Process for the manufacture of halocarbons and selected...

Details Process for the manufacture of halocarbons and selected... Process for the manufacture of halocarbons and selected...

1998-01-28

2001-09-18

Siegel, Alan (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Halogen containing

C570S164000, C570S172000, C570S257000, C558S378000, C558S357000, C560S226000, C560S227000

Reexamination Certificate

active

06291730

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to the manufacture of halogenated alkanes using the catalytic reaction of haloalkanes with halogenated olefins, compounds produced thereby, azeotropic compositions which can be obtained upon fluorination of such compounds, and use of azeotropes in separation processes.
BACKGROUND
The catalyzed radical addition of haloalkanes to olefins is a well known reaction. Typically, however, when a haloalkane (e.g., AB, where A is a substituted carbon atom and B is a halogen other than fluorine) is added to an olefin (e.g., CH
2
═CHR) to form the saturated adduct (e.g., CH
2
ACHBR), the products (i.e., halogenated addition compounds) also include varying amounts of telomers (e.g., A(CH
2
CHR)
n
B, where n is equal to 2 or more). For example, Canadian Patent No. 2,70,533 discloses a process for the manufacture of CCl
3
CH
2
CCl
3
by reacting carbon tetrachloride with vinylidene chloride using copper catalysts in acetonitrile. The selectivity for CCl
3
CH
2
CCl
3
with respect to converted vinylidene chloride was 87%. It has been shown in the art that the major by-product is the C
5
telomer, CCl
3
(CH
2
CCl
2
)
2
Cl. Furthermore, since the catalyzed addition of haloalkanes to olefins is done in a homogeneous medium, separation of the catalyst from the product can present difficulties. This is especially so when it is desired to run the reaction in a continuous manner.
The halogenated adducts are useful intermediates for the production of fluoroalkanes, particularly, hydrofluoroalkanes. These latter compounds are useful as refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, gaseous dielectrics, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids. There is an interest in developing more efficient processes for the manufacture of hydrofluoroalkanes.
SUMMARY OF THE INVENTION
A liquid phase process is provided in accordance with this invention for producing halogenated alkane adducts of the formula CAR
1
R
2
CBR
3
R
4
wherein R
1
, R
2
, R
3
, and R
4
are each independently selected from the group consisting of H, Br, Cl, F, C
1
-C
6
alkyl, CN, CO
2
CH
3
, CH
2
Cl, and aryl (e.g., phenyl), provided that when either R
3
or R
4
is selected from the group consisting of C
3
-C
6
alkyl, CN, CO
2
CH
3
, CH
2
Cl, and aryl, then R
1
, R
2
, and the other of R
3
and R
4
are H, and when R
3
and R
4
are selected from the group consisting of Cl, F, CH
3
and C
2
H
5
, then R
1
and R
2
are H, and when either R
1
or R
2
and either R
3
or R
4
are selected from the group consisting of Cl, F, CH
3
and C
2
H
5
, then the other of R
1
and R
2
and the other of R
3
and R
4
are H; A is selected from the group consisting of CX
3
, CH
3−a
X
a
, C
n
H
(2n+1)−b
X
b
and CH
c
X
2−c
R, where R is C
n
H
(2n+1)−b
X
b
(e.g., CF
3
and CCl
2
CF
3
), each X is independently selected from the group consisting of Br, F, Cl and I, 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; and B is selected from the group consisting of Br, Cl and I; provided that (1) when A is CX
3
then only one of X is I, (2) when A is CH
3−a
X
a
, then each X is B and a is 2 when B is Br or Cl, and a is an integer from 0 to 2 when B is I, and (3) when A is C
n
H
(2n+1)−b
X
b
, then each X is independently selected from Cl and F, and B is I. The process comprises contacting a halogenated alkane of the formula AB (where A and B are as indicated above) with an olefin of the formula CR
1
R
2
═CR
3
R
4
(where R
1
, R
2
, R
3
and R
4
are as indicated above) 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 optionally (ii) a promoter selected from the group consisting of aromatic or aliphatic heterocyclic compounds which contain at least one carbon-nitrogen double bond in the heterocyclic ring.
This invention further provides a process for producing hydrofluoro-alkanes (e.g., CF
3
CH
2
CHF
2
). This process comprises (a) producing a halogenated alkane adduct (e.g., CCl
3
CH
2
CHCl
2
) by reacting AB (e.g., CCl
4
) and CR
1
R
2
═CR
3
R
4
(e.g., CH
2
═HCl) as indicated above (provided that R
1
, R
2
, R
3
and R
4
are independently selected from H, CH
3
, C
2
H
5
, Cl and F, B and X are Cl and at least one of AB and CR
1
R
2
═CR
3
R
4
contains hydrogen), and (b) reacting the adduct produced in (a) with HF.
This invention also provides a process for the purification of at least one compound 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
1
a
and CH
c
X
1
2−c
R
9
where R
9
is C
n
H
(2n+1)−b
X
1
b
, each X
1
and B
1
is independently selected from the group consisting of Cl and F, R
5
, R
6
, R
7
, and R
8
are each independently selected from the group consisting of H, Cl and F, and a, b, c and n are as defined above, provided that at least one of A
1
, R
5
, R
6
, R
7
, or R
8
comprises hydrogen. The purification process comprises (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 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).
New compounds provided in accordance with this invention 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.
New compositions produced by this invention include azeotropic compositions of CF
3
CH
2
CHF
2
with HF and azeotropic compositions of CF
3
CH
2
CClF
2
with HF. A composition comprising from about 44 to 84 mole percent HF and from about 56 to 16 mole percent CF
3
CH
2
CHF
2
is provided which, when the temperature is adjusted within the range of −50° C. to 130° C., exhibits a relative volatility of about 1 at a pressure within the range of 5.5 kPa to 3850 kPa. Also, a composition comprising from about 63.0 to 90.1 mole percent HF and from about 37.0 to 9.9 mole percent CF
3
CH
2
CClF
2
is provided which, when the temperature is adjusted within the range of −40° C. to 110° C., exhibits a relative volatility of about 1 at a pressure within the range of about 9.3 kPa to 2194 kPa.


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