JP5576705B2 - Diaryliodonium salt mixture and process for producing the same - Google Patents

Description

  The present invention relates to a diaryl iodonium salt mixture and a method for producing a diaryl iodonium salt mixture.

A salt of a diaryliodonium compound is used as a polymerization initiator. For example, Patent Documents 1 to 5 disclose BF ₄ , PF ₆ , SbF ₆ and AsF ₆ salts of diaryliodonium compounds having various side chains as polymerization initiators. Among them, a salt of bis (dodecylphenyl) iodonium is also included.

  When a salt of a diaryliodonium compound is used as a polymerization initiator or the like, the phenyl moiety may be liberated by decomposition. As a result, for example, benzene, toluene and the like are produced, but these compounds have toxicity such as carcinogenicity and are restricted in use. In contrast, bis (dodecylphenyl) iodonium salt substituted with a long-chain alkyl group dodecyl group is said to be relatively low in toxicity of dodecylbenzene produced by decomposition, so that it can be applied to polymerization initiators and the like. I can expect.

By the way, as described above, BF ₄ salt of a diaryl iodonium compound is used as a polymerization initiator, but BF ₄ salt of bis (dodecylphenyl) iodonium has a problem of low compatibility with monomers. Such a problem is not important when a polymer is produced on a small scale at a laboratory level, but is problematic in industrial mass production because it leads to a decrease in production efficiency.

The BF ₄ salt of a diaryl iodonium compound is usually synthesized from a salt of a diaryl iodonium compound and a halide ion. Examples of such halide salts include bis (dodecylphenyl) iodonium chloride salts disclosed in Patent Documents 4 to 5. The chloride salt is a solid formed by reacting a mixture of sulfuric acid and acetic acid dropwise in a mixed solvent of acetic acid and acetic anhydride to a mixture of dodecylbenzene and potassium iodate, then adding a sodium chloride solution and cooling. Is produced by recrystallization.

  In Non-patent Document 1, bromide and iodide salts of bis (dodecylphenyl) iodonium are produced in the same manner as in Patent Documents 4 to 5 except that a sodium bromide solution or a potassium iodide solution is finally used. An example is described.

JP 2005-120311 A Japanese Patent Laid-Open No. 7-3028 JP 2001-11185 A JP-A-6-184170 Japanese Patent Laid-Open No. 6-41433

F. Marshall Beringer, 6 others, Journal of American Chemical Society, vol. 81, pp.342-351 (1959)

As described above, conventionally, a BF ₄ salt of a diaryliodonium compound or the like has been used as a polymerization initiator.

The present inventors, as a BF ₄ salt of safer diaryliodonium compound was prepared BF ₄ salt of bis (dodecyl phenyl) iodonium. However, the BF ₄ salt and the like have poor solubility in monomers and are unsuitable for industrial mass production of polymers. Therefore, in order to increase the solubility of the BF ₄ salt in a monomer, an attempt was made to produce a BF ₄ salt or the like of a mixture of diaryl iodonium compounds substituted with a long-chain alkyl group.

However, when trying to produce a BF ₄ salt of a mixture of diaryl iodonium compounds substituted with a long-chain alkyl group, the precursor chloride salt did not crystallize. It could not be purified by a simple method. Then, it is difficult to mass-produce industrially.

As described above, BF ₄ salts of diaryliodonium compounds and the like are required to be soluble in monomers when used as polymerization initiators, but are obtained as crystals at the precursor stage in order to increase production efficiency. There is a need for mutually conflicting characteristics that need to be achieved. Further, in order to use the BF ₄ salt or the like in mass production of a polymer or the like, it is necessary that the BF ₄ salt or the like itself can be efficiently produced.

Therefore, the present invention is a precursor of a diaryl iodonium compound such as a BF ₄ salt, which is obtained as a crystal at room temperature, is easily purified and can be efficiently produced, and is derived into a BF ₄ salt or the like. An object of the present invention is to provide a diaryliodonium salt mixture having excellent solubility in monomers and the like, and a method for producing the mixture.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, if a bromide salt or iodide salt, which is usually easy to color or has a low yield, can be avoided, it can be obtained as a crystal even if the diaryliodonium moiety substituted with a long-chain alkyl group is a mixture. And the present invention has been completed.

  The diaryl iodonium salt mixture according to the present invention includes two or more diaryl iodonium salts represented by the formula (I).

[Wherein, R ¹ and R ² each independently represent a C _8-20 alkyl group]

In the present invention, the “C _8-20 alkyl group” refers to a linear or branched aliphatic hydrocarbon group having _{8 to} 20 carbon atoms. If the number of carbon atoms is 8 or more, highly toxic lower alkylbenzene will not be produced by decomposition. On the other hand, when the number of carbon atoms exceeds 20, the mixture of diaryl iodonium salts becomes difficult to crystallize and purification becomes difficult, and therefore the number of carbon atoms is preferably 20 or less. Examples of the group include n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-icosyl, methylnonyl, methyldecyl. , Methylundecyl, methyldodecyl, dimethyloctyl, dimethylnonyl, dimethyldecyl, dimethylundecyl, ethylnonyl, ethyldecyl, ethylundecyl, ethyldodecyl, and the like. Of these, C _9-18 alkyl is preferred, and C _10-16 alkyl is more preferred.

As the diaryl iodonium salt mixture according to the present invention, a diaryl iodonium salt (I) having a highest content is preferably 50% by mass or less. Since the diaryliodonium salt mixture is obtained as a crystal, it is excellent in productivity. On the other hand, when it is derived into a BF ₄ salt, it does not become a solid at room temperature, and has excellent solubility in monomers and the like. It has the advantage of showing.

The manufacturing method of the diaryl iodonium salt mixture which concerns on this invention manufactures the mixture containing 2 or more types of the said diaryl iodonium salt;
Synthesizing a diaryl iodonium mixture containing two or more diaryl iodonium compounds represented by formula (III) from an alkyl aryl mixture containing two or more alkyl aryl compounds represented by formula (II);

[Wherein R ³ represents a C _8-20 alkyl group; R ¹ and R ² have the same meaning as described above]
Adding a bromide or iodide salt of an alkali metal or alkaline earth metal to a solution of the mixture of diaryliodonium compounds (III).

In the above-mentioned method of the present invention, it is preferable to use an alkylaryl mixture as a raw material having a ratio of the alkylaryl compound (II) having the highest content of 50% by mass or less. When such an alkylaryl mixture is used as a raw material, the diaryliodonium salt mixture can be obtained as a crystal more reliably. On the other hand, when the diaryliodonium salt mixture is derived into a BF ₄ salt or the like, it is solid at room temperature. In other words, it exhibits excellent solubility in monomers and the like.

  In the said method of this invention, it is preferable to adjust so that the ratio of what has the largest content among diaryl iodonium compounds (III) contained in a diaryl iodonium mixture may be 50 mass% or less.

As in the case of the raw material compound, according to such an embodiment, the diaryl iodonium salt mixture can be more reliably obtained as a crystal, and when derived into a BF ₄ salt or the like, a diaryl iodonium salt having high solubility in a monomer or the like Can be manufactured more reliably.

Since the mixture of diaryliodonium salts according to the present invention is crystalline at room temperature, it can be purified by a simple method suitable for industrial production such as washing with a poor solvent and recrystallization. In addition, when it is derived into a BF ₄ salt or the like, it does not become a solid at room temperature, so it has a high solubility in monomers and is excellent as a catalyst that can be used in industrial mass production processes. Further, according to the method of the present invention, a mixture of diaryliodonium salts that are crystalline at room temperature and highly soluble in monomers when derived into BF ₄ salts and the like can be efficiently produced. Therefore, the present invention is extremely useful industrially as a technique relating to a diaryliodonium salt mixture useful as a raw material compound for a polymerization initiator.

¹ is a ¹ H-NMR chart of a mixture of alkylaryl compounds used as raw materials in the method of the present invention. ^{1 is} a ¹ H-NMR chart of dodecylbenzene. ¹ is a ¹ H-NMR chart of a diaryl iodonium bromide salt mixture according to the present invention. ¹ is a ¹ H-NMR chart of a diaryl iodonium iodide salt mixture according to the present invention.

  The diaryl iodonium salt mixture according to the present invention contains two or more of the following diaryl iodonium salts (I).

[Wherein, R ¹ and R ² each independently represent a C _8-20 alkyl group]

The mixture is crystalline at room temperature and can be purified by a simple method such as washing, but it does not become a solid when induced to a BF ₄ salt or the like, and therefore has excellent solubility in monomers and the like.

In particular, when the ratio of the diaryl iodonium salt (I) having the highest content is 50% by mass or less, the solubility in a monomer or the like when derived into a BF ₄ salt or the like is improved. As the said ratio, 30 mass% or less is more preferable, and 25 mass% or less is further more preferable.

As described above, the mixture of the diaryl iodonium salt (I) according to the present invention is crystalline at room temperature, but when it is derived into a BF ₄ salt or the like, it does not become solid but has solubility in monomers and the like. Since it is excellent, it can be utilized as a raw material compound for industrially synthesizing a large amount of a polymerization initiator.

  The manufacturing method of the diaryl iodonium salt mixture which concerns on this invention is demonstrated according to the order of implementation.

  In the method of the present invention, a diaryl iodonium mixture containing two or more diaryl iodonium compounds (III) is first synthesized from an alkyl aryl mixture containing two or more alkyl aryl compounds (II).

  More specifically, for example, by mixing a mixture of an alkylaryl compound (II) with iodate or periodate in acetic anhydride and acetic acid, and then adding dropwise a mixture of concentrated sulfuric acid and acetic acid, To obtain a sulfate mixture.

  Since the alkylaryl compound (II) which is a raw material compound of the method of the present invention has a relatively simple structure, it may be purchased and used as long as it is commercially available, or a commercially available compound by a method known to those skilled in the art. It may be synthesized from For example, after synthesizing benzene having a long-chain acyl group as a substituent by Friedel-Crafts reaction using the corresponding acyl chloride and benzene, the carbonyl group is reduced to easily convert the alkylaryl compound (II). Can be synthesized.

In the method of the present invention, a mixture of alkylaryl compounds (II) is used as a raw material compound. This is because the target compound, diaryl iodonium salt, is obtained as a mixture. The number of alkylaryl compounds (II) contained in the alkylaryl mixture as a raw material is not particularly limited, but is naturally 2 or more. In order to increase the solubility in monomers and the like more reliably when the target compound diaryl iodonium salt mixture is derived into BF ₄ salt, the number of alkylaryl compounds (II) is preferably 5 or more, more preferably Is 10 or more. On the other hand, if the number of alkylaryl compounds (II) is excessively large, the diaryl iodonium salt mixture as the target compound may not be crystallized even if it is purified. 50 or less, more preferably 40 or less, further preferably 30 or less, and further preferably 25 or less.

The proportion of each alkylaryl compound (II) contained in the alkylaryl mixture as a raw material may be adjusted as appropriate, but if the content of a specific compound is prominent, even if the resulting diaryliodonium salt is a mixture, When induced to BF ₄ salt or the like, it may be crystallized. Therefore, the ratio of the alkylaryl compound (II) having the highest content is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

Examples of the iodate used in this reaction include potassium iodate (KIO ₃ ) and sodium iodate (NaIO ₃ ).

The periodate used in this reaction is M ¹ IO ₄ [wherein M ¹ represents an alkali metal] or M ² (IO ₄ ) ₂ [wherein M ² represents an alkaline earth metal] Can be mentioned. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium. Preferably, lithium periodate (LiIO ₄ ), potassium periodate (KIO ₄ ), or sodium periodate (NaIO ₄ ) is used.

  The amount of iodate or periodate used may theoretically be 0.5 mol times the alkylaryl mixture, but is preferably 0.3 mol times or more, more preferably 0.4 mol times or more. The molar ratio is preferably 1 mol times or less, more preferably 0.8 mol times or less.

  The ratio of acetic anhydride and acetic acid in the mixture of acetic anhydride and acetic acid to which the alkylaryl mixture and iodate or periodate are added may be adjusted as appropriate, but in general, acetic anhydride / acetic acid = 2 in terms of mass ratio. It may be in the range of / 1 to 1/2.

  The amount of the mixed solution of acetic anhydride and acetic acid may be appropriately adjusted. For example, the amount of the alkylaryl mixture and the amount of iodate or periodate used is about 1.2 times by mass or more and about 3 times by mass or less. can do. If the amount of the mixed solution of acetic anhydride and acetic acid is too small, it may be difficult to stir the reaction solution, whereas if the amount is too large, purification may be difficult.

  In this step, first, an alkylaryl mixture and iodate or periodate are added to a mixture of acetic anhydride and acetic acid and mixed. The mixed solution may be subjected to the reaction as it is, but since the temperature rises by adding sulfuric acid, it may be ice-cooled.

  Next, sulfuric acid is dropped into the mixed solution. The sulfuric acid used here is not dilute sulfuric acid but is called concentrated sulfuric acid. The usage-amount of a sulfuric acid should just be 0.5 mol times or more and 10.0 mol times or less with respect to an aryl compound. If the said ratio is 0.5 mol times or more, reaction can fully be advanced. On the other hand, if the ratio exceeds 10.0 mole times, post-treatment and purification of the reaction solution may take time and labor. The ratio is more preferably 0.8 mole times or more. If it is 0.8 mol times or more, the diaryliodonium compound (III), which is the target compound, can be more reliably obtained in a high yield. More preferably, it is 1 mol times or more and 3 mol times or less. The sulfuric acid to be dripped may be diluted with a solvent such as acetic acid. At this time, the solvent used for dilution can be about 0.2 volume times or more and 5.0 volume times or less with respect to sulfuric acid.

  If sulfuric acid is added dropwise, the temperature of the reaction solution rises and the reaction proceeds excessively, and the reaction solution may be colored. Therefore, the reaction rate may be adjusted by adjusting the dropping rate, cooling the reaction solution with water, or cooling with ice. It is preferable to adjust the temperature of the liquid to be about 30 ° C. or higher and 60 ° C. or lower.

After the dropping of sulfuric acid, it is preferable to continue the reaction at about 10 ° C. or more and 100 ° C. or less in order to complete the reaction. The reaction time is not particularly limited, but can be about 1 hour or more and 10 hours or less. The specific reaction time may be determined, for example, by confirming the consumption of the alkylaryl compound (II) by ¹ H-NMR or by preliminary experiments.

  As the treatment after the completion of the reaction, a conventional method can be used. For example, water may be added to remove by-products and impurities, and the resulting mixture of diaryliodonium compounds (III) may be extracted with an organic solvent.

  Since heat is generated when water is added to the reaction solution, the reaction solution may be cooled or water may be added dropwise. Moreover, it is preferable that the usage-amount of water shall be about 50 volume% or more and 500 volume% or less with respect to the reaction liquid. If the amount of water is too small, there is a risk that by-products and the like cannot be removed sufficiently, and conversely, if the amount of water is too large, the productivity may decrease.

  The extraction solvent for the diaryliodonium mixture is not particularly limited as long as it is excellent in solubility of the mixture and is immiscible with water. For example, cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, pentane, hexane, Chain hydrocarbon solvents such as heptane, octane, isooctane and isododecane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ethers such as diisopropyl ether, t-butyl methyl ether and dibutyl ether can be used. The obtained extract may be washed with water, an aqueous sodium hydrogen carbonate solution, an aqueous sodium sulfate solution, an aqueous sodium carbonate solution, an aqueous sodium hydrogen sulfate solution, or the like.

R ¹ and R ² which are substituents of the diaryl iodonium compound (III) contained in the reaction solution are the same as R ³ which is a substituent of any alkyl aryl compound (II) contained in the raw material mixture.

  After completion of the reaction, the diaryliodonium compound (III) is dissolved in the reaction solution or the extract and exists in the form of iodonium ions. If the diaryliodonium compound (III) is isolated at this stage, it can be obtained in the form of a salt with the anion present in the reaction solution or extract. Examples of the salt include sulfate, hydrogen sulfate, and acetate.

  Next, an alkali metal or alkaline earth metal bromide salt or iodide salt is added to a solution of the mixture of diaryl iodonium compound (III), and the mixture of compound (I) which is a bromide salt or iodide salt of diaryl iodonium is added. obtain.

  Examples of the alkali metal of the bromide salt or iodide salt used in this reaction include lithium, sodium, and potassium, and examples of the alkaline earth metal include magnesium and calcium.

  Among these bromide salts and iodide salts, it is preferable to use iodide salts. The diaryliodonium salt mixture according to the invention is obtained in a better yield in the iodide salt mixture than in the bromide salt mixture.

  An alkali metal or alkaline earth metal bromide salt or iodide salt may be added as an aqueous solution. The concentration of the aqueous solution to be used is not particularly limited, but may be about 5% by mass or more and 80% by mass or less. Moreover, the usage-amount of the said bromide salt etc. is not restrict | limited in particular, What is necessary is just to make it excess with respect to the mixture of a diaryl iodonium compound (III).

  After adding an aqueous solution such as an alkali metal bromide salt, the mixture may be stirred for about 10 minutes to 60 minutes and then separated. The operation of separating the liquid after adding the aqueous solution and stirring may be repeated a plurality of times.

  Next, the organic phase may be collected and concentrated under reduced pressure, or a crystal may be separated after adding a poor solvent and separated. Before that, the organic phase may be dried with anhydrous magnesium sulfate or the like.

  The residue obtained by concentration under reduced pressure of the organic phase mainly contains a plurality of diaryliodonium salts (I) according to the present invention, and is in a crystalline form despite being a mixture. Moreover, as mentioned above, the mixture of the diaryliodonium salts (I) according to the present invention can be obtained as crystals even when a poor solvent is added to the organic phase. These crystals can be further purified by a very simple method such as washing with a poor solvent such as methanol, ethanol, isopropanol or recrystallization.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

Example 1 Preparation of diaryliodonium bromide salt mixture Alkene L (manufactured by Nippon Oil Co., Ltd., average molecular weight: 241), which is a mixture of benzene substituted with a long-chain alkyl having 10 to 13 carbon atoms, was analyzed by GC-MS. The molecular weight of each peak was determined. Further, the content of each component was calculated from the area ratio of each peak. The results are shown in Table 1.

  As described above, the alkene L contained 18 kinds of long-chain alkylbenzenes, and the content thereof was 13.0% at the maximum.

A ¹ H-NMR chart of Alkene L is shown in FIG. As shown in FIG. 1, in the vicinity of 2.3 to 2.7 ppm, there are three broad peaks derived from protons of a methylene group (—CH ₂ — group) or a methine group (—CH <group) directly connected to the benzene ring. A peak is seen. Further, in the vicinity of 0.7 to 1.8 ppm, there is a complex peak derived from protons other than the above in the alkyl group. For comparison, FIG. 2 shows a ¹ H-NMR chart of dodecylbenzene alone. As shown in FIG. 2, there is only a triplet derived from a methylene group (—CH ₂ — group) directly connected to the benzene ring in the vicinity of 2.3 to 2.7 ppm. Moreover, the peak around 0.8 to 1.6 ppm is very simple compared to FIG. As can be seen from the ¹ H-NMR chart, alkene L is a mixture of benzenes substituted with various alkyl groups.

In a four-necked flask equipped with a reflux tube, a dropping funnel, a nitrogen introduction tube and a thermometer, Alkene L (manufactured by Nippon Oil Corporation, 50.00 g), potassium iodate (21.44 g), acetic anhydride (51.00 g) ) And acetic acid (99.04 g) were added, and the atmosphere in the reactor was replaced with nitrogen. A mixture of concentrated sulfuric acid (29.46 g) and acetic acid (20.20 g) was placed in the dropping funnel, and the mixture was added dropwise over 1.5 hours so that the reaction solution temperature did not exceed 40 ° C. while flowing nitrogen gas. After completion of dropping, the reaction solution was stirred at 40 ° C. for 2 hours. Then, water (100.44g) was dripped at the reaction liquid, cooling. Furthermore, hexane (100.68 g) was added to the reaction solution and stirred for 30 minutes. The organic phase was separated from the reaction solution separated into two layers and washed with a saturated aqueous sodium hydrogen carbonate solution (200.80 g). Separately, potassium bromide (12.80 g) was dissolved in water (101.19 g), and the obtained potassium bromide aqueous solution was added to the organic phase (200.08 g), stirred for 30 minutes, and separated into two layers. An organic phase was obtained from the reaction solution. Separately, potassium bromide (5.30 g) was dissolved in water (101.89 g), the organic phase was washed with the obtained aqueous potassium bromide solution, and then the organic phase was concentrated under reduced pressure. The obtained residue was solid. Isopropanol (252.87 g) was added to the residue and stirred, and the solid was collected by filtration. The obtained solid was washed with isopropanol and dried under reduced pressure at 60 ° C. to obtain a diaryliodonium bromide salt mixture (yield: 15.50 g, yield 22.5%). When the obtained bromide salt was analyzed by ¹ H-NMR, complex peaks based on a plurality of side chain alkyl groups were seen as shown in FIG. Was hardly observed and its purity was sufficiently high.

Example 2 Preparation of iodide salt mixture of diaryliodonium Alkene L (manufactured by Nippon Oil Corporation, 150.06 g), potassium iodate in a four-necked flask equipped with a reflux tube, a dropping funnel, a nitrogen introduction tube and a thermometer (66.56 g), acetic anhydride (158.90 g) and acetic acid (150.26 g) were added, and the atmosphere in the reactor was replaced with nitrogen. A mixture of concentrated sulfuric acid (91.66 g) and acetic acid (60.16 g) was placed in the dropping funnel, and the mixture was added dropwise over 1 hour so that the reaction solution temperature did not exceed 40 ° C. while flowing nitrogen gas. After completion of dropping, the reaction solution was stirred at 40 ° C. for 2 hours. Then, water (300.82g) was dripped at the reaction liquid, cooling. Furthermore, cyclohexane (150.42g) was added to the reaction liquid, and it stirred for 30 minutes. An organic phase (436.66 g) was obtained from the reaction solution separated into two layers. Separately, sodium iodide (156.00 g) was dissolved in water (56.48 g), and the obtained sodium iodide aqueous solution was added to the organic phase and stirred for 30 minutes. The reaction solution was separated to obtain an organic phase (460.00 g). When methanol (778.00 g) and ethanol (778.76 g) were added to the organic phase, a precipitate was formed. The resulting precipitate was collected by filtration, washed with ethanol (240.00 g), and then dried under reduced pressure at 60 ° C. to obtain a diaryliodonium iodide salt mixture (yield: 114.64 g, yield: 50.2%). As a result, as the diaryl iodonium salt mixture according to the present invention, the iodide salt mixture can be produced in a better yield. When the obtained iodide salt was analyzed by ¹ H-NMR, complex peaks based on a plurality of side chain alkyl groups were observed as shown in FIG. The peak was hardly observed and its purity was sufficiently high.

Example 3 Preparation of iodide salt mixture of diaryliodonium Dodecylbenzene soft type (average molecular weight: 246.43), which is a mixture of benzene substituted with a long-chain alkyl having 10 to 13 carbon atoms, was obtained from GC. -Analyzed by MS to determine the molecular weight of each peak. Further, the content of each component was calculated from the area ratio of each peak. The results are shown in Table 2.

  As described above, the dodecylbenzene soft type contained 18 kinds of long-chain alkylbenzenes, and its content was 15.2% at the maximum.

  In a four-necked flask equipped with a reflux tube, a dropping funnel, a nitrogen introduction tube and a thermometer, dodecylbenzene soft type (manufactured by Tokyo Chemical Industry Co., Ltd., 108.94 g), potassium iodate (47.01 g), acetic anhydride (113. 66 g) and acetic acid (221.10 g) were added, and the atmosphere in the reactor was replaced with nitrogen. A mixture of concentrated sulfuric acid (65.21 g) and acetic acid (44.14 g) was added to the dropping funnel, and the mixture was added dropwise over 1 hour so that the reaction solution temperature did not exceed 40 ° C. while flowing nitrogen gas. After completion of dropping, the reaction solution was stirred at 40 ° C. for 2 hours. Then, water (201.46g) was dripped at the reaction liquid, cooling. Furthermore, ethylcyclohexane (100.00 g) was added to the reaction solution and stirred for 30 minutes. The reaction solution separated into two layers was separated to obtain an organic phase (294.02 g). Separately, sodium iodide (166.35 g) was dissolved in water (109.28 g), and the resulting aqueous sodium iodide solution was added to the organic phase and stirred for 30 minutes. The reaction solution was separated to obtain an organic phase. When methanol (546.84 g) and ethanol (547.71 g) were added to the organic phase, a precipitate was formed. The resulting precipitate was collected by filtration, washed with methanol (150.91 g), and then dried under reduced pressure at 60 ° C. to obtain a mixture of iodide salts of diaryliodonium (yield: 70.25 g, yield). : 42.9%).

Comparative Example 1 Production of diaryliodonium chloride salt mixture In a four-necked flask equipped with a reflux tube, dropping funnel, nitrogen inlet tube and thermometer, Alkene L (manufactured by Nippon Oil Corporation, 20.02 g), potassium iodate (8.88 g), acetic anhydride (12.084 g) and acetic acid (39.972 g) were added, and the atmosphere in the reactor was replaced with nitrogen. A mixture of concentrated sulfuric acid (12.00 g) and acetic acid (8.138 g) was added to the dropping funnel, and the mixture was added dropwise over 1 hour so that the reaction solution temperature did not exceed 40 ° C. while flowing nitrogen gas. After completion of dropping, the reaction solution was stirred at 40 ° C. for 2.5 hours. Then, water (50.10g) was dripped at the reaction liquid, cooling. Furthermore, cyclohexane (50.06 g) was added to the reaction solution and stirred for 30 minutes. The reaction solution separated into two layers was separated to obtain an organic phase (294.02 g). Separately, sodium chloride (2.91 g) was dissolved in water (9.03 g), and the resulting aqueous sodium chloride solution was added to the organic phase and stirred for 30 minutes. The reaction solution was separated to obtain an organic phase. Separately, sodium chloride (2.81 g) was dissolved in water (8.69 g), the organic phase was washed with the obtained aqueous sodium chloride solution, and then the solvent was distilled off from the organic phase under reduced pressure.

  However, since the obtained residue did not solidify, it could not be purified by a simple method such as washing with a poor solvent.

Example 4 Production of diaryliodonium compound using sodium periodate Alkene L (manufactured by Nippon Oil Corporation, C _10-13 alkyl) was added to a four-necked flask equipped with a reflux tube, a dropping funnel, a nitrogen introduction tube and a thermometer. After adding a mixture of substituted benzene compounds, molecular weight: 241, 4.93 g), sodium periodate (NaIO ₄ , 2.14 g), acetic anhydride (4.09 g) and acetic acid (4.01 g) The atmosphere in the reactor was replaced with nitrogen. A mixture of concentrated sulfuric acid (2.94 g) and acetic acid (2.00 g) was placed in the dropping funnel and added dropwise over 1 hour so that the reaction solution temperature did not exceed 40 ° C. After completion of dropping, the mixture was stirred at 50 ° C. for 5 hours. Then, water (5.01g) was dripped at the reaction liquid, cooling. Further, cyclohexane (5.00 g) was added to the reaction solution and stirred for 30 minutes. An organic phase (15.76 g) was obtained from the reaction solution separated into two layers. Separately, sodium iodide (1.50 g) was dissolved in water (2.98 g), and the obtained aqueous sodium iodide solution was added to the organic phase and stirred for 30 minutes. The reaction solution was separated, and methanol (50.34 g) was added to the obtained organic phase, resulting in crystallization. The obtained crystal was separated from the solution by pressure filtration with a pressure of 0.14 MPaG loaded using a pressure filter with an inner diameter of 47 mm. The filtration time at that time was 9.5 seconds, the amount of the obtained filtrate was 55.4 g, and the filtration rate was 12166 kg / h · m ² . The obtained crystal was washed with methanol (10.34 g) and dried under reduced pressure at 60 ° C. to obtain a diaryliodonium compound crystal (yield: 4.50 g, yield: 60.4%).

When a part of the obtained crystal was analyzed by ¹ H-NMR, the presence of para-iodododecylbenzene as a by-product was not recognized.

Claims (5)

A diaryliodonium salt mixture comprising 15 or more diaryliodonium salts represented by the formula (I).
[Wherein, R ¹ and R ² each independently represent a C _8-20 alkyl group]   The diaryl iodonium salt mixture according to claim 1, wherein the ratio of the diaryl iodonium salt (I) having the highest content is 50% by mass or less. A process for preparing a diaryliodonium salt mixture;
The diaryliodonium salt mixture contains 15 or more diaryliodonium salts represented by formula (I);
[Wherein, R ¹ and R ² each independently represent a C _8-20 alkyl group]
Synthesizing a diaryl iodonium mixture containing 15 or more diaryl iodonium compounds represented by formula (III) from an alkyl aryl mixture containing 5 or more alkyl aryl compounds represented by formula (II);
[Wherein R ³ represents a C _8-20 alkyl group; R ¹ and R ² have the same meaning as described above]
Adding an alkali metal or alkaline earth metal bromide or iodide salt to a solution of the diaryliodonium compound (III) mixture;
The manufacturing method characterized by including.   The production method according to claim 3, wherein the alkylaryl mixture as a raw material is one having a ratio of the alkylaryl compound (II) having the highest content of 50% by mass or less.   The production method according to claim 3 or 4, wherein the proportion of the diaryl iodonium compound (III) contained in the diaryliodonium compound (III) having the highest content is 50% by mass or less.