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2,437,993
Patented Mar. 16, 1948
um'rao sures PATENT orncs
2.437.993
i
FLUORINATION OI" AOYOLIC OLEFINIC
‘
COMPOUNDS
Anthony F. ‘Banning. Woodstown, N. ‘1., and
Joseph D. Part, Wilmington, DeL, allignors to
E. L du Pont de Nemonrs a Com any, Wil
'
Del., a corporation of
IRE
No Drawing. Application July 12, 1946,
,
Serial No. seam
20 Claims. (01. zoo-ass)
This invention relates to the preparation oi’
?uorine compounds and more particularly to a
‘
2
in substantial yields from CF:CCl=CCla. Also, by
this method, we are able to readily prepare
method (or preparing such compounds by the
addition of fluorine to ole?nie compounds.
Organic ?uorine compounds have generally 5 in substantial yields without admixture with its
isomer. Still other compounds. obtainable with
been prepared by the substitution of chlorine or
“
di?iculty heretofore, maybe readily prepared by
bromine by ?uorine. Some organic ?uorine com
.this method.
pounds have also been prepared by the addition
The acyclic ole?nic compounds, which may be
of hydrogen ?uoride to an ole?ne and by the addi
tion of hydrogen chloride or hydrogen bromide
to a ?uorinated ole?ne. These processes gener
treated in accordance with out invention, are
those which consist of carbon and at least one of
the‘members of the group consisting of hydrogen,
chlorine, bromineand ?uorine, that is, they are
ally produce unsymmetrical ?uorinated com
pounds and do not produce certain types of valu
ole?nes, chloro ole?nes, chloro ?uoro oleilnes,
able compounds. For example, they will not, in
general, produce the type of compound which 15 ?uoro oie?nes, bromo ole?nes, bromo-?uoro ole
?nes, bromo-chloro ole?nes and bromo-chloro
would be produced theoretically by the addition
of two ?uorine atoms at the double bond of an
ole?nic compound. No satisfactory method has
?uoro ole?nes. Such terms are employed in their
ordinarily understood sense. For exam ple, an ‘
oie?n consists of carbon and hydrogen and con
been known heretofore for the addition of two
?uorine atoms to a double bond of an acyclic ole go tains one or more double bonds, 9. chloro ole?ne
is an ole?ne in which at least one hydrogen atom
?nic compound.
has been substituted by chlorine solely andpa
It is an object of the present invention to pro
chioro-?uoro ole?ne is an ole?ne in which at
vide a method for the preparation of orzanic
least one hydrogen atom has been replaced by
?uorine compounds by the addition of two ?uo
rine atoms to a double bond of an acyclic ole?nic as chlorine and at least one other hydrogen atom
has been replaced by ?uorine solely. Our inven
compound. Another object is to provide such a
method whereby compounds. not readily obtain
tion is particularly concerned with the treatment
of the acyclic ehloro-?uoro ole?nes and the
able by methods known heretofore, may be read
acyclic chloro ole?nes and especially those in
ily obtained in substantial yields. A further ob
ject is to provide a method for the preparation 3° which all of the hydrogens of the ole?ne have
been replaced by the halogen. The following are
of CFaCClFCChF. A still further object is to pro
representative of the‘vole?nic compounds which
vide a novel and improved method for making
may be treated‘ in accordance with our inven
CClzFCChF. Other objects are to advance the
tion:
‘
‘
art. Still other objects will appear hereinafter.
The above and other objects may be accom
plished in accordance with our invention which
comprises reacting an ole?nic compound with hy
drogen ?uoride and a metal oxide of the group
of C020: and MnOz in a closed reaction vessel
under conditions such that two atoms of ?uorine 40
are added to the double .bond of the ole?nic com
pound. We have found that, if an acyclic ole
?nic compound. which consists oi carbon and at
The ole?nic compound will be mixed with the
least one of the members of the group consisting
metal oxide in the proportion of at least 0.5,mole
of hydrogen, chlorine, bromine and ?uorine, is
oi the lole?nic compound for each mole 'of the
mixed with HF and one of C020: and MnOs at,
a temperature below 0° C., in such proportions
metal oxide. Generally. there will be from about
1 to about 4 moles of the ole?nic compound‘ to
that there is at least 0.5 mole of the ole?nic com
pound and at least 5 moles of HF to each mole of
each mole of the metal oxide and preferably in the
the metal oxide and causing the mixture to react 50 ratio of about2 to 1. Large excesses of the ole
in a closed vessel by causing the temperature to
?nic compound may be used, but without advan
rise above 0° 0.. two ?uorine atoms wili'be added
tage.
.‘
.
to the double bond of the ole?nic compound.
The hydrogen ?uoride will generally be used/‘in
By this method, we are able to prepare
the proportion of at least 5 moles toreach mole of
the metal oxide. Proportions‘ of ‘from about 5
CI'BCCIFCChF
sang,‘ a a.
3
2,437,093
moles to about 80 moles of HF for each mole of
metal oxide have been employed with satisfactory
results. Still larger excesses of HF may be em
ployed, if desired. Preferably, however, there
will be employed from about 10 to about 20 moles
of HF for each mole of metal oxide.
4
, subjected to anhydrous
fractional distillation to
separate substantially anhydrous H!‘ from the
organic material. Alternatively, the orBanic ma
terial and H2!‘ may be distilled out of the reaction
vessel and passed directly through scrubbers to
remove acidic constituents. followed by collection
The reaction is exothermic, but is quite slow
of the acid-free organic material in vessels cooled
at temperatures below 0' C. In the absence of
to the appropriate temperatures. The organic
cooling su?lcient to dissipate the heat as fast as
material may then be subjected to fractional dis
it is generated, the mixture will slowly warm up 10 tillation. The organic constituents may be sepa
with acceleration of the reaction until, at a
rated from each other and from 1-11" by fractional
temperature above 0°. (2., the reaction becomes
condensation. The metal compounds may be dis
quite vigorous. rapidly generating large amounts
carded or subjected to hydrolysis and dehydra
of heat. The temperature. at which the vigorous
tion to obtain metal oxides for reuse in the proc
exothermic reaction takes place, will depend upon 15 85S.
the particular oleilnic compound employed and
In order to more clearly illustrate our inven
the size and shape of the charge and of the re
tion preferred modes of carrying thmame into
action vessel. Generally. however, such temper
effect and the advantageous results to be obtained
ature is between 5" C. and 100’ C. and usually be
thereby, the following examples are given:
tween 5° C. and 60° C.
20
Example I
we have found that. in order to successfully
carry out the reaction with the production of
Into a steel autoclave, cooled to carbon-ice ace
substantial yields of the desired compounds, the
tone temperature, about -78° 0., were charged
metal oxide. hydrogen ?uoride and ole?nic mate
one mole of tetrachloroethylene. one mole ‘cobal
rial should be mixed together in the desired pro
tic oxide (C0103) and seven mole of anhydrous
portions at a temperature below 0° C. and the re
hydrogen ?uoride. The reaction mixture was al
action carried out in a closed reaction vessel.
lowed to come to room temperature and then di
Preferably, the reactants are mixed at a temper-_
gested at 200° C. for six hours with agitation.
ature below --14° 0. and particularly at a tem
After cooling to —30° C., the pressure was re
perature of from about —15‘ C. to about -'18° C., 80 leased and the reaction mass drowned in ice wa
so as to provide a margin of safety for the closing
ter and steam distilled. The resulting organic
of the vessel before the vigorous reaction starts.
layer was separated, dried over calcined calcium
The reaction vessel should be one which will
sulfate and fractionated. Fractionation yielded
withstand high pressures, as high autogenous
0.32 mole of CFCla-CFC]: with the following con
pressures are generated due to the high temper
stants: B. P. 92.8“ C. at 760 mm. of Hg; M. P. 265°
atures produced and the volatility of the react
0.; nn?‘ °-=1.41l5. As by-products. the com
ants. The reaction vessel may be constructed of
pounds CHCla-CClaF and CClzF-CCIF: were
any metal which does not readily react with ?uo
obtained.
rine or hydrogen ?uoride. Suitable metals are
Example 11
silver, nickel, Inconel. platinum and iron. The 40
body of the vessel may be made of other metals
One mole of CC12=CC1CF3 was placed in a steel
autoclave (cooled to carbon-ice acetone temper
ature, about -—78° C.) with 0.54 mole of manga
sel will usually be provided with means for agi
nese dioxide (M1102) and 10 moles of anhydrous
tation and a re?ux column. Usually. the reaction
vessel will be provided with means for cooling to 45 hydrogen ?uoride. After warming up to room
temperature. the autoclave was heated at 200° C.
the desired temperature for mixing so that the
for six hours with agitation. The reaction vessel
ingredients may be mixed directly in the reac
was then cooled to —30° 0., the pressure released
tion vessel.
and the reaction mass passed through water, then
After the ingredients are mixed and the vessel
is closed. the temperature of the mixture is 50 through calcined CaSO4 and condensed. This
condensate was then subjected to fractionation.
caused to rise above 0° C. to that at which the re
About 0.2 mole of CFsCClFCChF with the boiling
action proceeds rapidly. This may be accom
range of 73° to ‘735° C. at ‘160 mm. of Hg was ob
plished by removing the cooling from the vessel
tained. The major portion of the recovered ma
and allowing the heat. generated by the reaction,
I
to slowly raise the temperature the desired 55 terial was unreacted starting material
amount. If desired, the rise in temperature may
CFsCCl=CC12
be assisted by applying heat to the vessel. Due
Earample III
to the heat generated in the reaction, the tem
perature oi’ the mixture at the completion of the
reaction with 1 mole of CHCl=CCh, 0.4 mole
vigorous reaction will be substantially higher 60 of AMn‘Oz
and 8 moles of HF was carried out under
than that at which the vigorous reaction starts.
conditions similar to that described in Example
It will usually be desirable to maintain the mix
11. About 0.1 mole of CHCIFCClzF, boiling at ‘12°
ture at or above such temperature for a substan
73° 0., was isolated and identi?ed. By-product
tial period of time so as to complete the reaction
CHClzCHCIF was also identi?ed.
as far as possible. Preferably, after the vigorous 65
It will be understood that the preceding exam
reaction has subsided, the mixture is heated up to
ples are given for illustrative purposes solely and
about 200° C. and maintained at that point for
we do not intend to restrict our invention to the
several hours so as to insure completion of the
speci?c embodiments disclosed therein. but in
‘ and lined with the non-reactive metal. The ves
reaction.
'
tend to cover our invention broadly as in the ap
The reaction products, consisting essentially of 70 pended claims. Many variations and modi?ca
excess H1", ?uorinated organic material, unreact
tions may be made in the process without depart
ed ole?n and metal compounds, may be treated
ing from the spirit or scope of our invention. For
by various methods to separate ‘and recover the
example, other acyclic ole?nic compounds may be
valuable ingredients. The organic material and
empégyed
in place of those speci?cally men
,HMF may be distilled out of the autoclave and then 76 tion .
-
2,437,993
Metal oxides, in general. are not e?ective in
this process and it could not be predicted which
metal oxides would produce the desired results.
For example, attempts to obtain the sym
metrical addition of ?uorine to ole?ns. such as
CF5CC1=CCI:, CCh=CCls and CHI=CHCL by
employing in the process other metal oxides, such
as NizOs, T10: and SbrOs. were unsuccessful.
This invention provides a novel method for
preparing organic ?uorine compounds. It pro
vides a method for the symmetrical addition of
?uorine to ole?nic compounds, permitting the
synthesis oi’ compounds heretofore dii?cult and
tedious or impossible to prepare. For example,
6
or a member of the group consisting of 00:0: and
MnOa, closing the reaction vessel, causing the
temperature to rise above 0' C. to that at which
the reaction proceeds rapl
, maintaining the
mixture at at least the latter temperature until
the reaction is complete and then separating the
products.
4. The process of adding ?uorine to a double
bond 01' an acyclic ole?nic compound which con
sists of carbon and at least one of the members
of the group consisting of hydrogen, chlorine,
bromine and ?uorine which comprises mixing, in
a reaction vessel at a temperature below —l4'' 0.,
from about 1 to about 4 moles of the ole?nic com
it provides a new and more e?lcient method for
the preparation of CClaFCChF. Prior to our in 15 pound and from about 5 to about 30 moles oi’ HF
with one mole of a member oi’ the group consist
vention, CClaFCChF was obtained with dif?culty
ing of 00:0: and MnOz, closing the reaction ves
as an intermediate in the preparation of
sel, causing the temperature to rise above 0.“ C.
CClFrCClrF from CzCie and antimony ?uorides
to that at which the reaction proceeds rapidly,
and then in very small yields admixed with the
isomer CClFzCCh. By our process, two ?uorines 20 maintaining the mixture at at least the latter
temperature until the reaction is complete and
are symmetrically added to CC12=CC12 with the
then separating the products.
formation of CChFCClaF without admixture with
the isomer. Also, by our method, CFsCClFCChF
is readily obtained from CF3CC1=CC12.
5. The process oi’ adding ?uorine to a double
bond of an acyclic ole?nic compound which con
The products of the reaction are useful for 25 sists of carbon and at least one of the members
of the group consisting of hydrogen, chlorine,
various commercial purposes. They may be used
bromine and ?uorine which comprises mixing, in
as refrigerants and as intermediates for the prep
a reaction vessel at a temperature of from about
aration of ?uorine-containing ole?nes and per
?uorinated ole?nes, useful in the production of 30 —15° C. to about -78° C., from about 1 to about
4 moles of the ole?nic compound and from about
fluoro polymers and interpoiymers. The com
10 to about 20 moles of HF with one mole of a
pounds, produced by our method, may also be
member of the group consisting of C020: and
used as solvents and reaction media. Further
M1102, closing the reaction vessel, causing the
more, by our invention, we have provided a
temperature
to rise to a temperature of from 0°
method whereby two ?uorine atoms are added
C. to about 200° C. at which the reaction proceeds
to ole?nic compounds by an economical one
rapidly, maintaining the mixture at at least the
‘step process, not known or used heretofore.
latter temperature until the reaction is complete
We claim:
and then separating the products.
1. The process of adding ?uorine to a double
6. The process of adding ?uorine to a double
bond of an acyclic ole?nic compound which con
bond of an acyclic chloro-?uoro ole?n which com
sists of carbon and at least one of the members
prises mixing, in a reaction vessel at a tempera
of the group consisting of hydrogen, chlorine,
ture below 0° C., at least 0.5 mole of the ole?n
bromine and ?uorine which comprises mixing, in
and at least 5 moles of HF with one mole of a
a reaction vessel at a temperature below 0° C.,
at least 0.5 mole of the ole?nic compound and at 45 member of the group consisting 0! C020: and
least 5 moles of HF with one mole of a member
of the group consisting of C020: and MnOs, clos
ing the reaction vessel, causing the temperature
to rise above 0° C. to that at which the reaction
MnOz, closing the reaction vessel, causing the
temperature to rise above 0“ C. to that at which
the reaction proceeds rapidly, maintaining the
mixture at at least the latter temperature until
reaction is complete and then separating the
proceeds rapidly, maintaining the mixture at at 50 the
products.
least the latter temperature until the reaction
7. The process of adding ?uorine to a double
is complete and then separating the products.
bond of an acyclic chloro-fluoro ole?n which
2. The process of adding ?uorine to a double
consists of carbon, chlorine and ?uorine which
bond of an acyclic ole?nic compound which con
sists of carbon and at least one or the members 55 comprises mixing, in a reaction vessel at a tem
perature below —14° C., from about 1 to about
of the group consisting of hydrogen, chlorine,
4 moles of the ole?n and from about 5 to about
bromine and ?uorine which comprises mixing, in
30 moles of HF with one mole of a member of
a reaction vessel at a temperature below-14° C.,
at least 0.5 mole of the ole?nlc compound and
at least 5 moles of HIE‘ with one mole of a mem
the group consisting of C020: and Minor, closing
the reaction vessel, causing the temperature to
ber of the group consisting of C020: and Mp0s, 60 rise above 0° C. to that at which the reaction
proceeds rapidly, maintaining the mixture at at
least the latter temperature until the reaction is
ture to rise above 0° C. to that at which the re
complete and then separating the products.
action proceeds rapidly, maintaining the mixture
8. The process of adding ?uorine to a double
at at least the latter temperature until the re 65
bond of an acyclic chloro-?uoro olefin which
action is complete and then separating the prod
ucts.
consists of carbon, chlorine and ?uorine which
comprises mixing, in a reaction vessel at a tem
3. The process of adding ?uorine to a double
perature of from about —15° C. to about ~78“ 0.,
bond of an acyclic ole?nic compound which con
sists of carbon and at least one of the members 70 from about 1 to about 4 moles of the ole?n and
from about 10 to about 20 moles of HF with one
of the group consisting of hydrogen, chlorine,
mole of a member of the group consisting of
bromine and fluorine which comprises mixing, in
C020: and MnOa, closing the reaction vessel,
a reaction vessel at a temperature below 0’ 0., at
causing the temperature to rise to a tempera
least 0.5 mole of the ole?nic compound and from
about 5 to about 30 moles oi’ HI" with one mole 75 ture of from 0° C. to about 200° C. at which the
reaction proceeds rapidly. maintaining the mix
closing the reaction vessel, causing the tempera
7
until the
ture at at least the latter temperature
reaction is complete and then separating the
CFsCCl=CCh
8
a, temperature below 0° 0.. at least 0.5 mole of
‘the cCh=CCh and at least 5 moles of H!‘ with
one mole or a member of the group consisting of
C020: and MnOa. closing the reaction vessel,
causing the temperature to rise above 0° C. to
that at which the reaction proceeds rapidly.
maintaining the mixture at at least the latter
temperature until the reaction is complete and
then separating the CW .irom the reac
which comprises mixing, in a reaction vessel at
a temperature below 0° C., at least 0.5 mole oi
mixture.
the CFJCCI=CCI2 and at least 5 moles of H!" 10 tion
15. The process of making CChFCChF by add
with one mole of a member of the group con
ing ?uorine to the double bond of CCla==CCla
sisting oi C020: and MnOn, closing the reaction
which comprises mixing, in a reaction vessel at
vessel, causing the temperature to rise above
a temperature 01' trom about —15° C. to about
0° C. to that at which the reaction proceeds
-—78° 0., irom about 1 to about 2 moles or the
rapidly, maintaining the mixture at at least the 15 CCl===CClz and from about 10 to about 20 moles
latter temperature unil the reaction is complete
of HF with one mole of a member of the group
and then separating the CFaCClFCClzF' from
consisting 0! C020: and MnOa, closing the re
the reaction mixture.
action vessel, causing the temperature to rise to
10. The process of making CZF'zCClFCClzF by
a temperature of from 0° C. to about 200° C. at
20 which the reaction proceeds rapidly, maintaining
adding ?uorine to the double bond of
the mixture at at least the latter temperature
until the reaction is complete and then separating
which comprises mixing in a reaction vessel at a
the CClaFCClzF from the reaction mixture.
temperature oi’ from about —15“ C. to about —'l8°
16. The process or adding ?uorine to a double
C., from about 1 to about 2 moles of the 25 bond of an acyclic olefinic compound which con
CF3CC1=CC12 and from about 10 to about 20
sists of carbon and at least one of the members
moles of HF with one mole of a member of the
of the group consisting of hydrogen, chlorine,
group consisting of C020: and MnOa, closing the
bromine and ?uorine which comprises mixing,
reaction vessel, causing the temperature to rise
in a reaction vessel at a temperature of below
to a temperature of from 0° C. to about 200° C. 30 0° C., at least 0.5 mole of the ole?nic compound
at which the reaction proceeds rapidly, main
and at least 5 moles of HF with one mole of
taining the mixture at at least the latter tem
Ml’lOz, closing the reaction vessel, causing the
perature until the reaction is complete and then
temperature to rise above 0° C. to that at which
separating the CF'aCClFC-ClaF from the reaction
the reaction proceeds rapidly, maintaining the
35
mixture.
mixture at at least the latter temperature until
11. The process of adding ?uorine to a double
the reaction is complete and then separating
bond of an acyclic chloro ole?n which comprises
the products.
mixing, in a reaction vessel at a temperature be
1'7. The process of adding ?uorine to a double
low 0° C., at least 0.5 mole of the ole?n and at
bond
01’ an acyclic chloro-?uoro ole?n which
40
least 5 moles of HF with one mole of a member
comprises
mixing, in a reaction vessel at a tem
of the group consisting of C020: and Minor, clos
perature below 0° C., at least 0.5 mole of the
ing the reaction vessel, causing the temperature
ole?n and from about 5 to about 30 moles of
to rise above 0° C. to that at which the reaction
HF with one mole of M1102, closing the reaction
proceeds rapidly, maintaining the mixture at at
least the latter temperature until the reaction 45 vessel, causing the temperature to rise above
0° C. to that at which the reaction proceeds rap
is complete and then separating the products.
idly, maintaining the mixture at at least the
12. The process of adding ?uorine to a double
latter temperature until the reaction is complete
bond of an acyclic chloro ole?n consisting of
and then separating the products.
carbon and chlorine which comprises mixing.
18. The process of adding ?uorine to a double
in a reaction vessel at a temperature below 0°C., 50
bond of an acyclic chloro-?uoro ole?n which
at least 0.5 mole of the ole?n and at least 5 moles
consists of carbon, chlorine and ?uorine which
of HF with one mole of a member of the group
comprises mixing, in a reaction vessel at a tem
consisting of C020: and M1102, closing the reac
perature of from about —l5° to about -'l8° C..
tion vessel, causing the temperature to rise above
0° C. to that at which the reaction proceeds 55 from about 1 to about 4 moles oi’ the ole?n and
from about 10 to about 20 moles of HF with one
rapidly, maintaining the mixture at at least the
mole of MnOa, closing the reaction vessel, caus
latter temperature until the reaction is complete
ing the temperature to rise to a temperature
and then separating the products.
0! from 0° C. to about 200° C. at which the re
13. The process of adding ?uorine to a double
bond of an acyclic chloro ole?n consisting of 60 action proceeds rapidly, maintaining the mixture
at at least the latter temperature until the re
carbon and chlorine which comprises mixing, in
action is complete and then separating the
a reaction vessel at a temperature of from about
products.
~15° C. to about -78° C., from about 1 to about
19. The process of making CFaCClFCClaF by
4 moles of the ole?n and from about 10 to about
20 moles of HF with one mole of a member of 65 adding ?uorine to the double bond of
the group consisting of C010: and Minor, closing
CFaCCl: CClz
the reaction vessel, causing the temperature to
which comprises mixing, in a reaction vessel at a
rise to a temperature 01’ from 0° C. to about 200°
temperature below 0° C. at which the reaction
C. at which the reaction proceeds rapidly, main
taining the mixture at at least the latter tem 70 proceeds slowly, at least 0.5 mole of the
perature until the reaction is complete and then
separating the products.
and at least 5 moles oi’ HF with one mole of
14. The process of making CClsFCChF by add
M1102, closing the reaction vessel, causing the
ing ?uorine to the double bond of CCla==CCla
which comprises mixing, in a reaction vessel at 75 temperature to rise above 0° C. to that at which
9
2,487,998
10
the reaction proceeds rapidly, maintaining the
mixture at at least the latter temperature until
the reaction is complete and then separating the
CFsCClFCClzF from the reaction mixture.
20. The process of making CF'JCCIF‘CClzF by 5
adding ?uorine to the double bond of
at which the reaction proceeds rapidly. main
taining the mixture at at least the latter tem
perature until the reaction is complete and then
separating the CFEiCClFCChF from the reaction
mixture.
CFaCCi=CC12
ANTHONY F. BENNING.
JOSEPH D. PARK.
which comprises mixing, in a reaction vessel at
REFERENCES CITED
a temperature of from about —15° C. to about 10
The
following
references are of record in the
—78° C., from about 1, to about 2 moles of the
file of this patent:
CFhCCi=CCh and from about 10 to about 20
moles of HF with one mole of M1102, closing the
UNITED STATES PATENTS
reaction vessel, causing the temperature to rise
Number
Name
Date
to a temperature of from 0° C. to about 200° C. 15 2,062,743
Daudt et a1. ______ _. Dec. 1, 1936
Certi?cate of Correction
Patent No. 2,437,993.
March 16, 1948.
ANTHONY F. BENNING ET AL.
It is hereby certi?ed that errors appear in the
speci?cation of the above
numbered patent requiring correction as follows:
lumn 2, line 10, for the word
"out” read our; column 5, line 6, Example III, for “OHl—‘-CHC1" read OHOZ=
CHOZ; column 7, line 16, claim 9, for “nail” read "until; and that the said Letters
Patent should be read with these corrections therein that the same may conform to
the record of the case in the Patent O?ce.
Signed and sealed this 11th day of May, A. D. 1948.
[In-1
THOMAS F. MURPHY,
Assistant Uommkdoaero/ PM.
9
2,487,998
10
the reaction proceeds rapidly, maintaining the
mixture at at least the latter temperature until
the reaction is complete and then separating the
CFsCClFCClzF from the reaction mixture.
20. The process of making CF'JCCIF‘CClzF by 5
adding ?uorine to the double bond of
at which the reaction proceeds rapidly. main
taining the mixture at at least the latter tem
perature until the reaction is complete and then
separating the CFEiCClFCChF from the reaction
mixture.
CFaCCi=CC12
ANTHONY F. BENNING.
JOSEPH D. PARK.
which comprises mixing, in a reaction vessel at
REFERENCES CITED
a temperature of from about —15° C. to about 10
The
following
references are of record in the
—78° C., from about 1, to about 2 moles of the
file of this patent:
CFhCCi=CCh and from about 10 to about 20
moles of HF with one mole of M1102, closing the
UNITED STATES PATENTS
reaction vessel, causing the temperature to rise
Number
Name
Date
to a temperature of from 0° C. to about 200° C. 15 2,062,743
Daudt et a1. ______ _. Dec. 1, 1936
Certi?cate of Correction
Patent No. 2,437,993.
March 16, 1948.
ANTHONY F. BENNING ET AL.
It is hereby certi?ed that errors appear in the
speci?cation of the above
numbered patent requiring correction as follows:
lumn 2, line 10, for the word
"out” read our; column 5, line 6, Example III, for “OHl—‘-CHC1" read OHOZ=
CHOZ; column 7, line 16, claim 9, for “nail” read "until; and that the said Letters
Patent should be read with these corrections therein that the same may conform to
the record of the case in the Patent O?ce.
Signed and sealed this 11th day of May, A. D. 1948.
[In-1
THOMAS F. MURPHY,
Assistant Uommkdoaero/ PM.
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