Method for producing perfluorodiene compound

Abstract

The preparation method of the present invention comprises the steps of: in an organic solvent, in the presence of a nitrogen-containing compound and zinc or a zinc alloy, reacting a compound of the general formula (2): CF2X 1 -CFX 2 -(CF2) n－4 -CF2-CF2X 3 (2) [wherein, n is the same as in the specification. X 1 , X 2 and X 3 Same or Different, X 1 and X 2 represents a halogen atom, X 3 represents a chlorine atom, a bromine atom or an iodine atom. 1 and X 2 The reaction step of reacting the compound represented by the formula (2) with the nitrogen-containing compound and the solution containing zinc or zinc alloy and an organic solvent is mixed in sequence, thereby reducing the amount of impurities that are difficult to separate and obtaining a perfluorodiolefin compound in high yield.

Description

Technical Field

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

[0002] Perfluorodiene compounds are useful compounds as various refrigerants, foaming agents, heat transfer media, etc. in addition to being used as 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, is used in various applications.

[0003] As a method for producing the perfluorodiolefin compound, there is known a method of 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 of 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 aspects.

[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 and zinc or a zinc alloy.

[0013] The reaction step includes a mixing step of sequentially mixing a solution containing zinc or a zinc alloy and an organic solvent with a nitrogen-containing compound and a compound represented by the following general formula (2),

[0014] General formula (1):

[0015] CF2=CF-(CF2) n－4 -CF = CF2 (1)

[0016] [In the formula, n represents an integer of 4 to 20.]

[0017] General formula (2):

[0018] CF2X 1 -CFX 2 -(CF2) n－4 -CF2-CF2X 3 (2)

[0019] [wherein n is the same as above. X 1 , X 2 and X 3 Same or Different, X 1 and X 2 represents a halogen atom, X 3 represents a chlorine atom, a bromine atom or an iodine atom. 1 and X 2 Both sides of are not fluorine atoms. ].

[0020] Item 2. The production method according to Item 1, wherein the mixing step includes a step of mixing a solution containing zinc or a zinc alloy and an organic solvent with a nitrogen-containing compound,

[0021] The nitrogen-containing compound is added to the solution containing zinc or a zinc alloy and an organic solvent at an addition rate of 0.1 to 600 mol / hour relative to 1 mol of the zinc or the zinc alloy.

[0022] Item 3. The production method as described in Item 1 or 2, wherein the mixing step is a step of mixing the solution containing zinc or zinc alloy and organic solvent and the compound represented by the general formula (2), and then mixing the obtained mixed solution with the nitrogen-containing compound.

[0023] Item 4. The production method according to Item 1 or 2, wherein in the mixing step, the solution containing zinc or zinc alloy and organic solvent and the nitrogen-containing compound are mixed, and then the obtained mixed solution is mixed with the compound represented by the general formula (2).

[0024] Item 5. A manufacturing method as described in Item 4, wherein, in the above-mentioned mixing step, the compound represented by the general formula (2) is added to the mixed solution of the above-mentioned solution containing zinc or zinc alloy and organic solvent and the above-mentioned nitrogen-containing compound at an addition rate of 0.05 to 30 mol / hour relative to 1 mol of the above-mentioned zinc or zinc alloy.

[0025] Item 6. The production method according to any one of Items 3 to 5, wherein in the mixing step, when the solution containing zinc or a zinc alloy and an organic solvent and the nitrogen-containing compound are mixed, the solution has a temperature of 50 to 200°C.

[0026] Item 7. The production method according to any one of Items 1 to 6, wherein the nitrogen-containing compound is N,N-dimethylformamide.

[0027] Item 8. The production method according to any one of Items 1 to 7, wherein the boiling point of the organic solvent is lower than or equal to the boiling point of the nitrogen-containing compound.

[0028] Item 9. A perfluorodiene composition comprising a perfluorodiene compound represented by the general formula (1), a compound represented by the general formula (3), a compound represented by the general formula (4A), and / or a compound represented by the general formula (4B), and a compound represented by the general formula (5),

[0029] General formula (1):

[0030] CF2=CF-(CF2) n－4 -CF = CF2 (1)

[0031] [In the formula, n represents an integer of 4 to 20.]

[0032] General formula (3):

[0033] CF2=CF-(CF2) n－4 -CF2-CF2H (3)

[0034] [Wherein, n is the same as above.]

[0035] General formula (4A):

[0036] CF2X 1 -CFX 2 -(CF2) n－4 -CF = CF2 (4A)

[0037] [wherein n is the same as above. X 1 and X 2 are the same or different, representing a halogen atom. 1 and X 2 Both sides of are not fluorine atoms.]

[0038] CF2H-CFX 2 -(CF2) n－4 -CF2-CF2H (4B)

[0039] [wherein n is the same as above. X 2 represents a halogen atom.]

[0040] General formula (5):

[0041] CF2X 1 -CFX 2 -(CF2) n－4 -CF2-CF2H (5)

[0042] [wherein n is the same as above. X 1 and X 2 are the same or different, representing a halogen atom. 1 and X 2 Both sides of are not fluorine atoms. ].

[0043] Item 10. The perfluorodiene composition according to Item 9, wherein the content of the perfluorodiene compound represented by the general formula (1) is 30 to 99.8 mol % based on 100 mol % of the total amount of the perfluorodiene composition.

[0044] Item 11. The perfluorodiene composition according to Item 9 or 10, wherein the perfluorodiene compound represented by the general formula (1) is hexafluorobutadiene.

[0045] Item 12. An etching gas, a refrigerant, a heat transfer medium, a foaming agent, or a resin monomer comprising the perfluorodiene composition according to any one of Items 9 to 11.

[0046] Effects of the Invention

[0047] 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

[0048] In this specification, "comprising" is a concept including any one of "including", "consisting essentially of", and "consisting only of". In addition, in this specification, when "A to B" is used to express a numerical range, it means A or more and B or less.

[0049] 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 a compound represented by the general formula (2) in an organic solvent in the presence of a nitrogen-containing compound and zinc or a zinc alloy.

[0050] General formula (1):

[0051] CF2=CF-(CF2) n－4 -CF = CF2 (1)

[0052] [In the formula, n represents an integer of 4 to 20.]

[0053] General formula (2):

[0054] CF2X 1 -CFX 2 -(CF2) n－4 -CF2-CF2X 3 (2)

[0055] [wherein n is the same as above. X 1 , X 2 and X 3 Same or Different, X 1 and X 2 represents a halogen atom, X 3 represents a chlorine atom, a bromine atom or an iodine atom. 1 and X 2 Both sides of are not fluorine atoms.]

[0056] The reaction step includes a mixing step of mixing a nitrogen-containing compound with a solution containing zinc or a zinc alloy and an organic solvent.

[0057] The present invention has a higher yield than the methods of Patent Documents 1 and 2, and can obtain the target product by suppressing the amount of impurities such as 1,1,1,2,4,4,4-heptafluoro-2-butene which are difficult to separate compared to Patent Document 2.

[0058] In particular, since the compound represented by the general formula (2) has CF2X 3 The adjacent group is CF2, therefore, impurities such as ClCF2CFClCF2CF2CF2H, ICF2CF2CF2CF2H, BrCF2CF2CF2CF2H (compounds represented by the general formula (5) described later) are generated in the liquid phase of the gas collection bottle and are basically absent in the gas phase. Therefore, when only the gas phase of the gas collection bottle is collected, these impurities will not cause problems, but when the gas phase and liquid phase of the gas collection bottle are collected as described later, these impurities will cause problems. In the present invention, as described above, by mixing a solution containing zinc or a zinc alloy and an organic solvent with a nitrogen-containing compound (particularly, adding a nitrogen-containing compound to a solution containing zinc or a zinc alloy and an organic solvent), the amount of impurities generated can be reduced.

[0059] In the general formulae (1) and (2), n is an integer of 4 to 20, and more preferably an integer of 4 to 10. By setting it within this range, the amount of impurities generated that are difficult to separate can be further reduced, and the perfluorodiene compound can be obtained at a higher yield.

[0060] 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.

[0061] In the general formula (2), 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. 3 is a chlorine atom, a bromine atom or an iodine atom. 1 , X 2 and X 3 They can be the same or different. 1 and X 2 When both sides of X are fluorine atoms, the reaction does not proceed and a perfluorodiolefin compound cannot be obtained. 1 and X 2 Both of X and X cannot be fluorine atoms. From the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiolefin compound in a higher yield, 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 chlorine atom, a bromine atom, an iodine atom, etc. (particularly a bromine atom, an iodine atom, etc.).

[0062] Examples of compounds represented by the general formula (2) that satisfy 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 viewpoint of reducing the amount of impurities generated and obtaining a perfluorodiolefin compound in a 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 ClCF2-CFCl-CF2-CF2-CF2I, ClCF2-CFCl-CF2-CF2-CF2-CF2-CF2I, and more preferred are ClCF2-CFCl-CF2-CF2-CF2I, ClCF2-CFCl-CF2-CF2-CF2-CF2-CF2I.

[0063] From the viewpoint of being able to further reduce the amount of impurities that are difficult to separate and to obtain the perfluorodiolefin compound at 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.

[0064] In zinc or zinc alloy, as the element contained when using zinc alloy, for example, lead, cadmium, iron, etc. can be listed. In addition, commercially available zinc sometimes contains impurities such as lead, cadmium, iron, etc. The present invention also includes zinc or zinc alloy containing these impurities.

[0065] As the organic solvent, a non-polar organic solvent is preferred, particularly from the viewpoint of dissolving the compound represented by the general formula (2). From the viewpoint of suppressing the volatilization of the nitrogen-containing compound from the reaction system and particularly improving the yield of the perfluorodiolefin compound, the boiling point of the organic solvent is preferably lower than the boiling point of the nitrogen-containing compound. Examples of such an organic solvent include aromatic hydrocarbon compounds such as heptane, hexane, benzene, toluene, and xylene; and ether compounds such as tetrahydrofuran and diethyl ether.

[0066] 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.

[0067] 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 can be used alone or in combination of two or more. Among them, from the viewpoint of being able to further reduce the amount of impurities that are difficult to separate and to obtain a perfluorodiolefin compound in a higher yield, amide compounds are preferred, and N,N-dimethylformamide is more preferred.

[0068] The nitrogen-containing compound also includes compounds that are liquid at room temperature, but from the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiolefin compound at a 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.

[0069] In the manufacturing method of the present invention, from the viewpoint of being able to further reduce the amount of impurities that are difficult to separate and obtain the perfluorodiolefin compound with a higher yield, the above-mentioned mixing step preferably sequentially mixes a solution containing zinc or a zinc alloy and an organic solvent, a nitrogen-containing compound, and the compound represented by the above-mentioned general formula (2). As such a mixing step, for example, a solution containing zinc or a zinc alloy and an organic solvent and a nitrogen-containing compound can be mixed, and in particular, a nitrogen-containing compound can be added to a solution containing zinc or a zinc alloy and an organic solvent. In the solution containing zinc or a zinc alloy and an organic solvent, the content of each component is preferably adjusted in a manner that satisfies the content ratio of each component mentioned above. In addition, in the case of 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 based on the amount of the compound represented by the general formula (2) to be mixed (especially added).

[0070] When mixing a solution containing zinc or a zinc alloy and an organic solvent with a nitrogen-containing compound (adding a nitrogen-containing compound to a solution containing zinc or a zinc alloy and an organic solvent), it is preferred to mix the solution containing zinc or a zinc alloy and an organic solvent with the nitrogen-containing compound at a temperature of preferably 50 to 200° C., more preferably 100 to 150° C. In particular, it is preferred to add the nitrogen-containing compound while heating the solution containing zinc or a zinc alloy and an organic solvent to the above temperature. In addition, by adding the nitrogen-containing compound while refluxing the solution containing zinc or a zinc alloy and an organic solvent, the solvent will volatilize when the reaction temperature is reached because it is lower than the reaction temperature, and it can be cooled and returned to the reactor. In the case of adding the nitrogen-containing compound while refluxing the solution containing zinc or a zinc alloy and an organic solvent, it is most preferred to heat the solution containing zinc or a zinc alloy and an organic solvent at the reflux temperature.

[0071] If the boiling point of the organic solvent is lower than the boiling point of the nitrogen-containing compound, it is preferred because mixing of the solution containing zinc or a zinc alloy and the organic solvent with the nitrogen-containing compound is facilitated after the solution is heated.

[0072] After heating (particularly heating at reflux temperature), the solution containing zinc or zinc alloy and organic solvent is mixed with the nitrogen-containing compound, for example, when the nitrogen-containing compound is added to the solution containing zinc or zinc alloy and organic solvent, 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 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 general formula (1) at a higher yield. The addition time is preferably set to a degree that the reaction proceeds fully, and in particular, it is preferably adjusted so that the total amount after the addition of the nitrogen-containing compound is within the above range. Specifically, the addition time is preferably 0.002 to 10 hours, more preferably 0.02 to 3 hours.

[0073] In the above-mentioned production method of the present invention, when a solution containing zinc or a zinc alloy and an organic solvent is mixed with a nitrogen-containing compound (particularly, a nitrogen-containing compound is added to a solution containing zinc or a zinc alloy and an organic solvent), the compound represented by the general formula (2) as a substrate may be mixed with a solution containing zinc or a zinc alloy and an organic solvent to obtain a mixed solution, and the obtained mixed solution may be mixed with the nitrogen-containing compound (hereinafter, sometimes referred to as "pre-substrate addition"). Alternatively, the solution containing zinc or a zinc alloy and an organic solvent may be mixed with a nitrogen-containing compound (particularly, a nitrogen-containing compound is added to a solution containing zinc or a zinc alloy and an organic solvent), and the thus obtained mixed solution may be mixed with the compound represented by the general formula (2) as a substrate (particularly, a compound represented by the general formula (2) as a substrate is added to the thus obtained mixed solution) (hereinafter, sometimes referred to as "post-substrate addition"). Among these, post-substrate addition 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 that are difficult to separate is further suppressed by reacting the zinc or a zinc alloy with the nitrogen-containing compound in advance, and as a result, the yield of the perfluorodiolefin compound is further improved.

[0074] When the substrate is added first, the content of the compound represented by the general formula (2) contained in the solution containing zinc or a zinc alloy and an organic solvent is preferably adjusted to satisfy the content ratio of each component described above.

[0075] In the case of post-addition of the substrate, after adding the nitrogen-containing compound to the solution containing zinc or zinc alloy and the organic solvent, the addition rate (dropping rate) of the compound represented by the general formula (2) when adding the compound represented by the general formula (2) as the substrate to the mixed solution thus obtained is preferably 0.05 to 30 mol / hour, more preferably 0.17 to 6 mol / hour relative to 1 mol of 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) at a higher yield. The addition time is preferably set to a degree that the reaction is fully carried out, and it is particularly preferably adjusted so that the total amount after adding the compound represented by the general formula (2) is within the above range. Specifically, the addition time is preferably 0.02 to 10 hours, and more preferably 0.08 to 3 hours.

[0076] In the present invention, an iodine-containing inorganic material can also be used during the reaction, thereby further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiene compound represented by the general formula (1) at a higher yield.

[0077] As iodine-containing inorganic materials, as long as it is an inorganic material containing iodine atoms, there is no particular limitation, for example, iodine can be cited; metal iodides of typical metal iodides (sodium iodide, potassium iodide, magnesium iodide, calcium iodide, etc.), transition metal iodides (zinc iodide, etc.), etc. In addition, according to the manufacture method of the present invention, zinc halide (a mixture of zinc fluoride, zinc chloride and zinc iodide) can be generated as an impurity in the product. The zinc halide as an impurity contained in the product can also be reused in the manufacture method of the present invention as an iodine-containing inorganic material. These iodine-containing inorganic materials can be used alone or in combination of more than two kinds. Among them, from the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining perfluorodiolefin compounds with a higher yield, preferably iodine, transition metal iodide, zinc halide as an impurity in the product of the manufacture method of the present invention, more preferably iodine.

[0078] The amount of the iodine-containing inorganic compound used is preferably 0.0005 mol or more and below the solubility in the organic solvent per 1 mol of zinc or zinc alloy, and more preferably 0.001 to 0.1 mol per 1 mol of zinc or zinc alloy, from the viewpoint of further reducing the amount of impurities that are difficult to separate and obtaining the perfluorodiolefin compound in a higher yield.

[0079] In the case of using an iodine-containing inorganic material in the present invention, in order to further reduce the amount of impurities that are difficult to separate and obtain the perfluorodiolefin compound shown in the general formula (1) with a higher yield regardless of whether the substrate is added first or later, the iodine-containing inorganic material is preferably contained in a solution containing zinc or a zinc alloy and an organic solvent. In this case, it is preferably adjusted to a content of the iodine-containing inorganic material contained in the solution containing zinc or a zinc alloy and an organic solvent that satisfies the content ratio of the above-mentioned components.

[0080] 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 set to a degree that the reaction is fully carried out. After the reaction is completed, a purification treatment can be carried out according to a conventional method to obtain a perfluorodiene compound represented by the general formula (1).

[0081] The production method of the present invention is a method for further reducing the amount of impurities that are difficult to separate and improving the yield of the perfluorodiolefin compound represented by the general formula (1), and can effectively obtain the perfluorodiolefin compound represented by the general formula (1) while reducing the effort of separating the impurities that are difficult to separate. In addition, the impurities that are difficult to separate, for example, when hexafluorobutadiene is to be obtained as the perfluorodiolefin compound represented by the general formula (1), include 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) and the like.

[0082] The perfluorodiene compound represented by the general formula (1) thus obtained can be effectively used in various applications such as etching gas for forming the most advanced microstructures of semiconductors, liquid crystals, etc., refrigerants, heat transfer media, foaming agents, resin monomers, etc.

[0083] In this way, a perfluorodiene compound represented by the general formula (1) can be obtained, but it can also be obtained in the form of a perfluorodiene composition containing a perfluorodiene compound represented by the general formula (1), a compound represented by the general formula (3), a compound represented by the general formula (4A), and / or a compound represented by the general formula (4B), and a compound represented by the general formula (5).

[0084] General formula (3):

[0085] CF2=CF-(CF2) n－4 -CF2-CF2H (3)

[0086] [Wherein, n is the same as above.]

[0087] General formula (4A):

[0088] CF2X 1 -CFX 2 -(CF2) n－4 -CF = CF2 (4A)

[0089] [wherein n is the same as above. X 1 and X 2 are the same or different, representing a halogen atom. 1 and X 2 Both sides of are not fluorine atoms.]

[0090] General formula (4B):

[0091] CF2H-CFX 2 -(CF2) n－4 -CF2-CF2H (4B)

[0092] [wherein n is the same as above. X 2 represents a halogen atom.]

[0093] General formula (5):

[0094] CF2X 1 -CFX 2 -(CF2) n－4 -CF2-CF2H (5)

[0095] [wherein n is the same as above. X 1 and X 2 are the same or different, representing a halogen atom.1 and X 2 Both sides of are not fluorine atoms.]

[0096] Examples of the compound represented by the general formula (3) that satisfies such conditions include CF2=CF-CF2-CF2H, CF2=CF-CF2-CF2-CF2H, and CF2=CF-CF2-CF2-CF2-CF2H.

[0097] 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 Both of X and X are not fluorine atoms. 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-CF2-CF=CF2, BrCF2-CF2-CF=CF2, BrCF2-CF2-CF2-CF=CF2, BrCF2-CF2-CF2-CF2-CF=CF2, etc., which are represented by For the same reasons as in general formula (2), 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-CF=CF2, BrCF2-CF2-CF2-CF2-CF=CF2, etc. are preferred, and ClCF2-CFCl-CF=CF2, ClCF2-CFCl-CF2-CF2-CF=CF2, ClCF2-CFCl-CF2-CF2-CF=CF2, etc. are more preferred.

[0098] In the general formula (4B), X 2 is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 2, preferably a fluorine atom, a chlorine atom, a bromine atom, etc. (especially a fluorine atom, a chlorine atom, etc.). 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-CF2H, HCF2-CF2-CF2-CF2-CF2-CF2H, etc. For the same reasons as for the general formula (2), HCF2-CFCl-CF2-CF2-CF2H, HCF2-CFCl-CF2-CF2-CF2-CF2H, HCF2-CFCl-CF2-CF2-CF2-CF2H, etc. are preferred.

[0099] In the general formula (5), 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 Both of X and X are not fluorine atoms. 1 , preferably a chlorine atom, a bromine atom, an iodine atom, etc. (particularly a chlorine atom, a bromine atom, etc.), as X 2, preferably fluorine atom, chlorine atom, bromine atom, etc. (especially fluorine atom, chlorine atom, etc.). The compound represented by the general formula (5) is a compound generated when the group adjacent to the CF2X3 group in the compound represented by the general formula (2) as the substrate is CF2, but since it is produced in large quantities in the liquid phase and is basically absent in the gas phase, it is not detected when only the gas phase of the gas collection bottle is analyzed. That is, the perfluorodiolefin composition of the present invention is composed of impurities present in both the gas phase and the liquid phase of the gas collection bottle, and the perfluorodiolefin composition of the present invention cannot be obtained when only the gas phase of the gas collection bottle is collected. Examples of the compound represented by the general formula (5) that satisfies such conditions include ClCF2-CFCl-CF2-CF2-CF2H, ClCF2-CFCl-CF2-CF2-CF2-CF2H, ClCF2-CFCl-CF2-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-CF2H, etc. 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, BrCF2-CF2-CF2-CF2-CF2-CF2-CF2H, etc. are preferred, and ClCF2-CFCl-CF2-CF2-CF2H, ClCF2-CFCl-CF2-CF2-CF2-CF2-CF2H, ClCF2-CFCl-CF2-CF2-CF2-CF2-CF2H, etc. are more preferred.

[0100] In the perfluorodiene composition of the present invention, the content of the perfluorodiene compound represented by the general formula (1) is preferably 30 to 99.8 mol% (particularly 50 to 99 mol%), the content of the compound represented by the general formula (3) is preferably 0.1 to 30 mol% (particularly 2 to 25 mol%), the total content of the compounds represented by the general formula (4A) and / or (4B) is preferably 0.01 to 5 mol% (particularly 0.02 to 3 mol%), and the content of the compound represented by the general formula (5) is preferably 0.05 to 35 mol% (particularly 0.1 to 5 mol%), based on the total amount of the perfluorodiene composition of the present invention being 100 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 30 mol% (particularly 0.01 to 10 mol%). In the present invention, the group adjacent to the CF2X3 group in the compound represented by the general formula (2) as the substrate is CF2, so the compound represented by the general formula (5) will be generated in the liquid phase, but even in this case, the amount of the compound represented by the general formula (5) generated can be reduced. In addition, other components may contain impurities that are difficult to separate (in the case of obtaining hexafluorobutadiene as a perfluorodiolefin compound represented by the general formula (1), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) etc.), so it is preferred to minimize the content of other components.

[0101] The perfluorodiene composition of the present invention can be effectively used in various applications such as refrigerants, heat transfer media, foaming agents, resin monomers, etc., as typified by etching gases for forming the most advanced microstructures of semiconductors, liquid crystals, etc., similarly to the perfluorodiene compound alone.

[0102] Although the embodiments of the present invention have been described above, various changes in form or details may be made without departing from the spirit and scope of the claims.

[0103] Example

[0104] The following examples are provided to clarify the features of the present invention, but the present invention is not limited to these examples.

[0105] Example 1: ClCF2-CFCl-CF2-CF2I; first added; no iodine-containing inorganic material

[0106] 200 g (0.53 mol) of xylene and 34.93 g (0.53 mol) of zinc were added to an eggplant-shaped flask with a collector and a condenser, which was cooled to -78°C, and 92 g (0.24 mol) of the raw material (ClCF2CFClCF2CF2I) was added, and the internal temperature was heated to 140°C under stirring. After the internal temperature reached a certain level, N,N-dimethylformamide (DMF) was added at a dropwise rate of 0.53 mol / hour (1 mol / hour relative to 1 mol of zinc) for 1 hour while refluxing, and heating and reflux were continued for 3 hours while stirring. 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 result showed that the conversion rate was 100 mol%. Regarding the selectivity of each component, CF2=CFCF=CF2 was 46 mol%, CF2=CF-CF2-CF2H was 0.35 mol%, ClCF2-CFCl-CF=CF2 was 1.7 mol%, ClCF2-CFCl-CF2-CF2H was 26 mol%, and other by-products (CF3CF=CHCF3, etc.) totaled 26 mol%.

[0107] Example 2: ClCF2-CFCl-CF2-CF2I; post-addition; no iodine-containing inorganic material

[0108] 200 g (0.53 mol) of xylene and 34.93 g (0.53 mol) of zinc were added to an eggplant-shaped flask with a collector and a condenser, which was cooled to -78°C, and heated to an internal temperature of 140°C under stirring. After the internal temperature reached a certain level, 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 refluxing, 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 refluxing, 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 result showed that the conversion rate was 100 mol%. Regarding the selectivity of each component, CF2=CFCF=CF2 was 78 mol%, CF2=CF-CF2-CF2H was 14 mol%, ClCF2-CFCl-CF=CF2 was 0.66 mol%, ClCF2-CFCl-CF2-CF2H was 1.5 mol%, and other by-products (CF3CF=CHCF3, etc.) totaled 5.9 mol%.

[0109] Example 3: ClCF2-CFCl-CF2-CF2I; post-addition; ZnI2 0.18 mol%

[0110] The treatment was carried out in the same manner as in Example 2 except that 0.30 g (0.001 mol; 0.18 mol% relative to zinc) of ZnI2 was contained in the solution of xylene containing zinc. 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 88 mol% for CF2=CFCF=CF2, 8.2 mol% for CF2=CF-CF2-CF2H, 0.051 mol% for ClCF2-CFCl-CF=CF2, 0.32 mol% for ClCF2-CFCl-CF2-CF2H, and 3.4 mol% for other by-products (CF3CF=CHCF3, etc.).

[0111] Example 4: ClCF2-CFCl-CF2-CF2I; post-addition; ZnI2 0.6 mol%

[0112] The treatment was carried out in the same manner as in Example 2 except that 0.95 g (0.003 mol; 0.56 mol % relative to zinc) of ZnI2 was contained in the solution of xylene containing zinc. 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 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.).

[0113] Example 5: ClCF2-CFCl-CF2-CF2I; post-addition; ZnI2 1.6 mol%

[0114] The treatment was carried out in the same manner as in Example 2 except that 2.70 g (0.53 mol; 1.6 mol % relative to zinc) of ZnI2 was contained in the solution of xylene containing zinc. 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 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.).

[0115] Example 6: ClCF2-CFCl-CF2-CF2I; post-addition; I2 1.6 mol%

[0116] The treatment was carried out in the same manner as in Example 2 except that 2.20 g (0.009 mol; 1.6 mol% relative to zinc) of I2 was contained in the solution of xylene containing zinc. 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, 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.).

[0117] Example 7: ClCF2-CFCl-CF2-CF2I; post-addition; NaI 1.6 mol%

[0118] The treatment was carried out in the same manner as in Example 2 except that 1.27 g (0.0085 mol; 1.6 mol% relative to zinc) of NaI was contained in the solution of xylene containing zinc. 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 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 2.5 mol% for other by-products (CF3CF=CHCF3, etc.).

[0119] Example 8: ClCF2-CFCl-CF2-CF2I; post-addition; NaI 3.2 mol%

[0120] The treatment was carried out in the same manner as in Example 2 except that 2.54 g (0.017 mol; 3.2 mol % relative to zinc) of NaI was contained in the solution of xylene containing zinc. 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 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 0.74 mol % for other by-products (CF3CF=CHCF3, etc.).

[0121] Example 9: ICF2-CF2-CF2-CF2I; first added; no iodine-containing inorganic material

[0122] The same treatment as in Example 1 was performed except that ICF2-CF2-CF2-CF2-CF2I was used instead of ClCF2-CFCl-CF2-CF2I as the substrate. 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 35 mol% for CF2=CFCF=CF2, 10 mol% for CF2=CF-CF2-CF2H, 4.2 mol% for HCF2-CF2-CF2-CF2H, 30 mol% for ICF2-CF2-CF2-CF2H, and 21 mol% for other by-products (CF3CF=CHCF3, etc.).

[0123] Example 10: ICF2-CF2-CF2-CF2I; Post-addition; No iodine-containing inorganic material

[0124] The same treatment as in Example 2 was performed except that ICF2-CF2-CF2-CF2-CF2I was used instead of ClCF2-CFCl-CF2-CF2I as the substrate. 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.).

[0125] Example 11: ICF2-CF2-CF2-CF2I; post-addition; ZnI2 1.6 mol%

[0126] The same treatment as in Example 2 was performed except that ICF2-CF2-CF2-CF2-CF2I was used instead of ClCF2-CFCl-CF2-CF2I as the substrate, and 2.70 g (0.53 mol; 1.6 mol% relative to zinc) of ZnI2 was contained in the solution of zinc-containing xylene. 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.).

[0127] Example 12: BrCF2-CF2-CF2-CF2Br; first added; no iodine-containing inorganic material

[0128] The same treatment as in Example 1 was performed except that BrCF2-CF2-CF2-CF2-CF2Br was used instead of ClCF2-CFCl-CF2-CF2I as the substrate. 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 49 mol% for CF2=CFCF=CF2, 1.2 mol% for CF2=CF-CF2-CF2H, 3.8 mol% for HCF2-CF2-CF2-CF2H, 25 mol% for BrCF2-CF2-CF2-CF2H, and 21 mol% for other by-products (CF3CF=CHCF3, etc.).

[0129] Example 13: BrCF2-CF2-CF2-CF2Br; post-addition; no iodine-containing inorganic material

[0130] The same treatment as in Example 2 was performed except that BrCF2-CF2-CF2-CF2-CF2Br was used instead of ClCF2-CFCl-CF2-CF2I as the substrate. 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 76 mol% for CF2=CFCF=CF2, 13 mol% for CF2=CF-CF2-CF2H, 1.9 mol% for HCF2-CF2-CF2-CF2H, 2.1 mol% for BrCF2-CF2-CF2-CF2H, and 7.0 mol% for other by-products (CF3CF=CHCF3, etc.).

[0131] Example 14: BrCF2-CF2-CF2-CF2Br; post-addition; ZnI2 1.6 mol%

[0132] The same treatment as in Example 2 was performed except that BrCF2-CF2-CF2-CF2-CF2Br was used instead of ClCF2-CFCl-CF2-CF2I as the substrate, and 2.70 g (0.53 mol; 1.6 mol% relative to zinc) of ZnI2 was contained in the solution of xylene containing zinc. 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.).

[0133] The results are shown in Tables 1 and 2.

[0134] [Table 1]

[0135]

[0136] [Table 2]

[0137]

Claims

1. A method for producing a perfluorodiene compound represented by the following general formula (1), characterized in that: include: A reaction step of reacting a compound represented by the following general formula (2) in the presence of a nitrogen-containing compound and zinc or a zinc alloy in an organic solvent. General formula (1): CF2=CF-(CF2) n－4 -CF=CF2 (1) In formula (1), n ​​represents an integer of 4 to 20, General formula (2): CF2X 1 -CFX 2 -(CF2) n－4 -CF2-CF2X 3 (2) In formula (2), n is the same as above, X 1 , X 2 and X 3 Same or Different, X 1 and X 2 represents a halogen atom, X 3 represents a chlorine atom, a bromine atom or an iodine atom, wherein X 1 and X 2 Not both sides of are fluorine atoms, The reaction step includes a mixing step of sequentially mixing a solution containing zinc or a zinc alloy and an organic solvent with a nitrogen-containing compound and the compound represented by the general formula (2). The mixing step comprises heating the solution containing zinc or zinc alloy and organic solvent, mixing the solution with the nitrogen-containing compound, and then mixing the obtained mixed solution with the compound represented by the general formula (2). The nitrogen-containing compound is an amide compound.

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

3. The manufacturing method according to claim 1 or 2, characterized in that: In the mixing step, the compound represented by the general formula (2) is added to the mixed solution of the solution containing zinc or zinc alloy and organic solvent and the nitrogen-containing compound at an addition rate of 0.05 to 30 mol / hour per 1 mol of the zinc or zinc alloy.

4. The manufacturing method according to claim 1 or 2, characterized in that: In the mixing step, when the solution containing zinc or zinc alloy and organic solvent and the nitrogen-containing compound are mixed, the solution has a temperature of 50 to 200°C.

5. The manufacturing method according to claim 1 or 2, characterized in that: The nitrogen-containing compound is N,N-dimethylformamide.

6. The manufacturing method according to claim 1 or 2, 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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