Патент USA US2540584

2,540,580
Patented Feb. 8, 1951
UNITED STATES PATENT OFFICE
2,540,580
QUALITY '. 0F OLEFIN POLMB
LUBRICANTS
,
Raymond L. Heinrich, Baytown, Tex, assignor,
by mesne assignments, to Standard Oil ‘De
velopment Company, Elisabeth, N. 1., a corpo
ration of Delaware
No Drawing. Application September 11, 1947,
_.
Serial No. 173,501 '
.
s Claims. -(c|. zoo-sans)
_
‘2
.
'
The present invention relates to a process for
making lubricating oils and more particularly
relates to the preparation of lubricating oils of
improved stability characteristics from oie?ns.
It has heretofore been proposed to prepare
drous aluminum chloride although any‘of the
Friedel-Crafts catalysts may be used, such, for
and subsequently reacting the ole?n polymers
obtained therebywith various materials to im
ous reaction pressures may be maintained.
ample, it is known that lubricating oils prepared
by polymerizing voleiins may be stabilized and
otherwise improved by reacting, these ole?n
necessary to operate at pressures in excess of
vatmospheric but I prefer to opsrate at atmos
example, as boron ?uoride, zinc chloride, alumi
'num bromide, etc. when boron ?uoride is em‘
ployed, the temperature at which the reaction
lubricating oils from ole?ns by polymerizing al-. . is conducted will ordinarily be lower than when
aluminum chloride is used. Furthermore, vari
pha ole?ns in the presence of'a halide catalyst
When, for example, butene-l or propane is used
prove the stability of they polymer oil. '- For ex-' 10 in combination with ‘boron ?uoride, it will be
pheric pressurevwhenever possible. In my proc
ess, a diluent may be used to give greater con
trol over ‘the polymerization reaction though the
use of such diluent is‘ not necessary. when a
diluent is used, I prefer to use a relatively low
polymers with such materials as sulfur and com-_ .
pounds of'sulfur or phosphorus and compounds
of phosphorus. Material prepared-by such proc
esses are ;-known to have materially better _sta-'
boiling ' straight chain paraf?nic hydrocarbon
bility characteristics and to possess improved
oiliness and extreme pressure characteristics.
Such materials may themselves be used as lubri
since it is preferable to avoid-the use of branched
chain para?inic hydrocarbons as such hydro
carbons tend to react with the oleflns present
under the influence of the catalyst employed
cating oils but it-isalso known to blendsuch ma
terials with petroleum lubricant fractions to im
prove theaoxidation, oilness, andextreme pres
sure characteristics of such fractions.
thereby causing undesirable side reactions.
The reaction temperature maintained in prac
_
One of theobiects of this invention is to pre-' 25 ticing the process of my invention will be .de
termined by the particular alpha olefin to be
pare a lubricating oil fromalpha ole?ns which
polymerized, the element or compound thereof
has improved stability to oxidation. Another
chosen, the catalyst employed and in some in
object is to reduce-{the tendency of lubricating
stances by the pressure at which the reaction is
oils prepared byuthe polymerization of.,--alpha
oia?ns to further polymerize during use. Other 30 conducted. However, the reaction should ordi
narily be carried out at a temperature of not
objects will be apparent from the following de
lessthan' 50° F. and not in excess of about 250°
tailed description of my invention.
F. since the desired product cannot ordinarily
be secured if the reaction tmperature is main
In accordance with my invention, alpha ole- ~
?ns, preferably those ‘boiling below 450° F. at
atmosphericpressure, are polymerized in the
presence ‘of a Friedel-Crafts type catalyst, for
instance, preferably aluminum chloride, and
tained outside these limits.
.
Sufficient time should be allowed for the sub
stantial completion of the reaction and the time
required may vary from a few minutes to sev
are simultaneously reacted with an element or
eral hours depending upon the reaction mate
a compound of an element appearing in the
right-hand “columns of groups V and VI of 40 rials which are employ'.d and the reaction con- '
ditions maintained. I have found that ordi
Mendeleei‘fs periodic arrangement of the ele
narily the reaction should be permitted to con;
ments, the said elements being nitrogen, vphos
tinue for at least 30 minutes and ordinarily
phorus, arsenic, antimony, bismuth, oxygen, sul
should not be permitted to exceed 3 or 4 hours.
fur, “selenium, tellurium, and polonium. ‘Of the
eiements---,-.sppearing in the above-mentioned 45.. The reaction mixture is, of course, agitated
groupings. and; compounds‘ of such‘ elements,
' while the reaction is in progress.
On completion of the reaction, agitation
is discontinued and a sludge separates from
the reaction mixture. The sludge is withdrawn
phosphorus and phosphoruspentasuliide are the
preferred-‘materials used although it is under
"P‘re. stood that any of the others may be used. . The
and the‘ oily liquid remaining in the reactor ‘con
reaction-is carried out under such conditions of
time, temperature, pressure, and dilution as will
result in: securing aaproduct whichis of such.
tains the desired lubricant. It is» desirable to
ole?n employed, the catalyst used to catalyze
the polymerization reaction, and the particular
material which is selected from. the right hand
may be accomplished by any of the well-known
means such, for example, as atmospheric, vac
uum or steam distillation or steam stripping‘. By
quench any catalyst which may be suspended or
molecular weight and physical characteristics _ ‘ dissolved in this oily liquid and after such quench"
ingthe lubricant contained therein may be're‘~
as to make it- suitable for use as a lubricant.
covered. The recovery of the desired lubricant
55
'i‘hesev ‘conditions will, of course, vary with the
columnoi group .37 or VI. In carrying outthis
devout-ion. I were!‘ low
anhy
60
this means, the-desired lubricant boiling within
a selected boiling range may be recovered. or
4
course. the recovered lubricant may be subjected
to additional treatment such, for example, as clay
?ltration, but such additional treatment is no part
oi’ this invention and it will often be found that
no additional treatment is required.
As an example or my invention, pentene-l was
reacted with red phosphorus in the presence of
substantially anhydrous aluminum chloride for
2 hours at 95° F. and at atmospheric pressures.
The following materials were charged to the re
actor in mounts indicated as parts by weight:
aluminum chloride, 0.4 part; red phosphorus 1.0
part, matched, 50 parts; and normal pentane,
.50 parts.
‘a
was realized in the distillation operation and the
overhead vapor consisted of 10 parts or water and
1 part hydrocarbon.
'
The lubricating oil bottoms obtained in each
of the ?ve above-mentioned experiments were
tested. In addition, a sample of each of these ?ve
lubricating oil bottoms was subjected to oxidation
and the product from this oxidation was tested.
The conditions under which each or these ?ve ex
periments was conducted together with the physi
cal analysis or the lubricating oil bottoms ob
tained and the analysis of the samples of the bot
toms subjected to oxidation are shown in the
'
V tabulation below. .
BunNo ................................. ..
1
'
~
2
8
4
Phospho-
PsSl ....... -.
None ..... --
Pas! ...... --
5
Material Added ......................... ..
Bed
gllusprgi'éIjééIé:IIIIgéIéIgéIII
Pentene-l ..... .. Pentene-l_-. Pentene-l-.. Dodeeened. Dodeoene-l.
n~Pentane ..... ._ n-Pentane.__ n-Peutane__. n-Pentane... n-Pentane.
rus.
cm
M
on
118133
Add
’
AlCls C tslyst
a
Ole?n
y
.3
_
None.
'
..................... ..
-
Diluent ............................. _.
Peg- --
Yield, Wt. Percent of Ole?n
I :
; ; | ,
Tests on Polymer:
Beio‘re §>xidation'—
Percent Increase in Vis. 210° F. on
Oxidation.
Reaction 'l‘emp.. "F ..................... ._
Pressure ................................. -.
$4.
Atmos.
‘The method for conducting the oxidation is found in the 7th edition (1946) or “Standard Methods for Testing Penn:
learn
and Its Products," publ bed by lnstitu_te oi Petroleum. Manson House, London, page 266. Test designation
P ‘a
0
-
I
e
.
"The procedure for conducting this test is identi?ed as I. P. 14/45 and is found on page 62 ot the reference under '
above
In another example of my invention, 52 parts
It will be noted from the data that the lubricat
of pentene-l was reacted with 0.7 part of phos
ing oil treated with red phosphorus and a lubri
phorus pentasul?de and 0.7 part of aluminum
cating oil treated with phosphorus pentasul?de
chloride in the presence of 48 parts of normal
in accordance with this invention were consider
pentane. This reaction was conducted for 1% 45 ably more stable to oxidation and to viscosity
hours at a temperature of 95° F. and at atmos
pheric pressure.
.
increase on vigorous oxidation than was the lu
bricating oil prepared in the conventional man
In a still further example of my invention, 55
ner.
parts of dodecene-l was reacted with 0.9 part of
It is apparent from the foregoing tabulation
phosphorus pentasul?de and 1.1 parts of alumi 50 that I have prepared a lubricant from alpha ole
num chloride in the presence of 45 parts of normal
?ns capable of withstanding oxidation and poly
pentane for 1% hours at a temperature of 100°
merization. Although speci?c elements and com
F. and at atmospheric pressure.
,
pounds of elements appearing in the right-hand
Flor purpose of comparison, 51- parts of
columns of groups V and VI have been employed
pentene-l was reacted with 0.6 part oi’ aluminum 65 in the examples hereinbetore mentioned and spe
chloride in the presence of 49 parts of normal pen
ci?c reaction conditions have been employed
tane with ‘no additional materials added. The
therein, it will be understood that various changes
reaction time in this case was one hour and the
may be made in the materials employed and in
temperature and pressure was 100° F. and atmos
the time, temperature, pressure and reaction pe-'
pheric. respectively. Also for comparison, 53
riod without departing from the scope of the in
parts of dodecene-l was reacted with 1.1 parts of
vention. While only pentene-l and dodecene
aluminum chloride and 45 parts 01' normal pen
have been employed in the examples hereinbetore
tane with no additional material added. This
mentioned, it will be understood that propene,
latter reaction, which was conducted at 100° F.
butane-l, hexene-l, heptene-l, octane-1, nonene
and at atmospheric pressure, was concluded in
l. decene-l, undecene-l, or tridecene-l may be
1% hours.
. employed in the process 01' my invention.
Upon expiration of the above mentioned reac
What I wish to claim is:
.
tion periods in each example, the reaction mixture
l. A method of producing an improved lubri~
was allowed to stand for a sulllcient time to sep
eating all which includes the steps of contacting
arate the aluminum chloride sludge from the 70 a mixture of an alpha ole?n having a boiling
reactor hydrocarbon. The reactor hydrocarbon
point of less than 450° F. and a material selected
was then water washed in the absence of alumi
from the group consisting of phosphorus and
num chloride sludge to destroy catalyst dissolved
phosphorus pentasul?de with a Friedel-Craits
in the polymer.‘ The polymer was then steam
type catalyst in the presence of a diluent Ma
distilled until a bottoms temperature 01 400'’ F. 75 temperature in the range between 50° and 250° 8..
2,540,580
-
6
5
in the liquid phase for a time in the range be
tween 1 and 3 hours su?lcient for the simultane
ous polymerization of the said ole?n and for the
reaction of the said ole?n and its polymers with
the said material to form a product suitable for
use as a lubricating oil and recovering said prod
uct.
2. A method in accordance with claim 1 in
which the Friedel-Crafts type catalyst is substan
tially anhydrous aluminum chloride.
3. A method in accordance with claim 1 in
which the material is phosphorus pentasul?de.
4. A method'in accordance with claim 1 in
the range between 1 and 3 hours sumcient for the
simultaneous polymerization of said ole?ns and
for the reaction of said ole?ns and their poly
which the diluent employed is a low boiling.
straight chain para?lnic hydrocarbon.
Number
mers with the said material to form a product
suitable for use as a lubricating oil and recover
ing said product.
REFERENCES CITED
The following references are of record in the
?le of this patent:
UNITED STATES ‘PATENTS
Name
Date
2,082,518
2,316,080
5. A method in accordance with claim 1 in
2,360,699
which the material is phosphorus.
2,381,907 '
6. A method of producing an improved lubri
cating oil which includes the steps of contacting
2,389,240
a mixture of alpha ole?ns having a boiling point 20 2,449,934
of less than 450° F. and a material selected from
the group consisting of phosphorus and phos
phorus pentasul?de with a Friedel-Crafts type
catalyst at a temperature in the range between
50° F. and 250° F. in the liquid phase for a time in
'
RAYMOND L. HEINRICH.
Number
453,854
Ruthru?' _________ .. June 1, 193'!
'Loane et a1________ _- Apr. 6, 1948
McAllister et a1. __-_ Oct. 17, 1944
Hughes et al. _____.._ Aug. 14, 1945
Reid _____________ __ Nov. 20, 1945
Giammaria .._-____... ‘Sept. 21, 1948
FOREIGN PATENTS
Country
Date
Great Britain____ -_ Sept. 18, 1936