JPS6016361B2 - Manufacturing method of sulfur tetrafluoride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing sulfur tetrahydride, and in particular, a method for producing sulfur tetrahydride using a relatively inexpensive fluorine source without using fluorine gas obtained by abbreviation of hydrofluoric acid using expensive electricity. , sulfur tetrafluoride (SF) in high yield
4).

Conventional methods for producing SF4 include, for example, a method in which sulfur dichloride and sodium fluoride are reacted in an organic solution such as acetonitrile (see US Pat. No. 2,992,073); ℃ reaction and treatment of the reaction product with amines to separate SF4 (see OLS No. 238679); method of reacting sulfur dichloride with NOF/fine F (USP 4 Female 2);
(See total number specification) etc. are known.

Among these methods, the method typified by the above-mentioned US Pat. No. 29, No. 073 requires the reaction to be carried out in the form of a slurry, since the sodium fluoride reacted with sulfur dichloride and the salt used as the creation material are solids. It has drawbacks that are not very favorable in terms of reaction operation, such as the reaction operation being difficult to carry out and the yield of SF4 varying greatly depending on the particle size of the sodium fluoride.

In addition, the method typified by CLS23 Gap No. 679 is -
It requires a fairly low temperature of 5 pi, and also requires treatment with amines, resulting in complicated operations and high costs.

In addition, the method typified by USP4 female number 283 is NOF
However, it is corrosive, requires the use of special materials for counterfeiting, has a low yield of SF4, precipitates sulfur as a creation product, and has the drawbacks of complicated operations. Furthermore, Py(HF)9
．． 2 (Py: pyridine) and sulfur dichloride are reacted to form S
There is a report that F4 was obtained in a low yield of Satoshi%. (G
．． A evening. lahet, al, I dish rg, Chem, I6
2637 (77) Shortcommunicat
ion) However, according to additional tests by the present inventors, in this method, not only the yield was uneven, but no production of SF4 was observed.

That is, according to the results of subsequent studies by the present inventors,
After investigating various molar ratios of HF/Py and reacting with sulfur dichloride, it was found that when HF/Py exceeds 5 to 6, the fluorination ability is significantly reduced or completely eliminated. The present inventor has discovered that SF4 can be easily obtained with high purity and a yield of 90% or more by reaction with sulfur dichloride only when HF/Py=4 or less, and has already reported that issue(
It was proposed as Tsubaki Seki Sho 56 Ichizu No. 209).

After further investigation, the present inventors discovered that not only pyridine but also other amines such as picoline and quinoline can be used.
It was found that almost the same results as in the case of pyridine can be obtained.

Such an amiso compound of hydrofluoric acid has the general formula Am (
HF), ~4 (Am: amine excluding pyridine), where Am is a pyridine derivative such as picoline or quinoline, or a tertiary amine such as triethylamine or trimethylamine, and these are not necessarily pure alone. It is not necessary, and two or more types may be mixed as appropriate.
In the present invention, such an amine compound of hydrofluoric acid is
It is necessary that the molar ratio of F/Am is 1-4.

If the molar ratio is outside the above range, it is unsuitable because the production of SF4 is insufficient or the reaction does not proceed. In the present invention, strictly speaking, the ratio of the amine compounds of sulfur dichloride and hydrofluoric acid used is
It is usually appropriate to use 1 to 10 moles of Am(HF), ~4 compound per mole of sulfur dichloride, which is determined by the number of n in n, and as the number of n increases, within the above range. The amount of Am(HF)n used increases.

If these usage ratios deviate from the above range, SF4
It is not industrially advantageous because the yield of hydrofluoric acid decreases and the utilization rate of the amine compound of hydrofluoric acid decreases. If 2 to 6 moles of the acid-generating amine compound are used per 1 mole of sulfur dichloride in these proportions, SF4 can be obtained at an industrially satisfactory rate with a yield of 90% or more of the theoretical yield. Therefore, it is particularly preferable. There are no particular limitations on the method for synthesizing the amine compound of hydrofluoric acid, and any known method may be employed as appropriate.

For example, if we take the quinoline compound of hydrofluoric acid as an example and explain one example of its synthesis method, quinoline is placed in a hydrofluoric acid-resistant container such as polyethylene, and a predetermined amount of hydrogen fluoride is introduced while cooling from the outside. means are used. Other conditions for actually synthesizing SF4 using these raw materials include a temperature of 10 to 600, a pressure of usually normal pressure, and a pressurization of 5k9/g if desired. It is possible.

Further, although the reaction can be carried out in the absence of a solvent, it is preferable to use a solvent because handling and reaction can be carried out smoothly.

The solvent used is preferably one that is itself inert to the raw materials and products, and halogenated hydrocarbons are generally suitable. Among these, trichlorotrifluoroethane, fluorotrichloromethane, methylene chloride, chloroform, and carbon tetrachloride are preferred, and one or more of these can be used as appropriate. In particular, when trichlorotrifluoroethane is used, both liquids, sulfur chloride and an amine compound of hydrochloric acid, which are by-produced as a result of the production of SF4, are separated into separate layers in a solvent, and then collected. It is particularly preferred because it has the advantage of being reusable as a raw material.

Further, as for the ratio of the reaction raw materials and the solvent used, it is appropriate to use the solvent in an amount of about 10 to 20% by volume based on the total amount thereof.

As the apparatus for carrying out the reaction, for example, a complete mixing type reaction model having an appropriate concentration apparatus is preferable, and the material thereof is S.
It is preferable to use a chlorine-resistant and corrosion-resistant material for the hakama, such as US or fluororesin on the inner surface. Next, the present invention will be explained by examples.

Example modification Am Am (HF) n (mol) SC1
2 (mol) Solvent (Z) SF4 yield 1 Quinoline 2 1
0.5 94n=2
1'chlorotriphnoleoloethane 2 quinoline 6 1 〃 90n=4
〃3 o-picoline 4
1 0.4 91n=3
4 Triethylamine 4
1 0.5 92n=2
For methylene chloride, the reaction temperature was 30°C.
The reaction was carried out at ~45 qo and normal pressure.

Claims (1)

[Claims] 1. A method for producing sulfur tetrafluoride, which comprises reacting sulfur dichloride and Am(HF)_1_-_4 in the presence or absence of a solvent. However, Am is at least one selected from pyridine derivatives excluding pyridine such as picoline and quinoline, and tertiary amines such as trimethylamine and triethylamine. 2. The method according to claim 1, wherein the reaction ratio of sulfur dichloride and Am(HF)_1_-_4 is 1 to 10 mol of the latter to 1 mol of the former. 3. The method of claim 1, wherein the solvent is a halogenated hydrocarbon. 4. The method according to claim 3, wherein the halogenated hydrocarbons are trichlorotrifluoroethane, fluorotrichloromethane, methylene chloride, chloroform, and carbon tetrachloride.