KR102478267B1 - Continuous method for producing fluorine-containing cyclic sulfur compounds - Google Patents

Abstract

Disclosed herein is a method for continuously producing a fluorinated cyclic sulfur compound. The manufacturing method includes: 1) injecting a perfluoroolefin having 4 to 8 carbon atoms and sulfur into a reactor; 2) reacting sulfur with a perfluoroolefin having 4 to 8 carbon atoms in the reactor of step 1); 3) transferring the reaction product of step 2) to a separator via a condenser; 4) transferring liquid-phase reaction products from the separator of step 3) to a distillation column and moving gas-phase reaction products to a compressor; and 5) distilling the liquid reaction product transferred to the distillation column in step 4) to obtain a fluorinated cyclic sulfur compound, and recycling the gaseous reaction product transferred to the compressor to the reactor.

Description

Continuous method for producing fluorine-containing cyclic sulfur compounds {Continuous method for producing fluorine-containing cyclic sulfur compounds}

The present disclosure discloses a method for continuously producing a fluorinated cyclic sulfur compound.

Sulfur compounds such as thiolene or thiophene are widely used as raw materials for electronic materials or as biologically active materials. In particular, the fluorine-substituted cyclic sulfur compound is a material that can be used as a semiconductor material, a charge transfer material for optics, electronic optics, electronic equipment, and a semiconductor etching solution.

A fluorine-substituted thiorene or thiophene compound can be produced by introducing fluorine into a raw material that does not contain fluorine. For example, as a method of changing a CH group into a CF group, a method of directly using F ₂ is known. Thiophene may be reacted with F ₂ at -63 °C to produce 2-fluorothiophene or 3-fluorothiophene. However, the conventional method of changing a CH group or a CI group into a CF group has limitations in that fluorine can only be partially introduced into the molecule, and the yield of perfluorothiophene is not high.

Cerichelli, M. E. Creatoni, and S. Fornarini, Gazz. Chim. Ital., 120, 749 (1990)

In one aspect, an object of the present disclosure is to provide a method for continuously producing a fluorinated cyclic sulfur compound.

In one aspect, the present disclosure provides a method comprising: 1) injecting a perfluoroolefin having 4 to 8 carbon atoms and sulfur into a reactor; 2) reacting sulfur with a perfluoroolefin having 4 to 8 carbon atoms in the reactor of step 1); 3) moving the reaction product of step 2) to a separator via a condenser; 4) moving the liquid-phase reaction product from the separator of step 3) to a distillation column and moving the gas-phase reaction product to a compressor; and 5) distilling the liquid reaction product transferred to the distillation column in step 4) to obtain a fluorinated cyclic sulfur compound, and recycling the gaseous reaction product transferred to the compressor to the reactor. A continuous manufacturing method is provided.

In an exemplary embodiment, the perfluoroolefin having 4 to 8 carbon atoms in step 1) may be a compound represented by Formula 1 below.

[Formula 1]

In the above formula, R is F or CH ₃ .

In an exemplary embodiment, the perfluoroolefin having 4 to 8 carbon atoms in step 1) may be hexafluorobutadiene.

In an exemplary embodiment, in step 1), the perfluoroolefin having 4 to 8 carbon atoms may be injected in an amount of 0.1 to 5 g per minute.

In an exemplary embodiment, in step 1), sulfur may be injected in an equivalent ratio of 0.5 to 1.5 compared to a perfluoroolefin having 4 to 8 carbon atoms.

In an exemplary embodiment, the reaction temperature in step 2) may be carried out at 340 to 500 °C.

In an exemplary embodiment, the reaction pressure in step 2) may be carried out at 10 to 50 bar.

In an exemplary embodiment, the fluorine-containing cyclic sulfur compound in step 5) may be perfluorothiophene.

In an exemplary embodiment, the fluorine-containing cyclic sulfur compound in step 5) is 2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene (2,2,3,4 ,5,5-hexafluoro-2,5-dihydrothiophene).

In one aspect, the technology disclosed in the present disclosure has an effect of providing a method for continuously producing a fluorine-containing cyclic sulfur compound.

In another aspect, the method for continuously producing a fluorine-containing cyclic sulfur compound disclosed in the present disclosure has an effect of producing the fluorine-containing cyclic sulfur compound in a short time and in high yield.

1 is a schematic diagram of a method for continuously preparing a fluorine-containing cyclic sulfur compound according to an embodiment. In the schematic diagram, (1) is a reactor, (2) is a condenser, (3) is a separator (V-2 separator), (4) is a compressor, and (5) is a distillation column. means In the above production method, a perfluoroolefin having 4 to 8 carbon atoms and sulfur are continuously injected into a reactor (1), and a perfluoroolefin having 4 to 8 carbon atoms and sulfur are reacted in the reactor (1) to produce a reaction product. let it Thereafter, the reaction products are transferred to the separator (3) via the condenser (2), the liquid reaction products in the separator (3) are transferred to the distillation tower (5) and the gaseous reaction products are transferred to the compressor (4). A fluorine-containing cyclic sulfur compound is obtained through a distillation process from the liquid reaction product transferred to the distillation tower (5), and the gaseous reaction product transferred to the compressor (4) is recycled to the reactor (1) and reused as a reaction raw material, thereby continuously producing reaction is possible
2 shows the results of GC-chromatography analysis of the distilled product according to one embodiment.
Figure 3 shows the results of molecular weight fragmentation pattern (mass fragmentation pattern) analysis of distilled perfluorothiophene according to one embodiment.
MS: 194 (100) [M] ⁺ ; 175 (49) [MF] ⁺ ; 144 (79) [M-CF ₂ ] ⁺ ; 131 (96) [M-CFS] ⁺ ; 125 (69) [M-CF ₃ ] ⁺ ; 112 (27) [M-CF ₂ S] ⁺ ; 100 (12) [C ₂ F ₄ ] ⁺ ; 94 (38) [M- ₂ CF ₂ ] ⁺ ; 93 (83) [M-CF ₃ -S] ⁺ ; 87 (22) [C ₃ FS ⁺ ]; 82 (10) [CF ₂ S] ⁺ ; 69 (24) [CF ₃ ] ⁺ ; 63 (63) [CFS] ⁺ ; 31 (57) [CF] ⁺
4 shows the results of F-NMR analysis of the distilled product according to one embodiment.

Hereinafter, the present disclosure will be described in detail.

In one aspect, the present disclosure provides a method comprising: 1) injecting a perfluoroolefin having 4 to 8 carbon atoms and sulfur into a reactor; 2) reacting sulfur with a perfluoroolefin having 4 to 8 carbon atoms in the reactor of step 1); 3) moving the reaction product of step 2) to a separator via a condenser; 4) moving the liquid reaction product from the separator of step 3) to a distillation column and moving the gas reaction product to a compressor; and 5) distilling the liquid reaction product transferred to the distillation column in step 4) to obtain a fluorinated cyclic sulfur compound, and recycling the gaseous reaction product transferred to the compressor to the reactor. A continuous manufacturing method is provided.

The manufacturing method continuously injects a perfluoroolefin having 4 to 8 carbon atoms and sulfur into a reactor, and recycles the gaseous reaction product transferred to the compressor to the reactor and reuses it as a reaction raw material, thereby producing a continuous fluorine-containing cyclic sulfur compound. It is possible.

In the present disclosure, an olefin is an aliphatic unsaturated hydrocarbon compound, and means an unsaturated hydrocarbon compound containing a double bond between carbons in a molecule.

In the present disclosure, a fluorine-containing cyclic sulfur compound is a compound containing one or more fluorines, and refers to a heterocyclic compound having sulfur in the ring. For example, the fluorine-containing cyclic sulfur compound may mean a 5-membered heterocyclic unsaturated compound containing one or more fluorines and having sulfur in the ring.

In an exemplary embodiment, in step 1), a perfluoroolefin having 4 to 8 carbon atoms and sulfur are continuously injected into the reactor, or sulfur is injected into the reactor in advance and then a perfluoroolefin having 4 to 8 carbon atoms is continuously injected into the reactor. may be injected into

In an exemplary embodiment, step 1) may be to continuously inject two liquid raw materials into a reactor made of SUS 316 using an HPLC pump.

In an exemplary embodiment, the perfluoroolefin having 4 to 8 carbon atoms in step 1) may be a compound represented by Formula 1 below.

[Formula 1]

In the above formula, R is F or CH ₃ .

In an exemplary embodiment, the preparation method may be to prepare perfluorothiophene by reacting perfluoroolefin and S ₈ as shown in Scheme 1 below.

[Scheme 1]

In the above formula, R is F or CH ₃ .

In an exemplary embodiment, the perfluoroolefin may have 4 to 6 carbon atoms. In another exemplary embodiment, the perfluoroolefin may have 4 carbon atoms.

In an exemplary embodiment, the perfluoroolefin having 4 to 8 carbon atoms in step 1) may be perfluorobutadiene.

In an exemplary embodiment, the perfluoroolefin having 4 to 8 carbon atoms in step 1) may be hexafluorobutadiene.

In an exemplary embodiment, in step 1), the perfluoroolefin having 4 to 8 carbon atoms may be injected in an amount of 0.1 to 5 g per minute.

In another exemplary embodiment, the perfluoroolefin having 4 to 8 carbon atoms in step 1) is 0.1 g or more, 0.2 g or more, 0.3 g or more, 0.4 g or more, or 0.5 g or more per minute, 5 g or less, 4.8 g or less, 4.6 g or less, 4.4 g or less, 4.2 g or less, 4 g or less, 3.8 g or less, 3.6 g or less, 3.4 g or less, 3.2 g or less, 3 g or less, 2.8 g or less, 2.6 g or less, 2.4 g Or less, it may be injected in an amount of 2.2 g or less or 2 g or less. If the injection amount of the perfluoroolefin having 4 to 8 carbon atoms is too low, the residence time in the reactor becomes long, and thus the yield of the target product may increase, but the productivity may decrease. In addition, if the injected amount of the perfluoroolefin having 4 to 8 carbon atoms is too high, the retention time in the reactor is shortened and the yield of the target product may decrease. In this respect, it may be preferable to inject the perfluoroolefin having 4 to 8 carbon atoms in an amount of 0.4 to 3.8 g per minute or 0.4 to 2.8 g per minute in step 1).

In an exemplary embodiment, in step 1), sulfur is present in an equivalent ratio of 0.5 to 1.5, an equivalence ratio of 0.6 to 1.5, an equivalence ratio of 0.7 to 1.5, an equivalence ratio of 0.8 to 1.5, and an equivalence ratio of 0.9 to 1.5 relative to a perfluoroolefin having 4 to 8 carbon atoms. It may be preferable in terms of reaction efficiency to inject at an equivalent ratio of 1 to 1.5.

In an exemplary embodiment, the reaction temperature in step 2) may be carried out at 340 to 500 °C.

In another exemplary embodiment, the reaction temperature in step 2) is 340 °C or higher, 360 °C or higher, 380 °C or higher, 400 °C or higher, 420 °C or higher, 440 °C or higher, 460 °C or higher, or 480 °C or higher, and 500 It may be carried out at a temperature of 490 °C or less, or 480 °C or less. If the reaction temperature is too low, the reaction proceeds slowly and productivity may decrease, and if the reaction temperature is too high, the reaction product may be decomposed. In this respect, the reaction temperature in step 2) may be preferably carried out at 380 to 500 °C, 400 to 500 °C, 420 to 500 °C or 460 to 500 °C.

In an exemplary embodiment, the reaction pressure in step 2) may be carried out at 10 to 50 bar.

In another exemplary embodiment, the reaction pressure in step 2) is 10 bar or more, 15 bar or more, 20 bar or more, 25 bar or more, 30 bar or more, 35 bar or more, or 40 bar or more, 50 bar or less, It may be carried out at a pressure of 49 bar or less, 48 bar or less, 47 bar or less, 46 bar or less, 45 bar or less, 44 bar or less, 43 bar or less, 42 bar or less, 41 bar or less, or 40 bar or less. In terms of reaction efficiency, the reaction pressure in step 2) may be preferably carried out at 30 to 50 bar or 30 to 40 bar.

In one exemplary embodiment, the reaction pressure is adjustable with a back pressure regulator.

In an exemplary embodiment, the distillation in step 5) may be performed using a 20-stage glass distillation apparatus. At the top of the distillation column, it is cooled to 15 ° C using a circulator, and at the bottom of the distillation column, a round flask is filled with a crude product and heated at a constant output using a 360 W electric heater. Adjust heater output to a range where flooding or drying does not occur. After sufficiently refluxing for 2 hours or more, an amount small enough not to affect the refluxing amount is collected from the top of the distillation column. When the amount of reflux at the top of the tower decreases, the heater output is increased little by little and sampling is repeated. Finally, perfluorothiophene with a purity of 99% or more can be obtained.

In an exemplary embodiment, the fluorine-containing cyclic sulfur compound in step 5) may be perfluorothiophene.

In an exemplary embodiment, the fluorine-containing cyclic sulfur compound in step 5) may be perfluorothiophene having 4 to 8 carbon atoms.

In an exemplary embodiment, the fluorine-containing cyclic sulfur compound in step 5) may be perfluoro-2,5-dihydrothiophene.

In an exemplary embodiment, the fluorine-containing cyclic sulfur compound in step 5) is 2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene (2,2,3,4 ,5,5-hexafluoro-2,5-dihydrothiophene).

The above production method not only enables continuous production of a fluorine-containing cyclic sulfur compound, but also provides an effect of producing a fluorine-containing cyclic sulfur compound more rapidly and with a higher yield than a batch-type production method.

Hereinafter, the present disclosure will be described in more detail through examples. These examples are only for exemplifying the present disclosure, and it will be apparent to those skilled in the art that the scope of the present disclosure is not to be construed as being limited by these examples.

Example 1.

After injecting 25 g of sulfur into the 100 mL high-pressure reactor of FIG. 1, the reaction was performed by injecting 2.8 g of hexafluorobutadiene in a liquid state per minute while maintaining a temperature of 400 °C and a pressure of 30 bar. Inside the reactor, the reaction solution was mixed using a magnet. For 40 minutes, a total of 112 g of hexafluorobutadiene was injected into the reactor, the reaction was terminated for analysis of the reaction product, and the solution caught in the cold trap was obtained from the separator in FIG. 1 to measure the total amount of solution. confirmed to be The residence time of hexafluorobutadiene in the reactor in this example was determined to be 3.1 minutes.

As a result of analyzing the product using GC-Mass and GC-chromatography, substances shown in Table 1 below were detected. It was confirmed that the yield of 3,4,5,5-hexafluoro-2,5-dihydrothiophene) was 78.5% and the selectivity was 78.5%. In addition, it was confirmed that continuous production of perfluorothiophene was possible by continuously injecting hexafluorobutadiene into the high-pressure reactor of FIG. 1 and recycling the gaseous reaction product transferred to the compressor into the reactor.

Hexafluorobutadiene (FB) conversion rate (%) = 100 x (1-remaining amount of hexafluorobutadiene after reaction (mmol) / hexafluorobutadiene used (mmol))

Product yield (%) = 100 x amount of product produced (mmol) / hexafluorobutadiene used (mmol)

abbreviation constitutional formula compound name FB

1,1,2,3,4,4-hexafluoro-1,3-butadiene (1,1,2,3,4,4-hexafluoro-1,3-Butadiene) FCB

1,2,3,3,4,4-hexafluorocyclobutene (1,2,3,3,4,4-hexafluorocyclobutene) Thiolene

2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene (2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene) A

2,2,3,3,4,5-hexafluoro-2,3-dihydrothiophene (2,2,3,3,4,5-hexafluoro-2,3-dihydrothiophene) B

3,3,4,5,6,6-hexafluoro-3,6-dihydro-1,2-dithyine (3,3,4,5,6,6-hexafluoro-3,6-dihydro- 1,2-dithin) C

3,3,4,4,5,5-hexafluorodihydro-2(3H)-thiophenethione (3,3,4,4,5,5-hexafluorodihydro-2(3H)-thiophenethione) D1

1,2,3,3,4,4,5,6,7,7,8,8-dodecafluorotricyclo[3.3.0.0 ^2,6 ]octane (1,2,3,3,4,4 ,5,6,7,7,8,8-dodecafluorotricyclo[3.3.0.0 ^2,6 ]octane) D2

1,2,3,3,4,4,5,6,6-nonafluoro-5-(1,2,2-trifluoroethenyl)cyclohexene (1,2,3,3,4, 4,5,6,6-nonafluoro-5-(1,2,2-trifluoroethenyl)cyclohexene)

Example 2.

Perfluorothiophene was prepared in the same manner as in Example 1, but the reaction was carried out by changing the reaction temperature, and the results are shown in Table 2 below.

reaction temperature
℃ FB conversion rate (%) Product yield (%) FCB Thiolene A B C D1 D2 360 100 61.1 32.7 0.0 3.8 0.2 1.6 0.6 380 100 30.3 63.9 0.0 2.6 0.6 1.7 0.9 420 100 10.3 84.8 0.1 1.1 0.6 1.9 1.1 460 100 3.1 93.6 0.2 0.4 0.6 0.9 1.1 500 100 1.0 95.4 0.1 0.2 1.0 1.2 1.0

As a result, it was confirmed that the yield of perfluorothiophene increased as the reaction temperature increased. In addition, it was confirmed that when the reaction temperature exceeded 500 ° C., the reaction product was decomposed and the yield of the target product rather decreased.

Example 3.

Perfluorothiophene was prepared in the same manner as in Example 1, but the reaction was performed by changing the injected amount of hexafluorobutadiene, and the results are shown in Tables 3 and 4 below. Table 3 is the result carried out at a reaction temperature of 360 ℃, Table 4 is the result carried out at a reaction temperature of 400 ℃.

Hexafluorobutadiene injected amount (g/min), residence time (min) FB conversion rate (%) Product yield (%) FCB Thiolene A B C D1 D2 0.4, 23.7 100 35.1 59.4 0.0 2.4 0.4 1.6 1.0 0.7, 13.0 100 34.8 59.4 0.0 2.5 0.4 1.9 0.9 2.1, 4.4 100 34.2 59.8 0.1 2.8 0.5 1.6 1.0

Hexafluorobutadiene injected amount (g/min), retention time (min) FB conversion rate (%) Product yield (%) FCB Thiolene A B C D1 D2 3.8, 2.3 100 32.7 60.6 0.0 3.7 0.3 1.8 0.9 4.7, 1.8 100 49.1 43.0 0.0 4.5 0.4 1.9 1.0

As a result, it was confirmed that the perfluorothiophene yield decreased as the injection amount of hexafluorobutadiene increased when the reaction temperature and pressure conditions were the same. According to Table 2, when 2.8 g of hexafluorobutadiene was injected per minute at 360 ° C., the yield of perfluorothiophene was 32.7%, but when the amount of hexafluorobutadiene injected was reduced under the same conditions, perfluorothiophene The yield of opene increased. In addition, in Example 1, when 2.8 g of hexafluorobutadiene was injected per minute at 400 ° C., the yield of perfluorothiophene was 78.5%, but when the amount of hexafluorobutadiene injected was increased under the same conditions, The yield of rothiophene decreased.

Example 4.

Perfluorothiophene was prepared in the same manner as in Example 1, but the reaction temperature was set to 360 ° C. and the reaction was performed by changing the reaction pressure. The results are shown in Table 5 below. The injection amount of hexafluorobutadiene was 2.8 g per minute.

reaction pressure
(bar) FB conversion rate (%) Product yield (%) FCB Thiolene A B C D1 D2 10 100 58.2 39.9 0.0 0.2 0.4 0.8 0.5 20 100 57.8 38.6 0.0 0.4 0.4 1.9 0.9 30 100 63.4 33.9 0.0 0.2 0.2 1.7 0.6 40 100 40.3 55.5 0.0 0.6 0.6 2.0 1.0

As a result, it was confirmed that the yield of perfluorothiophene greatly increased when the reaction pressure was 40 bar.

As above, specific parts of the present disclosure have been described in detail, and for those skilled in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present disclosure is not limited thereby. something to do. Accordingly, the substantial scope of the disclosure will be defined by the appended claims and their equivalents.

Claims (9)

1) injecting a perfluoroolefin having 4 to 8 carbon atoms and sulfur into a reactor;
2) reacting sulfur with a perfluoroolefin having 4 to 8 carbon atoms in the reactor of step 1);
3) moving the reaction product of step 2) to a separator via a condenser;
4) moving the liquid-phase reaction product from the separator of step 3) to a distillation column and moving the gas-phase reaction product to a compressor; and
5) distilling the liquid reaction product transferred to the distillation column in step 4) to obtain a fluorinated cyclic sulfur compound, and recycling the gaseous reaction product transferred to the compressor to the reactor;
In step 1), the perfluoroolefin having 4 to 8 carbon atoms is hexafluorobutadiene, and in step 5), the fluorine-containing cyclic sulfur compound is 2,2,3,4,5,5-hexafluoro -2,5-dihydrothiophene (2,2,3,4,5,5-hexafluoro-2,5-dihydrothiophene),
In step 1), the perfluoroolefin having 4 to 8 carbon atoms is injected in an amount of 0.4 to 2.8 g per minute,
The reaction temperature and reaction pressure in step 2) are 400 to 500 ° C. and 35 to 40 bar, a continuous method for producing a fluorinated cyclic sulfur compound.
delete delete According to claim 1,
In step 1), the perfluoroolefin having 4 to 8 carbon atoms is injected in an amount of 0.5 to 2.8 g per minute, a continuous method for producing a fluorinated cyclic sulfur compound.
According to claim 1,
In step 1), sulfur is injected in an equivalent ratio of 0.5 to 1.5 compared to a perfluoroolefin having 4 to 8 carbon atoms, a continuous method for producing a fluorinated cyclic sulfur compound.
According to claim 1,
In step 2), the reaction temperature is carried out at 460 to 500 ° C., a continuous method for producing a fluorinated cyclic sulfur compound.
According to claim 1,
In step 2), the reaction pressure is carried out at 40 bar, a continuous method for producing a fluorine-containing cyclic sulfur compound. delete delete

Images