Method for producing perfluorodiene compound

Abstract

The present invention is to make the general formula (2): CF2X 1 -CFX 2 -(CF2) n－4 -CFX 3 -CF2X 4 (2) [wherein, n is the same as in the specification. X 1 , X 2 , X 3 and X 4 are the same or different, representing a halogen atom. 1 and X 2 are not all fluorine atoms, and X 3 and X 4 Not all of them are fluorine atoms.] The reaction of the compounds shown in can reduce the amount of impurities that are difficult to separate and can obtain a perfluorodiene compound in high yield.

Description

Technical Field

[0001] The invention relates to a method for preparing a perfluorodiene compound. Background Art

[0002] Perfluorodiene compounds are useful compounds as various refrigerants, foaming agents, heat transfer media, etc. in addition to dry etching gases for semiconductors, and have two double bonds between carbon and carbon. In particular, hexafluorobutadiene, which has four carbon atoms and double bonds at both ends, has been used in various applications.

[0003] As a method for producing the perfluorodiolefin compound, there is known a method for removing IF from a compound such as ICF2CF2CF2CF2I using an organic metal compound such as Mg, Zn, Cd, or Li as a reactant at a desired temperature in the presence of an organic solvent (for example, see Patent Document 1). On the other hand, as a method for producing a perfluorodiolefin compound, there is also known a method for removing IF from a compound such as ICF2CF2CF2CF2I in the presence of metallic zinc and a nitrogen-containing compound (for example, see Patent Document 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 62-26240

[0007] Patent Document 2: Japanese Patent Application Publication No. 2001-192345 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] An object of the present invention is to provide a method for obtaining a perfluorodiene compound in high yield while reducing the amount of impurities that are difficult to separate.

[0010] Technical solutions for solving technical problems

[0011] The present invention includes the following configurations.

[0012] Item 1. A method for producing a perfluorodiene compound represented by the general formula (1), comprising: a reaction step of reacting a compound represented by the general formula (2) in an organic solvent in the presence of a nitrogen-containing compound, an iodine-containing inorganic material, and zinc or a zinc alloy.

[0013] CF2=CF-(CF2) n－4 -CF = CF2 (1)

[0014] [In formula (1), n ​​represents an integer of 4 to 20.]

[0015] CF2X 1 -CFX 2 -(CF2) n－4 -CFX 3 -CF2X 4 (2)

[0016] [In formula (2), n is the same as above. X 1 , X 2 , X 3 and X 4 are the same or different, representing a halogen atom. 1 and X 2 are not all fluorine atoms, and X 3 and X 4 Not all are fluorine atoms.]

[0017] Item 2. The production method according to Item 1, wherein the amount of the iodine-containing inorganic material used is 0.0005 mol or more per mol of the zinc or zinc alloy and is equal to or less than the solubility in the organic solvent.

[0018] Item 3. The production method according to Item 1 or 2, wherein the iodine-containing inorganic material is iodine and / or metal iodide.

[0019] Item 4. The production method according to any one of Items 1 to 3, wherein the reaction step includes a first mixing step of mixing a solution containing the iodine-containing inorganic material, the zinc or zinc alloy, and the organic solvent with the nitrogen-containing compound.

[0020] Item 5. The production method according to Item 4, wherein in the first mixing step, the nitrogen-containing compound is added to the solution containing the zinc or zinc alloy at an addition rate of 0.1 to 600 mol / hour per 1 mol of the zinc or zinc alloy.

[0021] Item 6. The production method according to Item 4 or 5, wherein the reaction step includes, after the first mixing step, a second mixing step of mixing the obtained mixed solution with the compound represented by the general formula (2).

[0022] Item 7. The production method as described in Item 6, wherein, in the above-mentioned second mixing step, the compound represented by the above-mentioned general formula (2) is added to the mixed solution obtained in the above-mentioned first mixing step at an addition rate of 0.05 to 30 mol / hour relative to 1 mol of the above-mentioned zinc or zinc alloy.

[0023] Item 8. The production method according to any one of Items 4 to 7, wherein the first mixing step is performed at a temperature of 50 to 200° C. when mixing the solution containing the iodine-containing inorganic material, zinc or zinc alloy and the organic solvent with the nitrogen-containing compound.

[0024] Item 9. The production method according to any one of Items 1 to 8, wherein the nitrogen-containing compound is N,N-dimethylformamide.

[0025] Item 10. The production method according to any one of Items 1 to 9, wherein the boiling point of the organic solvent is lower than or equal to the boiling point of the nitrogen-containing compound.

[0026] Item 11. A perfluorodiene composition comprising: a perfluorodiene compound represented by the following general formula (1); a compound represented by the following general formula (3); a compound represented by the following general formula (4A) and / or a compound represented by the following general formula (4B); and a compound represented by the following general formula (5).

[0027] CF2=CF-(CF2) n－4 -CF = CF2 (1)

[0028] [In formula (1), n ​​represents an integer of 4 to 20.]

[0029] CF2=CF-(CF2) n－4 -CFX 3 -CF2H (3)

[0030] [In formula (3), n is the same as above. X 3 represents a halogen atom.]

[0031] CF2X 1 -CFX 2 -(CF2) n－4 -CF = CF2 (4A)

[0032] [In formula (4A), n is the same as above. X 1 and X 2 are the same or different, representing a halogen atom. 1 and X 2 Not all are fluorine atoms.]

[0033] CF2H-CFX 2 -(CF2) n－4 -CFX 3 -CF2H (4B)

[0034] [In formula (4B), n is the same as above. X 2 and X 3 The same or different, represents a halogen atom.]

[0035] CF2X 1 -CFX 2 -(CF2) n－4 -CFX 3-CF2H (5)

[0036] [In formula (5), n is the same as above. X 1 , X 2 and X 3 are the same or different, representing a halogen atom. 1 and X 2 Not all are fluorine atoms.]

[0037] Item 12. The perfluorodiene composition according to Item 11, wherein the content of the compound represented by the general formula (1) is 80 to 99.8 mol % when the total amount of the perfluorodiene composition is 100 mol %.

[0038] Item 13. The perfluorodiene composition according to Item 11 or 12, wherein the perfluorodiene compound is hexafluorobutadiene.

[0039] Item 14. An etching gas, a refrigerant, a heat transfer medium, a foaming agent or a resin monomer, comprising the perfluorodiene composition described in any one of Items 11 to 13.

[0040] Effects of the Invention

[0041] According to the present invention, the amount of impurities that are difficult to separate can be reduced and a perfluorodiene compound can be obtained at a high yield. DETAILED DESCRIPTION

[0042] In this specification, "comprising" is a concept that includes "including", "consisting essentially of", and "consisting of". In addition, in this specification, when a numerical range is expressed as "A to B", it means A or more and B or less.

[0043] The method for producing a perfluorodiene compound of the present invention is a method for producing a perfluorodiene compound represented by the general formula (1), comprising a reaction step of reacting the compound represented by the general formula (2) in an organic solvent in the presence of a nitrogen-containing compound, an iodine-containing inorganic material, and zinc or a zinc alloy.

[0044] CF2=CF-(CF2) n－4 -CF = CF2 (1)

[0045] [In formula (1), n ​​represents an integer of 4 to 20.]

[0046] CF2X 1 -CFX 2 -(CF2) n－4 -CFX 3 -CF2X 4 (2)

[0047] [In formula (2), n is the same as above. X 1 , X 2 , X 3 and X 4 are the same or different, representing a halogen atom. 1 and X 2 are not all fluorine atoms, and X 3 and X 4 Not all are fluorine atoms.]

[0048] The present invention has a higher yield than the methods of Patent Documents 1 and 2, and can suppress impurities such as 1,1,1,2,4,4,4-heptafluoro-2-butene that are difficult to separate compared to Patent Document 2, thereby obtaining the target product.

[0049] In the general formulae (1) and (2), n is an integer of 4 to 20, and more preferably an integer of 4 to 10. Within this range, the amount of impurities that are difficult to separate can be reduced, and the perfluorodiene compound can be obtained at a higher yield.

[0050] That is, the perfluorodiene compound represented by the general formula (1) to be produced includes hexafluorobutadiene (CF2=CF-CF=CF2), octafluoropentadiene (CF2=CF-CF2-CF=CF2), decafluorohexadiene (CF2=CF-CF2-CF2-CF=CF2), and the like.

[0051] In the general formula (2), X 1 , X 2 , X 3 and X 4 is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 1 , X 2 , X 3 and X 4 They can be the same or different. 1 and X 2 When all are fluorine atoms, or X 3 and X 4 When all of X are fluorine atoms, the reaction cannot proceed and no perfluorodiolefin compound can be obtained. 1 and X 2 are not all fluorine atoms, and X 3 and X 4 Among them, from the viewpoint of being able to further reduce the amount of impurities that are difficult to separate and to obtain the perfluorodiolefin compound in a higher yield, X 1 , preferably a chlorine atom, a bromine atom, an iodine atom, etc. (particularly a chlorine atom, a bromine atom, etc.); as X 2, preferably a fluorine atom, a chlorine atom, a bromine atom, etc. (particularly a fluorine atom, a chlorine atom, etc.); as X 3 , preferably a fluorine atom, a chlorine atom, etc. (especially a fluorine atom); as X 4 , preferably a chlorine atom, a bromine atom, an iodine atom, etc. (particularly a bromine atom, an iodine atom, etc.).

[0052] Examples of the compound represented by the general formula (2) that satisfies such conditions include ClCF2-CFCl-CF2-CF2-CF2I, ClCF2-CFCl-CF2-CF2-CF2-CF2I, ClCF2-CFCl-CF2-CF2-CF2-CF2-CF2I, ICF2-CF2-CF2-CF2-CF2I, ICF2-CF2-CF2-CF2-CF2-CF2I, ICF2-CF2-CF2-CF2-CF2-CF2I, BrCF2-CF2-CF2-CF2-CF2-CF2Br, BrCF2-CF2-CF2-CF2-CF2-CF2Br, and BrCF2-CF2-CF2-CF2-CF2-CF2-CF2Br. From the perspective of increasing the amount of production and being able to obtain perfluorodiene compounds in higher yield, preferred are ClCF2-CFCl-CF2-CF2-CF2I, ClCF2-CFCl-CF2-CF2-CF2-CF2I, ClCF2-CFCl-CF2-CF2-CF2-CF2-CF2I, BrCF2-CF2-CF2-CF2-CF2Br, BrCF2-CF2-CF2-CF2-CF2-CF2Br, BrCF2-CF2-CF2-CF2-CF2-CF2-CF2Br, and more preferred are BrCF2-CF2-CF2-CF2-CF2Br, BrCF2-CF2-CF2-CF2-CF2-CF2-CF2Br, and BrCF2-CF2-CF2-CF2-CF2-CF2-CF2-CF2Br.

[0053] From the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiolefin compound in a higher yield, the amount of the compound represented by the general formula (2) used is preferably 0.05 to 30 mol, more preferably 0.1 to 10 mol, and even more preferably 0.2 to 5 mol, relative to 1 mol of zinc or zinc alloy described later.

[0054] As the nitrogen-containing compound, there is no particular limitation as long as it is a compound containing a nitrogen atom, and examples thereof include amide compounds (N,N-dimethylformamide, N,N-diisopropylformamide, etc.), amine compounds (triethylamine, etc.), pyridine compounds (pyridine, picoline, N-methyl-2-pyrrolidone, etc.), quinoline compounds (quinoline, methylquinoline, etc.), etc. These nitrogen-containing compounds may be used alone or in combination of two or more. Among them, from the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining a perfluorodiolefin compound in a higher yield, amide compounds are preferred, and N,N-dimethylformamide is more preferred.

[0055] The nitrogen-containing compound also includes compounds that are liquid at room temperature. From the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiolefin compound in higher yield, it is preferably used as an additive (in a small amount) rather than a solvent. The amount of the nitrogen-containing compound used is preferably 0.25 to 4 moles, more preferably 0.5 to 2 moles, relative to 1 mole of zinc or zinc alloy described later.

[0056] As an iodine-containing inorganic material, as long as it is an inorganic material containing iodine atoms, there is no particular limitation, for example, iodine can be cited; metal iodides such as typical metal iodides (sodium iodide, potassium iodide, magnesium iodide, calcium iodide, etc.), transition metal iodides (zinc iodide, etc.), etc. In addition, using the manufacturing method of the present invention, zinc halide (a mixture of zinc fluoride, zinc chloride and zinc iodide) as an impurity will be generated in the product. The zinc halide as an impurity contained in the product can also be used as an iodine-containing inorganic material and reused in the manufacturing method of the present invention. These iodine-containing inorganic materials can be used alone or in combination of two or more. Among them, from the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining perfluorodiolefin compounds in a higher yield, iodine, transition metal iodides, zinc halides as impurities in the product obtained by the manufacturing method of the present invention, etc. are preferred, and iodine is more preferred. In addition, when using iodine-free materials such as zinc fluoride and zinc chloride as halogen-containing materials instead of iodine-containing inorganic compounds, the effect of improving the yield of perfluorodiolefin compounds cannot be obtained.

[0057] From the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiolefin compound in a higher yield, the amount of the iodine-containing inorganic compound used is preferably 0.0005 mol or more per 1 mol of zinc or zinc alloy and below the solubility in the organic solvent, and more preferably 0.001 to 0.1 mol per 1 mol of zinc or zinc alloy.

[0058] In zinc or zinc alloy, as the elements that can be contained when zinc alloy is used, for example, lead, cadmium, iron, etc., can be cited. Among them, commercially available zinc sometimes contains impurities such as lead, cadmium, iron, etc. In the present invention, substances containing these impurities are also included.

[0059] As the organic solvent, a non-polar organic solvent is preferred, particularly from the viewpoint of dissolving the compound represented by the general formula (1), the iodine-containing inorganic material, etc. The boiling point of the organic solvent is preferably below the boiling point of the nitrogen-containing compound. Examples of such organic solvents include aromatic hydrocarbon compounds such as heptane, hexane, benzene, toluene, and xylene; and ether compounds such as tetrahydrofuran and diethyl ether.

[0060] The amount of the organic solvent used is not particularly limited as long as it is the amount of the solvent, but is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, based on 1 mol of zinc or zinc alloy.

[0061] In the manufacturing method of the present invention, in an organic solvent, a compound represented by the general formula (2) is reacted in the presence of a nitrogen-containing compound, an iodine-containing inorganic material, and zinc or a zinc alloy. The order of addition is not particularly limited, and the addition can be made simultaneously or sequentially. Among them, from the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining perfluorodiolefin compounds in a higher yield, it is preferred to mix a solution containing an iodine-containing inorganic material, the above-mentioned zinc or zinc alloy, and an organic solvent with a nitrogen-containing compound (in particular, adding a nitrogen-containing compound to a solution containing an iodine-containing inorganic material, the above-mentioned zinc or zinc alloy, and an organic solvent).

[0062] In a solution containing an iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and an organic solvent, the content of each component is preferably adjusted in a manner that satisfies the above-mentioned content ratio of each component. In addition, when mixing (especially adding) the compound represented by the general formula (2) in a subsequent step, it is preferred to adjust the content of each component after considering the amount of the compound represented by the general formula (2) to be mixed (especially added).

[0063] When mixing the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent with the nitrogen-containing compound (adding the nitrogen-containing compound to the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent), it is preferred to mix the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent with the nitrogen-containing compound at a temperature of preferably 50 to 200° C., more preferably 100 to 150° C. It is particularly preferred to add the nitrogen-containing compound to the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent at a temperature of preferably 50 to 200° C., more preferably 100 to 150° C. In addition, by refluxing the solution containing the iodine-containing inorganic material, the zinc or zinc alloy and the organic solvent while adding the nitrogen-containing compound, since the solvent is lower than the reaction temperature, it can be volatilized when it becomes the reaction temperature, and after cooling it, it is returned to the reactor. When refluxing the solution containing the iodine-containing inorganic material, the zinc or zinc alloy and the organic solvent while adding the nitrogen-containing compound, it is most preferred to heat the solution at the reflux temperature.

[0064] After heating (particularly heating at reflux temperature), the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent is mixed with the nitrogen-containing compound. For example, when the nitrogen-containing compound is added to the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent, from the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiolefin compound represented by the general formula (1) in a higher yield, the addition rate (dropping rate) is preferably 0.1 to 600 mol / hour, more preferably 0.33 to 60 mol / hour relative to 1 mol of the above-mentioned zinc or zinc alloy. The addition time is preferably such that the reaction is fully carried out, and it is particularly preferred to adjust so that the total amount after adding the nitrogen-containing compound is within the above-mentioned range. Specifically, the addition time is preferably 0.002 to 10 hours, more preferably 0.02 to 3 hours.

[0065] In the above-mentioned production method of the present invention, when mixing the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent with the nitrogen-containing compound (especially adding the nitrogen-containing compound to the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent), the compound represented by the general formula (2) as a substrate may be contained in the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent (hereinafter, sometimes referred to as "pre-addition of substrate"). Alternatively, after mixing the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent with the nitrogen-containing compound (especially adding the nitrogen-containing compound to the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent), the solution thus obtained may be mixed with the compound represented by the general formula (2) as a substrate (especially adding the compound represented by the general formula (2) as a substrate to the solution thus obtained) (hereinafter, sometimes referred to as "post-addition of substrate"). Among these, post-addition of the substrate is particularly preferred from the viewpoint that the reaction of the compound represented by the general formula (2) with the nitrogen-containing compound to generate impurities which are difficult to separate is further suppressed by pre-reacting zinc or a zinc alloy with the nitrogen-containing compound, thereby further improving the yield of the perfluorodiolefin compound.

[0066] When the substrate is added first, the content of the compound represented by the general formula (2) contained in the solution containing the iodine-containing inorganic material, the zinc or zinc alloy and the organic solvent is preferably adjusted so as to satisfy the content ratio of each component mentioned above.

[0067] When the substrate is added later, after adding the nitrogen-containing compound to the solution containing the iodine-containing inorganic material, the above-mentioned zinc or zinc alloy and the organic solvent, when the compound represented by the general formula (2) as the substrate is added to the solution thus obtained, the addition rate (dropping rate) of the compound represented by the general formula (2) is preferably 0.05 to 30 mol / hour, and more preferably 0.17 to 6 mol / hour relative to 1 mol of the above-mentioned zinc or zinc alloy, from the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiolefin compound represented by the general formula (1) in higher yield. The addition time is preferably such that the reaction is fully carried out, and it is particularly preferred to adjust so that the total amount after adding the compound represented by the general formula (2) is within the above-mentioned range. Specifically, the addition time is preferably 0.02 to 10 hours, and more preferably 0.08 to 3 hours.

[0068] In addition, the reaction conditions other than those mentioned above are not particularly limited, for example, the reaction atmosphere is preferably an inert gas atmosphere (nitrogen atmosphere, argon atmosphere, etc.), and the reaction time (maintaining time at the highest temperature) can be such that the reaction is fully carried out. After the reaction is completed, a purification treatment can be carried out by a conventional method to obtain a perfluorodiene compound represented by the general formula (1).

[0069] By using such a production method of the present invention, the amount of impurities that are difficult to separate can be further reduced and the yield of the perfluorodiolefin compound represented by the general formula (1) can be increased, and the separation operation of the impurities that are difficult to separate can be reduced and the perfluorodiolefin compound represented by the general formula (1) can be effectively obtained. In addition, for example, when hexafluorobutadiene is to be obtained as the perfluorodiolefin compound represented by the general formula (1), the impurities that are difficult to separate include 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) and the like.

[0070] The perfluorodiene compound represented by the general formula (1) thus obtained can be effectively used in various applications such as a refrigerant, a heat transfer medium, a foaming agent, and a resin monomer, typified by an etching gas used to form the most advanced microstructures of semiconductors and liquid crystals.

[0071] In this way, the perfluorodiene compound represented by the general formula (1) can be obtained, but it can also be obtained in the form of a perfluorodiene composition, which contains:

[0072] A perfluorodiene compound represented by the general formula (1);

[0073] The compound represented by the following general formula (3);

[0074] A compound represented by the following general formula (4A) and / or a compound represented by the following general formula (4B); and

[0075] The compound represented by the following general formula (5),

[0076] CF2=CF-(CF2) n－4 -CFX 3 -CF2H (3)

[0077] [In formula (3), n is the same as above. X 3 represents a halogen atom.]

[0078] CF2X 1 -CFX 2 -(CF2) n－4 -CF = CF2 (4A)

[0079] [In formula (4A), n is the same as above. X 1 and X 2 are the same or different, representing a halogen atom. 1 and X 2 Not all are fluorine atoms.]

[0080] CF2H-CFX 2 -(CF2) n－4 -CFX 3 -CF2H (4B)

[0081] [In formula (4B), n is the same as above. X 2 and X 3 The same or different, represents a halogen atom.]

[0082] CF2X 1 -CFX 2 -(CF2) n－4 -CFX 3 -CF2H (5)

[0083] [In formula (5), n is the same as above. X 1 , X 2 and X 3 are the same or different, representing a halogen atom. 1 and X 2 Not all are fluorine atoms.]

[0084] In the general formula (3), X 3 is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. 3 , preferably a fluorine atom, a chlorine atom, etc. (especially a fluorine atom). Examples of compounds represented by the general formula (3) that satisfy such conditions include CF2=CF-CF2-CF2H, CF2=CF-CF2-CF2-CF2H, and CF2=CF-CF2-CF2-CF2-CF2H.

[0085] In the general formula (4A), X 1 and X 2 is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 1 and X 2 They may be the same or different. As in general formula (2), X 1 and X 2 As in the general formula (2), X 1 , preferably a chlorine atom, a bromine atom, an iodine atom, etc. (particularly a chlorine atom, a bromine atom, etc.); as X 2 , preferably a fluorine atom, a chlorine atom, a bromine atom, etc. (especially a fluorine atom, a chlorine atom, etc.). Examples of the compound represented by the general formula (4A) include ClCF2-CFCl-CF=CF2, ClCF2-CFCl-CF2-CF=CF2, ClCF2-CFCl-CF2-CF2-CF=CF2, ICF2-CF2-CF=CF2, ICF2-CF2-CF2-CF=CF2, ICF2-CF2-CF2-CF=CF2, ICF2-CF2-CF2-CF=CF2, BrCF2-CF2-CF=CF2, BrCF2-CF2-CF2-CF=CF2, BrCF2-CF2-CF2-CF2-CF=CF2, etc. For the same reasons as in general formula (2), preferred are ClCF2-CFCl-CF=CF2, ClCF2-CFCl-CF2-CF=CF2, ClCF2-CFCl-CF2-CF2-CF=CF2, BrCF2-CF2-CF=CF2, BrCF2-CF2-CF2-CF=CF2, BrCF2-CF2-CF2-CF2-CF=CF2, and more preferred are BrCF2-CF2-CF=CF2, BrCF2-CF2-CF2-CF=CF2, BrCF2-CF2-CF2-CF2-CF=CF2, and the like.

[0086] In the general formula (4B), X 2 and X 3 is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 2 and X 3 As in the general formula (2), X 2 , preferably a fluorine atom, a chlorine atom, a bromine atom, etc. (particularly a fluorine atom, a chlorine atom, etc.); as X 3, preferably a fluorine atom, a chlorine atom, etc. (especially a fluorine atom). Examples of compounds represented by the general formula (4B) that satisfy such conditions include HCF2-CFCl-CF2-CF2H, HCF2-CFCl-CF2-CF2-CF2H, HCF2-CFCl-CF2-CF2-CF2-CF2H, HCF2-CF2-CF2-CF2-CF2H, HCF2-CF2-CF2-CF2-CF2H, HCF2-CF2-CF2-CF2-CF2-CF2H, HCF2-CF2-CF2-CF2-CF2-CF2H, etc. For the same reasons as for the general formula (2), HCF2-CF2-CF2-CF2-CF2H, HCF2-CF2-CF2-CF2-CF2-CF2H, HCF2-CF2-CF2-CF2-CF2-CF2H, etc. are preferred.

[0087] In the general formula (5), X 1 , X 2 and X 3 is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 1 , X 2 and X 3 They may be the same or different. As in general formula (2), X 1 and X 2 As in the general formula (2), X 1 , preferably a chlorine atom, a bromine atom, an iodine atom, etc. (particularly a chlorine atom, a bromine atom, etc.); as X 2 , preferably a fluorine atom, a chlorine atom, a bromine atom, etc. (particularly a fluorine atom, a chlorine atom, etc.); as X 3 , preferably a fluorine atom, a chlorine atom, etc. (especially a fluorine atom). 3When it is a fluorine atom, the compound represented by the general formula (5) is usually produced in large quantities in the liquid phase and is almost non-existent in the gas phase. Therefore, it cannot be detected when only the gas phase of the gas collection bottle is analyzed. In other words, the perfluorodiene composition of the present invention is composed of impurities present in both the gas phase and the liquid phase of the gas collection bottle. Examples of the compound represented by the general formula (5) that satisfies such a condition include ClCF2-CFCl-CF2-CF2-CF2H, ClCF2-CFCl-CF2-CF2-CF2-CF2H, ClCF2-CFCl-CF2-CF2-CF2-CF2H, ICF2-CF2-CF2-CF2-CF2H, ICF2-CF2-CF2-CF2-CF2H, ICF2-CF2-CF2-CF2-CF2-CF2H, ICF2-CF2-CF2-CF2-CF2-CF2H, BrCF2-CF2-CF2-CF2-CF2-CF2H, BrCF2-CF2-CF2-CF2-CF2-CF2H, BrCF2-CF2-CF2-CF2-CF2-CF2 H, etc., and for the same reasons as in the general formula (2), ClCF2-CFCl-CF2-CF2-CF2H, ClCF2-CFCl-CF2-CF2-CF2-CF2H, ClCF2-CFCl-CF2-CF2-CF2-CF2-CF2H, BrCF2-CF2-CF2-CF2-CF2H, BrCF2-CF2-CF2-CF2-CF2-CF2H, BrCF2-CF2-CF2-CF2-CF2-CF2H, etc. are preferred, and BrCF2-CF2-CF2-CF2-CF2H, BrCF2-CF2-CF2-CF2-CF2-CF2H, BrCF2-CF2-CF2-CF2-CF2-CF2H, etc. are more preferred.

[0088] In the perfluorodiene composition of the present invention, when the total amount of the perfluorodiene composition of the present invention is 100 mol%, the content of the perfluorodiene compound represented by the general formula (1) is preferably 80 to 99.8 mol% (particularly 85 to 99 mol%), the content of the compound represented by the general formula (3) is preferably 0.1 to 12 mol% (particularly 0.5 to 10 mol%), the total content of the compounds represented by the general formula (4A) and / or (4B) is preferably 0.01 to 0.6 mol% (particularly 0.02 to 0.5 mol%), and the content of the compound represented by the general formula (5) is preferably 0.05 to 1 mol% (particularly 0.1 to 0.5 mol%). In addition, in the perfluorodiene composition of the present invention, the content of components other than the above (other components) is preferably 0 to 5 mol% (particularly 0.01 to 4 mol%). Since the other components include impurities that are difficult to separate (such as 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) when hexafluorobutadiene is desired as the perfluorodiene compound represented by the general formula (1), the content of the other components is preferably as small as possible.

[0089] The perfluorodiene composition of the present invention can be effectively used in various applications such as refrigerants, heat transfer media, foaming agents, and resin monomers, as exemplified by etching gases for forming the most advanced microstructures of semiconductors, liquid crystals, etc., similar to the above-mentioned perfluorodiene compounds alone.

[0090] Example

[0091] The following examples will clarify the features of the present invention, but the present invention is not limited to these examples.

[0092] Example 1: ClCF2-CFCl-CF2-CF2I; ZnI2 0.18 mol%

[0093] 200 g (0.53 mol) of xylene, 34.93 g (0.53 mol) of zinc, and 0.30 g (0.001 mol; 0.18 mol% relative to zinc) of ZnI2 were added to an eggplant-shaped flask with a condenser connected to a collector cooled to -78°C, and heated to an internal temperature of 140°C under stirring. After the internal temperature was constant, N,N-dimethylformamide (DMF) was added dropwise at a rate of 0.52 mol / hour (1.04 mol / hour relative to 1 mol of zinc) for 1 hour while reflux, and heating and reflux were continued for 0.5 hours while stirring. Then, the raw material (ClCF2-CFCl-CF2-CF2I) was added dropwise at a rate of 0.24 mol / hour (0.48 mol / hour relative to 1 mol of zinc) for 1 hour while reflux, and heating and reflux were continued for 3 hours while stirring to react. After the reaction, the gas phase, liquid phase and reaction liquid in the gas bottle were collected and analyzed by gas chromatography, and the conversion rate and selectivity were calculated taking into account each quantity. The conversion rate was 100 mol%. Regarding the selectivity of each component, CF2=CFCF=CF2 was 88 mol%, CF2=CF-CF2-CF2H was 8.2 mol%, ClCF2-CFCl-CF=CF2 was 0.051 mol%, ClCF2-CFCl-CF2-CF2H was 0.32 mol%, and the total of other by-products (CF3CF=CHCF3, etc.) was 3.4 mol%.

[0094] Example 2: ClCF2-CFCl-CF2-CF2I; ZnI2 0.6 mol%

[0095] The same treatment as in Example 1 was performed except that the amount of ZnI2 used was 0.95 g (0.003 mol; 0.56 mol% relative to zinc). After the reaction, the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 91 mol% for CF2=CFCF=CF2, 6.8 mol% for CF2=CF-CF2-CF2H, 0.042 mol% for ClCF2-CFCl-CF=CF2, 0.18 mol% for ClCF2-CFCl-CF2-CF2H, and 2.0 mol% for other by-products (CF3CF=CHCF3, etc.).

[0096] Example 3: ClCF2-CFCl-CF2-CF2I; ZnI2 1.6 mol%

[0097] The same treatment as in Example 1 was performed except that the amount of ZnI2 used was 2.70 g (0.53 mol; 1.6 mol% relative to zinc). After the reaction, the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 93 mol% for CF2=CFCF=CF2, 5.6 mol% for CF2=CF-CF2-CF2H, 0.082 mol% for ClCF2-CFCl-CF=CF2, 0.27 mol% for ClCF2-CFCl-CF2-CF2H, and 1.0 mol% for other by-products (CF3CF=CHCF3, etc.).

[0098] Example 4: ClCF2-CFCl-CF2-CF2I; I2 1.6 mol%

[0099] The same treatment as in Example 1 was performed except that 2.20 g (0.009 mol; 1.6 mol% relative to zinc) of I2 was used instead of 0.30 g (0.001 mol; 0.18 mol% relative to zinc) of ZnI2. After the reaction, the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 96 mol% for CF2=CFCF=CF2, 2.6 mol% for CF2=CF-CF2-CF2H, 0.031 mol% for ClCF2-CFCl-CF=CF2, 0.17 mol% for ClCF2-CFCl-CF2-CF2H, and 1.2 mol% for other by-products (CF3CF=CHCF3, etc.).

[0100] Example 5: ClCF2-CFCl-CF2-CF2I; NaI 1.6 mol%

[0101] The same treatment as in Example 1 was performed except that 1.27 g (0.0085 mol; 1.6 mol% relative to zinc) of NaI was used instead of 0.30 g (0.001 mol; 0.18 mol% relative to zinc) of ZnI2. After the reaction, the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 91 mol% for CF2=CFCF=CF2, 6.1 mol% for CF2=CF-CF2-CF2H, 0.053 mol% for ClCF2-CFCl-CF=CF2, 0.32 mol% for ClCF2-CFCl-CF2-CF2H, and the total amount of other by-products (CF3CF=CHCF3, etc.) was 2.5 mol%.

[0102] Example 6: ClCF2-CFCl-CF2-CF2I; NaI 3.2 mol%

[0103] The same treatment as in Example 1 was performed except that 2.54 g (0.017 mol; 3.2 mol% relative to zinc) of NaI was used instead of 0.30 g (0.001 mol; 0.18 mol% relative to zinc) of ZnI2. After the reaction, the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 94 mol% for CF2=CFCF=CF2, 5.1 mol% for CF2=CF-CF2-CF2H, 0.044 mol% for ClCF2-CFCl-CF=CF2, 0.12 mol% for ClCF2-CFCl-CF2-CF2H, and the total amount of other by-products (CF3CF=CHCF3, etc.) was 0.72 mol%.

[0104] Reference Example 1: ClCF2-CFCl-CF2-CF2I; no iodine-containing inorganic material

[0105] Except that ZnI2 was not used, the treatment was carried out in the same manner as in Example 1. After the reaction was completed, the gas phase, liquid phase and reaction liquid in the gas collection bottle were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 78 mol% for CF2=CFCF=CF2, 14 mol% for CF2=CF-CF2-CF2H, 0.66 mol% for ClCF2-CFCl-CF=CF2, 1.5 mol% for ClCF2-CFCl-CF2-CF2H, and 5.9 mol% for other by-products (CF3CF=CHCF3, etc.).

[0106] Example 7: ICF2-CF2-CF2-CF2I; ZnI2 1.6 mol%

[0107] As a substrate, ICF2-CF2-CF2-CF2-CF2I was used instead of ClCF2-CFCl-CF2-CF2I, and the amount of ZnI2 used was 2.70 g (0.53 mol; 1.6 mol% relative to zinc), and the treatment was carried out in the same manner as in Example 1. After the reaction was completed, the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 87 mol% for CF2=CFCF=CF2, 5.4 mol% for CF2=CF-CF2-CF2H, 2.2 mol% for HCF2-CF2-CF2-CF2H, 2.1 mol% for ICF2-CF2-CF2-CF2H, and 3.3 mol% for other by-products (CF3CF=CHCF3, etc.).

[0108] Reference Example 2: ICF2-CF2-CF2-CF2I; No iodine-containing inorganic materials

[0109] As a substrate, ICF2-CF2-CF2-CF2-CF2I was used instead of ClCF2-CFCl-CF2-CF2I, and ZnI2 was not used. The treatment was carried out in the same manner as in Example 1. After the reaction, the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 63 mol% for CF2=CFCF=CF2, 25 mol% for CF2=CF-CF2-CF2H, 2.2 mol% for HCF2-CF2-CF2-CF2H, 2.1 mol% for ICF2-CF2-CF2-CF2H, and 7.7 mol% for other by-products (CF3CF=CHCF3, etc.).

[0110] Example 8: BrCF2-CF2-CF2-CF2Br; ZnI2 1.6 mol%

[0111] As a substrate, BrCF2-CF2-CF2-CF2-CF2Br was used instead of ClCF2-CFCl-CF2-CF2I, and the treatment was carried out in the same manner as in Example 1. After the reaction was completed, the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography, and the conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol%, and the selectivity of each component was 96 mol% for CF2=CFCF=CF2, 3.0 mol% for CF2=CF-CF2-CF2H, 0.51 mol% for HCF2-CF2-CF2-CF2H, 0.28 mol% for BrCF2-CF2-CF2-CF2H, and 0.21 mol% for other by-products (CF3CF=CHCF3, etc.).

[0112] Reference Example 3: BrCF2-CF2-CF2-CF2Br; No iodine-containing inorganic material

[0113] As a substrate, BrCF2-CF2-CF2-CF2-CF2Br was used instead of ClCF2-CFCl-CF2-CF2I, and ZnI2 was not used. The same treatment as in Example 1 was performed except that the gas phase, liquid phase and reaction liquid in the gas trap were analyzed by gas chromatography after the reaction was completed. The conversion rate and selectivity were calculated by considering each amount. The conversion rate was 100 mol %. Regarding the selectivity of each component, CF2=CFCF=CF2 was 76 mol %, CF2=CF-CF2-CF2H was 13 mol %, HCF2-CF2-CF2-CF2H was 1.9 mol %, BrCF2-CF2-CF2-CF2-CF2H was 2.1 mol %, and the total of other by-products (CF3CF=CHC3, etc.) was 7.0 mol %. The results are shown in Tables 1 to 3.

[0114] [Table 1]

[0115]

[0116] [Table 2]

[0117]

[0118] [Table 3]

[0119]

Claims

1. A method for producing a perfluorodiene compound represented by general formula (1), characterized in that: include: A reaction step of reacting a compound represented by the general formula (2) in the presence of a nitrogen-containing compound, an iodine-containing inorganic material and zinc in an organic solvent. CF2=CF-(CF2) n－4 -CF=CF2 (1) In formula (1), n ​​represents an integer of 4 to 20, CF2X 1 -CFX 2 -(CF2) n－4 -CFX 3 -CF2X 4 (2) In formula (2), n is the same as above, X 1 , X 2 , X 3 and X 4 Same or different, X 1 represents a chlorine atom, a bromine atom or an iodine atom, X 2 represents a fluorine atom, a chlorine atom or a bromine atom, X 3 represents a fluorine atom or a chlorine atom, X 4 represents a chlorine atom, a bromine atom or an iodine atom, The reaction process includes a first mixing process of mixing a solution containing the iodine-containing inorganic material, the zinc and the organic solvent with the nitrogen-containing compound, The nitrogen-containing compound is an amide compound, The iodine-containing inorganic material is at least one selected from iodine, sodium iodide, potassium iodide, magnesium iodide, calcium iodide and zinc iodide.

2. The manufacturing method according to claim 1, characterized in that: The amount of the iodine-containing inorganic material used is 0.0005 mol or more relative to 1 mol of the zinc and is less than the solubility in the organic solvent.

3. The manufacturing method according to claim 1, characterized in that: In the first mixing step, the nitrogen-containing compound is added to the solution containing zinc at an addition rate of 0.1 to 600 mol / hour relative to 1 mol of the zinc.

4. The manufacturing method according to any one of claims 1 to 3, characterized in that: The reaction step includes a second mixing step of mixing the obtained mixed solution with the compound represented by the general formula (2) after the first mixing step.

5. The manufacturing method according to claim 4, characterized in that: In the second mixing step, the compound represented by the general formula (2) is added to the mixed solution obtained in the first mixing step at an addition rate of 0.05 to 30 mol / hour per 1 mol of the zinc.

6. The manufacturing method according to any one of claims 1 to 3, characterized in that: In the first mixing step, the temperature is 50 to 200° C. when the solution containing the iodine-containing inorganic material, zinc and the organic solvent is mixed with the nitrogen-containing compound.

7. The manufacturing method according to any one of claims 1 to 3, characterized in that: The nitrogen-containing compound is N,N-dimethylformamide.

8. The manufacturing method according to any one of claims 1 to 3, characterized in that: The boiling point of the organic solvent is lower than the boiling point of the nitrogen-containing compound.

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