CA2034479A1 - Process for producing a dichloropentafluoropropane - Google Patents
Process for producing a dichloropentafluoropropaneInfo
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- CA2034479A1 CA2034479A1 CA002034479A CA2034479A CA2034479A1 CA 2034479 A1 CA2034479 A1 CA 2034479A1 CA 002034479 A CA002034479 A CA 002034479A CA 2034479 A CA2034479 A CA 2034479A CA 2034479 A1 CA2034479 A1 CA 2034479A1
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- Prior art keywords
- reaction
- conducted
- tetrafluoroethylene
- catalyst
- reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
- C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
- C07C19/12—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine having two carbon atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT
A process for producing a dichloropentafluoropropane, which comprises subjecting CF2-CF2 and CC?3X (where X
is C?, F or H) to an addition reaction, and reducing and/or fluorinating the resulting C3C?3F4X to obtain C3C?2F5H.
A process for producing a dichloropentafluoropropane, which comprises subjecting CF2-CF2 and CC?3X (where X
is C?, F or H) to an addition reaction, and reducing and/or fluorinating the resulting C3C?3F4X to obtain C3C?2F5H.
Description
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 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-~ 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 (%) 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 (~) _ _ , ~226CI (C(e1`7cl`~cill;`2) R226cb ~cF2cF7cllceE~) (ca/(b=~s/ls) 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) _ 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~
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) .
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 (~) R226ca (CCeF2CF2CHF2) R226cb (CF3CF2CHCeF)(ca/cb=80/20) 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 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(, -, 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%).
~ 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 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-~ 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 (%) 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 (~) _ _ , ~226CI (C(e1`7cl`~cill;`2) R226cb ~cF2cF7cllceE~) (ca/(b=~s/ls) 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) _ 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~
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) .
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 (~) R226ca (CCeF2CF2CHF2) R226cb (CF3CF2CHCeF)(ca/cb=80/20) 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 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(, -, 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%).
Claims (15)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing a dichloropentafluoropropane, which comprises subjecting CF2=CF2 and CC?3x (wherein X
is C?, F or H) to an addition reaction, and reducing and/or fluolinating the resulting C3C?3F4X to obtain C3C?2F5H.
is C?, F or H) to an addition reaction, and reducing and/or fluolinating the resulting C3C?3F4X to obtain C3C?2F5H.
2. A process for producing dichloropentafluoropropane according to Claim 1, which comprises adding trichlorofluoromethane to tetrafluoroethylene to form trichloropentafluoropropane, and then reducing it.
3. The process according to Claim 2, wherein the reaction to form trichloropentafluoropropane by adding trichlorofluoromethane to tetrafluoroethylene, is conducted in the presence of a Lewis acid catalyst.
4. The process according to Claim 2, wherein the reducing reaction is conducted by using hydrogen in the presence of a reducing catalyst, or by using an organic compound having a hydrogen atom bonded thereto in the presence of zinc or under irradiation.
5. A process for producing dichloropentafluoropropane according to Claim 1, which comprises adding chloroform to tetrafluoroethylene to form 1,3,3-trichloro-1,1,2,2-tetrafluoropropane, and then fluorinating it to obtain dichloropentafluoropropane.
6. The process according to Claim 5, wherein the reaction to form 1,3,3-trichloro-1,1,2,2-tetrafluropropane by adding chloroform to tetrafluoroethylene, is conducted in the presence of a Lewis acid catalyst.
7. The process according to Claim 5, wherein the fluorination of 1,3,3-trichloro-1,1,2,2-tetrafluoropropane is conducted by using hydrogen fluoride in the presence of a catalyst, in a liquid phase or in a gas phase.
8. A process for producing dichloropentafluoropropane according to Claim 1, which comprises adding carbon tetrachloride to tetrafluoroethylene to form 1,1,1,3-tetrachlorotetrafluoropropane, then reducing it to form 1,3,3-trichloro-1,1,2,2-tetrafluoropropane, and then fluorinating it.
9. The process according to Claim 8, wherein the reaction to form 1,1,1,3-tetrachlorotetrafluoropropane by adding carbon tetrachloride to tetrafluoroethylene, is conducted in the presence of a Lewis acid catalyst.
10. The process according to Claim 8, wherein the reduction of 1,1,1,3-tetrachlorotetrafluoropropane is conducted by using hydrogen in the presence of a reducing catalyst, or by using an organic compound having a hydrogen atom bonded thereto in the presence of zinc or under irradiation.
11. The process according to Claim 8, wherein the fluorination of 1,3,3-trichloro-1,1,2,2-tetrafluoropropane is conducted by using hydrogen fluoride in the presence of a catalyst, in a liquid phase or in a gas phase.
12. The process for producing dichloropentafluoropropane according to Claim 1, which comprises adding carbon tetrachloride to tetrafluoroethylene to form 1,1,1,3-tetrachlorotetrafluoropropane, then fluoriding it to form trichloropentafluoropropane, and then reducing it.
13. The process according to Claim 12, wherein the reaction to form 1,1,1,3-tetrachlorotetrafluoropropane by adding carbon tetrachloride to tetrafluoroethylene, is conducted in the presence of a Lewis acid catalyst.
14. The process according to Claim 12, wherein the fluorination of 1,1,1,3-tetrachlorotetrafluoropropane is conducted by using hydrogen fluoride in the presence of a catalyst, in a liquid phase or in a gas phase.
15. The process according to Claim 12, wherein the reduction of trichloropentafluoropropane is conducted by using hydrogen in the presence of a reducing catalyst, or by using an organic compound having a hydrogen atom bonded thereto in the presence of zinc or under irradiation.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1187523A JP2738042B2 (en) | 1989-07-21 | 1989-07-21 | Method for producing 3,3-dichloro-1,1,1,2,2-pentafluoropropane |
| JP1-187523 | 1989-07-21 | ||
| JP1-217554 | 1989-08-25 | ||
| JP1-217553 | 1989-08-25 | ||
| JP21755589A JP2734671B2 (en) | 1989-08-25 | 1989-08-25 | Method for producing dichloropentafluoropropane |
| JP21755389A JP2734669B2 (en) | 1989-08-25 | 1989-08-25 | Manufacturing method of dichloropentafluoropropane |
| JP21755489A JP2734670B2 (en) | 1989-08-25 | 1989-08-25 | Method for producing 1,3-dichloro-1,1,2,2,3-pentafluoropropane |
| JP1-217555 | 1989-08-25 | ||
| JP26309889A JP2849129B2 (en) | 1989-10-11 | 1989-10-11 | Method for producing 1,3-dichloro-1,1,2,2,3-pentafluoropropane |
| JP1-263098 | 1989-10-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2034479A1 true CA2034479A1 (en) | 1991-01-22 |
Family
ID=27528941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002034479A Abandoned CA2034479A1 (en) | 1989-07-21 | 1990-07-18 | Process for producing a dichloropentafluoropropane |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0436031A1 (en) |
| KR (1) | KR920701092A (en) |
| CA (1) | CA2034479A1 (en) |
| WO (1) | WO1991001287A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2624595B2 (en) * | 1990-11-27 | 1997-06-25 | エイ・ジー・テクノロジー株式会社 | Method for producing dichloropentafluoropropane |
| US5177273A (en) * | 1991-02-01 | 1993-01-05 | E. I. Du Pont De Nemours And Company | Process for the manufacture of halogen-substituted propanes containing hydrogen and at least five fluorine substituents |
| US6534467B2 (en) | 2001-01-24 | 2003-03-18 | Honeywell International Inc. | Azeotrope-like composition of 1,2,2-trichloro-1,3,3,3-tetrafluoropropane and hydrogen fluoride |
| US20050096246A1 (en) | 2003-11-04 | 2005-05-05 | Johnson Robert C. | Solvent compositions containing chlorofluoroolefins |
| US7981311B2 (en) * | 2006-09-05 | 2011-07-19 | E. I. Du Pont De Nemours And Company | Process and methods of purification for the manufacture fluorocarbons |
| EP2091899A2 (en) * | 2006-10-31 | 2009-08-26 | E.I. Du Pont De Nemours And Company | Processes for producing 2,3,3,3-tetrafluoropropene, a process for producing 1-chloro-2,2,3,3,3-pentafluoropropane and azeotropic compositions of 1-chloro-2,3,3,3-tetrafluoropropene with hf |
| TW200837036A (en) | 2006-11-15 | 2008-09-16 | Du Pont | Process for producing 2,3,3,3-tetrafluoropropene |
| WO2010001768A1 (en) * | 2008-07-01 | 2010-01-07 | Daikin Industries, Ltd. | Process for producing fluorine-containing propene compounds |
| EP3421445B1 (en) * | 2016-02-26 | 2023-08-30 | Agc Inc. | Method for purifying 1-chloro-2,3,3,3-tetrafluoropropene and (z)-1-chloro-2,3,3,3-tetrafluoropropene |
| JP6881457B2 (en) * | 2016-08-09 | 2021-06-02 | Ａｇｃ株式会社 | Method for producing 1-chloro-2,3,3,3-tetrafluoropropene |
| JP2019156732A (en) * | 2018-03-08 | 2019-09-19 | ダイキン工業株式会社 | PROCESS FOR REFINING HCFC-224ca AND/OR CFO-1213ya, PROCESS FOR PRODUCING HCFC-224ca, AND PROCESS FOR PRODUCING CFO-1213ya |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE638397A (en) * | 1962-10-09 |
-
1990
- 1990-07-18 KR KR1019910700305A patent/KR920701092A/en not_active Withdrawn
- 1990-07-18 WO PCT/JP1990/000924 patent/WO1991001287A1/en not_active Application Discontinuation
- 1990-07-18 EP EP90910909A patent/EP0436031A1/en not_active Withdrawn
- 1990-07-18 CA CA002034479A patent/CA2034479A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991001287A1 (en) | 1991-02-07 |
| KR920701092A (en) | 1992-08-11 |
| EP0436031A1 (en) | 1991-07-10 |
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