RU2804970C2 - Method for isolating linear hydrocarbon containing double bond in which each hydrogen atom is replaced by fluorine atom or chlorine atom - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: invention relates to a method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine or chlorine atom, and includes bringing a treatment object containing a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine or chlorine atom, and alicyclic hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine or chlorine atom, in contact with at least one amino compound selected from the group consisting of a heterocyclic aromatic amino compound and a tertiary amine represented by the formula: NR¹R²R³, where each of R¹, R² and R³ independently represents an alkyl group, and two of R¹, R² and R³ may in combination represent an alkylene group, which is optionally interrupted by oxygen or sulphur.

EFFECT: simplicity of the method of selective separation of a linear compound in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom by bringing it into contact with a specific amino compound.

14 cl, 2 dwg, 1 tbl

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0001] The present invention relates to a method for isolating a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom from a treatment object that contains a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, and an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom.

BACKGROUND OF THE ART

[0002] Progress has been made in developing perfluorocarbons containing a double bond as ingredients for fluorine resins and as an alternative to saturated perfluorocarbons such as tetrafluoromethane (CF ₄ ) and hexafluoroethane (C ₂ H ₆ ), which have been used as etch gases and cleaning gases in semiconductor and liquid crystal production processes. Perfluorocarbons containing a double bond are highly regulated due to their potential to contribute to global warming at levels that, although improving, cannot be ignored, as well as concerns such as high vapor pressure and toxicity. For this reason, various methods have been proposed for the detection and removal of perfluorocarbons containing a double bond (Patent Literature (PTL) 1-5).

Bibliography

Patent literature

[0003] PTL 1: JP 2001-324492 A

PTL 2: JP 2001-302551 A

PTL 3: JP 2000-342931 A

PTL 4: JP 2012-121018 A

PTL 5: WO 2012/002239 A1

BRIEF DESCRIPTION OF THE INVENTION TECHNICAL PROBLEM

[0004] Each of the known techniques mentioned above considers the double bond-containing perfluorocarbons collectively as a detection or removal target and does not pay attention to the individual compounds included in the double bond-containing perfluorocarbons. The characteristics of perfluorocarbons containing a double bond may vary depending on the skeleton of the compound (eg, whether the compound is linear, alicyclic, etc.). Therefore, the ability to selectively separate or remove a compound included in a perfluorocarbon containing a double bond, depending on the skeleton of the compound, may be beneficial, for example from a reusability point of view.

[0005] The inventor has conducted extensive research, focusing on the backbones of perfluorocarbons containing a double bond. The inventor has discovered that when a linear compound and an alicyclic compound are included in perfluorocarbons containing a double bond, the linear compound can be selectively isolated by bringing a certain amino compound into contact with the perfluorocarbons containing a double bond. The inventor also discovered that this discovery applies not only to perfluorocarbons, but also to hydrocarbon compounds that are completely replaced by chlorine atoms, and hydrocarbon compounds that are completely replaced by fluorine and chlorine atoms. The present disclosure has been made in light of these findings.

[0006] In particular, the present disclosure relates to a method for isolating a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, comprising providing a treatment object containing a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced a fluorine atom or a chlorine atom, and an alicyclic hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, in contact with at least one amino compound selected from the group consisting of a heterocyclic aromatic amino compound and a tertiary amine represented by the formula : NR ¹ R ² R ³ wherein each of R ¹ , R ² and R ³ independently represents an alkyl group, and two of R ¹ , R ² and R ³ may in combination represent an alkylene group, which is optionally terminated by an oxygen atom or sulfur atom.

[0007] The term "double bond" as used herein refers to a carbon-carbon double bond.

The phrase "replaced by a fluorine atom or a chlorine atom" as used herein includes the case in which the replacement is made by fluorine atoms only, the case in which the replacement is made by both fluorine atoms and a chlorine atom, and the case in which the replacement is made by chlorine atoms only .

The term "perfluoro" as used herein refers to a compound in which each hydrogen atom of a hydrocarbon is replaced by a fluorine atom.

The term “heterocyclic aromatic amino compound” as used herein refers to an amino compound that includes a nitrogen atom among the ring-forming atoms of the heteroaromatic ring.

[0008] Hydrocarbon compounds containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom are generally difficult to selectively separate or remove by methods such as distillation purification and adsorption treatment because they are highly reactive due to the presence of the double bond and often have close boiling points and high vapor pressures. The method according to the invention allows to isolate a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, from a treatment object containing a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, and alicyclic a hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, by a simple method of bringing the treatment object into contact with a particular amino compound, and is also useful for reuse and the like. The separation method disclosed herein can also be used as a method for removing an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom from the above-mentioned treatment object.

[0009] The method of the invention makes it possible to separate a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, due to the fact that when a treatment object containing a linear hydrocarbon which contains a double bond and in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, and an alicyclic hydrocarbon which contains a double bond and in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom is brought into contact with a specified amino compound, an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, reacts selectively.

[0010] In the method disclosed herein, the amine compound contacted by the treatment object is preferably in the form of a liquid. The amino compound that is in the form of a liquid may be a liquid phase amino compound or may be in the form of a liquid obtained by dissolving or dispersing the amino compound in a solvent. The use of an amino compound that is in the liquid phase during contact with the treatment object is advantageous from the point of view that the reaction proceeds quickly via the amino compound that is in the liquid phase.

[0011] The interaction of the treatment object and the amine compound can be carried out within the reactor, and introduction of the treatment object into the reactor in the form of a gas is preferable from the point of view that it is easy to accurately control the introduced amount and from the point of view of suppressing reaction leakage. The treatment object may be subjected to heat or the like to generate gas.

[0012] The subject of treatment and the amino compound are preferably brought into contact at a lower temperature than the boiling point of an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, from the point of view that it is easy to ensure that the reaction proceeds smoothly until end point. In the case where a set of compounds is represented as an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, the temperature may be set lower than the boiling point of the compound that has the lowest boiling point.

[0013] The linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom is preferably a linear alkene in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, or a linear alkadiene in which each hydrogen atom is replaced a fluorine atom or a chlorine atom, from the point of view of stability as a compound resulting from the replacement of fluorine or chlorine atoms; and more preferably a linear perfluoroalkene or linear perfluoroalkadiene from the viewpoint that stability is further enhanced by the electronic structure, electron affinity and binding energy of the fluorine atoms resulting from substitution with fluorine atoms only.

[0014] A linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom is preferably a compound having a boiling point of 50° C. or lower, from the point of view that introducing the compound into the reactor in the form of a gas is easy.

[0015] An alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom may be a cycloalkene in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, or a cycloalkadiene in which each hydrogen atom is replaced by a fluorine atom or chlorine atom, and may be a perfluorocycloalkene or perfluorocycloalkadiene.

[0016] An alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom is preferably a compound having a boiling point of 30° C. or lower, from the point of view that introducing the compound into the reactor in the form of a gas is easy.

[0017] In the method of the invention, the tertiary amine as the specified amino compound is preferably trialkylamine, N-alkylmorpholine, N-alkylpiperidine or N-alkylpyrrolidine, and the heterocyclic aromatic amine compound as the specified amino compound is preferably pyridine, a pyridine derivative, pyridazine, pyridazine derivative, isoquinoline or isoquinoline derivative. The derivative may be a substituted derivative that is substituted with at least one substituent selected from alkyl, alkoxy, acyl, alkoxycarbonyl and acyloxy.

[0018] In the method disclosed herein, said specific amine compound may be a tertiary amine or may be a heterocyclic aromatic amine compound.

[0019] In the method disclosed herein, the amount of amino compound used is preferably no less than 0.01 and no more than 10 times the number of moles of an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom.

BENEFICIAL EFFECT

[0020] The method disclosed herein is useful in the case where the linear compound and the alicyclic compound are among hydrocarbon compounds containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, and allows the linear compound to be selectively separated by a simple method of contacting a certain amino compound.

BRIEF DESCRIPTION OF GRAPHIC MATERIALS

[0021] In the accompanying figures:

FIG. 1 illustrates the results of F-NMR measurements of compounds inside a second pressure-resistant vessel in Example 12; And

FIG. 2 illustrates the results of F-NMR measurements of compounds inside the first pressure-resistant vessel in Example 12.

DETAILED DESCRIPTION OF THE INVENTION

[0022] PROCESSING OBJECT

The subject of treatment according to the method disclosed herein contains a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom (hereinafter also referred to as "compound X"), and an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced a fluorine atom or a chlorine atom (hereinafter also referred to as “compound Y”).

[0023] A LINEAR HYDROCARBON CONTAINING A DOUBLE BOND IN WHICH EACH HYDROGEN ATOM IS REPLACED BY A FLUORINE ATOM OR A CHLORINE ATOM (HEREINAFTER ALSO REFERRED TO AS "COMPOUND X")

Compound X, which is a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, may be any compound in which each hydrogen atom of a linear hydrocarbon containing a double bond is replaced by a fluorine atom or a chlorine atom. In the case of substitution with a chlorine atom, it is preferred that one or two hydrogen atoms in compound X are replaced by a chlorine atom and that every other hydrogen atom in compound X is replaced by a fluorine atom.

[0024] The boiling point of compound X is preferably 50°C or lower, and more preferably 15°C or lower. The boiling point may be -80°C or higher.

[0025] The number of carbon atoms in compound X may be 2 or more, preferably not less than 2 and not more than 5.

[0026] The number of double bonds in compound X may be 1 or more, preferably 1 or 2.

[0027] Examples of compound X which includes both chlorine and fluorine atoms include CF ₂ =CFCl, CFCl=CFCl, CF ₃ CF=CFCl, CF ₃ CCl=CF ₂ , CF ₃ CCl=CFCl and CF ₃ CF= _CCl2 .

[0028] Examples of compound X which contains only fluorine atoms include linear perfluoroalkenes and linear perfluoroalkadienes. Examples of linear perfluoroalkenes include CF ₂ =CF ₂ , CF ₃ CF=CF 2, CF ₃ CF ₂ CF=CF ₂ , CF ₃ CF=CFCF ₃ , CF ₃ CF ₂ CF 2 CF=CF ₂ , CF _{3 CF 2 CF} = CFCF ₃ and the like, and examples of linear perfluoroalkadienes include CF ₂ =CFCF=CF ₂ , CF ₂ =CFCF=CFCF ₃ , CF ₂ =CFCF ₂ CF=CF ₂ and the like.

[0029] Connection X in a processing object may be represented by only one connection type or may be represented by two or more connection types.

[0030] AN ALICYCLIC HYDROCARBON CONTAINING A DOUBLE BOND IN WHICH EACH HYDROGEN ATOM IS REPLACED BY A FLUORINE ATOM OR A CHLORINE ATOM (HEREINAFTER ALSO REFERRED TO as “COMPOUND Y”)

Compound Y, which is an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, may be any compound in which each hydrogen atom of the alicyclic hydrocarbon containing a double bond is replaced by a fluorine atom or a chlorine atom. In the case of chlorine atom replacement, it is preferable that one or two hydrogen atoms in compound Y are replaced by a chlorine atom, and that every other hydrogen atom in compound Y is replaced by a fluorine atom, since stability generally increases and reactivity decreases with increasing number of chlorine atoms.

[0031] The boiling point of compound Y is preferably 30°C or lower, and more preferably 15°C or lower. The boiling point may be -20°C or higher.

[0032] The number of carbon atoms forming the carbocycle in compound Y may be 3 or more, preferably not less than 3 and not more than 6.

[0033] Compound Y may be a monocyclic compound or may be a polycyclic compound, but is preferably a monocyclic compound. Compound Y may include an alkyl group in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom (eg, a perfluoroalkyl group such as a trifluoromethyl group or a pentafluoroethyl group) on the carbocycle.

[0034] The number of double bonds in compound Y may be 1 or more, preferably 1 or 2.

[0035] Examples of compound Y which includes both chlorine and fluorine atoms include 1-chloropentafluorocyclobutene, 1,2-dichlorotetrafluorocyclobutene, 1,3-dichlorotetrafluorocyclobutene and the like.

[0036] Examples of compound Y that contains only fluorine atoms include perfluorocycloalkenes and perfluorocycloalkadienes. Examples of perfluorocycloalkenes include tetrafluorocyclopropene, hexafluorocyclobutene, octafluorocyclopentene, decafluorocyclohexene and the like, and examples of perfluorocycloalkadienes include tetrafluorocyclobutadiene, hexafluorocyclopentadiene, octafluoro-1,3-cyclohexadiene, octafluoro-1,4-cyclohexadiene, etc. .p. These compounds may include an alkyl group in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom (for example, a perfluoroalkyl group such as a trifluoromethyl group or a pentafluoroethyl group) on the carbocycle, and examples of such compounds include 3-trifluoromethylpentafluorocyclobutene, 3-trifluoromethylheptafluorocyclopentene, 4- trifluoromethylheptafluorocyclopentene, etc.

[0037] Connection Y in a processing object may be represented by only one connection type or may be represented by two or more connection types.

[0038] RATIO OF COMPONENTS

Although there is no specific limitation on the proportions of compound X and compound Y in the treatment object, their mass ratio (mass of compound X: mass of compound Y) can be, for example, from 0.1:99.9 to 99.9:0.1 . From the viewpoint of obtaining the effect of sufficient separation and easy recovery of compound X after separation, the mass ratio of compound X and compound Y (mass of compound X: mass of compound Y) is preferably 1:9 to 9:1, and more preferably 3:7 to 7 :3.

[0039] OTHER COMPONENTS

The treatment object may contain other components insofar as the effects of the disclosed method according to the invention are not lost. Examples of such other components include nitrogen, helium, argon, atmospheric air, aliphatic saturated hydrocarbons, ethers, aromatic hydrocarbons, and the like. The other components are preferably 99 mol. % or less, and more preferably 50 mol. % or less of the total quantity of the processed object. Moreover, the other components may be 0%, in which case the treatment object consists of compound X and compound Y. The treatment object must contain compound X and compound Y at the time it comes into contact with the specified amino compound.

[0040] SPECIFIC AMINE COMPOUND

The method disclosed herein uses at least one amino compound selected from the group consisting of a heterocyclic aromatic amino compound and a tertiary amine represented by the formula: NR ¹ R ² R ³ (each of R ¹ , R ² and R ³ independently represents an alkyl group, and two of R ¹ , R ² and R ³ may in combination represent an alkylene group, which is optionally terminated by an oxygen atom or a sulfur atom). The amine compound may be a tertiary amine, may be a heterocyclic aromatic amine compound, or may be a combination thereof.

[0041] The particular amino compound is preferably a liquid at room temperature (23°C) and atmospheric pressure. The melting point of the particular amino compound is preferably -120°C or higher, more preferably -50°C or higher, and preferably 50°C or lower, and more preferably 30°C or lower.

[0042] TERTIARY AMINE

A tertiary amine is represented by the formula: NR ¹ R ² R ³ (each of R ¹ , R ² and R ³ independently represents an alkyl group, and two of R ¹ , R ² and R ³ may in combination represent an alkylene group, which is optionally terminated oxygen atom or sulfur atom).

[0043] In the case where R ¹ , R ² and R ³ are each an alkyl group, the alkyl groups may be the same or different, but are preferably the same.

[0044] The alkyl group can be straight or branched. The alkyl group may be an alkyl group in which the number of carbon atoms is not less than 1 and not more than 4, and is preferably an alkyl group in which the number of carbon atoms is not less than 1 and not more than 3, examples of which include methyl, ethyl and drank

[0045] Two of R ¹ , R ² and R ³ may in combination represent an alkylene group that is optionally terminated by an oxygen atom or a sulfur atom, examples of which include the -(CH ₂ ) _p - group (p is an integer of at least 3 and no more than 6), -group (CH ₂ ) _q -O-(CH ₂ ) _q - (q is an integer not less than 1 and not more than 3, and each q may be the same or may be different), -group (CH ₂ ) _r -S-(CH ₂ ) _r - (r is an integer not less than 1 and not more than 3, and each r may be the same or may be different), etc. The remaining one of R ¹ , R ² and R ³ represents an alkyl group, and examples and preferred examples of the alkyl group are as described above.

[0046] The tertiary amine is preferably a trialkylamine such as triethylamine or methyldiethylamine, N-alkylmorpholine such as N-methylmorpholine, N-ethylmorpholine or N-butylmorpholine, N-alkylpiperidine such as N-methylpiperidine or N-ethylpiperidine, and N -alkylpyrrolidine such as N-methylpyrrolidine or N-ethylpyrrolidine, or the like.

[0047] HETEROCYCLIC AROMATIC AMINE COMPOUND

The heterocyclic aromatic amino compound may be a monocyclic compound or may be a polycyclic compound, but is preferably a monocyclic compound. It is preferable that the hydrogen atom is not present on the nitrogen atom that is part of the heteroaromatic ring.

[0048] Examples of the heterocyclic aromatic amino compound include pyridine, pyrazine, pyrimidine, pyridazine, quinoline, isoquinoline, bipyridine and derivatives thereof. The derivative may be a substituted derivative, and examples of possible substituents include alkyl, alkoxy, acyl, alkoxycarbonyl, acyloxy, cyano and the like. Said derivative may include one substituent or may include two or more substituents.

[0049] The alkyl moiety in any of the substituents mentioned above may be straight or branched, and the number of carbon atoms included therein is preferably no less than 1 and no more than 5. The alkyl may be methyl, ethyl, propyl, butyl and the like. ., alkoxy may be methoxy, ethoxy, propoxy, butoxy or the like, acyl may be acetyl, propionyl or the like, alkoxycarbonyl may be methoxycarbonyl, ethoxycarbonyl or the like, and acyloxy may be acetyloxy, propionyloxy or the like.

[0050] The heterocyclic aromatic amine compound is preferably pyridine, a pyridine derivative, pyridazine, a pyridazine derivative, isoquinoline or an isoquinoline derivative.

[0051] CONTACT STAGE

No particular restrictions are imposed on the method by which the treatment object and a particular amino compound are brought into contact. For example, a subject of treatment may be added to a reactor that contains a particular amine compound, or a subject of treatment may be introduced into a particular reactor, and then a particular amine compound may subsequently be introduced into the reactor.

[0052] Contacting the treatment object and the specified amino compound is preferably carried out when the specified amino compound is in the form of a liquid. For example, a particular amine compound may be brought into contact with the target in liquid form by bringing the temperature of the particular amine compound to at least its melting point or by dissolving or dispersing the particular amine compound in a solvent (e.g., an aliphatic saturated hydrocarbon, an ether, an aromatic hydrocarbon, or the like). P.).

[0053] The treatment object may be introduced into the reactor in the form of a gas. The treatment object may be subjected to heat or the like to give it a gas form. After the treatment object has been introduced into the reactor, the treatment object may be contacted with the specified amine compound in the gas phase, or may be partially or completely liquefied by cooling within the reactor and contacted with the specified amine compound in the liquid phase.

[0054] The subject of treatment is preferably brought into contact with a particular amine compound at a lower temperature than the boiling point of compound Y in the subject of treatment. In the case where multiple Y compounds are present, the temperature may be set below the boiling point of the Y compound that has the lowest boiling point.

[0055] The contact time of the treatment object and a certain amine compound is not particularly limited, but can be set as, for example, no less than 1 hour and no more than 24 hours, and preferably no less than 5 hours and no more than 18 hours. The reaction time can be shortened by stirring the reactor contents during contacting.

[0056] After the contacting has been carried out for a certain time, the gas inside the reactor is trapped, and the reaction product resulting from the contacting is collected. Compound X is released into the captured gas.

[0057] The number of moles of a particular amino compound can be defined as no less than 0.01 times and no more than 10 times, preferably no less than 0.03 times and no more than 5.0 times the number of moles of compound Y in the processing object. In the case where the particular amino compound is a tertiary amine, the mole number is preferably 0.5 times or more, more preferably 1.0 times or more, preferably 4.0 times or less, more preferably 3. 0 or less times more. In the case where the particular amino compound is a heterocyclic aromatic amino compound, the mole number is preferably 0.05 times or more, more preferably 0.1 times or more, and preferably 3.0 times or less, and more preferably 2.0 times or less.

[0058] Using the separation method disclosed herein, it is possible to obtain a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, with trace amounts of a particular amino compound contained therein. Due to the presence of a trace amount of a specific amino compound impurity in a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, detection of the gas is possible by the smell of the specific amino compound. For example, a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, may contain at least 0.001 vol. ppm (parts per million by volume) and not more than 1000 vol. ppm of at least one amino compound selected from the group consisting of a heterocyclic aromatic amino compound and a tertiary amine represented by the formula: NR ¹ R ² R ³ (each of R ¹ , R ² and R ³ independently represents an alkyl group, and two of R ¹ , R ² and R ³ may in combination represent an alkylene group, which is optionally terminated by an oxygen atom or a sulfur atom).

EXAMPLES

[0059] The following provides a more specific description of the present disclosure based on examples. However, the present disclosure is not limited to the following examples.

[0060] Each example uses a specific amino compound, a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom (compound X), and an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by an atom fluorine or chlorine atom (compound Y), which are listed in Table 1.

CF ₂ =CFCl (boiling point -28°C)

CF ₃ CF=CF ₂ (boiling point -29°C)

CF ₃ CF=CFCF ₃ (boiling point 1.2°C)

CF ₃ CF ₂ CF=CF ₂ (boiling point 6°C)

CF ₂ =CFCF=CF ₂ (boiling point 5°C to 6°C)

ts-C ₄ F ₆ : hexafluorocyclobutene (boiling point 5°C to 6°C)

c-C ₅ F ₈ : octafluorocyclopentene (boiling point 27°C)

[0061] Compound X and Compound Y were supplied in gas form in the mass ratio shown in Table 1 into the first pressure-resistant vessel, which had been internally depressurized and cooled to a temperature of -20° C. to -40° C. , through a valve connected to the first pressure-resistant vessel, and then the determined amine compound was subsequently loaded into the first pressure-resistant vessel. Regarding the amount of a particular amino compound used, the amount corresponding to the number of moles per 1 mole of compound Y is shown in Table 1. The first pressure-resistant vessel was placed in a thermostatic tank having the temperature indicated in Table 1 and left overnight (14 hours), while the inner contents of the vessel were stirred.

Thereafter, a second pressure-resistant vessel, which had been internally depressurized and cooled to a temperature of -20°C to -60°C, was connected to the first pressure-resistant vessel, the valves of these vessels were opened, and the gas remaining in the first pressure-resistant vessel was transferred to the second pressure-resistant vessel. The first pressure-resistant vessel was then gradually heated to 30° C. over 30 minutes. The valves of the vessels were then closed and the mass of the residue in the first pressure-resistant vessel and the mass of gas trapped in the second pressure-resistant vessel were determined.

The first pressure-resistant vessel and the second pressure-resistant vessel were sequentially cooled to a temperature of -20°C to -40°C, deuterated chloroform for NMR analysis was loaded into each of the vessels, and the compounds within the vessels were dissolved and then removed while cooling to in order to perform F-NMR measurements.

Measurement conditions: ¹⁹ P-NMR measurement (376 MHz, CDCl3, trifluoromethyltoluene added as internal standard)

[0062] The F-NMR measurement results in Example 12 are illustrated in FIG. 1.

FIG. 1 illustrates measurement results regarding connections within a second pressure-resistant vessel. The corresponding peaks are peaks originating from CF ₃ CF=CF ₂ . It should be noted that peaks for c-C ₄ F ₆ (-122.2 ppm (CF ₂ ) and -131.0 ppm (CF)) were not detected.

FIG. 2 illustrates measurement results for connections inside a first pressure-resistant vessel. No peaks were detected for 4-C ₄ F ₆ and it is assumed that peaks other than those arising from CF ₃ CF=CF ₂ originate from the reaction product.

[0063] The proportions of compound X, compound Y and reaction product within each of the pressure-resistant vessels were calculated from the integrated peak values for compound X, compound Y and reaction product in the F-NMR measurement, and the degree of conversion of compound Y and the degree of non-conversion of compound X calculated from the mass of the residue and the mass of the trapped gas, which were previously determined.

[0064] The conversion rate of compound Y is the fraction by which the amount of compound Y is reduced after contacting compared to the loaded amount of compound Y. The conversion rate is estimated as follows.

Compound conversion degree Y Conversion rate: 80% or more A Conversion rate: not less than 20% and less than 80% IN Conversion rate: less than 20% WITH Conversion degree: no reaction product D

[0065] The non-conversion rate of compound X is the proportion of compound X that remains after contacting, relative to the loaded amount of compound X. The non-conversion rate is estimated as follows.

Degree of non-conversion of a compound X Non-conversion rate: 99% or more A Non-conversion rate: not less than 95% and less than 99% IN Non-conversion rate: less than 95% WITH

[0066] Resolution of compound X was considered to be achieved when the degree of conversion was A or B, and the degree of non-conversion was A or B. The results are shown in Table 1.

INDUSTRIAL APPLICABILITY

[0068] The method disclosed herein is useful in the case where the linear compound and the alicyclic compound are among hydrocarbon compounds containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, and allows the linear compound to be selectively separated by a simple method of contacting a certain amino compound.

Claims (16)

1. A method for isolating a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, including bringing a treatment object containing a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, and alicyclic a hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, in contact with at least one amino compound selected from the group consisting of a heterocyclic aromatic amino compound and a tertiary amine represented by the formula: NR ¹ R ² R ³ , wherein each of R ¹ , R ² and R ³ independently represents an alkyl group, and two of R ¹ , R ² and R ³ may in combination represent an alkylene group, which is optionally terminated by an oxygen atom or a sulfur atom. 2. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to claim 1, in which the amino compound with which the treatment object is brought into contact is in the form of a liquid. 3. A method for isolating a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom according to claim 1 or 2, wherein contacting the treatment object and the amino compound is carried out inside a reactor, and the treatment object is introduced into the reactor at form of gas. 4. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-3, in which the subject of treatment is brought into contact with an amino compound at a temperature lower than the boiling point of an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom. 5. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-4, in which a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom is a linear alkene in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, or a linear alkadiene in which each atom hydrogen is replaced by a fluorine atom or a chlorine atom. 6. The method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to claim 5, in which the linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, is is a linear perfluoroalkene or linear perfluoroalkadiene. 7. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-6, in which a linear hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom is a compound having a boiling point of 50° C. or lower. 8. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-7, wherein the alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom is a cycloalkene in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, or a cycloalkadiene in which each hydrogen atom is replaced a fluorine atom or a chlorine atom. 9. The method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to claim 8, in which an alicyclic hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, is is a perfluorocycloalkene or perfluorocycloalkadiene. 10. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-9, in which the alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom is a compound having a boiling point of 30° C. or lower. 11. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-10, in which: the tertiary amine is a trialkylamine, N-alkylmorpholine, N-alkylpiperidine or N-alkylpyrrolidine, and the heterocyclic aromatic amino compound is pyridine, a pyridine derivative, pyridazine, a pyridazine derivative, isoquinoline or an isoquinoline derivative. 12. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-11, in which the amine compound is a tertiary amine. 13. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-11, wherein the amino compound is a heterocyclic aromatic amino compound. 14. A method for isolating a linear hydrocarbon containing a double bond, in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom, according to any one of claims. 1-13, in which the number of moles of the amino compound used is not less than 0.01 times and not more than 10 times the number of moles of an alicyclic hydrocarbon containing a double bond in which each hydrogen atom is replaced by a fluorine atom or a chlorine atom.