JP2016164238A - NOVEL π-CONJUGATED POLYMER AND METHOD FOR PRODUCING THE SAME, AND INTERMEDIATE AND USE THEREFOR - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a π-conjugated polymer intermediate which can be converted to a variety of functional and useful π-conjugated polymers.SOLUTION: An organic polymer having a repeating unit represented by the formula (1) is subjected to Diels-Alder reaction and oxidation, to produce a variety of functional and useful π-conjugated polymers (where Rand Rare the same or different to represent a linear or branched alkyl group).SELECTED DRAWING: None

Description

  INDUSTRIAL APPLICABILITY The present invention is useful for forming organic semiconductors and high refractive materials as semiconductor elements, photoelectric conversion elements, etc., and novel π-conjugated polymers, production methods, intermediates and applications (organic semiconductors and devices using the same Etc.).

  Many organometallic compounds typified by metal phthalocyanines form a unique electronic state or a very stable molecular structure due to the bond between the organic molecule and the metal. Due to these characteristics, it has been used as an organic pigment for a long time. In recent years, responsiveness to external energy such as heat, light, and electric field has led to widespread use in the electronics field, such as photosensitive materials for electrophotographic printers and recording media such as CD-Rs. In particular, recently, its function as an organic semiconductor has attracted attention, and its use for organic transistors and organic thin-film solar cells has been studied. Since an electronic device using an organic semiconductor can be manufactured by printing, it is expected that it can be mass-produced at a lower cost than an inorganic device. However, many of the conventional organometallic compounds are insoluble or hardly soluble in a solvent, and the film formation is mainly performed by a vacuum evaporation method, so that the manufactured electronic device is expensive.

  As a polymer capable of improving such a problem, Japanese Patent Application Laid-Open No. 2013-185209 (Patent Document 1) has an arene unit and a 5-membered ring unit containing a heteroelement nucleus (such as a heterometal atom) in the main chain. A polymer (conjugated polymer), for example, an organic heteropolymer having a repeating unit represented by the following formula (A) is disclosed.

(In the formula, ring Ar represents an aromatic ring, R represents a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkylthio group, and p represents 0 or an integer of 1 to 3 is shown, and M is S, Se or Te).

  In the examples of this document, an organic heteropolymer having a repeating unit represented by the following formula (A1) is produced.

  Although the conjugated polymer described in Patent Document 1 has high conductivity (carrier mobility) despite its high molecular weight, it is useful for forming a polymer organic semiconductor. There is a need for highly efficient conjugated polymers.

  In addition, since organic heteropolymers are excellent in optical properties, they can be used for highly refractive materials. However, organic heteropolymers having a repeating unit represented by the formula (A1) in Patent Document 1 have a refractive index. Not enough.

JP 2013-185209 A (Claim 2, Example 1)

  Accordingly, an object of the present invention is to provide an intermediate of a π-conjugated polymer that can be converted into various functional and useful π-conjugated polymers, a π-conjugated polymer obtained by using this intermediate, a method for producing the same, and use thereof. There is.

  Another object of the present invention is to provide a π-conjugated polymer that is highly soluble in an organic solvent and can be formed by a simple method such as coating, a production method thereof, and an application thereof.

  Still another object of the present invention is to provide a π-conjugated polymer having a high refractive index, a method for producing the same, and use thereof.

  Another object of the present invention is to provide a method for producing a π-conjugated polymer capable of producing various π-conjugated polymers with high yield.

  Still another object of the present invention is to provide a π-conjugated polymer having high conductivity (carrier mobility) and high stability despite its high molecular weight, a method for producing the same, an organic semiconductor formed from the polymer, and The object is to provide a device (semiconductor device) using the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a π-conjugated polymer having a fluorene unit and a thiophene oxide unit in the main chain is a functional and useful variety of π-conjugated polymers. The present invention has been completed.

  That is, the organic polymer of the present invention has a repeating unit represented by the following formula (1).

(In the formula, R ¹ and R ² are the same or different and are linear or branched alkyl groups).

In the formula (1), R ¹ and R ² may be the same or different and may be a linear or branched C _4-16 alkyl group.

  The present invention also includes an organic polymer having a repeating unit represented by the following formula (2).

(Wherein R ³ and R ⁴ are the same or different and are a hydrogen atom or a linear or branched alkyl group, and R ¹ and R ² are the same as above).

  In this invention, it has a repeating unit represented by the said Formula (2) including the reaction process which reacts the organic polymer which has a repeating unit represented by the said Formula (1), and acetylenedicarboxylic acid or its dialkyl ester. An organic polymer production method is also included.

  The present invention also includes an organic polymer having a repeating unit represented by the following formula (3).

(Wherein R ¹ and R ² are the same as above).

  The present invention also includes a method for producing an organic polymer having a repeating unit represented by the formula (3), which includes an oxidation step of oxidizing the organic polymer having a repeating unit represented by the formula (1). .

  The present invention includes a composition for forming an organic semiconductor, which includes an organic polymer having a repeating unit represented by the formula (2) or (3) and an organic solvent. The present invention also includes an organic semiconductor containing an organic polymer having a repeating unit represented by the formula (2) or (3). Furthermore, the present invention includes a method for producing an organic semiconductor in which the composition is applied to at least one surface of a substrate and dried to form an organic semiconductor.

  The present invention also includes an electronic device including an organic polymer having a repeating unit represented by the formula (2) or (3). This electronic device may be a kind selected from a photoelectric conversion element, a switching element, and a rectifying element.

  In the present invention, by combining a fluorene unit and a thiophene oxide unit with the main chain of the π-conjugated polymer, it can be easily converted into various functional and useful π-conjugated polymers as intermediates. In addition, when a long alkyl chain is introduced into the side chain, the solubility in an organic solvent can be improved, so that an organic semiconductor can be formed into a coating composition by a simple method such as coating. In addition, because of having a fluorene skeleton, the refractive index can be improved and it can be used as a high refractive material. Furthermore, various π-conjugated polymers can be produced with high yield. In particular, although the molecular weight is high, the conductivity (carrier mobility) is high and the stability is high, so that it is suitable as an organic semiconductor and a device (semiconductor device) using the organic semiconductor.

[Intermediate]
The organic polymer [organic polymer (1)] having a repeating unit represented by the formula (1) is used as an intermediate. In the formula (1), R ¹ and R ² are useful for imparting solvent solubility. Examples of the alkyl group represented by R ¹ and R ² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, neopentyl group, Examples thereof include linear or branched alkyl groups such as hexyl group, heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decanyl group, undecanyl group, and dodecanyl group. The alkyl group is usually a linear or branched C _4-16 alkyl group, preferably a linear or branched C _6-12 alkyl group, more preferably a linear or branched C _6-10. An alkyl group (particularly a linear C _6-10 alkyl group such as an n-octyl group). R ¹ and R ² may be different but are usually the same.

  The organic polymer (1) only needs to contain the repeating unit (1), and the proportion of the repeating unit (1) may be 10 mol% or more with respect to all units constituting the organic polymer. However, from the viewpoint of improving electrical conductivity and high refractive index, the repeating unit (1) may be contained as a main unit, for example, 50 to 100 mol%, preferably 60 to 100 mol% (for example, 70). ˜99 mol%), more preferably about 80 to 100 mol% (particularly 80 to 95 mol%). As long as the other repeating units are within the range not impairing the effects of the present invention, a unit copolymerizable with the repeating unit (1) can be used.

The molecular weight of the organic polymer (1) is not particularly limited. For example, when measured by gel permeation chromatography (GPC), the number average molecular weight is 1 × 10 ³ to 1 × 10 ⁵ , preferably 3 in terms of polystyrene. It may be about × 10 ^{3 to} 5 × 10 ⁴ , more preferably about 5 × 10 ³ to 1 × 10 ⁴ (particularly 6 × 10 ³ to 8 × 10 ³ ). The molecular weight distribution (Mw / Mn) is, for example, 1 to 5, preferably 1.5 to 4.5, and more preferably about 2 to 4.

  Although the organic polymer (1) is often linear, it may have a branched structure if necessary.

  The organic polymer (1) is obtained by reacting a diethynylfluorene compound and a low-valent titanium complex by a conventional method, for example, the production method described in Patent Document 1.

  The organic polymer (1) can be converted into various π-conjugated polymers due to the highly selective reactivity of the thiophene-1-oxide skeleton. For example, it can be converted into various π-conjugated polymers using Diels-Alder reaction of thiophene-1-oxide skeleton or oxidation reaction of sulfur atom.

  In the Diels-Alder reaction, it can be reacted with various dienophiles (parent diene compounds). For example, an olefin having an electron-withdrawing group (for example, a formyl group, an alkoxycarbonyl group, an acid anhydride group, a cyano group, etc.) It can be reacted with a dienophile such as a compound or an acetylene compound. Among these dienophiles, compounds having an ethylenically unsaturated bond (eg, maleic anhydride, norbornene, etc.) and acetylene compounds (eg, acetylenediol or derivatives thereof, acetylenedicarboxylic acid or derivatives thereof, etc.) are widely used and reacted. Acetylene compounds are preferred from the standpoint of properties, and dialkyl acetylenedicarboxylates are particularly preferred from the standpoints of reactivity and handling properties. By reacting the organic polymer (1) with a dialkyl acetylenedicarboxylate and Diels-Alder reaction, an organic polymer [organic polymer (2)] having a repeating unit represented by the formula (2) is obtained.

  On the other hand, in the oxidation reaction of sulfur atoms, the organic polymer (1) is oxidized to obtain an organic polymer [organic polymer (3)] having a repeating unit represented by the formula (3). it can.

[Organic polymer having a repeating unit represented by formula (2)]
In the formula (2), examples of the alkyl group of R ³ and R ⁴ constituting the alkyl ester (alkoxycarbonyl) group include a linear or branched alkyl group exemplified by R ¹ and R ^2. It can be illustrated. R ³ and R ⁴ are preferably an alkyl group rather than a hydrogen atom from the viewpoint of solubility in an organic solvent and the like, and a C _1-4 alkyl group such as a methyl group or an ethyl group (particularly an ethyl group such as a C _2-3). Alkyl groups) are particularly preferred.

  The organic polymer (2) only needs to contain the repeating unit (2), and the ratio of the repeating unit (2) may be 10 mol% or more with respect to all units constituting the organic polymer. However, the repeating unit (2) may be included as a main unit from the viewpoint of improving conductivity and high refractive index, for example, 50 to 100 mol%, preferably 60 to 100 mol% (for example, 70 to 99 mol%), more preferably about 80 to 100 mol% (for example, 80 to 95 mol%). As long as the other repeating units are within a range not impairing the effects of the present invention, a unit copolymerizable with the repeating unit (2) can be used.

The organic polymer (2) is characterized by a relatively large molecular weight. The molecular weight of the organic polymer (such as the organic polymer before doping) is not particularly limited. For example, when measured by gel permeation chromatography (GPC), the number average molecular weight is 1 × 10 ³ to 1 × 10 in terms of polystyrene. ⁵ , preferably 3 × 10 ^{3 to} 5 × 10 ⁴ , more preferably about 5 × 10 ³ to 1 × 10 ⁴ (particularly 6 × 10 ³ to 8 × 10 ³ ). The molecular weight distribution (Mw / Mn) is, for example, 1 to 5, preferably 1.5 to 4, and more preferably about 2 to 3.5.

  The organic polymer (2) is often linear, but may have a branched structure if necessary.

  The organic polymer (2) has a structure in which a fluorene ring having an alkyl chain and a benzene ring are conjugatedly bonded (π-electron conjugated bond), and thus exhibits semiconductor characteristics and also has a fluorene skeleton. Is also expensive. Furthermore, since it has an alkyl ester group in the side chain, it has excellent solubility in organic solvents.

  In addition, a structure film in which electron transfer between molecules is easy is obtained because of stacking between main chains after film formation. Further, even if there is an alkyl chain in the polymer, stacking is not hindered because the alkyl chain is arranged in parallel with the stacking direction (vertical direction). For this reason, the obtained film functions effectively as an organic semiconductor.

  The organic polymer (2) is obtained through a reaction process (Diels-Alder reaction) in which the organic polymer (1) is reacted with acetylenedicarboxylic acid or a dialkyl ester thereof.

Examples of dialkyl esters of acetylenedicarboxylic acid include dimethyl acetylenedicarboxylate, diethyl acetylenedicarboxylate, diisopropyl acetylenedicarboxylate, dibutyl acetylenedicarboxylate, dihexyl acetylenedicarboxylate, dioctyl acetylenedicarboxylate, and di-2-ethylhexyl acetylenedicarboxylate. And acetylenedicarboxylic acid di-C _1-12 alkyl. These dialkyl acetylenedicarboxylates and acetylenedicarboxylic acids can be used alone or in combination of two or more. Of these, acetylene dicarboxylic acid di C _1-4 alkyl (especially acetylene dicarboxylic acid di C _2-3 alkyl), such as acetylene dicarboxylic acid diethyl are preferred.

  The proportion of acetylenedicarboxylic acid or dialkyl ester is, for example, 0.5 to 3 mol, preferably 0.8 to 2 mol, more preferably, per 1 mol of the repeating unit (1) constituting the organic polymer (1). Is about 1 to 1.8 mol (particularly 1.2 to 1.6 mol).

  The reaction is usually performed in the presence of a solvent capable of dissolving the organic polymer (1). Examples of the solvent include hydrocarbons (for example, aliphatic hydrocarbons such as hexane, and alicyclic rings such as cyclohexane). Aromatic hydrocarbons such as aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (such as chloroform, dichloromethane, and trichloroethane), ethers (chain ethers such as diethyl ether, diisopropyl ether, and cyclopentyl methyl ether), dioxane , Cyclic ethers such as tetrahydrofuran), ketones (acetone, methyl ethyl ketone, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethyl) Acetamide), nitriles (eg If, acetonitrile, propionitrile and the like), sulfoxides (e.g., dimethyl sulfoxide), pyrrolidones (e.g., 2-pyrrolidone, 3-pyrrolidone, N- methyl-2-pyrrolidone, etc.), and others. These organic solvents can be used alone or as a mixed solvent.

  The amount of the solvent used can be selected from a range that does not impair the reactivity. For example, the concentration of the organic polymer (1) is 0.01 to 30% by weight, preferably 0.05 to 20% by weight (particularly 0.1 It may be in a range of about 10 wt% to 10 wt%.

  The reaction may be performed in the presence of a conventional catalyst (such as a Lewis acid) or may be performed in the absence of a catalyst. The reaction may be performed under heating or at room temperature. Furthermore, the reaction may be performed in an inert gas (eg, argon gas) atmosphere.

  After completion of the reaction, the organic polymer (2) can be obtained by a conventional separation and purification method such as concentration, decantation, reprecipitation, chromatography, and the like.

[Organic polymer having a repeating unit represented by formula (3)]
The organic polymer (3) only needs to contain the repeating unit (3), and the proportion of the repeating unit (3) may be 10 mol% or more with respect to the total units constituting the organic polymer. However, it is sufficient that the repeating unit (3) is contained as a main unit from the viewpoint of improving conductivity and high refractive index, for example, 50 to 100 mol%, preferably 60 to 100 mol% (for example, 70 to 99 mol%), more preferably about 80 to 100 mol% (for example, 80 to 95 mol%). As long as the other repeating units are within the range not impairing the effects of the present invention, a unit copolymerizable with the repeating unit (3) can be used.

The organic polymer (3) is characterized by a relatively large molecular weight. The molecular weight of the organic polymer (such as the organic polymer before doping) is not particularly limited. For example, when measured by gel permeation chromatography (GPC), the number average molecular weight is 1 × 10 ³ to 1 × 10 in terms of polystyrene. ⁵ , preferably 3 × 10 ^{3 to} 5 × 10 ⁴ , more preferably about 5 × 10 ³ to 1 × 10 ⁴ (particularly 6 × 10 ³ to 8 × 10 ³ ). The molecular weight distribution (Mw / Mn) is, for example, 1 to 5, preferably 1.5 to 4, and more preferably about 2 to 3.5.

  The organic polymer (3) is often linear, but may have a branched structure if necessary.

  The organic polymer (3) has a structure in which a fluorene ring having an alkyl chain and a thiophene ring are conjugatedly bonded (π-electron conjugated bond). That is, since a 5-membered ring structure containing a hetero atom (sulfur atom) is formed in the main chain skeleton, self-aggregation is weakened and a 5-membered ring structure is formed via an aromatic ring. It may have excellent semiconductor characteristics because the unique electronic state due to the organic-hetero sulfur atom bond is maintained throughout the main chain. In addition, since the sulfur atom is oxidized to the oxide or dioxide state, the stability of the organic polymer is also high. Further, by converting from an electron-donating thiophene to an electron-accepting thiophene oxide or thiophene dioxide, the molecule has a narrow energy band gap. Furthermore, the refractive index is high because it has a fluorene skeleton.

  As with the organic polymer (2), the organic polymer (3) can provide a structure film in which electron transfer between molecules is easy after film formation, and the obtained film functions effectively as an organic semiconductor. .

The organic polymer (3) is obtained through an oxidation process for oxidizing the organic polymer (1). As an oxidation method, oxidation may be performed using a conventional oxidizing agent. As the oxidizing agent, for example, various inorganic or organic peroxides can be used. From the viewpoint of handleability, organic peroxides (in particular, C _6-20 aromatics such as perbenzoic acid and metachloroperbenzoic acid) are available. Group peracids) are widely used.

  The ratio of the oxidizing agent is, for example, 0.5 to 3 mol, preferably 0.8 to 2 mol, more preferably 1 to 1 with respect to 1 mol of the repeating unit (1) constituting the organic polymer (1). About 8 mol (particularly 1.2 to 1.6 mol).

  The reaction is usually performed in the presence of a solvent capable of dissolving the organic polymer (1), and the solvent used in the production of the organic polymer (2) can be used as the solvent.

  The amount of the solvent used can be selected from a range that does not impair the reactivity. For example, the concentration of the organic polymer (1) is 0.01 to 30% by weight, preferably 0.05 to 20% by weight (particularly 0.1 It may be in a range of about 10 wt% to 10 wt%.

  The reaction may be carried out under heating or at room temperature. Furthermore, the reaction may be performed in an inert gas (eg, argon gas) atmosphere.

  After completion of the reaction, the organic polymer (3) can be obtained by a conventional separation and purification method such as concentration, decantation, reprecipitation, chromatography, and the like.

[Use of organic polymer]
The organic polymer obtained by converting the organic polymer (1) forms a conjugated system (π-conjugated system) with a fluorene skeleton and an aromatic ring or thiophene skeleton, and has an extremely high electron mobility. It has semiconductor characteristics. Further, since it has a fluorene skeleton, it has a high refractive index and is useful as a high refractive material. Since the organic polymer (1) itself has a fluorene skeleton and a thiophene skeleton, it can be used for an organic semiconductor or a high refractive material.

  Furthermore, among the organic polymers obtained by converting the organic polymer (1) or the organic polymer (1), an organic polymer into which a long-chain alkyl chain is introduced has excellent solubility in an organic solvent, and It has the feature of showing high semiconductor characteristics. Therefore, the present invention also includes a composition containing an organic polymer and an organic solvent, and this composition is useful for forming a thin film such as an organic semiconductor by an organic semiconductor, in particular, coating (application).

  Examples of the organic solvent include hydrocarbons (for example, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (chloroform, dichloromethane, trichloroethane, etc.), ethers, and the like. (Chain ethers such as diethyl ether, diisopropyl ether and cyclopentyl methyl ether, cyclic ethers such as dioxane and tetrahydrofuran), ketones (acetone, methyl ethyl ketone, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), amides (Eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), nitriles (eg, acetonitrile, propionitrile, etc.), sulfoxides (eg, dimethylsulfoxide, etc.) Pyrrolidones (such as 2-pyrrolidone, 3-pyrrolidone, N- methyl-2-pyrrolidone, etc.), and others. These organic solvents can be used alone or as a mixed solvent.

  The amount of the solvent used can be selected from a range that does not impair the coating property and film forming property. For example, the concentration of the organic polymer is 0.01 to 30% by weight, preferably 0.05 to 20% by weight (for example, 0.8%). The range may be about 1 to 10% by weight.

  The composition of the present invention may be prepared by a conventional method, for example, mixing an organic polymer and an organic solvent to dissolve the organic polymer, and filtering if necessary.

  The organic semiconductor may be manufactured through a step of applying the composition to a base material or a substrate (glass plate, silicon wafer, heat-resistant plastic film, etc.) and a step of drying the coating film to remove the solvent. In addition, as a coating method, for example, a conventional coating method, such as an air knife coating method, a roll coating method, a gravure coating method, a blade coating method, a dip coating method, a spray method, a spin coating method, a screen printing method, an ink jet printing method, etc. Can be illustrated.

  The thickness of the organic semiconductor is appropriately selected depending on the application, and may be, for example, 1 to 5000 nm, preferably 30 to 1000 nm, and more preferably about 50 to 500 nm.

  The organic semiconductor of the present invention may be an n-type semiconductor, a p-type semiconductor, or an intrinsic semiconductor. The organic semiconductor of the present invention has a photoelectric conversion ability, and can increase the mobility of electrons and holes generated by light absorption, for example, and can improve the photoelectric conversion rate. Therefore, the organic semiconductor of the present invention includes a photoelectric conversion device or a photoelectric conversion element (such as a solar cell element or an organic electroluminescence (EL) element), a rectifier element (diode), a switching element or a transistor [top gate type, bottom gate type ( Suitable for applications such as top contact type, bottom contact type).

  As a typical device, a solar cell has a structure in which a surface electrode is laminated on a pn junction type semiconductor. For example, a solar cell can be formed by laminating an organic semiconductor film on a p-type silicon semiconductor and laminating a transparent electrode (such as an ITO electrode) on the organic semiconductor film. In such a solar cell, a high open circuit voltage and a short circuit current can be obtained.

  In addition, organic EL forms a light-emitting layer in which an electron transport material and a hole transport material are dispersed in an organic polymer (light-emitting polymer) as necessary on a transparent electrode (ITO electrode, etc.). The structure which laminated | stacked the electrode (metal electrode etc.) on the layer can be illustrated.

  Furthermore, the organic thin film transistor is composed of a gate electrode layer, a gate insulating layer, a source / drain electrode layer, and an organic semiconductor layer. The organic thin film transistor can be classified into a top gate type and a bottom gate type (top contact type and bottom contact type) depending on the laminated structure of these layers. For example, an organic semiconductor film is formed on a gate electrode (such as a p-type silicon wafer on which an oxide film is formed), and a source / drain electrode (gold electrode) is formed on the organic semiconductor film, whereby a top contact type electric field is formed. An effect transistor can be manufactured.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

In Examples, diethyl ether was used after being dried with sodium and distilled under a nitrogen atmosphere or an air stream. Methylene chloride was used after being dried over diphosphorus pentoxide and distilled under a nitrogen atmosphere or a stream of air. Tetraisopropoxytitanium (Ti (OPr ⁱ ) ₄ ) and phenyldichlorophosphine were purified by vacuum distillation. Moreover, the characteristic of the obtained polymer was measured with the following method.

[ ¹ H-NMR spectrum]
¹ H-NMR spectrum was measured with a 300 MHz ¹ H-NMR (“JNM-ECP300” manufactured by JEOL Ltd.) apparatus using tetramethylsilane (TMS) as an internal standard and CDCl ₃ as a solvent.

  Example 1

(In the formula, R ^1a and R ^2a represent an n-octyl group).

The polymer having the repeating unit represented by the formula (1a) was synthesized according to the method described in the Journal of Organic Synthetic Chemistry Vol.66 No.5 2008 using the organic titanium polymer as a precursor. That is, 2,7-diethynyl-9,9-dioctylfluorene (0.24 g, 0.500 mmol) and tetraisopropoxy titanium (Ti (OPr ⁱ ) ₄ ) (0.20 g, 0.700 mmol) were added under an argon atmosphere. Dissolve in diethyl ether (20 ml) and stir the solution at −78 ° C. while stirring the solution against diethyl ether solution of isopropylmagnesium chloride ( ⁱ PrMgCl) (1.0 N, 1.25 ml, 1.25 mmol). Was added. Thereafter, the temperature was gradually raised to −50 ° C., followed by stirring for 12 hours. After stirring, thionyl chloride (0.083 g, 0.7 mmol) was added at this temperature, the temperature was raised to room temperature, and the mixture was further stirred for 3 hours. After completion of the reaction, water (20 ml) was added, the organic layer was recovered, and the aqueous layer was further extracted three times with methylene chloride (30 ml). The solvent was concentrated under reduced pressure, and then dissolved in a small amount of dichloromethane and reprecipitated in hexane (100 ml) to obtain a red polymer (1a) in a yield of 74% (0.22 g, 0.37 mmol unit (repeating unit (1a)). mmol)). ¹ H-NMR spectrum data of the obtained polymer (1a) are shown.

^{_{1 H-NMR: (300MHz,}} CDCl 3, ppm) 0.45-1.75 (-CH 2 -C 7 H 15, 30H), 1.93 (br, -C H 2 -C 7 H 15, 4H ), 7.05 (br, S—C═C H , 2H), 7.68-7.83 (aromatic, 6H) ppm.

  When the molecular weight of the polymer (1a) was measured by gel permeation chromatography (GPC) (solvent: THF), the number average molecular weight and molecular weight distribution were Mn = 7900 and Mw / Mn = 3.8 in terms of polystyrene. .

  Example 2

(Wherein R ^1a and R ^2a are the same as above).

Under an argon atmosphere, the polymer (1a) obtained in Example 1 (0.049 g, 0.10 mmol unit) and diethyl acetylenedicarboxylate (0.025 g, 0.15 mmol) were dissolved in methylene chloride (5 ml), and For 2 hours. After completion of the reaction, the yellow polymer (2a) having the repeating unit represented by the formula (2a) was obtained in a yield of 79% (0.048 g, 0.079 mmol unit (repeating) by reprecipitation in hexane (100 ml). Unit (2a) mmol)). ¹ H-NMR spectrum data of the obtained polymer (2a) are shown.

^{_{1 H-NMR: (300MHz,}} CDCl 3, ppm) 0.45-1.75 (-CH 2 -C 7 H 15 and -COOCH 2 -C H 3, 36H), 1.93 (br, -C H _{2 -C 7 H 15, 4H)} , 4.06 (br, -COOC H 2 -CH 3, 4H), 7.35-7.45 (aromatic, 4H), 7.52-7.81 (aromatic, 4H) ppm.

  When the molecular weight of the polymer (2a) was measured by gel permeation chromatography (GPC) (solvent: THF), the number average molecular weight and molecular weight distribution were Mn = 7500 and Mw / Mn = 2.9 in terms of polystyrene. .

  Example 3

(Wherein R ^1a and R ^2a are the same as above).

Under an argon atmosphere, the polymer (1a) obtained in Example 1 (0.049 g, 0.10 mmol unit) and metachloroperbenzoic acid (0.026 g, 0.15 mmol) were dissolved in methylene chloride (5 ml), and For 6 hours. After completion of the reaction, a red polymer (3a) having a repeating unit represented by the formula (3a) was obtained in a yield of 88% (0.044 g, 0.088 mmol unit (repeated) by reprecipitation in hexane (100 ml). Unit (3a) mmol)). ¹ H-NMR spectrum data of the obtained polymer (3a) are shown.

^{_{1 H-NMR: (300MHz,}} CDCl 3, ppm) 0.45-1.75 (-CH 2 -C 7 H 15, 30H), 1.93 (br, -C H 2 -C 7 H 15, 4H ), 7.17 (br, S—C═C H , 2H), 7.70-7.91 (aromatic, 6H) ppm.

  When the molecular weight of the polymer (3a) was measured by gel permeation chromatography (GPC) (solvent: THF), the number average molecular weight and molecular weight distribution were Mn = 7100 and Mw / Mn = 3.1 in terms of polystyrene. .

  The organic polymer of the present invention is a π-electron conjugated polymer, and is useful for forming an organic semiconductor (polymer organic semiconductor) having low resistance and high conductivity. Organic semiconductors include various devices such as rectifying elements (diodes), switching elements or transistors [junction transistors (bipolar transistors), field effect transistors (unipolar transistors), etc.], photoelectric conversion elements (solar cell elements, organic EL elements). Device).

  In addition, since the organic polymer of the present invention has a high refractive index, it is also used for high refractive materials for various optical applications (for example, lenses for electrical / electronic or precision equipment, optical equipment, lenses for cameras, glasses, etc.). it can.

Claims (11)

An organic polymer having a repeating unit represented by the following formula (1).

(Wherein R ¹ and R ² are the same or different and are linear or branched alkyl groups) The organic polymer according to claim 1, wherein, in the formula (1), R ¹ and R ² are the same or different and are linear or branched C _4-16 alkyl groups. An organic polymer having a repeating unit represented by the following formula (2).

(Wherein R ³ and R ⁴ are the same or different and are a hydrogen atom or a linear or branched alkyl group, and R ¹ and R ² are the same as above)   The method for producing an organic polymer according to claim 3, further comprising a reaction step of reacting the organic polymer according to claim 1 or 2 with acetylenedicarboxylic acid or a dialkyl ester thereof. An organic polymer having a repeating unit represented by the following formula (3).

(Wherein R ¹ and R ² are the same as above)   The manufacturing method of the organic polymer of Claim 5 including the oxidation process which oxidizes the organic polymer of Claim 1 or 2.   A composition for forming an organic semiconductor, comprising the organic polymer according to claim 3 or 5 and an organic solvent.   An organic semiconductor comprising the organic polymer according to claim 3.   The manufacturing method of the organic semiconductor which apply | coats the composition of Claim 7 to at least one surface of a base material, and dries and forms an organic semiconductor.   An electronic device comprising the organic polymer according to claim 3.   The electronic device according to claim 10, which is a kind selected from a photoelectric conversion element, a switching element, and a rectifying element.