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Патент USA US2409255

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Patented Oct. 15, 1946
2,409,248 -
UNITED STATES ' PATENT OFFICE
2,409,248
-~ POLYMEBIZAYITIION -
John WSBrooks, Wenonah, and Arlie A. O’KeIly,
Woodbury, N. J., and Robert H. LWork, Phila- »
I I delphia, Pa., assignors to .Socony-Vacuum. Oil
. Company, Incorporated,,a corporation ‘of New .
York
No Drawing. Application-lune 14, 1944,
Serial No. 540,316
12 Claims.
(01. 260-'683._15) .
1
vide aprocess- for gcatalytically promoting poly
merization reactions. Another object is tov pro
vide- an e?lcient process for catalytically poly
This invention relates to polymerization reac
tions, and is more particularly concerned with
the provision of new catalysts capable of pro
moting polymerization reactions.
'
merizingnormally gaseous ole?nic- hydrocarbons
.
for the purpose, of manufacturing motor-fuels.
A very important object of the present invention
It is well known in the art, to effect a union be
tween molecules of an unsaturated hydrocarbon
to produce a compound, called a copolymer, the
molecular weight of which, is an even multiple
is to afford a process capable of carrying out the
above objects by using new polymerization cata
of the molecular weight of the original hydrocar
A more speci?c object is to provide new poly
bon. The operation is called copolymerization 10
merization catalysts. Other objects and advan
and the conditions of temperature, pressure, etc.,
tages of the present invention will become appar
are called coplymerizing conditions. The union
ent to those skilled in the art from the following
may also take place among molecules of two or
description.
I
»_
more dissimilar unsaturated hydrocarbons, to
ysts.
produce compounds that represent additions of 15
'
.
.
.
Broadly stated, the present invention provides
a process for e?ecting the polymerization of
the two or more unsaturated hydrocarbons. The
compounds thus produced are referred to as in
ole?nic hydrocarbons, which comprises contact.
terpolymers, as distinguished from the compounds
ing the ole?nic hydrocarbon~ reactants in a reac
tion zone under polymerizing conditions, with a
obtained when molecules of an unsaturated hy
drocarbon condense with themselves, and theop 20
The new polyymerization, catalysts of our in
eration is called interpolymerization. In the
vention , are ~monofluophosphoric acid, HzPOsF,
interest of brevity, copolymerization and inter
and di?uophosphoric acid, HPO2F2. These acids
polymerization will be referred to hereinafter,
have been obtained from the Monsanto Chemical
broadly, as polymerization, and the conditions of
temperature, pressure, etc., will be referred to, ' C0mpany._ Mono?uophosphoricacid is a, viscous
liquid that fumes slightly on ‘contact withair,
accordingly, as polymerizing conditions, it vbeing
It hasa specificgravityof about, 1,25 at 29° ,C-,_'an_d
clearly understood, that the nature of the union
decomposes upon heating to an elevated temper;
will bcome apparent to those versed in the. art,
?uophosphoric
from the character of the reactants used in any
particular reaction.
'-
‘
temperatures and pressures; or may be carried
tion.
These substances are referred to as co
H
>
'
-
- _
"
-,
ature. " It can be used manytimes before 'it'loses
30 its activity. .Difluophosphoric ‘acid is also a
As-is well known to those familiar with the art,
polymerization reactions of the type referred to
hereinbefore, may be conducted at relatively high
out at lower temperatures and pressures, in the
presence of substances or of mixtures of sub
stances, that promote the polymerization reac
acid.,
35
viscous liquid‘; however, it fumes'strongly. on
contact with air and is highly corrosive towards
glass. It likewise decomposes upon heating to
an elevated temperature. Both of these acids
separate readily from hydrocarbons to form a
layer.
‘
‘
'
"
'
.
The amounts of ?uophosphoric acids used in
our process, may vary between about 5% and
about 50%, with respect to the weight of the
polymerization catalysts or interpolymerization
catalysts, depending on the type of reaction they 40 hydrocarbon reactants in the charge. Larger
amounts maybe used, if desired, although no
catalyze; or in keeping with the terminology es
additional advantages seem to result therefrom;
tablished herein, they may be referred to broadly,
The fluophosphori'c acids of our invention, may
be used to catalyzereactions involving coplymer
and amOng the most widely used are phosphoric 45 ization or interpolymerization of normally ‘gas
eousole?nic hydrocarbons, propene, butenes and
acid, sulfuric acid, hydrogen ?uoride, aluminum
pentenes, to produce coplymers or interpolymers,‘
chloride and boron tri?uoride.
that'boil ‘within the boiling range of motor fuels.
We have now-found that ?uophosphoric acids
These products are highly desirable in view of
are effective polymerization catalysts.
'
their highroctane ratings, and accordingly, the
It is an object of the present invention to pro-_
as polymerization catalysts.
Several substances
have been proposed as polymerization catalysts,
2,409,248
3
4
use of our new catalysts in the polymerization
of the products obtained, are proof that very
little alkylation, if any, occurs.
The amount of saturated hydrocarbon diluent
used, ordinarily varies between about 50% and
about 95%, with respect to the weight of the
ole?nic hydrocarbons in the charge.
processes for manufacturing high-octane motor
fuels, must be considered a preferred embodi
ment of our invention.
‘
The ole?nic hydrocarbons to be used in our
process may be derived from any suitable source,
as is well known in the art. A conventional and
preferred source of the hydrocarbons used in the
preferred embodiment of our invention, that of
l)
The process may be carried out as a batch,
continuous, or semi-continuous type of operation.
Particularly when the process is carried out on
manufacturing motor fuels, is the ?xed gases ob 10 a commercial scale, economic considerations
make it preferable to operate in a continuous
tained around petroleum re?neries, as is well
understood in the art. These hydrocarbons may
be used either in the pure state or in admixture
with other constituents not undesirable. Inthis
connection, it must be noted that when the poly
merization reaction involves for example, co
polymerization or interpolymerization of the nor
mally gaseous ole?nic hydrocarbons for the pur
pose of manufacturing motor fuels, under the
polymerizing conditions extant in the reaction
manner.
For efficient operation, whether the
process is carried out on a batch or continuous
basis, it is essential that the ole?nic hydrocarbon
reactants be intimately contacted with the
catalysts of our invention. This may be effected
in several ways. For example, when the reaction
involves interpolymerization, one of the ole?nic
hydrocarbon reactants may be pumped into a
zone, and in the presence of our new catalysts, it
mixture comprising the ?uophosphoric acid, the
other ole?nic hydrocarbon reactant, and, where
is di?icult to control the degree of copolymeriza-'
, desirable, a saturated hydrocarbon diluent; or,
tion and/or interpolymerization, with the result
that the products obtained contain large amounts
of copolymers and/or interpolymers, that have
boiling points outside the boiling range of motor
fuels.
a mixture of the ole?nic hydrocarbon reactants
may be pumped into a mixture comprising a
?uophosphoric acid and a mixture of saturated
hydrocarbon diluents; or, a mixture of the
We have found also, that the degree of co
be pumped into a reaction zone containing a
polymerization and/or of interpolymerlzation of
ole?nic hydrocarbon reactants and diluent may
?uophosphoric acid.
In the process of our invention, the tempera
the ole?nic hydrocarbons in the presence of our 30
ture to be used usually varies between about
novel polymerization catalysts, may be controlled
32° F. and about 140° F., and preferably, between
through the use of a saturated hydrocarbon
about 65° F. and about 85° F. The pressure to
diluent, thereby insuring a product that will con
be employed depends upon the temperature used,
tain predominantly, constituents that boil within
and ordinarily, a pressure su?icient to maintain
‘the boiling range of motor fuels. Accordingly,
the reactants in the liquid phase at the tem
the charge stock of our process may consist of
a re?nery C4-cut, containing, for example, 4.4%
isobutene, 13.4% 1- and 2-butenes, 1% propene,
and the balance mainly normal butane and iso
butane. In general, compounds or mixtures of
compounds that are inert under the polymerizing
conditions of our process, and which can be
perature employed, is adequate. The reaction
period, whether the operation involves copoly
merization or interpolymerization, depends, of
course, upon the temperature, the nature of the
reactants employed, and to a certain extent, upon
the pressure. vWe have found that in batch op
eration, a reaction period varying between about
one minute and 30 minutes ordinarily, is satis
easily separated and removed from the product,
if desired, are suitable diluents. Accordingly,
para?inic hydrocarbons have been found to be
very effective diluents of this type. Para?inic
hydrocarbons that are suitable diluents in the
reaction variables are more or less interdepend
process of manufacturing motor fuels, comprise
propane, normal butane, isobutane, normal
limits within which the others may be varied are
pentane and isopentane, and mixtures thereof. '
It must be understood, of course, that para?inic
hydrocarbons such as hexane, heptane, octane
and the like, may be used if desired; however,
and by way of example, if the product contains
c'z-oleflnic hydrocarbons, the diluent, if heptane,
can be separated and removed therefrom with
factory.
It must be understood, of course, that the
ent, hence, when one is arbitrarily ?xed, the
somewhat restricted. In any particular instance,
the most desirable conditions can be readily
ascertained by one skilled in the art, the working
ranges of these variables in the preferred opera
tion of our process, that of manufacturing motor
fuels, having been indicated hereinbefore.
Without any intended restriction of the scope
di?iculty. On the other hand, if not objection
of the present invention, the following examples
able, the diluent or diluents may be left in the
product. In commercial applications of our
are submitted as illustrative of the results ob
tainable in carrying out the process of our in
process, the charge stock containing the ole?nic
hydrocarbons to be copolymerized or interpoly
merized, may contain also the necessary diluent
or diluents. Thus, in a charge stock containing
vention:
light ole?nic hydrocarbons and higher para?lnic
hydrocarbons, the higher para?inic hydrocarbons
isobutene and 21.6% 1- and Z-butenes, were
pumped into an autoclave containing 175 grams
will act as the diluent and if not objectionable
for the intended use of the product of the poly
of mono?uophosphoric acid, at a rate of 80 c. 0.
per minute. The temperature was maintained
at 80° F. After debutanization, the polymer
product weighed 590 grams and had a speci?c
meri'zation operation, maybe left in the product.
It must be observed, that the desirable e?ect
produced through the use of these diluents, is
not to be attributed to an alkylation reaction
between the diluents and the ole?nic hydro
carbons involved in the polymerization operation.
The relatively low temperatures used in our
Example 1
5500 c. c. of a re?nery C4-cut containing 12.0%
gravity at 60°
of 0.732. The gaseous product
analyzed as follows:
Per cent
Isobutene _____________________________ __
0
1- and 2-butenes _______________________ __ 15.3
process, and the relatively high iodine number 75 These results indicate that 12 parts of isobutene
2,409,248
5
.6
and 6.3 parts of 1- ‘and 2-butenes were poly
v
I
and 5, were subjected to an A. S. T. M.’ distilla
tion and the following results ‘were obtained (the
merized.
Example 2
5500 c. c. of a re?nery, Ci-cut containing 6.4%
isobutene and 17.4% 1- and 2-butenes,r were
octenes boil between 209° F. and 270° F.) :
'
Example 4 Example 5
pumped into an autoclave containing 160 grams
I
of mono?uophosphoric acid which had been used
in the run described in Example 1, at a rate of
160 c. 0. per minute. The temperature was main
tained at 75° F. After debutanization, the poly
5% ........ -.>..___.Y.__
10
ci?c gravity at 60° F. of 0.742. Thegaseous prod
_
__
177
209
20%_ __
290
226
30%. ._
328
4070- _60%. ._
347
364
. . _ . _ _ ._
. . . _ . . . . . . _ .
_ _ _ . _ _ _ _ _ . . -_
90% ___________ ..
Percent residue .... . _
.
238
244
254
374
‘
..
___________ __
268
389
320
440;
365
528 ->
End point ..... __
Percent recovered“
Percent loss _____________________________ _ _
ized.
114
179
70%...
These results indicate that 6.2 parts of isobutene'
and 5.2 parts of 1- and 2-butenes were polymer
,
251
80%-.-
Isobutene ________ __' ___________________ _. 0.2;‘
l- and .Z-butenes ____________ _._ ______ _____. 12.2‘
° F.
96
_ _ _ _ . _ __
60% . . . . . . . . . . . . . . _ _ _ _
'
Per cent
° F.
___________ _.
10% _ _ _ . _ _ _ _ . _ _
mer product weighed 320 grams and had a spe
uct analyzed as follows:
,
"
Initial boiling point _____________________ _.
408
530_
490
92. 0'
96; 0
0. 7
1.8
7. 3,
2.2
The present invention may be embodied. in
other speci?cforms without departing'from the
spirit or ‘essential attributes thereof, and it. is
therefore desired that the present embodiments
'
The octene polymers produced were hydrogen¢
ated and the product was then subjected to in
fra-red analysis with the following results:
Percent
be considered in all respects as illustrative and
not restrictive, reference being had to ‘the ap
pended claims rather than to the foregoing de
scription to indicate the scope of the invention.
2,3-dimethyl hexane ____________________ __ 27.5
2,2,3-trimethy1 pentane-‘ ________________ __ 25.1
2,3,4-trimethyl pentane _________________ __ 21.6.
We claim:
,
y
'
1. The process of manufacturing high-octane
motor fuel, which comprises contacting normally
2,2-dimethyl hexane ____________________ __ 10.2
2,3,3-trimethy1 pentane _________________ __ 0.6. 30 gaseous ole?nic hydrocarbons with polymeriza
tion catalytic material selected from the group
consisting of monofluophosphoric acid and di
100.0 '
Example 3
?uophosphoric acid, in the presence of para?inic
2,2.4-trimethy1 pentane _________________ __ 15.0
hydrocarbon material, in a reaction zone, at tem
5000 c. c. of a re?nery C4-0llt containing 7.5% 35 peratures varying between about 32° F. and about
isobutene and 16.5% 1- and 2-butenes, were
140° F., and at a pressure‘suf?cient to maintain
pumped into an autoclave containing 245 grams
the ole?nic hydrocarbons in liquid phase, said
catalytic material being prepared outside said
of di?uophosphoric acid, at a rate of 200 c. 0.
per minute. The temperature was maintained at
74° F. After debutanization, the polymer prod
reaction zone.
40
uct weighed 172 grams and had a speci?c grav
ity at 60° F., of 0.763. The gaseous product ana
lyzed as follows:
~gaseous ole?nic hydrocarbons With- mono?uoe
phosphoric acid, in the presence of para?inic hy
1
_____________________________ __
'
motor fueLwhich comprises contacting normally
Per cent
Isobutene
.
2. The process of manufacturing high-octane
drocarbon material, in a reaction zone, at tem
3.6
peratures varying between about 65° F. and about
1- and 2-butenes ________________________ __ 13.4
85° F., and at a pressure su?icient to maintain
These results indicate that 3.9 parts of isobu
tene and 3.1 parts of 1- and Z-butenes were poly;
the olefinic hydrocarbons in liquid phase, said
mono?uophosphoric acid being prepared outside
merized.
'
50
said reaction zone.
1
3. The process of manufacturing high-octane
motor fuel, which comprises contacting normally
3000 c. c. of isobutylene were pumped into an
gaseous ole?nic hydrocarbons with polymeriza
autoclave containing 300 grams of mono?uo
tion catalytic material selected from the group
phosphoric acid, at a rate of 60-80 0. c. per minL
consisting of mono?uophosphoric acid and (ii
ute. The temperature was maintained at 70-75° 55 fluophosphoric acid, in the presence of 'para?inic
F. 1390 grams of polymer product having a Nor-'
hydrocarbon material selected from the group
wood bromine number of 114.1, were obtained.
consisting of propane, butane, pentane, isobutane,
and isopentane, in a, reaction zone, at tempera
Example 5
tures varying between about 32° F. and about
Example 4
1700 c. c. of a re?nery C4-cut containing 12.0% 60 140° F., and at a pressure sufficient to maintain
the ole?nic hydrocarbons in liquid phase, said
of isobutene and 19.6% 1- and 2-butenes, were
pumped into an autoclave containing 500 grams
catalytic material being prepared outside said
reaction zone.
of mono?uophosphoric acid, at a rate of 240 c. 0.
4. The process of manufacturing high-octane
per minute. The temperature was maintained
at 70—75° F. The gaseous product analyzed as 65 motor fuel, which comprises contacting normally
follows:
Per cent
Isobutene
_____________________________ __
4.1
1- and Z-butenes _______________________ __ 14.9
These results indicate that 7.9% isobutene and
4.7% 1- and Z-butenes were used up in the op
gaseous olefinic hydrocarbons with mono?uo
phosphoric acid, in the presence of para?inic
hydrocarbon material selected from the group
consisting of propane, butane, pentane, isobu
70 tane, and isopentane, in a reaction zone, at tem
peratures varying between about 65° F. and about
85° F., and at a pressure su?icient to maintain
eration. The polymer product had a Norwood
the ole?nic hydrocarbons in liquid phase, said
bromine number of 139.3.
mono?uophosphoric acid being prepared outside
The polymer products obtained in Examples 4 75 said reaction zone.
8
7
in; the presence of; para?‘inic hydrocarbon ma
5. The process of manufacturing high-octane
terial, in a reaction zone at temperatures vary-:
ing between about 32° F. and about 140° F., and
at a pressure sufficient to maintain the ole?nic
hydrocarbons in liquid phase,’ said catalytic ma
terial being prepared outside said reaction zone.
10. The process of polymerizing ole?nic hy
motor fuel, which comprises contacting a C4
re?nery cut with polymerization catalytic‘ ma
terial selected from the group consisting of mono
?uophosphoric acid and di?uophosphoric acid,
in a reaction zone, at temperatures varying be
tween about 32° F. and about 140° F., and at a
drocarbons, which comprises contacting said ole?
pressure sui?cient to maintain the ole?nic hy
?nic hydrocarbons with mono?uophosphoric'ac;
drocarbons in the charge in liquid phase, said
catalytic material being prepared outside said 10 id, in the presence of para?inic hydrocarbon ma
terial, in a reaction zone, at temperatures vary
reaction zone.
ing between about 65° Rand about 85° F., and
at a pressure su?icient to maintain the ole?nic
6. The process of manufacturing high-octane
motor fuel, which comprises contacting a Cl;
Vre?nery cut with mono?uophosphoric acid, in a
reaction zone, at temperatures varying between .
‘about 65° F. and about 85° F., and at a‘ pressure
I'su?icient to maintain the ole?nic hydrocarbons
in the charge in liquid phase, said mono?uo
phosphoric acid being prepared outside said re
hydrocarbons in liquid phase, said 'monofluophos
phoric acid being prepared outside said reaction
zone.
~
>
.
11. The process of polymerizing ole?nic hydro
carbons, which comprises contacting said ole?nic
hydrocarbons with polymerization catalytic ma20 terial selected from the group consisting of mon
action zone.
. 7. The process of polymerizing ole?nic hy
o?uophosphoric‘ acid and di?uophosphoric acid,
in the presence of paraf?nic hydrocarbon mate
rial selected from- the group consisting of pro
?nicvhydrocarbons with polymerization catalytic
pane, butane, pentane, isobutane, and isopen
material selected from the group consisting, of
mono?uophosphoric acid and di?uophosphoric 25 tane, in a reaction zone, at temperatures varying
between about 32° F. and about 140° F., and at
acid, in a reaction zone, at temperatures varying
a pressure su?icient to maintain the ole?nic hy
between about 32° F. and about 140° F., and at
drocarbons in liquid phase, said catalytic mate
a pressure suf?cient to maintain the ole?nic hy
rial being prepared outside said reaction zone.
drocarbons in liquid phase, said catalytic mate
12. The process of polymerizing ole?nic hydro
rial being prepared outside said reaction zone.
30
carbons, which comprises contacting said ole?nic
8. The process of polymerizing ole?nic hydro
drocarbons, which comprises contacting‘ said ole
carbons, which comprises contacting said ole?nic
hydrocarbons with mono?uophosphoric acid, in
a reaction zone, at temperatures varying between
about 65° F. and about 85° F., and at a pressure
su?icient to maintain the ole?nic hydrocarbons
in liquid phase, said mono?uophosphoric acid be
ing prepared outside said reaction zone.
-
hydrocarbons with mono?uophosphoric acid, in
the presence of para?inic hydrocarbon material
selected from the group consisting of propane,
butane, pentane, isobutane, and isopentane, in a
reaction zone, at temperatures varying between
about 65° F. and about 85° F., and at a pressure
suf?cient to maintain the ole?nic hydrocarbons
9. The process of polymerizing ole?nic hydro
in liquid phase, said mono?uophosphoric acid
carbons, which comprises contacting said ole?nic 40 being prepared outside said reaction zone.
hydrocarbons with polymerization catalytic ma
JOHN W. BROOKS.
terial selected from the group consisting of mon
o?uophosphoric acid and di?uophosphoric acid,
ARLIE A. O’KELLY.
ROBERT H. WORK.
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