KR100569245B1 - Preparation method of pentafluoroethyliodide over fluorinated metal catalysts - Google Patents

Abstract

The present invention relates to a method for preparing pentafluoroethyl iodide (C ₂ F ₅ I) using a metal fluoride catalyst, more specifically iodine (I ₂ ), iodine fluoride (IF ₅ ) and tetrafluoro In the reaction of ethylene (TFE), a specific metal fluoride catalyst selected from aluminum trifluoride (AlF ₃ ), chromium fluoride (CrF ₃ ) and magnesium fluoride (MgF ₂ ) is used as the reaction catalyst, or added to the metal fluoride catalyst. Pentafluoroethyl iodide (C ₂ ) in high yield while suppressing the formation of by-product ethane hexafluoride (C ₂ F ₆ ) by semi-continuous process using a composite metal catalyst mixed with a low-antimony catalyst. F ₅ I relates to a process for preparing a metal-based or composite metal-based catalyst capable of fluoride to pentafluoroethyl iodide by Id (C ₂ F ₅ I) obtained in).

Pentafluoroethyl iodide, tetrafluoroethylene, iodine fluoride, iodine, metal fluoride catalysts, composite metal catalysts, semicontinuous processes

Description

Preparation method of pentafluoroethyl iodide using metal fluoride catalysts {Preparation method of pentafluoroethyliodide over fluorinated metal catalysts}             

1 shows a conceptual diagram of a manufacturing apparatus of pentafluoroethyl iodide (C ₂ F ₅ I) according to the present invention.

[Explanation of the code | symbol about the principal part of the process blueprint of FIG. 1]

110: reactor 111: temperature controller 112: mass controller

210: IF ₅ In action 211: I ₂ and IF ₅ melting vessel 212: I ₂ and IF ₅ solution circulation pump

213: condenser for recovery of unreacted IF ₅ 214: condensed IF ₅ collection tank

310: alumina adsorption tower 311: silica gel adsorption tower

410: C ₂ F ₅ I liquefaction condenser 411: C ₂ F ₅ I recovery tank

The present invention relates to a method for preparing pentafluoroethyl iodide (C ₂ F ₅ I) using a metal fluoride catalyst, more specifically iodine (I ₂ ), iodine fluoride (IF ₅ ) and tetrafluoro In the reaction of ethylene (TFE), a specific metal fluoride catalyst selected from aluminum trifluoride (AlF ₃ ), chromium fluoride (CrF ₃ ), and magnesium fluoride (MgF ₂ ) is used, or added to the metal fluoride catalyst. In general, a pentafluoroethyl iodide (C) was produced in high yield while suppressing the formation of by-product ethane hexafluoride (C ₂ F ₆ ) in a semi-continuous process using a mixed metal catalyst in which antimony-based catalyst was mixed in a constant ratio. ₂ F ₅ I relates to a process for preparing a metal-based or composite metal-based catalyst capable of fluoride to pentafluoroethyl iodide by Id (C ₂ F ₅ I) obtained in).

Pentafluoroethyl iodide (C ₂ F ₅ I) is a low-energy surface functional material, and has various inorganic materials such as metals, ceramics, fibers, leather, paper, paints, water / oil repellent / antifouling agents, and interface characteristics. It is widely used in intermediate materials of surface modifiers such as fire fighting agents, high performance surfactants, and release agents, which are important variables, and in the third generation CFC field where chemical stability is important.

Pentafluoroethyl iodide (C ₂ F ₅ I) can be prepared by batch reaction by the telogen reaction shown in Scheme 1 below (US Pat. No. 3,132,185 (1964), US Pat. 3,829,512 (1974), US Patent No. 3,933,931 (1976), Japanese Patent Laid-Open No. 59-51225 (1984), Japanese Patent Laid-Open No. 60-23333].

2I ₂ + IF ₅ + 5C ₂ F ₄ → 5C ₂ F ₅ I

The telogen reaction should proceed in the absence of oxygen. If a small amount of oxygen is present during the reaction, abnormal radicals are generated, and the polymerization of tetrafluoroethylene (TFE) as a raw material may occur rapidly, resulting in explosion and loss of tetrafluoroethylene (TFE). Happens.

According to US Pat. No. 3,829,512, it is reported that in the telogen process, it is efficient to charge a catalyst such as metal or metal fluoride such as antimony, niobium, tantalum, titanium, tungsten, boron and molybdenum to carry out a batch reaction.

However, this batch reaction is not only difficult to maintain at quantitative molar ratios of I ₂ : IF ₅ : C ₂ F ₄ = 2: 1: 5 due to local exothermic reactions, but also has a low conversion rate and high carbon number due to difficulty in maintaining quantitative molar ratios. There is a problem that impurities must be generated to undergo an additional purification step after the reaction. In addition, the addition of tetrafluoroethylene (TFE) as a reaction raw material when performing the reaction should always be carried out under a high pressure of 7 atm or more, there is always a risk of explosion.

In order to improve this problem, Korean Patent Publication No. 10-2001-0019202 reported a method for improving the risk of the existing batch reaction and the purity of the product through an atmospheric pressure continuous reaction. Korean Patent Publication No. 10-2001-0019202 supplies unreacted tetrafluoroethylene (TFE) together with pure tetrafluoroethylene (TFE) to a reactor after addition of iodine fluoride over an antimony trifluoride catalyst. Due to atmospheric pressure, the risk of explosion is reported to be reduced even with the addition of additional tetrafluoroethylene (TFE).

However, as in the conventional batch reaction, impurities such as ethane hexafluoride (C ₂ F ₆ ) are generated due to the high activity of antimony trifluoride (SbF ₃ ), and are formed with unreacted tetrafluoroethylene (TFE) by circulation. A small amount of impurities such as carbon fluoride is re-introduced into the reactor in which catalytic activity remains, which promotes the generation of high boiling point impurities.

Thus, the present inventors conducted the present study to improve the problems such as process stability, economical efficiency, low conversion rate and impurity generation due to the high pressure of the conventional batch and atmospheric continuous telogen process as described above. As a result, aluminum trifluoride (AlF ₃ ), chromium fluoride (CrF ₃ ) and magnesium fluoride (MgF ₂ ) as reaction catalysts during the telogen process for the preparation of pentafluoroethyl iodide (C ₂ F ₅ I) When the reaction is carried out in a semi-continuous process using a metal fluoride catalyst selected from C) or a composite metal catalyst in which an antimony fluoride catalyst selected from antimony fluoride and antimony oxide in addition to the metal fluoride catalyst is mixed in a constant ratio, The present invention was completed by recognizing that a high yield of pentafluoroethyl iodide (C ₂ F ₅ I) can be prepared while suppressing a high boiling point hexafluoroethane (C ₂ F ₆ ) product.

Accordingly, the present invention provides a method for producing a high yield of pentafluoroethyl iodide (C ₂ F ₅ I) without a separate purification process by suppressing the production of by-product hexafluoroethane (C ₂ F ₆ ). Its purpose is to.

The present invention provides a method for preparing pentafluoroethyl iodide (C ₂ F ₅ I) by reacting iodine (I ₂ ), iodine fluoride (IF ₅ ) and tetrafluoroethylene (TFE) under a reaction catalyst. In

Pentafluoroethyl iodide (C ₂ F ₅₎ carried out using at least one metal fluoride catalyst selected from aluminum trifluoride (AlF ₃ ), chromium fluoride (CrF ₃ ) and magnesium fluoride (MgF ₂ ) as the reaction catalyst. The manufacturing method of I) has the characteristics.

In addition, the present invention reacts iodine (I ₂ ), iodine fluoride (IF ₅ ) and tetrafluoroethylene (TFE) under the reaction catalyst to prepare pentafluoroethyl iodide (C ₂ F ₅ I) In the method,

The reaction catalyst may include at least one metal fluoride catalyst selected from aluminum trifluoride (AlF ₃ ), chromium fluoride (CrF ₃ ) and magnesium fluoride (MgF ₂ ), and at least one antimony fluoride catalyst selected from antimony fluoride and antimony oxide. Another feature is a method for preparing pentafluoroethyl iodide (C ₂ F ₅ I), which is performed using a mixed metal catalyst mixed in a 1 to 5 molar ratio.

Hereinafter, the present invention will be described in detail.

The present invention is carried out under a specific metal fluoride catalyst or a composite metal catalyst in which an antimony catalyst is further added to the metal fluoride catalyst to produce a high yield without generating impurities including ethane hexafluoride (C ₂ F ₆ ). It relates to a process for preparing pentafluoroethyl iodide (C ₂ F ₅ I).

In the conventional telogen process for preparing pentafluoroethyl iodide (C ₂ F ₅ I), a fluorine-based catalyst, iodine and iodine fluoride are fed together, and then the temperature is increased. The vapor pressure of iodine fluoride is increased, and the rapid reaction proceeds initially during TFE injection, thereby increasing the amount of by-products. In addition, since the amount of iodine in the gas phase increases, it is difficult to maintain the molar ratio of iodine and iodine, and the flow rate of the reaction product is slowed because of clogging due to crystallization of iodine during the condenser. As a result, the pressure of the actual reaction increases. The use of Teflon-coated reactors was required because liquid iodine tends to corrode the inner walls of steel use stainless steel (SUS) reactors because of its high oxidizing power.

As a method for improving this, an antimony trifluoride (SbF ₃ ) catalyst was introduced to continuously react at atmospheric pressure to improve the process stability. However, the hexahexafluoroethane (C ₂ F) by the catalyst having high activity was solved. _By- products such as ₆ ) still remained a problem, and also has the disadvantage that the generation of high-boiling impurities by the reaction of unreacted TFE and trace impurities.

On the other hand, the present invention is characterized by the technical construction of using at least one metal fluoride catalyst selected from aluminum trifluoride (AlF ₃ ), chromium fluoride (CrF ₃ ) and magnesium fluoride (MgF ₂ ) as a catalyst for the reaction. Aluminum, chromium, magnesium, and the like forming the fluorinated metal catalysts are particularly by-products of hexafluoroethane (C ₂ F ₆₎ , compared with fluorides of metals such as tantalum, antimony, and molybdenum, which are generally used in conventional telogen reactions. Since it has the effect of suppressing the production of), these are selectively used in the present invention.

In addition, the same effects as described above may be obtained when the antimony-based catalyst is used in addition to the metal fluoride-based catalyst in the form of a mixed metal catalyst. That is, since the metal fluoride catalyst has an effect of inhibiting the production of high boiling point hexafluoroethane (C ₂ F ₆ ) as a by-product, high purity pentafluoroethyl iodide (C ₂ F _{5) is} required without further purification. The advantage is that I) can be manufactured. The antimony-based catalyst may be an fluoride and antimony oxide catalyst, and specifically, at least one selected from antimony trifluoride (SbF ₃ ), antimony fluoride (SbF ₅ ), and antimony oxide (Sb ₂ O ₃ ). It is desirable to. When used in the form of the above-described composite metal catalyst, the metal fluoride catalyst and the antimony catalyst may be mixed at a ratio of 1: 1 to 5. At this time, when the mixing ratio of the antimony-based catalyst is less than 1 molar ratio, it promotes the production of high boiling point fluorine compound and reduces the yield of the product, and when the mixing ratio of the metal fluoride catalyst exceeds 5 molar ratio, antimony fluoride and antimony oxide It is preferable to maintain the above range because the effect of yield improvement is not large compared to the use of the catalyst alone, and there is an uneconomic problem due to the increase in the catalyst price due to the mixed use.

Meanwhile, a method of preparing pentafluoroethyl iodide (C ₂ F ₅ I) using the metal fluoride catalyst according to the present invention will be described in more detail.

As shown in FIG. 1, the apparatus for preparing pentafluoroethyl iodide (C ₂ F ₅ I) of the present invention uses a temperature controller 111, a mass controller 112, a stirrer, and tetrafluoroethylene input. Reaction unit consisting of a semi-continuous reactor 110 is attached to the foaming machine for; Iodine fluoride input tank 210, dissolution tank 211 and circulating pump 212 for dissolving iodine in iodine fluoride, condenser 213 for iodine fluoride for recovery of vaporized unreacted raw materials and the collection tank ( Supply and recovery of iodine and iodine fluoride composed of 214); An adsorption unit including an alumina adsorption tower 310 for removing unreacted gaseous material and a silica gel adsorption tower 311 for removing a small amount of moisture not removed from the alumina adsorption tower; And a product recovery unit including a condenser 410 and a recovery tank 411 for recovering the product.

Looking at each step of the manufacturing process of pentafluoroethyl iodide (C ₂ F ₅ I), the complex of a specific metal fluoride-based catalyst or the metal fluoride-based catalyst and fluoride and antimony oxide catalyst in a single step To prepare a metal catalyst. The catalyst is prepared by a method generally performed in the art and is not particularly limited.

In a two-step process, the reaction ratio (I ₂ / IF ₅ ) between iodine (I ₂ ) and iodine fluoride (IF ₅ ) is maintained at 0.2 to 2 molar ratio, and refluxed at a temperature of 80 to 100 ° C. for 1 to 3 hours. After dissolution, it is injected into 150-250 mL of reactor filled with the specific catalyst. If the molar ratio of the iodine is less than 0.2, the yield of C ₂ F ₅ I is reduced, and if it exceeds 2, there is a problem that the generation of impurities is increased.

While injecting tetrafluoroethylene (TFE) at 20 to 100 mL / min into the reactor filled with the iodine fluoride iodine solution in which the iodine is dissolved and the specific catalyst in a three step process, while maintaining the reaction temperature at 75 to 85 ° C. To perform. When the injection rate of the tetrafluoroethylene (TFE) is less than 20 mL / min, the release of iodine and iodine fluoride gas together with the reaction product increases, which leads to an increase in clogging due to crystallized iodine and ultimately decreases productivity. In case of exceeding 100 mL / min, the contact time is short and the conversion rate is low. In the course of condensation of the final product, the product does not condense and the product is discharged together with the unreacted TFE to give pentafluoroethyl iodide ( The yield of C ₂ F ₅ I) is reduced, which is undesirable.

The condenser maintained at -20 ~ -30 ℃ after removing the impurities generated by the reaction in a four-step process, and removes a small amount of hydrofluoric acid, unremoved iodine fluoride, iodine and impurities through an adsorption tower filled with alumina and silica The pentafluoroethyl iodide (C ₂ F ₅ I) is separated and purified by condensation of the product. At this time, the clogging phenomenon caused by iodine is suppressed by the removal of the impurities, thereby solving the process problem.

If the condensation temperature is less than -30 ℃, the use of a refrigerant to maintain the cryogenic temperature raises the problem of cost increase, if the temperature exceeds -20 ℃ to maintain the temperature because the loss caused by the increase in the vapor pressure of the product good.

As described above, by using a specific metal fluoride catalyst according to the present invention or a composite metal catalyst in which a certain amount of fluoride and antimony oxide catalysts are additionally mixed with the metal fluoride catalyst, the hexafluoroethane (C ₂ F ₆ ) It is possible to produce a high yield of pentafluoroethyl iodide (C ₂ F ₅ I) without producing by-products such as these and is efficient.

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Examples, but the present invention is not limited to the Preparation Examples and Examples.

Catalyst Preparation Example

Catalyst Preparation Example 1 AlF ₃ Preparation of (A)

As shown in the following scheme 2, an AlF ₃ (A) catalyst was prepared by a fluorination reaction in which γ-Al ₂ O ₃ was reacted with hydrofluoric acid (HF).

Al ₂ O ₃ + 6HF → 2AlF ₃ + 3H ₂ O

The AlF ₃ was prepared by a conventional fluorination reaction of γ-alumina (Moon Dong-ju, Ph.D. thesis, Korea University).

20 g of γ-Al ₂ O ₃ (purity 99.9%, Engelhard Co., Ltd.) was pretreated by raising the temperature of the reactor from room temperature to 400 ° C. under a nitrogen atmosphere of 10 ° C./min. Then, the fluorinated reaction of γ-Al ₂ O ₃ was performed while supplying hydrofluoric acid (HF) (purity 99.8%, Ulsan Chemical Co., Ltd.) and nitrogen gas at a molar ratio of 1: 4 to the reactor maintained at 200 ° C. Thereafter, the reactor was heated up at a constant rate up to 450 ° C., and the mole fraction of nitrogen was reduced to finally supply only hydrofluoric acid (HF) to the reactor, and then maintained at a constant temperature at 450 ° C. for 15 to 300 minutes to fluoride the metal oxide. AlF ₃ (A) was produced by the reaction. At this time, unreacted hydrofluoric acid (HF) flowing out of the reactor was removed using an aqueous sodium hydroxide solution.

Catalyst Preparation Example 2 AlF ₃ (B)

As shown in Scheme 3 below, AlCl ₃ · H ₂ O was reacted with hydrofluoric anhydride (HF) to prepare an AlF ₃ (B) catalyst.

_{AlCl 3 · H 2 O + 3HF} → AlF 3 + 3HCl + 6H 2 O

0.5 M (121.2 g) of AlCl ₃ · H ₂ O (Aldrich) was added to 250 mL of distilled water, and 50% HF (Ulsan Chemical Co., Ltd.) was slowly added thereto while stirring with an excess of about 20%, and left at room temperature for 2 hours. The aqueous solution was dried at 140 ° C. for 12 hours to prepare 0.5 M (42 g) of AlF ₃ (B).

The AlF ₃ (B) prepared above was filled with 30 g of AlF ₃ (B) in an Inconel-600 reactor (30 cm in length, 1 inch in diameter) for activation. The packed catalyst was pretreated for 1 hour at 420 ° C. under 200 mL / min helium gas atmosphere, and then fluorinated alumina by supplying hydrofluoric acid at a flow rate of 400 mL / min for 2 hours at 200 ° C. After maintaining for 1 hour at 400 ℃ to prepare an AlF ₃ (B) catalyst.

Catalyst Preparation Example 3: MgF ₂ (C) Preparation

As shown in Reactor 4, MgF ₂ catalyst was prepared by fluorination reaction in which MgO was reacted with hydrofluoric acid (HF).

MgO + 2HF → MgF ₂ + H ₂ O

The fluorination reaction was carried out in the same manner as in Preparation Example 1 except that MgO (purity 99.9%, Aldrich) instead of Al ₂ O ₃ MgF ₂ (C) Catalyst was prepared.

Catalyst Preparation Example 4 CrF ₃ (D) Preparation

As shown in the following scheme 5, a CrF ₃ catalyst was prepared by a fluorination reaction in which Cr ₂ O ₃ was reacted with hydrofluoric acid (HF).

Cr ₂ O ₃ + 6HF → 2CrF ₃ + 3H ₂ O

The fluorination reaction was performed in the same manner as in Preparation Example 1 except that Cr ₂ O ₃ (purity 99%, Aldrich) was used instead of Al ₂ O ₃ to prepare a CrF ₃ (D) catalyst.

The surface area, pore volume and pore size of the BET (Brunaur Emett Teller) of the catalysts prepared in Preparation Examples 1 to 4 were measured using a N ₂ physical adsorption analyzer (AUTOSORB-1, Quantachrome Co.), and the results were measured. It is shown in Table 1 below.

division catalyst BET area (㎡ / g) Pore volume (cc / g) Pore size (Å) Catalyst Preparation Example 1 AlF ₃ (A) 35.13 0.181 117.66 Catalyst Preparation Example 2 AlF ₃ (B) 34.25 0.247 284.07 Catalyst Preparation Example 3 MgF ₂ (C) 32.85 0.278 265.97 Catalyst Preparation Example 4 CrF ₃ (D) 6.28 0.027 173.21

As shown in Table 1, the catalysts prepared in Examples 1 to 4 of the catalyst prepared according to the present invention had a BET area of 6.28 to 35.13 m 2 / g, a pore volume of 0.027 to 0.278 cc / g, and a pore size of 117.66 to 284.07. It was confirmed that it has a range. In particular, the surface area of the AlF ₃ and MgF ₂ catalyst was found to be higher than the conventional catalysts.

Example: Pentafluoroethyl Iodide (C ₂ F ₅ I) manufacture

Example 1

Next, pentafluoroethyl iodide (C ₂ F ₅ I) was prepared using the apparatus shown in FIG.

The reactor was evacuated for 30 minutes using a vacuum pump in a 0.25 L reactor 110 composed of a temperature controller, a stirrer, and a foaming machine for TFE injection, followed by purging with oxygen after removing oxygen. . After repeating the process three times, inert gas nitrogen was supplied to the reactor for 30 minutes at a rate of 20 mL / min to completely remove oxygen remaining. Thereafter, 16 g of iodine, 68 g of iodine fluoride, and 110 trifluoride of aluminum trifluoride (AlF ₃ ) obtained in the catalyst preparation example 1 in the dissolution tank 211. 0.42 g was added. In the dissolution tank 211, the mixture was refluxed at 90 ° C. for 2 hours for complete dissolution of iodine and then transferred to the reactor 110 maintained at 80 ° C. Next, TFE was flowed at a rate of 40 mL / min, and the reaction was performed by maintaining the reaction temperature at 80 ° C. The gas produced by the reaction was passed through the condenser 213 maintained at 20 ℃ to recover the unreacted iodine fluoride, and passed through the alumina adsorption tower 310 and the silica gel adsorption tower 311, a trace amount of iodine fluoride uncondensed The traces of hydrofluoric acid and water produced during the reaction were removed. At this time, adsorption was performed at room temperature. The reaction product was condensed in the condenser 410 where the gas passed through the adsorption column was maintained at −25 ° C., and the unreacted TFE was recycled to the reactor together with the pure TFE.

The reaction product was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 96.1%, TFE 2.2%, C ₃ F ₇ I 1.2%, and other byproducts 0.5%. Each was generated. At this time, the C ₃ F ₇ I produced in a small amount is a by-product, but may not necessarily be separated and purified because it may be used as a reactant to increase the purity of C ₂ F ₅ I in the telomerization process for preparing a fluorine-based water repellent.

Example 2

The reaction was carried out in the same manner as in Example 1, except that 0.31 g of magnesium fluoride (MgF ₂ ) was used instead of the aluminum trifluoride (AlF ₃ ) catalyst.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 95.4%, TFE 1.8%, C ₃ F ₇ I 1.9%, and others. By-products were each produced 0.9%.

Example 3

The reaction was carried out in the same manner as in Example 1 except that 0.54 g of chromium fluoride (CrF ₃ ) was used instead of the aluminum trifluoride (AlF ₃ ) catalyst.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 94%, TFE 3.8%, C ₃ F ₇ I 0.6%, and the like. By-products were produced 1.6% each.

Example 4

In the same manner as in Example 1, instead of the aluminum trifluoride (AlF ₃ ) catalyst aluminum trifluoride (AlF ₃ ) and antimony trifluoride (SbF ₃ ) mixed to a 1: 5 molar ratio mixed metal fluoride catalyst The reaction was carried out in the same manner as in Example 1 except that it was added to the reactor. In this case, a total of 11 g TFE was used for 6 hours, and a product produced 27 g.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not produced, C ₂ F ₅ I 99%, TFE 0.6%, C ₃ F ₇ I 0.1%, and others. By-products were produced 0.3% each.

Example 5

In the same manner as in Example 1, but instead of the aluminum trifluoride (AlF ₃ ) catalyst aluminum trifluoride (AlF ₃ ) and antimony trifluoride (SbF ₃ ) mixed in a 1: 2 molar ratio mixed metal fluoride catalyst The reaction was carried out in the same manner as in Example 1 except that it was added to the reactor.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 97.5%, TFE 1.2%, C ₃ F ₇ I 0.9%, and others. By-products were produced 0.5% each.

Example 6

In the same manner as in Example 1, instead of the aluminum trifluoride (AlF ₃ ) catalyst magnesium fluoride (MgF ₂ ) and antimony trifluoride (SbF ₃ ) mixed in a 1: 5 molar ratio of a mixed metal fluoride-based catalyst reactor The reaction was carried out in the same manner as in Example 1 except that it was added to.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not produced, C ₂ F ₅ I 98.5%, TFE 0.9%, C ₃ F ₇ I 0.3%, and others. By-products were produced 0.3% each.

Example 7

In the same manner as in Example 1, instead of the aluminum trifluoride (AlF ₃ ) catalyst, magnesium fluoride (MgF ₂ ) and antimony trifluoride (SbF ₃ ) mixed in a 1: 2 molar ratio of a mixed metal fluoride catalyst based on the reactor The reaction was carried out in the same manner as in Example 1 except that it was added to.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 97%, TFE 2.0%, C ₃ F ₇ I 0.4%, and others. By-products were produced 0.6% each.

Example 8

In the same manner as in Example 1, instead of the aluminum trifluoride (AlF ₃ ) catalyst, aluminum trifluoride, magnesium fluoride (MgF ₂ ) and antimony trifluoride (SbF ₃ ) mixed in a 1: 1: 5 molar ratio mixed The reaction was carried out in the same manner as in Example 1 except that a metal fluoride catalyst was added to the reactor.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 98.1%, TFE 0.7%, C ₃ F ₇ I 0.3%, and others. By-products were each produced 0.9%.

Example 9

In the same manner as in Example 1, instead of the aluminum trifluoride (AlF ₃ ) catalyst chromium trifluoride (CrF ₃ ) and antimony trifluoride (SbF ₃ ) mixed in a 1: 5 molar ratio mixed metal fluoride catalyst The reaction was carried out in the same manner as in Example 1 except that it was added to the reactor.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 95.5%, TFE 2.8%, C ₃ F ₇ I 0.2%, and others. Byproducts were produced 1.5% each.

Comparative Example 1

The reaction was carried out in the same manner as in Example 1, but using 1.01 g of antimony trifluoride (SbF ₃ ) instead of the aluminum trifluoride (AlF ₃ ) catalyst.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, C ₂ F _{6 as an} impurity 0.2%, C ₂ F ₅ I 97%, TFE 2.6%, and other byproducts 0.2%, respectively.

Comparative Example 2

In the same manner as in Example 1, but instead of the aluminum trifluoride (AlF ₃ ) catalyst aluminum trifluoride (AlF ₃ ) and antimony trifluoride (SbF ₃ ) mixed to a 1.5: 1 molar ratio of a mixed metal fluoride catalyst The reaction was carried out in the same manner as in Example 1 except that it was added to the reactor.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not produced, C ₂ F ₅ I 92%, TFE 3.5%, C ₃ F ₇ I 0.4%, and others. By-products were produced 4.1% each.

Comparative Example 3

In the same manner as in Example 1, but instead of the aluminum trifluoride (AlF ₃ ) catalyst aluminum trifluoride (AlF ₃ ) and antimony trifluoride (SbF ₃ ) mixed in a 2: 1 molar ratio of a mixed metal fluoride catalyst The reaction was carried out in the same manner as in Example 1 except that it was added to the reactor. At this time, the PTFE-based polymer material generated by the TFE polymerization was by-produced, and the polymer compound initially produced under the influence of aluminum fluoride blocked the tube through which the reactor flowed to increase the reaction pressure to promote the polymerization of TFE.

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 45%, TFE 5.0%, C ₃ F ₇ I 4.5%, and others. By-products were generated 45.5% each.

Comparative Example 4

In the same manner as in Example 1, instead of the aluminum trifluoride (AlF ₃ ) catalyst, magnesium fluoride (MgF ₂ ) and antimony trifluoride (SbF ₃ ) mixed so that the 2: 1 molar ratio of a mixed metal fluoride catalyst The reaction was carried out in the same manner as in Example 1 except that it was added to. At this time, the PTFE-based polymer material generated by the TFE polymerization is by-produced, and it is believed that the polymer compound initially produced under the influence of aluminum fluoride increases the reaction pressure by blocking the tube through which the reactor flows, thereby promoting the polymerization of TFE. .

The reaction product produced by the reaction was analyzed by gas chromatography. As a result, impurities C ₂ F ₆ were not formed, C ₂ F ₅ I 38%, TFE 6.2%, C ₃ F ₇ I 0.6%, and others. By-products were generated 55.2% each.

The results of gas chromatography analysis of reaction catalysts and reaction products used in Examples 1 to 9 and Comparative Examples 1 to 4 are summarized in Table 2 below.

division Catalyst (g) Product (%) SbF ₃ AlF ₃ MgF ₃ CrF ₃ C ₂ F ₅ I TFE C ₂ F ₆ C ₃ F ₇ I Other ^* Example One - 0.42 - - 96.1 2.2 - 1.2 0.5 2 - - 0.31 - 95.4 1.8 - 1.9 0.9 3 - - - 0.54 94 3.8 - 0.6 1.6 4 1.01 0.08 - - 99 0.6 - 0.1 0.3 5 1.01 0.21 - - 97.5 1.2 - 0.8 0.5 6 1.01 - 0.06 - 98.5 0.9 - 0.3 0.3 7 1.01 - 0.16 - 97 2.0 - 0.6 0.4 8 1.01 0.08 0.06 - 98.1 0.7 - 0.3 0.9 9 1.01 - - 0.11 95 2.8 - 0.2 1.5 Comparative example One 1.01 - - - 97 2.6 0.2 - 0.2 2 1.01 0.63 - - 92 3.5 - 0.4 4.1 3 1.01 0.84 - - 45 5 - 4.5 45.5 4 1.01 - 0.62 - 38 6.2 - 0.6 55.2 Etc^*: Unidentified polymer.

As shown in Table 2, Examples 1 to 9 using specific metal fluoride catalysts according to the present invention or composite metal catalysts in which a fluoride and antimony oxide catalyst and a metal fluoride catalyst were mixed at a constant ratio were compared to Comparative Examples 1 to 4, respectively. In comparison, the yield of C ₂ F ₅ I was improved and it was confirmed that no high-boiling C ₂ F ₆ was formed as an impurity.

In Comparative Examples 2 to 4, the mixing ratio of the fluorinated and antimony oxide catalyst and the metal fluoride catalyst was mixed within the range of the present invention, and there was no formation of C ₂ F ₆ , but the polymerization of TFE was promoted and The polymer material was produced and the yield of the target C ₂ F ₅ I tended to decrease relatively.

As described above, half of the unreacted tetrafluoroethylene (TFE) is circulated on a specific metal fluoride catalyst according to the present invention or a composite metal catalyst in which a fluoride and antimony oxide catalyst and the metal fluoride catalyst are mixed in a constant ratio. By carrying out the reaction in a continuous process, it is possible to produce a high yield of pentafluoroethyl iodide (C ₂ F ₅ I) while suppressing by-products such as high boiling point hexafluoroethane (C ₂ F ₆ ). The pentafluoroethyl iodide produced is a reaction raw material or a low energy surface functional material in the field of fluorine-based water repellents, surfactants, foaming agents, and third generation CFCs, metals, ceramics, fibers. It can be applied to various fields such as various polymer materials such as leather, paper and paint.

Claims (8)

In a method for preparing pentafluoroethyl iodide (C ₂ F ₅ I) by reacting iodine (I ₂ ), iodine fluoride (IF ₅ ) and tetrafluoroethylene (TFE) under a reaction catalyst, Pentafluoroethyl iodide characterized in that the reaction catalyst is carried out using at least one metal fluoride catalyst selected from aluminum trifluoride (AlF ₃ ), chromium fluoride (CrF ₃ ) and magnesium fluoride (MgF ₂ ) C ₂ F ₅ I) method of preparation. In the method for producing pentafluoroethyl iodide (C ₂ F ₅ I) by reacting iodine (I ₂ ), iodine fluoride (IF ₅ ) and tetrafluoroethylene (TFE) under a reaction catalyst, At least one metal fluoride catalyst selected from aluminum trifluoride (AlF ₃ ), chromium fluoride (CrF ₃ ) and magnesium fluoride (MgF ₂ ) as the reaction catalyst, At least one antimony catalyst selected from antimony fluoride and antimony oxide 1: A process for preparing pentafluoroethyl iodide (C ₂ F ₅ I), which is carried out using a mixed metal catalyst mixed in a 1 to 5 molar ratio. The pentafluoro of claim 2, wherein the fluorinated and antimony oxide catalyst is at least one selected from antimony trifluoride (SbF ₃ ), antimony fluoride (SbF ₅ ), and antimony oxide (Sb ₂ O ₃ ). Process for the preparation of ethyl iodide (C ₂ F ₅ I). The pentafluoroethyl iodide (C ₂ ) according to claim 1, wherein the iodine fluoride (IF ₅ ) and iodine (I ₂ ) are injected into the reactor in a ratio of 1: 0.2 to 2 molar. F ₅ I) method of preparation. The method for preparing pentafluoroethyl iodide (C ₂ F ₅ I) according to claim 1 or 2, wherein the tetrafluoroethylene (TFE) is added at a rate of 20 to 100 mL / min. . The method for preparing pentafluoroethyl iodide (C ₂ F ₅ I) according to claim 1 or 2, wherein the reaction is performed at 80 to 100 ° C. The pentafluoroethyl urea according to claim 1 or 2, wherein the reaction is carried out in a semi-continuous manner in which unreacted tetrafluoroethylene (TFE) is introduced into the reactor. Process for the preparation of Odide (C ₂ F ₅ I). The method of claim 1 or 2, wherein the pentafluoroethyl iodide (C ₂ F ₅ I) is A reaction unit including a temperature controller 111, a mass controller 112, a stirrer and a semi-continuous reactor 110 having a foamer for adding tetrafluoroethylene; Iodine fluoride input tank 210, dissolution tank 211 and circulating pump 212 for dissolving iodine in iodine fluoride, condenser 213 for iodine fluoride for recovery of vaporized unreacted raw materials and the collection tank ( Supply and recovery of iodine and iodine fluoride composed of 214); An adsorption unit including an alumina adsorption tower 310 for removing unreacted gaseous material and a silica gel adsorption tower 311 for removing a small amount of moisture not removed from the alumina adsorption tower; And Product recovery unit consisting of a condenser 410 and a recovery tank 411 for recovering the product Method for producing pentafluoroethyl iodide (C ₂ F ₅ I) characterized in that it is prepared using a device comprising a.

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