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Патент USA US3048641

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'itti tires
3,048,629
Patented Aug. 7, 1962
l
2
3 048,629
tained through carbonization of the raw material followed
by an activation step which involves the controlled oxida
PREPARATION 61F FLllJQRQSULFUR COMPOUNDS
Kenneth Vincent Martin, Wilmington, Del., assig‘nor to
tion of the carbonized material. The preparation of active
carbon is well-known in industry and a number of active
E. I. du Pont de Nemours and Company, Wilmington,
Del‘, a corporation of Deiaware
o
No Drawing. Filed Apr‘ 29, 1959, Sen No_ 809,598
5 Clainm
carbons are commercially available.
.
A large variety of ?uorooletins may be employed in the
(CL 269M544)
process of the present invention to prepare thiocarbonyl
compounds. Depending on the number of carbon atoms
The process of the present invention relates to the
in the ?uoroole?n and the location of the unsaturated
preparation of sulfur-containing, ?uorinated compounds, 10 bond, the products are either thioacetyl ?uorides or thio
and, more particularly, to the preparation of ?uorinated
ketones. In terminally unsaturated ?uoroole?ns, the
thiocarbonyl compounds from ?uorinated ole?ns.
ketones are formed in preference to the acetyl ?uorides.
Fluorothioacetyl halides and ?uorothioketones are a
The ?uoroole?ns employed may be branched, cyclic, or
novel class of chemical compounds which show outstandinternally unsaturated. As indicated by the general
ing technical promise as monomers for the preparation 15 formula hereina-bove, it is not essential that all of the
of thermally stable and corrosion-resistant elasto-mers.
substituents on the double bond the ?uorine or ?uoro
Low molecular weight liquid polymers of these comcarbon radicals. Representative examples of the ?uoro
pounds have properties which make them suitable for use
ole?ns are tetra?uoroethylene, hexa?uoropropylene, per
as dielectric media, hydraulic ?uids and inert solvents.
?uorobutene-l, per?uorobutene~2-, per?uoroisobutylene,
It is, therefore, the principal object of the present in- 20 per?uoropentene-l, per?uoropentene-Z, omega-hydroper
vention to provide a method for the preparation of ?uoro?uoropentene-l, per?uorooctene-l, per?uorododecene-l,
thiocarbonyl compounds.
omega - hydroper?uoroheptene - 1, per?uorocyclobutene,
The object of the present invention is accomplished by
per?uorocyclohexene, tri?uoroethylene, chlorotri?uoro
a process which comprises contacting a mixture of a
ethylene and the like. The preferred starting materials
?uoroole?n having the general formula
25 employed in the process of the present invention are those
R2
having the general formula CF2=CF—CI,F2,,X, where n
A}
is from 0 to 10 and X is selected from the class consisting
R‘TC: "R3
of ?uorine and hydrogen.
The ratio of the sulfur to the ?uoroole?n is not critical;
wherein R1 and R3 are the same or different radicals 30 howe‘fefi it is Preferred to emPlQY at least equal molar
selected from the class consisting of ?uorine, per?uoroquanti?es Ofsulfur and the ?uoTPole?n- _
_
carbon radicals and divalent ?uorocarbon radicals formed
The Process of lbs Present Invention 15 further mus‘
from the combination of R1 and R3, and R2 is a radical
t1" ated by the ‘followmg examples
selected from the class consisting of hydrogen, halogen
EXAMPLES I TO VI
and per?uorocarbon radicals, and vaporized sulfur at a 35
The attached table demonstrates the preparation of
temperature of 250° C- tO 750° C-r but pl'?fel‘ably at
thiocarbonyl compounds in accordance with the present
a temperature 05 350° C- to 450° C» With activated
invention and shows the conditions and results employed
carbon, and recovering a ?uorothiocarbonyl compound.
in each example_ vaporized Sulfur, obtained by heating
In accordance
the present invention, the ?uorothioSulfur in a Stainless ‘steel vessel and passing nitrogen
Carbonyl ‘Compounds are Obtained by Passing a miXtUI‘e 40 through the molten sulfur, is admixed with the ?uoroole
0f vapofiz'id Sulfur and the ?u?mole?n through an 805?n indicated, and passed into a 1 in. nickel tube placed
vated carbon bed maintained at the temperatures indiin an upright position in a tube furnace, The ?ow of
c?tefl- The P1"0C6§S may be Can'ied 011i With an inel-“l gas
sulfur was regulated by the temperature of the sulfur pot
Camel”, 311611 35 nltfog?n 01' any of the rare gases-
The
_ and the ?ow in the nitrogen.
The tube contained a 7
contact time of the gas mixture with the carbon should ‘in in. packed bed of activated carbon, “Cheney CH-Z,”
be long enough to alloW the gas to Come ‘to the term
commercially available from the Barnaby Cheney Corp.,
pcratllre 0f the active Carbon bed- Th6 ?IlOIO‘thiOCB-Fheated by the tube furnace to the temperature indicated.
bonyl compounds obtained are caught in a cold trap and
The effluent gas was passed into a cold trap maintained at
are then puri?ed by distillation.
F —78° C. which condensed the thiocarbonyl products
Any type of active carbon can vbe employed as the ‘)0 formed. The thiocarbonyl products were isolated and
catalyst in the present invention. In ‘general, however,
puri?ed by distillation from the cold trap‘.
Table I
Example
Fluoroole?n
Flow
Rate,
nil/mm.
Temp. of Flow
Sulfur
Rate of
Vessel,
° C.
Carbon
Bed
Reaction
Nitrogen Temp.,
ml./min.
Product
Time
° C.
tetratluoro-
150
422
150
422
120 min_ 8 ml. of tri?uorothloacetyl
._-_.do _____ _.
ehlorotri?uoroethylene.
150
150
420
440
150
150
500
480
240 min. 30?ml._ ‘(11f tri?uorothioacetyl
180 min. 64 lgmofe.ehlorodi?uorothio
acetyl ?uoride.
per?uoro~
150
420
100
470
240 min. 9.8 g. of per?uorothiophane
tri?uoro‘
ethylene.
150
420
150
400
120 min. ditluorothioaeetyl ?uoride.
hexa?uoro-
150
440
160
370-450
ethylene.
glfécbu»
propylene.
active carbon prepared from wood, sawdust, peat, lignite
and pulp-mill waste is preferred. Active carbon is ob
?uoride.
a-thione.
4hrs.___ 130 g. hexa?uorothioaeetone,
HgIéIlIGXS?UOI‘OthiOZLCGtOHB
The examples set forth are illustrations of the invention
described and are not to be construed as limiting the
3,048,629
3
4
of 350° C. to 450° C., a mixture of vaporized sulfur and
a ?uoroole?n having the general formula
invention. Various modi?cations of the process equip
ment will be apparent to those skilled in the art and are
included in the scope of the present invention. The proc
ess described provides an economic and ready manufac
where in is an integer from 0 to 10 and X is from the
ture of ?uorothiocarbonyl compounds from ?uoroole?ns
class consisting of hydrogen and ?uorine, with active
and sulfur.
I claim:
carbon.
3. The process as set forth in claim ‘1 wherein the ole
1. A process for the preparation of ?uorothiocarbonyl
compounds which comprises contacting at a temperature
?n is chlorotri?uoroethylene.
4. The ‘process as set forth in claim 1 wherein the
of 250° C. to 750° C., a mixture of vaporized sulfur and 10
a non-aromatic ?uoroole?n having the general formula
?uoroole?n is tetra?uoroethylene.
5. The process as set forth in claim 1 wherein the
?uoroole?n is hexa?uoropropylene.
15
wherein R1 and R3 are radicals selected from the class
consisting of fluorine, ?uorocarbon radicals and divalent
?uorocarbon radicals formed from the combination of
R1 and R3, and R2 is a radical selected from the class
consisting of hydrogen, ?uorine, chlorine, and ?uorocar
bon radicals, with active carbon.
2. A process for the preparation of ?uorothiocarbonyl
compounds which comprises contacting at a temperature
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,922,816
2,962,529
Bruce ______________ __ Jan. 26, 1960
Marquis ____________ __ Nov. 29, 1960
OTHER REFERENCES
Brandt et 211.: J. Chem. Soc. (London), vol. of 1952,
page 2201.
Lovelace: “Aliphatic Fluorine Compounds,” page 222
(1958).
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