Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/38—Separation; Purification; Stabilisation; Use of additives
  • C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C19/00—Acyclic saturated compounds containing halogen atoms
  • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
  • C07C19/16—Acyclic saturated compounds containing halogen atoms containing fluorine and iodine

Definitions

• the present disclosure relates to a method for producing diiodides and compositions containing diiodides.
• Patent Document 1 discloses a method for producing a compound represented by the following formula I(CF 2 CF 2 ) n I by reacting 1,2-diiodotetrafluoroethylene with tetrafluoroethylene in the presence of a catalytic amount of a free radical catalyst:
• a process for the preparation of alpha-omega-diiodinated fluoroalkanes is described which comprises forming a telomeric product of the formula: where n is 2 to 10, and absorbing the telomeric product from the reaction mixture.
• the objective of this disclosure is to provide a manufacturing method for producing high-purity diiodide.
• a method for producing a diiodide comprising the steps of: Diiodides represented by the general formula (1-1): I(CF 2 CF 2 ) n I (wherein n is an integer of 1 or more), and An ether represented by the general formula (1-2): I(CF 2 CF 2 ) m OR 1 (wherein m is an integer of 1 or more, and R 1 is an organic group), and A crude composition containing at least one selected from the group consisting of esters represented by the general formula (1-3): ICF 2 COOR 2 (wherein R 2 is an organic group); An aqueous solution containing a hydroxide represented by the general formula (2-1): M(OH) p (wherein p is 1 or 2, and M is an alkali metal or an alkaline earth metal) and water; A mixture is prepared by mixing The method includes separating the mixture into a phase containing the diiodide and a phase containing water, and recovering the phase containing the dii
• the present disclosure provides a manufacturing method for producing high-purity diiodide.
• Patent document 1 proposes a method for producing alpha-omega-diiodized fluoroalkanes by forming telomeric products through a telomerization reaction using 1,2-diiodotetrafluoroethylene as a telogen and tetrafluoroethylene as a taxogen. Patent document 1 also describes that the telomers can be separated by fractional distillation of the telomer mixture at reduced pressure if desired.
• the telomerization reaction produces ethers or esters in addition to diiodides, and that the ethers or esters in the reaction product prevent the diiodides from being separated by fractional distillation, which is why the yield does not improve.
• a method for removing the ethers or esters produced by the telomerization reaction from the reaction product was found, and that by fractional distillation of the reaction product from which the ethers or esters had been removed, it was possible to separate diiodides with different carbon numbers and recover each diiodide in high yield.
• a method for producing a diiodide comprising the steps of: A diiodide represented by the general formula (1-1): I(CF 2 CF 2 ) n I (wherein n is an integer of 1 or more), at least one member selected from the group consisting of an ether represented by the general formula (1-2): I(CF 2 CF 2 ) m OR 1 (wherein m is an integer of 1 or more, and R 1 is an organic group) and an ester represented by the general formula (1-3): ICF 2 COOR 2 (wherein R 2 is an organic group);
• a crude composition comprising: An aqueous solution containing a hydroxide represented by the general formula (2-1): M(OH) p (wherein p is 1 or 2, and M is an alkali metal or an alkaline earth metal) and water;
• a mixture is prepared by mixing The method includes separating the mixture into a phase containing the diiodide and a phase containing water, and recovering the
• the ether or ester in the crude composition containing the diiodide can be separated from the crude composition, and a composition containing the diiodide at high purity can be recovered in high yield. Furthermore, by distilling the composition containing the diiodide at high purity by a method such as fractional distillation or steam distillation, the diiodide having the desired n number can be separated and recovered in high yield.
• the present disclosure relates to a method for producing a composition containing a diiodide at high purity.
• the production method of the present disclosure comprises mixing a crude composition containing a diiodide and at least one selected from the group consisting of an ether and an ester with an aqueous solution containing a hydroxide and water to prepare a mixture, separating the resulting mixture into two phases, and recovering the phase containing the diiodide at high purity.
• the crude composition is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as a telogen and tetrafluoroethylene as a taxogen.
• This telomerization reaction produces a crude composition containing an ether represented by general formula (1-2) or an ester represented by general formula (1-3) in addition to the diiodide represented by general formula (1-1).
• the crude composition is mixed with an aqueous solution containing a hydroxide, the ether and ester in the crude composition react with the hydroxide and are decomposed. Meanwhile, the diiodide is maintained in the mixture without being decomposed.
• phase containing the diiodide as a main component When the resulting mixture is allowed to stand, it separates into two phases: a phase containing the diiodide as a main component and a phase containing water or hydroxide as a main component.
• a phase containing the diiodide By recovering the phase containing the diiodide as a main component, a composition containing the diiodide at a high purity can be produced.
• Compositions containing the above are important raw materials for producing compositions containing diiodides in high purity.
• the diiodide contained in the above crude composition is represented by the general formula (1-1): I(CF 2 CF 2 ) n I (wherein n is an integer of 1 or more). n may be an integer from 1 to 20, may be an integer from 1 to 10, or may be an integer from 1 to 8. In one embodiment, the crude composition contains at least a diiodide represented by the general formula (1-1) in which n is an integer from 1 to 8.
• 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.
• the crude composition may contain at least a diiodide represented by general formula (1-1), and may contain, for example, only one type of diiodide represented by general formula (1-1) where n is any numerical value. However, it is preferable that the crude composition contains at least two or more types of diiodides represented by general formula (1-1) where n is different numerical values. In other words, it is preferable that the crude composition is a diiodide mixture containing two or more types of diiodides represented by general formula (1-1) where n is different numerical values.
• the crude composition contains, as diiodides, at least I(CF 2 CF 2 ) I, I(CF 2 CF 2 ) 2 I, and I(CF 2 CF 2 ) 3 I. In one embodiment, the crude composition contains at least eight kinds of diiodides represented by general formula (1-1) in which n is 1 to 8.
• the crude composition further contains, in addition to the diiodide, at least one member selected from the group consisting of an ether represented by the general formula (1-2): I(CF 2 CF 2 ) m OR 1 (wherein m is an integer of 1 or more, and R 1 is an organic group) and an ester represented by the general formula (1-3): ICF 2 COOR 2 (wherein R 2 is an organic group).
• the crude composition is A crude composition containing a diiodide represented by general formula (1-1) and an ether represented by general formula (1-2), A crude composition containing a diiodide represented by general formula (1-1) and an ester represented by general formula (1-3), or It may be a crude composition containing the diiodide represented by the general formula (1-1), the ether represented by the general formula (1-2), and the ester represented by the general formula (1-3).
• the total content of the ether represented by general formula (1-2) and the ester represented by general formula (1-3) in the crude composition is preferably 20.0 mass% or less, more preferably 10.0 mass% or less, relative to the mass of the crude composition, and although there is no particular lower limit, it may be 1.0 mass% or more.
• the total content of the ether and ester in the crude composition can be measured by gas chromatography analysis.
• the content of the diiodide represented by the 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.
• 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.
• the crude composition contains at least an ether represented by general formula (1-2) in which m is an integer of 2 to 5.
• the crude composition contains an ether represented by general formula (1-2) in which m is an integer of 2 to 5, and also contains a diiodide represented by general formula (1-2) in which m is an integer of 6 or more.
• R 1 is an organic group.
• R 1 is preferably a hydrocarbon group, more preferably an alkyl group or an aryl group.
• the number of carbon atoms in the hydrocarbon group and the 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.
• R 1 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a phenyl group.
• R 1 is formed by a hydrocarbon group derived from the organic peroxide.
• R 2 is an organic group.
• R 2 is preferably a hydrocarbon group, more preferably an alkyl group or an aryl group.
• the number of carbon atoms in the hydrocarbon group and the 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.
• R 2 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a phenyl group.
• R 2 is formed by a hydrocarbon group derived from the organic peroxide.
• R 1 in general formula (1-2) and R 2 in general formula (1-3) may be the same or different. In one embodiment, R 1 in general formula (1-2) and R 2 in general formula (1-3) are the same.
• the aqueous solution to be mixed with the above-mentioned crude composition contains a hydroxide represented by the general formula (2-1): M(OH) p (wherein p is 1 or 2, and M is an alkali metal or alkaline earth metal), and water.
• M is an alkali metal or an alkaline earth metal, preferably at least one selected from the group consisting of Li, K, and Na, and more preferably K.
• the hydroxide represented by the general formula (2-1) is preferably at least one selected from the group consisting of LiOH, KOH, and NaOH, and more preferably KOH.
• the content of the hydroxide in the aqueous solution is preferably 1% by mass to the saturated solubility concentration of each hydroxide at 20°C.
• a mixture is prepared by mixing a crude composition with an aqueous solution.
• the mixing ratio of the crude composition to the aqueous solution expressed as the mass ratio of the crude composition to the aqueous solution (crude composition: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.
• the mixture can be prepared, for example, by adding the aqueous solution to the crude composition all at once, or stepwise or continuously. Mixing can be performed with stirring. A stirrer or impeller can be used for stirring. Alternatively, the crude composition and the aqueous solution can be continuously circulated and mixed in a static mixer or packed tower. A phase transfer catalyst or emulsifier can be added to the system to promote mixing of the crude composition and the aqueous solution. When the aqueous solution is added to the crude composition, the mixture may generate heat, so for example, the aqueous solution can be added stepwise or continuously to the crude composition so as to maintain the temperature of the mixture within the range of 40 to 100°C.
• the crude composition and the aqueous solution can be mixed at a temperature range of, for example, 40 to 150°C. If the temperature is too low, the crude composition, the aqueous solution, or the mixture may be heated to adjust the temperature to the above range. If the temperature at which the crude composition and the aqueous solution are mixed is too high, the diiodide may volatilize or decompose, resulting in a decrease in yield, so it is preferable to determine the mixing temperature taking into account the boiling point of the diiodide.
• the mixing temperature is preferably 50 to 90°C.
• the mixing temperature is preferably 50 to 150°C.
• the resulting mixture may be left to stand for 10 minutes to 24 hours while maintaining the temperature of the resulting mixture within the above temperature range.
• a phase containing diiodide as a main component a phase containing water or hydroxide as a main component.
• a phase containing water or hydroxide as a main component When the resulting mixture is allowed to stand, it usually separates into two phases: a lower phase containing diiodide as a main component, and an upper phase containing water or hydroxide as a main component.
• a main component means a component that accounts for more than 50% of the mass of the phase.
• the total content of the ether represented by the general formula (1-2) and the ester represented by the general formula (1-3) in the composition containing the diiodide obtained by the manufacturing method of the present disclosure is preferably 500 mass ppm or less, more preferably 100 mass ppm or less, relative to the mass of the composition, and although there is no particular lower limit, it may be 0.1 mass ppm or more, or 1.0 mass ppm or more.
• the total content of the ether and ester in the composition can be measured by gas chromatography analysis.
• the content of the diiodide represented by the general formula (1-1) in the composition is preferably more than 99.0 mass% relative to the mass of the composition, and more preferably 99.9 mass% or more.
• the content of the diiodide in the composition can be measured by gas chromatography analysis.
• the crude composition may be prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as the telogen and tetrafluoroethylene as the taxogen.
• 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 distilling the reaction product produced by the telomerization reaction may be used as the crude composition.
• the distillation of the reaction product produced by the telomerization reaction may be carried out by known methods such as fractional distillation and steam distillation.
• the 1,2-diiodotetrafluoroethylene used in the telomerization reaction can be produced by known production methods such as the production method described in JP-B-43-11884 and the production method described in U.S. Pat. No. 2,424,667.
• the telomerization reaction can be carried out using an organic peroxide.
• the organic peroxide decomposes to generate radicals, which then abstract the iodine atom from 1,2-diiodotetrafluoroethylene to generate new alkyl radicals, and the reaction proceeds by adding tetrafluoroethylene to the alkyl radicals.
• organic peroxides examples 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 di-t-butyl peroxide, and diacyl peroxides such as benzoyl peroxide.
• the amount of tetrafluoroethylene used is preferably 0.01 to 100 moles per mole of 1,2-diiodotetrafluoroethylene.
• the amount of organic peroxide used is preferably 0.01 to 2 moles per mole of 1,2-diiodotetrafluoroethylene.
• the temperature for the reaction between 1,2-diiodotetrafluoroethylene and tetrafluoroethylene can be selected as appropriate, but is preferably -78 to 200°C.
• the temperature for the reaction between 1,2-diiodotetrafluoroethylene and tetrafluoroethylene is preferably equal to or higher than the temperature corresponding to the 10-hour half-life of the organic peroxide, and is preferably lower than the decomposition temperatures of the substrate and product.
• the pressure for the reaction between 1,2-diiodotetrafluoroethylene and tetrafluoroethylene can be selected as appropriate, but is preferably 0 to 5.0 MPaG.
• a diluent gas such as carbon dioxide or nitrogen may be allowed to coexist with tetrafluoroethylene in the gas phase of the reaction, as is done in Japanese Patent No. 6545187 and JP-A-53-144507.
• the time for the reaction between 1,2-diiodotetrafluoroethylene and tetrafluoroethylene can be selected as appropriate, but is preferably 0.1 to 96 hours.
• the phase may be distilled.
• the recovered diiodide-containing phase is a composition containing the diiodide at a high purity, in which the ether represented by general formula (1-2) and the ester represented by general formula (1-3) have been removed or reduced.
• the diiodide having the desired n number can be separated and recovered in a higher yield than in the case of distilling a composition containing at least either the ether represented by general formula (1-2) or the ester represented by general formula (1-3).
• the distillation can be carried out by a known method such as fractional distillation or steam distillation. Since the diiodide has a high boiling point and is easily thermally decomposed, it is preferable to distill the phase containing the diiodide under reduced pressure.
• the pressure during the distillation is preferably 0 MPaG or less, more preferably -0.09 MPaG or less.
• a fraction containing I(CF 2 CF 2 ) 3 I as a main component is recovered from the diiodide-containing phase by distillation.
• a fraction containing I(CF 2 CF 2 ) I as a main component, a fraction containing I(CF 2 CF 2 ) 2 I as a main component, and a fraction containing I(CF 2 CF 2 ) 3 I as a main component are each recovered from the diiodide-containing phase by distillation.
• a crude composition is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as a telogen and tetrafluoroethylene as a taxogen, the crude composition containing at least I(CF 2 CF 2 )I, I(CF 2 CF 2 ) 2 I, and I(CF 2 CF 2 ) 3 I, and further containing at least one member selected from the group consisting of an ether represented by the general formula (1-2) and an ester represented by the general formula (1-3), distilling the crude composition to recover a fraction containing I(CF 2 CF 2 )I as a major component;
• the residue obtained by the above distillation (the residue remaining after recovering the fraction containing I(CF 2 CF 2 ) I as a main component) is distilled to recover the fraction containing I(CF 2 CF 2 ) 2 I as a main component;
• the residue obtained by the above distillation the residue remaining after recovering the fraction containing I(CF 2 CF 2 ) I as a
• I(CF 2 CF 2 ) 3 I can be recovered with high purity and in high yield.
• a crude composition is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as a telogen and tetrafluoroethylene as a taxogen, the crude composition containing at least I(CF 2 CF 2 )I, I(CF 2 CF 2 ) 2 I, and I(CF 2 CF 2 ) 3 I, and further containing at least one member selected from the group consisting of an ether represented by the general formula (1-2) and an ester represented by the general formula (1-3), preparing a mixture by mixing the crude composition with an aqueous solution containing a hydroxide represented by the general formula (2-1) and water; The resulting mixture is separated into a diiodide-containing phase and a water-containing phase, and the diiodide-containing phase is recovered; distilling the phase containing the diiodide to recover a fraction containing I(CF 2 CF 2 )I as a main component; The residue obtained
• I(CF 2 CF 2 )I, I(CF 2 CF 2 ) 2 I and I(CF 2 CF 2 ) 3 I can be recovered with high purity and in high yield.
• a method for producing a diiodide comprising the steps of: Diiodides represented by the general formula (1-1): I(CF 2 CF 2 ) n I (wherein n is an integer of 1 or more), and An ether represented by the general formula (1-2): I(CF 2 CF 2 ) m OR 1 (wherein m is an integer of 1 or more, and R 1 is an organic group), and A crude composition containing at least one selected from the group consisting of esters represented by the general formula (1-3): ICF 2 COOR 2 (wherein R 2 is an organic group); An aqueous solution containing a hydroxide represented by the general formula (2-1): M(OH) p (wherein p is 1 or 2, and M is an alkali metal or an alkaline earth metal) and water; A mixture is prepared by mixing The method includes separating the mixture into a phase containing the diiodide and a phase containing water, and recovering the phase
• a process according to the first aspect is provided in which the diiodide-containing phase is recovered and then distilled.
• the crude composition contains at least I( CF2CF2 ) I, I( CF2CF2 ) 2I and I( CF2CF2 ) 3I .
• a production process according to a third aspect in which a phase containing the diiodide is recovered and then the phase is distilled to recover a fraction containing I(CF 2 CF 2 ) 3 I as a main component.
• a production process according to any one of the first to fourth aspects, in which the crude composition is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as a telogen and tetrafluoroethylene as a taxogen.
• a production method according to any one of the first to fourth aspects, in which a reaction product is prepared by a telomerization reaction using 1,2-diiodotetrafluoroethylene as a telogen and tetrafluoroethylene as a taxogen, and the crude composition is prepared by distilling the reaction product.
• the diiodide is General formula: I(CF 2 CF 2 ) n I (wherein n is an integer from 1 to 8) It is a diiodide represented by the formula:
• the ether is General formula: I(CF 2 CF 2 ) m OR 1 (wherein R 1 is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 2 to 5).
• the ester is General formula: ICF 2 COOR 2 (wherein R 2 is an alkyl group having 1 to 4 carbon atoms) is an ester represented by the formula:
• the content of the diiodide in the crude composition is preferably 80.0 to 99.0% by mass based on the mass of the crude composition, a total content of the ether and the ester in the crude composition is 1.0 to 20.0% by mass based on the mass of the crude composition;
• the hydroxide is at least one selected from the group consisting of LiOH, KOH, and NaOH;
• the content of the hydroxide in the aqueous solution is 1% by mass or more and is equal to or less than the saturated solubility concentration of the hydroxide at 20° C., a mass ratio of the crude composition to the aqueous solution (crude composition:aqueous solution) of 20:80 to 90:10;
• the composition contains at least one selected from the group consisting of esters represented by the general formula (1-3): ICF 2 COOR 2 (wherein R 2 is an organic group),
• the composition has a total content of the ether and the ester of 500 ppm by mass or less, based on the mass of the composition.
• the diiodide is General formula: I(CF 2 CF 2 ) n I (wherein n is an integer from 1 to 8) It is a diiodide represented by the formula:
• the ether is General formula: I(CF 2 CF 2 ) m OR 1 (wherein R 1 is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 2 to 5).
• ester is General formula: ICF 2 COOR 2 (wherein R 2 is an alkyl group having 1 to 4 carbon atoms) is an ester represented by the formula:
• Example 1 The procedure for decomposing and removing ethers and esters by adding an aqueous KOH solution to the telomer mixture obtained in Synthesis Example 1 is shown below.
• telomer mixture obtained in Synthesis Example 1 was charged into a 100 ml three-necked flask equipped with a stirrer and a reactor connected to a condenser. After heating to 50°C, 35 g of 48% by mass aqueous KOH solution was charged and reacted while adjusting the amount charged so that the temperature inside the vessel was 50-60°C. After the KOH charge was completed, the temperature was maintained at 50-60°C and the reaction was continued for another 2 hours.
• the reaction product after the reaction was obtained as a mixture of two phases: a KOH aqueous solution phase and a telomer phase.
• the results of analyzing the lower phase (telomer phase) using gas chromatography are shown in Table 1. It was confirmed that the ethers and esters had disappeared. When the liquid was separated from the reaction mixture, 142 g of the telomer phase was recovered. Considering that the ethers and esters had been decomposed and removed, this amount was almost quantitative.
• diiodides, ethers and esters are compounds represented by the following chemical formulas, respectively.
• Diiodide I(CF 2 CF 2 ) 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
• Example 2 shows an example of decomposing and removing ethers in a residue produced by fractional distillation of a reaction product obtained by a telomerization reaction.
• the results of the residue analysis using gas chromatography are shown in Table 2.

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