Note: Descriptions are shown in the official language in which they were submitted.
2~3~79
Dl:'';(`K' :LPTI()N
~ rr,~ . .[Nvr~ N~rIol~]
P~-~o~l.S(~ L~R~L~[~CIN~ ~ ~Ic~lrJol~opE~ o~opRopANE
T l~CI~Nl~ ;t~L, D
'l~he presellt invelltioll relates to a process for
producing a (-I;.chl.olol~ent.lf.lllol.opropane (1~25) SIICIl as
3,3-dichloro-1,1,1,2,2-penta~1uoropropane (R225ca) or
1,3-dichloro-1,1,2,?,3-pentaEluoropropal~e (R225cb). Such
a dichloropentafLuoroproparle is expectecl to be useful as
a foaming agent, a cooling medium or a cleaning agent
like conventional chlorofluorocarbons (~FCs).
BACKGROUND TECIINIQUE
As a method for producing the
dichloropentafluoropropane (R225), lt is Icnown to
synthesi~e it by adding dichlorofluoromethane to
tetrafluoroethylene in the presence of aluminum chloride.
However, this method produces, in addition to the desired
products, by-products which are hardly separable by a
usual method such as distillation since their boiling
points are elose to that of the desired products, and
thus has a disadvantage that a multi-step-purification
process is required to obtain the products in high
purity.
25DISCLôSURE OF THE INVENTION
The present inventors have conducted extensive
studies on a process for efficiently producing the
203~7~
. ,~
lc)~ o~ c~ e~ , th~y
~la~e foui~(l it i)o;sihle t(, obtain ~l
clichlolopellt:afluorc)prol)ane ((`3C~2i;`,;EI) in good yield by
c-.ubjec~ c~ tetL-aL:l.uoroetlly:lene (C`F~=CF`2) and cce3x
(wllerei~ ; (`e, F or ll) to al) rl~lditiOII r~act;on, and
reduci.ng alld//Or f l.UOrillat:in9 the l e'Sll].tin9 C3Ce3F,~X. The
present invenl:ion l~as beell accoll)~lishecl Oll tl~e basis oE
this discovery.
Thus, ~-he present inventioll provides a process for
10 producillcJ rl dichloropentaLluoropropaller Wilich comprises
subjecting CF2=CE'2 and CCe3X (wherein X is ce, F or H) to
an addition reaction, and reducing and/or f]uorinating
the resulting C3Ce3F~X to obtain C3Ce2F5H.
_E T MODE OF CARRYING O~T THE Il EN'rION
Now, the present invention will be described in
detail with reference to the-preferred embodiments.
When trichlorofluoromethane ~Rll) is reacted with
tetrafluoroethylene (4F) in the presence of a Lewis acid
catalyst, trichloropentafluoropropanes such as 1,1,3-
trichloro-1,2,2,3,3-pentafluoropropane (R215ca) and
1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R215cb) are
obtained in good yield.
The proportionas of R215ca and R215cb formed by this
addition reaction vary depending upon the catalyst and
reaction conditions employed.
As the I,ewis acid catalyst useful for the reaction
of the present invention, it is possible to employ a
~0~47~
",~ "i~l,t ~ t f~ected ~rom the
c~ f 13, ~, G~ i, Co, Sb, Nb,
Sn, ~ri, ,~ f al~d ~ -1, such as a clll(.,ride, e.g. BCe3,
ACCe3, (;~ICe~ nCe3, i~eCe~, NiCe~, cOCe2, ~bCes, SnCe2,
" llr ~ l''5, ~:1 p~ c~ y
f.lllorill.-lt.e~l colll~o~ln(l tll~-eol:, a bromide or iodide, e.g.
C~a:r3, lli-BI~, ilL:[~, :rnBr3~ ~n]3, Til31:~, rl~lBI-5, ~eBr~, ~eI3,
BBr3 or Bl3, a part;.ally cll:Lorinated or f:Luorinated
compound thereof, or a fluoride such as BF3 or SbF5. The
reacticn can be conducted in an inert solvent such as
perfluorooctane or perfluorobutyltetrahydrofuran.
However, to make the purificatioll easy, it is usually
preferred to conduct the reaction in the absence of any
solvent. The catalyst is used usually in an amount of
15 from 0.01 to 50~ by weight, preferably from 0.1 to 10~ by
weight, relative to the starting material. The reaction
temperature is usually within a range of from -80 to
200C, preferably from -20 to 100C, and the reaction
pressure is usua].ly from 0 to 20 kg/cm2, preferab].y from
20 0 to 10 kg/cm2. For the reaction, 4F is used usually 1.0
to 1.5 times the molar quantity of Rll. The Lewis acid
eatalyst is usually used in an amount of from 0.1 to 50
weight%~ preferably from 0.1 to 10 weight~, relative to
Rll.
The reduction of triehloropentafluoropropane (R215)
obtained by this reaetion ean be eondueted by using
various redueing methods such as a method of eondueting
'~03447~
the reclllclioll ul~deJ ilradi~ltion, a lileLIn~(l for conducting
the Leductic)ll t~y n~eal)s c,f ~inc, c~n a melt~ocl for
conducLil-y the recluction by usinc3 hydro-Jell in the
~resencc c,f a cat:aly~t, ~h~reby
dicl-~orc)L)el-ltclfLuol:c-}~ropal-e (R225), such ~s 3,3-dichloro-
1,1,~,2,2-~elltcl~luoroL~ropal~e (k225ca) ol- 1,3-dichloro-
1,1,2,2,3--pelltaf]uolopropalle (~225ch) can be obtained.
In the case ol con(]uctil-g the reduetioll ullder
irradiation, as a compound used as a proton souree, an
organie compound having a hydrogell atom bonded thereto is
used. F`or exampJe, an alcohol sueh as methanol, ethanol,
isopropyl aleohol or see-butyl aleohol, an alkanè sueh as
hexane or heptane, or an aromatic compoulld sueh as
toluene or xylene, is preferred. Among them, a seeondary
aleohol sueh as isopropyl aleohol, is partieularly
preferred. Further, a solvent mixture thereof may also
be employed.
The light souree to be used in the present invention
is not partieularly limited so long as it is eapable of
emitting light having a wavelength of shorter than 400
nm. For example, a high pressure mereury lamp, a
moderate pressure mercury lamp or a low pressure mereury
lamp, may preferably be employed. The reaetion is
eondueted usually within a temperature range of from -80
to 100C, preferably from 0 to 40C. There is no
partieular restrietion as to the pressure. ~owever, the
reaetion is eondueted usually within a pressure range of
~34~79
,
) t ~ r~ r~ y r~, <,l,~ o ~ g/cln2~.
'L'he ~c.~lvellt~ ;ed Lor the rC~ llC`tiOIl L~y means of zinc,
is not p~ ti(nllal-ly :limit(d. Howe~el-, it is preferred to
.Oy .~ 1 <15 Ill~'t~ llC)I, ~t~ ol or isopropyl
, C~ oll(~ c~.ll~i(~,l(:i(l c;~l~ll c~ etic:.lcid ~r ormic
acid, all clhel- su(ll as tetrahydrofurall o~: water, or a
mi2~ture thel-e~oL. 11l partiCUI.-.lr, an alcollo] such as
methallo~, cthanol or isopropyl alcohol i-s preferred.
Zinc mdy ~e used in any form such as a powder, granules
or fragments. However, it: is most preferred to employ
zinc powder. It is unllecessary to apply any special
pretreatmellt such as activating treatment before use.
The amount of zinc is not particularly limited. But it
is usually preferred to employ it at least stoichiometric
amount relative to the starting material. The reaction
is conducted usually within a temperature range of from
room temperature to 150C, preferably from 50 to 80C.
There is no particular restriction as to the pressure,
but the reaction is conducted usually wit-hin a pressure
range of from 0 to ln kg/cm2G, preferably from 0 to 3
kg/cm2G .
In a case where the reduction is conducted by using
hydrogen in the presence of a catalyst, the reaction may
be carried out either in a liquid phase or a gas phase.
The reducing catalyst may be a noble metal catalyst such
as platinum, pal~adium, rhodium or ruthenium, or a base
metal cata]yst such as nickel. However, it is
t,
.ic~ r ~ t, ~ ; f ' C ~ C ~ a]. ~atalyst. A.s
t~ c~ f ~ (al~ ly(.-;t, ~ nil~a or active
C.lrbOn i' ~ ~01 (:',;allll?ll', Slli ln-lb]i`. rrhfi c-nvelltional
method J:c~r ~.~lc~ r.l~:ion of a nobl.e metal (:atalyst can be
~, a~ Li.e(l a: n ~n~ o(l lor ~::U~ oLti~ tlle (atalyst on the
~arriel-. 1`() ll ;u ~l~e c It ~Iy-;t, it iS pr~ rrec] to
prelimillcll-i.l.y al)pl.y leduc~:i.oll treatmellt lo the catalyst
to obtai.n l:he c~on ;tant lle r fol-mallce. ~lo~ ver, such a
pretreatlllent is not neces.sari.ly required. ~t least a
part oE such a metal compound is reduced.
The ratio of hydrogen to the starting material may be
varied to a large extent. Usually, the halogen atom is
removed by using hydrogen in a stoichiometrical amount.
E~owever, in order to let the starting material react
almost compl.ftely, the molar ratio of the hydrogen to the
starting meterial may be larger than one to one, for
example, four to one or higher.
In the gas phase reaction, the reacti.on temperature
is usually from ].00 to 350C, preferably from 100 to
200C. The contact time is usually from 0.1 to 300
seconds, preferably from 2 to 60 seconds. When the
reaction is conducted in a liquid phase, a~ the solvent,
an alcohol such as ethanol or isopropyl alcohol, acetic
acid or pyridine may be used. However, the reaction can
be conducted without any solvent. The reaction
temperature for the liquid phase reaction is preferably
from room temperature to 150C, and the reacti.on pressure
203~7i3
- 7
l. '; pl- ~' f ~ ! .! ) ~ ] `; I 1 ( `!11 .1 ~ lil()';~)~li` l: i , ~1 I_'SSII i (' 1~ 1. [) k9~cl~ G .
Oll t~ c)'~ forl~ reacted
~i.th tetr,lrl.~)roetllylelle ill t:he pLtsenc~-~ of- a I,ewi.s acid
catalyst, 1,~,3--tri.clll.oro---l.,1,2,2--tetr.lf.llioIopropane
22~ca) i-. obt:.ajlle~d i.n q<)od yicld, as ~:~lOWIl in the
followillg f o r lT~
CE`2 - ( F2 1' C~iC~
Lewis acid ccltalycit
___ _____ ._ ~ CCeF2CF2Cllce2
This reaction is conducted under the same conditions
as in the above mentioned addition reaction of 4F with
Rll.
The fluorination of l,3,3-trichloro-l,l,2,2-
tetrafluoropropane (R224ca) obtained by this reaction, is
conducted preferably in a gas phase in the presence of a
catalyst, or in a li.quid phase by using hydrogen
fluoride. The proportions of R225ca and R225cb formed hy
the fluorination vary depending upon the catalyst and
reaction conditions empolyed. As the caralyst used in
the gas phase, it is possible to employ a halide or an
oxide contai.ning at least one element selected from the
group consisting of Ae, Cr, Mg, Ca, Ba, Sr-/ Fe, Ni, Co
and Mn. As a method for the preparation of the catalyst,
any method may be employed so long as it is a method
capable of uniformly dispersing the hali.de or oxide
containing at least one element selected from the above
elements. For example, a coprecipit.ation method or a
~34~79
-- ~3 -
~ e~ )(J l!l~ i linl'. h~' usec]. r~ar~:iCIIlal Iy preferieCl iS a
mc~llo(l ol. (ollr~ i.t.ltil~9 l~ydrate!; f rom all a~ueous
solution of saLts ol the above nlellt-iolle(llnetal elements,
or a metho(l c~f Icnecldillg or att:ritillg a c.lke of hydroxides
by a ball Inill oL a llomo9el1i%er. AS the hydroxides,
those precipit:a~ecl l~rolll an aqueous solution of inorganic
salts such as nitl-clt:es or sulfates by IllCallS of aqueous
ammonia or urea, Or those prepared by th-- hydroLysis o~
organic salts, may be employed.
The cata]yst in the form of hydrates is preferably
dried at a temperature of from 120 to 150C, followed by
calcining usually at a temperature of Erom 300 to 600C,
preferably from 350 to 450C. In the present invention,
it is preferred to conduct activation of the catalyst.
This object can be accomplished usually by applying
fluorinating treatment usually at a temperature of from
100 to 450C, preferably from 200 350C. The activation
can be conducted in the fluorination reaction system, or
by heating witll a fluorinated hydrocarbon. The reaction
is conducted usually in a gas phase under atmospheric
pressure or an elevated pressure within a temperature
range of from 150 to 550C, preferably from 250 to 450C.
The ratio of hydrogen fluoride to the starting material
may be varied to a large extent. The ch]orine atom is
substituted usually by using a stoichiometrical amount of
hydrogen fluoride. However, it is possible to use
hydrogen fluoride in a larger amount, for example, four
2~3~479
,
~0~ ` ' (`t`';' 0~ L; CCII amo~ t
OL thC t:Ot;l~ al!lOUllt (.)~ t~le sl:cl{ti.ll(J mCIter jaJ. The
contact: t inlfe iC; usually frC)II1 0.1 tO 300 ~eCOndS,
Pre~eI-abIV I-LOI11 5 t:O 30 SeeOI1dS. i~S t:he catalyst USed
5 ill the l.i~lui(:l ~,h~ , it: ;s L~ossi.~):le to ll~;e a Ll.uo~ ation
catalyst: COllsistill9 of .1 halide o~ e.g. ';b, ~b, Ta or ~n,
such <~ )L`", Sb('('~, SbCe~l`3, NbCe,j, Nbl`;, ShGe5, NbC~'5,
NbF5, TaL~5, 'I`aCe5 or SnCe~. The fluorillclt:ion reaction is
conducted in a liquid phase under atmospheric pressure or
all elevated pressure usually within a temperature range
of from 0 to 2U0C, preferably frorn room temperature to
150C. In the present invention, the reactioll is usually
conducted in the absence of any solvent. However, a
solvent may be employed. The solvent employed in such a
case is not particularly limited so long as it is capable
of dissolving propanes as the starting materials, and the
solvent itself is hardly fluorinated as compared with the
starting material. Further, the reaction pressure is
usually from 0 to 10 kg/cm2G, and when a solvent is used,
the reaction pressure depends upon the type of the
solvent.
Hydrogen fluoride may be charged before the
reaction. However, it is more effective to feed it into
the liquid phase as the reaction proceeds.
As another embodiment, when carbon tetrachloride
(R10) is reacted with tetrafluoroethylene in the presence
of a Lewis acid catalyst, 1,1,1,3-
4 7 9
~ c~ c)E)iop~ 2~4c~)) o~tail)ed il~ good
yield, rlS SilC)WIl i.ll lhe fOll.OWillC~ Eormula:
CF -~F I CC~'
I,ewis ~Ic.i.d cat,llyst
r) ''--~~--~~-~-----~-------------------`,~ C`cel~2C~2cce3
This Leactioll i; condllc~ed uncler th~ sallle conditions
as the ad(~itiol~ re,lctioil ol 4F with R]] mclltioned above.
The reductiol-l o~ tlle resulting R2]4cb is conducted in the
same manller as the reduction of R215ct) described above,
to obtain ~ ,3-trictlloro-1,1,2,2-tetrafluoropropane
(R224ca).
The fluorinat;on of the resulting R224ca is also
conducted in the same manner as the above described
fluorination described above to obtain
dichloropentafluoropropane.
Further, R214cb obtained-by the addition reaction of
4F with R10, may firstly be fluorinated in the same
manner as the fluorination oE R224ca, to form
trichloropentafluoropropane such as R215ca or R215cb,
which is then reduced in the same manner to obtain
dichloropentafluoropropane such as R225cb or R225ca.
The proportions of R215ca and R215cb formed by the
fluorination vary depending upon the catalyst and
reaction conditions employed.
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
~3~7~
-- 1. l
e~lc; ~ c:ific E~clmp:lr~.
I:~c~ pl.~ :l
~ nto a 1.() ~ lla-;te:l.l.oy C autoc:l.ave, 0.5 kg (3.7 mol)
of anhydrouc-; cllumi.l~um chlori.de was added, and the
~j autocl.clve wc~c; de~ierated. 'l~llell, 5 kg (3G~.4 mols) of Rll
was added thereto. 'l`he autoclave was cooled to 0C, and
thell tetrafluoroet}lylelle was contilluousl.y added while
maintainil.g the reacti.on temperature between 10 and 20C.
After adding 4 kg (40 mol) of tetrafluoroethylene,
stirring was continued for further one hour. Then, the
reaction mixture was filtered, and the products were
purified by distillation to obtain 6.1 kg of R 215cb
(yield: 71%). Then, into an Inconel 600 U-shaped reactor
with an inne~r di.ameter of 2.54 cm and a length of 100 cm,
100 me of a platinum catalyst supported on active carbon
(supported rate: 0.5~) was packed to obtain a reactor for
reduction, and the reactor was maintained at a
temperature of 120C. To this reactor, gasified R215c~
was supplied at a rate of 96 me/min and hydrogen gas was
supplied at a rate of 144 me/min, and the reaction was
conducted. After removing an acid content, 4.5 kg of the
products were recovered in a trap cooled to -78C, and
analyzed by gas chromatography and l9F-NMR. The results
are shown in Table 1.
2~3~7~
C .1
_~_ ~ .__
(`onlpc~-iitiol~ o~ c~ plc)ducts Molar ratio (o~)
_
ci~3(`~'`7('~ c`~>)_ 9
r CL~'3CL~ C'~12Ce (l~35(~b)
_ .
CF3C1;`2C~lCe2 (1~25ca) 74
_ ____
CF3CF2CCe3 (R215c~) 10
Other componellts 6
The products were purified by disti:llation to obtain
3.6 kg of R225ca (yield: 63o)~
Example 2
Into a ~0 e Hastelloy C autoclave, 0.5 kg (3.7 mol)
o~ aluminum chloride was added, and the autoclave was
deaerated under reduced pressure. Then, S kg (36.4 mo].)
of Rll was added thereto. The autoclave was cooled to
0C, and tetrafluoroethylene was continuously added while
maintaining the reaction temperature between 10 and 20C.
After adding 4 kg (40 mol) of tetrafluoroethylene,
stirring was continued for further one hour. The
reaction mixture was filtered, and the products were
purified by distillation to obtain 6.1 kg of R215cb
(yield: 71%). Then, into a 1,000 me glass three-necked
round bottom flask, 200 g (6 mol) of methanol and 300 of
(4.6 mol) zinc powder were added, while stirring the
mixture at 0C, 1,000 g (4.2 mol) of R215cb was dropwise
- ~03~7~
a(l(led ~l~elet(~ r coln~ iol~ of the ~1LOPWiSe
acl(litic~ Lillg waC; eolll:ilnled for fllrlher ~ hours at
0~C. Thcll, t-lle rea(t:ioll so:Lution was washed with a 2N
hydrocl-l:Loric ~cid aqlleous ~;o~ution. 900 g o~ the organic
layer was l e( ovel(~d allcl all~ ly%ed by gas (hromatography
ancl ]-9F-Ni~ . 'I`lle r(~su~ -s aL~ showll in 'L`al-)l~ 2.
Table 2
Compositioll of the products Molar ratio (%)
.
CF3CF=CHCe (R1224yd) 3
_ _
CF3CF=CCe2 (R1214ya) 14
CF3CF2C~Ce2 (R225ca) 51
CF3CF2CCe3 (R215cb) 30
,
Other components 2
The reaction mixture was-purified by distillation to
obtain 350 g of R225ca (yield: 41%).
Preparation Fxample 1
1,200 g of Cr(NO3)3-9H2O and 100 9 oE Mg(NO3)2-6H2O
were dissolved in 2.5 e of water. This solution and
2,000 g of a 23% ammonium hydroxide aqueous solution were
added into 4 e of heated water under stirring to obtain
precipitates of hydroxides. The precipitates were
collected by filtration, washed with distilled water and
dried, and then they were calcined at 450C for 5 hours
to obtain the oxide powder. This powder was molded into
cylinders having a diameter of 5 mm and a height of 5 mm
- 2 ~ 7 ~
.. 1 ,~ .
by meanl-; o' a ~ai~ ing maci)il~e. The catalyst thus
ob~ainecl was r~ uorinatecl in a stream o , gas mixture of
hydrogeil Lluoricie,~ rogen at a ~elllperatllre of from 200
~o 400C for activation prior to t:he reaction.
Preparation Txamp]e 2
1,100 9 of ~e(No3)3-9ll2O as gllaralltied reagent, 125 9
of Cr(NO3!3~9~l2O and 4() g oE ~y(NO3)~ 6~ were dissolved
in 2.5 e of water. This solution and 2,n()0 9 of a 28%
ammonium hydroxide aqueous solution were added into 4 e
of heated water under stirring to obtain precipitates of
hydroxides. The precipitates were collected by
filtration, washed with distilled water and dried, and
then they were calcined at 450C for 5 hours to obtain
the oxide powder. This powder was molded into cylinders
having a diameter o 5 mm and a height of 5 mm by means
of a tabletting machine. The catalyst thus obtained was
fluorinated in a stream of a gas mixture of hydrogen
fluoride/nitrogen at a temperature of from 200 to 400C
for activation prior to the reaction.
Example 3
Into a 10 e Hastelloy C autoclave, 0.5 kg (3.7 mols)
of anhydrous aluminum chloride was added, and the
autoclave was deaerated under reduced pressure. Then, 9
kg (75.3 mol) of R20 (CHCe3) was added thereto. The
autoclave was heated to 65C, and then
tetrafluoroethylene was continuously added while
maintaining the reaction temperature at a level of from
7 ~
'. ...
~5 t:o ~ f'~ L c~ ing ~ cJ (~
tetrafluoroetl~ylenc, stirring wa~, col~tin~led for further
one hour. 'l`heil, the rcac~ioll solution ~as ~iltered, and
the reaction Ini,.tllre was purified by di~ illation to
, obtain 1.5 kg of l~2~ca (I,3,3-trichloro-1,1,2,2-
tetrafluoropl-opallc) (yield: 85O6). Then, USil)9 an Inconel
600 ~-sl~aL)ecl reactol: with an inllel diamet,er o~ 2.54 cm
and a lcllyth or 100 cm as a reactor for ~luorination, 200
m~ of a fluorillat:ioll catalyst prepared as described in
Preparation Example 1 was paclced therein. The reactor
was heated to 280C, and 160 me/min of gasi~ied R224ca
and 440 me/min of hydrogen fluoride were supplied
thereto, and the reaction was conducted. The reaction
crude gas was passed througll an aqueous alkaline
solution, and 6.8 kg of the reaction mixture was
recovered and analyzed by gas chromatography and l9F-NMR.
The results are shown in Table 3.
Table 3
Composition of the products Mo],ar ratio (%)
R226 10
R226ca (CCeF2CF2CHF2)
R226cb (CF3CF2CHCeF) (ca/cb=80/20)
R225 ' 72
R225ca (CF3CF2CHCe2)
R225cb (CCeF2CF2CHCeF) (ca/cb=10/90)
R224ca 15
~, Other components
203~79
- lG --
The` I eac~ i.OIl mi~;~ure ~as puri~ied i,~,~ distillation to
obtain g.7 I;cJ of ~l2?5 (dicl~loropel~tafluol-o~ropane)
(yield: 68%).
E~;anlple 4
Intc) a ~0 e ~laste]loy C autoc]ave, 0.~ Icg (3.7 mols)
of anhydrous alum;nulll chloride was added, and the
autoclave waC; deaerclted under reduce pressllre. Then, 9
kg (75.3 mol) of R20 (CHCe3) was added thereto. The
autoclave was heated to 65C, and tetrafluoroethylene was
continuously added while maintaining the reaction
temperature at a level of from 65 to 80C. After adding
4 kg (40 mol) of tetrafluoroethylene, stirring was
continued for further one hour. The reaction solution
was filtered, and the reaction crude solution was
purified by distillation to obtain 7.5 kg of R224ca
(1,3,3-trichloro-1,1,2,2-tetrafluoropropane) (yield:
85%). Then, using an Inconel 600 U-shaped reactor with
an inner diameter of 2.54 cm and a length of 100 cm as a
reactor for fluorination, 200 me of a fluorination
catalyst prepared as described in Preparation Example 2,
was packed. The reactor was heated to 320C, and 160
me/min of gasified R224ca and 440 me/min of hydrogen
fluoride were supplied, and the reaction was conducted.
The reaction crude gas was passed through an a~ueous
alkaline solution, and 6.9 kg of the reaction mixture was
recovered and analyzed by gas chromatography and l9F-NMR.
The results are shown in Table 4.
203~47~
1 ,~ .
Table 4
__
Composition o~ ~he products ~olar ratio (~)
_ _ ,
R22G 6
~226CI (C(e1`7cl`~cill;`2)
R226cb ~cF2cF7cllceE~) (ca/(b=~s/ls)
R225 59
R225ca (CF3CF2CHC e 2)
R225cb (CCeF2CF`2CHCeF) (ca/cb=7/93)
R224ca 32
Other components 3
The reaction mixture was purified by distillation to
obtain 3.8 kg of R225 (dichloropentafluoropropane)
(yield: 5S%~. ~
Example 5
Into a l0 e Hastelloy C autoclave, 0.5 kg (3.7 mols)
of anhydrous aluminum chloride was added and the
autoclave was deaerated under reduced pressure. Then, 9
kg (58.5 mols) of Rl0 (CCe4) was add thereto. The
autoclave was heated to 65C, and then
tetrafluoroethylene was continuously added while
maintaining the reaction temperature at a level of from
65 to 80C. After adding 4 kg (40 mols) of
tetrafluoroethylene, stirring was continued for further
one hour. Then, the reaction mixture was filtered, and
~034~7~
~ 3 -
the pro~ s ~ r(~ -ified by dist:illal:ion to obtain 6.5
kc3 of ~21~cl~ l,3-tet~ ch]orot:cltraf]lloropropane)
(yield: 8')~). Tl~ l, into an lncollel G00 U-shaped reactor
havillg wi.th inller diameter of 2.54 cm an~l a length of 100
S Clll, lO()Ille of a pl.a-illUIII cat:alyst support~d Ol- active
CarbOIl (supL)()rtecl late: 0.5~) wa5 packed to ~orm a
reactor for reduct;oll, and the reactor ~as maintalned at
120C. To this reactor, 120 me/min of gasified R214cb
and 180me/min of hydrogell gas were supplied, and the
reaction was conducted. An acid content was removed, and
then 5.4 kg of the reaction mixture was recovered in a
trap cooled to -78C and analyzed by gas chromatography
and l9F-NMR. The results are shown in Table 5.
Table 5
Composition of the products Molar ratio (%)
CCeF2CF2CH3 (R244cb) 1 10
CCeF2CF2CH2Ce (R234cb)
CCeF2CF2CHCe2 (R224ca) j 75
CCeF~CF2CCe3 (R214cb) 9
Other components 4
203~47~
The~ reactioll mi.~ re was puriLicd l~y distillation to
~btain ~.] kg of l'~22~ca (1,3,3--trichloro L,1,3-trichloro-
I,l,2,2-tetl-aI:IuoL-opropalle) (yield: 73%). Then, using an
Lncollel 600 ~--sllaL~ed reactor with an ;nller diameter of
~, 2.59 Clll and a le~ J~:~l of 1()0 cm as a reac~or for
LluorinLItion, 200 "le of a ~luorillation c.ltalyst prepared
as described in Preparatioll Example 1, was packed. The
reactor was heated ~o 280C, and 160 me/min of gasified
R224ea and 440 me/mill of hydrogen fluoride were supplied
thereto, and the reaction was eondueted~. The reaetion
erude gas was passed through an aqueous alkaline
solution, and 3.7 kg of the reaetion mixture was
reeovered and analyzed by gas ehromatogr,aphy and l9F-NMR.
The results are shown in Table 6.
Table 6
Composition of the produets Molar ratio (%)
_
R226 ]0
R226ea (CCeF2CF2CHF2)
R226eb (CF3CF2C~CeF) (ea/eb=80/20)
_
R225 72
R225ea (CF3CF2CHCe2)
R225eb (CCeFCF2CHCeF) (ea/eb=10/go)
R229ea 15
Other eomponents 3
203~79
, (,
Thc leclC`tl(!ll mi~ture was E-uriiecl by (listillation to
obtain 2.', ~g of 1~2?5 (dichloropelltafLuolopropane)
(yielcl: 67~).
E~amp~ 6
~, Into a l0 e lla-;tclloy C autoclave, U.5 ky (3.7 mols)
of anhydrous alumillum ollloride was a-lded and the
autoclave was deaerated under reduced pressure. Then, 9
kg (58.5 IllO].S) of ~10 (cce~) was added t~lereto. The
autoclave was heated to 65C, and then
tetrafluoroethylene was continuously added while
maintaining the reaction temperature at a level of from
65 to 80C. After adding 3 Icg (30 mols) of
tetraf]uoroethylene, stirring was continued for further
one hour. Then, the reaction mixtuer was filtered, and
the products were purified by distillation to obtain 6.5
kg of R214cb (1,1,1,3-tetrachlorotetrafluoropropane)
(yield: 85%). Then, into an Inconel 600 U-shaped reactor
with an inner diameter of 2.54 cm and a length of 100 cm,
lOOme of a platinum catalyst supported on active carbon
(supporting rate: 0.5%) was packed to form a reactor for
reduction, and the reactor was maintalned at 120C. To
the reactor, 120 mQ/min of gasified R214cb-and l80 me/min
of hydrogen gas were supplied, and the reaction was
conducted. An acid content was removed, and then 5.5 kg
of a reaction mixture was recovered in a trap cooled to -
78C and analyzed by gas chromatography and l9F-N~R. The
results are shown in Table 7.
2~34~7~3
-- 21. -
Tab]e 7
Compos.i.ti.on o~ tlle products ~lolar ratio (%)
CC~I7CY,CII3 (Y-~44cb) 1 n
CCeF2CF2CII7Ce (R~34cb)
_ ~
CCeF2CF~CIlC~. 2 ( R224ca) ~ 75
CCeF2CF2CCe3 (R214cb) 9
_
Other components
The reaction mixture was purified by distillation to
obtain 4.1 kg of R224ca (1,3,3-trichloro-1,1,2,2-
tetrafluoropropane) (yield: 73%). Then, using an Inconel
600 U-shaped reactor with an inner diameter of 2.54 cm
and a length of 100 cm as a reactor for fluorination, 200
me of a fluorinatlon catalyst prepared as descr;.bed in
Preparation Example 2, was packed thereto. The reactor
was heated to 320C, and 160 me/min of gasified R224ca
and 440 me~min of hydrogen fluoride were supplied
thereto, and the reaction was conducted. The reaction
crude gas was passed through an aqueous alkaline
solution, and 3.8 kg of the reaction mixture was
recovered and analyzed by gas chromatography and l9F-NMR.
The results are shown in Table 8.
~3447~
--- 22 -
Table 8
__
Composition of t~le products ~olar Latio (%)
.
r~226 G
~j R 2 2 G c .l ( cc e ~ c ~ 2 )
R22Gcb (CF2CF2CIfCeF)(~a/cb-85/]5)
.
R225 59
R225c~ (CF3CF2C~ICe2)
R225cb (CCeF`2CF2CHCeF)(ca/cb=7/g3)
R224ca 32
Other components 3
The reaction mixture was purified by distillation to
obtain 2.1 kg of R225 (dichloropentafluoropropane)
(yield: 57%).
Example 7
Into a 10 e Hastelloy C autoclave, 0.5 kg (3.7 mol)
of anhydrous aluminum chloride was added and the
autoclave was deaerated under reduced pressure. Then, 9
kg (58.5 mol) of R10 (CCe4) was added thereto. The
autoclave was heated to 65C, and then
tetrafluoroethylene was continuously added while
maintaining the reaction temperature at a level of from
65 to 80C. After adding 3 kg (30 mols) of
tetrafluoroethylene, stirring was continued for further
one hour. Then, the reaction mixturc was filtered, and
2~3~473
th~ ~?I ()(~ i`L 1~ ie(l ~)y dist:.illd t.i !)1l t,o obtain 6.5
kg o~ l~21~ .,:I,3-tetrachloroletra~ oroE)ropane)
(yield: ~35Ot,). ~rllell~ inLo a 1,000 ~lle of gl.ass three-
necked roulld bo~tolll fl.ask, 200 g (6 mo].s) of methanol and
30U 9 (~.6 mc):ls) of ~,inc ~-)owder wc~re ad-led. While
stirril~c~ the mixture at 0C, 1,00U 9 (3.'~ mo]s) of R214cb
was dropwise added. ~fter completioll o~ the dropwise
addition, stirring was continued 'cor furlher ~ hours at
0C. Then, the reaction solution was washed with a 2N
hydrochloric acid aqueous solution. 900 g of the organic
layer was recovered and analy~ed by gas chromatography
and l9F-NMR. The results are shown in Table 9.
Table 9
Composition of the products Molar ratio (%)
CCeF2CF=CHCe (R1223yd) 2
cceF2cF=cce 2 ( R1213ya) 1.2
CCeF2CF2CHCe~ (R224ca) 54
_
CCeF2CF2CCe3 (R214cb) 28
Other components 4
.
2~3~73
'l~he Le.:l( t ;~n llm~.ture W,-IS puririec1 b~ distillaiton to
ob~ain 19() g c,f: l~.'24ca (:l,3,3-trichloro--l,1,2,2-
tetrafluoropropalle). Tllell~ using an Inconel 600 U-shaped
rcactor with all i.nller diameter o~ 2.5 Clll and a length of
~, :l00 cm as a reclct(lr for fluorillation, 20n rne of a
~luorinal-ioll catalyst prepared as descril,ed in
Preparatioll ~xample -1., was packed. The reactor was
heated to 280C, alld 160 me/lllill of R224-cl and 440 me/min
of hydrogen ~luoride were supplied thereto, and the
reaction was conducted. The reaction was stopped when 1
kg of R224ca was supplied, and the reacti.on crude gas was
passed through an aqueous allcaline solution, and 0.9 ky
of a reaction mixture was recovered and analyzed by gas
chromatography and l9F-NMR. The results are shown in
Table 10.
:
Table 10
Composition of the products Molar rati.o (~)
R226 10
R226ca (CCeF2CF2CHF2)
R226cb (CF3CF2CHCeF)(ca/cb=80/20)
R225 72
R225ca (CF3CF2CHCe2)
R225cb (CCeF2CF2CHC4F)(ca/cb=lo/go)
R224ca 15
Other components 3
.
203llA79
~ e r".~ .i'!ll lid,:~UI-l' wa~ nll iL.ied L)`,' dist:i]latioll to
obtaill O.G kcJ or l~j (di.ch.Loro~ellta~1uolc)propane)
(yi~ld: 68O6).
.~:;ample 8
Into a :L0 e ll.lste].loy C autoc~ ve, ~).5 k~l (3.7 mo].s)
of anhydro-ls alu~ lum chloride was added and the
autoclave was deaelated UlldeL redllcecl p~-essLIre. Thell, 9
kg (58.5 mo].r;) o~ l~10 (CCe~) was added ~:hereto. The
autoclave was heated to 65C, and then
tetrafluoroethylelle was continuously added while
maintaining the reaction temperature at a level of from
65 to 80C. After adding 3 kg (30 mols) of
tetrafluoroettly].ene, stirring was contil-ued for further
one hour. The reaction mixture was filtered, and the
products were purified by distillation to obtain 6.5 kg
of R214cb (1,1,1,3-tetrachlorotetrafluoropropane) (yield:
85%). Then, into a photochemical reactor (EHB-WlF-500
Model, manufactured by Eiko Co., LTD.), 800 me of
isopropanol and 400 g of R214ca were charged, and the
reaction solution was irradiated by a high pressure
mercury lamp for 20 hours under cooling at 10C. After
washing with water, the organic layer was recovered and
analyzed by gas chromatography and l9F-NMR. The results
are shown in Table 11.
203~47~
-- ~6
Table 11
(ompc)C;itioll of the ~1Olar rc1tio (~)
I ".lC t i 011 !Ø1 U t ~011
_ !-
CCe~C1;2C11Ce~ 2~4c~) 7~
ccel;~2cE~2cc e (~ 4ca) 23
I _
Other compo1le1lt:s 3
The reaction mixture was purified by distillaiton to
obtain 240 g of R224ca (l,3,3-trichloro--l,l,2,2-
tetrafluoropropane) (yield: 70%). Then, using ~n Inconel
600 U-shaped reactor with an inner diameter of 2.54 cm
and a length of lnO cm as a reactor for fluorination, 200
me of a fluorination catalyst prepared as described in
Preparation Example l was packed thereto. The reactor
was heated to 280C, and 160 me/min of gasified R224ca
and 490 me/min of hydrogen fluoride we~e supplied
thereto, and the reaction was conducted. The reaction
was stopped ~hen 3 kg of R224ca was supplied. The
reaction crude gas was passed through an aqueous alkaline
solution, and 2.7 kg of the reactoin mixture was
recovered and analyzed by gas chromatography and l9F NMR.
The results are shown in Table 12.
~03~47~
Table 12
.
Cotnpo~-il;oll oE theMolar ratio (%)
reactiot~ solut~on
~, 1~7?G 10
R22Gca (CCeF~CF2C1lF2)
R225ch (CF3CF~CHCeF)(ca/cb--80/20)
I .
~225 72
R225ca ( CF3C~2CHCe2 )
R22Scb (CCeF2CE`2CHCeF) (ca/cb=lo~'go)
R224ca 15
IOther components 3
The reaction mixture was purified by distillation to
obtain l.9 kg of R225 (dichloropentafluoropropane)
(yield: 68~).
Example 9
Into a lO e Hastelloy C autoclave, Q.5 kg (3.7 mols)
of anhydrous aluminum chloride was added and the
autoclave was deaerated under reduced pressure. Then, 9
kg (58-5 mols) of RlO (CCe4) was added thereto. The
autoclave was heated to 65C, and then
tetrafluoroethylene was continuously added while
maintaining the reaction temperature at a level of from
65 to 80C. After adding 3 kg (30 mols) of
tetrafluoroethylene, stirring was continued for further
one hour. The reaction mixture was filtered, and the
reaction crude solution was purified by distillation to
~03~479
--- ?.8 -
ob~ain 6..', l~ of~ cb (:L,].,1.,3-
tetraclllorotetrc~ oropro~)ane) (yield 8f;~). Then, using
an Incolle~. 600 ~-sllaL)ed reactor with an inner di.ameter of
2 . 5~ Clll an-l a l.engl:h o~ 100 cln as a reac--or ~or
5 flllOrillclti~ 200 IllQ of a r].uorination catalvst prepared
as descril-ed in l~lc~ rati.oll Jxampl.e ]. was packed. Tlle
reactor wa-: heated to 280C, an~l 210 me~ l of ga~ified
R214cb and 360 me/nlin of hydrogen fluoride were supplied
thereto, and the reaction was conducted. The reaction
crude gas was passed through an aqueous alka].ine
solution, and 6.0 kg of the reaction mixture was
recovered and purified by distillation to obtain 5.1 Icg
of R215ca (1,1,3-trichloropelltafluoropropane)(yield:
83~). Then, into an Inconel 600 ~-shape~l reactor with an
inner dialneter of 2.54 cm and a length o~ 100 cm, 100 me
of a platinunl catalyst suppoEted on active carbon
(supported rate:0.5 %) was packed to form a reactor for
reduction, and the reactor was maintained at 170C. To
this reactor, 96 me/min of gasified R215ca and ].44 me/min
of hydrogen gas were supplied, and the react.ion was
conducted. An acid content was removed, and 4.1 kg of a
reaction mixture was recovered in a trap cooled to -78C,
and analyzed by gas chromatography and l9F-NMR. The
results are shown in Table 13.
~3~47~
~9
'i`able 13
ComE)osi~:;ol~ o~ t-he Molar ratio (~)
react i.OIl so,lution
~-
CCe~`2CI`2C113 (1'2~ CC) ~ l
CCeF2CI`2CH2E` (~35cc) j
CCeF2CF2CHCeF (R225cb) 75
_
CCeF2CF2CCe2F (R~15ca)
Other components
_ __
The reaction mixture was purified by distillation to
obtain 3.0 kg of R225ca (3,3-dichloro-1,1,2,2,3-
pentafluoropropane) (yield: 69%).Example 10
Into a 10 e Hastelloy C autoclave, 0.5 kg (3.7 mols)
of anhydrous aluminum chloride was added, and the
autoclave was deaerated under reduced pressure. Then, 9
kg (58-5 mols) of R10 (CCQ4) was added thereto. The
autoclave was heated to 65C, and then
tetrafluoroethylene was continuously added-while
maintaininq the reaction temperature to a level of from
65 to 8~C. After adding 3 kg (30 mols) of
tetrafluoroethylene, stirring was continued for further
one hour. Then, the reaction mixture was filtered, and
the products were purified by distillation to obtain 6.5
~03~47~
-- 3()
k9 of ~ lch t:l,l,.l,3-te~:rcl(:hlorot:et~ f~ oropl-opane)
~yield: 8,~ ell, llSil)(J cln InCOllel 6()0 ~-shaped
reactol- witll a~ UICI: dialne~er of 2.5 Cl!l and a length of
100 cm ac a reac~c)l f.or fl.uorinatiorl, 2no me of a
l.uori.lu~l~ion ca~:alyst preparecl acs desc~ d ill
PrepaLa-io~ alllp.l.~:~ 2 was packed. 'l`he le~actor was heated
to 320C, alld ,'~0 Ill~/mill oE gasiri.ed R21~cb and 360
me/min of hydrogell El.uoride were supplied, and the
reaction was cond~lcted. The reaction crude gas was
passed through an aqueous alkaline solution, and 5.2 kg
of the reactioll mixture was recovered an-l purified by
distillation to obtain 4.9 kg of R215ca (1,1,3-
trichloropentafluoropropane) (yield: 80~). Then, into an
Inconel 600 U-shaped reactor with an inner diameter of
2.54 cm and a length of 100 cm, 100 me oE a platinum
catalyst supported on active-carbon (supported rate:
0.5%) was packed to form a reactor for reduction, and the
reactor was maintained at 170C. To this reactor, 96
me/min of gasified R215ca and 144 m~/mill of hydrogen gas
were supplied, and the reaction was conducted. An acid
content was removed, and then 3.9 kg of a reaction
mixture was recovered in a trap cooled to 78C, and
analyzed by gas chromatography and l9F-NMR. The results
are shown in Table 14.
20~4~73
-- 31 -
Tabl.e 1'1
Com}?oc;i.l ion o~ l,he Mo:lar ral:;.o ($i)
r ea c l: i oll so l ~l ~ i oll
'. .__ _ .
cceF2cl~2(ll3 (1~2~cc) I
CCeF2CF~Cil2F (1~235cc) l,'
_
cceE~2cF2cllceF (R225cb) 75
CCeF2CF2CCe2F (R215ca)
Other components
The reaction mixture was purified by distillation to
obtain 2.9 k-l of R225cb (3,3-dichloro~ ,2,2,3-
pentafluoropropane) (yield: 69%).Example ll
Into a 10 e Hastelloy C autoclave, 0.5 kg (3.7 mol)
of anhydrous aluminum chloride was added and the
autoclave was deaerated under reduced pressure. Then, 9
kg (58-5 mols) of Rl0 (CCe~) was added thereto. The
autoclave was heated to 65C, and then
tetrafluoroethylene was continuously addrd-while
maintaining the reaction temperature at a level of f rom
65 to 80C. After adding 3 kg (30 mols) of
tetrafluoroethylene, stirring was continued for further
one hour. Then, the reaction mixture was filtered, and
the products were purified by distillation to obtain 6.5
2n3~L~7~
- ~? ---
~ -f l~ f~ clllorote~laf~ ropropalle)
(yield 85~ `hell, using an Incc)l-el G0() U-shaped
reactor with an inner diallleter of 2.5~ cm and a length of
I00 cm as a reacto] for f]uo~ ation, 2()0 lne of a
ori~ t~ly~;~ r)r~ ed a~ cri!-t~d ill
Preparatio~ alllE~ie I was paci;ed. 'l`he leacLor was heated
to 280C, and 240 m~/mil- o~ gasified R2]~cb and 360
me/min of hydrogell fluoride were supplie(l, and the
reaction was conducted. The reaction crude gas was
passed through an aqueous alkaline solution, and 6.0 kg
of the reaction mixture was recovered. The products were
pur;fied by distillation to obtain 5.1 kg of R215ca
(1,1,3-trichloropentafluoropropane) (yield: 83%). Then,
into a photochemical reactor (EHB-WlF-500 Model,
manufactured by Eiko Co., Ltd.), 800 me of isopropanol
and 400 g of R215ca were charged. While cooling the
reaction solution to 10C, irradiation by a high pressure
mercury lamp was conducted for 10 hours. After washing
with water, the organic layer was recovered and analyzed
by gas chromatography and l9F-NMR. The results are shown
in Table 15.
Table 15
Composition of the
Molar ratio (%)
reactlon solutlon
CCeF2CF2C~ICeF (R225cb) 70
CCeF2CF2CCe2F (R215ca) 27
Other components 3
~03~-73
, ~ ..
; L) ~ . t i l. l. ci t i o ll t o
c)l)tc~ l() (J c)~ ) (3r ~ ic~lor~ 3--
pf~ a~ ?~ `) (;~ G~b)
AS showl~ y ttle~ Loregoil~g E~alllples~ .Iccc){dillg to the
, .i t~ 11 ~ V ( ' ~ 3 ~ i c ~ I. o L o ---~ t ~
pentaflllol{)l~ro~)al~e (l~2?5ca) alld l,3---dichloro-l,~,2,2,3-
penlaf1uol-c)l)lc)~alle (l~225cb) which ucecl t(~ be difficult to
obtain in .I highly ~ure form, can be pro(1llced in good
yield.
Example 12
Into a 10 e ~lastelloy C autoclave, 0.05 kg (0.37 mol)
of anhydrous aluminum chloride was added, and the
autoclave was deaerated. Then, 5 kg (36.4 mol) of Rll
was added thereto. The autoclave was cooled to 0C, and
then tetrafluoroethylene was continuously added while
maintaining the reaction temperature between 10 and 20C.
AEter adding 4 kg (40 mol) of tetrafluoroethylene,
stirring was continued for further one hour. Then, the
reaction mixture was filtered, and the products were
purified b~ distillation to obtain 7.6 kg of a mixture of
R215cb and R215ca (yield: 88%). The ratio of R215cb to
R215ca formed was 87:13. Then, into an Inconel 600 U-
shaped reactor with an inner diameter of 2.54 cm and a
length of 100 cm, 100 me of a platinum catalyst supported
on active carbon (supported rate: 0.5%) was packed to
obtain a reactor for reduction, and the reactor was
maintained at a temperature of 150C. To this reactor, a
~3~479
~ ,,
mi::tuLc of ya;i f~it~ l5cb al~d R2~ c;l wa; supplied at a
rate of 96 m~/mill dlld tlydlogen 9as was suF)p1ied at a rate
of 1~4 me~ inr alld tile reactioll was condllcted. After
relllovillg all acicl contellt:, 5.1 ky o~ the products were
recovered i~l a lral~ ~ooled to -7~C, and analyzed by gas
chromatography alld l9F-NMR. 'l`he results are shown in
Table lG.
~l~able 16
_ I
Compositioll o~ the products Molar ratio (%)
jCF3CF2CH3 (R245Cb) l
CCeF2CF2CH3 (R244cc) I
CF3CF2CH2Ce (R235cb)
ICCeF2CF2CH2F (R235cc)
ICF3CF2CHCe2 (R225ca) 67
CCeF2CF2CHCeF (R225cb) -
CF3CF2CCe3 (R215cb) I
CCeF2CF2CCe2F (R215ca) 3
IOther components
The products were purified by distillation to obtain
4.7 kg of a mixture of R225ca and R225cb (yield: 72%).
Example 13
Into a 10 e Hastelloy C autoclave, 0.5 kg (2.6 mol)
of titanium tetrachloride was added, under a nitrogen
stream, 5 kg (36.4 mol) of Rl] was added thereto. The
autoclave was heated to 40C, and tetrafluoroethylene was
- 203~7~
_. 3tj .
~ollti~ C~ ile I~ tai~ tll~ }-ea~tioll
temperat:-ll e bC`tWC't'~ 0 and 50C. ~fter adding ~I kg (40
mol) oi tetr.lf~l.uc)l:(>etl~ylene, stirl.ing was contillued for
Eurtller one llour. '.I`he reacLion ln:ixtllre ,~as washed with
waler, and Llle Ol(~lnic solutioll waC pur.ii~iecl by
distil.latioll to Obtdill 7.2 kg o~ a mixt:ure of R215cb and
~215ca tyiel.(l~ .). Tl~e ratio of l~215(l) to ll2l.5ea
formed was 53:47. Then, into an Incollel 600 U--shaped
reactor with an inller diameter of 2.54 cm and a length of
]o 100 cm, 100 me of a platinum catalyst supported on aetive
carbon (supported rate: 0.5%) was packed to obtain a
reactor for reduction, and the reactor was maintained at
a temperature of 170C. To this reactor, a mixture of
gasif.ied R215eb and R215ea was supplied at a rate of 96
me/min and hydrogen gas was supplied at a rate of 144
me/min, and the reaetion was-condueted. After removing
an acid content, 5.6 kg of the products were recovered in
a trap cooled to -78C, and analyzed by gas
chromatography and 19F-NMR. The results are shown in
Table 17.
3~73
- 3(, -
17
,
Collpositiot- of the pl:c)ducts Molar ratio (~)
_ __
~, CF`-~C~2(-ll3 (I~ ) _ i
CCeF2CF2CH3 (~4'1Cc)
CF3CF2CII~Ce (1~',?3')C~)) _
CCQE`2CE`2Cil2E` (~35cc) _ _ l
CF3CF2CIIC~2 (R22Sca) 41 I
CCeF2CF2CHCeF (R225cb) 32
cr~ , ~ 4
CCeE`2CF2CCe2F (R215ca) 8
Other components - 3
_
The products were purified by distillation to obtain
4.2 kg of a mixtuer of R225ca and R225cb (yield: 69%).
Example 14
Into a 10 e Hastelloy C autoclave, 0 1 kg (0.43 mol)
of zirconium (IV) chloride was added, under a nitrogen
stream and 5 kg (36.4 mol) of Rll was added thereto. The
autoclave was cooled to 0C, and then tetrafluoroethylene
was eontinuously added while maintaining the reaetion
temperature between 0 and 10C. After adding 4 kg (40
mol) of tetrafluoroethylene, stirring was eontinued for
further two hours. Then, the reaction mixture was washed
with water, and the organic solution was purified by
2Q3~47~
- :31 --
disti.ll.atic?n l.O o')laill 7.G kcl o~ a mi:~tu~e oL R215cb and
~215ca (~iel(:l: 88OO). Then, illtO clll Inconel 600 U-shaped
reactor wi~ a~l illll'.~r dialllCLer of 2.54 C~ and a length of
1.00 cm, 10() me o~ a p]atillum cata:Lyst su~-ported on active
[, carboll (~ )ol-~ecl rate: (). 5b ) was packecl to obtain a
reactor fc)r recluctioll, ancl tl-le reactor wc,ci maintained at
a temperature of l70C. To this reactor, a mixture of
gasified R2l5cb and R215ca was supplied at a rate of 96
me/min and hydrogen gas was supplied at a rate of 144
me/min, and the reaction was conducted. After removing
an acid content, 5.6 kg of the products were recovered in
a trap coo]ed to -78C, and analy~ed by gas
chromatography and 1~F-NMR. The results are shown in
Table 18.
Table 18
Composition of the products Molar ratio ( 6 )
_ _
CF3CF2CH3 (R245Cb) 3
CCeF2CF2CH3 (R244cc) 4
CF3CF2CH2Ce (R235cb)
CCeF2CF2CH2F (R235cc) 5
CF3CF2CHCe2 (R225ca) 32
CCeF2CF2CHCeF (R225cb) 40
CF3CF2CCe3 (R215cb~ 3
CCeF2CF2CCe2F (R215ca) 10
__
. Other components 2
20`3~473
~r~e ~)L()clu(~s wel~ purific~d by clisti!~ tioll t-.o obtain
~.l. kg of a I~ t~ e of R225ca and R225cb (yi.eld: 63%).
E~ample 1.5
Thl' reac~io~ ducted in the same manller as in
~ alllple l.~ e~:ceL)l: t:llclL instead of -~:ircollium (IV)
~ l.ori~:le, 0.5 kg o~ titanium ~luoro(}~loli.de (~l~iCeF3) was
used. As a resul.'-c;, 7.2 kcJ of R215 as the react;.on
intermediat:e (R215ca : R215cb = 50 : 50) and 5.7 kg of
the products of R225 were obtained. The results of the
analyses by gaschromatography and 19F-NM}~ are shown in
Table 19.
Table 19
. Composition of the products Molar ratio (%)
CF3CF2CH3 (R245cb)
CCeF2CF2CH3 (R244cc)
CF3CF2CH2Ce (R235cb)
CCeF2CF2CH2F (R235cc) j I
CF3CF2CHCe2 (R225ca) 42
CCeF2CF2CHCeF (R225cb) 32
_
. ICF3CF,CCe3 (R215cb) 3 I
CCeF2CF2CCe2F (R215ca) 8
Other components 3
The products were purified by distillation to obtain
4.3 kg of a mixture of R225ca and R225cb (yield: 70%).
