The method of obtaining fluorinated hydrocarbons

 

(57) Abstract:

Describes how to obtain a fluorinated hydrocarbon interaction chlorinated hydrocarbon with hydrogen fluoride in the presence of a catalyst based on at least one of tin compounds and additives, heating the specified liquid-phase mixture, and the allocation of mixtures containing fluorinated hydrocarbon, wherein the liquid mixture contains at least one chlorinated hydrocarbon selected from the group corresponding to the formula R1R2C = CR3R4and CR5R6R7R8where at least one of R1R4in R1R2C = CR3R4and at least one of R5R8in CR5R6R7R8represents chlorine, the rest of R1-R4in R1R2C = CR3R4and R5R8in CR5R6R7R8are the same or different and are selected from the group consisting of H, F, Cl, Br and C(y)Z(2y+1)where Z is the same or different and is selected from the group consisting of H, F, Cl or Br, y is an integer from 1 to 6, in use as an additive, at least one additive selected from g, ostoja from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ti, B, Al, Si, Ge, Sn, Rb, R9selected from the group consisting of C1-C6of alkyl, x is from 1 to 4, when the molar ratio of the additive to the catalyst equal to 0.25 to 1, and the obtained fluorinated hydrocarbons essentially free of oligomeric and polymeric compounds. The technical result - obtaining fluorinated hydrocarbons chlorinated hydrocarbons while minimizing the formation of oligomeric and polymeric by-products. 8 C.p. f-crystals, 1 Il.

The scope of the invention

The present invention relates to a method of selective obtaining high yield of fluorinated hydrocarbons and more specifically to such methods that include contacting a chlorinated hydrocarbon with hydrogen fluoride in the liquid phase, in the presence of a tin catalyst and additives alkoxide of a metal or nonmetal.

The background to the invention

In U.S. patent N 4968850 Franklin et al. disclosed is a method of obtaining fluorocarbons (HFCs) and chlorofluorocarbons (HCFCsthrough the interaction of unsaturated chloropetalum (HCC) with hydrogen fluoride (HF) in the liquid phase in the presence of a tin catalyst and f is which increases the activity of the used catalyst and/or improved stability additives, and in which is formed a small amount of oligomers and selectivity toward valuable products high. However, although demonstrated a decrease in the number of the formed oligomers, the examples illustrate the way in which the selectivity in the formation of higher fluorinated hydrocarbons is reduced or changed only slightly.

In U.S. patent N 4766258 Komatsu et al. disclosed is a method of obtaining HFCsand HCFCsthrough interaction HCCswith HF in the presence of a tin catalyst and an additive selected from compounds containing oxygen or nitrogen. In most cases, the examples showed that the supplements reduce the activity of the tin catalyst and thereby adversely affect the efficiency of this process in obtaining sufficient outputs of higher fluorinated hydrocarbons.

In Japanese Kokai publication N SHO 62 [1987]-246528 Komatsu et al. describes how to obtain HFCsand HCFCscharacterized by the implementation of the interaction of a hydrogen-containing halogenated hydrocarbons with HF in the liquid phase in the presence of the reaction product of the compound acting as a base in HF, a tin catalyst and HF. Komatsu of polluter and tin tetrachloride and sodium fluoride. The reaction was carried out as batch process at a temperature of from 90 to 98oC and a pressure of 980 kPa for three hours and a specified molar ratio of reagents was 1,1,2-trichloroethane(16,7): HF (33,3): SnCl4(1,0):NaF(1,0). In this example, the selected mixture of products contained 32% (weight. ) 1,2-dichloro-1-floridana (HCFC-141), 1% 1-chloro-1,2-differetn (HCFC-142a) and 67% recovered starting compound (1,1,2-trichloroethane) in the absence of detected dimers. Based on this single example, it is assumed that all operations described in this publication Kokai additives used in the method, in other respects identical to the U.S. patent N 4766258 issued by the same authors, provide the same advantages.

Currently interested HFCsand they can be used either individually or in mixtures with other substances as refrigerants, blowing agents, rocket fuels, cleaning agents, or as intermediates for other fluorinated hydrocarbons. HFCssuch as 1,1-differetn (HFC-152a) and 1,1,1-trifluoroethane (HFC-143a), are acceptable from the point of view of environmental protection substitutes of chlorofluorocarbons (CFCs), because they do not have Izvestia HCCsand HF through halogenoalkane in the presence of metal find wide industrial application. The whole process is that in HCC carbon-chlorine burst, and in their place are formed of carbon-fluorine. The metal affects the catalytic ability, leading to a more productive exchange process, requiring milder reaction conditions. Similarly, using a liquid-phase or gas-phase processes have a broad range of HFCsand HCFCs. Fluorinated hydrocarbons of wide application, such as 1,1,1,2-Tetrafluoroethane (HFC-134a, HFC-143a, 1-chloro-1,1-differetn (HCFC-142b), HFC-152a and 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), in the art get in bringing together a suitable chlorinated hydrocarbons with HF in the presence of various salts oksidirovannykh metals. Found that salts of compounds of metals, such as tin (IV), titanium (IV), antimony (III) and antimony (V), lead to a productive process halogenoalkane. The use of such processes with the use of these metal compounds and HF to obtain HFCsand HCFCsprovides various degrees of success in this field of technology. Rather often than never, upon receipt of higher fluorinated hydrocarbons atakje low output due to the formation of undesirable oligomeric and polymeric by-products.

By-products such conventional processes include a range of oligomeric and polymeric compounds; low molecular weight halogenated dimers and oligomers to halogenated polymers with higher molecular weight, taking the form of oils, resins and dark carbonaceous solids. These by-products typically have a higher molecular weight, for example predominantly 50000, with a standard distribution of weights from 2,000 to 75,000 range of polymeric halogenated hydrocarbons with branched chain and an average molecular weight which may contain metal elements acquired from the catalyst and other additives, if present. Such compounds with a higher molecular weight can be formed by the polymerization of dimers, trimers and oligomers of lower molecular weight or with a halogenated carbon-containing reagents and their fluorinated adducts. These by-products are harmful to the process of halogenoalkane because they harm the activity of the catalyst, reduce the volume of the reactor and reduce the yield of fluorinated hydrocarbon, and also cause problems and costs associated with such problems as separation, about what bauleni compounds, which are inert with respect to fluoridation, but reactive with compounds of tin (IV) HF leads to catalysts of tin with properties different from the parent compounds. The ideal Supplement for the exchange process is the one which minimizes the formation of by-products while increasing the reaction rate and selectivity towards the desired product.

Conventional methods of obtaining fluorinated hydrocarbons, such as HFC-152a and HFC-143a, chlorinated hydrocarbons, such as harstyle and 1,1-dichlorethylene unacceptable because of the formation of a large number of resins. The method according to the present invention solves problems associated with conventional methods by reducing the speed of resins.

Brief description of the invention

In the present invention proposes a method of selective receipt of fluorinated hydrocarbons chlorinated hydrocarbons while minimizing the formation of oligomeric and polymeric by-products. The method includes: providing a liquid-phase mixture containing chlorinated hydrocarbons, HF, at least one tin catalyst and at least one compound from the group consisting of alkoxides metally reaction can be loaded into the reaction vessel in any order, but it is preferable to first load in a container of tin catalyst, HF, alkoxide of a metal or nonmetal. The temperature of this mixture is maintained within the range from about 20 to 160oC during the period of reaction. During this period, add chlorinated hydrocarbons and reaction conditions is becoming fluorinated hydrocarbon.

The method according to the present invention may be implemented as a periodic process. It is preferable to engage in a continuous process by continuously adding HF, tin alkoxide catalyst and metal or non-metal in the reaction vessel together with chlorinated hydrocarbons, accompanied by destruction of fluorinated hydrocarbons and HCl. The analysis of this process shows a high and selective transformation of chlorinated hydrocarbons in fluorinated hydrocarbons while minimizing the quantities of oligomeric and polymeric by-products.

Description of drawings

The drawing shows a diagram of a continuous process used to obtain fluorinated hydrocarbons.

Detailed description of the invention

The present invention is a method to izbiratelnomu education products. The method includes: providing a liquid mixture containing HF, at least one chlorinated hydrocarbon, at least one tin catalyst and at least one compound selected from the group consisting of an alkoxide of metal and non-metal; heating the mixture and isolation of fluorinated hydrocarbon, obtained essentially without oligomeric and polymeric compounds, i.e. in amounts less than about 0.5 g per 100 g podawanego chlorinated hydrocarbon.

It was found that the method provides high efficiency when used by an alkoxide of a metal or a nonmetal is tetraalkyllead, such as triethylborane (B(OC2H5)3), or tetrachlorozincate, such as tetraethylorthosilicate (Si(OC2H5)4). As shown in example 1 of this specification, the use of triethylborane in the way, including the synthesis of HFC-152a from chlorethylene, provides increased 3.3 times the molar selectivity of HFC-152a/HCFC-151a and decrease of 2.3 times the number of educated resins in comparison with the conventional method, which is not used additive Borat. In example 4, this illustrates that the use of tetraethylorthosilicate in the way, including the synthesis of HFC-143a from 1 ti of resins in comparison with the conventional method, which is not used additive silicate. These processes also discovered that when using alkoxides of metals and nonmetals such benefits increase when fluorinated hydrocarbons receive as co-products by submitting a mixture of chlorinated hydrocarbons. The synergistic effect of the increased selectivity of the product and increased output (reduced education resins), along with the ability to use a wide range of additives alkoxides of metals or nonmetals, provide great advantages.

Tin catalyst for use in the method according to the present invention can be selected from the family of halides of tin, oxyhalogenation tin and organic tin compounds. Of these three families preferred are the halides of tin, and tin halides most preferred is tin chloride (IV) (SnCl4, tin tetrachloride). Other acceptable halides of tin (IV) include SnBr4and the connection SnCl3F, SnCl2F2, SnClF3and SnF4; such compounds that are formed when SnCl4promotes interaction with HF. From oxyhalogenation tin are suitable sedimentable a connection, in which the tin atom is linked to from one to four carbon atoms. Suitable for use in the method are organic compounds of tin, such as tin-tetramethyl (Sn(CH3)4), tin-oxidiation (OSn(C2H5)2and tin-dichlorodimethyl (SnCl2(CH3)2).

Supplements alkoxides of metals and non-metals for use according to the present invention have the General empirical formula M(OR)x; where R represents a linear or branched C1-C6alkyl, x is 1-4 and M is chosen from the family of metals and nonmetals in the Periodic Table of elements. Metals according to the present invention include light metals of groups IA and IIA, with the exception of hydrogen (where the group belongs to a particular group standard Periodic Table of elements, such as shown on the inside front cover "Lang''s Handbook of Chemistry", Fourteenth edition, John A. Dean, Editor, McGraw Hill, Inc., 1992), transition metals of groups IB, IIB, IIIB, IVB, VB, VIB and VIIIB and postperiod metals of groups IIIA, IVA, VA and VIA, with the exception of phosphorus. Such additives alkoxides of metals and nonmetals can be used in the method according to the present invention individually or in any composition of the sludge is mi are B and Si.

Preferred postpartum metals are boron and silicon. The preferred boron alkoxides according to the present invention are boron-containing organic compounds, such as trialkylborane B(OR)3where each R independently represents a linear or branched C1-C6alkyl. Preferred silicone alkoxides according to the present invention are orthosilicate of tetraalkyl Si(OR)4where each R independently represents a linear or branched C1-C6alkyl. R preferably is the same and represents a C1-C4alkyl, most preferably C1-C2alkyl.

The amount of boron alkoxide for use in the method according to the present invention is typically in the range from 0.05 to 0.6 moles per mole of the used tin catalyst. Preferably, the method is used from 0.05 to 0.5 moles of a boron alkoxide per mole of tin catalyst. The amount of silicon alkoxide for use in the method according to the present invention is typically in the range from 0.05 to 0.4 moles per mole of the used tin kawanago catalyst. Typically, the amount of additive alkoxide of metal or non-metal used in the method according to the present invention is in the range from 0.1/x-2.0/x moles of alkoxide of metal or non-metal per mole of tin catalyst, where x represents the number alkoxide groups (-OR) on the metal atom, i.e., M(OR)x. Preferably, the method is used from 0.5/x 1,2/x moles of alkoxide of metal or non-metal per mole of tin catalyst, where x represents the number alkoxide groups per atom of metal or non-metal (M). Typically, the molar ratio of additive to tin catalyst will not exceed 1 to 1 and will not be less than, approximately, of 0.025 to 1.

Chlorinated hydrocarbons suitable for the present invention are selected from the main collections R1R2C=CR3R4and CR5R6R7R8where at least one of R1-R4in R1R2C= CR3R4and at least one of R5-R8in CR5R6R7R8represents chlorine and where are the rest of the groups R1-R8independently or together, consist of H, F, Cl, Br or C(y)Z(2y+1)where Z, independently or together, represent H, F, Cl or Br, and y is one who etenia, are chlorethylene (CH2=CHCl), 1,1-dichlorethylene (CH2=CCl2), tetrachlorethylene (CCl2=CCl2), 1,1,1-trichloroethane (CCl3-CH3), 1,1,2-trichloroethane (CHCl2-CH2Cl) and 1,1,1,3,3,3-hexachloropropane (CCl3-CH2-Cl3).

One aspect of the invention the method is performed in periodic mode. Can be used any suitable autoclave, such as a Mini-reactor with a capacity of 450 cm3Parrseries 4560, made of Hastelloy C. As a rule, autoclave equipped with a turbine impeller for mixing the liquid contents of the autoclave, the hole wall to enter or drainage of liquids from the autoclave through a method using a syringe or cannula with valve hole for entry or removal of gaseous or liquid substances enclosed in the jacket tube reflux condenser with a diameter of 0.25 inch (6.35 mm) from the valve outlet hole in the upper part, and an external heating jacket. Periodic method according to the present invention typically can be performed in any desired scale. Equipment and associated supply piping, piping for flowing streams, and associated components must be manufactured the region of fluoridation, include stainless steel and alloys with a high Nickel content, such as copper-Nickel alloys Monel, Nickel-based alloys Hastelloyand chromium-Nickel alloys Inconel.

Dry autoclave is transferred into a drying oven and autoclave load the required amount of at least one tin catalyst and at least one compound selected from the group consisting of alkoxides of metals and nonmetals. These materials are required to download in the autoclave, using any procedure that will minimize contact with the present in the air of moisture, i.e., the standard procedure of working with a drying Cabinet.

The autoclave is sealed and removed from the drying chamber. Then the opening of the autoclave is attached to the vacuum pump and cool the lower portion of the liquid nitrogen and produce pumping out of the autoclave. By establishing a vacuum in the autoclave potentially harmful air is removed, thus providing a more efficient transfer of gaseous HF. Transfer HF facilitates liquid nitrogen due to the condensation of gaseous HF in the autoclave. Then the autoclave is attached to the container with HF, and the required number of HF tolerated due to the vacuum in the car the clave, can vary in a wide range of effective work. The number of substances used in the method according to the present invention, is typically in the range of from about 0.1 to at least about 10 (kg filed chlorinated hydrocarbon/h)/kg tin catalyst, typically about 0.2 (kg filed chlorinated hydrocarbon/h)/kg tin catalyst, when tin catalyst contains SnCl4. The original number download with HF tin catalyst is generally in the range of from about 5 to at least about 35 wt.%, for example SnCl4in HF, usually from about 10 to about 20 wt.% tin catalyst in HF.

After entering the starting substances in a sealed autoclave, the autoclave is then disconnected from the vacuum pump and sources of HF and allowed to warm to ambient temperature. Then the autoclave is heated to a temperature of from about 20 to about 160oC, preferably from about 50 to about 95oC, and maintain the total pressure in the autoclave from about 60 kPa to about 3000 kPa, preferably about 350 kPa. The pressure in the autoclave can be maintained by using any suitable means, such as R. the speed, which varies as a function of the amount of HF and tin catalyst in an autoclave, for example, adding a chlorinated hydrocarbon with a speed of from about 10 to about 100 sccm (standard cm3/min) (from about 0.01 to about 0.5 kg/h/kg of catalyst). Gaseous effluent stream leaving the reflux condenser, which is connected through a fluid autoclave, accumulate through the condensation and control. The composition of the discharge flow control through the use of built-in installation of a gas chromatograph (GC). After stopping the addition of the chlorinated hydrocarbon from the autoclave to remove excess liquid and gaseous substances by purging with nitrogen. Then remove solid contents of the autoclave, pour water and filtered. The filtrate is washed with 10% aqueous hydrochloric acid, water and dried in a vacuum oven until constant weight. After that, analyze the composition of the dry weight to determine the amount of the formed resin.

Although you can use the above periodic way, from the industry point of view is especially desirable to use a continuous way. Now, with regard to Fig. 1, it shows a diagram of a continuous method polucheniya reverse flow from about 2 to about 20 under a pressure of from about 340 to about 3000 kPa and a temperature of from about 50 to about 150oC. Pre-defined amount (as previously described for periodic way) HF, at least one tin catalyst and at least one compound selected from the group consisting of alkoxides of metals and nonmetals, add in the reactor 1. The contents of the reactor 1 is stirred by using a two-bladed stirrer 3 with downward directed Sipper effect, heat and cook until phlegmy at the required working temperature/pressure. When necessary working conditions are set, start a continuous feed to the reactor HF and chlorethylene through one or more supply lines 4. The gas exits from the reactor 1 and is transferred to irrigated column 2 through one or more supply lines 5. The gas stream exiting the irrigated column 2, as a rule, consists essentially of HFC-152a and HCl. Return line 6 to the liquid attached to the bottom of irrigated column 2. On line 6 you are returned to the reactor 1 storable intermediate products, such as HCFC-151a and 1,1-dichloroethane, and any HF. The gas stream exiting the reactor 1 or irrigated columns 2, you can clean any acceptable manner, such as by using conventional two-stage distillation (Fig. 1 not poisonality products and HF, that retrieve and, if necessary, recycle to the reactor 1.

Like the above-described periodic method of manufacturing equipment continuous method and associated pipelines to supply and piping for flowing streams, as well as any control units shall be constructed of materials resistant to HF and HCl.

Although in the above description, and special attention is paid to obtaining a flow of the product in which the main component was a separate fluorinated hydrocarbon, the method according to the present invention may also operate in a mode in which get together with other required connections. For example, when using the method according to the present invention can be obtained from chlorethylene one HFC-152a or HFC-152a in conjunction with one or more of 1,1-dichloro-1-floridana (HCFC-141b), HCFC-142b, HFC-143a, along with others, for example chlorinated hydrocarbons, such as 1,1-dichlorethylene. Together the resulting product can be removed and used as a useful mixture, or divided into its individual components.

The following examples are given to further illustrate the present invention without its limitations, as defined in the attached the mi. For example, chlorethylene received from the company Fluka Incorporated, Ronkonkoma, new York, HF received from the company Air Products (Allentown, Pennsylvania).

Examples

Example 1.

The addition of borate upon receipt of HFC-152a from chlorethylene

The tin tetrachloride (SnCl4, 37,5 g, 0,144 mole) is added in a Mini-reactor with a capacity of 450 cm3Parrseries 4560 alloy Hastelloy Cplaced in a drying Cabinet. The upper part of the reactor, which is equipped with a tubular column with a diameter of 0.25 inch (6.35 mm), and then attached to the reactor, remote from the drying chamber, and is connected with the vacuum pipe from stainless steel. The base of the reactor is immersed in liquid nitrogen and under vacuum in the reactor is transferred HF (150 g, and 7.5 mol). Remove the cooling bath of liquid nitrogen and the reactor through the opening in the bulkhead by means of a syringe loaded triethylborane (B(OC2H5)3, 6,35 g, 0,0435 mol). Using external heating temperature of the reactor was raised to until internal temperature is about 25oC, and begin circulation of cooling water (3,7oC) through the condenser. Around the reactor is placed the heating jacket and adjusted the temperature inside the reactor to 50o3/min, 8,210-7m3/sec) and methane as an internal standard (9,5 standard cm3/min, 1,610-7m3/sec). Gaseous effluent stream control every hour for 16.5 hours add chlorethylene. The measurement showed that the molar yield of HFC-152a, based on the submitted chlorethylene, was 86%. Using the built-in gas chromatograph (GC) found that the amount of HFC-152a in stemming the flow was 98%. The ratio of HFC-152a/HCFC-151a (averaged on the data from the 4th to the 16th hour of the experiment), the measured GC, amounted to 131. In the end, in the reactor establish atmospheric pressure for removal of volatile substances (HF and organic compounds). The additional removal of volatiles provided by purging with nitrogen. Solids remaining in the autoclave is immersed in water and filtered on a membrane filter Teflon. The filtrate is washed with 10% HCl and then with water and dried in a vacuum oven until constant weight. The number formed during the experience resins averaged 1,00 g per 100 g of submitted chlorethylene.

Example 2.

The addition of silicate upon receipt of HFC-152a from chlorethylene

Apparatus, procedure and materials used in this when the differences of the procedure of its implementation from example 1.

As additives used tetraethylorthosilicate (Si(OC2H5)4that being 9.61 g, 0,0461 mol) was added together with SnCl4. The molar yield of HFC-152a, based on the submitted chlorethylene was 83%. Measurements using the built-in gas chromatograph (GC) showed that the amount of HFC-152a was 98% discharge flow. The molar ratio of HFC-152a/HCFC-151a (averaged on the data from the 4th to the 16th hour of the experiment) measured by GC, was 53. After 16.5 hours, the reaction was stopped and treated as in example 1. The number formed in this experience resins, on average, 0.19 g per 100 g of submitted chlorethylene.

Comparative example 1.

Receive HFC-152a from chlorethylene without the use of additives

Apparatus, procedure and materials used in this comparative example were identical to those described in example 1. The following are the results obtained in this example, and differences of procedure of its implementation from example 1.

In this reaction was not used any additives of alkoxides. According to the measurements of the built-in GC the amount of HFC-152a was 98% discharge flow. The molar ratio of HFC-152a/HCFC-151a (averaged on the data from the 4th to the 17th hour exp is e 1. The number formed in this experience resins averaged 2,30 g per 100 g of submitted chlorethylene.

Example 3.

The addition of silicate upon receipt of HFC-143a from 1,1-dichlorethylene

Apparatus, procedure and materials used in this example were identical to those described in example 1. The following are the results obtained in this example, and differences of procedure of its implementation from example 1.

Tetraethylorthosilicate (Si(OC2H5)4, 6,00 g 0,029 mole) is loaded into the reactor with SnCl4. Used chlorinated hydrocarbon was 1,1-dichlorethylene (CH2= CCl2, 15,4 standard cm3/min, 2,610-7m3/s) methane (10,3 standard cm3/min, 1,710-7m3/s), used as internal standard. The number of gaseous discharge flow was monitored every hour during 16,0 hours adding 1,1-dichlorethylene. The absolute yields of HFC-143a, HCFC-142b, and 1,1,1-trichloroethane was 88.7%, 11,5% and 0.1%, respectively, based on the submitted 1,1-dichlorethylene. The molar ratio of HFC-143a/HCFC-142b (averaged data from the 5th to the 16th hour of the experiment) measured by GC, was 7.7. After 16 hours the reaction is stopped and obrabecim the comparative example 2.

Receive HFC-143a from 1,1-dichlorethylene without the use of additives

Apparatus, procedure and materials used in this comparative example were identical to those described in example 3. The following are the results obtained in this example, and differences of procedure of its implementation from example 3.

No additives of alkoxides was not used. The number of gaseous discharge flow was measured every hour for 16 hours adding 1,1-dichlorethylene. Absolute molar outputs HFC-143a, HCFC-142b, and 1,1,1-trichloroethane was 59,3%, 36.7% and 0.7%, respectively based on the submitted 1,1-dichlorethylene. The molar ratio of HFC-143a/HCFC-142b (averaged data from the 5th to the 16th hour of the experiment) measured by GC, was 1.6. After 16 hours the reaction is stopped and treated as in example 1. No measurable amount of the formed resin was not found, but the orange color of the filter membranes indicated the formation of oligomers or low molecular weight.

Example 4.

Receive HFC-143a from 1,1,1-trichloroethane using supplements silicate

Apparatus, procedure and materials used in this example were identical to those described in example 1. ="ptx2">

Tetraethylorthosilicate (Si(OC2H5)4, 6,00 g 0,029 mole) is loaded into the reactor with SnCl4. Used chlorinated hydrocarbon was 1,1,1-trichloroethane (CCl3-CH3, 12,3 standard cm3/min, 2,110-7m3/s) methane (10,3 standard cm3/min, 1,710-7m3/s), used as internal standard. The number of gaseous discharge flow was measured every hour for 14 hours added 1,1,1-trichloroethane. Absolute molar outputs HFC-143a, HCFC-142b, and 1,1,1-trichloroethane was 89,6%, 15.3% and 0.0 percent, respectively, based on the submitted 1,1,1-trichloroethane. The molar ratio of HFC-143a/HCFC-142b (averaged data from the 5th to the 14th hour of the experiment), the measured GC, amounted to 5.9. After 14 hours, the reaction stopped and treated as in example 1. No measurable amount of the resulting resins were found.

Comparative example 3.

Receive HFC-143a from 1,1,1-trichloroethane without using supplements

Apparatus, procedure and materials used in this example were identical to those described in example 4. The following are the results obtained in this example, and differences of procedure of its implementation from example 4.

Example 5.

Joint production of HFC-143a (1,1-dichlorethylene) HFC-152a (chloroethylene) using an additive silicate

Apparatus, procedure and materials used in this example were identical to those described in example 1. The following are the results obtained in this example, and differences of procedure of its implementation from example 1.

Tetraethylorthosilicate (Si(OC2H5)4, 6,00 g 0,029 mole) is loaded into the reactor with SnCl4. Two chlorinated hydrocarbons were jointly filed in the reactor: 1,1-dichlorethylene (CH2= CCl2, 10,5 standard cm3/min, 1,7510-7m3/sec) and chlorethylene (25,3 standard cm3/min, 4,2310-7m3/s) methane (10,3 standard cm3/min, 1,710-7m3/s), used as internal scalene chlorinated hydrocarbon. Molar outputs HFC-143a (based on 1,1-dichlorethylene), HCFC-142b (based on 1,1-dichlorethylene) and HFC-152a (based chlorethylene) was 79,4%, 15.9% and 100%, respectively. The molar ratio of HFC-143a/HCFC-142b (averaged data from the 5th to the 13th hour of the experiment) measured by GC, were 5.0, and the ratio of HFC-152a/HCFC-151a measured by GC, was 51. After 13 hours the reaction is stopped and treated as in example 1. The number formed in this experience resins averaged 0.05 g per 100 g filed a chlorinated hydrocarbon.

1. A method of obtaining a fluorinated hydrocarbon interaction chlorinated hydrocarbon with hydrogen fluoride in the presence of a catalyst based on at least one of tin compounds and additives, heating the specified liquid-phase mixture, and the allocation of mixtures containing fluorinated hydrocarbon, wherein the liquid mixture contains at least one chlorinated hydrocarbon selected from the group corresponding to the formula

R1R2C = CR3R4and CR5R6R7R8,

where at least one of R1- R4in R1R2C = CR3R4and at least one of R5- R8in CR5R6R7<5- R8in CR5R6R7R8are the same or different and are selected from the group consisting of H, F, Cl, Br and C(y)Z(2y+1)where Z is the same or different and is selected from the group consisting of H, F, Cl or Br, y is an integer from 1 to 6, in use as an additive, at least one additive selected from the group consisting of alkoxides represented by the formula

M(OR9)x,

where M is chosen from the group of elements consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ti, B, Al, Si, Ge, Sn and Pb;

R9selected from the group consisting of C1- C6-alkyl;

x is from 1 to 4,

when the molar ratio of the additive to the catalyst equal to 0.25 to 1, and the obtained fluorinated hydrocarbons essentially free of oligomeric and polymeric compounds.

2. The method according to p. 1, wherein the chlorinated hydrocarbon selected from the group consisting of CH2= CHCl, CH2= CCl2, CCl2= CCl2, CCl3-CH3, CHCl2-CH2Cl and CCl3-CH2-CCl3; the catalyst is selected from the group consisting of SnCl4, SnCl3F, SnCl2F2, SnClF3and SnF4; additive selected from the group consisting of alkoxides of boron and silicon is the present of C1- C6-alkyl.

3. The method according to p. 1, wherein the chlorinated hydrocarbon selected from the group consisting of

CH2= CHCl, CH2= CCl2, CCl2=CCl2, CCl3-CH3, CHCl2-CH2Cl, CCl3-CH2-CCl3, CHClF-CH3, CClF2-CH3, CFCl2-CH3, CHCl2-CCl2F, CHCl2-CClF2, CHCl2-CF3, CHClF-CClF2, CHClF-CClH2, CHCl2-CFH2, CHF2-CClH2, CHFCl-CFH2, CCl3-CH2-CCl2F, CCl3-CH2-CClF2, CCl3-CH2-CF3, CCl2F-CH2-CF3,

CClF2-CH2-CF3, CCl2F-CH2-CCl2F, CCl2F-CH2-CClF2, CClF2-CH2-CClF2. 4. The method according to p. 1, wherein the fluorinated hydrocarbon is at least one compound selected from the group consisting of

CHF2-CH3, ClCHF-CH3, CF3-CH3, CClF2-CH3, CCl2F-CH3, CHCl2-CCl2F, CHCl2-CClF2, CHClF-CCl2F, CHCl2-CF3, CHClF-CClH2, CHCl2-CFH2, CHF2-CClH2,

CHFCl-CFH2, CHF2-CFH2, CCl3-CH2-CCl2F, CCl3-CH2-CClF2, CCl3-CHF-CH2-CCl2F, CCl2F-CH2-CClF2,

CClF2-CH2-CClF2.

5. The method according to p. 1, characterized in that the catalyst comprises at least one compound from the group consisting of SnCl4, SnBr4, SnCl3F, SnCl2F2, SnClF3, SnF4, SnCl2O, SnF2O, SnClFO, Sn(CH3)4, OSn(C2H5)2, SnCl2(CH3)2. 6. The method according to p. 1, characterized in that the heating is carried out at a temperature in the range of 20 - 160oC.

7. The method according to p. 6, characterized in that the heating is carried out at a temperature in the range of 50 - 95oC.

8. The method according to p. 1, characterized in that the catalyst is 5 to 35% by weight hydrogen fluoride.

9. The method according to p. 1, characterized in that it is continuous.

Priority from 05.01.96 installed because the materials of the first application 60/009,668 contain the above features of the invention.

 

Same patents:

The invention relates to a method for producing 1,1-diflorasone, which is used as a component of the refrigerant, propellant, the steam generator foams and raw material for production of fluorine-containing monomers

The invention relates to the field of chemical technology of fluorine compounds

The invention relates to the production of tetrafluoroethylene - raw material for a wide class of fluoropolymers

The invention relates to technology for deep cleaning perfluorinated aliphatic and cyclic compounds, such as performability, perpendicular, perfluorooctane, and perfluorinated polyethers, from chemically active fluorine-containing impurities

The invention relates to the technology for performancenow, in particular freon, OCTAFLUOROPROPANE, deceptibot used as insulators, refrigerants, components in the foaming and other compositions

The invention relates to a method of hydroperiodide of farolatino

The invention relates to the production of ozone-safe refrigerants ethane series, in particular 1,1,1,2-Tetrafluoroethane, which is obtained by fluorination 1,1,1-triptorelin fluoride of a metal of variable valence in the presence of a diluent

The invention relates to methods of allocation Pentafluoroethane (also known as HFC-125), particularly to the method of separation of HFC-125 from a mixture comprising HFC-125 and at least CHLOROPENTAFLUOROETHANE (also known as CFC-115) as a component (that is, the crude mixture contains at least HFC-125 and CFC-115)

The invention relates to a method for 1,1,2,2-Tetrafluoroethane, which consists in the catalytic hydrogenation of tetrafluoroethylene at elevated temperatures using as a catalyst the aluminum-palladium catalyst

The invention relates to the synthesis of perfluorocarbons General formula CnF2n+2where n = 1 to 4

The invention relates to a method for producing 1,1-diflorasone, which is used as a component of the refrigerant, propellant, the steam generator foams and raw material for production of fluorine-containing monomers

The invention relates to the field of chemical technology of fluorine compounds
The invention relates to the field of chemical technology of obtaining hexaferrite and its mono - and disubstituted derivatives of General formula C6F4XY, where X=F, Cl, H, CF3, CCl3, CN, COR, Y=F, CN, H, CF3, CCl3, COR, Cl, which are used as intermediates in the synthesis of dyes, pharmaceuticals and monomers for the synthesis of heat-resistant polymeric materials

The invention relates to a method of obtaining deformity

The invention relates to a method for producing 1,1,1,3,3-pentafluoropropane, which can be used as a substitute for CFC and HCFC used as the cooling medium (refrigerant), blowing agents or detergents, and especially as urethane hatebreeder tools

The invention relates to chemical technology perhalogenated, namely the method of production of mono - and dibromopropanol or their chlorinated analogues, which are used as intermediates in the synthesis of dyes, pharmaceuticals, monomers, etc

The invention relates to methods isomerization,1,2 trifter-1,2-dichloroethane (hereinafter designated as AA/ 1,1,1-Cryptor-2,2-dichloroethane (hereinafter designated as a/

The invention relates to the field of organic chemistry, in particular to a method for the chemical treatment of polychlorinated biphenyls, which until recently was used in electrotechnical products as an insulating and heat transfer materials

The invention relates to the process of obtaining 1,1,1-triptorelin and 1,1,1,2-Tetrafluoroethane, more specifically, to the process of obtaining 1,1,1-tryptophanate reaction of trichloroethylene with hydrogen fluoride and obtain 1,1,1,2-Tetrafluoroethane further fluoridation 1,1,1-tryptophanate

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to preparation of alkylaromatic intermediates including perfluorinated carbon atom utilized in production of agrochemically important active compounds. Intermediates simultaneously containing aniline function are obtained from homocyclic arylcarbamoyl fluoride including at least one perhalogenated carbon atom preferably bearing at least two halogen atoms capable of being replaced by fluorine atoms when in liquid-phase contact with hydrofluoric acid and water. During this reaction, molar ratio of hydrofluoric acid to arylcarbamoyl fluoride is maintained equal to 4, preferably to 5 and not higher than 11. Water is added to reaction mixture (at 10 to 90°C) when only one exchangeable halogen atom remains unreplaced. Arylcarbamoyl fluoride is obtained in situ by adding corresponding isocyanate to liquid hydrofluoric acid at temperature not exceeding 10°C. Process is carried out continuously in two reactors, the first one serving for halogen exchange reaction and the second for addition of water. Temperature 40°C is maintained until only one exchangeable halogen atom remains unreplaced.

EFFECT: increased yield and improved quality of desired product and economical characteristics.

9 cl, 4 ex

Up!