Note: Descriptions are shown in the official language in which they were submitted.
7 .. ~ ^ 21 ~7~9~
Process for Combining Chlorine-Containing Molecules
to SynthesiZe Fluorine-Containing Products
BACKGROUND OF THE INVENTION
The global effort to replace chlorofluorocarbons
with alternative products has resulted in an intensive
search for such_ products. Currently,
chlorofluorocarbons (CFCs) are widely used for
applications such as blowing agents, solvents,
10 refrigerants, propellants, cooling fluids, working
fluids, and rinse agents. Unfortunately, CFCs are
sufficiently stable to diffuse into the stratosphere,
where they are eventually decomposed into ~eactive
chlorine-containing radicals. These radicals have been
15 found to catalytically decompose the protective ozone
layer.
EP 0 499 984 A1 (Daikin Industries) discloses
dimerization of certain fluorine-containing ethanes
by hydrogenation over a nic~el on silica catalyst.~In
20 comparative examples it is shown that a chromium on
silica catalyst is not effective for the reaction.
EP 0 442 087 A1 (Bayer AG) discloses the
preparation of chlorine-free fluorocarbons by gas-
phase hydrogenation of unsaturated fluorocarbons over
25 a suitable catalyst.
SUMMARY OF THE INVENTION
Alternatives to chlorofluorocarbons are provided
by the inventive process for synthesizing fluorine-
cont~;ning products RCF~+a_lHf+t_lF~CR' which may
30 optionally be carried out without the isolation of any
intermediate in a single reactor or a series of
.J reactors. The process comprises combining chlorine-
~; cont~i n ing reactants RCClaF~ and R'CCldFeHf in the
presence of hydrogen and at least one catalyst. R and
~ 35 R' are chosen from th~e group consisting of halogens,
S~
1~ A~END~ S~-~EET
- 2167698
halogenated hydrocarbons, and hydrocarbons, and at
least one of R and R' contains fluorine, a and d are
integers from 1 to 3, b, c, e, and f are integers from
5 O to 2, the sum of a, b, and c is 3, and the sum of d,
e, and f is 3, and further treating the coupled
products with hydrogen or a fluorinating agent.
Examples of the chlorine-containing reactants, RcclaFbHc
and R~CCldFeHf, are FCl2C-CClF2, F3C-CCl3, F3C-CF2-CCl3,
10 F3C-CF2-CHC12, CF2C12, F3C-CHC12, F3C-CH2Cl. Examples of
the fluorine-containing product, RcFbHc~a-lHf~d-lFecR~ are
F3C-CH2-CH2-CF3, F2CH-CHF-CHF-CHF2, F3C-CF2-CH2-CH2-CF3,
F3C CH2-CHF2, and F3C-CF2-CH2-CH2-CF2-CF3.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 is the gas chromatographic spectrum of
the products of the synthesis of CFC-151-10 from CFC-
215. The ordinant shows the total ion current from the
mass spectroscopy detector and the abscissa represents
the retention time of the gas chromatograph.
Figure 2 shows the mass spectroscopy fragmentation
pattern for one of the products in the spectrum in
Figure 1.
Figure 3 provides an interpretation of the mass
spectroscopy fragmentation pattern of Figure 2 to
25 verify the intermediate product composition.
Figure 4 is the gas chromatographic spectrum of
the products of the synthesis of HFC-55-10 from CFC-
215~
Figure 5 is the mass fragmentation pattern for the
30 peak in Figure 4 that has been assigned to HFC-55-10.
DETAILED DESCRIPTION OF THE INVENTION
The detriments to the use of chlorofluorocarbons
ca~ be abated by substituting relatively more fluorine
and less chlorine into the compounds and by introducing
35 hydrogen to make the compounds more reactive at lower
~ 1 6 7 ~ 9 8~
, . .. .. .......
e 2a
altitudes. Substituting fluorine for the chlorine of
traditional CFC products decreases the boiling point.
It is therefore generally necessary to increase the
! 5 number of carbon atoms in the molecule to achieve the
/ product boiling points required by the applications.
/ The synthesis of the traditional CFC molecules such as
; dichlorodifluoromethane (CFC-12),
~ .
~E~
~ 09s/05353 pcT~s94lo8s86
~ 1 67698
chlorotrifluoromethane (CFC-13), and trichlorofluoro-
methalne (CFC-ll) are relatively easy and can be
produced in concert with each other. However,
synthesizing the more advanced higher carbon number
hydrofluorocarbons (HFC's) greatly complicates the
manufacturing process. This invention discloses an
efficient method for manufacturing advanced HFC and
other products such as blowing agents, solvents,
refrigerants, propellants, cooling fluids, working
fluids, and rinse agents.
The inventive process involves preparing the
fluorine-cont~in;ng product RCFbH~.1Hf~1F,CR' by
coupling two chlorine c~"~in~ng reactants, RCCl,FbHc
and X'CCldF.Hf in the pre~en~e of hydrogen and a first
catalyst, and further treating the coupled product~
with hydrogen or a fluorinating agent, optionally in
the presence of a ~qcon~ cataly~t, to form the
fluorine _G..~n~ng product. R and R' are cho~n from
the group consisting of halogens, halogenated
hydrocarbons, and hydrocarbons, and at least one of R
and R' contains fluorine, a and d Are integers from 1
to 31 b, c, e, and f are integers from 0 to 2, the sum
of a" b, and c is 3, and the sum of d, e, and f i8 3 .
R An~ R' may have functional y,oU~L or other moieties
that contAin oxygen, nitrogen, sulfur, phosphorous,
iodine, bromine, or other components which are not
directly involved in the coupling. These funct~onAl
yLo~ or moieties may be used to enhance application
properties or to mask certain reactive sites during the
~ynthesis ~.. -^~. Examples of R and R' are -CF~, -
CCl2F, -CF2CF3, -F, or -Cl, chlorine- and fluorine-
containing alkyl groups, chlorine- ~nd fluorine-
containing aromatic compounds. There is no known upper
limit to the molecular weight of the react~nts.
2 1 6:7 6 ~ 8 ~
- .. .....
The invention also contemplates a process for
preparing the fluorine-containing products comprising
combining the two chlorine-containing reactants in the
5 presence of hydrogen and a catalyst to form at least
i one intermediate, RCFqHhCliCl~HkFlR', and subsequently
treating the intermediate in the presence of an
optional second catalyst with either a fluorinating
agent, or with hydrogen and a catalyst to form the
10 fluorine-containing product, wherein the sum of g, h,
and i is an integer from 1 to 2, the sum of j, k, and l
is an integer from 1 to 2, g, h, i, ~, k, and l are
integers from 0 to 1.
The catalyst used in the coupling reaction is a
15 group VIII metal and may be chosen from the group
consisting of nickel, ruthenium, rhodium, palladium,
osmium, iridium, platinum, iron, or cobalt. The
catalyst may be dispersed on a high surface area
support such as alumina, carbon, chromium oxide,
20 chromium oxyfluoride, chromium fluoride, or may be used
as an unsupported high surface area metal oxide, metal
fluoride, or elemental metal. The preferred catalys.
for the coupling reaction is a reduced ruthenium
catalyst dispersed on a high surface area support such
25 as alumina or carbon.
- The molar ratio of hydrogen to reactant in the
coupling reaction may vary from 0.5 to 10. The
pressure may vary from ambient to 6895 kPa gauge (1,000
psig), and the li~uid hourly space velocity (LHSV) may
t 30 vary from 0.1 to 10. The reaction may be carried out
at temperatures in the range of from 20C to 500C,
preferably in the range of from 100C to 250C, and most
preferably in the range of from I50c to 200C.
Substantial reaction occurs to produce substantlal
35 conversion and selectivity at temperatures below 200C.
. .
~ 21676~8 : ::
. ", .-:
Further treating the fluorine-cont~;n;ng product
with hydrogen and an optional second catalyst will
reduce the product to a hydrofluorocarbon. Treatment
5 with a fluorinating agent will `produce a hydro-
fluorocarbon or perfluoroalkane. The catalyst selected
for the hydrogen treatment may be the same catalyst
used for the coupling reaction or may be selected from
metals known to provide substantial hydrogenolysis
10 activity on high surface area supports such as alumina
or carbon. The most preferred metals include group
VIII metals such as platinum, cobalt, nickel, iridium,
ruthenium and palladium which may be modified by
promoters including but not limited to rhenium,
15 iridium, cobalt, and nickel. Alternatively, the metals
may be attenuated by components including but not
limited to sulfur, germanium, or tin. The
hydrogenation reaction may be carried out at a liquid
hourly space velocity (LHSV) in the range of from ~'.05
20 to 10, preferably in the range of from 0.2 to 1.0, a
temperature in the range of from 20C to 550C,
preferably 100C to 350C, and a pressure in the range
of from 6.895 kPa (0 psig) to 13,78~ kPa (2000 psig),
preferably 207 kPa gauge (30 psig) to 2,968 kPa gauge
(300 psig).
The fluorinating agent may be chosen from the
group consisting of hydrogen fluoride, uranium
fluoride, elemental fluorine, or fluoride salts.
Examples of fluoride salts are potassium fluoride,
30 sodium fluoride, and cesium fluoride. The catalysts
for hydrofluorination may be a chromium-based
heterogeneous system, a catalyst system based on
quid-phase contact with antimony pentahalide in
~. .
A
`~ 7`~8: ::. ::
hydrogen fluoride, or electrofluorination in hydrogen
fluoride. The hydrofluorination reaction may be
carried out at a liquid hourly space velocity (LHSV) in
5 the range of from 0.05 to 5, preferably in the range of
from 0.1 to 1.0, a temperature in the range of from
100C to 450C, preferably 250C to 350C, and a
pressure in the range of from 6.895 kPa gauge (0 psig)
to 3,447 kPa (500 psig), preferably 345 kPa gauge (50
10 psig) to 1379 kPa (200 psig). Where the fluorinating
agent is elemental fluorine, however, the reaction is
preferably carried out without a catalyst and at
temperatures in the range of from -50C toi +100C,
preferably -20C to +20C.
In addition, the acid nature of the support may be
removed with a basic substance such as an alkali metal
to avoid unwanted acid-catalyzed isomerizations. For
example, lithium, sodium, or potassium may be added, to
the alumina for either or both of the reactions.
20 ~ The novel fluorine-containing products may be
synthesized by first coupling the chlorine-containing
reactants in the presence of hydrogen and a catalyst to
form an intermediate compound, isolating the
intermediate by procedures such as distillation,
25 membranes, absorbents or other separation devices, and
then treating the intermediate with hydrogen, a
fluorinating agent such as elemental fluorine, or a
hydrofluorinating agent such as hydrogen fluoride with
an optional second catalyst to form the fluorine-
30 containing product. Alternatively, the fluorine-
containing product may be synthesized and further
treated with hydrogen- or a fluorinating agent without
isolation of an intermediate in a single reactor or a
series of reactors A heat exchanger may be used with
35 the series of reactors to adjust temperature.
~..
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~ 095/05353 PCT~S94/08986
2 1 67~98
The reactions leading to the fluorine-
containing products produce HCl and are therefore very
exothermic. The hydrochloric acid may be neutralized,
recovered as a byproduct, discarded, or converted into
chlorine using the Deacon reaction for recycle or sale.
The ~xcess heat must be managed in order to control the
reac1:or temperature profile. Although very high
reacl:or temperatures lead to hiqh reaction rates, they
also lead to loss of product selectivity. Heat
dispersing t~chn;ques such as quench hydrogen, inert
fluids such as nitrogen, and/or product recycle streams
may be used to provide adequate thermal management.
As disc~s~^~ above, fluorine-containing
products may be synthesized by combining A chlorine-
containing reactant using an excess of hydrogen and asuitable catalyst to form an intermediate, then a
product, or to form a product directly. An
intermediate may be a saturated compound or an olefin.
An olefin may be hydrogenated to form the desired
product using catalytic hydrogenation. Examples of
possible syn~hec~fi ~re as follows:
Synthesis of HFC-356mff from CFC-113. HFC-
356mff (1,1,1,4,4,4-hexafluorobutane) may be
synthesized using CFC-113 (1,1,2-trichloro-1,2,2-tri-
fluoroethane) in the presence of a catalystsufficiently acidic to cause an isomerization to CFC-
113a. For example, the catalyst CrF3 may be phy~ically
mixed in with a ruthenium catalyst or itself
impregnated with ruthenium. The entire reaction may be
carried out without the isolation of any intermediate
in a~ single reactor or a series of reactors. CFC-113
rearranges to form CFC-113a and then couples to form
the desired HFC-356mff.
W095/05353 PCT~S94/08986
21 67698 ~
Synthesis of HFC-356pee from CFC-113. HFC-
356pee (1,1,2,3,4,4-hexafluorobutane) may be
synthesized by coupling CFC-113 (1,1,2-trichloro-1,2,2-
trifluoroethane) to form a four-carbon olefin (CFC-1316
lyy, F2ClCCF~CFCClF2) as was HFC-356mff above. The
four-carbon olefin is hydroqenated to form the desired
product using catalytic hydrogenat$on.
Synthesis of HFC-356mff from CFC-113a. HFC-
356mff (1,1,1,4,4,4-hexafluorobutane) may be
synthesized by coupling CFC-113a (l,l,l-trichloro-
2,2,2-trifluoroethane) without isolating any
intermediates in a single reactor or a series of
reactors.
Synthesis of HFC-356mff from CFC-113a. HFC-
356mff (1,1,1,4,4,4-hexafluorobutane) may be
synthesized by coupling CFC-113a (l,l,l-trichloro-
2,2,2-trifluoroethane) to form the four-carbon olefin
CFC-1316mxx (F3CCCl~CClCF3). The olefin may then be
hydrogenated to form HFC-356mff or may be converted to
a ~?.CQn~ intermediate, HCFC-336 (F3CCHClCHClCF3). The
second intermediate can then be reacted with hydrogen
to produce the desired HFC-356mff product.
Synthesi~ of HFC-338 from CFC-113a. HFC-338
(1,1,1-2,3,4,4,4-octafluorobutane) may be synthes~zed
by coupling CFC-113a (1,1,1-trichloro-2,2,2-
trifluoroethane) to form a four-carbon olefin
intermediate (CFC-1316mxx, F3CCCl~CClCF3). The
intermediate may then be hydrogenated to form a ~e~on~
intermediate product (HCFC-336, F3CCHClCHClCF3) using
catalytic hydrogenation and relatively mild conditions.
The second intermediate can then be reacted with HF
over a suitable catalyst such as a Cr-based
heterogeneous system, a catalyst system based on
liquid-phase contact with antimony pentahalide in HF,
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7 2~67~
. . .
.-,, ..- , .....
I g
/ or electrofluorination in HF to produce the desired
HFC-338 product. H~C-356mff may also be co-produced
/ with HFC-338 by coupling CFC-113a and the ratio of the
/ 5 products can be adjusted by varying the reactor process
/ conditions. Co-production is expected to enhance the
economics relative to the production of either product
alone.
Synthesis of HFC-356mff and/or FC-31-10 from CFC-
10 113a. HFC-356mff and/or FC-31-10 (perfluorobutane) may
be synthesized by coupling CFC-113a to produce a
substantial amount of CFC-316 (F3CCCl2CCl2CF3). CFC-316
-~ can then be electrofluorinated in HF to producejFC-31-
10 or treated with hydrogen to produce HFC-356mff.
15 HFC-356mff and FC-31-1~ may be co-produced by coupling
CFC-316 and the ratio of the products can be adjusted
by varying the reactor process conditions.
Synthesis of HFC-346mdf from CFC-113a. HFC-346mdf
(1,1,1,4,4,4-hexafluoro-2-chlorobutane) may ~e
20 synthesized by coupling CFC-113a (1,1,1-trichloro-
2,2,2-trifluoroethane) to form the four-carbon olefin
CFC-1316mxx (F3CCCl=CClCF3). The olefin may then be
partially hydrodechlorinated to form HFC-346mdf.
Synthesis of CFC-1418 fro~ CFC-113a and CFC-215.
25 CFC-1418 (2,3-dichlorooctafluoro-2-pentene) may be
synthesi~ed by reductively coupling CFC-113a and CFC-
215 (CF3CF2CCl3). CFC-1418 may be further treated,
e.g., hydrodechlorinated and/or fluorinated, to form
other products, e.g., CFC-43-10 (1,1,1,2,2,3,4,5,5,5-
30 decafluoropentane), HFC-458 (1,1,1,2,2,5,5,5-octa-
fluoropentane), or FC-41-12 ~perfluoropentane).
Synthesis of CFC-1418 from CFC_113a and CFC-225.
CFC-1418 may be synth-esized by reductively coupling
CFC-113a and CFC-225 (1,1-dichloro-2,2,3,3,3-
_ _
-
2 t ~ 7 6 9 8
I pentafluoropropane). CFC-1418 may be further treated
/ as discussed aboYe~
/ Synthesis of HFC-245fa from CFC-12 and CFC-113a.
/ 5 HFC-245fa (1,1,1,3,3-pentafluoropropane) may be
/ synthesized by coupling CFC-12 and CFC-113a to form a
three-carbon olefin (CFC-1215, F3CCCl=CF2). The olefin
is hydrogenated to for~ the desired product using
t catalytic hydrogenation. As the reductive coupling
10 reaction of CFC-113a is ~uch faster than the reductive
coupling reaction for CFC-12, a high ratio of CFC-
12:CFC-113a is preferred in the charge stock to promote
cross-coupling and reduce coupling of two CFC-113a
molecules.
Synthesis of HFC-356mff and/or HFC-338 from CFC-
123. HFC-356mff and/or HFC-338 may be synthesized by
coupling CFC-123 (1,1-dichloro-2,2,2-trifluoroethane)
to form a four-carbon intermediate (HCFC-336,
F3CCHClCHClCF3). The intermediate is then
20 hydrodechlorinated to for~ the desired product using
catalytic hydrogenation.
Synthesis of HFC-245fa from CFC-12 and CFC-123.
HFC-245fa may be synthesized by coupling CFC-123 (1,1-
dichloro-2,2,2-trifluoroethane) and CFC-12
25 (dichlorodifluoromethane). This molecule is coupled to
form a three-carbon olefin (HFC-1225, F3CCH=CF2). The
three-carbon olefin is then hydrogenated to form the
desired product using catalytic hydrogenation. As the
reductive coupling reaction of CFC-123 appears to be
` 30 much faster than the reductive coupling reaction of
CFC-12, a high ratio of CFC-12:CFC-123 would be
preferably used in the charge stock to promote cross-
coupling and reduce coupling of two CFC 123 molecules.
: .
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2 ~ 67698
/ Synthesis of HFC-356mff from HCFC-133a. HFC-
356mff may be synthesized by reductively coupling HCFC-
133a (1-chloro-2,2,2-trifluoroethane).
/ 5 Synthesis of HCFC-558 and HFC-578 from CFC-214.
/ HCFC-558 (ClCF2CF2CH2C~2CF2CF2Cl) and HFC-578
(HCF2CF2CH2CH2CF2CF2H) may be synthesized by coupling
CFC-214 (ClCF2CF2CCl3) to form a six-carbon olefin (CFC-
1518, ClCF2CF2CCl=CClCF2CF2Cl). The olefin may then be
10 hydrogenated to form the desired products using
catalytic hydrogenation.
Synthesis of HFC-55-10 from CFC-215. HFC-55-10
(1,1,1,2,2,5,5,6,6,6-decafluorohexane) may be
synthesized by coupling CFC-215 (CF3CF2CCl3) to form a
15 six-carbon olefin (CFC-151-10, F3CF2CCl=CClCF2CF3). The
olefin is then hydrogenated to form the desired product
using catalytic hydrogenation.
Synthesis of CFC-51-10 from CFC-215. CFC-51-1~
(3,3,4,4-tetrachlorodecafluorohexane) may be
20 synthesized by reductively coupling CFC-215. CFC-51-10
may then be further treated, e.g., hydrodechlorinated,
to form another product, e.g., CFC-55-10.
Synthesis of HFC-55-10 from CFC-225. HFC-55-10
may be synthesized by reductively coupling CFC-225
(1,1-dichloro-2,2,3,3,3-pentafluoropropane) to form the
intermediate HFC-153-10 (1,1,1,2,2,5,5,6,6,6-deca-
fluoro-3-hexene). The olefin is then hydrogenated to
form the desired product using catalytic hydrogenation.
Example 1 - Synthesis of HFC-356mff from CFC-113a
The following data were obtained using a
microreactor consisting of a syringe pump driven liquid
feed system, a mass flow meter controlled hydrogen
addition system, a reactor, a reactor outlet effluent
35 sampling system, and an on-line/off-line GC/MS
r
2~ 67698
/ 12
analytical system. The area under the peaks in a plot
of the total ion current (TIC) from the GC/MS as a
.function of retention time provides an estimate of the
5 concentration of the effluent from the reactor. CFC-
113a was the reactant and the catalyst used was 2%
ruthenium on carbon. The results shown in Table I
provide the product analysis. The results show a high
yield to CFC 1316mxx, which is the desired four-carbon
10 intermediate. These data were obtained at 2 LHSV, 10:1
H2:CFC-113a molar ratio, and 207 kPa gauge ~30 psig)
pressure as a function of temperature. It can be
clearly seen that a high yield of CFC-1316mxx can be
obtained. Further refinements in the process
lS conditions will lead to an increasing concéntration of
this product. The product CFC-1316mxx may be further
subjected to catalytic hydrogenation to obtain the
desired HFC-356mff.
TABLE I - Area % from GC/MS
90C 125C 225C
HFC-143a1 0.34 19.71 19.83
CFC-13262 0 2.67 6.74
CFC-13163 9.15 58.22 30.22 t
CFC-316 1.46 0 0
CFC-113a 88.41 0 0
CFC-123 0 5.76 3.79
lF3CCH3
2CFC-1326 (F3CClC=CHCF3)
3CFC-1316mxx (F3CClC=CClCF3)
Example 2 - Synthesis of HFC-356mff in a Single
Reactor from CFC-113a
HFC-356mff was synthesized by loading a single
reactor sequentially with io mL of a 2~ ruthenium
catalyst on a carbon support and 10 mL of a 2%
palladium catalyst on a carbon support. A quantity
~r
2i67698
/ 13
/of 4 mL per hour of CFC-113a (Cl3CCF3) was conducted to
/this reactor along with a mole ratio of hydrogen gas to
CFC-113a equal to 10Ø The reactor effluent was
~ 5 characterized by GC/MS. The data shown in Table II
/ were obtained by maintaining the inlet section of the
/ reactor containing the ruthenium catalyst at 225C.
The temperature of the butlet section of the reactor
was varied. The data pro~ide proof-of-principle that
10 HFC-356 can be synthesized in this manner. Moreover,
the primary byproduct of this reactions, F3CCH3 (HFC-
143a) is a desirable third-generation refrigeration
fluid.
TABLE II - Area ~ from GC/MS
139C 149C 175C 193C 231C 247C
356l 31.05 36.06 37.77 42.79 54.51 62.43
3462 23.3 29.86 28.35 21.67 5.74 0
143a 18.85 23.33 21.28 23.55 26.68 27.39
133a 5.87 7.35 8.02 13.06 10.18
123 4.09 5.25 3.97 0 0
lHFC-356mff
2HCFC-346 (CF3CClHCH2CF3)
Example 3 - Synthesis of HFC-356mff from CFC-123
precursor to HFC-356mff was synthesi~ed from
20 CFC-123 using the microreactor of Example 1. The GC/MS
results show a high yield to the four-carbon
intermediate. The data shown in Table III provide the
conversion and selectivity as functions of temperature.
The reactant was CFC-123 and the catalyst was 10%
25 ruthenium on alumina. These data were obtained at 2
LHSV, 10:1 H2:CFC-l23 molar ratio, and 207 kPa gauge
(30 psig) pressure as a function of temperature. It
can be clearly seen that HCFC-336 (CF3CHClCHClCF3) can
be produced in this manner. Further refinements in the
30 process conditions
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WO 95/05353 PCT/US9~/08986
~676q8 .
will lead to an increasing concentration of this
product. Because the internal carbon atoms are chiral,
two peaks are obtained for the products; one peak is
the meso compound while the other i8 a d/l pair. This
intermediate can be subjected to catalytic
hydrodechlorination to obtain the desired HFC-356mff.
TABn~ III - Selectivities and Conversion
209 - C 245 - C 265 - C 404 - C
HFC--13361 2.9 2.7 4.4 12.8
HCFC--336 32.2 53.2 ~7.4 7.9
Coupling 35.1 55.9 51.8 20.7
Selectivity
HCFC-123 6.5 16.5 18.6 72.1
Conversion
lHFC--1336 ( F3CCH=CHCF3)
~m~le 4 - SYnthesis of HFC-55-10 from CFC-~15
H~C-55-10 was synthesized ~rom CFC-215 using
the microreactor of Example 1. CFC-215 was the
reactant ~nd the catalyl;t was 15% ruthenium on alumina.
The data shown in Figure 1 represent the total ion
~urLel~ (TIC) from th~ GC/MS at a 197-C maximum reactor
temperature. ~igure 2 shows the MS fragmentation
pattern for the CF3CF2CCl~CClCF2CF3 intermediate. Both
of the peaks between 12. 5 and 14 minutes have
essentially the same fragmentation pattern, and have
been assigned to the cis and trans isomers. Figure 3
provides an analy~is of the MS fragmentation pattern to
verify the intermediate product composition. The GC/MS
results show a high yield to CFC-151-10, which is the
desired four-carbon intermediate. These data were
obtained at 0.1 LHSV, 10:1 H2:CFC-215 molar ratio, and
- . 2 ~ 6 ;~ 6 ~ 8. - ~
2068 kPa gauge (300 psig) pressure as a function of
temperature. It can be clearly seen that a high yield
of CFC-151-10 can be obtained. Further refinements in
5 the process conditions will lead -to an increasing
concentration of this product.
The synthesis of HFC-55-10 was demonstrated by
increasing the peak reactor temperature to 269C. the
catalyst provided significant hydrogenation and
10 hydrodechlorination activity at this temperature to
convert the intermediate CFC-151-10 to HFC-55-10. The
data shown in Figure 4 prove that we have prepared the
HFC-55-10 by this technique. The mass fragm~ntation
pattern in Figure 5 can be assigned to this product.
15 The peak at 8.6 minutes was identified as HFC-151-10
(CF3CF2CH=CHCF2CF3). This product can also be
hydrogenated to HFC-55-10.
,_
:
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t
