Method for producing diaiodide and composition containing diaiodide
By separating diiodides from a crude composition using an aqueous hydroxide solution to remove ethers and esters, the method addresses low yield issues in conventional diiodide production, achieving high-purity and high-yield diiodide recovery.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- DAIKIN INDUSTRIES LTD
- Filing Date
- 2024-03-14
- Publication Date
- 2026-07-30
AI Technical Summary
Conventional methods for producing diiodides through telomerization reactions face issues with low yield due to the presence of ethers and esters generated during the process, which hinder effective separation and recovery of diiodides by fractional distillation.
A method involving mixing a crude composition containing diiodides with an aqueous solution of hydroxide to separate into phases, allowing for the recovery of high-purity diiodides by removing ethers and esters, followed by distillation to achieve high yield and purity.
The method enables the separation and recovery of diiodides in high purity and yield by eliminating impurities, improving the efficiency of diiodide production.
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Abstract
Description
Technical Field
[0001] The present disclosure relates to a method for manufacturing a diode and a composition containing a diode.
Background Art
[0002] In Patent Document 1, 1,2-diiodotetrafluoroethylene and tetrafluoroethylene are reacted in the presence of a catalytic amount of a free radical catalyst to form a telomeric product of the following formula I(CF2CF2) n I (where n is 2 to 10), and a method for producing alpha-omega-diiodinated alkanes is described in which this telomeric product is absorbed from the reaction mixture.
Prior Art Documents
Patent Documents
[0003] <0002 (In the formula, R 2 Esters represented by (an organic group) At least one selected from the group consisting of A crude composition containing, General formula (2-1):M(OH) p A hydroxide represented by (wherein p is 1 or 2, and M is an alkali metal or alkaline earth metal), and an aqueous solution containing water, A mixture is prepared by mixing the following: The mixture is separated into a phase containing the diaiodide and a phase containing water, and the phase containing the diaiodide is recovered. A manufacturing method is provided. [Effects of the Invention]
[0006] This disclosure provides a method for producing high-purity diiodide. [Modes for carrying out the invention]
[0007] The following describes specific embodiments of this disclosure in detail, but this disclosure is not limited to the embodiments described below.
[0008] Patent Document 1 proposes a method for producing alpha-omega-diiodized fluoride alkanes by a telomerization reaction in which 1,2-diiodotetrafluoroethylene is used as the telogen and tetrafluoroethylene as the taxogen to form telomerized products. Patent Document 1 also states that the telomers can be separated by fractional distillation of the telomer mixture under reduced pressure, if desired.
[0009] However, when attempting to separate and recover telomeres (dioidides) by fractional distillation of telomeric products produced by such conventional manufacturing methods, there is a problem in that each telomer cannot be recovered in sufficient yield.
[0010] Therefore, as a result of intensive studies on the cause of this problem, it was found that in addition to the diiodide, an ether or an ester was generated by the telomerization reaction, and moreover, the ether or ester in the generated reaction product was preventing the separation of the diiodide by fractional distillation, which was the cause of the low yield. Furthermore, as a result of intensive studies on the solution to this problem, a means for removing the ether or ester generated by the telomerization reaction from the reaction product was found, and by fractional distilling the reaction product from which the ether or ester had been removed, it was found that diiodides having different numbers of carbon atoms could be separated and each diiodide could be recovered in a high yield.
[0011] That is, according to the present disclosure, there is provided a method for producing a diiodide, comprising: a diiodide represented by the general formula (1-1): I(CF2CF2) n I (where n is an integer of 1 or more), an ether represented by the general formula (1-2): I(CF2CF2) m OR 1 (where m is an integer of 1 or more, and R 1 is an organic group), and at least one selected from the group consisting of an ester represented by the general formula (1-3): ICF2COOR 2 (where R 2 is an organic group), and a crude composition containing the same, a hydroxide represented by the general formula (2-1): M(OH) p (where p is 1 or 2, and M is an alkali metal or an alkaline earth metal), and an aqueous solution containing water, and preparing a mixture by mixing the same, separating the mixture into a phase containing the diiodide and a phase containing water, and recovering the phase containing the diiodide.
[0012] According to the manufacturing method of this disclosure, ethers or esters in a crude composition containing diaoidide can be separated from the crude composition, and a composition containing diaoidide in high purity can be recovered in high yield. Furthermore, by distilling the composition containing diaoidide in high purity using methods such as fractional distillation or steam distillation, diaoidide having the desired n number can be separated and recovered in high yield.
[0013] The manufacturing method of this disclosure will be described in more detail below.
[0014] This disclosure relates to a method for producing a composition containing diiodide in high purity. The method of production according to this disclosure involves mixing a crude composition containing diiodide and at least one selected from the group consisting of ethers and esters with an aqueous solution containing hydroxide and water to prepare a mixture, separating the resulting mixture into two phases, and recovering the phase containing diiodide in high purity.
[0015] In one embodiment, the crude composition is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as the telogen and tetrafluoroethylene as the taxogen. This telomerization reaction produces a crude composition containing a diaiodide represented by general formula (1-1), as well as an ether represented by general formula (1-2) or an ester represented by general formula (1-3). When the crude composition is mixed with an aqueous solution containing hydroxide, the ether and ester in the crude composition react with the hydroxide and decompose. On the other hand, the diaiodide is maintained in the mixture without decomposition. When the resulting mixture is allowed to stand, it separates into two phases: a phase mainly containing diaiodide and a phase mainly containing water or hydroxide. By recovering the phase mainly containing diaiodide, a composition containing diaiodide in high purity can be produced.
[0016] In other words, General formula (1-1): I(CF2CF2) nA diaoidide represented by I (where n is an integer greater than or equal to 1), General formula (1-2): I(CF2CF2) m Ure 1 (In the formula, m is an integer greater than or equal to 1, R 1 Ethers represented by (an organic group), and general formula (1-3): ICF2COOR 2 (In the formula, R 2 At least one selected from the group consisting of esters represented by (an organic group), Compositions containing this material are important raw materials for producing compositions containing diaiodide in high purity.
[0017] The diaiodide contained in the above crude composition is of general formula (1-1):I(CF2CF2) n It is represented by formula I (wherein n is an integer of 1 or more). n may be an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 8. In one embodiment, the crude composition contains at least a diiodide represented by general formula (1-1) where n is an integer from 1 to 8.
[0018] In one embodiment, the crude composition contains a diiodide represented by general formula (1-1) where n is an integer from 1 to 8, and also contains a diiodide represented by general formula (1-1) where n is an integer of 9 or more.
[0019] The crude composition only needs to contain at least one dioiodide represented by general formula (1-1), for example, it may contain only one type of dioiodide represented by general formula (1-1) where n is an arbitrary value. However, it is preferable that the crude composition contains at least two or more dioiodides represented by general formula (1-1) with different values of n. That is, it is preferable that the crude composition is a dioiodide mixture containing two or more dioiodides represented by general formula (1-1) with different values of n.
[0020] In one embodiment, the crude composition contains at least I(CF2CF2)I, I(CF2CF2)2I, and I(CF2CF2)3I as diiodides. In one embodiment, the crude composition contains at least eight types of diiodides represented by general formula (1-1) where n is 1 to 8.
[0021] The crude composition, in addition to diaiodide, contains the general formula (1-2):I(CF2CF2) m Ure 1 (In the formula, m is an integer greater than or equal to 1, R 1 Ethers represented by (an organic group), and general formula (1-3): ICF2COOR 2 (In the formula, R 2 It further contains at least one selected from the group consisting of esters represented by an organic group.
[0022] Crude composition, A crude composition containing a dioidide represented by general formula (1-1) and an ether represented by general formula (1-2), A crude composition containing a dioidide represented by general formula (1-1) and an ester represented by general formula (1-3), or A crude composition containing a dioidide represented by general formula (1-1), an ether represented by general formula (1-2), and an ester represented by general formula (1-3). That's fine.
[0023] The total content of ethers represented by general formula (1-2) and esters represented by general formula (1-3) in the crude composition is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, with no particular lower limit, but may be 1.0% by mass or more, based on the mass of the crude composition. The total content of ethers and esters in the crude composition can be measured by gas chromatography analysis.
[0024] The content of the diiodide represented by general formula (1-1) in the crude composition is preferably 80.0% by mass or more, more preferably 90.0% by mass or more, and preferably 99.0% by mass or less, based on the mass of the crude composition. The content of the diiodide in the crude composition can be measured by gas chromatography analysis.
[0025] In general formula (1-2), m is an integer of 1 or more. m may be an integer of 2 or more, an integer of 20 or less, an integer of 10 or less, an integer of 8 or less, or an integer of 5 or less. In one embodiment, the crude composition contains at least an ether represented by general formula (1-2) where m is an integer from 2 to 5. In one embodiment, the crude composition contains an ether represented by general formula (1-2) where m is an integer from 2 to 5, and also contains a dioidide represented by general formula (1-2) where m is an integer of 6 or more.
[0026] In general formula (1-2), R 1 R is an organic group. 1 The group is preferably a hydrocarbon group, more preferably an alkyl or aryl group. The number of carbon atoms in the hydrocarbon group and alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 4. The aryl group is preferably a phenyl group. 1 Examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and phenyl group. When a crude composition is prepared by a telomerization reaction using an organic peroxide, R 1 It is formed by hydrocarbon groups derived from organic peroxides.
[0027] In general formula (1-3), R 2 R is an organic group. 2The group is preferably a hydrocarbon group, more preferably an alkyl or aryl group. The number of carbon atoms in the hydrocarbon group and alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 4. The aryl group is preferably a phenyl group. 2 Examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and phenyl group. When a crude composition is prepared by a telomerization reaction using an organic peroxide, R 2 It is formed by hydrocarbon groups derived from organic peroxides.
[0028] R in general formula (1-2) 1 And, R in general formula (1-3) 2 These may be the same or different. In one embodiment, R in general formula (1-2) 1 And R in general formula (1-3) 2 It is identical to this.
[0029] The aqueous solution to be mixed with the crude composition described above is of the general formula (2-1): M(OH) p It contains a hydroxide represented by (wherein p is 1 or 2, and M is an alkali metal or alkaline earth metal) and water.
[0030] In general formula (2-1), M is an alkali metal or alkaline earth metal, preferably at least one selected from the group consisting of Li, K, and Na, with K being more preferred.
[0031] The hydroxide represented by general formula (2-1) is preferably at least one selected from the group consisting of LiOH, KOH, and NaOH, with KOH being more preferred.
[0032] The hydroxide content in the aqueous solution is preferably 1% by mass to the saturation dissolution concentration of each hydroxide at 20°C, relative to the aqueous solution.
[0033] In the manufacturing method of this disclosure, a mixture is prepared by mixing a crude composition with an aqueous solution. The mixing ratio of the crude composition and the aqueous solution is preferably 1:99 to 99:1, more preferably 10:90 to 95:5, and even more preferably 20:80 to 90:10, in terms of the mass ratio of the crude composition to the aqueous solution (crude composition: aqueous solution).
[0034] The mixture can be prepared, for example, by adding an aqueous solution to the crude composition all at once, or sequentially or continuously. Mixing can be carried out while stirring. A stirring bar or impeller may be used for stirring. Alternatively, the crude composition and aqueous solution may be continuously passed through and mixed using a static mixer, packed column, etc. A correlation transfer catalyst or emulsifier may be added to the system to promote mixing of the crude composition and aqueous solution. Since the mixture may generate heat when the aqueous solution is added to the crude composition, the aqueous solution can be added sequentially or continuously to the crude composition to maintain the temperature of the mixture within the range of 40 to 100°C, for example.
[0035] The crude composition and aqueous solution can be mixed, for example, in a temperature range of 40 to 150°C. If the temperature is too low, the crude composition, aqueous solution, or mixture may be heated to adjust it to the above temperature range. If the temperature when mixing the crude composition and aqueous solution is too high, the diaiodide may volatilize or decompose, reducing the yield, so it is preferable to determine the mixing temperature considering the boiling point of the diaiodide. When using a crude composition obtained by distillation of the reaction product prepared by the telomerization reaction, the mixing temperature is preferably 50 to 90°C. When using the reaction product prepared by the telomerization reaction as is as the crude composition, the mixing temperature is preferably 50 to 150°C.
[0036] After mixing the crude composition with the aqueous solution, the resulting mixture may be left to stand for 10 minutes to 24 hours while maintaining the temperature of the mixture within the above temperature range.
[0037] Next, the mixture obtained by mixing the crude composition with an aqueous solution is allowed to stand to separate into two phases: a phase mainly containing diiodide and a phase mainly containing water or hydroxide. When the resulting mixture is allowed to stand, it usually separates into two phases: a lower phase mainly containing diiodide and an upper phase mainly containing water or hydroxide. By recovering the phase mainly containing diiodide, a composition containing diiodide in high purity can be produced. In this disclosure, "main component" means a component whose mass ratio in the phase exceeds 50%.
[0038] The total content of the ether represented by general formula (1-2) and the ester represented by general formula (1-3) in the composition containing the dioidide obtained by the manufacturing method of this disclosure is preferably 500 ppm by mass or less, more preferably 100 ppm by mass or less, with no particular lower limit, but may be 0.1 ppm by mass or more, or 1.0 ppm by mass or more, based on the mass of the composition. The total content of the ether and ester in the composition can be measured by gas chromatography analysis.
[0039] The content of the diaiodide represented by general formula (1-1) in the composition is preferably more than 99.0% by mass, and more preferably 99.9% by mass or more, relative to the mass of the composition. The content of the diaiodide in the composition can be measured by gas chromatography analysis.
[0040] In the manufacturing method of this disclosure, the crude composition may be prepared by a telomerization reaction in which 1,2-diiodotetrafluoroethylene is used as the telogen and tetrafluoroethylene is used as the taxogen.
[0041] Furthermore, in the manufacturing method of this disclosure, the reaction product produced by the telomerization reaction may be used as the crude composition, or a portion of the fraction or residue obtained after distillation of the reaction product produced by the telomerization reaction may be used as the crude composition. Distillation of the reaction product produced by the telomerization reaction can be carried out by known methods such as fractional distillation or steam distillation.
[0042] 1,2-diiodotetrafluoroethylene used in the telomerization reaction can be produced by known production methods such as the production method described in Japanese Patent Publication No. 43-11884 and the production method described in U.S. Patent No. 2,424,667.
[0043] Telomerization reactions can be carried out using organic peroxides. In telomerization reactions carried out in the presence of organic peroxides, the organic peroxide decomposes to generate radicals, and these radicals abstract the iodine atom from 1,2-diiodotetrafluoroethylene to generate new alkyl radicals, and a reaction proceeds in which tetrafluoroethylene is added to the alkyl radical.
[0044] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as dit-butyl peroxide, and diacyl peroxides such as benzoyl peroxide.
[0045] The amount of tetrafluoroethylene used is preferably 0.01 to 100 moles per mole of 1,2-diiodotetrafluoroethylene.
[0046] The amount of organic peroxide used is preferably 0.01 to 2 moles per mole of 1,2-diiodotetrafluoroethylene.
[0047] The reaction temperature between 1,2-diiodotetrafluoroethylene and tetrafluoroethylene can be appropriately selected, but is preferably -78 to 200°C. Furthermore, the reaction temperature between 1,2-diiodotetrafluoroethylene and tetrafluoroethylene is preferably above the temperature corresponding to the 10-hour half-life of the organic peroxide, and preferably below the decomposition temperature of the substrate and product.
[0048] The reaction pressure between 1,2-diiodotetrafluoroethylene and tetrafluoroethylene can be appropriately selected, but is preferably 0 to 5.0 MPaG. Diluting gases such as carbon dioxide or nitrogen may be present in the gas phase of the reaction with tetrafluoroethylene, as demonstrated in Japanese Patent No. 6545187 and Japanese Unexamined Patent Publication No. 53-144507. The reaction time between 1,2-diiodotetrafluoroethylene and tetrafluoroethylene can be appropriately selected, but is preferably 0.1 to 96 hours.
[0049] In the manufacturing method of this disclosure, after recovering the phase containing the diaoidide, the phase may be distilled. The recovered phase containing the diaoidide is a composition containing the diaoidide in high purity, from which the ether represented by general formula (1-2) and the ester represented by general formula (1-3) have been removed or reduced. By distilling such a composition, the diaoidide having the desired n number can be separated and recovered in a higher yield than when distilling a composition containing at least one of the ether represented by general formula (1-2) or the ester represented by general formula (1-3).
[0050] Distillation can be carried out by known methods such as fractional distillation and steam distillation. Since diiodides have a high boiling point and readily decompose thermally, it is preferable to distill the phase containing diiodides under reduced pressure. The pressure during distillation is preferably 0 MPaG or less, and more preferably -0.09 MPaG or less. By distillation, fractions containing I(CF2CF2)I as the main component, fractions containing I(CF2CF2)2I as the main component, fractions containing I(CF2CF2)3I as the main component, etc., can be recovered from the phase containing diiodides.
[0051] In one embodiment, a fraction containing I(CF2CF2)3I as the main component is recovered from the phase containing diiodide by distillation. In another embodiment, a fraction containing I(CF2CF2)I as the main component, a fraction containing I(CF2CF2)2I as the main component, and a fraction containing I(CF2CF2)3I as the main component are recovered from the phase containing diiodide by distillation.
[0052] In one embodiment of the manufacturing method of this disclosure, A crude composition is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as the telogen and tetrafluoroethylene as the taxogen, which contains at least I(CF2CF2)I, I(CF2CF2)2I and I(CF2CF2)3I, and also contains at least one selected from the group consisting of ethers represented by general formula (1-2) and esters represented by general formula (1-3). The crude composition is distilled to recover a fraction containing I(CF2CF2)I as the main component. The residue obtained by the above distillation (the residue remaining after recovering the fraction containing I(CF2CF2)I as the main component) is distilled to recover the fraction containing I(CF2CF2)2I as the main component, Using the residue obtained by the above distillation (the residue remaining after recovering the fraction mainly containing I(CF2CF2)2I) as a crude composition, a mixture is prepared by mixing the residue with an aqueous solution containing a hydroxide represented by general formula (2-1) and water. The resulting mixture is separated into a phase containing diaiodide and a phase containing water, and the phase containing diaiodide is recovered. The phase containing diaiodide is distilled to recover a fraction containing I(CF2CF2)3I as the main component.
[0053] According to the manufacturing method of this embodiment, I(CF2CF2)3I can be recovered with high purity and high yield.
[0054] In one embodiment of the manufacturing method of this disclosure, A crude composition is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as the telogen and tetrafluoroethylene as the taxogen, which contains at least I(CF2CF2)I, I(CF2CF2)2I and I(CF2CF2)3I, and also contains at least one selected from the group consisting of ethers represented by general formula (1-2) and esters represented by general formula (1-3). A mixture is prepared by mixing the crude composition with an aqueous solution containing a hydroxide represented by general formula (2-1) and water. The resulting mixture is separated into a phase containing diaiodide and a phase containing water, and the phase containing diaiodide is recovered. The phase containing diiodide is distilled to recover a fraction containing I(CF2CF2)I as the main component. The residue obtained by the above distillation (the residue remaining after recovering the fraction containing I(CF2CF2)I as the main component) is distilled to recover the fraction containing I(CF2CF2)2I as the main component, The residue obtained from the above distillation (the residue remaining after recovering the fraction containing I(CF2CF2)2I as the main component) is distilled to recover the fraction containing I(CF2CF2)3I as the main component.
[0055] According to the manufacturing method of this embodiment, I(CF2CF2)I, I(CF2CF2)2I, and I(CF2CF2)3I can be recovered with high purity and high yield.
[0056] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.
[0057] <1> According to the first aspect of this disclosure, A method for producing diaiodide, General formula (1-1): I(CF2CF2) n The diaodiide represented by I (where n is an integer greater than or equal to 1), and, General formula (1-2): I(CF2CF2) m Ure 1 (In the formula, m is an integer greater than or equal to 1, R 1 Ethers represented by (organic groups), and General formula (1-3): ICF2COOR 2 (In the formula, R 2 Esters represented by (an organic group) At least one selected from the group consisting of A crude composition containing, General formula (2-1):M(OH) p A hydroxide represented by (wherein p is 1 or 2, and M is an alkali metal or alkaline earth metal), and an aqueous solution containing water, A mixture is prepared by mixing the following: The mixture is separated into a phase containing the diaiodide and a phase containing water, and the phase containing the diaiodide is recovered. A manufacturing method is provided. <2> According to the second aspect of this disclosure, A first-party method for producing a product is provided, which involves recovering a phase containing diiodide and then distilling the phase. <3> According to the third aspect of this disclosure, A method for producing the crude composition according to a first or second aspect is provided, wherein the crude composition contains at least I(CF2CF2)I, I(CF2CF2)2I, and I(CF2CF2)3I. <4> According to the fourth aspect of this disclosure, A third method of production is provided, which involves recovering a phase containing diiodide and then distilling the phase to recover a fraction mainly containing I(CF2CF2)3I. <5> According to the fifth aspect of this disclosure, A method for producing the crude composition is provided according to any one of the first to fourth aspects, which involves preparing the crude composition by a telomerization reaction using 1,2-diiodotetrafluoroethylene as the telogen and tetrafluoroethylene as the taxogen. <6> According to the sixth aspect of this disclosure, A manufacturing method is provided according to any one of the first to fourth aspects, comprising preparing a reaction product by a telomerization reaction using 1,2-diiodotetrafluoroethylene as the telogen and tetrafluoroethylene as the taxogen, and then preparing the crude composition by distilling the reaction product. <7> According to the seventh aspect of this disclosure, A method for producing a substance according to a fifth or sixth aspect is provided, in which a telomerization reaction is carried out in the presence of an organic peroxide. <8> According to the eighth aspect of this disclosure, The aforementioned diaiodide is General formula: I(CF2CF2) n I (where n is an integer from 1 to 8) This is a diaiodide shown by, The aforementioned ether, General formula: I(CF2CF2) m Ure 1 (In the formula, R 1 (where m is an alkyl group with 1 to 4 carbon atoms, and m is an integer between 2 and 5 carbon atoms) It is the ether represented by, The aforementioned ester, General formula: ICF2COOR 2 (In the formula, R 2 (A C1-C4 alkyl group) It is an ester represented by, The content of the dioidide in the crude composition is preferably 80.0 to 99.0% by mass relative to the mass of the crude composition. The total content of the ether and the ester in the crude composition is 1.0 to 20.0% by mass relative to the mass of the crude composition. The hydroxide is at least one selected from the group consisting of LiOH, KOH, and NaOH. The hydroxide content in the aqueous solution is 1% by mass or more relative to the aqueous solution and less than or equal to the saturation dissolution concentration of the hydroxide at 20°C. The mass ratio of the crude composition to the aqueous solution (crude composition: aqueous solution) is 20:80 to 90:10. The temperature at which the crude composition and the aqueous solution are mixed is 40 to 150°C. A manufacturing method is provided that is based on any of the first to seventh aspects. <9> According to the ninth aspect of this disclosure, General formula (1-1): I(CF2CF2) n The diaodiide represented by I (where n is an integer greater than or equal to 1), and, General formula (1-2): I(CF2CF2) m Ure 1 (In the formula, m is an integer greater than or equal to 1, R 1 Ethers represented by (organic groups), and General formula (1-3): ICF2COOR 2 (In the formula, R 2 Esters represented by (an organic group) It contains at least one selected from the group consisting of, A composition is provided in which the total content of the ether and the ester is 500 ppm by mass or less, relative to the mass of the composition. <10> According to the tenth aspect of this disclosure, The aforementioned diaiodide is General formula: I(CF2CF2) n I (where n is an integer from 1 to 8) This is a diaiodide shown by, The aforementioned ether, General formula: I(CF2CF2) m Ure 1 (In the formula, R 1 (where m is an alkyl group with 1 to 4 carbon atoms, and m is an integer between 2 and 5 carbon atoms) It is the ether represented by, The aforementioned ester, General formula: ICF2COOR 2 (In the formula, R 2 (A C1-C4 alkyl group) It is an ester represented by, A composition according to a ninth aspect is provided, wherein the content of the dioidide is greater than 99.0% by mass with respect to the mass of the composition. [Examples]
[0058] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to such embodiments.
[0059] Synthesis Example 1 ICF2CF2I (222g) and diisopropyl peroxydicarbonate (IPP) (4.4g) were charged into a 200ml SUS316 autoclave equipped with stirring blades. After cooling the vessel to -15°C and evacuating it, tetrafluoroethylene (TFE) (54g) was charged in from the gas phase. The temperature was raised to 55°C to allow the TFE and ICF2CF2I to react. The reaction pressure decreased as the TFE was consumed in the reaction (the reaction pressure was 2.8 MPaG at the start of the reaction, and decreased to 1.8 MPaG after 14 hours of reaction).
[0060] After the reaction was carried out for 14 hours, the vessel was allowed to cool to room temperature, and the residual pressure was released to atmospheric pressure. 249 g of the crude reaction material remaining in the reaction vessel was recovered, and the composition of the resulting telomer mixture (crude reaction material) was confirmed by gas chromatography. The results are shown in Table 1.
[0061] Gas chromatography was performed under the following conditions. Measuring device: Shimadzu Corporation GC-2014 Column: Silicone SE-30 (15%) Column temperature conditions: 50°C, 5 min; 10°C / min; 250°C, 5 min Evaporation chamber temperature: 250℃ Detector temperature: 250℃ Detector: TCD Carrier gas type: Helium Sample injection volume: 1 μl
[0062] Example 1 The procedure for decomposing and removing the ether and ester by adding an aqueous KOH solution to the telomer mixture obtained in Synthesis Example 1 is shown below.
[0063] 153g of the telomer mixture obtained in Synthesis Example 1 was charged into a reactor consisting of a 100ml three-necked flask equipped with a stirring bar and connected to a condenser. After heating to 50°C, 35g of 48% by mass KOH aqueous solution was added, adjusting the amount to maintain the reactor temperature at 50-60°C, and the reaction was carried out. After the KOH addition was complete, the temperature was maintained at 50-60°C and the reaction was continued for another 2 hours.
[0064] The reaction product was obtained as a mixture consisting of two phases: a KOH aqueous solution phase and a telomer phase. Table 1 shows the results of analysis of the lower phase (telomer phase) using gas chromatography. It was confirmed that the ether and ester had disappeared. 142 g of the telomer phase was recovered by liquid-liquid separation from the reaction mixture. This amount was nearly quantitative, considering that the ether and ester had been decomposed and removed.
[0065] In Tables 1 and 2, diaoidides, ethers, and esters are compounds represented by the following chemical formulas, respectively. Diaiodide: I(CF2CF2) n I (wherein n is an integer as shown in Table 1) Ether: I (CF2CF2) mOCH(CH3)2 (where m is an integer as shown in Table 1) Ester: ICF2COOCH(CH3)2
[0066] [Table 1]
[0067] Example 2 Example 2 shows an example of decomposing and removing ether from the residue produced by fractional distillation of the reactants obtained by the telomerization reaction.
[0068] The telomer mixture obtained in Synthesis Example 1 was separated and recovered by fractional distillation to obtain diaiodide (n=1) and diaiodide (n=2), respectively, and the residue was also recovered. The results of the residue analysis using gas chromatography are shown in Table 2.
[0069] A 100 ml three-necked flask equipped with a stirring bar and connected to a condenser was used to charge 125 g of the residue. After heating to 50°C, the 48% KOH aqueous solution was added. The reaction began upon addition of KOH, and exothermic reaction was observed. The amount of 48% KOH aqueous solution added was adjusted to maintain the vessel temperature at 90-100°C. 34 g of KOH was added over 2 hours. After the KOH addition was complete, the temperature was maintained at 90-100°C and the reaction was continued for another 3 hours.
[0070] The reaction product separated into a liquid-liquid phase of KOH aqueous solution and a telomer phase. The results of gas chromatography analysis of the telomer phase are shown in Table 2.
[0071] [Table 2]
[0072] Comparative Example 1 The telomer mixture obtained in Synthesis Example 1 was subjected to vacuum distillation at 4.5 kPa in a 15-stage glass O-Dasho distillation apparatus, following conventional procedures. The results are shown below. Isolation yield of diaiodide (n=1) (purity 90% or higher): 85% Isolation yield of diaiodide (n=2) (purity 90% or higher): 52%
[0073] Example 3 The telomer phase obtained in Example 1 was subjected to vacuum distillation at 4.5 kPa in a 15-stage glass O'Dashaw distillation apparatus, following a conventional method. The results are shown below. Isolation yield of diaiodide (n=1) (purity 90% or higher): 89% Isolation yield of diaiodide (n=2) (purity 90% or higher): 94%
[0074] The results from Comparative Example 1 and Example 3 confirmed that neutralizing and removing impurities in the raw material improves the recovery yield of telomers (dioidides).
Claims
1. A method for producing diaiodide, General formula (1-1): I(CF ２ CF ２ ) ｎ The diaodiide represented by I (wherein n is an integer greater than or equal to 1), and, General formula (1-2): I(CF ２ CF ２ ) ｍ OR １ (In the formula, m is an integer greater than or equal to 1, R １ Ethers represented by (organic groups), and General formula (1-3): ICF ２ COOR ２ (where R ２ is an organic group) represents an ester At least one selected from the group consisting of A crude composition containing, General formula (2-1): M(OH) ｐ A hydroxide represented by (wherein p is 1 or 2, and M is an alkali metal or alkaline earth metal), and an aqueous solution containing water, A mixture is prepared by mixing the following: The mixture is separated into a phase containing the diaiodide and a phase containing water, and the phase containing the diaiodide is recovered. Manufacturing method.
2. The manufacturing method according to claim 1, wherein the phase containing diiodide is recovered and then the phase is distilled.
3. The crude composition is I(CF ２ CF ２ ) I, I (CF ２ CF ２ ) ２ I and I(CF ２ CF ２ ) ３ The manufacturing method according to claim 1 or 2, comprising at least I.
4. After recovering the phase containing diiodide, the phase is distilled to obtain I(CF ２ CF ２ ) ３ The manufacturing method according to claim 3, wherein a fraction containing I as the main component is recovered.
5. The manufacturing method according to claim 1 or 2, wherein the crude composition is prepared by a telomerization reaction in which 1,2-diiodotetrafluoroethane is used as the telogen and tetrafluoroethylene is used as the taxogen.
6. The manufacturing method according to claim 1 or 2, wherein a reaction product is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethane as the telogen and tetrafluoroethylene as the taxogen, and the crude composition is prepared by distilling the reaction product.
7. The manufacturing method according to claim 5, wherein the telomerization reaction is carried out in the presence of an organic peroxide.
8. The aforementioned diaiodide is General formula: I(CF ２ CF ２ ) ｎ I (wherein n is an integer from 1 to 8) This is a diaiodide shown by, The aforementioned ether, General formula: I(CF ２ CF ２ ) ｍ OR １ (In the formula, R １ (where m is an alkyl group with 1 to 4 carbon atoms, and m is an integer between 2 and 5 carbon atoms) It is the ether represented by, The aforementioned ester, General formula: ICF ２ COOR ２ (In the formula, R ２ (These are alkyl groups with 1 to 4 carbon atoms.) It is an ester represented by, The content of the dioidide in the crude composition is 80.0 to 99.0% by mass relative to the mass of the crude composition. The total content of the ether and the ester in the crude composition is 1.0 to 20.0% by mass relative to the mass of the crude composition. The hydroxide is at least one selected from the group consisting of LiOH, KOH, and NaOH. The hydroxide content in the aqueous solution is 1% by mass or more relative to the aqueous solution and less than or equal to the saturation dissolution concentration of the hydroxide at 20°C. The mass ratio of the crude composition to the aqueous solution (crude composition: aqueous solution) is 20:80 to 90:
10. The temperature at which the crude composition and the aqueous solution are mixed is 40 to 150°C. The manufacturing method according to claim 1 or 2.
9. General formula (1-1): I(CF ２ CF ２ ) ｎ The diaodiide represented by I (wherein n is an integer greater than or equal to 1), and, General formula (1-2): I(CF ２ CF ２ ) ｍ OR １ (In the formula, m is an integer greater than or equal to 1, R １ Ethers represented by (organic groups), and General formula (1-3): ICF ２ COOR ２ (In the formula, R ２ Esters represented by (an organic group) It contains at least one selected from the group consisting of, A composition in which the total content of the ether and the ester is 500 ppm by mass or less, relative to the mass of the composition.
10. The aforementioned diaiodide is General formula: I(CF ２ CF ２ ) ｎ I (wherein n is an integer from 1 to 8) This is a diaiodide shown by, The aforementioned ether, General formula: I(CF ２ CF ２ ) ｍ OR １ (In the formula, R １ (where m is an alkyl group with 1 to 4 carbon atoms, and m is an integer between 2 and 5 carbon atoms) It is the ether represented by, The aforementioned ester, General formula: ICF ２ COOR ２ (In the formula, R ２ (These are alkyl groups with 1 to 4 carbon atoms.) It is an ester represented by, The composition according to claim 9, wherein the content of the dioidide is more than 99.0% by mass with respect to the mass of the composition.