JP7072153B2 - Method for producing 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene or 1,2-dichlorohexafluorocyclobutane - Google Patents

Description

The present disclosure relates to a method for producing 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene or 1,2-dichlorohexafluorocyclobutane.

1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane are promising applications for etching gas or cleaning gas.

Among them, hexafluoro-1,3-butadiene is synthesized, for example, by performing a dehalogenation reaction using zinc using a halogen-containing alkane as a raw material compound (see, for example, Patent Document 1).

Chinese Patent Application Publication No. 105732301

The present disclosure comprises at least one selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane under mild conditions and high selectivity. The purpose is to provide a method that can be obtained.

The present disclosure includes the following configurations:

Item 1. At least one production method selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane.
A production method comprising a step of reacting 1,1,2-trifluoro-2-chloroethylene with a zero-valent alkali metal.

Item 2. Item 2. The production method according to Item 1, wherein the zero-valent alkali metal is at least one selected from the group consisting of lithium metal, sodium metal and potassium metal.

Item 3. Item 2. The production method according to Item 1 or 2, wherein the zero-valent alkali metal is a sodium metal.

Item 4. Item 6. The production method according to any one of Items 1 to 3, wherein the zero-valent alkali metal is dispersed in the dispersed oil.

Item 5. Any of Items 1 to 4, wherein the step of reacting the 1,1,2-trifluoro-2-chloroethylene with the zero-valent alkali metal is carried out in the presence of mineral oil or an organic solvent having a boiling point of 30 to 800 ° C. The manufacturing method according to item 1.

Item 6. Item 6. The production method according to any one of Items 1 to 5, wherein the temperature at which the 1,1,2-trifluoro-2-chloroethylene is reacted with the zero-valent alkali metal is −110 to 800 ° C. ..

Item 7.1,1,2-Trifluoroethylene and / or 1,2-dichlorohexafluorocyclobutane and hexafluoro-1,3-butadiene are contained, and the total amount of the composition is 100 mol%. The content of -1,3-butadiene is 3 to 90 mol% and the content of 1,1,2-trifluoroethylene and / or 1,2-dichlorohexafluorocyclobutane is 10 to 97 mol%. Composition.

Item 8. Item 6. The composition according to Item 7, which is used as a cleaning gas or an etching gas.

According to the present disclosure, at least one selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane is selected under mild conditions and with high selection. Can be obtained at a rate.

As used herein, "contains" is a concept that includes any of "comprise," "consist essentially of," and "consist of." Further, in the present specification, when the numerical range is indicated by "A to B", it means A or more and B or less.

As used herein, the term "selectivity" is the ratio (mol%) of the total molar amount of the target compound contained in the gas phase portion to the total molar amount of the compound other than the raw material compound in the gas phase portion in the reactor. Means.

In the present specification, the term "zero-valent alkali metal" is intended as a simple substance of an alkali metal, and does not include a compound containing an alkali metal. The same applies to "lithium metal", "sodium metal", "potassium metal" and the like.

1. 1. Production Method At least one production method selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane of the present disclosure is 1,1,1. It comprises a step of reacting 2-trifluoro-2-chloroethylene with a zero-valent alkali metal. As a result, at least one selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane is selected while the zero-valent alkali metal is chlorinated. Obtainable.

Conventionally, hexafluoro-1,3-butadiene has been synthesized, for example, by performing a dehalogenation reaction using zinc using a halogen-containing alkane as a raw material compound. In this method, the raw material compounds that can be used are limited, and it is necessary to induce a compound capable of performing a dehalogenation reaction. Therefore, many steps of reaction steps are required, which is not economical and produces a large amount of waste. On the other hand, 1,2-dichlorohexafluorocyclobutane was synthesized by, for example, a thermal decomposition reaction using 1,1,2-trifluoro-2-chloroethylene as a raw material compound. According to this method, it is difficult to control the reaction because the reaction is carried out under high temperature conditions.

According to the present disclosure, as described above, 1,1,2-trifluoroethylene and hexafluoro-1 are reacted by reacting 1,1,2-trifluoro-2-chloroethylene with a zero-valent alkali metal. At least one selected from the group consisting of, 3-butadiene and 1,2-dichlorohexafluorocyclobutane can be obtained under mild conditions and with high selectivity.

(1-1) 1,1,2-Trifluoro-2-chloroethylene As a raw material compound that can be used in the production method of the present disclosure, 1,1,2-trifluoro-2-chloroethylene is used. That is, unlike the conventional method for synthesizing hexafluoro-1,3-butadiene, the raw material compound can be prepared inexpensively and easily.

(1-2) Zero-valent alkali metal In the present disclosure, the above-mentioned 1,1,2-trifluoro-2-chloroethylene is reacted with the zero-valent alkali metal.

The zero-valent alkali metal is not particularly limited, and examples thereof include lithium metal, sodium metal, and potassium metal. Among them, at least one selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane is selected under milder conditions and higher selectivity. Sodium metal and potassium metal are preferable, and sodium metal is more preferable. These zero-valent alkali metals can be used alone or in combination of two or more.

In the present disclosure, the zero-valent alkali metal can be used as it is as the zero-valent alkali metal, but in consideration of safety, the zero-valent alkali metal (specifically, the zero-valent alkali metal particles) is a dispersed oil. It is preferable to use a zero-valent alkali metal dispersion dispersed therein.

It is preferable that the dispersed oil of the zero-valent alkali metal dispersion contains 3 to 20% by mass of an aromatic component, with the dispersed oil as 100% by mass.

As the dispersed oil, one of commercially available mineral oils containing an aromatic component in the above ratio can be appropriately selected and used.

It is also possible to mix two or more kinds of oils having different content ratios of aromatic components and adjust the total content of aromatic components to 3 to 20% by mass.

Further, the dispersed oil preferably contains oleic acid, sorbitan trioleate, flaxseed oil and the like in order to improve the dispersibility of the zero-valent alkali metal, and the content thereof is preferably 0.005% by mass or more. , 0.05 to 0.5% by mass, more preferably.

If necessary, two or more of oleic acid, sorbitan trioleate, and flaxseed oil can be contained in the dispersed oil, and even in that case, the total content is 0.005 to 0. 5% by mass is preferable.

The content of the aromatic component in the dispersed oil is 5 to 1 from the viewpoint of the selectivity of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane. 15% by mass is preferable, and 10 to 15% by mass is more preferable.

The content of this aromatic component is measured based on ASTM D 3238.

Further, the ratio of the dispersed oil to the zero-valent alkali metal particles in the zero-valent alkali metal dispersion is not particularly limited, and can be appropriately selected depending on the intended use and the like. Among them, the total amount of the zero-valent alkali metal dispersion is 100% by mass from the viewpoint of selectivity of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane. The 0-valent alkali metal particles are preferably contained in an amount of 1 to 50% by mass, more preferably 10 to 25% by mass.

As the zero-valent alkali metal particles, those having an average particle diameter of 10 μm or less can be usually used, and 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichloro can be used. From the viewpoint of the selectivity of hexafluorocyclobutane and the like, it is preferable to use the zero-valent alkali metal particles having an average particle diameter of 5 μm or less. The average particle size of the zero-valent alkali metal particles is measured by microscopic observation.

A known or commercially available product can be used for such a zero-valent alkali metal dispersion, and it can also be produced according to the method described in JP-A-2009-102678.

In the present disclosure, the amount of the zero-valent alkali metal used is not particularly limited, but selection of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane is selected. From the viewpoint of rate and the like, it is preferable to use 0.01 to 10 mol, and more preferably 0.1 to 2.0 mol, based on 1 mol of 1,1,2-trifluoro-2-chloroethylene. preferable. When a 0-valent alkali metal dispersion is used, it is preferable to adjust so that the 0-valent alkali metal present in the 0-valent alkali metal dispersion is within the above range.

(1-3) Solvent The above-mentioned reaction of the present disclosure is a solvent from the viewpoint of selectivity of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane and the like. It is preferable to carry out a liquid phase reaction in the presence.

When a zero-valent alkali metal dispersion is used as the existing form of the zero-valent alkali metal, a separate solvent may not be used, or a separate solvent may be used. Further, when a form other than the zero-valent alkali metal dispersion is adopted as the existing form of the zero-valent alkali metal, it is preferable to use a solvent separately.

Such a solvent is not particularly limited, but in consideration of safety in handling zero-valent alkali metals, mineral oil or an organic solvent having a boiling point of 30 to 800 ° C. (particularly 50 to 600 ° C.) may be used. preferable.

The mineral oil is not particularly limited, and examples thereof include liquid paraffin, petrolatum, selecin, solid paraffin, and microcrystalline wax. These mineral oils can be used alone or in combination of two or more.

The organic solvent that can be used is not particularly limited, and is, for example, hydrocarbons such as hexane, heptane, octane, and decane; aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, diethyl ether, and dibutyl ether. Etc., such as ether.

In the reaction of the present disclosure, the target product to be produced differs depending on the type of solvent, and when a solvent is not used, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane are likely to be produced. When hydrocarbons and aromatic hydrocarbons are used, 1,1,2-trifluoroethylene is likely to be produced, and when ether is used, 1,2-dichlorohexafluorocyclobutane is likely to be produced. Further, when trying to obtain 1,1,2-trifluoroethylene, it is preferable to use a solvent containing hydrogen as a solvent.

The amount of the above-mentioned solvent used is not particularly limited, but from the viewpoint of selectivity of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane and the like. , 1,1,2-trifluoro-2-chloroethylene is preferably 0.05 mol to 5 mol, more preferably 0.1 mol to 2.5 mol, based on 1 mol.

(1-4) Additives In the production method of the present disclosure, it is preferable to use ether as the solvent for the purpose of reducing action, and an alkali metal hydride such as sodium hydride or potassium hydride is added as an additive. Can also be used as. In particular, when trying to obtain 1,1,2-trifluoroethylene, it is preferable to use these alkali metal hydrides as additives.

The amount of the above-mentioned additives used is not particularly limited, but from the viewpoint of selectivity of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane and the like. Therefore, 0.1 to 10 mol is preferable, and 1 to 5 mol is more preferable with respect to 1 mol of 1,1,2-trifluoro-2-chloroethylene.

(1-5) Reaction temperature In the step of reacting 1,1,2-trifluoro-2-chloroethylene with a zero-valent alkali metal in the present disclosure, the reaction temperature is 1,1,2-trifluoroethylene, hexa. From the viewpoint of selectivity of fluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane, etc., usually −110 to 800 ° C. is preferable, −78 to 400 ° C. is more preferable, and −50 to 200 ° C. is further preferable. .. That is, the reaction of the present disclosure can proceed even under mild conditions.

(1-6) Reaction time In the step of reacting 1,1,2-trifluoro-2-chloroethylene with a zero-valent alkali metal in the present disclosure, the reaction time may be a time during which the reaction proceeds sufficiently. Yes, specifically, the reaction can proceed until the pressure fluctuation disappears after closing the lid of the container.

(1-7) Reaction pressure In the step of reacting 1,1,2-trifluoro-2-chloroethylene with a zero-valent alkali metal in the present disclosure, the reaction pressure is not particularly limited, and the raw material is used at the start of the reaction. The compound 1,1,2-trifluoro-2-chloroethylene is preferably filled at 0.01 to 1.0 MPa, more preferably 0.1 to 0.7 MPa. In this disclosure, the pressure is a gauge pressure unless otherwise specified.

In the reaction in the present disclosure, the shape and structure of the reactor are not particularly limited as long as they can withstand the above temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, a multi-tube reactor and the like. Examples of the material of the reactor include glass, stainless steel, iron, nickel, iron-nickel alloy and the like.

(1-8) Example of reaction In the step of reacting 1,1,2-trifluoro-2-chloroethylene with a zero-valent alkali metal, the raw material compound (1,1,2-trifluoro-2-) was used in the reactor. It can be carried out by a liquid phase reaction (batch type reaction) filled with chloroethylene) and zero-valent alkali metal.

After completion of the reaction, if necessary, purification treatment is carried out according to a conventional method, and the mixture is selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane. At least one species can be obtained.

(1-9) Target Compound At least one selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane thus obtained. Can be effectively used in various applications such as etching gas and cleaning gas for forming state-of-the-art fine structures such as semiconductors and liquid crystals.

2. 2. Composition As described above, at least one selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane can be obtained. , May also be obtained in the form of a composition.

Such a composition contains, for example, 1,1,2-trifluoroethylene and / or 1,2-dichlorohexafluorocyclobutane and hexafluoro-1,3-butadiene, and the total amount of the composition is 100. As mol%, the content of hexafluoro-1,3-butadiene is 3 to 90 mol% (particularly 5 to 85 mol%), 1,1,2-trifluoroethylene and / or 1,2-dichlorohexafluorocyclobutane. The content of ethylene can be 10 to 97 mol% (particularly 15 to 95 mol%).

More specifically, as described above, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane are likely to be produced when no solvent is used. Therefore, the total amount of the composition is 100 mol%, which is 1,1. , 2-trifluoroethylene 0-25 mol% (especially 5-20 mol%), hexafluoro-1,3-butadiene 35-55 mol% (especially 40-50 mol%), 1,2-dichlorohexa Fluorocyclobutane can be contained in an amount of 30 to 55 mol% (particularly 35 to 50 mol%).

Further, as described above, when hydrocarbons and aromatic hydrocarbons are used, 1,1,2-trifluoroethylene is likely to be produced. Therefore, the total amount of the composition is 100 mol%, and 1,1,2-trifluoroethylene is easily produced. It can contain 70-95 mol% (particularly 75-90 mol%) of ethylene and 5-30 mol% (particularly 10-25 mol%) of hexafluoro-1,3-butadiene.

Further, as described above, when 1,2-dichlorohexafluorocyclobutane is easily produced when ether is used, the total amount of the composition is 100 mol%, and 1,1,2-trifluoroethylene is 0 to 15 mol%. (Especially 3-10 mol%), Hexafluoro-1,3-butadiene 3-15 mol% (especially 5-10 mol%), 1,2-Dichlorohexafluorocyclobutane 80-95 mol% (especially 85-85- 90 mol%) can be contained.

Such a composition of the present disclosure can be effectively used in various applications such as a cleaning gas as well as an etching gas for forming a state-of-the-art fine structure such as a semiconductor or a liquid crystal display.

Although the embodiments of the present disclosure have been described above, various changes can be made in the form and details without departing from the spirit and scope of the claims.

Examples are shown below to clarify the features of the present disclosure. The present disclosure is not limited to these examples.

Examples 1 to 3
A 50 cc glass autoclave, which is a reaction tube, was charged with 0.3 mmol of sodium dispersion (sodium sodium dispersion; sodium content 25% by mass) in terms of sodium. Further, 5 mL of hexane, 5 mL of benzene or 10 mL of commercially available mineral oil was added to the reaction tube. The lid of the reaction tube was closed, and the starting compound 1,1,2-trifluoro-2-chloroethylene (CTFE) was filled to 0.2 MPaG. Then, the reaction was carried out by cooling to 0 ° C. or −40 ° C., and when the pressure fluctuation disappeared, the reaction was terminated. The gas phase part of the reaction tube was sampled and analyzed by GC. Table 1 shows the results of converting the amount of CTFE input in excess.

Examples 4-9
A 50 cc glass autoclave, which is a reaction tube, was charged with 0.3 mmol of sodium dispersion (sodium sodium dispersion; sodium content 25% by mass) in terms of sodium. Further, 5 mL of tetrahydrofuran, 1 mL of commercially available mineral oil or 5 mL of commercially available mineral oil were added to the reaction tube as needed, and 0.3 mmol of sodium hydride was added as needed. The lid of the reaction tube was closed, and the starting compound 1,1,2-trifluoro-2-chloroethylene (CTFE) was filled to 0.2 MPaG. Then, the reaction was carried out by cooling to 0 ° C. or −40 ° C., and when the pressure fluctuation disappeared, the reaction was terminated. The gas phase part of the reaction tube was sampled and analyzed by GC. Table 2 shows the results of converting the amount of CTFE input in excess.

Claims (9)

A method for producing at least one selected from the group consisting of 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene and 1,2-dichlorohexafluorocyclobutane.
A production method comprising a step of reacting 1,1,2-trifluoro-2-chloroethylene with a zero-valent alkali metal. The production method according to claim 1, wherein the zero-valent alkali metal is at least one selected from the group consisting of lithium metal, sodium metal and potassium metal. The production method according to claim 1 or 2, wherein the zero-valent alkali metal is a sodium metal. The production method according to any one of claims 1 to 3, wherein the zero-valent alkali metal is dispersed in the dispersed oil. The step of reacting the 1,1,2-trifluoro-2-chloroethylene with the zero-valent alkali metal is carried out in the presence of mineral oil or an organic solvent having a boiling point of 30 to 800 ° C., according to claims 1 to 4. The manufacturing method according to any one. The production according to any one of claims 1 to 5, wherein the temperature at which the 1,1,2-trifluoro-2-chloroethylene is reacted with the zero-valent alkali metal is −110 to 800 ° C. Method. It contains 1,2-dichlorohexafluorocyclobutane and hexafluoro-1,3-butadiene, and the total content of the composition is 100 mol%, and the content of hexafluoro-1,3-butadiene is 3 to 90 mol%. A composition in which the content of 1,2-dichlorohexafluorocyclobutane is 10 to 97 mol%. It contains 1,1,2-trifluoroethylene and hexafluoro-1,3-butadiene, and the total content of the composition is 100 mol%, and the content of hexafluoro-1,3-butadiene is 5 to 30 mol. %, And the content of 1,1,2-trifluoroethylene is 70 to 95 mol%. The composition according to claim 7 or 8 , which is used as a cleaning gas or an etching gas.