Note: Descriptions are shown in the official language in which they were submitted.
2~2~6~ :
Our Ref.: AA-562 (F~9-49)
DESCRIPTION
TITLE OF THE INVENTION
PROCESS FOR PRODUCING A CHLORINE-CONTAINING
2, 2-DIFLUOROPROPANE
TECHNICAL FIELD
The present invention relates to a process for
producing a chlorine-containing 2,2-difluoropropane.
BACKGROVND TECHNIQ~E
As a synthetic route for a chlorine-containing 2,2-
difluoropropane, a method has been known in which
dichloroEluoromethane or chloromethane i5 added to an .
ethylene having a difluoromethylene unit, such as 1,1-
dichloro~2,2-di~luoroethylene or l-chloro-1,2,2-
trifluoroethylene in the presence of aluminum chloride.
However, by such a method, not only the desired product,
but also a by-product will be formed which has a : ~;
methylene group other than 2,2-difluoromethylene and
which has a boiling point close to that of the desired
product. There~ore, in order to obtain a product having
a high purity, a multi-stage purification process is
required.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to overcome
:25 such a dra~back of the conventional method and to provide : .
a process for efficiently producing~ a chlorine-containing ~.
2,2-difluoropropane.
,
.
.
- 2~2~6i~
-- 2
The present inventors have conducted an extenslve
research for a process for efficiently producing a
chlorine-containing 2,2-difluoropropane and, as a result,
have found that a chlorine-containing 2,2-difluoropropane
of the following formula (2) can be obtained in good
yield by substltuting the hydrogen atoms of a 2,2~
difluoropropane of the formula (1) by chlorine atoms by
chlorination. The present invention is based on this
discovery.
The present invention provldes a process for ;:.
producing a chlorine-containing 2,2-difluoropropane of
the following formula (2)/ which comprises chlorinating a
2,2-difluoropropane oE the Eollowing ~ormula tl):
C3HaclbFc
C3Ha_xclb+xF~ ~2) : -
wherein a, b, c and x are integer~ satisfying the `
following conditions:
a 2 1, b 2 o, c 2 2, x 2 1 and a ~ b ~ c = 8.
The chlorine-containing 2,2-difluoropropane of the
formula (2) is expected to be useful as a foaming agent,
a cooling agent, a propellant or a solvent like
conventional chloro~luorocarbons. Particularly, it
includes a promising sùbstitute for 1,1,2-
trichlorotrifluoroethane as a solvent. -
BEST MODE OF CARRYING OVT THE INVENTION ; :
Reactions of the following formulas (3) to ~6) may be
~mentioned as specific embodiments for the preparation of
. . .
'. :.
' -: :. ' ' . ', , ' : ~ ';
2~2~6i~
3 -
a chlorine-containing 2,2-difluoropropane of the Eormula
(2) from a 2,2-difluoropropane of the formula (1).
C12
C3HmlC15_mlF3 ' C3HnlC15-nlF3 ( )
1 _ ml c 5 o ~ nl ~ 4I ml > nl
The 2,2-difluoropropane (C3HmlCl5_mlF-~ wherein 1 ~ ml
~ 5) to be used as the starting material includes, for
example, 1,2,2-trifluoropropane (R-263c), 1-chloro-2,2,3- .
trifluoropropane (R-253ca), 1-chloro-1,2,2-
trifluoropropane (R-253cb), 1,3-dichloro-1,2,2-
trifluoropropane (R-243ca), 1,1-dichloro-2,2,3~
trifluoropropane (R-243cb), 1,1-dichloro-1,2,2- : `.
trifluoropropane ~R-243cc), 1,1,3-trichloro-1,2,2~ :
tri~luoropropane (R-233cb), 1,1,3,3-tetrachloro-1,2,2-
trifluoropropane ~R-223ca) and 1,1,1,3-tetrachloro-2,2,3-
trifluoropropane (R-223cb).
The chlorine-containing 2,2-difluoropropane -:
( C3HnlCls_nlF3 wherein O ~ nl 5 4) to be formed by the
reaction includes l-chloro-2,2,3-trifluoropropane (R-
253ca), 1-chloro-1,2,2-trifluoropropane (R-253cb), 1,3-
dichloro-1,2,2-trifluoropropane (R-243ca~, l,l-dichloro- :
2,2,3-trifluoropropane (R-243cb) r 1,1-dichloro-1~2,2-
trifluoropropane ~R-243cc), 1,1,3-trichloro-2,2,3-
tri~luoropropane (R-233ca), 1,1,3-trichloro-1,2,2-
trifluoropropane (R-233cb), 1,1,1-trichloro-2,2,3- `
triEluoropropane (R-233cc), 1,1,3,3-tetrachloro-1,2,2- ~:
trifluoropropane (R-2-3ca), 1,1,1,3-tetrachloro-2,2,3-
2~2$~S~
-- 4 --
trifluoropropane (R-223cb) and 1,1,1,3,3-pentachloro-
2,2,3-trifluoropropane (R-213c).
C3Hm2Cl~_m2F4 C3Hn2Cl4_n2F4 (4)
1 _ m2 ~ 4 0 < n2 ~ 3, m2 > n2
The 2,2-difluoropropane (C3Hm2Cl4_m2Fq wherein 1 ~ m2
~ 4) to be used as the starting materia:L includes :~
1,2,2,3-tetrafluoropropane (R-254ca), 1,1,2,2-
tetrafluoropropane ~R-254cb), 1-chloro-2,2,3,3-
tetrafluoropropane ~R-244ca), 1-chloro-1,2,2l3-
tetrafluoropropane (R-244cb), 1-chloro-1,1,2,2-
tetrafluoropropane (R-244cc), 1,3-dichloro-lr2,2,3- :i :
tetra1uoropropane (R-234ca), 1,1-dichloro-2,2,3,3-
tetraEluoropropane ~R-234cb), 1,3-dichloro-1,1,2,2-
tetrafluoropropane ~R-234cc), 1,1-dichloro-1,2,2,3-
tetrafluoropropane (R-234cd), 1,1,3-trichloro-2,2,3,3- ~ ;
tetrafluoropropane (R-224ca), 1,1,3-trichloro-1,2,2,3-
tetrafluoropropane (R-224cb) and 1,1-trichloro-2,2,3,3- ...
tetraEluoropropane (R-224cc).
The chlorine-containing 2,2-difluoropropane
~C3Hn2C14_n2F~ wherein O ~ n2 ~ 3) to be formed by the
reaction includes l~chloro-2,2,3,3-tetra~luoropropane ~R-
244ca) r 1-chloro-1,2,2,3-tetra~luoropropane tR-244cb), 1-
chloro-1,1,2,2-tetrafluoropropane ~R-244cc), 1,3- - : :
dîchloro-1,2,2,3-tetrafluoropropane (R-234ca), 1,1- -
dichloro-2,2,3,3-tetrafluoropropane (R-234cb), 1,3
dichloro-1,1,2/2-tetrafluoropropane (R-234cc), 1,1- :
'''"'`'-''
,"'"'
2 ~ 6 ~
- 5 -
dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,lr3-
trichloro-2,2,3,3-tetrafluoropropane (R-224ca), 1,1,3- :
trichloro-1,2,2,3-tetrafluoropropane ~R-224cb), 1,1,1-
trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 1,1,3,3-
tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca) and
1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb).
These products can be separated by a usual method such as
distillation~
C3Hm3Cl3_m3Fs ' C3Hn3Cl3-n3F5 (5)
1 ~ m3 ~ 3 ~ n3 ~ 2, m3 > n3
The 2r2-difluoropropane (C3Hm3Cl3_m3F5 wherein 1 ~ m
~ 3 to be used as the starting material includes
1,1,2,2,3-pentafluoropropane (R-245ca), 1,1,1,2,2-
pentaEluoropropane (R-245cb), 1-chloro-1,2,2,3,3- ;
pentafluoropropane (R-235ca), 1-chloro-2,2,3,3,3-
pentafluoropropane (R-235cb), 1-chloro-1,1,2,2,3-
penta~luoropropane (R-235cc), 1,1-dichloro-2,2,3,3,3-
penta1uoropropane (R-225ca), 1,3-dichloro-1,1,2,2,3-
pentafluoropropane (R-225cb) and 1,1-dichloro-1,2,2,3,3-
pentafluoropropane (R-225cc).
The chlorine-containing 2,2-difluoropropane
(C3Hn3C13_n3F5 wherein 0 ~ n3 ~ 2) to be formed by the
reaction includes l-chloro-l,ll2,2,3,3-pentafluoropropane
(R-235ca), 1-chloro-2,2,3,3,3-pentafluoropropane (R-
235cb~, 1-chloro-1,1,2,2,3-pentafluoropropane (R-235cc),
lJl-dichloro-2,2,3,3,3-pentafluoropropane (R-225ça), 1,3- `
,':
- 2 ~ 2 ~
6 --
dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), 1,1-
dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), 1,1,3-
trichloro-1,2,2,3,3-pentafluoropropane (R-215ca) and
1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb).
Cl~
C3Hm4cl2-m4F6 -~ C3Hn2C12-n4F5 (6)
1 S m4 5 2 _ n4 ~ 1, m4 > n4
The 2,2-difluoropropane (C3Hm~Cl2_m~F~ wherein 1 ~ m4
~ 2) to be used as the starting material includes
1,1,2,2,3,3-hexafluoropropane (R-236ca), 1,1,1,2,2,3-
hexafluoropropane (R-236cb), 1-chloro-1,2,2,3f3,3-
hexafluoropropane (R-226ca) and 1-chloro-1,1,2,2,3,3-
hexafluoropropane (R-226cb).
The chlorine-containing 2,2-diEluoropropane
(C3HnCl2_nF6 wherein 0 ~ n 5 1) to be Eormed by the
reaction includes l-chloro-1,2,2,3,3,3-hexa~luoropropane
~R-226ca), 1-chloro-1,1,2,2,3,3-hexfluoropropane ~R-
226cb), 1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-
216ca) and 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (R-
216cb). The~e products can be separated by a usual
20method such as distillation.
For the reaction, a radical-generating source such as
light, heat or a radical initiator, or a combination
thereof, may be used. The radical initiator to be used
is not particularly limited so long as it is oil-soluble
and may be an azo compound or an organic peroxide as
shown in the following example. The azo compound may,
~,
' ;~ ,.
2~2~
- 7 -
for example, be a,a'-azobisisobutylonitrile (hereinafter
referred to simply as AIBN) or 2,2-azobis-2,4-
dimethylvaleronitrile (hereinafter referred to simply as
ACVN). The organic peroxide may, for example, be di~t-
butyl peroxide.
The reaction ratio between chlorine and the starting
material may be varied in a wide range. In order to
control the chlorination selectively at a stage where
only single chlorine is introduced, chlorine is used in a `
low stoichiometrical amount relative to the 2,2-
difluoropropane (C3HaClbFC). Whereas, to let all the
hydrogen atoms o~ the 2,2-difluoropropane react
substantially completely, chlorine is used in an amount
larger than stoichiometry relative to total molar amount
of the starting material, for exampler in an amount of 2
or more molar times.
The reaction temperature may suitably be chosen
depending upon the radical-generating source and is
usually from -78 to 450C.
In the present invention, when the reaction is
conducted in a liquid phase, a solvent may be employed.
The solvent to be used is not particularly limited so
long as it is capable of dissolving the propane as the
starting material and the radical initiator if used, and
will hardly be chlorinated itself. For example, a
halogenated hydrocarbon such as carbon tetrachloride may
suitably be used.
` .. ',
:
2 ~ 6 ~
- 8 -
There is no specific limitation to the reaction
pressure, when the reaction is conducted in a gas phase.
The pressure for the reaction is not particularly limited
and may range from reduced pressure to above atmospheric.
5 ~hen the reaction is conducted in a liquid phase, the -
pressure is chosen so that the starting material 2,2-
difluoropropane can adequately be present in the liquid
phase and may vary depending upon the type of the
solvent.
In the case o~ a gas phase reaction, chlorine may be
introduced into a reactor together with the starting
material as in a flow system, or may be charged
initially. In the case of a liquid phase reaction, it
may also be charged initially, but it is preEerable to ;~
bubble into the liquid phase.
Now, the present invention will be described in
further detail with reference to Examples~ However, it
should be understood that the present invention is by no
means restricted by such speciic Examples.
EXAMPLE 1-1
A 1,000 cc glass reactor equipped with a condenser of
-78C, was cooled to -20C, and 300 g o~ 1,2,2-
triEluoropropane was charged. Then, 107 g of chlorine
gas was gradually introduced while stirring under
25 irradiation by a high pressure mercury lamp of 500 W. ;~ -
After the reaction for 6 hours, the product after removal
of acid components, was analyzed by gas chromatography
'. ' ..
~2~6~
g : :
and by l9F-NMR and lH-NMR. The results are shown in
Table 1-1.
EXAMPLE 1-2
The reaction was conducted for 6 hours in the same
5 manner as in Example 1-1 except that 300 g of 1,1,2-
trifluoropropane and 214 g of chlorine gas were used.
The product was analyzed by gas chromatography and by
19F-NMR and lH-NMR. The results are shown in Table 1~
EXAMPLE 1-3 .
The reaction was conducted for 6 hours in the same
manner as in Example 1-1 except that 300 g of 1,2,2-
trifluoropropane and 430 g of chlorine gas were used.
The product was analyzed by gas chromatography and by
l9F-NMR and lEI-NMR. The results are shown in Table 1-1.
1S EXAMPLE 1-4
The reaction was conducted for 6 hours in the same
manner as in Example 1-1 except that 300 g of 1,2,2- ~
trifluoropropane and 214 g of chlorine gas were used, and
200 g of CC14 was used as the solvent for the reaction.
The product was analyzed by gas chromatography and by
19F-NMR and lH-NMR. The results are shown in Table 1-1.
''
. . .
.:
2 ~
- 10 -
Table 1-1
_ _ _ _ _
Example No. 1-1 1-2 1-3 1-4
_ . _ _ _ _
Conversion for CH2FCF2CH3 (~) 40 65 85 57
_ _ _ . _~ _. _ ,, .
Selectivity for CHClFCF2CH3 (~) 76 56 20 60
_ _ __ _
Selectivity for CCl2FCF2CH3 ~%) 8 18 29 20
_ _ _ _ . . .. _ . ..... . _ , .
Selectivity for CH2FCF2CH2Cl (%) 8 5 1 5
_ _ _ _ _ _ . . . . . ,.
Selectivity for CHClFCF2CH2C1 (%) _ _ 1 _ ~
. _ _ _ . ,._ _ _ _
Selectivity for CCl2FCP2CH2Cl (%) _ 2 5 1 ... ~ .
__ _ _ _ _ . __ _ ~ . _ .
Selectivity for CH2FCF2CHCl2 ~j%) 3 10 13 10 :
. _ _ _ _ _ _ _ _, _ . . _-- -- .
Selectivity for CHClFCF2CHCl2 (%) 1 _ 3 _ :
. ~ . . _ ~ _ _ ..
Selectivity for CCl2FCF2CHCl2 (%) 1 2 8 1
_ _ __~ _ .
Selectivity for CH2FCF2CC13 (~) 2 3 10 1
_ _ - _ _ _ ~,
Selectivi.ty ~or CHClFCF2CC13 ~) _ 1 4 _
__ . __ _ __ _ _ : ,,
Selectivity for CC12FCF2CCl3 ~) 1 2 6 2
_ _ ._ _ _ _ _
Other products (%) _ _ _ _
. _ _
EXAMPLE 1-5
Into a 1,000 cc Hastelloy C autoclave, 300 g of
1,2,2-trifluorolpropane and 20 g of di-~-butyl peroxide
were charged. Then, thei temperature was raised to 120C, .
and while stirring, 214 g of chlorine gas was supplied at .: .
a rate of 50 g/hr over a period of 4 hours. Then, the
reaction was continued for further 12 hours. The product
25 after removal of acid components, was analyzed by gas :
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 1-2.
':'
.
2~2~
EXAMPLE 1- 6
The reaction was conducted in the same manner as in
Example 1-5 except that 20 g of AIBN was used as a
radical initiator. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 1-2.
EXAMPLE 1-7
~n Inconel 600 reactor having a~ inner diameter of
1.27 cm and a length of 20 cm, ~as maintained at 430C,
and gasified 1,2,2-trifluoropropane and chlorine gas were
supplied at a rate of 300 ml/min, respectively. The
reaction was conducted continuously for 4 hours. The
product ~fter removal of acid components was analyzed by
gas chromatography and by 19F-NMR and lH-NMR. The
results are shown in Table 1-2.
Table 1-2
_ . _ _ _ . . _ _ _
Example NQ. 1-5 1-6 1-7
_ _ _ _ _ :. . ,.
Conversion for CH2FCF2CH3 (%) 56 45 50
_ _ . __ ~r_: ~
Selectivity for CHClFCF2CH3 (%) 47 60 42
. _ ~ _ _ _ _ _ _
Selectivity for CC12FCF2CH3 (~) 21 23 17
~ . . . :
Selectivity for CH2FCF2CH2C1 (%) 5 7 2
. _ _ .
Selectivity for CHClFCE'2OEI2Cl (%) _ _ _
._ _ . __ _
Seleativity for CC12FCF2CH2Cl (%) 1 1 _
_ _ __ _ _
Selectivity for CH2FCF2CHC12 (~) 12 6 5
. _ ~ _ _ .
Selectivity for CHClFCF2CHCl2 (%) _ _ 3
~ . _ . ,_ .:
Selectivity for CC12FCF2CHC12 (%) 4 _ 4 -
~ _ ~
Selectivity for CH2FCF2CCl3 (%~ 4 2 10
~ __ _ ....
Selectivity for CHClFCF2CC13 (%) 2 _ 4
~ _ _ . . ,
Selectivity for CC12FCF2CC13 (%) 4 1 6 ~
. . ~ . _
Other products (%) _ _ _ 7
_ _. __ . _ ' ,i,
2~2~
- 12 -
EX~MPLE 1-8
The reaction was conducted for 6 hours in the same
manner as in Example 1-1 except that 300 g l-chloro- . :~
2,~,3-trifluoropropane and 160 g of chlorine gas were :
used. The product was analyzed by gas chromatography and ~i
by l9F-NMR and lH-NMR. The results are shown in Table 1-
3 :.:
. .
Table 1-3 -
. , ~ _
Conversion for CH2ClCF2CH2F (%) 67
. , _ . , . .
Selectivity Eor CHCl2CF2CH2F ~) 52
Selectivity for CC13CF2CH2F ~%) 14
. . ,
Selectivity for CH2ClCF2CHClF t~) 18
.~
Selectivity Eor CHC12CF2CHClF (%) 7
~ _ __ I ...
. . Selectivity for CC13CF2CHClF ~%) 4
, _ _ _
Selectivity for CH2ClCF2CCl2F ~%) 3
~ .
Selectivity for CHC12CF2CC12F (%) 2 -:
_ _ _ , ~
Selectivity for CC13CF2CC12F (%) _ :. .
":' '.: '
EXAMPLE 1-9
The reaction was conducted for 6 hours in the same
manner as in Example 1-1 except that 300 g oE l-chloro-
1,2,2-trifluoropropane and 160 g of chlorine gas were
used. The product was analyzed by gas chromatography and .
by l9F-NMR and lH-NMR. The results are shown in Table 1- :
2S 4~
':
"."'
. .
',,'
. -
2 ~
- 13 -
Table 1-4
_ __ _ .
Conversion for CHClFCF2CH3 ~%) 77
Selectivity for CCl2FCF2CH3 (%) 77
. . _ _., _ _ ...
Selectivity for CHClFCF2CH2Cl (%) 4
, . , _ _
Selectivity for CCl2FCF2CH2Cl (%) 4
~ _ ..
Selectivity for CHClFCF2CHCl2 (%) _ _
Selectivity for CCl2FCF2CHCl2 (%) 5
Selectivity for CHClFCF2CCl3 (%) 3
_ _ _ .
Selectivity for CCl2FCF2CCl3 (%3 1
EXAMPLE 1-10 .
The reaction was conducted for 6 hours in the same
rnanner as in Example 1-1 except that 300 g of 1,3- :
dichloro-1,2,2-trifluoropropane and 130 9 of chlorine gas
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 1-5.
Table 1-5
_ _ _
Conversion for CHClFCF2CH2Cl (~) 74 . .
20. _ _ _
Selectivity for CC12FCF2CH2C1 (~) 26 i
Selectivity for CHClFCF2CHCl2 (%) 44 . .
_ _ _ . _ . _.
Selectivity for CCl2FCF2CHCl2 (~) 13 .
~ _ . .,
Selectivit~ for CHClFCF2CCl3 (%) 12
_ _ , .
Selectivity for CCl2FCF2CCl3 (%) 5
~2~6 i;~3
-
- 14 -
EXAMPLE 1-11 ;
The reaction was conducted for 6 hours in the same
manner as in Example 1-1 except that 300 g of 1,1-
dichloro-2,2,3-trifluoropropane and 130 g of chlorine gas
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 1-6.
'.... "
Table 1-6
~ . _ . : .
Conversion for CHC12CF2CH2F (%) 73
_ _ . . .
10Selectivity for CCl3CF2CH2F (%) 57 :~
, _ _ _ _ _ : i .
Selectivity for CHC12CF2CHClF (%) 11
_ _ _
Selectivity for CC13CF2CHClF (%) 25 .. :
_ : ':
Selectivity ~or CHC12CF2CC12F (~i) 3
. _
Selectivity for CC13CF2CC12F ~i) 4
:
EXAMPLE 1-12
The reaction was conducted for 6 hours in the same .
manner as in Example 1-1 except that 300 g of 1,1- .
dichloro-1,2,2-trifluoropropane and 130 g of chlorine gas
20 were used, The product was analyzed by gas ~.
chromatography and by 19F-NMR and l~-NMR. The results
are shown in Table 1-7. ~.
- 2~2~6~3
Table 1-7
_ . _ _ _ _ _ ..
Conversion for CC12FCF2OEI3 ~ 40
Selectivity for CCl2FCF2CH2Cl (%) _ _
Selectivity for CCl2FCF2CHCl2 (%) 67
Selectivity for CCl2FCF2CCl3 (%) 29
EXAMPLE 1-13
The reaction was conducted for 6 hours in the same ~.
manner as in Example 1-1 except that 300 g of 1,1,3-
trichloro-2,2,3-trifluoropropane and 105 g of chlorine
ga~ were used. The product was analyzed by gas
chromatography and by l9F-NMR and l~I~NMR. The results
are shown in Table 1-8.
Table 1-8
. _
Conversion for CHCl2CF2CHClF (%) 85
.. ._ _ _ _ . _ . ~ .
Selectivity for CCl3CF2CHClF (%) 70
Selectivity for CHC12CF2CC12F ~) 20
ISelectivity for CCl3CF2CCl2F (%) 10
`.
EXAMPLE 1-14
The reaction was conducted for 6 hours in the same
manner as in Example 1-1 except that 300 g of 1,1,3-
trichloro-1,2,2-trifluoropropane and 53 g of chlorine gas .:
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 1-9.
:'.
2 ~
- 16 -
Table 1-9
Conversion for CC12FCF2CH2Cl t~) 38 :.
_ . . T . _ _ .
Selectivity for CC12FCF2CHCl2 (%) 78
_~
~ ~ ~ _ 22 ~,
S
EXAMPLE 1-15
The reaction was conducted for 6 hours in the same .~.
manner as in Example 1-1 except that 300 g of 1,1,1- :
trichloro-2,2,3-trifluoropropane and 53 g oE chlorine gas
were used. The product was analyzed by gaæ
chromatography and by l9F-NMR and lH-NMR. q'he results
are shown in Table 1-10.
Table 1-10
_ _ .
Conversion for CCl3CF2CH2F (%) 38
_ . ~
Selectivity for CCl3CFzCHClF (%) 78 ..
. _ _ _ _ _ _ .
Selectivity for CCl3CF2CCl2F (%) 22
EXAMP~E 1-16
The reaction was conducted for 6 hours in the same
manner as in Example 1-1 except that 300 g of 1,1,3,3-
tetrachloro-1,2,2~trifluoropropane and 90 g of chlorine
ga9 were u5ed. The product was analy2ed by gas
chromatography and by 19F-NMR and lH-NMR The results
are shown in Table 1-11. 7
" '
'"
2~2~6~ ~:
--
Table 1-11
. _
Conversion for CC12FCF2CHC12 (%) 98
ISelectivity for CCl2FCF~CCl3 (%) 100
EXAMPLE 1-17 ~ .
~ he reaction was conducted for 6 hours in the same
manner as in Example 1-1 except that 300 9 of 1,1,1,3-
tetrachloro-2,2,3-trifluoropropane and 90 9 of chlorine
gas were used. The product was analyzed by gas
chromatography and by l9F-NMR and lH-NMR. The results
are shown in Table 1-12.
Table 1-12
.. _ _ _ . . .
. Conversion or CC13CF2CHClF t%) 97
. I . ~
Selectivity for CCl3CF2CCl2~ (%) 100 :~
~.
EXAMPLE 2
A 1,000 cc glass reactor e~uipped with a condenser o~
-78C, was cooled to -20C, and 300 g of 1,2,2,3-
tetrafluoropropane was charged. Then, 95 9 of chlorine
gas was gradually introduced while stirring under
irradiation by a high pressure mercury lamp of 500 W.
After the reaction for 6 hours, the product after removal :
25 o~ acid components, was analyzed by gas chromatography :.
and by 19F-NMR and IH-NMR. The results are shown in ~ :
- .:
Table 2-1. ~
. . .
. :
~. .
~ ~ 2 ~
- lB -
EXAMPLE 2-2
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 g o~ 1,2,2,3-
tetrafluoropropane and 185 g of chlorine gas were used.
The product was analyzed by gas chromatography and by
19F-NMR and lH-NMR. The results are shown in Table 2
EXAMPLE 2-3
- The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 g of 1,2,2,3-
tetrafluoropropane and 370 g of chlorine gas were used.
The product was analyzed by gas chromatography and by
19F-NMR and lH-NMR. The results are shown in Table 2-1.
EXAMPLE 2-4
The reaction was conducted Eor 6 hours in the same
lS manner as in Example 2-1 except that 300 g of 1,2,2l3-
tetxafluoropropane, 185 g oE chlorine gas and 200 9 of
CC14 as a solvent were used. The product was analyzed by
gas chromatography and by 19F-NMR and lH-NMR. The
results are shown in Table 2~1.
6 ~
-- 19 --
Table 2-1
. . _ __ .
Example N~. 2-1 2-2 2-3 2-4
_ _ , _ .
Conversion for CH2FCF2CH2F (%) 40 66 92 65
Selectivity for CHClFCF2CH2F (%) 90 61 30 70 _ . _~ ,, ,_
Selectivity for CCl2FCF2CH2F (%) 5 18 25 15
~ _, . _ ~ ~
Selectivity for CHClFCF2CHClF (~ 3 11 15 g
_ . _ . _ _ _
Selectivity for CCl2FCF2CHClF (%) 2 8 19 5
. _ _ _ _ _ _ _ . ., .__ . ,
Selectivity for CCl2FCF2CClF2 (~) _ 2 11 1
. . ~ . , _. _ . . ,'
EXAMPLE 2-5
Into a 1,000 cc Hastelloy C autoclave, 300 g of
1,2 r 2,3-tetrafluorolpropane and 20 g of di t-butyl
peroxide were charged. Then, the temperature was raised
to 120C, and while stirring, 185 g of chlorine gas was
supplied at a rate of 50 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product ater removal of acid components, was
analyzed by gas chromatography and by l9F-NMR and l~-NMR.
~he results are shown in Table 2-2.
EXAMP~E 2-6
The reaction was conducted in the same manner as in
Example 2-5 except that 300 g of 1,2,2,3-
tetrafluoropropane and 20 g of AIBN as a radical
initiator were used. The product was analy~ed by gas
,
~ .,
, .
2 0 2 6 ~ 6 ~
- 20 -
ch~omatography and by l9F-NMR and lH-NMR. The results
are shown in Table 2-2.
BXAMPLE 2-7
An Inconel 600 reactor having an inner diameter of
1.27 cm and a length of 20 cm, was maintained at 430C,
and gasified 1,2,2,3-tetra~luoropropane and chlorine gas
were supplied at a rate of 150 ml/min, xespectively. The
reaction was conducted continuously for 4 hours. The
product after removal of acid components was analyzed by
gas chromatography and by 19F-NMR and lH-NMR. The
results are shown in Table 2-2.
Table 2-2
Example No. 2-5 Z-6 2-7
,- _
Conversion Eor CH2FCF2CH2F ~%) 50 35 54
15Selectivity for CHClFCF2CH2F ~) 60 66 53
_ _ _ ,
Selectivity ~or CC12FCF2CH2F (~) 15 12 16
. ~ ~ . . . . ..
Selectivity for CHClFCF2CHClF (%) 11 7 12 ~ -
, ~ _ _ _ _ _ . , .
Selectivity for CC12FCF2CHClF (%) 10 5 7
,. _ _ .
Selectivity for CC12FC~2CC12F (%) 4 3 5
_ _ . _ . -- . .
. .
EX~MPLE 2-8
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 9 of 1,1,2,2-
tetrafluoropropane and 185 g of chlorine gas were usedand the reaction was carried out at -30C. The product
was analyzed by gas chromatography and by l9F-NMR and lH-
. .
, , . . . . . .... .. : .. ; .. .. . ,.. ., ,;, ,. . . ~ . .,., ", ~, : .. .,:. . . . .
2~2~6`~
,. .. :
- 21 -
NMR. The results are shown in Table 2-3.
Table 2-3
_ , _ ~
Conversion for CHF2CF2CH3 (%? 54
Selectivity for CClF2CF2CH3 (~) 45
_ _ _ _ _ . __ _ _
Selectivity for CHF2CF2CH2C1 (%) 2
. . . _ .
Selectivity for CClF2CF2CH2Cl (%) 4
~ . .
Selectivity for CHF2CF2CHCl2 (%) 20 .~ .
_ . .
Selectivity for CClF2CF2CHCl2 (%) 13
Selectivity for CHF2CF2CC13 (%) 15
. . -
Selectivity for CClF2CF2CCl3 (%) l :
. _ "... ..
. . . .
EXAMPLE 2-9
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 g oE l-chloro-
2,2,3,3-tetrafluoropropane and 140 g of chlorine gas were .
used. The product was analyzed by gas chromatography and
by 19F-NMR and lH-NMR. The results are shown in Table 2-
4. ;!
Table 2-4
___ ~ . -
Conversion ~or CH2ClCF2CHF2 (%) 57 :~
. __ . .
Selectivity ~ 4
: Selectivity for CHCl2CF2CHF2 (%) 12
, _ . _ _ _ . _ _ ~ __. . ..
Selectivity for CHCl2CF2CCl~2 ~) _
Selectivity for CC13CF2CHF2 (~) 21
. .. _ _ ___,_ . , :
Selectivity ~or CC13CF2CClF2 (%) l . :
, _ _ _ _ _ . ~ .-- ' ,
.
,
~2~ ~3~ ~
- 22 -
EXAMPLE 2-10
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 g of l-chloro-
1,2,2,3-tetrafluoropropane and 140 g of chlorine gas were
used. The product was analyzed by gas chromatography and
by 19F-NMR and lH-NMR. The results are shown in Table 2-
5.
Table 2-5
, , , , _ . , ..
Conversion for C~ClFCF2CH2F ~%) 80
, ,, ............. _ . . .
10Selectivity for CCl2FCF2CH2F ~%) 54
_ . .... . . _ ..
Selectivity ~or CHClFCF2CHClF (%) 28
.. ... . ............. . _ .
Selectivity for CC12FCF2C~ClF ~%) 16
, ...... . __ _
:..
EXAMPLE 2-11
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 g of l-chloro- -
1,1,2,2-tetrafluoropropane and 140 g of chlorine gas were
usedO The product was analyzed by gas chromatography and
by 19F-NMR and lH-NMR. The results are shown in Table 2-
6.
Table 2-6
. ..
l Conversion for CClF2CF2CH3 (%) . .
~ _ ~) S
Selectivity for CClF2CF2CHC12 (%) 65
.. . - . . . . . ~
SPlectivity for CClF2CF2CC13 (%) 30
: .
2 ~
- 23 -
EXAMPLE 2-12
The reaction was conducted for 6 hours in the same
manner as in Example 2-l except that 300 g oE 1,3-
dichloro-1,2,2,3-tetrafluoropropane and 115 9 of chlorine
gas were used. The product was analyzed by gas
chromatography and by 19F-~MR and lH-NMR. The results
are shown in Table 2-7.
Table 2-7
_ _ . _ , .
Conversion for CHClFCF2CHClF (%) 88
, _ . __ __ _
10Selectivity for CCl~FCF2CHClF (%) ~9 : :
. _ . _ ~
5electivity for CCl2FCF2CCl2F (%) 11 :
~ _ ,:
EXAMPLE 2-13
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 9 of l,l- ~:
dichloro-2,2,3,3-tetrafluoropropane and 115 9 of chlorine
gas were used. The product was analyzed by gas :.
chromatography and by 19F-NMR and lH-NMR. The results ~ .
20 are shown in Table 2-8.
q'able 2-8
Conversion for C~IC12CF2CHF2 ~) 95
_ _ , ,.
Selectivity for CC13CF2CHF2 (%) 97 ..
. _ __ _
Selectivity for CHC12CF2CC1~2 (~) 3 : ~ :
. . _, _ ~ ___ . .
Selectivity for CCl3CF2CClF2 (%) _ : -
_ __ __ . :.. :" .
,
.....
2 ~ 2 ~ ~ 6 b
-- 24 --
EXAMPLE 2-14
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 g of 1,3-
dichloro-1,1,2,2-tetrafluoropropane and 58 g of chlorine
gas were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 2-9.
~ ;~
Table 2-9
. _ . .
Conversion for CClF2CF2CH2Cl (%) 35
, .
Selectivity for CClE'2CF2CHC12 (%) 80
~ . ~
Selectivity for CClE`2CF2CCl3 (~) 20
. _ _
EXAMPhE 2-15
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except ~hat 300 9 of 1,1-
dichloro-1,2,2,3-tetrafluoropropane and 58 g of chlorine
gas were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 2-10.
~able 2-10
_
Conversion ~or CC12FCE'2CH2F (%) 38 -:
_ _
Selectivity for CC12FCF2CHClF ~%) 78 ~ ~
, _ _ . . . .
Selectivity ~or CCI~/Cr~CCI~ 22 ;
2~26~
-- 25 --
EXAMPLE 2-16
The reaction was conducted for 6 hours in the same
manner as in Example 2-l except that 300 9 o~ l,1,3-
trichloro-2,2,3,3-tetrafluoropropane and lO0 g of
chlorine gas were used. The product was analy~ed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 2-ll.
Table 2-11
_ _ _ _
Conversion for CHC12CF2CClF2 (%) 98
. ,~_ _ _ _ . .
lUSelectivity ~or CC13CF2CClF3 (%) 100
._ _ __._ .. :''
':
. . ,:
EXAMPLE 2-17
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 g of 1,1,3-
trichloro-1,2,2,3-tetrafluoropropane and 100 g of
chlorine gas were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
20 are shown in Table 2-12.
:. ::..
Table 2-12
__ __ _ .
Conversion for CCl2FCF2C~IClF ~%~ 97 ~.
. . .
Selectivity for CC12FCF2CCl2F (%) 100
- 26- 2~2~ 3
EXAMPLE 2-18
The reaction was conducted for 6 hours in the same
manner as in Example 2-1 except that 300 g of 1,1,1-
trichloro-2,2,3,3-tetrafluoropropane and 100 9 of
chlorine gas were used. The product was analyzed by gas
chromatography and by l9F-NMR and lH-NMR. The results
are shown in Table 2-13.
Table 2-13
~ r - ~
Conversion for CCl3CF2CEF2 (%) ¦ 91 ..
_ . _ _ I _ _ . .
Selectivity Eor CC13CF2CClF2 (% ~ 100
EXAMPLE 3-1 .
A 1,000 cc glass reactor equipped with a condenser of
-78C, was cooled to -20C, and 300 g of 1,1,2,2,3-
pentafluoropropane was charged. Then, 80 g oE chlorine
gas was gradually introduced while stirring under
irradiation by a high pressure mercury lamp of 500 W.
A~ter the reaction for 6 hours, the product after removal
oE acid components, was analyzed by gas chromatography
and by 19F-NMR and lH-NMR. The results are shown in
Table 3-1.
EXAMPLE 3-2
The reaction was conducted for 6 hours in the same
manner as in Example 3-1 except that 300 g of 1,1,2,2,3- .
pentafluoropropane and 160 g of chlorine gas were used.
' ',
'' ',
'.
2 ~
- 27 -
The product was analy~ed by gas chromatography and by
l9F-NMR and lH-NMR. The results are shown in Table 3-1.
EX~MPLE 3-3
The reaction was conducted for 6 hours in the same
manner as in Example 3-1 except that 300 g of 1,1,2,2,3-
pentafluoropropane and 320 9 of chlorine gas were used.
The product was analyzed by gas chromatography and by
19F-NMR and lH-NMR. The results are shown in Ta~le 3-1. ~:~
EXAMPLE 3-4
The reaction was conducted for 6 hours in the same
manner as in Example 3~1 except that 300 g Of 1 r 1 r 2,2,3-
pentafluoropropane, 160 g o~ chlorine gas and 200 g oE
CC14 as a solvent were used. q'he product was analyzed by
gas chromatography and by 19F-NMR and lH-NMR. The
results are shown in Table 3-1.
.:~
....... ..
.,:. ~,
Table 3-1 .~
_ _ _ _ ~
Example No. 3-1 3-2 3-3 3-4
__ _ _ _ __
Conversion for CHF2CF2CH2F ~i)32 60 97 55 ..
_ _ _
Selectivity for CClF2CF2C~2F (%) 12 12 4 12
~ . . _ . _ ...
Selectivity for CHF2CF2CHClF (~i) 78 71 20 75 . ..
_ _ _ _ . . _ _ _ . .... ..
Selectivity for CClF2CF2CHClF (%): . 2 5 12 4
. : ~ _ . . _ _
Selectivity for CHF2CF2CC12F (%) 8 11 47 8 .
~_ _ -- . ! - '
Selectivity for CC}F2CF2CC12F (%) . ~ 1 17 1
_ . - . _ _ _ .
. .. . .... .... ..
2632~6i~
-- 28 --
EXAMPLE 3--5
Into a l,000 cc Hastelloy C autoclave, 300 g of
1 j1,2,2, 3-pentafluorolpropane and 20 g oE di-t-butyl
peroxide were charged. Then, the temperature was raised
to 120C, and while stirring, 200 g of chlorine gas was
supplied at a rate of 50 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product after removal of acid components, was
analyzed by gas chromatography and by 19F-NMR and lH-NMR.
The results are shown in Table 3-2.
EXAMPLE 3-6 ;
The reaction was conducted while 200 g of chlorine
gas was supplied at a rate of 50 g/hr for 4 hours in the
same manner as in Example 3-5 except that 300 g of
15 1,1,2,2,3-pentafluoropropane and 20 g of AIBN as a
radical initiator were used. The product was analyzed by
gas chromatography and by 19F-NMR and lH-NMR. The
results are shown in Table 3-2.
EXAMPLE 3-7 ~ -
An Inconel 600 reactor having an inner diameter of
1,27 cm and a leng~h of 20 cm, was maintained at 430C,
and gasified 1,1,2,2,3-pentafluoropropane and chlorine
gas were supplied at a rate of 150 ml/min, respectively.
The reaction was conducted continuously for 4 hours. The
product after removal of acid components was analyzed by
gas chromatography and by 19F-NMR and lH-NMR. The
results are shown in Table 3-2.
, . , ,', . '. . ' ~' ' .; " ' ' " " " ~ .' ' ' " ' ' " ' ', '' " ' '' , ', ' ~ ' ', ' ' , ' ' ' ,., ' " ' ' '
2 ~
- 29 -
Table 3-2
. _. _ ~ . .
Example No. 3-5 3-6 3-7
_ __ .
Conversion for CHF2CF2CH2F (%) 60 45 50
_ . ,_
Selectivity for CClF2CF2CH2F (%)15 12 20
S - . . ............................. _ .
Selectivity for CHF2CF2CHClF (~) 58 62 58
. . . . , , . ._ ~ ~ _ . . _
Selectivity for CClF2CF2CHClF (%) 5 6 ~ :
Selectivity for CHF2CF2CC12F ~%) 17 15 9 ..
. . ~ _ . . .
Selectivity for CClF2CF2CCl2F (%) ~ ~ 5 6
- . :'
EXAMPLE 3-8 ::
The reaction was conducted for 6 hours in the same
manner as in Example 3-1 except that 300 g of 1,1,1,2,2-
pentafluoropropane and 160 g of chlorine gas were used
and the reaction was carried out at -30C. The product
was analyzed by gas chromatography and by 19F-NMR and lH- `
NMR. The results are shown in Table 3-3.
Table 3-3
~ __
Conversion for CF3CF2CH3 (%) 40
Selectivity for CF3CF2CH2Cl (~) 6 . :.:
_ .................. ,.. _ ... . i '
Selectivity for CF3CF2CHC12 (~) 64
. ., .
Selectivity for CF3CP2CC13 (%) 30
~ '
'','
' ,~
'.
.':' ,
2 ~ 6 ~ :
- 30 -
EXAMPLE 3-9
The reaction was conducted for 6 hours in the same
manner as in Example 3-1 except that 300 g of l-chloro-
1,2,2,3,3-pentafluoropropane and 130 9 of chlorine gas
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 3-4.
Table 3-4
. _ _ _ . _
~ 9~ . ~"
Selectivity for CC12FCF2CHF2 (%) 90
_ ..
Selectivity for CHClFCF2CClF2 (%) 8
_ _ _ _ __
Selectivity for CC12FCF2CClF2 (%) 2
EXAMPLE 3-10
The reaction ~as conducted for 6 hours in the same
manner as in Example 3-1 except that 300 g of l-chloro-
2,2,3,3,3-pentafluoropropane and 65 g of chlorine gas
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 3-5.
¦convers~ ~ F 3 1
: Selectivit ~ 9
2:5 ~ ~ 19 i ~ .
2 a~
- 31 -
EXAMPLE 3-11
The reaction was conducted for 6 hours in the same
mianner as in Example 3-1 except that 300 g of l-chloro-
1,1,2,2,3-pentafluoropropane and 65 g of chlorine gas
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results ;~ .
are shown in Table 3-6.
Table 3-6
_ _ _ _ _
Conversion for CClF2CF2CH2F (~i) 36
__ ..
10Selectivity for CClF2CF2CHClF (%) 76 .
_ . . . ~ _
Selectivity for CClF2CF2CC12F ~%) 24
EXAMPLE 3-12
The reaction was conducted for 6 hours in the same `:
manner as in Example 3-1 except that 300 g of 1,1- :.
dichloro-2,2,3,3,3-pentafluoropropane and 105 g of
chlorine gas were used. The product was analyzed by gas ,
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 3-7. :':
Table 3-7 _ , .
IConversion for CF3CF2CHC12 (~) _ _
25j5electivity for cr~Cr~cc~ ) 100 ::
; ~
'.
. i
~2~6~
- 32 -
EXAMPLE 3-13
The reaction was conducted for 6 hours in the same
manner as in Example 3-l except that 300 y of 1,3-
dichloro-1,1,2,2,3-pentafluoropropane and 105 g of
chlorine gas were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 3-8.
Table 3-8
. _ _ _ _ _ _ _
Conversion for CClF2CF2CHClF (%) 97
, ~ . .
Selectlvity for CClF2CF2CCl2F ~%) lO0 r
. . _ ____ . - _ _ . .
EXAMPLE 3-14
The reaction was conducted for 6 hours in the same
manner as in Example 3-1 except that 300 g of l,l-
dichloro-1,2,2,3,3-pentafluoropropane and 105 g of
chlorine gas were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 3 9.
Table 3-9
. . _ ..
Conversion for CCl2FCF2CHF2 t%) 91
_ _
Selectivity for CCl2FCF2CClF2 (%) lO0
_ _ , __ _
~5
.
2~26~
- 33 - :
EXAMPLE 4-1
A 1,000 cc glass reactor equipped with a condenser of
-78C, was cooled to -20C, and 300 g of 1,1,2,2,3,3- -
hexafluoropropane was charged. Then, 70 g of chlorine
gas was gradually introduced while stirring under
irradiation by a high pressure mercury lamp of 500 W.
After the reaction for 6 hours, the product after removal
of acld components, was analyzed by gas chromatography
and by 19F-NMR and lH-NMR. The results are shown in ;~
Table 4-1.
EXAMPLE 4-2
The reaction was conducted for 6 hours in the same
manner as in Example 4-1 except that 300 g of ;~
1,1,2,2,3,3-hexafluoropropane and 140 g of chlorine gas
lS were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 4-1.
EXAMP~E 4-3
The reaction was conducted for 6 hours in the same
manner as in Example 4-1 except that 300 g of
1,1,2,2,3,3-hexafluoropropane and 280 g of chlorine gas
were used. The product was analyzed by gas
chromatography and by l9F-NMR and lH-NMR. The results
are shown in Table 4-1.
ExAMpLE 4-4
The reaction was conducted for 6 hours in the same
manner as in Example 4-1 except that 300 g of
~2~6~
~ 34 -
1,1,2,2,3,3-hexafluoropropane, 140 g of chlorine gas and
200 g of CC14 as a solvent ~ere used~ The product was
analyzed by gas chromatography and by 19F-NMR and lH-NMR.
The results are shown in Table 4-1.
Table 4-1
. . . ._ . , _ . , .. . _ ..
Example No. 4-1 4-2 4-3 4-4
. . . . . . . . . ~ _
Conversion for CHF2CF2CHF2 (%) 32 64 92 52
. . _
Selectivity for CClF2C~2CHF2 t%) 98 81 32 89
.~ . . . _ ~ . . . ,._
Selectivity for CClF~CF2CClF2 (%) 2 19 68 11
. _ . . . . . .,
Other products (~) _ _ _ . _
. _ _ . _ .
,
EXAMPLE 4-5
Into a 1,000 cc ~astelloy C autoclave, 300 9 of
1,1,2,2,3,3-hexafluorolpropane and 20 g of di-t~butyl
peroxide were charged. Then, the temperature was raised
to 120C, and while stirring, 160 g of chlorine gas was
supplied at a rate o~ 40 g/hr over a period of 4 hours.
Then, the reaction was continued for further 12 hours.
The product a~ter removal o~ acid components, was -
- analyzed by gas chromatography and by l9F-NMR and l~-NMR.
The results are shown in Table 4-2.
EXAMP~E 4-6
The reaction was conducted in the same manner as in
:~ "
` ;;
.
, , .
2 a 2 ~
- 35 -
Example 4-5 except that 300 9 of 1,1,2,2,3,3-
hexafluoropropane and 20 g of AIBN as a radical initiator
were used. 160 of chlorine gas was supplied at a rate of
40 g/hr over a period of 4 hours, and then the reaction :
was continued for further 12 hours. The product was
analyzed by gas chromato~raphy and by 19F-NMR and lH-NMR.
The results are shown in Table 4-2. ~.
EXAMPLE 4--7
An Inconel 600 reactor having an inner diameter of ~'
1.27 cm and a length of 20 cm, was maintained at 430~C,
and gasified 1,1,2,2,3,3-hexafluoropropane and chlorine
gas were supplied at a rate of 150 ml/min, respectively. ;
The reaction was conducted continuously for 4 hours. The
product after removal o acid components was analyzed by
gas chromatography and by 19F-NMR and lH-NMR. The
results are shown in Table 4-2.
Table 4-2
_ . _ __ .................... .. _ ,.:'.
Example No. 4-5 4-6 4-7 -
~ _ . _ _ _ __ _ _ __
Conversion for CHF2CF2CHF2 (%) 50 25 66
- _ _ ~ _ __
Selectivity for CClF2CF2CHF2 (%) 80 95 72
. _ __ .
Selectivity Eor CClF2CF2CClF2 ~%) 20 __ 20
Other products ~) _ _ 8
.. ~ ,. _ _
,."~
, :'
2 ~ 6 ~
- 36 -
EXAMPLE 4-8
The reaction was conducted for 6 hours in the same
manner as in Example 4-1 except that 300 9 of
1,1,1,2,2,3-hexafluoropropane and 70 g of chlorine gas
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMRo The results
are shown in Table 4-3.
Table 4-3
~ ..
Conversion for CF3CF2CH2F (%) 38
1 0 , . ~
Selectivity for CF3CF2CHClF (%) 74
_ _ _ _ .
Selectivity for CF3CF2CC12F (%) 26 ~:
. "
EXAMPLE 4-9
The reaction was conducted for 6 hours in the same
manner as in Example 4-1 except that 300 g of l-chloro-
1,2,2,3,3,3-hexafluoropropane and 120 9 of chlorine gas
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 4-4.
Table 4-4 :
. _ _ _ _.
Conversion for CF3CF2CHClF (~i) 97
. ~ . ' ~:
Selectivity for CF3CF2C.Cl2F (%) 100 . .
_ _ . .
',:
., .:
,',
' ~'':
:, :.
~ ~ 2 ~
- 37 - -
EXAMPLE 4-10
The reaction was conducted for 6 hours in the same
manner as in Example 4-1 except that 300 g of l-chloro-
1,1,2,2,3,3-hexafluoropropane and 120 g of chlorine gas
were used. The product was analyzed by gas
chromatography and by 19F-NMR and lH-NMR. The results
are shown in Table 4-S.
Table 4-5 :
. , , ,
Conversion for CClF2CF2CHF2 (%) 95 :.
. . _ .,
Selectivity for CClF2CF2CClF2 (%) 100 ;.
The present invention is effective for producing a
chlorine-containing 2,2~difluoropropane sele~tively by
chlorinating a 2,2-difluoropropane.
~, . ,, , . , . ,, . . . - . .. ..
. . : . ........ . . ............. . ....... .
.. . . . . ..
