Method for producing fluorine-containing phthalic acid derivatives and compositions

Abstract

To provide a method for producing a fluorine-containing phthalic acid derivative capable of obtaining a fluorine-containing phthalic acid derivative by a simple step.SOLUTION: There is provided a method for producing a fluorine-containing phthalic acid derivative which is a method for producing a fluorine-containing phthalic acid derivative from a fluorine-containing aromatic compound, which comprises a step of performing the oxidation reaction of the fluorine-containing aromatic compound using an oxidation accelerator in the presence of a metal catalyst, wherein the fluorine-containing aromatic compound is a compound in which at least two alkyl groups are bonded to an aromatic ring and the oxidation accelerator includes at least one compound selected from the group consisting of an aldehyde compound and a ketone compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a fluorine-containing phthalic acid derivative and a composition thereof. [Background technology]

[0002] BACKGROUND ART Various methods for producing a fluorinated aromatic polycarboxylic acid such as a phthalic acid derivative by oxidizing a fluorinated aromatic compound such as a fluorinated xylene compound with oxygen (air) have been known in the past.

[0003] For example, Patent Document 1 discloses a method for oxidizing a fluorine-containing aromatic compound having a specific structure in the presence of hydrogen bromide, and Patent Document 2 discloses a method for producing a tetracarboxylic acid compound by oxidizing a fluorine-containing xylene compound with oxygen in the presence of bromine or the like. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 1-165544 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-97168 Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure aims to provide a method for producing a fluorine-containing phthalic acid derivative, and also aims to provide a composition containing a specific compound, etc. [Means for solving the problem]

[0006] The present disclosure encompasses the configurations described in the following sections. Item 1 A method for producing a fluorine-containing phthalic acid derivative from a fluorine-containing aromatic compound, comprising the steps of: carrying out an oxidation reaction of the fluorine-containing aromatic compound using an oxidation promoter in the presence of a metal catalyst, The fluorine-containing aromatic compound is represented by the following general formula (1):

[0007] [ka]

[0008] (In formula (1), R 1 and R 2 are the same or different and represent a fluorine-containing alkyl group; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are the same or different and represent hydrogen or an alkyl group having 1 to 12 carbon atoms; R 3 , R 4 , R 5 , R 6 and R 7 At least two of R are alkyl groups having 1 to 12 carbon atoms; 8 , R 9 , R 10 , R 11 and R 12 At least two of R are alkyl groups having 1 to 12 carbon atoms; 7 and R 8 may join together to form an -O- bond) is a compound represented by A method for producing a fluorine-containing phthalic acid derivative, wherein the pro-oxidant contains at least one compound selected from the group consisting of aldehyde compounds and ketone compounds. Section 2 The fluorine-containing aromatic compound is a fluorine-containing xylene derivative, In the formula (1), R 3 , R 4 , R 5 , R 6 and R 7 At least two of R are methyl groups. 8 , R 9 , R 10 , R 11 and R12 Item 2. The method according to Item 1, wherein at least two of the groups are methyl groups. Section 3 In the formula (1), R 1 and R 2 is a trifluoromethyl group, R 4 , R 5 , R 10 and R 11 is a methyl group, R 3 , R 6 , R 7 , R 8 , R 9 and R 12 is hydrogen. Section 4 Item 4. The method according to any one of Items 1 to 3, wherein the aldehyde compound has 1 to 10 carbon atoms. Section 5 Item 5. The method according to Item 4, wherein the aldehyde compound is at least one selected from the group consisting of paraldehyde, acetaldehyde, propionaldehyde, and metaldehyde. Section 6 Item 6. The method according to Item 5, wherein the aldehyde compound is paraldehyde. Section 7 Item 7. The method according to any one of Items 1 to 6, wherein the ketone compound has 3 to 10 carbon atoms. Section 8 Item 7. The method according to Item 7, wherein the ketone compound is acetone or methyl ethyl ketone. Item 9. The method according to any one of items 1 to 8, wherein the pro-oxidant is used in an amount of 1 equivalent or more relative to the functional group to be oxidized in the fluorine-containing aromatic compound. Section 10 Item 4. The method according to Item 2 or 3, wherein the pro-oxidant is used in an amount of 2 equivalents or more per xylene skeleton of the fluorine-containing xylene derivative. Section 11 Item 11. The method according to any one of items 1 to 10, wherein the metal catalyst contains a transition metal. Section 12 Item 12. The method according to Item 11, wherein the transition metal comprises one or more selected from the group consisting of Mn, Co, Zr, Rh, Pd, Ru, Pt, Ni, Fe, W, and Cu. Item 13 Item 13. The method according to item 12, wherein the transition metal comprises Co. Item 14 Item 14. The method according to any one of items 1 to 13, wherein the oxidation reaction is carried out at 140° C. or lower. Item 15 15. A method for producing an anhydride of a fluorine-containing phthalic acid derivative, comprising a step of dehydrating the fluorine-containing phthalic acid derivative obtained by the production method according to any one of items 1 to 14 in the presence of acetic anhydride. Item 16 Item 17 is a method for purifying an anhydride of a fluorine-containing phthalic acid derivative, comprising a step of recrystallizing the anhydride using a mixed solvent containing one or more solvents selected from the group consisting of ketone compounds, ether compounds, and nitrile compounds, and acetic anhydride in an amount of 0.05 times or more based on the total mass of the solvents. Item 17. The purification method according to Item 16, wherein the step comprises dissolving a crude anhydride of a fluorine-containing phthalic acid derivative in the mixed solvent, incompletely distilling off the mixed solvent from the resulting solution, adding an aromatic hydrocarbon to crystallize the anhydride of a fluorine-containing phthalic acid derivative, and separating the crystals. Section 18 A composition comprising a metal and an anhydride of a fluorine-containing phthalic acid derivative, and not containing bromine. Section 19 Item 19. The composition according to Item 18, wherein the total content of the metals is 0.01 to 50 ppm by mass relative to the anhydride of the fluorine-containing phthalic acid derivative. Section 20 Item 19. The composition according to Item 18, wherein the content of each of the metals is 0.01 to 50 ppm by mass relative to the anhydride of the fluorine-containing phthalic acid derivative. Section 21 21. The composition according to any one of items 18 to 20, wherein the metal is at least one selected from the group consisting of Na, K, Ca, Si, Co, Fe, Ni, Cr, and Mo. Section 22 22. The composition according to any one of items 18 to 21, wherein the metal is a transition metal. Section 23 Item 23. The composition according to Item 22, wherein the total content of the transition metals is 0.01 to 50 ppm by mass based on the anhydride of the fluorine-containing phthalic acid derivative. Section 24 Item 23. The composition according to Item 22, wherein the transition metals are each contained in an amount of 0.01 to 50 ppm by mass relative to the anhydride of the fluorine-containing phthalic acid derivative. Section 25 25. The composition according to any one of items 22 to 24, wherein the transition metal is at least one selected from the group consisting of Co, Fe, Ni, Cr, and Mo. Section 26 Contains an anhydride of a fluorine-containing phthalic acid derivative and an aliphatic carboxylic acid, The composition, wherein the content of the aliphatic carboxylic acid is 2000 ppm by mass or less based on the total mass of the anhydride and the aliphatic carboxylic acid. Section 27 A composition comprising an anhydride of a fluorine-containing phthalic acid derivative and a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring. Section 28 A composition comprising an anhydride of a fluorine-containing phthalic acid derivative and at least one compound selected from the group consisting of an aldehyde compound and a ketone compound. Section 29 an anhydride of a fluorine-containing phthalic acid derivative; A composition comprising at least one compound selected from the group consisting of a compound represented by the following formula (21-1), a compound represented by the following formula (21-2), a compound represented by the following formula (21-3), a compound represented by the following formula (21-4), a compound represented by the following formula (22-1), a compound represented by the following formula (22-2), a compound represented by the following formula (22-3), a compound represented by the following formula (22-4), a compound represented by the following formula (23-1), a compound represented by the following formula (23-2), a compound represented by the following formula (23-3), and a compound represented by the following formula (23-4).

[0009] [ka]

[0010] Item 30 Contains an anhydride of a fluorine-containing phthalic acid derivative, The composition, wherein the anhydride of the fluorine-containing phthalic acid derivative has an apparent density of 0.4 g / mL or more. Item 31 Contains an anhydride of a fluorine-containing phthalic acid derivative, A composition having a fluorine ion content of 5 ppm by mass or less based on the total mass of the anhydride of a fluorine-containing phthalic acid derivative. Section 32 Contains an anhydride of a fluorine-containing phthalic acid derivative, A composition having a Hazen color scale of 150 or less. Item 33 Contains an anhydride of a fluorine-containing phthalic acid derivative, A composition having a water content of 2000 mass ppm or less based on the total mass of the anhydride of a fluorine-containing phthalic acid derivative. [Effects of the Invention]

[0011] The method for producing a fluorine-containing phthalic acid derivative according to the present disclosure can obtain a fluorine-containing phthalic acid derivative through a simple process. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present inventors have conducted extensive research to easily obtain fluorine-containing phthalic acid derivatives. First, they found that the methods disclosed in the aforementioned Patent Documents 1 and 2, etc., use bromine and the like, which makes the reactor susceptible to corrosion, necessitating the use of a special reactor. Furthermore, halogens such as bromine have adverse effects on electronic devices, so there is a need to reduce the halogen content. The methods disclosed in Patent Documents 1 and 2, etc., require a reaction in a high temperature range, which requires a lot of energy, and also has problems such as the combustion of acetic acid used in the reaction and the coloration of the product.

[0013] The production method of the present disclosure can suppress the occurrence of the above-mentioned various problems, and can easily obtain the target fluorine-containing phthalic acid derivative with a reduced halogen content.

[0014]

[0023] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, the expressions "contain" and "comprise" include the concepts of "contain," "comprise," "substantially consist," and "consist only of."

[0015] In this specification, numerical ranges indicated using "to" indicate ranges that include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper limit or lower limit of a numerical range in one stage can be arbitrarily combined with the upper limit or lower limit of a numerical range in another stage. In numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example.

[0016] 1. Manufacturing method for fluorine-containing phthalic acid derivatives The production method of the present disclosure is a method for producing a fluorinated phthalic acid derivative from a fluorinated aromatic compound, and includes a step of carrying out an oxidation reaction of the fluorinated aromatic compound using an oxidation promoter in the presence of a metal catalyst. This step will be referred to as "Step A."

[0017] In step A, the fluorine-containing aromatic compound is a compound in which an alkyl group is bonded to an aromatic ring, and the pro-oxidant includes at least one compound selected from the group consisting of aldehyde compounds and ketone compounds.

[0018] (Fluorine-containing aromatic compound) The fluorine-containing aromatic compound is a raw material for the oxidation reaction carried out in step A. The fluorine-containing aromatic compound is a compound represented by the following general formula (1).

[0019] [ka]

[0020] In formula (1), R 1 and R 2 are the same or different and represent a fluorine-containing alkyl group; R3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are the same or different and represent hydrogen or an alkyl group having 1 to 12 carbon atoms; R 3 , R 4 , R 5 , R 6 and R 7 At least two of R are alkyl groups having 1 to 12 carbon atoms; 8 , R 9 , R 10 , R 11 and R 12 At least two of R are alkyl groups having 1 to 12 carbon atoms; 7 and R 8 may be taken together to form an —O— bond.

[0021] R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is an alkyl group having 1 to 12 carbon atoms, such an alkyl group will be referred to as "alkyl group R" and such an alkyl group will be referred to as "alkyl group R." The alkyl group R is a group that can be oxidized in the oxidation reaction of step A.

[0022] The alkyl group R preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and particularly preferably 1. More specifically, alkyl groups having 1 to 12 carbon atoms (alkyl group R) include methyl, ethyl, n-propyl, and isopropyl groups, and among these, methyl is particularly preferred. The alkyl group R may have a substituent, or may be unsubstituted and composed only of carbon atoms and hydrogen atoms. The alkyl group R may be either linear or branched.

[0023] In the fluorine-containing aromatic compound, the number of alkyl groups R is not particularly limited. More specifically, it is preferable that at least two or more alkyl groups R are bonded to one aromatic ring in the fluorine-containing aromatic compound, and it is preferable that two alkyl groups R are bonded to one aromatic ring, and in this case, it is preferable that the two alkyl groups R are arranged at the ortho position relative to each other. In the fluorine-containing aromatic compound, the multiple alkyl groups R may all be the same, or some or all may be different types. Furthermore, in the multiple aromatic rings in the fluorine-containing aromatic compound, the number of alkyl groups R may be the same or different.

[0024] In formula (1), R 7 and R 8 can also combine to form an -O- bond. In other words, the compound represented by formula (1) may have a structure in which two benzene rings are directly linked by an -O- bond (ether bond).

[0025] In formula (1), the fluorine-containing alkyl group is the aforementioned fluoroalkyl group. Therefore, examples of the fluorine-containing alkyl group include fluoroalkyl groups having 1 to 6 carbon atoms, preferably fluoroalkyl groups having 1 to 3 carbon atoms, and more preferably fluoroalkyl groups having 1 carbon atom. The number of fluorines in the fluoroalkyl group is not particularly limited as long as the fluoroalkyl group has at least one fluorine atom, and among these, perfluoroalkyl groups are preferred, and trifluoromethyl groups are particularly preferred.

[0026] The fluorine-containing aromatic compound is preferably a fluorine-containing xylene derivative. Therefore, the fluorine-containing aromatic compound is a compound represented by formula (1) in which R 3 , R 4 , R 5 , R 6 and R 7 At least two of R are methyl groups. 8 , R 9 , R 10 , R 11 and R 12 At least two of these are preferably methyl groups.

[0027] Among these, in formula (1), R 1 and R 2 is a trifluoromethyl group, and R 4 , R 5 , R 10 and R 11 is a methyl group, and R 3 , R 6 , R 7 , R 8 , R 9 and R 12 In this case, the raw materials are easily obtained, the oxidation reaction proceeds easily, and the target product can be obtained in a high yield even at a low temperature.

[0028] In the following, in the above formula (1), R 1 and R 2 is a trifluoromethyl group, and R 4 , R 5 , R 10 and R 11 is a methyl group, and R 3 , R 6 , R 7 , R 8 , R 9 and R 12 Compounds where is hydrogen are sometimes abbreviated as "6FXY".

[0029] In step A, the fluorinated aromatic compound may be used alone or in combination of two or more different compounds. Usually, the fluorinated aromatic compound used as the raw material in step A is a single compound.

[0030] (prooxidant) As described above, the pro-oxidant contains at least one compound selected from the group consisting of aldehyde compounds and ketone compounds. The pro-oxidant plays a role in accelerating the oxidation reaction carried out in step A.

[0031] The type of aldehyde compound is not particularly limited, and a wide variety of known aldehyde compounds can be used as long as they have the effect of promoting the oxidation reaction. The number of carbon atoms in the aldehyde compound can be, for example, 1 to 10, preferably 1 to 8, and more preferably 2 to 6.

[0032] Specific examples of the aldehyde compound include at least one selected from the group consisting of paraldehyde, acetaldehyde, propionaldehyde, and metaldehyde.

[0033] Among these, the aldehyde compound is more preferably paraldehyde, since in this case the effect of promoting the oxidation reaction is particularly strong, and the target product can be obtained in a higher yield even at a low temperature.

[0034] The type of ketone compound is not particularly limited, and a wide variety of known ketone compounds can be used as long as they have the effect of promoting the oxidation reaction. The number of carbon atoms in the ketone compound can be, for example, 3 to 10, preferably 3 to 8, and more preferably 3 to 6.

[0035] Among these, the ketone compound is preferably acetone or methyl ethyl ketone, since this has a particularly strong effect of promoting the oxidation reaction, allowing the target product to be obtained in a higher yield even at a low temperature.

[0036] The pro-oxidant may be used alone or in combination of two or more. The pro-oxidant may contain a pro-oxidant other than an aldehyde compound and a ketone compound, or may consist solely of an aldehyde compound and / or a ketone compound, as long as the pro-oxidant does not inhibit the progress of the oxidation reaction.

[0037] It is particularly preferable to use paraldehyde as the oxidation promoter, since this makes it easier to obtain the target product in a higher yield even at a low temperature.

[0038] In step A, the amount of the pro-oxidant used is not particularly limited as long as it does not inhibit the progress of the oxidation reaction. From the viewpoint of facilitating the progress of the oxidation reaction, it is preferable to use the pro-oxidant in an amount of 1 equivalent or more relative to the functional group to be oxidized in the fluorine-containing aromatic compound. The functional group to be oxidized in the fluorine-containing aromatic compound referred to here can be, for example, the alkyl group R. Therefore, it is more preferable to use the pro-oxidant in an amount of 1.0 equivalent or more relative to the alkyl group R in the fluorine-containing aromatic compound, and even more preferable to use 1.2 equivalents or more. It is more preferable to use the pro-oxidant in an amount of 20 equivalents or less relative to the alkyl group R in the fluorine-containing aromatic compound, and even more preferably 10 equivalents or less.

[0039] When the fluorine-containing aromatic compound is the fluorine-containing xylene derivative (for example, the 6FXY), the pro-oxidant is preferably used in an amount of 2 equivalents or more relative to one xylene skeleton of the fluorine-containing xylene derivative. In this case, the oxidation reaction proceeds more easily, and the target product can be obtained in a higher yield even at a low temperature. When the fluorine-containing aromatic compound is the fluorine-containing xylene derivative (for example, the 6FXY), the pro-oxidant is more preferably used in an amount of 2.0 equivalents or more relative to one xylene skeleton of the fluorine-containing xylene derivative, and even more preferably used in an amount of 2.4 equivalents or more. The amount of the pro-oxidant used is more preferably 40 equivalents or less relative to one xylene skeleton of the fluorine-containing xylene derivative, and even more preferably 20 equivalents or less.

[0040] (metal catalyst) The metal catalyst used in step A can exert a catalytic effect in the oxidation reaction. The type of metal catalyst is not particularly limited, and for example, a wide range of known metal catalysts used in oxidation reactions can be used.

[0041] In particular, the metal catalyst preferably contains one or more transition metals, as this facilitates the oxidation reaction in step A. The transition metal is preferably one or more selected from the group consisting of Mn, Co, Zr, Rh, Pd, Ru, Pt, Ni, Fe, W, and Cu, and Co is particularly preferred.

[0042] The metal catalyst may contain metals other than transition metals as long as the oxidation reaction is not inhibited. Alternatively, the metal catalyst may contain only transition metals, and in this case, the metal catalyst may contain metals other than transition metals that are inevitably contained in the metal catalyst.

[0043] Specific examples of metal catalysts include the simple transition metals, as well as oxides, salts (organic or inorganic salts), and complexes containing the transition metals. More specific examples include acetates, oxalates, formates, and succinates of transition metals. Examples of metal catalysts include cobalt acetate, cobalt naphthenate, zirconium acetate oxide, zirconium acetate, and zirconium naphthenate. The organic or inorganic salts containing the transition metals may be hydrates.

[0044] In step A, the metal catalyst can be used alone or in combination of two or more kinds.

[0045] The amount of the metal catalyst used in the oxidation reaction is not particularly limited as long as the oxidation reaction can proceed. For example, the amount can be the same as that used in the oxidation reaction, or the metal catalyst can be used in a so-called catalytic amount. Specifically, the amount of the metal catalyst used in the oxidation reaction is preferably 0.01 to 1 mol, more preferably 0.01 to 0.5 mol, and even more preferably 0.01 to 0.3 mol per mol of the fluorinated aromatic compound. When a solvent described below is used in the oxidation reaction, the amount of the metal catalyst used in the oxidation reaction can be 0.6 mol or less, preferably 0.3 mol or less, more preferably 0.2 mol or less, and even more preferably 0.1 mol or less per 1 L of solvent. When a solvent described below is used in the oxidation reaction, the amount of the metal catalyst used in the oxidation reaction is preferably 0.01 mol or more, more preferably 0.03 mol or more, even more preferably 0.05 mol or more, and especially preferably 0.07 mol or more per 1 L of solvent.

[0046] (oxidation reaction) The fluorine-containing aromatic compound as a raw material is oxidized in the oxidation reaction carried out in step A. The conditions and method for this oxidation reaction are not particularly limited, as long as it is carried out in the presence of a metal catalyst, using an oxidation promoter, and in the presence of oxygen.

[0047] In the oxidation reaction, a solvent can be used as needed. The type of solvent is not particularly limited, and examples thereof include aliphatic carboxylic acids. A wide variety of known compounds can be used as the aliphatic carboxylic acid, and among them, it is preferable that the aliphatic carboxylic acid has 1 to 7 carbon atoms. More specifically, examples of the aliphatic carboxylic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, and heptanoic acid. Acetic acid is particularly preferable as the solvent because it facilitates the oxidation reaction and is easily available.

[0048] When a solvent is used in the oxidation reaction, the amount thereof is not particularly limited. For example, the amount of the solvent used per 100 parts by mass of the fluorinated aromatic compound is preferably 50 to 3,000 parts by mass, more preferably 50 to 2,000 parts by mass, and even more preferably 80 to 1,000 parts by mass.

[0049] When a solvent is used in the oxidation reaction, one solvent may be used alone, or two or more solvents may be used.

[0050] In the oxidation reaction of step A, various other additives can also be used as long as they do not inhibit the progress of the reaction.

[0051] The temperature of the oxidation reaction is not particularly limited and can be selected appropriately depending on the type of raw material used, etc. In terms of preventing corrosion of the reactor, preventing combustion of the solvent used (especially acetic acid), and preventing coloration of the product, the temperature of the oxidation reaction is preferably 140°C or less, more preferably 130°C or less, even more preferably 125°C or less, and particularly preferably 120°C or less. The lower limit of the temperature of the oxidation reaction is not particularly limited as long as the oxidation reaction proceeds. For example, the lower limit of the temperature of the oxidation reaction is preferably 70°C, more preferably 80°C.

[0052] The reaction vessel in which the oxidation reaction is carried out is not particularly limited, and a wide variety of reaction vessels can be used. As described above, since corrosion of the vessel is unlikely to occur during the oxidation reaction, a reaction vessel made of stainless steel or the like can also be used.

[0053] The method for carrying out the oxidation reaction is not particularly limited. For example, the oxidation reaction of step A can be carried out by placing the raw material fluorine-containing aromatic compound, a metal catalyst, an oxidation promoter, and a solvent used as needed in a container, and heating the container to a predetermined temperature in the presence of oxygen. The oxidation reaction can be carried out by adding the oxidation promoter in portions to the container; for example, a portion can be added before the predetermined reaction temperature is reached, and then the remainder can be added to the container after the predetermined reaction temperature is reached. Alternatively, the oxidation promoter can be added after diluting it with the solvent used for the reaction.

[0054] The method of supplying oxygen to the reaction system is not particularly limited. In an oxidation reaction, for example, the reaction proceeds by supplying oxygen into the atmosphere in which the reaction is taking place (for example, into a container). The oxygen used in the oxidation reaction may contain components other than oxygen, such as various components contained in air, and may also contain an inert gas.

[0055] The oxidation reaction can be carried out under any of the following conditions: pressurized, reduced, or atmospheric pressure (0 MPaG). The "G" after the pressure unit MPa means gauge pressure. When the oxidation reaction is carried out under pressurized conditions, the pressure is preferably 0.2 to 10 MPaG, more preferably 0.5 to 5 MPaG, and even more preferably 0.7 to 3 MPaG. Pressurization can be achieved, for example, by supplying an inert gas such as nitrogen or argon to the reactor.

[0056] The oxidation reaction may be carried out in either a continuous or batch manner.

[0057] The time for the oxidation reaction is not particularly limited and can be set appropriately depending on various conditions such as the type of raw material, the reaction temperature, etc. For example, the time for the oxidation reaction is preferably 1 to 50 hours, more preferably 3 to 40 hours, and even more preferably 5 to 30 hours.

[0058] (product) The oxidation reaction in step A produces a product containing the target fluorine-containing phthalic acid derivative.

[0059] The fluorine-containing phthalic acid derivative obtained in step A is determined depending on the structure of the fluorine-containing aromatic compound used as a raw material. In particular, in step A, the alkyl group R of the fluorine-containing aromatic compound is oxidized to a carboxylic acid. Therefore, the oxidation reaction in step A converts all or part of the alkyl groups R in the fluorine-containing aromatic compound into carboxy groups (-COOH).

[0060] In a fluorine-containing aromatic compound, only some of the alkyl groups R among the multiple alkyl groups R in one molecule may be oxidized, so the product may contain multiple types of carboxylic acid compounds. For example, monocarboxylic acid compounds, dicarboxylic acid compounds, tricarboxylic acid compounds, tetracarboxylic acid compounds, etc. may be mixed in the product. In the oxidation reaction of step A, all of the alkyl groups R are easily oxidized, so the main component may be a carboxylic acid compound in which all of the alkyl groups R are oxidized.

[0061] For example, when the fluorine-containing aromatic compound is a fluorine-containing xylene derivative, the product will be mainly composed of a tetracarboxylic acid compound, and may contain tricarboxylic acid compounds, dicarboxylic acid compounds, etc. as by-products.

[0062] When the fluorine-containing aromatic compound is the above-mentioned 6FXY, the fluorine-containing phthalic acid derivative contained in the product is mainly composed of a tetracarboxylic acid compound represented by the following formula (2). Even in this case, tricarboxylic acid compounds, dicarboxylic acid compounds, etc. may be present as by-products.

[0063] [ka]

[0064] The product obtained in step A can be subjected to purification treatment, etc., if necessary. The method of purification treatment is not particularly limited, and for example, a wide range of known purification treatment methods can be adopted.

[0065] The types of compounds contained in the product obtained by the oxidation reaction in step A can be analyzed, for example, by HPLC analysis. Such analysis makes it possible to know whether the raw materials have disappeared and whether carboxylic acid compounds are present.

[0066] Since the oxidation reaction can be carried out at a lower temperature, the product obtained in step A is less likely to be discolored than when the reaction is carried out at a higher temperature. Therefore, the fluorine-containing phthalic acid derivative obtained in step A can be used for various purposes.

[0067] As described above, the oxidation reaction of step A makes it possible to obtain the target fluorine-containing phthalic acid derivative in a simple manner and in a high yield.

[0068] Therefore, step A is a suitable step as a method for oxidizing a fluorine-containing aromatic compound, and an oxidation method including step A is suitable as a method for obtaining a fluorine-containing phthalic acid derivative.

[0069] 2. Method for producing anhydrides of fluorine-containing phthalic acid derivatives The fluorine-containing phthalic acid derivative obtained in step A can be used to produce an anhydride of the fluorine-containing phthalic acid derivative.

[0070] The method for producing an anhydride of a fluorine-containing phthalic acid derivative according to the present disclosure can include, for example, a step of dehydrating the fluorine-containing phthalic acid derivative obtained by the production method according to the present disclosure including step A in the presence of acetic anhydride. Hereinafter, such a step will be referred to as "step B." The anhydride can be obtained by step B.

[0071] In step B, the dehydration conditions are not particularly limited, and can be, for example, the same conditions as those used in a known dehydration reaction using acetic anhydride.

[0072] Acetic anhydride can be used in an amount equal to or greater than the stoichiometric amount required to dehydrate two carboxyl groups to anhydride. The temperature of the dehydration reaction is not particularly limited, and is preferably, for example, 20 to 200°C, more preferably 20 to 150°C, and even more preferably 20 to 100°C. The time for the dehydration reaction is also not particularly limited, and can be appropriately selected depending on the temperature. After dehydration, the target product can be purified, isolated, etc. by appropriate means.

[0073] The product obtained by step B contains the target anhydride of a fluorine-containing phthalic acid derivative. The product obtained by step B may contain by-products in addition to the anhydride of a fluorine-containing phthalic acid derivative. When the fluorine-containing phthalic acid derivative used in step B is a compound represented by formula (2), such by-products are typically at least one compound selected from the group consisting of compounds represented by formula (21-1), (21-2), (21-3), (21-4), (22-1), (22-2), (22-3), (22-4), (23-1), (23-2), (23-3), and (23-4).

[0074] [ka]

[0075] The compounds represented by the formulae (21-1), (21-2), (21-3), (21-4), (22-1), (22-2), (22-3) and (22-4) are likely to be produced in step B when the oxidation reaction in step A does not proceed sufficiently.

[0076] Therefore, by step B, it is possible to obtain a composition containing an anhydride of a fluorine-containing phthalic acid derivative and at least one compound selected from the group consisting of the compound represented by the formula (21-1), the compound represented by the formula (21-2), the compound represented by the formula (21-3), the compound represented by the formula (21-4), the compound represented by the formula (22-1), the compound represented by the formula (22-2), the compound represented by the formula (22-3), the compound represented by the formula (22-4), the compound represented by the formula (23-1), the compound represented by the formula (23-2), the compound represented by the formula (23-3), and the compound represented by the formula (23-4).

[0077] When the fluorine-containing phthalic acid derivative used in step B is a compound represented by the formula (2), at least one compound selected from the group consisting of compounds represented by the formula (21-1), compounds represented by the formula (21-2), compounds represented by the formula (22-1), compounds represented by the formula (22-2), compounds represented by the formula (23-1) and compounds represented by the formula (23-2) is likely to be produced as a by-product.

[0078] The content ratio of the compounds represented by the formulae (21-1), (21-2), (21-3), (21-4), (22-1), (22-2), (22-3), (22-4), (23-1), (23-2), (23-3), and (23-4) relative to the anhydride of the fluorine-containing phthalic acid derivative can be 10,000 ppm by mass or less, preferably 5,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, still more preferably 500 ppm by mass or less, and particularly preferably 100 ppm by mass or less. In particular, when the anhydride of the fluorine-containing phthalic acid derivative is the anhydride of the formula (2) (i.e., 6FDA described in the Examples), the contents of the compounds represented by the formulae (21-1), (21-2), (21-3), (21-4), (22-1), (22-2), (22-3), (22-4), (23-1), (23-2), (23-3), and (23-4) tend to fall within the above ranges.

[0079] The product containing the anhydride of the fluorine-containing phthalic acid derivative obtained in step B can be purified by an appropriate method. For example, the anhydride of the fluorine-containing phthalic acid derivative obtained by the dehydration reaction using acetic anhydride in step B can be purified by recrystallization. In order to further increase the purity of the anhydride of the fluorine-containing phthalic acid derivative, the anhydride of the fluorine-containing phthalic acid derivative obtained by recrystallization can also be subjected to a dehydration reaction using acetic anhydride. This allows the unreacted fluorine-containing phthalic acid derivative to be converted to the anhydride, and the purity of the anhydride of the fluorine-containing phthalic acid derivative obtained can be further increased.

[0080] The anhydride of the fluorine-containing phthalic acid derivative obtained in step B may have an apparent density of 0.4 g / mL or more as measured in accordance with ASTM D1895. This allows for an increased amount of packing into a drum, thereby reducing transportation costs. The apparent density is more preferably 0.45 g / mL or more, even more preferably 0.5 g / mL or more, and particularly preferably 0.55 g / mL or more.

[0081] The apparent density of the anhydride of the fluorine-containing phthalic acid derivative can be adjusted, for example, by selecting the solvent used in recrystallization. The solvent used in recrystallization is not particularly limited, and examples thereof include ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents, nitrile solvents, amide solvents, and aliphatic hydrocarbon solvents, preferably ketone solvents, ether solvents, ester solvents, nitrile solvents, and amide solvents, more preferably ketone solvents, ether solvents, and nitrile solvents, and even more preferably ketone solvents and ether solvents.

[0082] The product containing the anhydride of the fluorine-containing phthalic acid derivative obtained in step B contains fluorine ions (F - ) can be, for example, 5 ppm by mass or less, preferably 3 ppm by mass or less, more preferably 1 ppm by mass or less, based on the total mass of the anhydride of the fluorine-containing phthalic acid derivative. Therefore, the product containing the anhydride of the fluorine-containing phthalic acid derivative obtained in step B contains fluorine ions (F -) content is low, so corrosion of the container during the reaction is easily suppressed. - ) can be measured using a commercially available fluoride ion meter.

[0083] The product containing the anhydride of a fluorine-containing phthalic acid derivative obtained in step B can have a Hazen color number of 150 or less, preferably 100 or less, and more preferably 70 or less. This makes it easier to obtain a polymer with little coloration when the anhydride of a fluorine-containing phthalic acid derivative is used in, for example, a polymerization reaction. The Hazen color number can be measured in accordance with JIS K0071-1 (Color test methods for chemical products - Part 1: Hazen color number (platinum-cobalt scale)).

[0084] The product containing the anhydride of the fluorine-containing phthalic acid derivative obtained in step B can have a water content of 2000 mass ppm or less, preferably 300 mass ppm or less, more preferably 250 mass ppm or less, even more preferably 200 mass ppm or less, and particularly preferably 100 mass ppm or less, relative to the total mass of the anhydride of the fluorine-containing phthalic acid derivative. This suppresses decomposition of the anhydride of the fluorine-containing phthalic acid derivative, enabling long-term storage, and also allows the molecular weight to be increased during the polymerization reaction due to the small amount of decomposition products. The water content can be measured using a Karl Fischer coulometric titrator.

[0085] 3. Purification method for anhydrides of fluorine-containing phthalic acid derivatives The present disclosure includes a method for purifying an anhydride of a fluorine-containing phthalic acid derivative. The purification method includes a step of recrystallizing the anhydride using a mixed solvent containing one or more solvents selected from the group consisting of ketone compounds, ether compounds, and nitrile compounds, and acetic anhydride in an amount 0.05 times or more relative to the total mass of the solvents. The anhydride of a fluorine-containing phthalic acid derivative used in the purification method of the present disclosure can be obtained, for example, by the aforementioned method for producing an anhydride of a fluorine-containing phthalic acid derivative.

[0086] In the purification method of the present disclosure, the type of the ketone compound is not particularly limited, and a wide variety of known ketone compounds can be used, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, diethyl ketone, etc.

[0087] In the purification method of the present disclosure, the type of the ether compound is not particularly limited, and a wide variety of known ether compounds can be used, for example, diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, ethyl methyl ether, dibenzyl ether, tetrahydropyran, methyl tert-butyl ether, diisopropyl ether, dimethyl ether, diglyme, 1,2-dimethoxyethane, etc.

[0088] In the purification method of the present disclosure, the type of the nitrile compound is not particularly limited, and a wide variety of known nitrile compounds can be used, for example, acetonitrile and the like.

[0089] In the purification method of the present disclosure, the amount of the solvent used is not particularly limited, and can be, for example, 1 to 20 times, preferably 3 to 10 times, and more preferably 4 to 8 times the amount of the anhydride of the fluorine-containing phthalic acid derivative used.

[0090] Specifically, in the recrystallization step, the anhydride of the fluorine-containing phthalic acid derivative is dissolved in the mixed solvent, optionally treated with activated carbon, cooled, and the precipitated crystals are collected to obtain the anhydride, thereby obtaining a highly pure anhydride of the fluorine-containing phthalic acid derivative.

[0091] In one embodiment of the recrystallization, the mixed solvent can be distilled off by heating, etc. For example, after the activated carbon treatment and before cooling, the mixed solvent can be completely or incompletely distilled off.

[0092] In the above step, the crude anhydride of the fluorine-containing phthalic acid derivative is dissolved in the above-mentioned mixed solvent, and the mixed solvent is incompletely distilled off from the resulting solution. An aromatic hydrocarbon is then added to crystallize the anhydride of the fluorine-containing phthalic acid derivative, and the crystals are separated. This allows for the production of an anhydride with a higher purity. The type of hydrocarbon is not particularly limited, and a wide variety of known aromatic hydrocarbons can be used, such as toluene, benzene, cyclohexane, heptane, hexane, octane, pentane, petroleum ether, and xylene. The amount of the aromatic hydrocarbon used is not particularly limited, and can be, for example, 0.1 to 20 times, preferably 0.3 to 10 times, and more preferably 0.4 to 8 times the amount of the anhydride of the fluorine-containing phthalic acid derivative used.

[0093] The purification method of the present disclosure makes it possible to obtain a highly pure fluorine-containing phthalic acid derivative anhydride. Because the obtained fluorine-containing phthalic acid derivative anhydride is highly pure, it is particularly suitable as a fluorine-containing phthalic acid derivative anhydride for functional materials.

[0094] According to the purification method of the present disclosure, it is possible to obtain Composition A, Composition B, Composition C, Composition D, Composition E, Composition F, Composition G, Composition H, and Composition I, which will be described later.

[0095] 3. Composition Compositions of the present disclosure include, for example, Composition A, Composition B, Composition C, Composition D, Composition E, Composition F, Composition G, Composition H, and Composition I below.

[0096] Composition A contains a transition metal and an anhydride of a fluorine-containing phthalic acid derivative, and does not contain bromine.

[0097] Composition B contains an anhydride of a fluorine-containing phthalic acid derivative and an aliphatic carboxylic acid. In Composition B, the content of the aliphatic carboxylic acid is 2000 ppm by mass or less based on the total mass of the anhydride and the aliphatic carboxylic acid.

[0098] Composition C contains an anhydride of a fluorine-containing phthalic acid derivative and a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring.

[0099] Composition D contains an anhydride of a fluorine-containing phthalic acid derivative and at least one compound selected from the group consisting of aldehyde compounds and ketone compounds.

[0100] Composition E contains an anhydride of a fluorine-containing phthalic acid derivative and at least one compound selected from the group consisting of the compound represented by the formula (21-1), the compound represented by the formula (21-2), the compound represented by the formula (22-1), the compound represented by the formula (22-2), the compound represented by the formula (23-1) and the compound represented by the formula (23-2).

[0101] Composition F contains an anhydride of a fluorine-containing phthalic acid derivative, and the anhydride of the fluorine-containing phthalic acid derivative can have an apparent density of 0.4 / mL or more as measured in accordance with ASTM D1895.

[0102] Composition G contains an anhydride of a fluorine-containing phthalic acid derivative, and the fluorine ion content is 5 ppm by mass or less, preferably 3 ppm by mass or less, and more preferably 1 ppm by mass or less, based on the total mass of the anhydride of a fluorine-containing phthalic acid derivative.

[0103] Composition H contains an anhydride of a fluorine-containing phthalic acid derivative and has a Hazen color number of 150 or less.

[0104] Composition I contains an anhydride of a fluorine-containing phthalic acid derivative, and has a water content of 2,000 ppm by mass or less relative to the total mass of the anhydride of a fluorine-containing phthalic acid derivative. If the water content exceeds 20,000 ppm by mass, the quality of the composition will deteriorate.

[0105] Compositions A, B, C, D, E, F, G, H, and I can be obtained, for example, by the above-mentioned step B. Alternatively, compositions A, B, C, D, E, F, G, H, and I can also be obtained by the above-mentioned method for purifying anhydrides of fluorine-containing phthalic acid derivatives. In this case, compositions with few impurities can be obtained.

[0106] Each component contained in each composition will be described in detail below.

[0107] (metal) Examples of the metal include various metals that can exert a catalytic effect in the oxidation reaction, specifically, the metal is preferably at least one selected from the group consisting of Mn, Co, Zr, Rh, Pd, Ru, Pt, Ni, Fe, W, Cu, Cr, Mo, Al, Zn, Ti, Si, Li, Mg, P, As, Ca, K, and Na, and particularly preferably at least one selected from the group consisting of Na, K, Ca, and Si.

[0108] (transition metal) The metal may be a transition metal. Examples of the transition metal include various metals that can exhibit catalytic activity in the oxidation reaction. Specific examples of the transition metal include Mn, Co, Zr, Rh, Pd, Ru, Pt, Ni, Fe, W, Cr, Mo, Zn, Ti, and Cu, and one or more metals selected from the group consisting of Co, Fe, Ni, Cr, and Mo are particularly preferred.

[0109] The metal may be an elemental metal, and the transition metal may also be an elemental metal. Alternatively, both the metal and the transition metal may be an oxide, a salt (organic salt or inorganic salt), or a complex, such as an acetate, an oxalate, a formate, or a succinate, and examples thereof include cobalt acetate, cobalt naphthenate, zirconium acetate oxide, zirconium acetate, and zirconium naphthenate. The organic salt or inorganic salt containing the metal or transition metal may be a hydrate.

[0110] (Fluorine-containing phthalic acid derivative anhydride) In the anhydride of a fluorine-containing phthalic acid derivative, the fluorine-containing phthalic acid derivative is, for example, a product of an oxidation reaction of a fluorine-containing aromatic compound. The oxidation reaction here can be, for example, the same as the oxidation reaction in the step A.

[0111] The fluorine-containing aromatic compound can be a fluorine-containing aromatic compound represented by formula (1) used in the production method of the present disclosure. In formula (1), the fluorine-containing alkyl group is the fluoroalkyl group described above. Therefore, the fluorine-containing alkyl group can be a fluoroalkyl group having 1 to 6 carbon atoms, preferably a fluoroalkyl group having 1 to 3 carbon atoms, and more preferably a fluoroalkyl group having 1 carbon atom. The number of fluorines in the fluoroalkyl group is not particularly limited as long as it has at least one fluorine atom. Among these, a perfluoroalkyl group is preferred, and a trifluoromethyl group is particularly preferred. Furthermore, in formula (1), the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom. More specifically, the alkyl group having 1 to 12 carbon atoms can be a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, with a methyl group being particularly preferred.

[0112] The fluorine-containing aromatic compound is preferably a fluorine-containing xylene derivative. 3 , R 4 , R 5 , R 6 and R 7 At least two of R are methyl groups. 8 , R 9 , R 10 , R 11 and R 12 Preferably, at least two of R 1 and R 2 is a trifluoromethyl group, and R 4 , R 5 , R 10 and R 11 is a methyl group, and R 3 , R 6 , R7 , R 8 , R 9 and R 12 is particularly preferably hydrogen. In other words, the fluorine-containing aromatic compound in which an alkyl group is bonded to an aromatic ring as component (1) is preferably 6FXY.

[0113] The anhydride of a fluorine-containing phthalic acid derivative can be obtained by anhydriding a fluorine-containing phthalic acid derivative. The method for this anhydridization is not particularly limited, and for example, a known method can be adopted, thereby obtaining the anhydride of a fluorine-containing phthalic acid derivative.

[0114] An example of the anhydride of a fluorine-containing phthalic acid derivative is 6FDA, which is an anhydride of a tetracarboxylic acid compound represented by the above formula (2).

[0115] (aliphatic carboxylic acids) Examples of the aliphatic carboxylic acid include aliphatic carboxylic acids having 1 to 7 carbon atoms, more specifically, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, etc., and it is particularly preferable that the aliphatic carboxylic acid is acetic acid.

[0116] (Aldehyde compounds and ketone compounds) The aldehyde compound has, for example, a carbon number of 1 to 10, preferably 1 to 8, and more preferably 2 to 6. Specific examples of the aldehyde compound include at least one selected from the group consisting of paraldehyde, acetaldehyde, propionaldehyde, and metaldehyde, and among these, the aldehyde compound is more preferably paraldehyde.

[0117] The ketone compound has, for example, a carbon number of 3 to 10, preferably 3 to 8, and more preferably 3 to 6. Of these, the ketone compound is preferably acetone or methyl ethyl ketone.

[0118] (Composition A) As described above, composition A is a composition containing a metal and an anhydride of the fluorine-containing phthalic acid derivative (hereinafter simply referred to as "anhydride"), but not containing bromine. Since such a composition does not contain bromine, it is unlikely to cause corrosion to a reactor even when used as a raw material for a reaction. The anhydride contained in composition A may be one type alone, or may be two or more types.

[0119] The absence of bromine in Composition A means that the bromine concentration is below the detection limit when the composition is analyzed by ion chromatography. The detection limit for bromine in Composition A can be 5 ppm. Ion chromatography can be performed under the following conditions. 1. Dissolve 10 g of fluorine-containing phthalic acid derivative anhydride in 100 mL of dichloromethane. 2. Add 0.001% potassium sulfite aqueous solution (5 mL) and stir. 3. Analyze the aqueous layer by ion chromatography. The analytical conditions are as follows: Column used: Shimadzu Corporation "IC-SA3" Detector: Electrical conductivity

[0120] The type of metal contained in composition A is not particularly limited. For example, the metal contained in composition A is preferably one or more selected from the group consisting of Na, K, Ca, Si, Co, Fe, Ni, Cr, and Mo. The metal contained in composition A may also be a transition metal. Examples of the transition metal include one or more selected from the group consisting of Co, Fe, Ni, Cr, and Mo. The metal contained in composition A may be one type alone or two or more types, preferably two or more types.

[0121] The total content of metals contained in Composition A is preferably 0.01 to 50 ppm by mass, for example, relative to the anhydride of the fluorine-containing phthalic acid derivative. The total content of metals contained in Composition A is more preferably 0.02 ppm by mass or more, even more preferably 0.1 ppm by mass or more, and more preferably 10 ppm by mass or less, and even more preferably 5 ppm by mass or less, relative to the anhydride of the fluorine-containing phthalic acid derivative. Furthermore, the content of each metal contained in Composition A is preferably 0.01 to 50 ppm by mass, relative to the anhydride of the fluorine-containing phthalic acid derivative. The content of each metal contained in Composition A is more preferably 0.02 ppm by mass or more, even more preferably 0.1 ppm by mass or more, and more preferably 10 ppm by mass or less, and even more preferably 5 ppm by mass or less, relative to the anhydride of the fluorine-containing phthalic acid derivative. In another embodiment, the content of each metal contained in composition A can be 0.01 ppm by mass or more and less than 0.1 ppm by mass, and preferably 0.01 ppm by mass or more and less than 0.05 ppm by mass.

[0122] When the metals contained in Composition A are transition metals, the total content of the transition metals is preferably 0.01 to 50 ppm by mass relative to the anhydride of the fluorine-containing phthalic acid derivative. The total content of the transition metals contained in Composition A is more preferably 0.02 ppm by mass or more, even more preferably 0.1 ppm by mass or more, and more preferably 10 ppm by mass or less, and even more preferably 5 ppm by mass or less, relative to the anhydride of the fluorine-containing phthalic acid derivative. Furthermore, the content of each of the transition metals contained in Composition A is preferably 0.01 to 50 ppm by mass relative to the anhydride of the fluorine-containing phthalic acid derivative. The content of each of the transition metals contained in Composition A is more preferably 0.02 ppm by mass or more, even more preferably 0.1 ppm by mass or more, and more preferably 10 ppm by mass or less, and even more preferably 5 ppm by mass or less, relative to the anhydride of the fluorine-containing phthalic acid derivative. In another embodiment, the content of each transition metal contained in composition A can be 0.01 ppm by mass or more and less than 0.1 ppm by mass, and preferably 0.01 ppm by mass or more and less than 0.05 ppm by mass.

[0123] The total content of metals or transition metals can be analyzed using ICP-MASS, ICP-AES, or ICP-OES. The analytical procedure is not limited to, but can be performed, for example, by the following procedure. 1. Weigh out approximately 10 g of fluorine-containing phthalic acid derivative into a quartz beaker. 2. Place the sample in an electric furnace and ash it. 3. After cooling, add 3% nitric acid solution and heat to dissolve. 4. After cooling, add 3% nitric acid solution and dilute to 10 mL. 5. Analyze using ICP-MASS, ICP-AES or ICP-OES. The detection limit is preferably 0.01 ppm by mass, more preferably 0.02 ppm by mass, and even more preferably 0.04 ppm by mass, relative to the anhydride of the fluorine-containing phthalic acid derivative.

[0124] Composition A is (A-1) a composition further containing other components; (A-2) The composition according to (A-1), wherein the other component contains an aliphatic carboxylic acid; (A-3) The composition according to (A-1) or (A-2), wherein the other components contain a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring; (A-4) The composition according to any one of (A-1) to (A-3), wherein the other component contains at least one selected from the group consisting of aldehyde compounds and ketone compounds; (A-5) The composition according to any one of (A-1) to (A-4), wherein the other component contains at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4); (A-6) The composition according to any one of (A-1) to (A-5), wherein the other component contains water; It can be.

[0125] In composition A, the contents of "aliphatic carboxylic acids," "fluorine-containing aromatic compounds having at least two alkyl groups bonded to an aromatic ring," "at least one selected from the group consisting of aldehyde compounds and ketone compounds," "the compounds represented by formula (21-1), the compounds represented by formula (21-2), the compounds represented by formula (21-3), the compounds represented by formula (21-4), the compounds represented by formula (22-1), the compounds represented by formula (22-2), the compounds represented by formula (22-3), the compounds represented by formula (22-4), the compounds represented by formula (23-1), the compounds represented by formula (23-2), the compounds represented by formula (23-3), and the compounds represented by formula (23-4)," and "water," which are contained as other components, are preferably the same as those in compositions B, C, D, E, F, G, H, or I.

[0126] (Composition B) Composition B contains the anhydride of the fluorine-containing phthalic acid derivative (hereinafter simply referred to as "anhydride") and the aliphatic carboxylic acid, and the content of the aliphatic carboxylic acid is 2000 ppm by mass or less based on the total mass of the anhydride and the aliphatic carboxylic acid. When the content of the aliphatic carboxylic acid is within this range, decomposition of the anhydride of the fluorine-containing phthalic acid derivative is suppressed. The content of the aliphatic carboxylic acid is preferably 500 ppm by mass or less, more preferably 100 ppm by mass or less, even more preferably 50 ppm by mass or less, even more preferably 30 ppm by mass or less, and particularly preferably 10 ppm by mass or less, relative to the total mass of the anhydride and the aliphatic carboxylic acid. The content of the aliphatic carboxylic acid is preferably 0.5 ppm by mass or more, more preferably 1.0 ppm by mass or more, relative to the total mass of the anhydride and the aliphatic carboxylic acid.

[0127] The anhydride contained in composition B may be a single type or two or more types. The aliphatic carboxylic acid contained in composition B may be a single type or two or more types.

[0128] Composition B is (B-1) a composition further containing other components; (B-2) The composition according to (B-1), wherein the other component contains a metal or a transition metal; (B-3) The composition according to (B-1) or (B-2), wherein the other components contain a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring; (B-4) The composition according to any one of (B-1) to (B-3), wherein the other component contains at least one selected from the group consisting of aldehyde compounds and ketone compounds; (A-5) The composition according to any one of (B-1) to (B-4), wherein the other component contains at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4); (B-6) The composition according to any one of (B-1) to (B-5), wherein the other component contains water; It can be.

[0129] In composition B, the contents of "metal or transition metal," "fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring," "at least one selected from the group consisting of aldehyde compounds and ketone compounds," "at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4)," and "water," which are contained as other components, are preferably the same as those in compositions A, C, D, E, F, G, H, or I.

[0130] (Composition C) Composition C contains the anhydride of the fluorine-containing phthalic acid derivative (hereinafter simply referred to as "anhydride") and the fluorine-containing aromatic compound (i.e., the fluorine-containing aromatic compound in which the at least two alkyl groups are bonded to an aromatic ring). The fluorine-containing aromatic compound in Composition C has the same meaning as the fluorine-containing aromatic compound that can be used to obtain the fluorine-containing phthalic acid derivative by oxidation reaction.

[0131] The anhydride contained in composition C may be a single type, or two or more types. The fluorinated aromatic compound contained in composition C may be a single type, or two or more types. The fluorinated aromatic compound contained in composition C may be a single type, or two or more types.

[0132] In composition C, the content ratio of the fluorinated aromatic compound relative to the anhydride is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, even more preferably 1,000 ppm by mass or less, and particularly preferably 100 ppm by mass or less.

[0133] Composition C is (C-1) a composition further containing other components; (C-2) The composition according to (C-1), wherein the other component contains an aliphatic carboxylic acid; (C-3) The composition according to (C-1) or (C-2), wherein the other component contains a metal or a transition metal; (C-4) The composition according to any one of (C-1) to (C-3), wherein the other component contains at least one selected from the group consisting of aldehyde compounds and ketone compounds; (C-5) The composition according to any one of (C-1) to (C-4), wherein the other component contains at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4); (C-6) The composition according to any one of (C-1) to (C-5), wherein the other component contains water; It can be.

[0134] In composition C, the contents of "aliphatic carboxylic acid," "metal or transition metal," "at least one selected from the group consisting of aldehyde compounds and ketone compounds," "at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4)," and "water," which are contained as other components, are preferably the same as those in compositions A, B, D, E, F, G, H, or I.

[0135] (Composition D) Composition D contains an anhydride of the fluorine-containing phthalic acid derivative (hereinafter simply referred to as "anhydride") and at least one compound selected from the group consisting of the aldehyde compounds and ketone compounds.

[0136] The anhydride contained in Composition D may be a single type or two or more types. The aldehyde compound contained in Composition D may be a single type or two or more types. The ketone compound contained in Composition D may be a single type or two or more types.

[0137] In composition D, the content ratio of the aldehyde compound and the ketone compound relative to the anhydride is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, even more preferably 1,000 ppm by mass or less, and particularly preferably 100 ppm by mass or less.

[0138] Composition D is (D-1) A composition further containing other components; (D-2) The composition according to (D-1), wherein the other component contains an aliphatic carboxylic acid; (D-3) The composition according to (D-1) or (D-2), wherein the other components contain a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring; (D-4) The composition according to any one of (D-1) to (D-3), wherein the other component contains a metal or a transition metal; (D-5) The composition according to any one of (D-1) to (D-4), wherein the other component contains at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4); (D-6) The composition according to any one of (D-1) to (D-5), wherein the other component contains water; It can be.

[0139] In composition D, the contents of "aliphatic carboxylic acid", "fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring", "metal or transition metal", "at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4)", and "water" contained as other components are preferably the same as those in compositions A, B, C, E, F, G, H, or I.

[0140] (Composition E) Composition E contains an anhydride of a fluorine-containing phthalic acid derivative and at least one compound selected from the group consisting of the compound represented by the formula (21-1), the compound represented by the formula (21-2), the compound represented by the formula (21-3), the compound represented by the formula (21-4), the compound represented by the formula (22-1), the compound represented by the formula (22-2), the compound represented by the formula (22-3), the compound represented by the formula (22-4), the compound represented by the formula (23-1), the compound represented by the formula (23-2), the compound represented by the formula (23-3), and the compound represented by the formula (23-4). In composition E, the content ratio of the compounds represented by the formulae (21-1), (21-2), (21-3), (21-4), (22-1), (22-2), (22-3), (22-4), (23-1), (23-2), (23-3) and (23-4) relative to the anhydride of the fluorine-containing phthalic acid derivative can be 10,000 ppm by mass or less, preferably 5,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, even more preferably 500 ppm by mass or less, and particularly preferably 100 ppm by mass or less. In composition E, the content of the compounds represented by the formulae (21-1), (21-2), (21-3), (21-4), (22-1), (22-2), (22-3), (22-4), (23-1), (23-2), (23-3) and (23-4) relative to the anhydride of the fluorine-containing phthalic acid derivative is preferably 1.0 ppm by mass or more, and more preferably 5.0 ppm by mass or more.

[0141] In composition E, the anhydride of the fluorine-containing phthalic acid derivative may have an apparent density of 0.4 g / mL or more as measured in accordance with ASTM D1895. This allows for an increased amount of packing into a drum, reducing transportation costs. The apparent density is more preferably 0.45 g / mL or more, even more preferably 0.5 g / mL or more, and particularly preferably 0.55 g / mL or more. The apparent density is preferably 1.5 g / mL or less, more preferably 1.0 g / mL or less.

[0142] Composition E is (E-1) A composition further containing other components; (E-2) The composition according to (E-1), wherein the other component contains an aliphatic carboxylic acid; (E-3) The composition according to (E-1) or (E-2), wherein the other components contain a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring; (E-4) The composition according to any one of (E-1) to (E-3), wherein the other component contains at least one selected from the group consisting of aldehyde compounds and ketone compounds; (E-5) The composition according to any one of (E-1) to (E-4), wherein the other component contains a metal or a transition metal; (E-6) The composition according to any one of (E-1) to (E-5), wherein the other component contains water; It can be.

[0143] In composition E, the contents of the "aliphatic carboxylic acid," "fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring," "at least one member selected from the group consisting of aldehyde compounds and ketone compounds," "metal or transition metal," and "water" contained as other components are preferably the same as those in compositions A, B, C, D, F, G, H, or I.

[0144] (Composition F) Composition F contains an anhydride of a fluorine-containing phthalic acid derivative, and the anhydride of the fluorine-containing phthalic acid derivative has an apparent density of 0.5 g / mL or more as measured in accordance with ASTM D1895. Since Composition F contains an anhydride of a fluorine-containing phthalic acid derivative with a low apparent density, the amount packed into a drum can be increased, thereby reducing transportation costs. Composition F can be obtained by the above-mentioned step B.

[0145] The apparent density of the anhydride of the fluorine-containing phthalic acid derivative is preferably 0.4 g / mL or more, more preferably 0.45 g / mL or more, even more preferably 0.5 g / mL or more, and particularly preferably 0.55 g / mL or more. The apparent density of the anhydride of the fluorine-containing phthalic acid derivative is preferably 1.5 g / mL or less, more preferably 1.0 g / mL or less.

[0146] The apparent density of the anhydride of the fluorine-containing phthalic acid derivative can be adjusted, for example, by purifying the anhydride by recrystallization, and specifically, the apparent density can be adjusted by selecting the solvent used for recrystallization. The solvent used for recrystallization is not particularly limited, and examples thereof include ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents, nitrile solvents, amide solvents, and aliphatic hydrocarbon solvents, preferably ketone solvents, ether solvents, ester solvents, nitrile solvents, and amide solvents, more preferably ketone solvents, ether solvents, and nitrile solvents, and even more preferably ketone solvents and ether solvents.

[0147] Composition F is (F-1) A composition further containing other components; (F-2) The composition according to (F-1), wherein the other component contains an aliphatic carboxylic acid; (F-3) The composition according to (F-1) or (F-2), wherein the other components contain a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring; (F-4) The composition according to any one of (F-1) to (F-3), wherein the other component contains at least one selected from the group consisting of aldehyde compounds and ketone compounds; (F-5) The composition according to any one of (F-1) to (F-4), wherein the other component contains at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4); (F-6) The composition according to any one of (F-1) to (F-5), wherein the other component contains water; (F-7) The composition according to any one of (F-1) to (F-6), wherein the other component contains a metal or a transition metal; It can be.

[0148] In composition F, the contents of "aliphatic carboxylic acid", "fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring", "at least one selected from the group consisting of aldehyde compounds and ketone compounds", "at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4)", "metal or transition metal", and "water" contained as other components are preferably the same as those in compositions A, B, C, D, E, G, H, or I.

[0149] (Composition G) Composition G contains an anhydride of a fluorine-containing phthalic acid derivative, F -The content of fluorine ions (F - ) content is low, so when used as a raw material for a reaction, corrosion of the container is easily suppressed. - ) can be measured using a commercially available fluoride ion meter.

[0150] In composition G, F - The content of ions is preferably 3 ppm by mass or less based on the total mass of the anhydride of the fluorine-containing phthalic acid derivative. This makes it difficult for corrosion to occur in the reactor even when Composition G is used as a raw material for the reaction. - The content of the ions is more preferably 1 ppm by mass or less based on the total mass of the anhydride of the fluorine-containing phthalic acid derivative. - The content of the ions is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, based on the total mass of the anhydride of the fluorine-containing phthalic acid derivative.

[0151] Composition G is (G-1) A composition further containing other components; (G-2) The composition according to (G-1), wherein the other component contains an aliphatic carboxylic acid; (G-3) The composition according to (G-1) or (G-2), wherein the other components contain a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring; (G-4) The composition according to any one of (G-1) to (G-3), wherein the other component contains at least one selected from the group consisting of aldehyde compounds and ketone compounds; (G-5) The composition according to any one of (G-1) to (G-4), wherein the other component contains at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4); (G-6) The composition according to any one of (G-1) to (G-5), wherein the other component contains water; (G-7) The composition according to any one of (G-1) to (G-6), wherein the other component contains a metal or a transition metal; It can be.

[0152] In composition G, the contents of "aliphatic carboxylic acid", "fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring", "at least one selected from the group consisting of aldehyde compounds and ketone compounds", "the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4)", "metal or transition metal", and "water" contained as other components are preferably the same as those in compositions A, B, C, D, E, F, H, or I.

[0153] (Composition H) Composition H contains an anhydride of a fluorine-containing phthalic acid derivative and has a Hazen color index of 150 or less. When such composition H is used in, for example, a polymerization reaction, a polymer with little coloration is likely to be obtained. In other words, the Hazen color index and YI value of a polymer produced using composition H can be reduced. The Hazen color index can be measured in accordance with JIS K0071-1 (Color testing methods for chemical products - Part 1: Hazen color index (platinum-cobalt scale)).

[0154] In composition H, the Hazen color unit number is preferably 100 or less, more preferably 70 or less. In composition H, the Hazen color unit number is preferably 1 or more, more preferably 5 or more.

[0155] Composition H is (H-1) A composition further containing other components; (H-2) The composition according to (H-1), wherein the other component contains an aliphatic carboxylic acid; (H-3) The composition according to (H-1) or (H-2), wherein the other components contain a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring; (H-4) The composition according to any one of (H-1) to (H-3), wherein the other component contains at least one selected from the group consisting of aldehyde compounds and ketone compounds; (H-5) The composition according to any one of (H-1) to (H-4), wherein the other component contains at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4); (H-6) The composition according to any one of (H-1) to (H-5), wherein the other component contains water; (H-7) The composition according to any one of (H-1) to (H-6), wherein the other component contains a metal or a transition metal; It can be.

[0156] In composition H, the contents of "aliphatic carboxylic acid", "fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring", "at least one selected from the group consisting of aldehyde compounds and ketone compounds", "at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4)", "metal or transition metal", and "water" contained as other components are preferably the same as those in compositions A, B, C, D, E, F, G, or I.

[0157] (Composition I) Composition I contains an anhydride of a fluorine-containing phthalic acid derivative, and has a water content of 2000 ppm by mass or less relative to the total mass of the anhydride of the fluorine-containing phthalic acid derivative. Since the water content is within the above range, decomposition of the anhydride of the fluorine-containing phthalic acid derivative is suppressed, improving storage stability. Furthermore, since the amount of decomposition products is small, the molecular weight can be increased during the polymerization reaction, making Composition I an excellent starting material for polymerization. The water content can be measured using a Karl Fischer coulometric titrator.

[0158] In Composition I, the water content is preferably 300 ppm by mass or less, more preferably 250 ppm by mass or less, still more preferably 200 ppm by mass or less, and particularly preferably 100 ppm by mass or less, relative to the total mass of the anhydride of the fluorine-containing phthalic acid derivative. In Composition I, the water content is preferably 5.0 ppm by mass or more, more preferably 10.0 ppm by mass or more, relative to the total mass of the anhydride of the fluorine-containing phthalic acid derivative.

[0159] Composition I is (I-1) A composition further containing other components; (I-2) The composition according to (I-1), wherein the other component contains an aliphatic carboxylic acid; (I-3) The composition according to (I-1) or (I-2), wherein the other components contain a fluorine-containing aromatic compound having at least two alkyl groups bonded to an aromatic ring; (I-4) The composition according to any one of (I-1) to (I-3), wherein the other component contains at least one selected from the group consisting of aldehyde compounds and ketone compounds; (I-5) The composition according to any one of (I-1) to (I-4), wherein the other component contains at least one compound selected from the group consisting of the compound represented by formula (21-1), the compound represented by formula (21-2), the compound represented by formula (21-3), the compound represented by formula (21-4), the compound represented by formula (22-1), the compound represented by formula (22-2), the compound represented by formula (22-3), the compound represented by formula (22-4), the compound represented by formula (23-1), the compound represented by formula (23-2), the compound represented by formula (23-3), and the compound represented by formula (23-4); (I-6) The composition according to any one of (I-1) to (I-6), wherein the other component contains a metal or a transition metal; It can be.

[0160] In composition I, the contents of "aliphatic carboxylic acids," "fluorine-containing aromatic compounds having at least two alkyl groups bonded to an aromatic ring," "at least one compound selected from the group consisting of aldehyde compounds and ketone compounds," "at least one compound selected from the group consisting of compounds represented by formula (21-1), compounds represented by formula (21-2), compounds represented by formula (21-3), compounds represented by formula (21-4), compounds represented by formula (22-1), compounds represented by formula (22-2), compounds represented by formula (22-3), compounds represented by formula (22-4), compounds represented by formula (23-1), compounds represented by formula (23-2), compounds represented by formula (23-3), and compounds represented by formula (23-4)," and "metals or transition metals," which are contained as other components, are preferably the same as those in compositions A, B, C, D, E, F, G, or H.

[0161] The anhydride of the fluorine-containing phthalic acid derivative contained in Composition A, B, C, D, E, G, H, or I, like Composition F, preferably has an apparent density of 0.5 g / mL or more as measured in accordance with ASTM D1895. In this case, since the anhydride of the fluorine-containing phthalic acid derivative, which has a low apparent density, is contained, the amount packed into a drum increases, thereby reducing transportation costs. The apparent density of the anhydride of the fluorine-containing phthalic acid derivative is preferably 0.4 g / mL or more, more preferably 0.45 g / mL or more, even more preferably 0.5 g / mL or more, and particularly preferably 0.55 g / mL or more. The apparent density of the anhydride of the fluorine-containing phthalic acid derivative is preferably 1.5 g / mL or less, more preferably 1.0 g / mL or less.

[0162] As with composition F, the apparent density of the anhydride of the fluorine-containing phthalic acid derivative can be adjusted, for example, by purifying the anhydride by recrystallization.

[0163] Compositions A, B, C, D, E, F, H or I are the same as composition G. -The content of fluorine ions (F - ) content is low, so when used as a raw material for a reaction, corrosion of the container is easily suppressed. - ) can be measured using a commercially available fluoride ion meter. - The content of the ions is preferably 3 ppm by mass or less based on the total mass of the anhydride of the fluorine-containing phthalic acid derivative. - The content of the ions is more preferably 1 ppm by mass or less based on the total mass of the anhydride of the fluorine-containing phthalic acid derivative. - The content of the ions is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, based on the total mass of the anhydride of the fluorine-containing phthalic acid derivative.

[0164] In compositions A, B, C, D, E, F, G, or I, as in composition H, it is preferable that the Hazen color scale be 150 or less. This makes it easier to obtain a polymer with less coloration when the composition is used in a polymerization reaction or the like. In other words, the Hazen color scale and YI value of the produced polymer can be reduced. The Hazen color scale can be measured in accordance with JIS K0071-1 (Color testing methods for chemical products - Part 1: Hazen color scale (platinum-cobalt scale)). The Hazen color scale is preferably 100 or less, more preferably 70 or less, and preferably 1 or more, more preferably 5 or more. [Example]

[0165] Hereinafter, the present disclosure will be described more specifically with reference to examples, but the present disclosure is not limited to the aspects of these examples.

[0166] Example 1 <Process A> An oxidation reaction was carried out according to the reaction formula (3) below. A 500cc pressure-resistant reactor made of SUS316 steel was charged with 40g (0.111mol) of 6FXY as the raw material, 236g of acetic acid as the solvent, 4.147g (0.017mol) of Co(OAc)2 tetrahydrate (Ac represents an acetyl group) as the metal catalyst, and 2.54g (0.019mol) of paraldehyde as an oxidation promoter. Nitrogen was supplied to the reactor to increase the pressure inside the vessel to 2MPaG. Under this pressurized condition, the inside of the reactor was maintained at 100°C, and air and paraldehyde (0.077mL / min) were supplied to the reactor. This oxidation reaction was carried out for approximately 20 hours (Step A). ​​The total amount of paraldehyde used in Step A was 82.1g.

[0167] [ka]

[0168] Thereafter, the reaction solution was sampled from the reaction vessel and analyzed by HPLC. As a result, it was confirmed that the peak derived from 6FXY had disappeared, and that the tetracarboxylic acid, tricarboxylic acid, and dicarboxylic acid compounds had been produced in a ratio of 92:8:1. The yield of the tetracarboxylic acid was 58%. Therefore, it was found that the obtained reaction solution contained the compound represented by formula (2) as the main component. Furthermore, analysis of the reaction solution revealed that bromine was below the detection limit (5 ppm or less), 6FXY was 0.01% (excluding acetic acid), compounds (21-1) to (21-4) were 0.5% (excluding acetic acid), compounds (23-1) to (23-4) were 0.3% (excluding acetic acid), and F - The content of ions was 4300 ppm, and the content of each metal other than cobalt listed in Table 3 was 1000 ppm or less. Furthermore, when the inside of the reactor was visually inspected, no corrosion of the reactor was observed.

[0169] <Process B> The resulting reaction solution was heated to 100°C and maintained at this temperature. 33 g (0.323 mol) of acetic anhydride was added to the reaction solution, and the mixture was stirred for 1 hour. After that, the mixture was cooled to 10°C and recrystallized to obtain crude 6FDA as shown in the following formula.

[0170] [ka]

[0171] To the crude 6FDA obtained, 62 g of methyl ethyl ketone and 3.6 g of acetic anhydride were added, and the mixture was stirred under reflux for 5 hours. After treatment with activated carbon, the mixture was cooled to 10°C, and the precipitated crystals were collected by filtration and dried to obtain 35.1 g of 6FDA (purity: 99.90%). The bromine content of the obtained 6FDA was analyzed by ion chromatography, and it was confirmed to be below the detection limit.

[0172] Example 2 280 g of methyl ethyl ketone and 15 g of acetic anhydride were added to crude 6FDA obtained by the same method as in Example 1, and the mixture was heated to 70°C to dissolve the solid components. The resulting solution was treated with activated carbon, and 185 g of methyl ethyl ketone was distilled off. The mixture was then cooled to 10°C, and the precipitated crystals were collected by filtration and dried to obtain 36.9 g of 6FDA (purity: 99.84%). The amount of bromine in the resulting 6FDA was analyzed by ion chromatography, and it was confirmed to be below the detection limit.

[0173] Example 3 280 g of methyl ethyl ketone and 15 g of acetic anhydride were added to crude 6FDA obtained by the same procedure as in Example 1, and the mixture was heated to 70°C to dissolve the solid components. The resulting solution was treated with activated carbon, and 230 g of methyl ethyl ketone was distilled off, followed by the addition of 150 g of toluene. 100 g of toluene was distilled off from the solution, and the mixture was cooled to 10°C. The precipitated crystals were collected by filtration and dried to obtain 35.9 g of 6FDA (purity: 99.82%). The amount of bromine in the resulting 6FDA was analyzed by ion chromatography, and it was confirmed to be below the detection limit.

[0174] (Product Analysis) Table 1 shows the results of analyzing the crude 6FDA obtained in Examples 1 to 3 and the amounts of other components contained in the 6FDA.

[0175] [Table 1]

[0176] Table 2 shows the results of measuring the apparent density, fluorine ion content, Hazen color unit and water content of the 6FDA obtained in Examples 1 to 3.

[0177] [Table 2]

[0178] Tables (3-1), (3-2), and (3-3) below show the results of measuring the metal content of 6FDA obtained in Examples 1, 2, and 3. The metal content was analyzed using ICP-MASS, ICP-AES, or ICP-OES. The detection limits for each metal are shown in Table (3-4).

[0179] [Table 3]

[0180] [Table 4]

[0181] Table 5 shows the results of a storage stability test of the 6FDA obtained in Example 1. In this test, the 6FDA obtained in Example 1 was stored in an aluminum-laminated bag in a thermo-hygrostat at 40°C and 80% humidity for a predetermined period of time, and after storage, the amount of decomposition products (amount of newly generated components), the purity of 6FDA, and the melting point were analyzed to confirm the storage stability. In Table 5, a storage period of "0" indicates the state of 6FDA immediately before storage.

[0182] [Table 5]

[0183] From the results shown in Table 5, it was found that the 6FDA obtained in Example 1 had a high purity with few decomposition products even after storage for 10 months, and had excellent storage stability.

[0184] Example 4 <Process A> An oxidation reaction was carried out according to the following reaction formula (A). A 500cc pressure-resistant reactor made of SUS316 steel was charged with 40g (0.107mol) of 2,3,6,7-Tetramethyl-9,9-bis(trifluoromethyl)-9H-xanthene (4) as the raw material, 240g of acetic acid as the solvent, 3.985g (0.016mol) of Co(OAc)2 tetrahydrate (Ac represents an acetyl group) as the metal catalyst, and 2.38g (0.018mol) of paraldehyde as an oxidation promoter. Nitrogen was supplied to the reactor to increase the pressure inside the vessel to 2MPaG. Under this pressurized condition, the inside of the reactor was maintained at 100°C, and air and paraldehyde (0.077mL / min) were supplied to the reactor. The oxidation reaction was carried out for approximately 20 hours (Step A). ​​The total amount of paraldehyde used in Step A was 94.2g.

[0185] [ka]

[0186] The reaction mixture was then collected from the reaction vessel and analyzed by HPLC. The peak derived from 2,3,6,7-Tetramethyl-9,9-bis(trifluoromethyl)-9H-xanthene (4) was confirmed to have disappeared. The yield of the target compound, 9,9-Bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid (5), was 70%. Analysis of the reaction mixture revealed that bromine was below the detection limit (5 ppm or less), 2,3,6,7-Tetramethyl-9,9-bis(trifluoromethyl)-9H-xanthene (4) was 0.01% (excluding acetic acid), and F was 0.01%. -The content of ions was 3900 ppm, and the content of each metal other than cobalt listed in Table 3 was 1200 ppm or less. Furthermore, when the inside of the reactor was visually inspected, no corrosion of the reactor was observed.

[0187] <Process B> The resulting reaction mixture was heated to 100°C and maintained at this temperature. 32.8 g (0.321 mol) of acetic anhydride was added to the reaction mixture, and the mixture was stirred for 1 hour. The mixture was then cooled to 10°C and recrystallized to obtain crude 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6), as shown in formula (6). [ka]

[0188] The crude 11,11-bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) was added to 60 g of methyl ethyl ketone and 3.5 g of acetic anhydride, stirred under reflux for 3 hours, treated with activated carbon, cooled to 10 °C, and the precipitated crystals were collected by filtration and dried to obtain 31.3 g of 11,11-bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) (purity: 99.80%). The bromine content of the resulting 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3′,4′-i]xanthene-1,3,7,9(11H)-tetrone (6) was analyzed by ion chromatography and confirmed to be below the detection limit.

[0189] Example 5 The crude 11,11-bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) obtained in the same manner as in Example 4 was added with 280 g of methyl ethyl ketone and 15 g of acetic anhydride, and heated to 70 ° C. to dissolve the solid components. The resulting solution was treated with activated carbon, and 173 g of methyl ethyl ketone was distilled off. The mixture was then cooled to 10 ° C., and the precipitated crystals were collected by filtration and dried to obtain 30.5 g of 11,11-bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) (purity: 99.79%). The bromine content of the resulting 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3′,4′-i]xanthene-1,3,7,9(11H)-tetrone (6) was analyzed by ion chromatography and confirmed to be below the detection limit.

[0190] Example 6 The crude 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) obtained by the same procedure as in Example 4 was added with 280 g of methyl ethyl ketone and 15 g of acetic anhydride and heated to 70 ° C to dissolve the solid components. The resulting solution was treated with activated carbon, and 225 g of methyl ethyl ketone was distilled off, followed by the addition of 150 g of toluene. 105 g of toluene was distilled off from the solution, and the mixture was cooled to 10 ° C. The precipitated crystals were collected by filtration and dried to obtain 29.0 g of 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) (purity: 99.80%). The bromine content of the resulting 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3′,4′-i]xanthene-1,3,7,9(11H)-tetrone (6) was analyzed by ion chromatography and confirmed to be below the detection limit.

[0191] (Product Analysis) Table 6 shows the results of analyzing the crude 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) obtained in Examples 4 to 6 and the amounts of other components contained in 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6).

[0192] [Table 6]

[0193] Table 7 shows the results of measuring the apparent density, fluorine ion content, Hazen color scale, and water content of 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) obtained in Examples 4 to 6.

[0194] [Table 7]

[0195] Tables (8-1), (8-2), and (8-3) show the results of measuring the metal content of 11,11-Bis(trifluoromethyl)-1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetrone (6) obtained in Examples 4, 5, and 6. The metal content was analyzed using ICP-MASS, ICP-AES, or ICP-OES. The detection limits for each metal are the same as those in Table 3-4.

[0196] [Table 8]

[0197] Example 7 <Process A> The oxidation reaction was carried out according to the reaction formula (3) described above. A 500 cc pressure-resistant reactor made of SUS316 steel was charged with 40 g (0.111 mol) of 6FXY as the raw material, 236 g of acetic acid as the solvent, 4.147 g (0.017 mol) of Co(OAc)2 tetrahydrate (Ac represents an acetyl group) as the metal catalyst, and 2.54 g (0.019 mol) of paraldehyde as an oxidation promoter. Nitrogen was supplied to the reactor to increase the pressure inside the vessel to 2 MPaG. Under this pressurized condition, the inside of the reactor was maintained at 100 °C, and air and paraldehyde (0.077 mL / min) were supplied to the reactor. The oxidation reaction was carried out for approximately 20 hours (Step A). ​​The total amount of paraldehyde used in Step A was 82.1 g. Thereafter, the reaction solution was sampled from the reaction vessel and analyzed by HPLC. As a result, it was confirmed that the peak derived from 6FXY had disappeared, and that the tetracarboxylic acid, tricarboxylic acid, and dicarboxylic acid compounds had been produced in a ratio of 92:8:1. The yield of the tetracarboxylic acid was 80%. Therefore, it was found that the obtained reaction solution contained the compound represented by formula (2) as the main component. Furthermore, analysis of the reaction solution revealed that bromine was below the detection limit (5 ppm or less), 6FXY was 0.01% (excluding acetic acid), compounds (21-1) to (21-4) were 0.5% (excluding acetic acid), compounds (23-1) to (23-4) were 0.3% (excluding acetic acid), and F - The content of ions was 4300 ppm, and the content of each metal other than cobalt listed in Table 3 was 1000 ppm or less. Furthermore, when the inside of the reactor was visually inspected, no corrosion of the reactor was observed.

[0198] <Process B> The resulting reaction solution was heated to 100°C and maintained at this temperature. 33 g (0.323 mol) of acetic anhydride was added to the reaction solution and stirred for 1 hour. The mixture was then cooled to 10°C and recrystallized to obtain crude 6FDA. 62 g of methyl ethyl ketone and 3.6 g of acetic anhydride were added to the resulting crude 6FDA, and the mixture was stirred under reflux for 5 hours. After treatment with activated carbon, the mixture was cooled to 10°C. The precipitated crystals were filtered and dried to obtain 35.1 g of 6FDA (purity: 99.90%). The amount of bromine in the resulting 6FDA was analyzed by ion chromatography, and it was confirmed to be below the detection limit.

[0199] Example 8 280 g of methyl ethyl ketone and 15 g of acetic anhydride were added to crude 6FDA obtained in the same manner as in Example 7, and the mixture was heated to 70°C to dissolve the solid components. The resulting solution was treated with activated carbon, and 185 g of methyl ethyl ketone was distilled off. The mixture was then cooled to 10°C, and the precipitated crystals were collected by filtration and dried to obtain 36.9 g of 6FDA (purity: 99.84%). The amount of bromine in the resulting 6FDA was analyzed by ion chromatography, and it was confirmed to be below the detection limit.

[0200] Example 9 280 g of methyl ethyl ketone and 15 g of acetic anhydride were added to crude 6FDA obtained by the same procedure as in Example 7, and the mixture was heated to 70°C to dissolve the solid components. The resulting solution was treated with activated carbon, and 230 g of methyl ethyl ketone was distilled off, followed by the addition of 150 g of toluene. 100 g of toluene was distilled off from the solution, and the mixture was cooled to 10°C. The precipitated crystals were collected by filtration and dried to obtain 35.9 g of 6FDA (purity: 99.82%). The amount of bromine in the resulting 6FDA was analyzed by ion chromatography, and it was confirmed to be below the detection limit.

[0201] (Product Analysis) Table 9 shows the results of analyzing the crude 6FDA obtained in Examples 7 to 9 and the amounts of other components contained in the 6FDA.

[0202] [Table 9]

[0203] Table 10 shows the results of measuring the apparent density, fluoride ion content, Hazen color unit and water content of the 6FDA obtained in Examples 7 to 9.

[0204] [Table 10]

[0205] Tables (11-1), (11-2), and (11-3) show the results of measuring the metal content of 6FDA obtained in Examples 7, 8, and 9. The metal content was analyzed using ICP-MASS, ICP-AES, or ICP-OES. The detection limits for each metal are shown in Table 3-4.

[0206] [Table 11]

[0207] Table 12 shows the results of a storage stability test of the 6FDA obtained in Example 7. In this test, the 6FDA obtained in Example 7 was stored in an aluminum laminated bag in a thermo-humidistat chamber at 40°C and 80% humidity for a predetermined period of time, and after storage, the amount of decomposition products (amount of newly generated components), the purity of 6FDA, and the melting point were analyzed to confirm the storage stability. In the table below, a storage period of "0" means the state of 6FDA immediately before storage.

[0208] [Table 12]

[0209] The results shown in Table 12 demonstrate that the 6FDA obtained in Example 7 had high purity and contained few decomposition products even after storage for 10 months, and had excellent storage stability. [Industrial Applicability]

[0210] The fluorine-containing phthalic anhydride provided by the production method of the present disclosure has a reduced metal content and is therefore useful as a raw material for polyimide, which is an electronic material such as an insulating / protective agent for semiconductor devices and electronic components.

Claims

1. A method for producing a fluorine-containing phthalic acid derivative from a fluorine-containing aromatic compound, comprising the steps of: carrying out an oxidation reaction of the fluorine-containing aromatic compound using an oxidation promoter in the presence of a metal catalyst, The oxidation reaction is carried out under a pressure of 0.2 to 10 MPaG at a temperature of 125°C or less, The fluorine-containing aromatic compound is The following general formula (1) 【Chemistry 1】 (In formula (1), R １ and R ２ is a trifluoromethyl group, R 3 , R 6 , R 7 , R 8 , R 9 and R 12 are hydrogen, and R 4 , R 5 , R 10 and R 11 are methyl groups). is a compound represented by The fluorine-containing phthalic acid derivative is represented by the following general formula (2): 【Chemistry 2】 is a tetracarboxylic acid compound represented by the formula: A method for producing a fluorine-containing phthalic acid derivative, wherein the pro-oxidant comprises at least one compound selected from the group consisting of paraldehyde, acetaldehyde, propionaldehyde, metaldehyde, acetone, and methyl ethyl ketone.

2. The method according to claim 1 , wherein the pro-oxidant is used in an amount of at least 1 equivalent based on the functional group to be oxidized in the fluorine-containing aromatic compound.

3. The method of claim 1 , wherein the metal catalyst comprises a transition metal.

4. 4. The method according to claim 3, wherein the transition metal comprises at least one selected from the group consisting of Mn, Co, Zr, Rh, Pd, Ru, Pt, Ni, Fe, W, and Cu.

5. The method of claim 4 , wherein the transition metal comprises Co.

6. A step of obtaining a fluorine-containing phthalic acid derivative by the production method according to any one of claims 1 to 3; A method for producing an anhydride of a fluorine-containing phthalic acid derivative, comprising a step of dehydrating the fluorine-containing phthalic acid derivative in the presence of acetic anhydride.

7. A method for purifying an anhydride of a fluorine-containing phthalic acid derivative, comprising the steps of: a step of producing the fluorine-containing phthalic acid derivative by the production method according to any one of claims 1 to 3; a step of producing an anhydride of the fluorine-containing phthalic acid derivative by dehydrating the fluorine-containing phthalic acid derivative in the presence of acetic anhydride; a purification method comprising a step of recrystallizing the anhydride of the fluorine-containing phthalic acid derivative using a mixed solvent containing one or more solvents selected from the group consisting of ketone compounds, ether compounds and nitrile compounds, and acetic anhydride in an amount of 0.05 times or more based on the total mass of the solvents.

8. 8. The purification method according to claim 7, wherein the recrystallization step comprises dissolving a crude anhydride of a fluorine-containing phthalic acid derivative in the mixed solvent, incompletely distilling off the mixed solvent from the obtained solution, adding an aromatic hydrocarbon to crystallize the anhydride of a fluorine-containing phthalic acid derivative, and separating the crystals.