Process for the manufacture of halocarbons and selected compounds and azeotropes with HF

Abstract

A liquid phase process is disclosed for producing halogenated alkane adducts of the formula CAR 1 R 2 CBR 3 R 4 (where A, B, R 1 , R 2 , R 3 , and R 4 are as defined in the specification) which involves contacting a corresponding halogenated alkane, AB, with a corresponding olefin, CR 1 R 2 ═CR 3 R 4 in a dinitrile or cyclic carbonate ester solvent which divides the reaction mixture into two liquid phases and in the presence of a catalyst system containing (i) at least one catalyst selected from monovalent and divalent copper; and optionally (ii) a promoter selected from aromatic or aliphatic heterocyclic compounds which contain at least one carbon-nitrogen double bond in the heterocyclic ring. When hydrochlorofluorocarbons are formed, the chlorine content may be reduced by reacting the hydrochlorofluorocarbons with HF. New compounds disclosed include CF 3 CF 2 CCl 2 CH 2 CCl 3 , CF 3 CCl 2 CH 2 CH 2 Cl and CF 3 CCl 2 CH 2 CHClF. These compounds are useful as intermediates for producing hydrofluorocarbons. Azeotropes of CClF 2 CH 2 CF 3 with HF and azeotropes of CF 3 CH 2 CHF 2 with HF are also disclosed; as are process for producing such azeotropes. A process for purification of certain hydrofluorocarbons and/or chloro-precursors thereof from mixtures of such compounds with HF is also disclosed.

1 - 12 . (canceled) 
     
     
         13 . A composition comprising:
 (a) from about 44 to 84 mole percent HF; and   (b) from about 56 to 16 mole percent CF 3 CH 2 CHF 2 ; said composition exhibiting a relative volatility of about 1 at a pressure within the range of 5.5 kPa to 3850 kPa when the temperature is adjusted within the range of −50° C. to 130° C.   
     
     
         14 . The azeotrope of  claim 13  produced by reacting CCl 4  with CH 2 ═CHCl to produce CCl 3 CH 2 CHCl 2  and reacting said CCI 3 CH 2 CHCl 2  with HF. 
     
     
         15 - 17 . (canceled) 
     
     
         18 . A process for the purification of CF 3 CH 2 CHF 2  from a mixture comprising HF and CF 3 CH 2 CHF 2  comprising:
 (a) subjecting the mixture to a distillation step in which a composition enriched in either (i) HF or (ii) CF 3 CH 2 CHF 2  is removed as a first distillate with the bottoms being enriched in the other of said components (i) or (ii);   (b) subjecting said first distillate to an additional distillation conducted at a different pressure in which the component enriched as bottoms in (a) is removed as a second distillate with the bottoms of the additional distillation enriched in the component enriched in the first distillate; and   (c) recovering CF 3 CH 2 CHF 2  essentially free of HF as bottoms from either the distillation of (a) or the distillation of (b).   
     
     
         19 . The process of  claim 18  wherein CF 3 CH 2 CHF 2  is purified from its HF azeotrope. 
     
     
         20 . The process of  claim 19  wherein CF 3 CH 2 CHF 2 , is purified from its binary azeotrope with HF. 
     
     
         21 . A composition consisting essentially of:
 (a) Hydrogen fluoride; and   (b) CF 3 CH 2 CHF 2  in an amount effective to form an azeotropic combination with hydrogen fluoride.   
     
     
         22 . The azeotrope of  claim 21  produced by reacting CCl 4  with the CH 2 ═CHCl in a dinitrile or cyclic carbonate ester solvent which divides the reaction mixture into two liquid phases, and in the presence of a catalyst system containing (i) at least one catalyst selected from the group consisting of monovalent and divalent copper and (ii) a promoter selected from aromatic and aliphatic heterocyclic compounds which contain at least one carbon-nitrogen double bond in the heterocyclic ring, to produce CCl 3 CH 2 CHCl 2 , and reacting said CCl 3 CH 2 CHCl 2  with HF. 
     
     
         23 . A process for the purification of at least one compound other than CF 3 CH 2 CHF 2  of the formula CA 1 R 5 R 6 CB 1 R 7 R 8  from a mixture comprising HF and said at least one compound, wherein
 A 1  is selected from the group consisting of CH 3-a X a   1  a and CH c X 2-c   1 R 9  where R 9  is C n H (2n+1)-b X b   1 , a is an integer from 0 to 3, n is an integer from 1 to 6, b is an integer from 1 to 2n+1 and c is an integer from 0 to 1;   each X 1  and B 1  is independently selected from the group consisting of Cl and F, and   R 5 , R 6 , R 7 , and R 8  are each independently selected from the group consisting of H, Cl and F, provided that at least one of A 1 , R 5 , R 6 , R 7 , or R 8  comprises hydrogen, comprising:   (a) subjecting the mixture of HF and said at least one compound to a distillation step in which a composition enriched in either (i) HF or (ii) said at least one compound is removed as a first distillate with the bottoms being enriched in the other of said components (i) or (ii);   (b) subjecting said first distillate to an additional distillation conducted at a different pressure in which the component enriched as bottoms in (a) is removed as a second distillate with the bottoms of the additional distillation enriched in the component enriched in the first distillate; and   (c) recovering at least one compound other than CF 3 CH 2 CHF 2  of the formula CA 1 R 5 R 6 CB 1  R 7 R 8  essentially free of HF as bottoms from either the distillation of (a) or the distillation of (b).   
     
     
         24 . The process of  claim 23  wherein a compound of said formula other than CF 3 CH 2 CHF 2  is purified from its HF azeotrope. 
     
     
         25 . The process of  claim 24  wherein a compound selected from the group consisting of CF 3 CH 2 CF 3 , CF 3 CH 2 CClF 2 , CHCl 2 CH 2 CF 3 , CHClFCH 2 CClF 2 , CHClFCH 2 CF 3  and CHF 2 CH 2 CClF 2  is purified from its binary azeotrope with HF. 
     
     
         26 . The process of  claim 23  wherein a compound selected from the group consisting of CF 3 CF 2 CCl 2 CH 2 CCl 3 , CF 3 CCl 2 CH 2 CH 2 Cl and CF 3 CCl 2 CH 2 CHClF is purified.