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Патент USA US2404788

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_ Patented July 30,, 1946
2,404,788
UNITED STATES PATENT OFFICE
2,404,7 88
‘
‘
POLYMERIZIN G OLEFIN S
Robert E. Burk and Everett 0. Hughes, Cleveland
Heights, 0hio,;assignors to The Standard Oil
Company, Cleveland, Ohio, a corporation of
Ohio
NoDrawing. Application October 22, 1941,
1 _ .Serial No. 416,104
12‘ Claims.
7
(Cl. 260-68315)
2
1
‘This invention relates ‘to polymerization, such
as by halides. 'In‘ polymerizing ole?ns, it has
Aluminum silicates in the form of active clays,
as “?oridin.”
,
‘
been usual to employ in addition to a halide cata
Acid activated alumina-silicates, such as “?ltrol.”
lyst, a promoter closely allied to the catalyst in
as precipitated alumina, bauxite, “alun
chemical composition, a common practice involv 5 Alumina,
dum.”
ing, for instance, boron ?uoride, and a hydro
Silica, as silica gel.
gen halide promoter. We have now found that
Oxides of iron, prepared by precipitation, or nat
superior results may be obtained by application
ural, as limonite.
of agents which we ?nd act as promoters in the
Oxides of nickel.
sense of assisting the action of the catalyst, but 10
Oxides of chromium, as CrO, Cl‘zOs prepared by
which are heterogeneous 0r non-miscible and are
precipitation, or as Guignet’s green. This may
chemically quite unrelated to halide catalysts.
be mixed with aluminum oxide.
‘ To the accomplishment of the foregoing and
Oxides of titanium, manganese, cobalt, vanadium,
related ends, the invention, then, comprises the
and phosphorus.
features hereinafter fully described, and particu 15
larly pointed out in the claims, the following de
In cases Where salts are deposited on the pro
scription setting forth in detail certain illustrative
moter agent, the amount may be in general
embodiments of the invention, these being in
around 10% by weight with respect to the pro
dicative, however, of but a few of the various ways
moter.
in which the principle of the invention may be 20
employed.
As an example: Propylene 37.4 mol per cent in
propane is subjectedto the action of boron ?uo
ride at 180 poundspressure per square inch, and
a silicate in the form of Utah clay 0.3 mol per
cent at a temperature of 80° F. After two and
The materials to be polymerized may be any
ole?n as desired, as ethylene, propylene, butenes,
or higher ole?ns, and the polymerization'may be
applied to relatively pure ole?ns or any mixture. 25 one-half hours the product yield‘was 74.6% of
The ole?ns may be diluted with thecorrespond
the charge, and at atmospheric pressure 35.6%
ing para?ins or with other inert hydrocarbons.
boiling above 500° F. was taken oil, and having
Fractionated re?nery gases containing both paraf
a viscosity of 57 centistokes, and viscosity index
?ns and ole?ns may be used, for instance, With
122.5, and under vacuum of 15 mm. of mercury
out separation. The catalyst is of the halide type, 30 19.1% of the product was taken off which boiled
forinstance, boron ?uoride. And, with the cata
lyst, in accordance with the present‘invention,
above 395° F. and had a viscosity of 1580 centi
stokes and viscosity index 11.9.
there is applied an agent which is heterogeneous
As another example: A similar ole?n stock
with‘respect thereto and which is an oxygen-con
treated with similar catalysts and temperature
taining compound of an element of atomic num 35 and pressure conditions, but with 1 mol per cent
bers‘13, 14, and 22-28 inclusive, of the periodic
of alumina and 0.335 of water, gave a. yield of
table. Of the ?rst mentioned, we prefer alumi
num silicates, such as active clays, illustrated by
98.6%, of which at atmospheric pressure 89.8%
boiled above 500° F. and had a viscosity of 15.3
centistokes and a viscosity index 93.4, and at 15
40 mm. mercury 32.9% of the product boiled above
The polymerizing operation is carried out with
395° F., and had a viscosity of 92 centistokes and
pressures up to 300 pounds per square inch, and
viscosity index75.1.
_ _
temperatures of 0-120° F., preferably about 80° F.
As another example: With similar ole?n and
The boron ?uoride as a catalyst is ordinarily sup
halide catalyst and treatment. but with 1 mol per
plied in amount of 0.2—2‘5 mol‘per cent of the 45 cent of Utah clay, containing 12.3% of water and
ole?n feed. The heterogeneous agent as’ above
10% of KCl, a yield of 66% was obtained, of which
noted is supplied also .in amount of 005-5 mol
28.8% boiled above 500° F. at atmospheric pres
' per cent based on the ole?n. In some cases we
sure and had a viscosity of 33.9 centistokes and
prefer to include with the heterogeneous agent
acting as promoter, a minor amount of an inor- 50 viscosity index 131.2, and at 15 mm. mercury
12.2% of the product boiled above 395° F., and
ganic salt, particularly a salt of a strong acid,
“?oridin,” and alumina-silicates, illustrated by
“?ltrol,” also alumina, silica, etc.
as for instance, potassium chloride, zinc chloride,
aluminumv sulphate, etc. It is preferred also to
have from 0.3 to 4 mols of water per mol of oxide
promoten This hydration may be attained by
either passing water-saturated air or inert gas
over the oxide, or by controlled drying of the Wet
solid or precipitate' More particularly illustrat
had a viscosity of 1800 centistokes.
‘
As another example: ‘With similar stock and
conditions, except with application of 1 mol per
cent of A1203 containing 25.9% of Waterand 10%
of A12(SO4)3 as promoter, a yield of 100% was ob-‘
’ tained, of which 68.1% boiled above 500° F. at at
mospheric pressure and. had a viscosity of 13.6
ing the heterogeneous type of agent which we
centistokes and viscosity index 94.6, and at 15
employ as promoters, are the following:
50 mm. mercury 14.1% or the product boiled above
2,404,788
3
viscosity ‘index 82.3.
'
comprises contacting an ‘ole?n with 0.2 to 25 mol
per cent (based on the ole?n) of boron ?uoride
'
Other modes of applying the principle of the
invention may be employed, change being made
as regards the details described, provided the fea
V as the catalyst for polymerizing the ole?n, while
promoting the catalytic activity of the boron ?u-r
oride with 0.05 to 5 mol per cent (based on the
tures stated in any ofthe following claims, or the
ole?n) of an active clay, the amount of the clay
promoter being less than the amount of the boron
?uoride, together with a minor amount of a salt
equivalent of such, be employed.
‘
We therefore particularly point out and dis
tinctly claim as our invention:
1. A process of the character described, which
comprises contacting an ole?n with 0.2 to 25 mol
per cent (based on the ole?n) of boron ?uoride
as the catalyst for polymerizing the ole?n, while
promoting the catalytic activity of the boron ?uo
4.
6. A process of the character described, which
395° F., and had a viscosity of 561 centistokes and
of a strong acid.
'
7. A process of the character described, which
comprises contacting an ole?n with 0.2 to 25 mol
’ "per cent (based on the ole?n) of boron ?uoride
of elements having atomic numbers of 13 and 14,
as the catalyst for polymerizing the ole?n, while
promoting the catalytic activity of the boron ?u
oride with 0.05 to 5- mol per cent (based on-the
ole?n) of an active clay, the amount of the clay
promoter being less than the amount ,ofthe boron
?uoride, together with a minor amount of potas
the amount of the oxygen-containing promoter
sium chloride.
being less than the amount of the boron fluoride.
2. A process of the character described. which
comprises contacting an ole?n with 0.2 to 25 mol
per cent (based on the ole?n) of boron ?uoride
8. A process of the character described, which
comprises contacting an ole?n with 0.2'to 25 mol
ride with 0.05 to 5 mol per cent (based on the
ole?n) of an oxygen-containing compound of an
element from the third series of- the periodic
classi?cation selected from the group consisting
,. '
per cent (based on the ole?n) of boron ?uoride as
the catalyst for polymerizing the ole?n, while
as the catalyst for polymerizing the ole?n, while . . promoting the catalytic activity of the boron‘?u
oride with 0.05 to 5 mol per cent (based on the
, V promoting the catalytic activity of the boron ?uo
ride with 0.05 to 5 mol per cent (based on the
ole?n) of an oxygen-containing compound of an
‘element from the third series of the periodic
classi?cation selected from the group consisting 30
of elements having atomic numbers of 13 and 14,
the amount of the oxygen-containing promoter
being less than the amount of the boron ?uoride,
together with a minor amount of a salt of a
strong acid.
,
3. A process of the character'described, which
comprises contacting an ole?n with 0.2v to 25 mol
per cent (based‘on the ole?n) of boron '?uoride
as the catalyst for polymerizing th‘e ole?n, while
promoting the catalytic activity of the'boron ?uo
ride with 0.05 to 5 mol per cent (based on the
ole?n) of an oxygen-containing compound of an'
element from the third series of the periodic
classi?cation selected from the group consisting
of elements having atomic numbers of 1.3 and 14,
ole?n) of an active clay, the amount of the clay
promoter being less than the amount of the boron
?uoride, together with 0.3 to 4 mols ‘of-water
per mol of clay.
'
‘
'
V
9. A process of the character described, which
comprises contacting an ole?n with 0.2 to 25 mol
per cent (based 0n the ole?n) of boron'?uoride
as the catalyst for polymerizing the ole?n, while
promoting the catalytic activity of the boron ?u
oride with 0.05 to 5 mol per cent (based 'on the
ole?n) of an active clay, the amount of the ‘clay
promoter being less than the amount of the boron
?uoride, together with 0.3 to 4 mols of water
40 per mol of clay and a minor amount of a salt of
,a strong acid.
‘
10. A process of the character described, ‘whichv
comprises contacting an ole?n with 0.2lto 25'mol
per cent (based on the ole?n) of boron ?uoride
the amount of the oxygen-containing promoter
as the catalyst for polymerizing 'the ole?n,'while
promoting the catalytic activity of ‘the boron ?u~
being less than the amount of the boron ?uoride,
together with‘ 0.3 to 4 mols of Water per ‘mol of
oride with 0.05 to 5 mol percent (based on the"
ole?n) of an active clay, the amount of the clay
the oxygen-containing promoter.
.
'
, promoter being less than the amount of the boron
4. A process of the character described, which 50 ?uoride, together with 0.3 to 4 ‘mols of water per
comprises contacting an ole?n with 0.2 to 25 mol
per cent, (based on the ole?n) of boron ?uoride
as the catalyst for polymerizing the ole?n, while
promoting the catalytic activity of the boron ?uo
mol of clay and a minor amount of potassium
chloride.
ll.’
'
process of the character described, which
comprises contacting an ole?n with 0.2 to 25xmol
ride with 0.05-to 5 mol per cent (based 0n the .a CI per cent (based on the ole?n) of boron ?uoride
ole?n) ‘of an oxygen-containing compound of an
element from the third series of the periodic
classi?cation selected from the group consisting
as the catalyst for polymerizing the ole?n; while
promoting the catalytic activity of the boron ?u
oride with’ 0.05 to 5 mol per cent (based on the
ole?n) of alumina, the amount of the alumina
the amount of the oxygen-containing promoter 60 promoter being less than the amount of the boron
being’ less than the amount of the boron ?uoride,
12. A process of the character described, which
together with 0.3 to 4 mols of water per mol of
comprises contacting an ole?n with'0.2 to 25 mol
the oxygen-containing promoter and a minor
per cent (based on the ole?n) of boron ?uoride
amount of a salt of a strong acid.
‘
5. A process of the character described, which 65 as the catalyst for polymerizing the ole?n, .While'
promoting the catalytic activity of the boron ?u
comprises contacting an ole?n with‘ 0.2 to .25 mol
oride with‘ 0.05 to 5 mol per cent (based on the
per cent (based on the ole?n) of boron ?uoride as
of elements having atomic numbers of 13 and 14, "
?uoride.
'
‘
the catalyst for polymerizing the ole?n, while
promoting the catalytic activity of the boron 'flu
ole?n) of alumina, the amount of the alumina
promoter being less than the amount of the boron
oride with 0.05 to 5 mol per cent (based on the 70 ?uoride, together with 0.3 to 4 mols of water per‘
ole?n) of an active clay, the amount of the clay
promoter being less than the amount of the boron
?uoride.
'
'
‘
mol of alumina.
.
ROBERT E. BURK.
..
‘
EVERETT c. HUGHES.’ 1
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