TW201319011A - Catalytical synthesis of hydrohalocarbons - Google Patents

Abstract

A process is disclosed for producing addition compound CF3CCl2CH2CClXR, wherein X = H, F, Cl or Br, and R = H or a perhalogenated alkyl group, provided that X and R are not both H. The process involves a liquid phase reaction of 1, 1, 1-trichlorotrifluoroethane with CH2=CXR in the presence of an addition catalyst.

Description

Catalytic Synthesis of Hydrohalocarbides

The present invention is generally directed to a catalytic addition reaction of 1,1,1-trichlorotrifluoroethane (CF ₃ CCl ₃ , CFC-113a) with a monohalogen olefin.

Halogenated alkanes, such as CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons), have been used in a wide range of applications including push sprays, refrigerants, detergents, thermoplastics and thermoset foams. Expanding agent, heat transfer medium, gas dielectric, fire extinguishing agent and fire suppressant, power cycle working fluid, polymerization medium, particle removal fluid, carrier fluid, polishing abrasive and displacement desiccant. They can also be used as intermediates for more highly fluorinated compounds such as HFCs (hydrofluorocarbons) and HFOs (hydrofluoroolefins). HFCs have replaced CFCs and HCFCs in many applications, including as refrigerants or foam expanders, due to concerns that certain CFC and HCFC products can cause ozone depletion. HFOs have been seen as an excellent alternative to traditional CFCs, HCFCs and HFCs because they do not destroy the ozone layer and have low global warming potentials (GWPs).

The present invention provides a liquid phase process to produce a product mixture comprising an addition compound CF ₃ CCl ₂ CH ₂ CClXR wherein X = H, F, Cl or Br, and R = H or a perhalogenated alkyl group, provided that It is X and R are not H at the same time. The process involves reacting 1,1,1-trichlorotrifluoroethane with CH ₂ =CXR in the presence of an addition catalyst.

The above general description and the following detailed description are merely illustrative and illustrative, and are not limiting of the invention as defined by the appended claims. Other features and advantages of one or more of the embodiments will be apparent from the detailed description and appended claims.

The terms "comprising," "comprising," "having," For example, a process, method, article, or device that comprises a series of elements is not necessarily limited to the elements, but may include other elements not specifically listed or inherent to the process, method, article, or device. In addition, unless expressly stated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, any of the following conditions satisfies condition A or B: A is true (or exists) and B is false (or non-existent), A is false (or non-existent) and B is true ( Or existing), and A and B are both true (or exist).

Also, "a" or "an" is used to describe the elements and components described herein. This is for convenience only and provides a general sense of the scope of the invention. This description should be understood to include one or at least one, and the singular also includes the plural unless the

Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although methods or materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are still described below. All publications, patent applications, patents, and other references herein are hereby incorporated by reference in their entirety in their entirety herein In the event of a conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting.

The present invention is a liquid phase process comprising reacting 1,1,1-trichlorotrifluoroethane with CH ₂ =CXR in the presence of an addition catalyst to form an addition compound comprising CF ₃ CCl ₂ CH ₂ CClXR A product mixture wherein X = H, F, Cl or Br, and R = H or a perhalogenated alkyl group, provided that X and R are not H at the same time.

The starting materials for the addition reaction in the present invention, i.e., 1,1,1-trichlorotrifluoroethane and CH ₂ =CXR, can be synthesized by a method known in the prior art.

The term "alkyl" as used herein, alone or in the compound word, for example, "perhalogenated alkyl", includes cyclic or acyclic and straight or branched alkyl groups such as methyl, ethyl, n-propyl. Base, isopropyl or its different isomers.

The term "perhalogenated alkyl" as used herein means a monoalkyl group wherein all of the hydrogen on the carbon atom is replaced by a halogen such as F, Cl, Br and I. Examples of perhalogenated alkyl groups include -CF ₃ and -CF ₂ CF ₃ .

The term "addition catalyst" as used herein means a catalyst which promotes the addition reaction.

In certain embodiments of the invention, X = H, F or Cl. In certain embodiments of the invention, CH ₂ =CXR is selected from the group consisting of CF ₃ CH=CH ₂ , CF ₃ CF ₂ CH=CH ₂ , CF ₃ CF=CH _{2 ,} and ClCH=CH ₂ .

Examples of the addition compound CF ₃ CCl ₂ CH ₂ CClXR in the present invention include CF ₃ CCl ₂ CH ₂ CHClCF ₃ , CF ₃ CCl ₂ CH ₂ CHClCF ₂ CF ₃ , CF ₃ CCl ₂ CH ₂ CFClCF ₃ and CF ₃ CCl ₂ CH ₂ CHCl ₂ .

In certain embodiments of the invention, CH ₂ =CXR is CF ₃ CH=CH ₂ and the resulting product CF ₃ CCl ₂ CH ₂ CClXR is CF ₃ CCl ₂ CH ₂ CHClCF ₃ .

In certain embodiments of the invention, CH ₂ =CXR is CF ₃ CF ₂ CH=CH ₂ and the resulting product CF ₃ CCl ₂ CH ₂ CClXR is CF ₃ CCl ₂ CH ₂ CHClCF ₂ CF ₃ .

In certain embodiments of the invention, CH ₂ =CXR is CF ₃ CF=CH ₂ and the resulting product CF ₃ CCl ₂ CH ₂ CClXR is CF ₃ CCl ₂ CH ₂ CFClCF ₃ .

In certain embodiments of the invention, CH ₂ =CXR is ClCH=CH ₂ and the resulting product CF ₃ CCl ₂ CH ₂ CClXR is CF ₃ CCl ₂ CH ₂ CHCl ₂ .

The addition reaction involving 1,1,1-trichlorotrifluoroethane and CH ₂ =CXR in the present invention is 1 mol of 1,1,1-trichlorotrifluoroethane per CH ₂ = CXR per mole. The stoichiometry is the benchmark. In practice, an excess of 1,1,1-trichlorotrifluoroethane can be used as needed. Typically, the molar ratio of 1,1,1-trichlorotrifluoroethane to CH ₂ =CXR is from about 1:1 to about 10:1.

The addition reaction process of the present invention can be carried out by placing 1,1,1-trichlorotrifluoroethane and a CH ₂ =CXR starting material and an addition catalyst into a reaction vessel, followed by heating and stirring the mixture. The process can be achieved by batch or continuous system.

At the end of the addition reaction, the desired product CF ₃ CCl ₂ CH ₂ CClXR can be recovered from the product mixture via conventional methods. In certain embodiments of the invention, the solid residue may be removed via decantation or filtration at the end of the addition reaction and the desired product may be purified or recovered via distillation of the resulting liquid product mixture.

In certain embodiments of the invention, the addition catalyst is a copper catalyst comprising copper chloride and a suitable reducing agent.

The copper chloride used in the present invention may be anhydrous (CuCl ₂ ) or hydrated (eg, CuCl ₂ ‧2H ₂ O). In certain embodiments of the invention, the amount of CuCl ₂ ‧2H ₂ O used in the addition reaction is the starting material (ie 1,1,1-trichlorotrifluoroethane and CH ₂ =CXR) The total weight is from about 0.5 to about 10 weight percent based on the basis. In certain embodiments of the invention, the amount of CuCl ₂ ‧2H ₂ O used in the addition reaction is from about 1 to about 5 weight percent based on the total weight of the starting material. In certain embodiments of the invention, the amount of CuCl ₂ used in the addition reaction is from about 0.4 to about 8 weight percent based on the total weight of the starting material. In certain embodiments of the invention, the amount of CuCl ₂ used in the addition reaction is from about 0.8 to about 4 weight percent based on the total weight of the starting material.

A suitable reducing agent in the present invention is a compound capable of reducing a Cu(II) compound (for example, CuCl ₂ ) to a Cu(I) compound (for example, CuCl) under the reaction conditions of the present invention, but not with the starting material 1,1, a reducing agent for the reaction of 1-trichlorotrifluoroethane and CH ₂ =CXR. In certain embodiments of the invention, a stoichiometric amount of reducing agent is used in the addition reaction of the present invention. In certain embodiments of the invention, more than a stoichiometric amount of reducing agent is used in the addition reaction of the present invention.

Examples of suitable reducing agents include hydrazine (N ₂ H ₄ ) and its derivatives (for example, monomethyl hydrazine (CH ₃ (NH) NH ₂ ) and 1,1-dimethyl hydrazine ((CH ₃ ) ₂ ) NNH ₂ ), etc.), disulfites (eg Na ₂ S ₂ O ₄ , K ₂ S ₂ O ₄ and (NH ₄ ) ₂ S ₂ O _{4 ,} etc.), copper (zero valence >, eg copper powder) ) and magnesium (zero price), and iron (zero price, such as iron powder). In certain embodiments of the invention, low molecular weight nitriles can also be used as a suitable reducing agent, such as acetonitrile and propionitrile.

Generally, a solvent is used with the copper catalyst in the present invention. In certain embodiments of the invention, the solvent is a low molecular weight nitrile such as acetonitrile and propionitrile. In certain embodiments of the invention, the solvent is a guanamine selected from the group consisting of dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone.

A total of the catalyst may be used together with the copper catalyst in the addition reaction of the present invention, as needed. Suitable cocatalysts are those which form a coordination compound with Cu(I) or Cu(II). Examples of co-catalysts suitable for the copper catalyst system include bis ([or oxime] oxazoline), 2,2-bipyridine and derivatives thereof.

When the addition reaction in the present invention is carried out in the presence of a copper catalyst, the temperature used is usually in the range of from about 60 ° C to about 240 ° C. In certain embodiments of the invention, the temperature used in such addition reactions is in the range of from about 130 °C to about 190 °C. The pressure used in the addition reaction is not critical. Usually, the addition reaction is carried out under autogenous pressure.

In certain embodiments of the invention, the addition catalyst is an iron catalyst comprising iron and ferric chloride.

The ferric chloride used in the present invention may be anhydrous (FeCl ₃ ) or a hydrated person (e.g., FeCl ₃ ‧6H ₂ O). The iron used in the present invention is a metal ion having a zero valence. In certain embodiments of the invention, iron powder is used in the addition reaction. Generally, the molar ratio of iron to ferric chloride used in the addition reaction of the present invention is from about 1:1 to about 10:1. In certain embodiments of the present invention, the total amount used in the addition reaction of iron and FeCl ₃ in 1,1,1-trichlorotrifluoroethane as a reference from about 5 to about 30 weight percent.

Generally, a total of catalysts can be used with the iron catalyst in the addition reaction of the present invention. In certain embodiments of the invention, the cocatalyst is an alkyl phosphate or an aryl phosphate such as triethyl phosphate, tributyl phosphate, diethyl phenyl phosphate, diethyl phosphate, dibutyl phosphate. , phenyl phosphate, butyl phosphate and the like. Typically, the iron catalyst has a molar ratio to the phosphate cocatalyst of from about 2:1 to about 20:1. In certain embodiments of the invention, the iron catalyst has a molar ratio to the phosphate cocatalyst of from about 5:1 to about 10:1.

A solvent may be used together with the iron catalyst in the present invention, as needed. In certain embodiments of the invention, the starting material 1,1,1-trichlorotrifluoroethane can also be used as a solvent. In certain embodiments of the invention, the solvent is an inert compound that does not react with other compounds or catalysts during the reaction. If such an inert solvent is used, it should be boiled at a temperature such that it can be derived from the unconverted starting material 1,1,1-trichlorotrifluoroethane and CH ₂ =CXR and the product CF ₃ CCl ₂ CH ₂ CClXR separation.

When the addition reaction of the present invention is carried out in the presence of an iron catalyst, the temperature used is usually in the range of from about 60 ° C to about 240 ° C. In certain embodiments of the invention, the temperature used in the addition reaction is in the range of from about 130 °C to about 190 °C. The pressure used in this addition reaction is not critical. Usually, the addition reaction is carried out under autogenous pressure.

The reactor, distillation column and its combined supply pipe, effluent pipe and related units used in the process of the embodiment of the invention may be constructed of corrosion-resistant materials. Typical materials of construction include glass and Teflon ^TM. Typical constituent materials also include stainless steel, especially austenitic type are known high nickel alloys (Monel ^TM e.g. nickel-copper alloy, Hastelloy ^TM nickel-based alloys and Inconel ^TM nickel-chromium alloy), and copper-clad steel.

The various aspects and embodiments described above are illustrative only and not limiting. After reading this specification, those skilled in the art will appreciate that other aspects and embodiments may be possible without departing from the scope of the invention.

Instance

The concepts described herein are further illustrated by the following examples, which do not limit the scope of the invention described in the claims.

Example 1

Example 1 illustrates the addition reaction of CF ₃ CCl ₃ with CF ₃ CH=CH ₂ in the presence of a copper catalyst to form the addition compound CF ₃ CCl ₂ CH ₂ CHClCF ₃ .

21.25 g of CuCl ₂ ‧2H ₂ O, 13.5 g of phenyl hydrazine, 75 ml of acetonitrile and 522 g (2.8 mol) of CF ₃ CCl _{3 were} charged into a 1 L Hastelloy ^TM autoclave. The autoclave was cooled, evacuated and fed with 120 g of CF ₃ CH=CH ₂ . The reaction mixture was heated to 185 ° C and maintained at this temperature for 20 hours. The product mixture was distilled to obtain 150 g of the desired product CF ₃ CCl ₂ CH ₂ CHClCF ₃ (bp 54 ° C / 100 mm Hg). The yield of CF ₃ CCl ₂ CH ₂ CHClCF ₃ was 42%.

Example 2

Example 2 illustrates the addition reaction of CF ₃ CCl ₃ with CF ₃ CH=CH ₂ in the presence of an iron catalyst to form the addition compound CF ₃ CCl ₂ CH ₂ CHClCF ₃ .

The tributyl 7 g of iron powder, 7 g phosphoric acid, 4 g FeCl ₃ and 140 g (0.75 mole) CF ₃ CCl ₃ was charged in a 400 ml Hastelloy ^TM tube. The tube was cooled, evacuated and fed _{48 g (0.5 mole) CF 3} CH = CH 2. The reaction mixture was heated to 150 ° C and maintained at this temperature for 3 hours. The product mixture is distilled to obtain a product _{CF 3 CCl 2 CH 2 CHClCF 3} (bp 54 ℃ / 100 mm Hg), 75% yield desired.

Example 3

Example 3 illustrates the addition reaction of CF ₃ CCl ₃ with CF ₃ CF ₂ CH=CH ₂ in the presence of an iron catalyst to form the addition compound CF ₃ CCl ₂ CH ₂ CHClCF ₂ CF ₃ .

The tributyl 6 g of iron powder, 6 g phosphoric acid, 3.5 g FeCl ₃ and 135 g (0.72 mole) CF ₃ CCl ₃ was charged in a 400 ml Hastelloy ^TM tube. The tube was cooled, evacuated and fed 45 g (0.3 _{mole) CF 3 CF 2 CH = CH} 2. The reaction mixture was heated to 150 ° C and maintained at this temperature for 3 hours. The product mixture was distilled to obtain the product CF (bp 70 ℃ / 90 mm Hg), yield _{63% 3 CCl 2 CH 2 CHClCF} 2 CF 3 desired.

Example 4

Example 4 illustrates the addition reaction of CF ₃ CCl ₃ with CF ₃ CF=CH ₂ in the presence of an iron catalyst to form the addition compound CF ₃ CCl ₂ CH ₂ CFClCF ₃ .

The tributyl 7 g of iron powder, 7 g phosphoric acid, 4 g FeCl ₃ and 112 g (0.6 mole) CF ₃ CCl ₃ was charged in a 400 ml Hastelloy ^TM tube. The tube was cooled, evacuated and fed 40.8 g (0.35 mole) CF ₃ CF = CH _2. The reaction mixture was heated to 150 ° C and maintained at this temperature for 3 hours. The product mixture was distilled to obtain the desired product CF ₃ CCl ₂ CH ₂ CFClCF ₃ (bp 57.9 ° C / 80 mm Hg) in a yield of 60%.

Example 5

Example 5 illustrates the addition reaction of CF ₃ CCl ₃ with vinyl chloride (ClCH=CH ₂ ) in the presence of a copper catalyst to form the addition compound CF ₃ CCl ₂ CH ₂ CHCl ₂ .

Shake a CF ₃ CCl ₃ (150 g, 0.80 mol), vinyl chloride (9.15 g, 0.147 mol), CuCl ₂ ‧2H ₂ O (3.3 g, 19) in a 200 ml stainless steel autoclave at 170 ° C to 175 ° C the mixture mmol), copper powder (1.1 g, 17.3 mmol) and CH ₃ CN (10 ml) of 17 hours. The conversion of vinyl chloride is complete. The product mixture was decanted from the solid residue and evaporated, and then the product mixture was distilled under reduced pressure to obtain 32.6 g of fractions which were boiled at (38 to 157 ° C) under a pressure of 30 mm Hg. GLC analysis showed that the fraction contained 88.35 _{mole% CF 3 CCl 2 CH 2 CHCl} 2, which represents the amount of vinyl chloride as a _{reference, CF 3 CCl 2 CH 2 CHCl} 2 in 78% yield. The above fraction was further distilled under atmospheric pressure to recover CF ₃ CCl ₂ CH ₂ CHCl _{2 having a} boiling point of 146 to 147 °C.

It should be noted that not all of the acts described in the general description or examples above are necessary, and one of the specific actions may not be necessary, and one or more other actions may be performed in addition to the actions described. Moreover, the order of the actions listed is not necessarily the order in which the steps are performed.

In the above description, the concept of a particular embodiment has been described. However, it will be understood by those skilled in the art that various modifications and changes can be made without departing from the scope of the invention. Accordingly, the description is to be considered as illustrative and not restrictive.

Benefits, other advantages, and solutions to problems with respect to particular embodiments have been described above. However, benefits, advantages, problem solutions, and any features that would make these benefits, advantages, or problem solutions more prominent are not to be construed as critical, essential, or essential features of any or all of the patent applications.

It is to be understood that some of the features of the various embodiments described herein may be combined in a separate embodiment for the purpose of clarity. Conversely, for the sake of brevity, many of the features described herein are in the same embodiment, which may also be provided separately or in any sub-combination. Further, the relevant numerical values described in the range include each and every value within the range.

Claims (17)

A liquid phase process comprising reacting 1,1,1-trichlorotrifluoroethane with CH ₂ =CXR in the presence of an addition catalyst to form a product mixture comprising an addition compound CF ₃ CCl ₂ CH ₂ CClXR, Wherein X = H, F, Cl or Br, and R = H or a perhalogenated alkyl group, provided that X and R are not H at the same time. The liquid phase process of claim 1, wherein the addition catalyst is a copper catalyst comprising copper chloride and a suitable reducing agent. The liquid phase process of claim 2, wherein the suitable reducing agent is selected from the group consisting of hydrazines and derivatives thereof, dithionite, copper, magnesium, and iron. The liquid phase process of claim 2, wherein a solvent is used together with the copper catalyst. The liquid phase process of claim 4, wherein the solvent is selected from the group consisting of acetonitrile, propionitrile, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. . The liquid phase process of claim 2 wherein the reaction is carried out at a temperature of from about 60 ° C to about 240 ° C. The liquid phase process of claim 1, wherein the addition catalyst is an iron catalyst comprising iron and ferric chloride. The liquid phase process of claim 7, wherein the ferric chloride is FeCl ₃ . The liquid phase process of claim 7, wherein a cocatalyst is used with the iron catalyst, and wherein the cocatalyst is an alkyl phosphate or an aryl phosphate. The liquid phase process of claim 9, wherein the cocatalyst is selected from the group consisting of triethyl phosphate, tributyl phosphate, diethyl phenyl phosphate, diethyl phosphate, dibutyl phosphate, and phenyl phosphate. And a group consisting of butyl phosphate. The liquid phase process of claim 7, wherein the reaction is carried out at a temperature of from about 60 ° C to about 240 ° C. The liquid phase process of claim 1, wherein the CH ₂ =CXR is CF ₃ CH=CH ₂ and the addition compound CF ₃ CCl ₂ CH ₂ CClXR is CF ₃ CCl ₂ CH ₂ CHClCF ₃ . The liquid phase process of claim 1, wherein the CH ₂ =CXR is CF ₃ CF ₂ CH=CH ₂ and the addition compound CF ₃ CCl ₂ CH ₂ CClXR is CF ₃ CCl ₂ CH ₂ CHClCF ₂ CF ₃ . The liquid phase process of claim 1, wherein the CH ₂ =CXR is CF ₃ CF=CH ₂ and the addition compound CF ₃ CCl ₂ CH ₂ CClXR is CF ₃ CCl ₂ CH ₂ CFClCF ₃ . The liquid phase process of claim 1, wherein the CH ₂ =CXR is ClCH=CH ₂ and the addition compound CF ₃ CCl ₂ CH ₂ CClXR is CF ₃ CCl ₂ CH ₂ CHCl ₂ . The liquid phase process of claim 1 further comprising recovering the addition compound CF ₃ CCl ₂ CH ₂ CClXR from the product mixture. The liquid phase process of claim 16, wherein the addition compound CF ₃ CCl ₂ CH ₂ CClXR is recovered from the product mixture via distillation.