High-purity fluorine-containing diepoxy compound and method for purifying fluorine-containing diepoxy compound

Abstract

To provide a composition including fluorine-containing diepoxy compound which can be used suitably for optical materials, electronic materials or the like, improves production efficiency by decrease of variation in materials, and is advantageous in economical efficiency such as the production cost of final products, and to provide a purifying method for the fluorine-containing diepoxy compound, capable of simply obtaining the above composition.SOLUTION: Disclosed are a high-purity fluorine-containing diepoxy compound obtained by adding Zn or Zn-including metal, water and an acid anhydride to a fluorine-containing diepoxy compound represented by a below-mentioned general formula (1) (in the formula, n is an integer of 1 to 8) for treatment to simultaneously remove iodine-including impurities and unsaturated impurities, and a purifying method for the fluorine-containing diepoxy compound capable of simply obtaining the above compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a high-purity fluorine-containing diepoxy compound. The fluorine-containing diepoxy compound can be polymerized alone or with compounds having various epoxy groups and amino groups, and can also be derived into a polymerizable acrylic acid ester derivative, and is a compound useful as an intermediate for the production of optical materials and electronic materials. The polymer obtained from the fluorine-containing epoxy compound has high physical properties derived from fluorine such as low refractive index and light resistance durability, and is utilized in various applications in optical materials including antireflection films, plastic optical waveguides and related material raw materials. In electronic materials, it is used for encapsulants for solar cells and LED light sources that require heat resistance and light resistance durability.

Background Art

[0002] The fluorine-containing epoxy compound is usually produced through a first reaction step of obtaining an unsaturated alcohol-fluoroalkyl iodide adduct by reacting a fluoroalkyl iodide with an unsaturated alcohol in the presence of a radical catalyst as disclosed in Patent Document 1, and a second reaction step of reacting the obtained adduct with a basic compound to obtain a fluorine-containing epoxy compound. Therefore, impurities containing iodine atoms, which can cause coloring even in trace amounts, are present. However, a simple purification method for fluorine-containing epoxy compounds containing impurities containing iodine atoms is not known.

[0003] Also, the fluorine-containing epoxy compound is usually purified by distillation. Here, in the production process of the fluorine-containing diepoxy compound, it is known that an unsaturated alcohol exists as an impurity (Non-Patent Document 1), and since the boiling point of this unsaturated alcohol is close to the boiling point of the target fluorine-containing epoxy compound, there is a problem that it is difficult to separate the two. Furthermore, since the unsaturated bond has ultraviolet absorption, it is known that when a compound having an unsaturated bond such as the above unsaturated alcohol is contained in the epoxy resin, it causes coloring due to photo-degradation (Patent Document 2). However, a simple purification method for a fluorine-containing epoxy compound containing impurities having an unsaturated alcohol has not been known. For this reason, in order to obtain a high-purity target compound, it is necessary to spend a great deal of time on a purification process such as precision distillation, and in that case, there has been a problem that the yield is low and the cost is high.

[0004] Specifically, the following methods can be considered. 1) Repeatedly distill a mixture containing a target fluorine-containing diepoxy compound, a fluorine-containing unsaturated alcohol compound and a fluorine-containing iodine compound by-produced during synthesis. However, by repeating the distillation, the yield of the target fluorine-containing diepoxy compound will be greatly reduced. 2) Increase the reflux ratio in the distillation process. However, in order to increase the reflux ratio, it is necessary to distill over time, and the efficiency for obtaining the target fluorine-containing diepoxy compound becomes poor.

[0005] Even if either or both of the above two methods are adopted, in any case, it is inevitable that it takes time, and it is also conceivable that the reactants polymerize and obstacles such as the polymer adhering to the production apparatus occur. For this reason, there has been a demand for a method for simply and efficiently obtaining a fluorine-containing diepoxy compound according to the application.

[0006] Especially in recent years, the functions and performances required for members have become increasingly sophisticated, and even slight differences in coloring, refractive index, etc., and their changes over time are no longer allowed. Therefore, a high-purity fluorine-containing epoxy compound with a reduced amount of impurities is required for preventing coloring and stabilizing the refractive index, etc.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

[0008] [Non-Patent Document 1] Oldrich Paleta et al., Jounal of Fluorine Chemistry (2000), 102, 349-361. [Summary of the Invention] [Problems to be Solved by the Invention]

[0009] In view of the above prior art, an object of the present invention is to provide a highly pure fluorine-containing diepoxy compound that can be suitably used for optical materials, electronic materials, etc., and has an improved yield when the material is molded into a member, thereby being advantageous also in terms of economy such as the manufacturing cost of the final product, and a method for purifying a fluorine-containing diepoxy compound for easily obtaining the compound. [Means for Solving the Problems]

[0010] Therefore, in order to solve the above problems, the present inventors earnestly studied a method for reducing impurities contained therein in order to purify a crude fluorine-containing diepoxy compound using a fluorine-containing diiodo compound as a raw material. As a result, zinc or a metal containing zinc, an acid anhydride, and water were added to and treated with a crude fluorine-containing diepoxy compound containing a compound other than the target compound, particularly a fluorine-containing unsaturated alcohol compound and a fluorine-containing iodine compound, generated during the synthesis of the target compound, and then this was distilled, and it was found that both the fluorine-containing unsaturated alcohol compound and the fluorine-containing iodine compound present during production could be significantly reduced simultaneously, and thus the present invention was completed.

[0011] That is, the present invention relates to the following inventions. [1] The following general formula (1) [Chemical formula] (In the formula, n represents an integer of 1 to 8) The fluorine-containing diepoxy compound represented by is 94% by weight or more (based on GC area percentage), the following general formula (2)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] The following general formula (5) [Chemical formula] (wherein n represents an integer of 1 to 8) A crude fluorine-containing diepoxy compound obtained by reacting a perfluorojodide represented by the formula with allyl alcohol in the presence of a radical initiator and then dehydrogenating iodine with a basic compound is treated by adding zinc or a metal containing zinc, an acid anhydride, and water to obtain a high-purity fluorine-containing diepoxy compound according to any one of [1] to [7]. A method for purifying a fluorine-containing diepoxy compound.

[11] The high-purity fluorine-containing diepoxy compound according to [6] or [7], characterized in that the amount of the acid anhydride used is 0.01 mol% to 100 mol% based on the fluorine-containing diepoxy compound.

[12] A method for purifying a fluorine-containing diepoxy compound, which comprises obtaining a high-purity fluorine-containing diepoxy compound according to any one of [8] to

[10] , characterized in that the amount of the acid anhydride used is 0.01 mol% to 100 mol% based on the fluorine-containing diepoxy compound.

[13] The high-purity fluorine-containing diepoxy compound according to [6] or [7], characterized in that the amount of water is 0.01 mol% to 50 mol% based on the fluorine-containing diepoxy compound.

[14] A method for purifying a fluorine-containing diepoxy compound, which comprises obtaining a high-purity fluorine-containing diepoxy compound according to any one of [8] to

[10] , characterized in that the amount of water is 0.01 mol% to 50 mol% based on the fluorine-containing diepoxy compound.

[15] The high-purity fluorine-containing diepoxy compound according to [6] or [7], characterized in that the amount of zinc contained in zinc or a metal containing zinc is 0.01 mol% to 200 mol% based on the fluorine-containing diepoxy compound.

[16] A method for purifying a fluorine-containing diepoxy compound, which comprises obtaining a high-purity fluorine-containing diepoxy compound according to any one of [8] to

[10] , characterized in that the amount of zinc contained in zinc or a metal containing zinc is 0.01 mol% to 200 mol% based on the fluorine-containing diepoxy compound. [Effect of the Invention]

[0012] The present invention provides a high-purity fluorine-containing diepoxy compound and an industrial method for purifying a fluorine-containing diepoxy compound, which can efficiently obtain the high-purity fluorine-containing diepoxy compound.

Brief Description of the Drawings

[0013]

Figure 1

Embodiments for Carrying Out the Invention

[0014] Hereinafter, the present invention will be described in detail. The high-purity fluorine-containing diepoxy compound of the present invention is represented by the general formula (1). Specific examples include bis(2’,3’-epoxypropyl)-difluoromethane, 1,2-bis(2’,3’-epoxypropyl)-perfluoroethane, 1,3-bis(2’,3’-epoxypropyl)-perfluoropropane, 1,4-bis(2’,3’-epoxypropyl)-perfluorobutane, 1,5-bis(2’,3’-epoxypropyl)-perfluoropentane, 1,6-bis(2’,3’-epoxypropyl)-perfluorohexane, 1,7-bis(2’,3’-epoxypropyl)-perfluoroheptane, and 1,8-bis(2’,3’-epoxypropyl)-perfluorooctane.

[0015] The high-purity fluorine-containing diepoxy compound of the present invention is characterized in that the components shown below, which may be contained, are present in a specific weight ratio or less.

[0016] The fluorine-containing diepoxy compound of the present invention has a purity of 94% by weight or more (based on GC area percentage). More preferably, it is 95% by weight or more (based on GC area percentage). Here, "wt%" means the ratio of the GC area of the fluorine-containing diepoxy compound to the total GC area of each peak attributed to each component contained in the fluorine-containing diepoxy compound when the fluorine-containing diepoxy compound is analyzed or measured by gas chromatography (GC), that is, the GC percentage. In this specification, this "wt%" is referred to as "based on GC area percentage" or simply "GC percentage".

[0017] The first component that may be contained in the high-purity fluorine-containing diepoxy compound of the present invention is an unsaturated alcohol compound represented by the general formula (2). The content of the unsaturated alcohol compound represented by the general formula (2) in the high-purity fluorine-containing diepoxy compound of the present invention is 2.5% by weight or less (based on GC area percentage), preferably 2% by weight or less (based on GC area percentage).

[0018] The second component that may be contained in the high-purity fluorine-containing diepoxy compound of the present invention is an unsaturated alcohol compound represented by the general formula (3). The content of the unsaturated alcohol compound represented by the general formula (3) in the high-purity fluorine-containing diepoxy compound of the present invention is 1.5% by weight or less (based on GC area percentage), preferably 1% by weight or less (based on GC area percentage).

[0019] The third component that may be contained in the high-purity fluorine-containing diepoxy compound of the present invention is a fluorine-containing iodine compound represented by the general formula (4). The content of the fluorine-containing iodine compound represented by the general formula (4) in the high-purity fluorine-containing diepoxy compound of the present invention is 0.5% by weight or less (based on GC area percentage), preferably 0.2% by weight or less (based on GC area percentage).

[0020] Specific examples of the unsaturated alcohol compound represented by the general formula (2) include 2-(1-(2’,3’-epoxypropyl)-1,1-difluoromethyl)-2-propen-1-ol, 2-(2-(2’,3’-epoxypropyl)-1,1,2,2-tetrafluoroethyl)-2-propen-1-ol, 2-(3-(2’,3’-epoxypropyl)-1,1,2,2,3,3-hexafluoropropyl)-2-propen-1-ol, 2-(4-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4-octafluorobutyl)-2-propen-1-ol, 2-(5-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4,5,5-decafluoropentyl)-2-propen-1-ol, 2-(6-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)-2-propen-1-ol, 2-(7-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7-tetradecafluoroheptyl)-2-propen-1-ol, 2-(8-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorooctyl)-2-propen-1-ol.

[0021] Specific examples of the unsaturated alcohol compound represented by the general formula (3) include 4-(2’,3’-epoxypropyl)-4,4-difluoro-2-buten-1-ol, 5-(2’,3’-epoxypropyl)-4,4,5,5-tetrafluoro-2-penten-1-ol, 6-(2’,3’-epoxypropyl)-4,4,5,5,6,6-hexafluoro-2-hexen-1-ol, 7-(2’,3’-epoxypropyl)-4,4,5,5,6,6,7,7-octafluoro-2-hepten-1-ol, 8-(2’,3’-epoxypropyl)-4,4,5,5,6,6,7,7,8,8-decafluoro-2-octen-1-ol, 9-(2’,3’-epoxypropyl)-4,4,5,5,6,6,7,7,8,8,9,9-dodecafluoro-2-nonen-1-ol, 10-(2’,3’-epoxypropyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10-tetradecafluoro-2-decen-1-ol, 11-(2’,3’-epoxypropyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-hexadecafluoro-2-undecen-1-ol.

[0022] Specific examples of the fluorine-containing iodine compound represented by the general formula (4) include (2’,3’-epoxypropyl)-difluoroiodomethane, 1-(2’,3’-epoxypropyl)-1,1,2,2-tetrafluoro-2-iodoethane, 1-(2’,3’-epoxypropyl)-1,1,2,2,3,3-hexafluoro-3-iodopropane, 1-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4-octafluoro-4-iodobutane, 1-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4,5,5-decafluoro-5-iodopentane, 1-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-6-iodohexane, 1-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7-tetradecafluoro-7-iodoheptane, 1-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-8-iodooctane.

[0023] The number entered for n in the general formula (1), the number entered for n in the general formula (2), the number entered for n in the general formula (3), and the number entered for n in the general formula (4) are the same. For example, when the high-purity fluorine-containing epoxy compound is 1,4-bis(2’,3’-epoxypropyl)-perfluorobutane, the combinations of impurities included are 2-(4-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4-octafluorobutyl)-2-propen-1-ol, 7-(2’,3’-epoxypropyl)-4,4,5,5,6,6,7,7-octafluoro-2-hepten-1-ol, 1-(2’,3’-epoxypropyl)-1,1,2,2,3,3,4,4-octafluoro-4-iodobutane.

[0024] The high-purity fluorine-containing diepoxy compound of the present invention can efficiently obtain by adding zinc or a metal containing zinc, an acid anhydride, and water to the crude fluorine-containing diepoxy compound represented by the general formula (1) containing the unsaturated alcohol compound represented by the general formula (2), the unsaturated alcohol compound represented by the general formula (3), and the fluorine-containing iodine compound represented by the general formula (4), treating, and then distilling to simultaneously remove impurities containing iodine and impurities containing unsaturated alcohol.

[0025] By performing the above treatment, acylation of the alcohol moiety in the unsaturated alcohol compounds represented by the general formula (2) and the general formula (3) proceeds, and the corresponding ester compounds are generated. By performing the above treatment, the fluorine-containing iodine compound represented by the general formula (4) undergoes decomposition to the following general formula (6) [Chemical formula] (wherein n represents an integer of 1 to 8) or the following general formula (7) [Chemical formula] (wherein n represents an integer of 1 to 8) and the like are generated. The generated compounds can be easily separated from the fluorine-containing diepoxy compound by distillation, and a high-purity fluorine-containing diepoxy compound can be obtained.

[0026] The crude fluorine-containing diepoxy compound can be produced by a well-known method. For example, as disclosed in Patent Document 1, a first reaction step of obtaining an unsaturated alcohol-fluoroalkyl iodide adduct by reacting fluoroalkyl iodide with allyl alcohol in the presence of a radical catalyst, and a second reaction step of reacting the obtained adduct with a basic compound to obtain a fluorine-containing epoxy compound.

[0027] The purification method of the fluorine-containing diepoxy compound of the present invention can be applied not only to the crude fluorine-containing diepoxy compound but also to the fluorine-containing diepoxy compound purified by well-known methods such as recrystallization and distillation. Regarding the crude fluorine-containing diepoxy compound to which the method for purifying the fluorine-containing diepoxy compound of the present invention can be applied, other components contained therein are indicated in parts by weight based on the parts by weight of the fluorine-containing diepoxy compound. That is, with respect to 100 parts by weight of the fluorine-containing diepoxy compound, the fluorine-containing unsaturated alcohol compound represented by the general formula (2) is 0.1 to 20 parts by weight (based on GC area percentage), preferably 1 to 10 parts by weight (based on GC area percentage), the fluorine-containing unsaturated alcohol compound represented by the general formula (3) is 0.1 to 40 parts by weight (based on GC area percentage), preferably 1 to 20 parts by weight (based on GC area percentage), and when it contains 0.1 to 20 parts by weight (based on GC area percentage), preferably 1 to 10 parts by weight (based on GC area percentage) of the fluorine-containing iodine compound represented by the general formula (4), it is applicable. Here, "parts by weight" is based on the ratio of the total GC area of each peak attributed to each component contained in the fluorine-containing diepoxy compound and the GC area of each component when a predetermined amount of the fluorine-containing diepoxy compound is analyzed or measured by gas chromatography (GC), that is, the GC percentage. In this specification, this "parts by weight" is referred to as "based on GC area percentage" or simply "GC percentage".

[0028] The acid anhydrides applicable to the purification of the fluorine-containing diepoxy compound of the present invention are not particularly limited, but carboxylic acid anhydrides are preferred. A plurality of acid anhydrides may be used in combination. Specific examples of the acid anhydride include acetic anhydride, 4-methoxyphenylacetic anhydride, phenylacetic anhydride, diphenylacetic anhydride, 2-methoxyacetic anhydride, phenoxyacetic anhydride, propionic anhydride, butyric anhydride, oxalic anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, nonanoic anhydride, decanoic anhydride, dodecanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, chlorodifluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, bromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, bromodifluoroacetic anhydride, isobutyric anhydride, isovaleric anhydride, pivalic anhydride, acrylic anhydride, methacrylic anhydride, crotonic anhydride, cyclohexanecarboxylic anhydride, 1,1-cyclopentanediacetic anhydride, 1,1-cyclohexanediacetic anhydride, succinic anhydride, phenylsuccinic anhydride, glutaric anhydride, 3-methylglutaric anhydride, 3,3-dimethylglutaric anhydride, itaconic anhydride, allylsuccinic anhydride, diglycolic anhydride, phthalic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 4,5-dichlorophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, tetrafluorophthalic anhydride, 3-bromophthalic anhydride, 4-bromophthalic anhydride, 3-fluorophthalic anhydride, 4-fluorophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, 2-methylphthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 4-tert-butylphthalic anhydride, 3-methylcyclohexane-1,2-dicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,4'-biphthalic anhydride, 4,4'-biphthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(4,4’-Isopropylidenediphenoxy)phthalic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, het acid anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4,4’-carbonyldiphthalic anhydride, maleic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, 2,3-dimethylmaleic anhydride, citraconic anhydride, benzoic anhydride, 3,4,5-trimethoxybenzoic anhydride, 2-trifluoromethylbenzoic anhydride, 3-trifluoromethylbenzoic anhydride, 4-trifluoromethylbenzoic anhydride, 2-methylbenzoic anhydride, 3-methylbenzoic anhydride, 4-methylbenzoic anhydride, 2-methyl-6-nitrobenzoic anhydride, 2-methoxybenzoic anhydride, 3-methoxybenzoic anhydride, 4-methoxybenzoic anhydride, 3,4-dichlorobenzoic anhydride, 2-chlorobenzoic anhydride, 3-chlorobenzoic anhydride, 4-chlorobenzoic anhydride, 2-fluorobenzoic anhydride, 3-fluorobenzoic anhydride, 4-fluorobenzoic anhydride, 2-bromobenzoic anhydride, 3-bromobenzoic anhydride, 4-bromobenzoic anhydride, 1,2-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 4-chloro-1,8-naphthalic anhydride, 4-bromo-1,8-naphthalic anhydride, benzo[de]isochromene-1,3-dione, 3,3’,4,4’-benzophenonetetracarboxylic dianhydride, and the like can be mentioned.,

[0029] The amount of the acid anhydride applicable to the purification of the fluorine-containing diepoxy compound of the present invention is preferably 0.01 mol% to 100 mol%, more preferably 0.1 mol% to 100 mol%, and still more preferably 9 mol% to 90 mol% with respect to the crude fluorine-containing diepoxy compound containing impurities used for the treatment. It is desirable to use 0.5 mol times or more with respect to the total amount of the unsaturated alcohol impurities represented by the general formulas (2) and (3) contained in the crude fluorine-containing diepoxy compound used for the treatment. When the amount of the acid anhydride is too small, it is difficult to remove impurities, and when the amount of the acid anhydride is too large, there is a risk that the fluorine-containing diepoxy compound may be partially damaged.

[0030] As the abundance of water applicable to the purification of the fluorine-containing diepoxy compound of the present invention, 0.01 mol% to 50 mol% is preferable with respect to the fluorine-containing diepoxy compound represented by the general formula (1). Particularly preferably, it is 0.1 mol% to 50 mol%, and still more preferably 1 mol% to 45 mol%. When the abundance of water is too small, it is difficult to remove impurities containing iodine, and when the abundance of water is too large, it is difficult to remove impurities containing unsaturated alcohol. When sufficient water is contained in the fluorine-containing diepoxy compound containing impurities used for the treatment, there is no need to add it.

[0031] The metal containing zinc applicable to the purification of the fluorine-containing diepoxy compound of the present invention is not particularly limited, and various metals containing zinc such as brass, nickel silver, zinc alloys such as zinc alloy die cast defined in JIS H5301:2009, and galvanized iron and zinc plating defined in JIS H8641:2007 can be applied.

[0032] The amount of zinc used, which is applicable to the purification of the fluorine-containing diepoxy compound of the present invention and is contained in zinc or a metal containing zinc, may be 1.0 molar equivalent or more with respect to the impurity containing iodine represented by the general formula (4) contained in the crude fluorine-containing diepoxy compound used for the treatment. 0.01 mol% to 200 mol% is preferable with respect to the fluorine-containing diepoxy compound used for the treatment. Particularly preferably, it is 0.1 mol% to 200 mol%, and more preferably 1 mol% to 200 mol%. When the amount of zinc is too small, it is difficult to remove the impurity containing iodine. When it is too much, an operation for removing the remaining zinc is required and the work becomes complicated.

[0033] In the purification of the fluorine-containing diepoxy compound of the present invention, any solvent may be used as long as it is inert to the reaction based on common general technical knowledge, for example, aromatic solvents such as toluene, ethylbenzene, xylene, etc., ether solvents such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, tetrahydrofuran, cyclopentyl methyl ether, methyltetrahydrofuran, etc., halogenated hydrocarbon solvents such as chloroform, etc., nitrile solvents such as acetonitrile, etc., or a combination of a plurality of solvents may be used, or no solvent may be used. From the viewpoints of simplicity of operation and economy, it is preferable that the solvent content is as small as possible, and more preferably no solvent is used.

[0034] In the purification of the fluorine-containing diepoxy compound of the present invention, zinc or a metal containing zinc, an acid anhydride and water are added to the fluorine-containing diepoxy compound represented by the general formula (1) containing the unsaturated alcohol compound represented by the general formula (2), the unsaturated alcohol compound represented by the general formula (3), and the fluorine-containing iodine compound represented by the general formula (4), and the treatment is carried out. The preferable treatment temperature and time at that time are in the temperature range of 25°C to 150°C for 0.5 hour to 72 hours. The more preferable treatment temperature and time are in the temperature range of 50°C to 120°C for 1 hour to 24 hours.

[0035] In the purification of the fluorine-containing diepoxy compound of the present invention, zinc or a metal containing zinc, an acid anhydride, and water are added to the fluorine-containing diepoxy compound represented by the general formula (1) containing the unsaturated alcohol compound represented by the general formula (2), the unsaturated alcohol compound represented by the general formula (3), and the fluorine-containing iodine compound represented by the general formula (4), and after treatment, distillation is performed. However, there are no particular regulations for the operations after treatment, and it can be carried out by well-known methods. For example, after treatment, a 15% aqueous potassium hydrogen carbonate solution is added and stirred, the organic layer is recovered, 15 g of water is added to the recovered organic layer for washing with water to obtain an organic layer, and the obtained organic layer is purified by distillation or the like to obtain a high-purity fluorine-containing diepoxy compound represented by the general formula (1).

Example

[0036] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited only to these examples.

[0037] The following instruments were used for analysis. 1 H-NMR(400MHz), 19 F-NMR(376MHz), 13 C-NMR(100MHz): Bruker Avance 400. GC: GC-2025 manufactured by Shimadzu Corporation

[0038] The symbols and abbreviations in the examples are used in the following meanings. GC: Gas chromatography GC%: GC Area% (GC area percentage) Ph: Phenyl group Compound 1-4a: 1,4-bis(2’,3’-epoxypropyl)-perfluorobutane Compound 1-6a: 1,6-bis(2’,3’-epoxypropyl)-perfluorohexane Compound 1-4a is a compound in which n = 4 in the general formula (1). Compound 1-6a is a compound in which n = 6 in the general formula (1). Similarly, compound X-Ya represents a compound in which n = Y in the general formula (X). Since the unsaturated alcohol compounds represented by the general formula (2) and the general formula (3) become the corresponding ester compounds by treatment, the compounds produced by treating compound X-Ya are defined as needed in the form of X-Yb, X-Yc, X-Yd, etc. Compound 2-4a: A compound represented by the following formula (2-4a)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0039] The measurement conditions of GC are as follows. Column: DB-5 (Agilent Technologies, inner diameter 0.25 mm, film thickness 1.0 μm, length 30 m) Carrier gas: Helium, 1.7 mL / min Injection conditions: 220 °C, split ratio 1 / 50 Detection conditions: FID mode, 280 °C Column temperature conditions: Hold at 120 °C for 3 minutes, heat up to 280 °C at 10 °C / min

[0040] <Synthesis of fluorine-containing diepoxy compound>[ Synthesis Example 1 Synthesis of crude 1,6-bis(2’,3’-epoxypropyl)-perfluorohexane 802 g (1.44 mol) of 1,6-diiodoperfluorohexane and 392 g of water were mixed, and a solution prepared by dissolving 10 g (60.9 mmol) of azobisisobutyronitrile, a radical initiator, in 220 g (3.78 mol) of allyl alcohol was added dropwise so that the reaction temperature became 80 to 100°C. After the addition, the mixture was stirred for 5 hours, 362 g of 1-propanol was added to the resulting solution containing the allyl alcohol adduct of 1,6-diiodoperfluorohexane, and then the mixture was cooled to 60°C. 848 g of a 20% aqueous potassium hydroxide solution (3.02 mol as potassium hydroxide) was added so that the reaction temperature became 30 to 60°C. After stirring for 30 minutes, the organic layer was obtained, the aqueous layer was extracted with diethyl ether, and the combined organic layers were dried over sodium sulfate, filtered, and concentrated to obtain 596 g of a crude product of compound (1-6a) (containing 1.10 mol of compound (1-6a)).

[0041] When the obtained crude product was analyzed by the GC method, the analysis results were as follows. The peak assignments are also shown in Fig. 1 as an analysis example. Compound (1-6a): 76.9 GC%, Compound (6-6a): 1.0 GC%, Compound (4-6a): 1.7 GC%, Compound (2-6a): 3.8 GC%, Compound (3-6a): 4.3 GC%, 1-Propanol: 0.7 GC% Also, when the water content was measured with a Karl Fischer moisture meter, it was 215 ppm.

[0042] The analysis results were as follows. TIFF0007699006000036.tif160146

[0043] Synthesis Example 2 Synthesis of Crude 1,4-bis(2’,3’-epoxypropyl)-perfluorobutane 800 g (1.76 mol) of 1,4-diiodoperfluorobutane and 476 g of water were mixed, and a solution prepared by dissolving 11.6 g (70.4 mmol) of azobisisobutyronitrile, a radical initiator, in 307 g (5.28 mol) of allyl alcohol was added dropwise so that the reaction temperature became 75 - 95°C. After stirring for 5 hours after the addition dropwise, the resulting solution containing the allyl alcohol adduct of 1,4-diiodoperfluorobutane was cooled to 60°C, then 254 g of ethanol was added, and then 1036 g (3.70 mol as potassium hydroxide) of a 20% aqueous potassium hydroxide solution was added so that the reaction temperature became 30 - 60°C. After stirring for 30 minutes, the organic layer was obtained, the aqueous layer was extracted with diethyl ether, the combined organic layers were washed with 10% brine, and the washed organic layer was dried over sodium sulfate, filtered, and concentrated to obtain 453 g of a crude product of compound (1-4a) (containing 1.12 mol of compound (1-4a)).

[0044] When the obtained crude product was analyzed by GC method, the analysis results were as follows. Compound (1-4a): 78.3 GC%, Compound (6-4a): 1.0 GC%, Compound (4-4a): 0.8 GC%, Compound (2-4a): 2.8 GC%, Compound (3-4a): 2.7 GC%, Ethanol: 0.01 GC%. Also, when the water content was measured with a Karl Fischer moisture meter, it was 250 ppm.

[0045] The analysis results were as follows. TIFF0007699006000037.tif155145

[0046] Example 1 Purification Treatment of Crude 1,6-bis(2’,3’-epoxypropyl)-perfluorohexane 50 g of the crude product synthesized in Synthesis Example 1 (92.3 mmol of compound (1-6a)) was added to a reactor. After replacing the gas phase with nitrogen, 1.0 g (14.8 mmol) of zinc was added, 5.2 g (23.1 mmol) of benzoic anhydride was added, 50 mg (2.8 mmol) of water was added, and heat treatment was carried out at 100 °C for 3 hours. After cooling to room temperature, 93 g of a 15% aqueous potassium hydrogen carbonate solution (139.3 mmol as potassium hydrogen carbonate) was added and stirred, and the organic layer was recovered. 25 g of water was added to the recovered organic layer for washing with water to obtain 53 g of the organic layer.

[0047] When the obtained organic layer was analyzed by the GC method, the analysis results were as follows. Compound (1-6a): 73.4 GC%, Compound (6-6a): 0.7 GC%, Compound (4-6a): 0.01 GC%, Compound (2-6a): 1.3 GC%, Compound (3-6a): 1.1 GC%, Compound (2-6b): 4.5 GC%, Compound (3-6b): 5.8 GC%, 1-Propanol: 0.01 GC%

[0048] From the results of Example 1, when a crude fluorine-containing diepoxy compound containing a fluorine-containing diepoxy compound obtained from a diiodo-containing fluorine compound, a by-produced fluorine-containing unsaturated alcohol compound, and a fluorine-containing iodine compound is purified by adding zinc, water, and an acid anhydride, it can be seen that all of the by-produced fluorine-containing unsaturated alcohol compound and fluorine-containing iodine compounds (compound (6-6a), compound (4-6a), compound (2-6a), compound (3-6a)) decrease. However, since the purity was insufficient at this level, it was further purified in the following Example 2.

[0049] Example 2 Obtaining High-Purity 1,6-Bis(2’,3’-epoxypropyl)-perfluorohexane 53 g of the organic layer obtained in Example 1 was distilled under reduced pressure to an absolute pressure of 0.2 kPa using a simple distillation apparatus, and 33 g of the product was obtained.

[0050] When the obtained product was analyzed by gas chromatography (GC), the analysis results were as follows. Compound (1-6a): 95.1 GC%, Compound (6-6a): 0.3 GC%, Compound (4-6a): 0.002 GC%, Compound (2-6a): 0.9 GC%, Compound (3-6a): 0.7 GC%, Compound (2-6b): 0.1 GC%, Compound (3-6b): 0.1 GC%, 1-Propanol: Not detected

[0051] From the results of Example 2, it can be seen that by subjecting the product purified by adding zinc, water, and acid anhydride to vacuum distillation, the fluorine-containing unsaturated alcohol compound and the fluorine-containing iodine compound (Compound (6-6a), Compound (4-6a), Compound (2-6a), Compound (3-6a)) contained in the fluorine-containing diepoxy compound are all sufficiently reduced. It can also be seen that the compounds (3-6b) and (2-6b) generated by the treatment of Example 1 are also sufficiently reduced.

[0052] Comparative Example 1 Distillation of Crude 1,6-Bis(2’,3’-Epoxypropyl)-Perfluorohexane 50 g of the crude product obtained in Synthesis Example 1 was depressurized to an absolute pressure of 0.2 kPa using a simple distillation apparatus and distilled to obtain 28 g of the product.

[0053] When the obtained product was analyzed by gas chromatography (GC), the analysis results were as follows. Compound (1-6a): 90.1 GC%, Compound (6-6a): 0.6 GC%, Compound (4-6a): 1.0 GC%, Compound (2-6a): 3.1 GC%, Compound (3-6a): 2.6 GC%, 1-Propanol: Not detected

[0054] From the results of Comparative Example 1, it can be seen that simply subjecting the crude fluorine-containing diepoxy compound containing the fluorine-containing diepoxy compound obtained from the iodine-containing fluorine compound, the by-produced fluorine-containing unsaturated alcohol compound, and the fluorine-containing iodine compound to vacuum distillation still leaves a considerable amount of the by-produced fluorine-containing unsaturated alcohol compound and the fluorine-containing iodine compound (Compound (6-6a), Compound (4-6a), Compound (2-6a), Compound (3-6a)), indicating that further purification treatment is necessary. That is, the purity of the fluorine-containing diepoxy compound (1-6a) is as low as 90.1 GC%, and a considerable amount of Compound (4-6a) remains at 1.0 GC%, Compound (2-6a) at 3.1 GC%, and Compound (3-6a) at 2.6 GC%, indicating that further purification is required. However, if the purification time is prolonged, the components contained may polymerize, so there is a risk that efficient purification cannot be achieved.

[0055] Examples 3 to 13 Obtaining High-Purity 1,6-Bis(2’,3’-epoxypropyl)-perfluorohexane 25 g of the crude product synthesized in [Synthesis Example 1] (46.2 mmol of Compound (1-6a)) was added to a reactor. After replacing the gas phase part with nitrogen, zinc, acid anhydride, and water were added in the predetermined amounts shown in Table 1, and heat treatment was performed at the reaction temperature and reaction time shown in Table 1. After cooling to room temperature, a 15% aqueous potassium hydrogen carbonate solution was added in a molar amount 4 times that of the acid anhydride used in terms of potassium hydrogen carbonate, and the mixture was stirred, and the organic layer was recovered. 15 g of water was added to the recovered organic layer for washing with water to obtain the organic layer. The obtained organic layer was depressurized to an absolute pressure of 0.2 kPa in a simple distillation apparatus and distilled.

[0056] The obtained product was analyzed by the GC method. The results are shown in Table 1.

[0057]

Table 1

[0058] From the results of Examples 3 to 13 shown in Table 1, a crude fluorine-containing diepoxy compound containing a fluorine-containing diepoxy compound obtained from a diiodo fluorine compound, a by-produced fluorine-containing unsaturated alcohol compound, and a fluorine-containing iodine compound was first purified by adding zinc, water, and an acid anhydride, and then distilled under reduced pressure. It can be seen that both the fluorine-containing unsaturated alcohol compound and the fluorine-containing iodine compound (Compound (4-6a), Compound (2-6a), Compound (3-6a)) contained in the fluorine-containing diepoxy compound were sufficiently reduced. It can also be seen that all of the fluorine-containing diepoxy compounds (Compound (1-6a)) have a purity of 94% by weight or more (based on GC percentage), and the purity is sufficiently high.

[0059] Example 14 Purification Treatment of Distilled Crude 1,6-Bis(2’,3’-Epoxypropyl)-Perfluorohexane 25 g (46.2 mmol of Compound (1-6a)) of the product obtained in Comparative Example 1 was added to a reactor. After replacing the gas phase part with nitrogen, 0.2 g (3.1 mmol) of zinc was added, 2.6 g (11.6 mmol) of benzoic anhydride was added, 54 mg (1.4 mmol) of water was added, and heat treatment was carried out at 100 °C for 2 hours. After cooling to room temperature, 29 g (43.6 mmol as potassium hydrogen carbonate) of 15% aqueous potassium hydrogen carbonate solution was added and stirred, and the organic layer was recovered. 15 g of water was added to the recovered organic layer for washing, and the obtained organic layer was distilled under reduced pressure to an absolute pressure of 0.2 kPa using a simple distillation apparatus.

[0060] When 18 g of the obtained product was analyzed by the GC method, the analysis results were as follows. Compound (1-6a): 98.5 GC%, Compound (6-6a): 0.5 GC%, Compound (4-6a): 0.001%, Compound (2-6a): 0.01 GC%, Compound (3-6a): 0.002 GC%, Compound (2-6b): 0.04 GC%, Compound (3-6b): 0.03 GC%

[0061] From the results of Example 14, it can be seen that the distillation operation shown in Comparative Example 1 alone is insufficient. After further adding zinc, water, and acid anhydride for purification and then performing vacuum distillation, the fluorine-containing unsaturated alcohol compound and fluorine-containing iodine compound (Compound (4-6a), Compound (2-6a), Compound (3-6a)) contained in the fluorine-containing diepoxy compound are all sufficiently reduced. Also, similar to Example 2, it can be seen that the by-produced Compound (2-6b) and Compound (3-6b) are also sufficiently reduced. Furthermore, it can be seen that the fluorine-containing diepoxy compound (Compound (1-6a)) is 98.5% by weight (based on GC percentage), and the purity is extremely high.

[0062] Comparative Examples 2 to 4 Purification Treatment of Crude 1,6-bis(2’,3’-epoxypropyl)-perfluorohexane 25 g of the crude product synthesized in Synthesis Example 1 (46.2 mmol of Compound (1-6a)) was added to a reactor. After replacing the gas phase part with nitrogen, the predetermined amounts of zinc, acid anhydride, and water shown in Table 1 were added, and heat treatment was performed at the reaction temperature and reaction time shown in Table 1. After cooling to room temperature, the amount of 15% aqueous potassium hydrogen carbonate solution shown in Table 1 was added and stirred, and the organic layer was recovered. 15 g of water was added to the recovered organic layer for washing with water to obtain the organic layer. The obtained organic layer was depressurized to an absolute pressure of 0.2 kPa in a simple distillation apparatus and distilled.

[0063] The obtained product was analyzed by the GC method. The results are shown in Table 2.

[0064]

Table 2

[0065] From the results of Comparative Example 2, for the crude fluorine-containing diepoxy compound containing the fluorine-containing diepoxy compound obtained from the diiodo fluorine-containing compound, the by-produced fluorine-containing unsaturated alcohol compound, and the fluorine-containing iodine compound, even after adding zinc and acid anhydride for purification and then performing distillation under reduced pressure, the fluorine-containing iodine compound (Compound (4-6a)) still remains considerably, indicating that further purification treatment is necessary. It can be inferred that water addition is required in the first purification step. From the results of Comparative Example 3, for the crude fluorine-containing diepoxy compound containing the fluorine-containing diepoxy compound obtained from the diiodo fluorine-containing compound, the by-produced fluorine-containing unsaturated alcohol compound, and the fluorine-containing iodine compound, even after adding zinc, water, and acid anhydride for purification and then performing distillation under reduced pressure, the purity of the fluorine-containing diepoxy compound is low (91.2% by weight), and the fluorine-containing unsaturated alcohol compounds (Compound (2-6a), Compound (3-6a)) still remain considerably, indicating that further purification treatment is necessary. It can be inferred that the amount of water added was excessive in the first purification step, or the balance with other additives was poor. From the results of Comparative Example 4, for the crude fluorine-containing diepoxy compound containing the fluorine-containing diepoxy compound obtained from the diiodo fluorine-containing compound, the by-produced fluorine-containing unsaturated alcohol compound, and the fluorine-containing iodine compound, even after adding water and acid anhydride for purification and then performing distillation under reduced pressure, the purity of the fluorine-containing diepoxy compound is low (93.5% by weight), and the fluorine-containing iodine compound (Compound (4-6a)) still remains considerably, indicating that further purification treatment is necessary. It can be inferred that zinc addition is required in the first purification step.

[0066] From the above, in any of Comparative Examples 2, 3, and 4, even when performing the same steps as in the examples (the step of adding additives and the distillation step), depending on the conditions, it can be seen that the purity of the fluorine-containing diepoxy compound (1-6a), and the remaining fluorine-containing unsaturated alcohol compound and fluorine-containing iodine compound as by-products will be affected. Therefore, further purification is required, but if the purification time is prolonged, the components contained may polymerize, so there is a risk that efficient purification cannot be achieved.

[0067] Example 15 Obtaining High-Purity 1,4-Bis(2’,3’-Epoxypropyl)-Perfluorobutane 50 g of the crude product synthesized in Synthesis Example 2 (123 mmol of Compound (1-4a)) was added to a reactor. After replacing the gas phase with nitrogen, 1.3 g (20.2 mmol) of zinc was added, 7.0 g (30.9 mmol) of benzoic anhydride was added, 66 mg (3.7 mmol) of water was added, and heat treatment was performed at 100 °C for 3 hours. After cooling to room temperature, 82.6 g of a 15% aqueous potassium hydrogen carbonate solution (123.8 mmol as potassium hydrogen carbonate) was added and stirred. The organic layer was recovered, and again 82.6 g of a 15% aqueous potassium hydrogen carbonate solution (123.8 mmol as potassium hydrogen carbonate) was added and stirred, and the organic layer was recovered. 25 g of water was added to the recovered organic layer for washing, and 52 g of the organic layer was obtained. 51 g of the obtained organic layer was distilled under reduced pressure to an absolute pressure of 0.2 kPa using a simple distillation apparatus, and 34 g of the product was obtained.

[0068] When the obtained product was analyzed by the GC method, the analysis results were as follows. Compound (1-4a): 94.4 GC%, Compound (6-4a): 0.3 GC%, Compound (4-4a): 0.002 GC%, Compound (2-4a): 0.5 GC%, Compound (3-4a): 0.4 GC%, Compound (2-4b): 0.2 GC%, Compound (3-4b): 0.1 GC%, Ethanol: Not detected

[0069] From the results of Example 15, it can be seen that after adding zinc, water, and acid anhydride to the crude fluorine-containing diepoxy compound for purification and then performing vacuum distillation, both the fluorine-containing unsaturated alcohol compound and the fluorine-containing iodine compound (Compound (4-4a), Compound (2-4a), Compound (3-4a)) contained in the fluorine-containing diepoxy compound are sufficiently reduced. Also, similar to Example 2, it can be seen that the by-produced Compound (2-4b) and Compound (3-4b) are also sufficiently reduced. Furthermore, the fluorine-containing diepoxy compound (compound (1-4a)) is 94.4% by weight (based on GC percentage), indicating that its purity is extremely high.

[0070] In Example 2, crude 1,6-bis(2’,3’-epoxypropyl)-perfluorohexane was purified, while in Example 15, it was crude 1,4-bis(2’,3’-epoxypropyl)-perfluorohexane. It can be seen that both show the same tendency.

[0071] Comparative Example 5 Distillation of Crude 1,4-bis(2’,3’-epoxypropyl)-perfluorohexane 50 g of the crude product obtained in Synthesis Example 2 was distilled under reduced pressure to an absolute pressure of 0.2 kPa using a simple distillation apparatus, and 36 g of the product was obtained.

[0072] When the obtained product was analyzed by the GC method, the analysis results were as follows. Compound (1-4a): 87.8 GC%, Compound (6-4a): 0.2 GC%, Compound (4-4a): 0.6 GC%, Compound (2-4a): 2.6 GC%, Compound (3-4a): 1.6 GC%, Ethanol: Not detected

[0073] From the results of Comparative Example 5, it can be seen that simply subjecting the crude fluorine-containing diepoxy compound containing the fluorine-containing diepoxy compound obtained from the diiodo fluorine-containing compound, the by-produced fluorine-containing unsaturated alcohol compound, and the fluorine-containing iodine compound to vacuum distillation still leaves a considerable amount of the by-produced fluorine-containing unsaturated alcohol compound and the fluorine-containing iodine compounds (compound (4-4a), compound (3-4a), compound (2-4a)), indicating that further purification treatment is required. That is, the fluorine-containing diepoxy compound (1-4a) has a low purity of 87.8 GC%, and a considerable amount of the compound (4-4a) remains at 0.6 GC%, the compound (2-4a) at 2.6 GC%, and the compound (3-4a) at 1.6 GC%, indicating that further purification is necessary. However, if the purification time is prolonged, the components contained may polymerize, so there is a risk that efficient purification cannot be achieved.

[0074] In Comparative Example 1, crude 1,6-bis(2’,3’-epoxypropyl)-perfluorohexane was purified, while in Comparative Example 5, it was crude 1,4-bis(2’,3’-epoxypropyl)-perfluorohexane, and it can be seen that both show the same tendency.

Industrial Applicability

[0075] The high-purity fluorine-containing diepoxy compound obtained by the method of the present invention is useful as a monomer for copolymerization in optical materials, electronic materials, etc., and can be used in various optical materials and electronic materials that require high quality.

Claims

1. A fluorine-containing diepoxy compound represented by the following general formula (1): 【Chemical 36】 (wherein n represents an integer of 1 to 8), a fluorine-containing unsaturated alcohol compound represented by the following general formula (2): 【Chemical 37】 (wherein n represents an integer of 1 to 8), a fluorine-containing unsaturated alcohol compound represented by the following general formula (3): 【Chemical 38】 (wherein n represents an integer of 1 to 8), a fluorine-containing iodine compound represented by the following general formula (4): 【Chemical 39】 (wherein n represents an integer of 1 to 8), A high-purity fluorine-containing diepoxy compound composition containing the same, wherein the fluorine-containing diepoxy compound represented by the general formula (1) is 94% by weight or more (based on GC area percentage) in the total amount of the composition, the fluorine-containing unsaturated alcohol compound represented by the general formula (2) is 2.5% by weight or less (based on GC area percentage) in the total amount of the composition, the fluorine-containing unsaturated alcohol compound represented by the general formula (3) is 1.5% by weight or less (based on GC area percentage) in the total amount of the composition, and the fluorine-containing iodine compound represented by the general formula (4) is 0.5% by weight or less (based on GC area percentage) in the total amount of the composition, A composition containing a fluorine-containing diepoxy compound.

2. The fluorine-containing diepoxy compound represented by the general formula (1) is 95% by weight or more (based on GC area percentage) in the total amount of the composition, the fluorine-containing unsaturated alcohol compound represented by the general formula (2) is 2% by weight or less (based on GC area percentage) in the total amount of the composition, the fluorine-containing unsaturated alcohol compound represented by the general formula (3) is 1% by weight or less (based on GC area percentage) in the total amount of the composition, and the fluorine-containing iodine compound represented by the general formula (4) is 0.2% by weight or less (based on GC area percentage) in the total amount of the composition, A composition containing the fluorine-containing diepoxy compound according to Claim 1.

3. A composition containing the fluorine-containing diepoxy compound according to Claim 1 or Claim 2, wherein n in the general formulas (1), (2), (3) and (4) is 4 and / or 6.

4. A composition containing the fluorine-containing diepoxy compound according to Claim 1 or Claim 2, wherein n in the general formulas (1), (2), (3) and (4) is 4.

5. A composition containing the fluorine-containing diepoxy compound according to Claim 1 or Claim 2, wherein n in the general formulas (1), (2), (3) and (4) is 6.

6. 100 parts by weight of a fluorine-containing diepoxy compound represented by the following general formula (1): 【Chemical 52】 (wherein n represents an integer of 1 to 8), and relative to the fluorine-containing diepoxy compound represented by the general formula (1), - The following general formula (2): 【Chemical 53】 (In the formula, n represents an integer of 1 to 8) 0.1 to 20 parts by weight (based on GC area percentage) of a fluorine-containing unsaturated alcohol compound represented by the formula, and - The following general formula (3): 【Chemical 54】 (In the formula, n represents an integer of 1 to 8) 0.1 to 40 parts by weight (based on GC area percentage) of a fluorine-containing unsaturated alcohol compound represented by the formula, and - The following general formula (4): 【Chemical Formula 55】 (In the formula, n represents an integer of 1 to 8) 0.1 to 20 parts by weight (based on GC area percentage) of a fluorine-containing iodine compound represented by the formula, and A composition containing a fluorine-containing diepoxy compound containing the above is Zinc or a metal containing zinc and an acid anhydride and 0.1 mol% to 50 mol% of water are added to the fluorine-containing diepoxy compound represented by the above general formula (1), treated, and then distilled. A method for purifying a fluorine-containing diepoxy compound represented by the above general formula (1).

7. The following general formula (5): 【Chemical 56】 (In the formula, n represents an integer of 1 to 8) The perfluorodiiodide represented by the formula is reacted with allyl alcohol in the presence of a radical initiator, and then dehydroiodinated with a basic compound to obtain a crude fluorine-containing diepoxy compound. To the obtained crude fluorine-containing diepoxy compound Zinc or a metal containing zinc, an acid anhydride, and 0.1 mol% to 50 mol% of water with respect to the fluorine-containing diepoxy compound represented by the following general formula (1) are added, treated, and then distilled. A method for purifying a fluorine-containing diepoxy compound represented by the following general formula (1). 【Chemical 57】

8. The method for purifying a fluorine-containing diepoxy compound according to claim 6 or claim 7, wherein the amount of the acid anhydride used is 0.01 mol% to 100 mol% with respect to the fluorine-containing diepoxy compound.

9. The method for purifying a fluorine-containing diepoxy compound according to claim 6 or claim 7, wherein the amount of water is 1 mol% to 45 mol% with respect to the fluorine-containing diepoxy compound.

10. The method for purifying a fluorine-containing diepoxy compound according to claim 6 or claim 7, wherein the amount of zinc contained in zinc or a metal containing zinc is 0.01 mol% to 100 mol% with respect to the fluorine-containing diepoxy compound.

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