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Патент USA US2109772

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hummer-1,1938 _
4-
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0
2,109,7'l’2
UNITED STATES PATENT OFFICE
THIOKENED LUBRICATING OIL .
Per 1:. Frolich, Roselle, N. 1., escignor to stand;
ard-Oil Development Company, a corporation '
V of Delaware
"
,
.No Drawing.‘ Application October 21, 19:3,
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_
Serial No. 694,616
_ 5 Claims.
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(01. 196-151)
_ 'Ihis invention relates to improved lubricating
from unsaturated hydrocarbons.
Many such
compositions comprising" solutions of synthetic‘ products are insoluble in practically all solvents
' resinous bodies in lubricating oils and relates
and are obviously unsuited for the ‘present in
,more particularly to the improvement of the ventlon. The polymerization and condensation
5 viscosity and viscosity indexof inferior quality products intended for use in this invention are- 5
lubricating oils by addition thereto of resins pre- those resins and resinous products of relatively
pared by polymerization and/or condensation high molecular weight, say above 800 to 1000,
of oleilnes and diole?nes or mixtures thereof such and including the range to 2,000, 5,000, 10,000
‘as are found in cracked naphthas.
and even higher. which are soluble in benzol, and 10
A class of hydrocarbon resins of varying melt-
which preferably are brittle and readily friable 10 r
in: point, friability and color, and which are solids which'become. plastic on‘ heating. Such
soluble in benzol and gasoline and are insoluble
products are designated. by th'e term resin as
in ethyl alcohol and acetone is obtained by the
used in the claims.
polymerization -and condensation of cracked
15 naphthas or of the unsaturated components
thereof by the application of heat and pressure
or by action of suitable polymerizing agents such
as the active halides, for example aluminum chlo-ride, zinc chloride, boron ?uoride, and the like.
go It has now been found that these resins are soluble in lubricating oils; particularly those derived
from asphaltic or naphthenic base crudes, and
that the resulting solutions have a materially
higher viscosity and _ viscosity index than the
‘
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It is recognized that the presence of a relatives
ly smaller proportion of impurities, such as heavy 15
oils, ‘which may have been present in the initial
materials or may be formed during the polymer
ization and condensation reaction, may so affect
the physical properties of [the crude product that
it may be semi-solid, tacky, so toughened as not 20'
to be brittle or pulverizalile. or otherwise modi
lied. The crude product Containing the resin
may also be used for the purpose of this inven
tion, provided the impurities are not present in .
25 original lubricating oil. ,It is an object of this
invention to increase the viscosity and to im-
sumcieht' quantities to offset the advantageous g5
effect of the resin. However. it'is generally pref
.prove the lubricating and other qualities ‘of such
inferior lubricating oils by addition thereto of
such resins.
‘
3o Resins suitable for this invention may be prepared in a great varietyof ways; for example rel-
erable to use resins that are su?iciently pure to
be brittle and pulverizable solids at room tem
perature. The resin may be puri?ed by distll1a-<
tion of vaporlzable oils, preferably in high vac- 3o
um and may be separated from Oils and 55
atively pure oleilnes or mixtures of oleiines and
diole?nes, such as amylene and isoprene, may
be condensed to resins by addition of aluminum
35 chloride or other suitable halide polymerizing,
phallic matter by Suitable Selective Solvents, Such
as lique?ed hydrocarbon eases. petroleum ether.
naphthas. a mixture of benzol and acetone. and
the like.
35
agent‘, as described in German Patent 278,4;86 to .
Schering. Cracked naphthas such as the condensates or oil ‘gas drips boiling below 200° 1?.
obtained in the gasiiication of gas oil may ,be
40 treatedwithasmallamountofalmninumchlw
ride as described in U. S. Patent 811,563'to
Ihart. .The mixture is ?ltered and a resin ob-
tained from the ?ltrate as a residue by distilla-
tion vor evaporation oi volatile constituents. As
45 another example a resin may be prepared by
contacting a cracked naphtha boiling from 60 to
15.0“ C. with
‘zinc chloride as described
in British Patent 3572 of 1914. By still another
method the liquid fraction obtained in cracking
5o petroleum oil in vapor phase at 650° C.,may be
polymerized to a hard resin by the application
of heat without a catalyst as described in U. 8.
' 1,703,950.
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'
Itisrecognized that many types of polymerlza55 tlon and condensation products can be obtained
The above resins may be used to thicken and
.
to improve the viscosity index and other lubri
veating characteristics of lubricating oils. This
is illustrated in the following examples:
sample 1
_
49
A petroleum naphtha obtained by cracking gas ‘
oil in vapor phase, 'at high temperature and lbw
pressure, is carefullyfractionated bydistlllation.
The fraction boiling below about-180° C. is agi- 45
tated with about 20% by weight of anhydrous
aluminum chloride which is added in smallquan
titles during continuous and vigorous agitation
and cooling to'maintain the‘ reagents at about
room temperature and preferably below about 50
40° 0., as described by Thomas and Carmody,
J. Ind. 8: Eng. Chem. 24 (1932) p. 1125, and in
U. 8. Patent 1,836,629. The reaction mixture is
then hydrolyzed. the sludge withdrawn and the
resin obtained as a residue on distillationof the so
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2
2,109,772
oil layer. A solution of 51% by weight of this resin
is prepared with a Coastal lubricating oil. The
characteristics of the original lubricating oil and
the resulting blend are as follows:
Coastal oil Blend
Saybolt viscosity:
Seconds at 100° F___________ __> 360
Seconds at 210° F__________ _Viscosity index. _____________ __.._
10
50
38
543
58.5
55
lubricating composition will depend upon the
solubility of the resin in the oil used and on the
extent of improvement desired. Generally, with
oils having a viscosity index of 0 to 50, improved
lubricants are prepared with about 2 to 10% of
the resin in the composition, although lower or
higher concentrations such as 1/2% or 1% to 15%
or 25% or moremay be used, and will be found
suitable with oils of unusually high or low vis
cosity and viscosity index.
The color, purity, solubility in petroleum sol
10
A fraction boiling _in the gasoline range, con
vents, and other qualities of these resins may be
taining ole?n and diole?n, and probably aromatic - “modi?ed" or improved by various methods, and
and substituted aromatic hydrocarbons, and pro
the improved resins may also be used to prepare
15 duced by vapor phase cracking of a petroleum gas
blends with lubricating oils as described above. 15
oil fraction at high temperatures and low pres
The resins may be puri?ed and improved by suit- .
sures by the “Gyro” process, is cooled to —70" F.
able‘re?ning methods such as clay treating, sul
Boron ?uoride is bubbled through this fraction - furic acid treating, hydrogenation, and the like.
for about one hour, with addition of carbon di
The solubility of the resins in petroleum oils,
20 oxide snow to maintain the temperature con
especially in paraffin base oils, may be improved 20
tinuously at about —'70° F. (It is desirable when by alkylation with suitable alkyl radicals such as
'
'
EmampleZ
usingboron ?uoride to work at low temperatures,
30
45
50
60
methyl, ethyl, etc. to octyl, decyl and higher in
such as 0° F. to —90° F.) A noticeable thicken
cluding the alkyl groupsof fatty acids and alco
ing of the mixture occurs. The mixture is then ' hols, and the liquid ole?nes obtained by cracking
allowed to warm up to room temperature. Any para?in wax. ,
25
boron ?uoride present is hydrolyzed, and the gaso
The resin may be used in oil blends together
line hydrocarbons are removed by distillation. with pour point depressing agents, oxidation
There is thus obtained a residue consisting of inhibitors, load bearing or “extreme pressure lu
about equal portions of a resin and an oil, the
bricant” agents, lead soaps, sulphur compounds,
total residue corresponding to 30% of the original’ sulfurized oils, dyes and the like as will be under 30
gasoline. The oil is removed by distillation under stood.
a vacuum of about 5 mm. of mercury to a tem
This inventlon is not to be limited to any spe-_
perature of about 450° F., the resin being obtained ci?c examples which have been presented herein
as the residue. A 10% blend of this resin in the‘ solely for purpose of illustration, but only by the
Coastal oil described in Example 1 gives the fol
following claims in which it is desired to claim 35
lowing inspection:
all novelty insofar as the prior art permits.
I claim:
Saybolt viscosity:
1. Lubricant comprising a mineral oil and a
Seconds at 100° F ____________________ __ 655
normally solid thickener produced by the con
Seconds at 210° F ____________________ __ 62.2
densation of ole?n and diole?n hydrocarbons.
40
V. I __________________________________ __ 52
2. Lubricant comprising a mineral oil and a
Similar blends may be prepared with resins pre
normally solid thickener produced by the con
pared by other methods as described above and densation of ole?n and diole?n hydrocarbons in
with other types of lubricating oils. . It has been
the presence of boron ?uoride at a low temperaf
found that these resins are soluble only with ture.
45
diiiiculty in high grade lubricating oils such as
3. Method for improving the lubricating char
those of the Pennsylvania type. This invention - acteristics of- lubricating oils of petroleum origin
is accordingly particularly suited for the improve: having a viscosity index below 50, which comprises
ment of inferior quality lubricating oils such as dissolving therein about 1/2 to 25% of a resin pre
lubricating oils having a viscosity index from pared by treating a cracked naphtha with an
about 50 to 0, or lower. Such lubricating oils are
active halide polymerizing agent under conditions
obtained from asphaltic, naphthem'c and aro
adapted to produce condensation products of
matic base crudes such as Coastal and California, ~ ole?ne and di-ole?ne hydrocarbons present in
and may also be obtained from othermineral said cracked naphtha.
.
I
»
carbonaceous materials, as by the liquefaction or
4.'Method according to claim 3 in which the 55
destructive distillation of coal, shale, and the like. cracked naphtha boils below 180° C.
'
Similar hydrocarbon oils may be prepared syn
5. Method according to claim 3 in which the
thetically or by polymerization and condensation resin is prepared by treating a cracked naphtha
of lower molecular weight hydrocarbons. Of I boiling below 180° C. with anhydrous aluminum
course, with resins of suitable solubility, blends chloride at a temperature below about 40° C. and 60
of exceptionally high viscosity index may be pre
separating the resin from the resulting mixture.
pared with high grade Pennsylvania type oils.
The amount of the resin used in any particular
PER K. EROLICH.
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