazolyl group, an oxazolyl group, a triazolyl group, and a condensed ring group described later. Among them, a thienyl group, a pyridyl group, a pyrimidyl group, a thiazolyl group, an oxazolyl group, and the following These fused ring groups are preferred.

Examples of the substituent that the aromatic hydrocarbon group and aromatic heterocyclic group of A may have include those described above as the substituent that R ¹ and R ² may have.

  A is preferably a condensed ring group obtained by condensing 2 to 6, preferably 2 to 3, aromatic hydrocarbon rings and / or aromatic heterocycles from the viewpoint of maintaining solubility. Examples of the condensed ring group include those exemplified below.

  Among these, the condensed ring group of A is an aromatic hydrocarbon group in which an aromatic heterocyclic ring such as a benzene ring is condensed with an aromatic heterocyclic ring such as a thiadiazole ring, a triazole ring, a pyrazine ring, or a pyridazine ring. Preferably there is.

These condensed ring groups may have a substituent, and as the substituent, among those exemplified as the substituents that R ¹ and R ² may have, an alkyl group, an alkoxy group, A halogen atom such as a chlorine atom, a fluorine atom, or a bromine atom is preferred, and a fluorine atom is particularly preferred, and the substitution position is on the aromatic hydrocarbon ring, and only one substitution is performed. This is preferable from the aspect of orientation.

  Two A in formula (1) may be the same or different, but are preferably the same in synthesis.

  Examples of the halogen atom of X in the formula (1) include a chlorine atom, a bromine atom, and an iodine atom, but a bromine atom or an iodine atom is particularly preferable from the viewpoint of reactivity.

  The two Xs in formula (1) may be the same or different, but are preferably the same in terms of synthesis.

[Monomer (2)]
Next, a monomer represented by the following formula (2) (hereinafter sometimes referred to as “monomer (2)”), which is the other of the polymerization raw materials in the method for producing a conjugated polymer of the present invention, will be described. .

(In the above formula (2), R ³ and R ⁴ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. And R represents an aliphatic hydrocarbon group.)

The aliphatic hydrocarbon group which may have a substituent of R ³ and R ⁴ in the above formula (2) and the aromatic hydrocarbon group which may have a substituent include R in the formula (1) ^1, R ² of aliphatic optionally substituted hydrocarbon group include those exemplified as aromatic hydrocarbon group which may have a substituent, preferable ones are also same.

R ³ and R ⁴ may be the same or different, but are preferably the same in synthesis. For the same reason, R ³ and R ⁴ are preferably the same as R ¹ and R ² in formula (1).

The aliphatic hydrocarbon group represented by R in the formula (1) is preferably a lower alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group having high reactivity. The two SnR ₃ groups in the formula (2) are particularly preferably trimethylstannyl (—Sn (CH ₃ ) ₃ ), and the two SnR ₃ groups in the formula (2) are the same. Is preferred.

[Quantity ratio of trimer (1) and monomer (2)]
The amount ratio of the trimer (1) and the monomer (2) in the polymerization by the coupling reaction depends on the molecular weight distribution of the target conjugated polymer, but the trimer (1) and the monomer (2). Is usually 0.75 or more, preferably 0.85 or more, and is usually 1.3 or less, preferably 1.2 or less. When the molar ratio is within the above range, a high molecular weight product can be obtained with a higher yield.

[Reaction solvent]
In the method for producing a conjugated polymer of the present invention, preferably, the homogeneous transition metal complex catalyst and the heterogeneous transition metal complex catalyst are added to the reaction solution containing the trimer (1) and the monomer (2). Simultaneously mixed and polymerized by a coupling reaction.

  Examples of the solvent used in this coupling reaction include aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, and xylene; halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; triethylamine, diisopropylethylamine, and pyrrolidine. Amine type solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like. These solvents may be used alone or in a mixture of two or more solvents.

The amount of the solvent used is usually 1 × with respect to 1 g of the total weight of the trimer (1) and the monomer (2) in order to sufficiently dissolve the trimer (1) and the monomer (2) and the resulting conjugated polymer. 10 ⁻² mL or more, preferably 1 × 10 ⁻¹ mL or more, more preferably ¹ mL or more. On the other hand, in order to facilitate the purification of the conjugated polymer, it is usually 1 × 10 ⁵ mL or less, preferably 1 × 10 ³ mL or less, more preferably 2 × 10 ² mL or less.

[Reaction conditions]
<Reaction atmosphere>
In order to prevent the deterioration of the transition metal complex catalyst, the coupling reaction is preferably performed under an inert gas. In particular, the reaction is preferably performed in a nitrogen atmosphere or an argon atmosphere.

<Reaction temperature>
Although reaction temperature is not specifically limited, Usually, it carries out at the temperature below room temperature and the boiling point of a solvent. In order to increase the reaction rate, pressurization and / or heating may be performed using an autoclave or a microwave. In the case of an autoclave or microwave, it may be carried out at a temperature not lower than the boiling point of the solvent, but is preferably 250 ° C. or lower in order to prevent decomposition of the resulting conjugated polymer.

  In the case of microwave heating, Biotage Microwave Initiators + is preferably used, and heating is preferably performed in a stepwise manner from 60 to 80 ° C. to 100 to 130 ° C. and 150 to 180 ° C. In the case of autoflavor heating, it is preferably performed at a boiling point of the solvent to be used up to about 150 ° C.

<Reaction time>
The reaction time depends on the reactivity of the trimer (1) and the monomer (2), the reaction temperature, and the like, but from the viewpoint of sufficiently completing the reaction in a short time, it is usually 5 minutes or more, preferably 30 minutes or more, more preferably On the other hand, it is usually 48 hours or less, preferably 24 hours or less, more preferably 15 hours, still more preferably 12 hours, particularly preferably 6 hours, and particularly preferably 3 hours. This time does not include the time required for the end treatment described later. Usually, it is confirmed whether or not a desired molecular weight conjugated polymer is obtained by a method such as using analytical GPC, and a terminal treatment described later is performed.

  In the present invention, since the reaction time can be shortened by using two or more transition metal complex catalysts and a high molecular weight conjugated polymer can be produced, for example, in the case of microwave heating, The target high molecular weight conjugated polymer can be obtained in a reaction time of 20 minutes and in the case of autoclave heating in a total reaction time of 30 minutes to 2 hours.

<End treatment>
The terminal treatment is preferably performed on the conjugated polymer after the polymerization reaction. By terminal treatment of the conjugated polymer, a halogen atom such as bromine (Br) or iodine (I) or a terminal residue of the alkylstannyl group contained in the conjugated polymer (X or formula in formula (1)) it is possible to reduce the residual amount of -SnR ₃₎ in (2). This terminal treatment is preferable because a conjugated polymer having better performance can be obtained in terms of semiconductor performance and durability.

  The method for treating the halogen atom at the terminal of the conjugated polymer is not particularly limited, and examples thereof include a method in which aryltrialkyltin is added as a terminal treating agent in the reaction system and then heated and stirred. By this operation, the halogen atom at the terminal of the conjugated polymer can be converted into an aryl group. This is preferable because the conjugated polymer becomes more stable due to the conjugated stability effect.

Examples of aryltrialkyltin that can be used include phenyltrimethyltin and thienyltrimethyltin. The amount of aryltrialkyltin added is not particularly limited, but is usually 1.0 × 10 ⁻² equivalent or more, preferably 0.1 equivalent or more, more preferably, relative to the trimer (1) having a halogen atom. Is 1 equivalent or more, and is usually 50 equivalents or less, preferably 20 equivalents or less, more preferably 10 equivalents or more. The heating time is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 50 hours or shorter, preferably 20 hours or shorter. By performing the reaction under these reaction conditions, the terminal treatment can be performed in a shorter time and with a higher conversion rate.

There is no particular limitation on the method for treating the terminal alkylstannyl group (—SnR ₃ ) of the conjugated polymer, but there is a method in which an aryl halide is added as a terminal treatment agent in the reaction system and then heated and stirred. Can be mentioned. By this operation, the alkylstannyl group at the terminal of the conjugated polymer can be converted to an aryl group. This is preferable because the conjugated polymer can be more stable due to the conjugated stability effect. Moreover, since the alkylstannyl group which is easily thermally decomposed does not exist in the conjugated polymer, it is expected that deterioration with time of the conjugated polymer can be suppressed.

Examples of aryl halides that can be used include iodothiophene, iodobenzene, bromothiophene, and bromobenzene. The addition amount of the aryl halide is not particularly limited, but is usually 1.0 × 10 ⁻² equivalent or more, preferably 0.1 equivalent or more, more than the monomer (2) having an alkylstannyl group. The amount is preferably 1 equivalent or more, and is usually 50 equivalents or less, preferably 20 equivalents or less, more preferably 10 equivalents or more. The heating time is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 50 hours or shorter, preferably 10 hours or shorter. By performing the reaction under these reaction conditions, the terminal treatment can be performed in a shorter time and with a higher conversion rate.

  Although there are no particular restrictions on the operation of these terminal treatments, it is preferable to perform the halogen atom treatment and the alkylstannyl group treatment independently to prevent the end treatment agents from reacting with each other. Either the halogen atom treatment or the alkylstannyl group treatment may be performed first. Further, the terminal treatment may be performed before the purification of the conjugated polymer or after the purification of the conjugated polymer.

  When the end treatment is performed after purification, after dissolving the conjugated polymer and one of the end treatment agents (aryl halide or aryltrimethyltin) in an organic solvent, a transition metal catalyst such as a palladium catalyst is added, and under nitrogen. Stir with heat. Further, the other end treating agent (aryltrimethyltin or aryl halide) is added and heated and stirred. The heating time is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 25 hours or shorter, preferably 10 hours or shorter. It is preferable to perform such a procedure because the terminal residue can be efficiently removed at a high conversion rate in a short time.

[Purification of Conjugated Polymer]
The conjugated polymer can be purified by simple reprecipitation of the conjugated polymer with a poor solvent, Soxhlet extraction, gel permeation chromatography, or scavenger. Purification is performed by the following method (1) and / or (2) after purification by the conventional method or without performing these purifications.
(1) After completely dissolving the conjugated polymer in a halogen-based solvent, it is brought into contact with basic silica gel and acidic silica gel, and the resulting solution is concentrated to a certain amount.
(2) An ester solvent such as an ethyl acetate solvent or an alcohol solvent is added to the halogen solvent of the obtained conjugated polymer with stirring to precipitate the conjugated polymer.

  In the case of the above purification method (1), for example, after adding an alcohol solvent to the reaction solution to precipitate a conjugated polymer once and filtering this, the resulting solid is completely dissolved in a halogen solvent such as chloroform or dichloromethane. After that, the remaining catalytic metal is removed by contacting with basic silica gel, and further, it is purified by contacting with acidic silica gel to remove large high molecular weight substances, organic impurities, and inorganic salts that are hardly soluble in halogenated solvents. The treatment with basic silica gel and acidic silica gel may be a batch treatment in which silica gel is added to a conjugated polymer solution and stirred and mixed, or a continuous treatment in which the conjugated polymer solution is passed through a column packed with silica gel. For example, after the column silica gel is filled with acidic silica gel, it can be purified at the same time by filling it with basic silica gel. It is efficient to charge and process the packed column tube.

  After this silica gel treatment, the treatment solution is concentrated and dissolved again in a minimal halogen solvent, and ester solvents (specifically, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, etc.) ) Or an alcohol solvent (specifically, methanol, ethanol, 2-propanol, etc.) is appropriately mixed with a halogen solvent (the mixing ratio is determined by a spot test of the above mixed solution), and the high molecular weight Only the body is precipitated, and the precipitate is collected by filtration. The filtered precipitate is washed with a multiple solvent system in the above ratio. After dissolving the obtained high molecular weight precipitate in a halogen-based solvent, the solvent is removed, and an alcoholic solvent is added to the precipitate on the obtained film, and then peeled off from the container and filtered. Recover.

  In the case of the purification method (2), for example, Soxhlet extraction is performed, and finally the above ester solvent (specifically, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, etc.) Alternatively, a method in which an alcohol solvent such as methanol, ethanol, 2-propanol or the like is added to a conjugated polymer solution obtained by extraction with a halogen-based solvent to precipitate a conjugated polymer, and the method according to the above-described method after column treatment is also included.

  In either case, the quantitative ratio of the halogen-based solvent in the conjugated polymer solution to the ester solvent or alcohol solvent to be added is v / v ratio: halogen-based solvent: ester solvent or alcohol solvent = 1: 10-1 : 0.1, especially in the range of 1: 3 to 1: 0.3 is preferable in terms of the purification effect of the conjugated polymer by removing low molecular weight substances.

[Conjugated polymer]
The conjugated polymer obtained by the method for producing a conjugated polymer of the present invention (hereinafter sometimes referred to as “conjugated polymer of the present invention”), preferably the weight average molecular weight (Mw) of the aligned conjugated polymer is Usually, it is 20K or more, more preferably 50K or more, further preferably 75K or more, and particularly preferably 100K or more. On the other hand, it is preferably 350K or less, more preferably 250K or less, further preferably 200K or less, and particularly preferably 150K or less. The range of the weight average molecular weight (Mw) of the conjugated polymer is preferable in view of increasing the light absorption wavelength and increasing the absorbance. Moreover, this range is preferable at the point which a mobility improves when it uses for the material of a photoelectric conversion element.

  Further, the PDI of the conjugated polymer of the present invention is usually 1.0 or more, preferably 1.2 or more, more preferably 1.5 or more, and further preferably 1.75 or more. On the other hand, it is usually 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less, and further preferably 2.5 or less. From the viewpoint that the low molecular weight can be removed, the PEI is preferably in this range. Moreover, this range is preferable in terms of improving mobility and element reproducibility when used as a material for a photoelectric conversion element.

  The weight average molecular weight (Mw) and PDI of the aligned conjugated polymer are determined by gel permeation chromatography (GPC). Specifically, Agilent PL-gel 10um MIXED-B (Agilent, 300 mm x 7.5 mm) is connected in series as two columns, LC-20AT manufactured by Shimadzu Corporation as a pump, CTO-20A as an oven, It can be measured by using a differential refractive index detector (manufactured by Shimadzu Corp .: RID-20A) and a UV-vis detector (manufactured by Shimadzu Corp .: SPD-20A) as a detector. As a procedure, first, 3 mg of a conjugated polymer to be measured is weighed in, for example, a 5 mL vial, and 3 mL of orthodichlorobenzene is heated and dissolved on a hot plate at 80 ° C. for 1 hour at 400 rpm. 5 μL of the solution is injected into a column kept at 80 ° C. Measurement is performed at a flow rate of 1.0 mL / min using orthodichlorobenzene as the mobile phase. LC-Solution (Shimadzu Corporation) is used for the analysis.

[Method for producing trimmer]
The method for producing a trimer according to the present invention includes the above-described monomer (2) and a monomer represented by the following formula (3) (hereinafter sometimes referred to as “monomer (3)”) in two or more transition metals. It includes a step of performing a coupling reaction in the presence of a complex catalyst, and a trimer corresponding to the trimer (1) serving as a polymerization raw material in the above-described method for producing a conjugated polymer of the present invention can be produced.

(In said formula (3), A represents the aromatic hydrocarbon group which may have a substituent, or the aromatic heterocyclic group which may have a substituent, X represents a halogen atom. .)

  In the above formula (3), A and X have the same meanings as A and X in the above formula (1), respectively, and preferred ones are also the same.

  Also, the two or more transition metal complex catalysts used in the method for producing a trimer of the present invention are the same as the two or more transition metal complex catalysts used in the method for producing a conjugated polymer of the present invention. The use ratio and the like are as described above.

Also in the trimer production method of the present invention, the above-mentioned homogeneous transition metal complex catalyst and heterogeneous transition metal complex catalyst are mixed at the same time in the reaction solvent containing the monomer (2) and the monomer (3). A coupling reaction is preferably performed.
The amount ratio of the monomer (2) and the monomer (3) during the coupling reaction is usually 1.8 or more, preferably 2.0 or more in terms of the molar ratio of the monomer (2) and the monomer (3). On the other hand, it is usually 2.5 or less, preferably 2.3 or less. By setting the quantitative ratio of the monomer (2) and the monomer (3) within the above range, the target trimer (1) can be produced in a high yield.

As the solvent used in the reaction, those mentioned above as the reaction solvent used in the production of the conjugated polymer can be used, and the monomer (2), (3) and the generated trimer are sufficiently solvented with respect to the amount of solvent used. From the viewpoint, it is usually 1 × 10 ⁻² mL or more, preferably 1 × 10 ⁻¹ mL or more, more preferably ¹ mL or more with respect to 1 g of the total weight of the monomers (2) and (3). On the other hand, in order to facilitate purification of the trimer (1) to be obtained, it is usually 1 × 10 ⁵ mL or less, preferably 1 × 10 ³ mL or less, more preferably 2 × 10 ² mL or less.

  In order to prevent deterioration of the transition metal complex catalyst to be used, the reaction atmosphere is preferably performed under an inert gas. In particular, the reaction is preferably performed in a nitrogen atmosphere or an argon atmosphere.

  Although reaction temperature is not specifically limited, Usually, it carries out at the temperature below room temperature and the boiling point of a solvent.

Although the reaction time depends on the reactivity of the monomers (2) and (3), it is usually at least 10 minutes, preferably at least 20 minutes, more preferably at least 30 minutes from the viewpoint of sufficiently completing the reaction in a short time. On the other hand, it is usually 90 minutes or less, preferably 60 minutes or less, more preferably 45 minutes or less. Usually, the reaction is completed after confirming whether the reaction is completed by a method such as using analytical GPC.
According to the present invention, the target trimer can be obtained in high yield by using two or more transition metal complex catalysts and setting the reaction time short as described above.

  The trimer obtained by the reaction is precipitated by adding an alcohol solvent such as methanol to the reaction solvent, filtered, and purified by silica gel or the like to obtain the desired trimer.

  The monomer (2) used for the production of the trimer and the conjugated polymer in the present invention is usually produced by lithiation of a cyclopentadithiophene compound represented by the following formula (2A) and then tinization.

(In the above formula (2A), R, R ³ and R ⁴ have the same meanings as in formula (2).)

At this time, as shown in Examples described later, a lithium salt obtained from a reaction between a disubstituted amine and butyl lithium, for example, a weak nucleophilic lithiation reagent such as lithium diisopropylamide (LDA) is used. by performing stepwise in a plurality of times and subsequent stanylated, and cyclopentadithiophene unreacted compound of -SnR ₃ group is not introduced, -SnR ₃ group is not introduced only one By preventing the residue of the monotin-substituted cyclopentadithiophene compound and increasing the purity of the reaction product, it is possible to increase the yield in the method for producing a trimer of the present invention, and to produce a trimer at a high yield.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.

[Example 1]
<Manufacture of distin body>

  In a 500 mL three-necked flask, compound 1 (14.1 g, 224 mmol) was placed under a nitrogen atmosphere, dissolved in tetrahydrofuran (THF, 100 mL), and cooled to -78 ° C. Further, a tetrahydrofuran / hexane solution of lithium diisopropylamide (LDA) (manufactured by Kanto Chemical Co., 1.04M, 26 mL, 1.2 eq) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 20 minutes. Again, it cooled to -78 degreeC, the tetrahydrofuran solution (The product made by TCI, 5.5g / THF7.5mL, 1.2eq) of trimethyltin chloride was dripped, and it heated up to room temperature, and stirred for 20 minutes. The mixture was cooled again to −78 ° C., a tetrahydrofuran / hexane solution of lithium diisopropylamide (LDA) (manufactured by Kanto Chemical Co., 1.04 M, 26 mL, 1.2 eq) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 20 minutes. . Again, it cooled to -78 degreeC, the tetrahydrofuran solution (The product made by TCI, 5.5g / THF7.5mL, 1.2eq) of trimethyltin chloride was dripped, and it heated up to room temperature, and stirred for 20 minutes. The mixture was cooled again to −78 ° C., a tetrahydrofuran / hexane solution of lithium diisopropylamide (LDA) (manufactured by Kanto Chemical Co., 1.04M, 26 mL, 1.2 eq) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 20 minutes. . The mixture was cooled again to −78 ° C., a tetrahydrofuran solution of trimethyltin chloride (manufactured by TCI, 5.5 g / THF 7.5 mL, 1.2 eq) was added dropwise, and the mixture was warmed to room temperature and stirred for 20 minutes. Water at 0 ° C. was added to the reaction solution, and the mixture was extracted with hexane at 0 ° C., and then the organic layer was washed with water. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and dried under vacuum to obtain Compound 2 quantitatively as a gray solid.

<Manufacture of trimmer>

  In a 200 mL three-necked flask, compound 2 (2.43 g, 2.55 mmol) and compound 3 (1.67 g, 5.36 mmol) were placed and purged with nitrogen. Add 50 mL of anhydrous toluene and 12.5 mL of anhydrous N, N-dimethylformamide (DMF), add 0.27 g of tetrakistriphenylphosphine palladium (0) and 0.36 g of Pd EnCat (registered trademark) 30 TPP, and heat at 100 ° C. for 30 minutes. did. Thereafter, it was cooled to 50 ° C., 100 mL of methanol was added, and the mixture was allowed to stand at room temperature with stirring. This was filtered, and the resulting crude product was purified by silica gel column chromatography to obtain Compound 4 as an orange solid in 84% yield.

<Manufacture of conjugated polymer>

  Compound 4 (232 mg, 0.231 mmol) and compound 2 (228 mg, 0.21 mmol) are added to a microwave reaction vessel, and 12 mg of tetrakistriphenylphosphine palladium (0) and Pd EnCat (registered trademark) TPP30 in a glove box. 25 mg and 4 mL of anhydrous xylene were added, and microwave reaction was performed in a nitrogen atmosphere using a microwave reactor (Biotage Microwave Initiators +) during this period, 80 ° C., 2 minutes; 130 ° C., 2 minutes; 160 ° C., 2 minutes; 200 ° C., 40 minutes; Then, it returns to room temperature, moves this microwave reaction container to a glow box, and after adding 6 mg of tetrakistriphenylphosphine palladium (0), 0.2 mL of 2-bromothiophene and 4 mL of anhydrous xylene as a terminal treatment, The microwave reaction was performed in the same manner as described above, and the temperature was raised to 80 ° C., 2 minutes; 130 ° C., 2 minutes; 160 ° C., 20 minutes; Then, it cooled to room temperature and added methanol and obtained the crude polymer.

The reaction solution was poured into methanol, and the deposited precipitate was collected by filtration.
The obtained solid was dissolved in chloroform, diamino silica gel was added, and the mixture was stirred for 10 minutes at room temperature, and then passed through a short column of acidic silica gel. The column effluent solution was concentrated, and solvent conjugate polymer 5 was precipitated with chloroform / ethyl acetate (40 mL / 30 mL, 1: 1.5 v / v) to obtain 238 mg thereof.
The obtained conjugated polymer 5 had a weight average molecular weight (Mw) of 54,000 and a molecular weight distribution (PDI) of 2.4.

[Example 2]
In a 50 mL eggplant flask under a nitrogen atmosphere, compound 4 (221 mg, 0.220 mmol), compound 2 (225 mg, 0.207 mmol), tetrakis (triphenylphosphine) palladium (0) (10.4 mg), Pd EnCat (registered trademark). ) TPP30 (22 mg) and anhydrous xylene (4.6 mL) were added, and the mixture was stirred at 90 ° C for 1 hour and then at 100 ° C for 2 hours. After the reaction solution was diluted 4-fold with xylene and further stirred with heating for 0.5 hour, as a terminal treatment, 0.2 mL of 2-bromothiophene was added and stirred with heating for 1 hour, and then bromobenzene (2 mL) was added. The reaction solution was poured into methanol, and the deposited precipitate was collected by filtration.

The obtained solid was dissolved in chloroform, diamino silica gel was added, and the mixture was stirred for 10 minutes at room temperature, and then passed through a short column of acidic silica gel. The column effluent solution was concentrated, reprecipitation was performed using chloroform / ethyl acetate as a solvent, and the deposited precipitate was separated by filtration to obtain 246 mg of conjugated polymer 5.
The obtained conjugated polymer 5 had a weight average molecular weight (Mw) of 60,000 and a molecular weight distribution (PDI) of 2.1.

[Comparative Example 1]
The conjugated polymer 5 was produced according to Non-Patent Document 1 (Chem. Commun. 2106, 52, 3207).
Compound 4 (232 mg, 0.231 mmol) and Compound 2 (228 mg, 0.21 mmol) were added to the same microwave reactor as used in Example 1, and tetrakistriphenylphosphine palladium (0 ) 12 mg and 4 mL of anhydrous xylene were added, and the microwave reaction was carried out in the same manner as in Example 1. The temperature was raised to 80 ° C., 2 minutes; 130 ° C., 2 minutes; 160 ° C., 2 minutes; It was. Thereafter, the temperature is returned to room temperature, and the microwave reaction vessel is transferred to a glow box. After adding 6 mg of tetrakistriphenylphosphine palladium (0), 0.2 mL of 2-bromothiophene, and 4 mL of anhydrous xylene, the microwave reaction is performed again. The temperature was raised to 80 ° C., 2 minutes; 130 ° C., 2 minutes; 160 ° C., 20 minutes; Then, it cooled to room temperature and added methanol and obtained crude polymer.

Using the Soxhray method, this crude product was continuously extracted in the order of methanol, dichloromethane, and chloroform. Only the chloroform solution was removed under reduced pressure, the solvent was removed, passed through a silica gel column, the solvent was removed again under reduced pressure, methanol was added, and the polymer was collected by filtration to obtain 260 mg.
The obtained conjugated polymer 5 had a weight average molecular weight (Mw) of 18,000 and a molecular weight distribution (PDI) of 2.9.

  From the above examples and comparative examples, according to the present invention, the trimer of the raw material for polymerizing the alignment conjugated polymer is produced in a high yield by a short-time coupling reaction, and the trimer is used to obtain a higher yield. It can be seen that a high molecular weight aligned conjugated polymer having a molecular weight distribution can be produced.

Claims (13)

Including a step of polymerizing a trimer represented by the following formula (1) and a monomer represented by the following formula (2) by a coupling reaction in the presence of two or more transition metal complex catalysts. A method for producing a conjugated polymer.

(In the above formula (1), R ¹ and R ² each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. A represents an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, and X represents a halogen atom.

(In the above formula (2), R ³ and R ⁴ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. And R represents an aliphatic hydrocarbon group.)   The method for producing a conjugated polymer according to claim 1, wherein at least one of the two or more transition metal complex catalysts is a heterogeneous transition metal complex catalyst.   The at least one of the two or more transition metal complex catalysts is a heterogeneous transition metal complex catalyst, and at least one of the transition metal complex catalysts is a homogeneous transition metal complex catalyst. A method for producing a conjugated polymer.   A step of mixing a reaction solution containing the trimer represented by the formula (1) and the monomer represented by the formula (2), and the homogeneous transition metal complex catalyst and the heterogeneous transition metal complex catalyst. The method for producing a conjugated polymer according to claim 3, wherein:   The method for producing a conjugated polymer according to any one of claims 1 to 4, wherein each of the transition metals constituting the two or more transition metal complex catalysts is palladium.   The method for producing a conjugated polymer according to any one of claims 1 to 5, wherein the conjugated polymer is an aligned conjugated polymer.   The conjugated polymer obtained by the method for producing a conjugated polymer according to any one of claims 1 to 6 is dissolved in a halogen-based solvent, and then contacted with basic silica gel and acidic silica gel. A method for purifying a conjugated polymer.   The conjugated polymer obtained by the method for producing a conjugated polymer according to any one of claims 1 to 6 is dissolved in a halogen-based solvent, and then the alcohol-based solvent or ester-based solution is added to the obtained conjugated polymer solution. A method for purifying a conjugated polymer, comprising adding a solvent to precipitate the conjugated polymer. Including a step of coupling a monomer represented by the following formula (2) and a monomer represented by the following formula (3) in the presence of two or more transition metal complex catalysts. Trimmer manufacturing method.

(In the above formula (2), R ³ and R ⁴ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. And R represents an aliphatic hydrocarbon group.)

(In said formula (3), A represents the aromatic hydrocarbon group which may have a substituent, or the aromatic heterocyclic group which may have a substituent, X represents a halogen atom. .)   The method for producing a trimer according to claim 9, wherein at least one of the two or more transition metal complex catalysts is a heterogeneous transition metal complex catalyst.   The at least one of the two or more transition metal complex catalysts is a heterogeneous transition metal complex catalyst, and at least one of the transition metal complex catalysts is a homogeneous transition metal complex catalyst. Trimmer manufacturing method.   A step of mixing a reaction solution containing the monomer represented by the formula (2) and the monomer represented by the formula (3) with the homogeneous transition metal complex catalyst and the heterogeneous transition metal complex catalyst. The method for producing a trimer according to claim 11, wherein:   The method for producing a trimer according to any one of claims 9 to 12, wherein each of the transition metals constituting the two or more kinds of transition metal complex catalysts is palladium.