JP2008266607A - Method for producing polymer of iso-indoles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing polymers of iso-indoles without using iso-indoles as starting materials, which require complicated handling and are difficult to obtain. <P>SOLUTION: The method for producing a polymer of iso-indoles having a repeating unit represented by formula (2) comprises subjecting phthalonitriles represented by formula (1) to catalytic hydrogenation in the presence of acid, where Z represents a halogen atom, R<SP>1</SP>, OR<SP>2</SP>, or SR<SP>3</SP>(where R<SP>1</SP>, R<SP>2</SP>, and R<SP>3</SP>each independently represents alkyl, aryl, or alkyl aryl) and p represents an integer 0 to 4. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a conductive polymer (specifically, an isoindole polymer).

  Isoindole polymers are known to have superior properties compared to other conductive polymers. For example, Patent Document 1 describes that polyisoindole has higher stability than polyacetylene and is less likely to be dedoped than polythiophene. Therefore, isoindole polymers are expected to be applied to a wide range of applications such as organic thin film transistors, organic solar cells, organic EL, electrophotographic photoreceptors, photorefractive materials, secondary batteries, capacitors, antistatic agents, and electrochromic materials. ing.

As a method for producing this isoindole polymer, oxidative polymerization of isoindoles (or their reduced isoindolines) has been known (for example, Patent Documents 1 and 2). However, isoindoles which are starting materials are unstable and are difficult to handle. Furthermore, isoindoles themselves have not been readily available. This is because the conventionally known methods for producing isoindoles consist of a multi-step reaction process, and isoindoles cannot be easily produced.
JP-A-62-270621 Japanese Unexamined Patent Publication No. 63-223031

  The present invention has been made paying attention to the above-mentioned circumstances, and the object thereof is to use isoindole polymers without using isoindoles which are difficult to handle and difficult to obtain as starting materials. It is to provide a method of manufacturing.

  The present invention that has achieved the above object includes a repeating unit represented by the following formula (2), characterized in that the phthalonitrile represented by the following formula (1) is catalytically hydrogenated in the presence of an acid. It is a manufacturing method of the isoindole polymer which has. In the present invention, the “polymer” means “one having 2 or more repeating units”.

In the above formula, Z represents a halogen atom, R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ each independently represents an alkyl, aryl or alkylaryl group), p represents an integer of 0 to 4.

  In the present invention, (I) at least one selected from the group consisting of acetic acid, trifluoroacetic acid, phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid is used as the acid, (II) a palladium catalyst, a rhodium catalyst, a platinum catalyst and In a preferred embodiment, at least one selected from the group consisting of nickel catalysts is used as a catalyst for catalytic hydrogenation.

  Moreover, the manufacturing method which manufactures the isoindole polymer which has a repeating unit shown by following formula (4) using the phthalonitrile shown by following formula (3) as a preferable one aspect | mode of this invention is mentioned.

In the above formula, X represents a halogen atom, Y represents R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ each independently represents an alkyl, aryl or alkylaryl group) ), M represents an integer of 1 to 4 and n represents an integer of 0 to 3 on condition that m + n ≦ 4.

  In the following, “phthalonitrile represented by the above formula (1) (or (3))” is referred to as “phthalonitrile (1) (or (3))” and “the following formula (2) (or ( The “isoindole polymer having a repeating unit represented by 4))” may be abbreviated as “isoindole polymer (2) (or (4))”.

  By using phthalonitriles, which are more stable than isoindoles and easily available, as starting materials, it is possible to produce isoindole polymers at a simpler and lower cost than conventional production methods.

  One feature of the process for producing an isoindole polymer of the present invention is that phthalonitrile is used as a starting material instead of isoindoles. These phthalonitriles are much more stable and easier to handle than isoindoles. Phthalonitriles are sold as raw materials for pigments and the like and can be easily obtained.

  As a result of intensive studies by the present inventors, it was surprisingly found that an isoindole polymer can be produced by catalytic hydrogenation of phthalonitriles in the presence of an acid. As this reaction mechanism, one represented by the following chemical formula is presumed. However, the present invention is not limited to this estimation mechanism.

  As shown in the above chemical formula, intermediate (a) (1-imino-1H-isoindoles) is formed by first adding hydrogen to the cyano group of phthalonitrile (1) and then cyclizing. The By adding an acid (proton in the above chemical formula) to the tertiary amine nitrogen of the intermediate (a), the intermediate (b) is formed. On the other hand, by adding hydrogen to the tertiary amine portion of intermediate (a), intermediate (c) (1-iminoisoindolines) is formed, and further, hydrogen is added to the imino group of intermediate (c). Addition and subsequent elimination of the amino group as ammonia forms intermediate (d) (2H-isoindoles). Thus, by adding either acid or hydrogen to intermediate (a), intermediate (b) or (d) is formed, and by adding these, intermediate (e) (imino group is added). A dimer having an isoindoline skeleton and an isoindole skeleton. From this intermediate (e), the dimer (f) of 2H-isoindoles is formed by hydrogenation to the imino group and elimination of the amino group as described above (note that the dimer (f) ) Are also included within the scope of the isoindole polymers (2) of the present invention). By repeating such a reaction, it is considered that an isoindole polymer (2) having a repeating number of 2 or more is formed from the phthalonitriles (1).

  In the production method of the present invention, it is presumed that isoindoles are formed in the reaction system by reduction of the cyano group moiety as shown above, and then these are added to form an isoindole polymer. . Therefore, it is presumed that the substituent Z of the phthalonitriles (1) does not greatly affect this reaction (particularly the reduction reaction). Therefore, in the production method of the present invention, all kinds of phthalonitriles (1), more specifically, unsubstituted phthalonitrile (p = 0 in formula (1)), or phthalonitrile having any kind of substituent Z Can be used.

  The phthalonitriles (1) used in the present invention include phthalonitrile (unsubstituted phthalonitrile) or substituted phthalonitriles having a substituent such as a halogen atom as described above. Substituted phthalonitriles include those having only one substituent (for example, a halogen atom) or two or more substituents (for example, a halogen and an alkyl group).

  The halogen atom is preferably a fluorine, chlorine or bromine atom, more preferably a fluorine or chlorine atom, still more preferably a fluorine atom. In the phthalonitriles (1), a plurality of types of halogen atoms may be present simultaneously.

R ¹ , R ² and R ³ in the above formula are preferably each independently a C ₁ -C ₂₀ alkyl group, more preferably a C ₁ -C ₁₀ alkyl group, and even more preferably a C ₁ -C ₅ alkyl group; preferably C ₆ -C ₂₀ aryl group, more preferably C ₆ -C ₁₂ aryl group; or preferably C ₇ -C ₂₀ alkylaryl group, more preferably C ₇ -C ₁₅ alkylaryl group, more preferably C ₇ ~C ₁₀ alkyl aryl group. R ¹ , R ² and R ³ may contain a halogen atom on the carbon skeleton. When any one of R ¹ , OR ² and SR ³ is present as the substituent Z, the plurality of R ¹ , R ² and R ³ may be different substituents (for example, an alkyl group and an aryl group). good.

Among the phthalonitriles (1), phthalonitriles (3) having a halogen atom X are preferable. Isoindole polymers (4) produced from phthalonitriles (3) having halogen atoms (especially fluorine atoms which are strong electron-attracting groups) can be used in new applications such as n-type semiconductors. Because it is expected. In the above formula (3), the number m of halogen atoms X is preferably 2 or more, more preferably 3 or more, and still more preferably 4. Examples of the halogen atoms X, R ¹ , R ² and R ^{3 in} the above formula (3) include those described above.

  Phthalonitriles are used as raw materials for pigments and the like, and are sold from various companies (for example, Aldrich, Shinquest, Azmax Co., Ltd., or Central Pharmaceutical Co., Ltd.) and can be easily obtained. Further, phthalonitriles having various substituents can be produced from commercially available phthalonitriles by a known method.

  Examples of substituted phthalonitriles include halogen-containing phthalonitriles having only halogen atoms. Halogen-containing phthalonitrile is sold by Aldrich. In addition, commercially available halogen-containing phthalonitriles can also be produced from commercially available halogen-containing phthalonitriles by a conventionally known halogen substitution reaction.

  For example, in JP-A-2002-332254, a fluorine atom of fluorine-containing isophthalonitrile is used by using a bromating agent (for example, sodium bromide, potassium bromide and lithium bromide, preferably sodium bromide and potassium bromide). A technique for substituting with a bromine atom is disclosed. By JM Birchell, RN Haszeldlne, and JO Morley, "Polyfluoroarenes. Part XI. Reactions of Tetrafluorophthalronitrile with Nucleophilic Reagents", J. Chem. Soc. (C), 1970, p. 456-462 A technique for substituting a fluorine atom of a nitrile with a chlorine atom using LiCl is disclosed.

  Specific examples of the halogen-containing phthalonitrile include 4-fluorophthalonitrile, tetrafluorophthalonitrile, 4,5-dichlorophthalonitrile, tetrachlorophthalonitrile, 4-chloro-3,5,6-trifluorophthalonitrile, and the like. It is done. Among these, tetrafluorophthalonitrile is preferable.

Phthalonitriles having an R ¹ group as a substituent can be produced by coupling reactions well known in the field of synthetic chemistry. For example, a phthalonitrile having an R ¹ group is obtained by conducting a coupling reaction between a halogen-containing phthalonitrile and a Grignard reagent in the presence of a nickel or palladium catalyst. Can be obtained by substitution with an alkyl, aryl or alkylaryl group from This coupling reaction is well known in the field of synthetic chemistry as the Kumada-Tamao coupling. The phthalonitrile having an R ¹ group can also be obtained by conducting a coupling reaction between a halogen-containing phthalonitrile and an organic boron compound in the presence of a palladium catalyst. This coupling reaction is also well known in the field of synthetic chemistry as the Suzuki-Miyaura coupling.

Phthalonitriles having an OR ² group or SR ³ group as a substituent can be converted to a halogen atom of a halogen-containing phthalonitrile by a conventionally known method, for example, a method described in JP-A No. 2002-302477. Can be prepared by substituting with ² and / or HSR ³ . The halogen-containing phthalonitrile used in the aromatic nucleophilic substitution reaction is preferably fluorine-containing and / or chlorine-containing phthalonitrile, more preferably fluorine-containing phthalonitrile, and still more preferably tetrahedral, from the viewpoint of reactivity with the halogen substitution reaction. Fluorophthalonitrile. The nucleophilic substitution reaction of halogen-containing phthalonitrile proceeds preferentially at the 4th and 5th positions of phthalonitrile. Therefore, from the viewpoint of availability, phthalonitriles having an OR ² group or an SR ³ group can be represented by the following formula (5) or (8), particularly the following formula (6) or (7), or the following formula (9). Or the phthalonitrile shown by (10) is preferable.

In the above formulas (5) to (10), Z ¹ and Z ² each independently represent OR ² or SR ³ , and R ² and R ³ are each independently preferably a C _{1 to} C ₂₀ alkyl group, more preferably C ₁ -C ₁₀ alkyl group, more preferably a C ₁ -C ₅ alkyl group; preferably C ₆ -C ₂₀ aryl group, more preferably C ₆ -C ₁₂ aryl group; or preferably C ₇ -C ₂₀ alkylaryl groups, more preferably C ₇ -C ₁₅ alkylaryl group, more preferably represents a C ₇ -C ₁₀ alkylaryl group. R ² and R ³ may contain a halogen atom on the carbon skeleton. R ² and ³ in the above formula (9) or (10) may be the same or different, but are preferably the same.

  The acid used in the production method of the present invention is preferably an inorganic or organic proton acid. Examples of the inorganic protonic acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid; phosphoric acid such as orthophosphoric acid and pyrophosphoric acid; perhalogen acids such as perchloric acid; phosphomolybdic acid, silicomolybdic acid, Examples thereof include heteropolyacids such as phosphotungstic acid, silicotungstic acid, phosphotungstomolybdic acid, and phosphovanadmolybdic acid.

  Examples of the organic protonic acid include aryl sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid; methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, t- Alkylsulfonic acids such as butylsulfonic acid; formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, n-butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, Saturated aliphatic carboxylic acids such as caprylic acid, capric acid, lauric acid, myristic acid, cyclohexanecarboxylic acid; acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid, etc. Of unsaturated fat Group carboxylic acid; benzoic acid, phthalic acid, isophthalic acid, and aromatic carboxylic acids such as terephthalic acid.

Among the protonic acids, acetic acid, trifluoroacetic acid, phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid are preferable. When a protonic acid is used as the acid, it is recommended that the amount of proton (H ⁺ ) be equimolar or more with the starting phthalonitrile. This is because the polymerization can be promoted by using equimolar or more protons. The proton amount is preferably 1 to 10 mol, more preferably 1.05 to 7 mol, and still more preferably 1.1 to 5 mol, per 1 mol of phthalonitriles.

  In the present invention, “catalytic hydrogenation of phthalonitriles” means adding hydrogen to phthalonitriles in the presence of a catalyst. As a catalyst used for catalytic hydrogenation, a normal metal catalyst known in the technical field can be used. The metal catalyst in an amount such that the central metal of the catalyst is preferably 0.01 to 30 mol%, more preferably 0.1 to 20 mol%, still more preferably 1 to 10 mol% with respect to phthalonitriles. It is recommended to use

  Examples of the metal catalyst include a homogeneous catalyst constituted by coordination of phosphine or the like with ruthenium or rhodium. However, in view of reactivity, recovery after reaction, and ease of regeneration, it is preferable to use a heterogeneous catalyst in the present invention. Among heterogeneous catalysts, a catalyst in which a fine metal powder is supported on a carrier is preferred in order to increase the surface area and improve the catalytic activity. As a heterogeneous catalyst, for example, nickel, Raney nickel, copper-chromium oxide, ruthenium, palladium, rhodium, platinum, platinum oxide and the like, or those metal fine powders supported on a support such as activated carbon, alumina, diatomaceous earth, etc. Can be mentioned. Among these metal catalysts, a palladium catalyst, a rhodium catalyst, a platinum catalyst, and a nickel catalyst are preferable. From the viewpoint of catalytic activity, a catalyst in which palladium is supported on activated carbon is more preferable.

  When a heterogeneous catalyst is used, a catalyst activation step in which the catalyst and the protonic acid are mixed in a hydrogen atmosphere before catalytic hydrogenation may be employed as necessary. The activation temperature is usually about room temperature to 50 ° C., and the activation time is preferably 10 minutes or more, more preferably 30 minutes or more, further preferably 1 hour or more, preferably 5 hours or less, More preferably, it is 3 hours or less, More preferably, it is 2 hours or less.

  Catalytic hydrogenation is usually performed using a solvent. Although there is no limitation in particular as a solvent, The thing which can melt | dissolve the phthalonitrile which is a starting material is preferable. Solvents such as aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as THF, dioxane, cyclopentylmethyl ether, diisopropyl ether and diethyl ether; alcohols such as methanol, ethanol and propanol; methyl acetate and ethyl acetate , Esters such as propyl acetate and butyl acetate; amides such as dimethylformamide and dimethylacetamide; sulfolanes such as sulfolane, 3-methylsulfolane and 2,4-dimethylsulfolane; and formic acid, acetic acid, propionic acid and trifluoroacetic acid And the like. In the catalytic hydrogenation method, a mixed solvent of amides or acetic acids and water can also be used. A solvent can be used individually or in combination of 2 or more types. Among these solvents, solvents having high solubility of isoindole polymers, such as ethyl acetate, propyl acetate, dimethylformamide, dimethylacetamide, sulfolane, 3-methylsulfolane and 2,4-dimethylsulfolane are preferable. When a solvent is used, the concentration of phthalonitriles is preferably about 0.01 to 5M, more preferably about 0.05 to 1M.

  Although the temperature of catalytic hydrogenation is influenced also by the solvent etc. to be used, Preferably it is 0 degreeC or more, More preferably, it is 20 degreeC or more, Preferably it is 150 degrees C or less, More preferably, it is 120 degrees C or less. The time for the catalytic hydrogenation reaction is preferably 30 minutes or longer, more preferably 1 hour or longer, even more preferably 2 hours or longer, preferably 48 hours or shorter, more preferably 24 hours or shorter. In order to promote catalytic hydrogenation, it is preferable to use hydrogen under pressure. The hydrogen pressure is preferably 1.1 atmospheres or more, more preferably 1.5 atmospheres or more, and further preferably 2 atmospheres or more. However, the hydrogen pressure is preferably 5 atm or less, more preferably 3 atm or less, due to equipment limitations.

  Catalytic hydrogenation can be performed by continuously supplying hydrogen gas to the reaction system. Alternatively, after supplying hydrogen gas to a certain pressure, the reaction system is sealed and contact hydrogenation is performed, and the hydrogen gas can be supplied again after the pressure in the system decreases as the reaction proceeds. It is desirable to reduce the pressure of the reaction system before supplying hydrogen gas. Further, in order to adsorb a large amount of hydrogen to the catalyst, it is a preferred embodiment to repeat the reduced pressure and supply of hydrogen gas a plurality of times, particularly when catalytic hydrogenation is performed in the presence of a solvent.

  The number of repeating units of the isoindole polymer to be produced is 2 or more, preferably 3 or more, more preferably 5 or more. This is because as the number of repeating units of the isoindole polymer increases and its molecular weight increases, the mechanical properties of the polymer, particularly as a polymer, improve. However, isoindole polymers having an excessively large molecular weight are difficult to produce, and the handleability of the polymer itself is reduced. Therefore, the weight average molecular weight (value by GPC measurement in terms of polystyrene) of the isoindole polymer is preferably about 1,000 to 500,000, more preferably about 3,000 to 300,000, and still more preferably 5,000 to About 100,000.

  After the isoindole polymer is produced by the production method of the present invention, doping may be performed by a known method in order to improve the conductivity of the polymer.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is possible to implement them, and both are included in the technical scope of the present invention.

Example 1: Production of (4,5,6,7-tetrafluoro-2H-isoindole) polymer A catalyst in which palladium was supported on activated carbon in a 500 ml three-necked flask (purchased from Aldrich, Pd: 10 (Mass%) 5.12 g (Pd amount: 4.81 mmol), methanol 200 ml, 3M sulfuric acid 12.5 ml (37.5 mmol) were added. Subsequently, the operation of supplying hydrogen (replacement with hydrogen) was repeated three times after reducing the pressure in the system, and then the catalyst was activated by stirring for 10 minutes at room temperature while being pressurized with a hydrogen balloon. Thereafter, a solution prepared by dissolving 10.0 g (49.98 mmol) of tetrafluorophthalonitrile in 200 ml of toluene was added to the flask, and the mixture was vigorously stirred at room temperature for 17 hours. The reaction solution was neutralized with aqueous sodium bicarbonate, and the palladium catalyst was removed by celite filtration. The filtrate was extracted by adding ethyl acetate, washed with distilled water and then saturated brine, dehydrated with anhydrous sodium sulfate, and then the extract was concentrated by an evaporator. This concentrate was purified by silica gel column chromatography (solvent: ethyl acetate), and 6.19 g (equivalent yield) of the desired (4,5,6,7-tetrafluoro-2H-isoindole) polymer. 65.5%). The average molecular weight (measured by GPC in terms of polystyrene) of the obtained polymer was Mn = 1,000 and Mw = 1,600.

Example 2: Preparation of (4,7-difluoro-5,6-bis (2,5-dimethylphenoxy) -2H-isoindole) polymer Catalyst in which palladium is supported on activated carbon in a 100 ml three-necked flask (Purchased from Aldrich, Pd: 10% by mass) 1.01 g (Pd amount: 0.94 mmol), methanol 5.1 g, 3M sulfuric acid 1.5 ml (4.5 mmol) were added. Next, the operation of supplying hydrogen (replacement with hydrogen) was repeated three times after reducing the pressure in the system, and then the catalyst was activated by stirring for 10 minutes at room temperature under pressure with a hydrogen balloon (approximately 1.1 atm). Made it. Thereafter, a solution prepared by dissolving 3.00 g (7.42 mmol) of 3,6-difluoro-4,5-bis (2,5-dimethylphenoxy) phthalonitrile in 15 ml of ethyl acetate was added to the flask, and the mixture was stirred at room temperature for 14 hours. Stir. The reaction solution was neutralized with aqueous sodium bicarbonate, and the palladium catalyst was removed by celite filtration. Toluene was added to the filtrate for extraction, washed with distilled water and then saturated brine, dehydrated with anhydrous sodium sulfate, and then the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: chloroform) to obtain the desired (4,7-difluoro-5,6-bis (2,5-dimethylphenoxy) -2H-isoindole) polymer. 1.01 g (converted yield 34.9%). The average molecular weight (measured by GPC in terms of polystyrene) of the obtained polymer was Mn = 1,800 and Mw = 2,100.

Example 3: Production of (4,7-difluoro-5,6-bis (pentafluorophenyl) -2H-isoindole) polymer A catalyst in which palladium is supported on activated carbon in a 20 ml two-necked flask (from Aldrich) Purchased, Pd: 10% by mass) 0.3 g (Pd amount: 0.28 mmol), 3 g of methanol, 0.4 ml (1.2 mmol) of 3M sulfuric acid were added. Next, the operation of supplying hydrogen (replacement with hydrogen) was repeated three times after reducing the pressure in the system, and then the catalyst was activated by stirring for 10 minutes at room temperature under pressure with a hydrogen balloon (approximately 1.1 atm). Made it. Thereafter, a solution prepared by dissolving 1.00 g (2.02 mmol) of 3,6-difluoro-4,5-bis (pentafluorophenyl) phthalonitrile in 5.1 g of ethyl acetate was added to the flask and stirred at room temperature for 14 hours. did. The reaction solution was neutralized with aqueous sodium bicarbonate, and the palladium catalyst was removed by celite filtration. Toluene was added to the filtrate for extraction, washed with distilled water and then saturated brine, dehydrated with anhydrous sodium sulfate, and then the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: chloroform), and the desired (4,7-difluoro-5,6-bis (pentafluorophenyl) -2H-isoindole) polymer was reduced to a concentration of 0. 34 g (converted yield 43.1%). The average molecular weight (measured by GPC in terms of polystyrene) of the obtained polymer was Mn = 1,300 and Mw = 1,500.

Example 4: Production of (5,6-dichloro-2H-isoindole) polymer Catalyst in which palladium was supported on activated carbon in a 200 ml three-necked flask (purchased from Aldrich, Pd: 10% by mass) 00 g (Pd amount: 0.94 mmol), 5 g of methanol, and 4.1 ml (12.3 mmol) of 3M sulfuric acid were added. Next, the operation of supplying hydrogen (replacement with hydrogen) was repeated three times after reducing the pressure in the system, and then the catalyst was activated by stirring for 10 minutes at room temperature under pressure with a hydrogen balloon (approximately 1.1 atm). Made it. Thereafter, a solution prepared by dissolving 3.00 g (15.23 mmol) of 4,5-dichlorophthalonitrile in 90 ml of ethyl acetate was added to the flask and stirred at room temperature for 14 hours. The reaction solution was neutralized with aqueous sodium bicarbonate, and washed with ethyl acetate while removing the palladium catalyst by Celite filtration. The filtrate was washed with distilled water and then with saturated brine, dehydrated with anhydrous sodium sulfate, and concentrated by an evaporator. After adding methanol to this concentrate and stirring vigorously, low molecular weight substances were removed by filtration, and 0.71 g (equivalent yield 25) of the desired (5,6-dichloro-2H-isoindole) polymer was obtained. .3%). The average molecular weight (measured by GPC in terms of polystyrene) of the obtained polymer was Mn = 5,900 and Mw = 6,900.

Example 5: Production of a (methyl-2H-isoindole) polymer (the methyl groups of the polymer are randomly present at the 5th and 6th positions)
After adding 1.00 g (Pd amount: 0.94 mmol) of a catalyst in which palladium is supported on activated carbon (purchased from Aldrich, Pd: 10% by mass) to a 200 ml three-necked flask, the inside of the system was depressurized. After performing the operation of supplying nitrogen from (nitrogen replacement), methanol (6.3 ml) and 3M sulfuric acid (4.1 ml) (12.3 mmol) were added. Next, the inside of the system was replaced with hydrogen, and the catalyst was activated by stirring for 10 minutes at room temperature while being pressurized with a hydrogen balloon (about 1.1 atm). Thereafter, a solution prepared by dissolving 4.00 g (28.14 mmol) of 4-methylphthalonitrile in 70 ml of ethyl acetate was added to the flask and vigorously stirred at room temperature for 16 hours. The reaction solution was neutralized with aqueous sodium bicarbonate, and the palladium catalyst was removed by celite filtration. The filtrate was extracted by adding ethyl acetate, washed with distilled water and then with saturated brine, dehydrated with anhydrous sodium sulfate, and then the extract was concentrated with an evaporator. Methanol was added to the concentrate and stirred, followed by filtration to recover the residue. The filtrate was dried under reduced pressure to obtain 0.8 g (converted yield: 22.01%) of the desired product (methyl-2H-isoindole) polymer. The average molecular weight (measured by GPC in terms of polystyrene) of the obtained polymer was Mn = 7,200 and Mw = 7,700.

  The production method of the present invention can produce an isoindole polymer using a phthalonitrile which is more stable and easily available than isoindole as a starting material. The isoindole polymer obtained by the production method of the present invention is useful as a conductive material, more specifically as an electrode material, a display material, an electromagnetic wave shielding material and the like in the field of organic thin film transistors and organic solar cells.

Claims (3)

A method for producing an isoindole polymer having a repeating unit represented by the following formula (2), wherein the phthalonitrile represented by the following formula (1) is catalytically hydrogenated in the presence of an acid.

[Wherein, Z represents a halogen atom, R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ each independently represents an alkyl, aryl or alkylaryl group); p represents an integer of 0 to 4. ]   The production method according to claim 1, wherein at least one selected from the group consisting of acetic acid, trifluoroacetic acid, phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid is used as the acid.   The production method according to claim 1 or 2, wherein at least one selected from the group consisting of a palladium catalyst, a rhodium catalyst, a platinum catalyst and a nickel catalyst is used as a catalyst for catalytic hydrogenation.