Note: Descriptions are shown in the official language in which they were submitted.
1 3 ~
IMPROVED 10W-30 and 15W-40
SYNTHETIC HyDRocARsoN ENGINE OILS
The present invention relates to non-polymer
thickened multigrade engine oils based on synthetic hydro-
5 carbons. More specifically, SAE 10W-30 and SAE 15W-40
engine oils derived from hydrogenated decene-l oligomers
and which do not contain viscosity index improvers are
provided.
SAE 10W-30 is the engine oil viscosity grade
10 recommended by most manufacturers for gasoline passenger
car service whereas, for diesel truck operation,
SAE 15W-40 is the most widely recommended engine oil
viscosity grade. Both of these oils are multigrade or cross-
graded which, in general terms, means that they are acceptable
for use in either a summer or winter environment. More
precisely, these oils must meet the current SAE J~00 APR84
specifications. For an SAE 10W-30 oil, a viscosity of 3500
centipoise or below at -20C. as determined in accordance
with ASTM D-2602 and a viscosity between 9.3 and 12.5 centi-
stokes at 100C. as determined in accordance with ASTM D-445
is required. Additionally, the oil must have a borderline
pumping temperature (ASTM D-3~29) of -25C. or below and
a stable pour point (FTMS 791b-203) of -30C. or below.
An SAE 15W-40 oil must have a maximum viscosity of 3500
centipoise at -15C., and a viscosity between 12.5 and
16.3 at 100C., and borderline pumping temperature of
- -20C. or below.
In addition to satisfying these viscosity criteria,
multigrade engine oils must also meet certain service classi-
3o fications of the American Petroleum Institute (API). Thisis accomplished by the addition of appropriate performance
additives to the oil. It should be noted that the formulated
oil, i.e., the base oil containing all addi~ives, must meet
the SAE J-300 APR84 viscosity criteria.
.
,,
: . - .
', ~. :. :.
, ~
~: :
~3~ 6~
l To obtain multigrade motor oils using petroleum base
stocks, it is also necessary to add a viscosity index (VI)
improver. VI improvers are polymeric materials, such as
ethylene-propylene copolymers, hydrogenated styrene-diene block
copolymers, polyalkyl methacrylates, polyisobutylenes,
ethylene-vinyl acetate copolymers or the like, which modify the
rate of change of viscosity of the basestock with temperature
when added thereto. ~1hile the polymeric VI improvers are
necessary to achieve cross-grading with petroleum ~asestocXs,
the addition of these polymers is not without problem.
It is well docu~ented in the prior art that the high
molecular weight polymeric VI improvers can undergo shear, i.e.,
breakdown, under conditions of thermal and mechanical stress.
Breakdown of the VI improver alters the viscosity characteristics
of the formulated motor oil and can also contribute to the
formation of sludge and engine deposits. Field studies have
shown, for example, that a SAE 15W-40 diesel engine oil can drop
to SAE 15W-30 after only several thousand miles of service. This
presents a very ~eal problem with heavy duty over-the-road trucks
where it is not uncommon to accumulate 30,000 miles between service
intervals. Breakdown of VI improvers is even a problem with
gasoline engines, particularly in view of the longer drain inter-
vals which are now being promoted and the fact that today's
smaller engines operate at higher RPM's and higher temperatures.
The general problems associated with the b~eakdown of polymeric VI
improvers is presented by W. Wunderlich and H. Jost in their
entitled "Polymer Stability in Engines", Society of Automotive
Engineers, Inc., SAE-429, Paper No. 780372.
One approach to overcoming the problems associated
3 with the use of VI improvers is to develop improved polymers
which are more resistant to shear under conditions o~ thermal
and mechanical stress. While the development of new polymeric
thickeners is a viable approach, it would be even more desirable
and advantageous if VI improvers could be totally eliminated
from multigrade motor oil formulations~
1 3 ~
--3--
l Canadian Patent 1,2Q3,196 issued July 22, 1986 and European Patent
Applications 115,069 and 119,070 both published September 19, 1984, disclose
multigrade l~bricants which are combinations of synthetic fluids having dif-
ferent viscosities. The lubricants consist of blends of hi~h viscosity
ethylene-alphanolefin copoly~ers ~ith lower viscosity synthetic hydrocarbons,
such as an alkylated benzene or polyalphaolefin, or ester, such as a
monoester, diester or polyester. 5~-40 and 10W--40 oils indicated
as being suitable for use as diesel cran~case lubricants
obtained by blending different synthetic products are disclosed.
It would be highly desirable and advantageous if
non-polymex thickened multigrade engine oils suitable for most
passenger car and diesel truck service could be obtained using a
single synthetic hydrocarbon bases,ock. This would preclude
compatability problems which can be encountered when different
basestocks are blended. It would also eliminate the need for
multiple processes and/or suppliers and otherwise minimize
problems and capi~al costs associated with storage and transfer
of different types of produc-ts within a plant.
; We have now une~pectedly discovered SAE 10W-30 and SAE
~ 15W-40 motor oils obtained from a single synthetic hydrocarbon
. .
basestoc~ without the addition of polymeric VI improversO The
multigrade engine oils of the invention are mixtures of
conventional oligomers of decene-l ~ith higher decene-1
oligomers, said oligomers being present in specific proportions.
The oligomeric composite is formulated with performance
additives to meet the desired API service classification.
For the multigrade non-polymer thic~ened lubricants of
this invention, signiicant amounts of hydrogenated hexamer (C60
oligomer), heptamer (C70 oligomer) and higher decene-l oligomers
are present with hydrogenated trimer (C30 oligomer), tetramer
(C40 oligomer) and pentamer (C50 oligomer). These compositions
are most generally obtained by judicious blending of frac~ions
having different oligomer distributions. However, with proper
~ 3 ~
4--
l desisn and control of process equipment, compositions having
oligomer distributions within the specified limits and suitable
for formulation with additives to produce non-poly~er thickened
SAE lOW-30 and SAE 15W-40 engine oils can be obtained directly.
Accordingly, the present invention provides a non-polymer
thickened engine oil capable of meeting SAE requirements
as low as SAE lOW and as high as SAE ao comprising 80 to 95% by
weight of a hydrogenated decene-l-oligomer mixture
and .5 to 20~ by weight of engine performance additives
such that the for~ulated oil meets API Service Requirements,
characterized by the oligomer mixture containing o.5% to 20%
C3~ oligomer, 43~ to 68~ C4~ oligomer, 14% to 34% C50 oligomer
3% to 16% C60 oligomer and 3% to 16% C70~ oligomers~
More specifically, non-polymer thickened SAE lOW-30
oils suitable for use in gasoline engines contain 5~ to lO~ by
weight gasoline engine performance-additives which meet the
requirements set forth in the appropriate API Engine Service
Classification System and 90~ to 95~ by weight of a hydrosenated
decene-l oligomer mixture containing 0.5~ to 20~ C30 oligomer,
43~ to 66~ C40 oligomer, 16~ to 26% C50 oligomer, 5~ to ll~ C60
oligomer and 5~ to ll~ C70~ oligo~ers. SAE lOW-30 oils suitable
for use as diesel engine oils and as universal engine oils
contain lO~ to 203 by weight ~lniversal performance additives
which meet the requirements set forth in the appropriate API
Engine Service Classification 5ystem znd 80% to 90~ by weisht of
a hydrogenated decene-l oligomer mixture containing 0.5% to 16
C30 oligomer, 55~ to 68~ C~0 o1igomer, 14~ to 23~ C50 oligomex,
3~ to 9~0 C60 oligomer and 3~ to 9% C70~ oligomers. S~E 15~i-40
diesel engine or universal engine oils contain from lO~ to 20~
3 by weight diesel or universal per,ormance additives t~hich meet
the requirements set ~orth in the appropriate API Engine Service
Classification System with 80~ to 90~ by weight of a
hydrogenated decene-l oligomer mixture containing up to 2.53 C30
oligomer, 44% to 56% C40 oligomer, 23~ to 34~ C50 olisomer, 7
to 16~ C60 oligomer, ,nc 7~ to 16~ C~0+ o1}gomers.
~31~ ~6~
l In accordance with the present invention, cross-graded
motor oils suitable for passenger car and diesel truck service
are obtained using a single synthetic hydrocarbon basestock,
namely polyalphaolefins comprised of specific decene-1 oligomers
present in specified amounts. The multigrade engine oils of the
invention are obtained without the use of polymeric VI
improvers. SAE lOW-30 and SAE 15W-40 engine oils,are obtained
simply by addition of appropriate performance additives, i.e.,
additives which meet the designated API service classification,
to the oligomer mixture.
Synthetic lubricants derived from alpha-olefins and
processes for their production are well known. The
polyalphaolefins are obtained using conventional polymerization
techniques such as those described in U.S. Patent Nos~
3,149,178; 3,7'63,244; 3,780,128; 4,045,508; and 4,239,920.
These processes generally entail oligomerizing an alpha-olefin,
such as octene-l or decene-1, using a boron trifluoride catalyst
in combination with a promoter, such as alcohol or water. Such
oligomerization processes typically yield mixtures comprised
predominantly of dimer, trimer, tetramer and pentamer. The
exact oligomer distribution will vary depending on reaction
conditions, however, oligomers above pentamer have heretofore
been produced in such small amounts that they typically have not
even been reported.
As a result o changes in reactor design and better
control of process conditions, it is now possible to produce
polyalphaolefin products which contain substantial amounts of
higher decene-l oligomers. For example, products containing 20
or more he~amer, heptamer and higher oligomers can consistently
be obtained from the decene-l oligomerization process. In
accordance with the present invention, it has now been found
that oligomer mixtures containing substantial amounts of higher
oligomers can be formulated with suitable performance additives
to yield multigrade engine oils without the addition of
. . .
,
. .
-6- ~3~
l polymeric viscosity index improvers. SAE 10W-30 and SAE 15W-40
engine oils, the two principal viscosity grades recommended for
most passenger car and diesel truck service, can be obtained in
this manner.
For this invention, specific mixtures of decene-l
oligomers, also referred to as oligomer composite(s~ which
contain substantial amounts of C60 and higher oligomers are
employed. The useful oligomer mixtures are obtained by
oligomerizing decene-1 using an alcohol-promoted boron
trifluoride catalvst in accordance with the conventional
procedures known to the art. It is especially advantageous for
the present invention to utilize oligomex mixtures obtained from
the oligomerization of decene-1 wherein the catalyst is boron
trifluoride promoted with propanol. It will, ho~ever, be
understood by those skilled in the art that any oligomerization
procedure whereby compositions having the hereinafter specified
oligomer distributions can be employed. Similarly, whereas all
of the oligomeric composites utllized herein are mixtures of
decene-1 oligomers, oligomeric products derived from o~her
alpha-olefins in the C8 12 range can also be utilized. The
ranges specified herein for the oligomer composites derived from
decene-l will not, however, apply ~o oligomers derived from
other olefins.
It is possible to obtain the oliyomer composite
directly from the reactor without further blending~ This can be
accomplished by controlling the reaction conditions and by
proper reactor design. One or more distillation operations may
be necessary to achieve the desired oligomer distribution.
Also, as with all alpha-olefin derived oligomer~ used for
lubrication applications, the oligomer mixture should be
hydrogenated prior to use in order to obtain optimum oxidative
and thermal stability.
-7- ~3~
1 Most generally, the oligomer composite which is
combined with the performance additives to obtain the multigrade
engine oils of the invention are blends of two or more fractions
having different oligomer distributions. A fraction rich in
lower oligomers is typically blended with a fraction rich in
higher oligomers to achieve the desired oligomer distribution;
however, any combination of fractions which ~il~ yield a
composite having the required distribution of oligomers is
acceptable. The fractions employed for such blending may be
different distillation cuts from the same process or may be
obtained from entirely different oligomerization processes. A
particular fraction may be used in the blending of both SAE
lOW-30 and SAE 15W-40 oils. For example, a fraction rich in
higher oligomers can be blended in one operation with a first
fraction rich in lower oligomers to obtain a composite for S~E
lOW-30 usage and in another operation with a different
lower-oligomer-rich fraction to produce a composite acceptable
for SAE 15W-40 usage. If the ~ame lower-oligomer-rich fraction
is employed, it is apparent that the proportions of the
fractions must be different to produce SAE lOW 30 and SAE 15~-40
oils or that a di~ferent high-oligomer-rich fraction must be
used. The composite obtained after blending can b~ hydrogenated
or the individual fractions can be hydrogenated before they are
blended.
The ollgomers are hydrogenated using conventional
methods known to the art which typically involve combining the
- oligomer with a suitable hydrogenation catalyst and pressurizing
with hydrogen at an elevated temperature. Conventional
catalysts, such as platinum or palladium supported on charcoal,
3 Raney nickel, nickel on kieselguhr, and the like, are employed.
Pressures can range from about several hundred psig up to about
2000 psig and temperatures range from about 50C to about 300C
The hydrogenation is terminated when the desired bromine n~mber
is achieved, typically less than 1.
-8- ~ 3~
1 Oligomer composites having specific oligomer
distributions are necessary if engine oils which are
cross-graded without the addition of VI improvers are to be
obtained. Additionally, performance additives must be included
in the formulation to obtain the desired service rating. An SAE
10~-30 or SAE 15W-40 engine oil which meets the manufacturer's
specifications therefore requires both the proper selection of
oligomers and additives -- the oligomer combination to impart
the desired viscosity characteristics and the additives to
impart the necessary service characteristics. Acceptable
formulations cannot be obtained when either the specified
oligomer composite or the specified additives are not used.
While SAE 10W~30 and SAE 15W-40 are the broadest
multigrade formulations possible, it will be understood by those
skilled in the art that narrower multigrade oils within the
broader viscosity range are also possible. For example, SAE
15W-30 and SAE 10~~20 formulations can also be obtained and are
within the scope of SAE 10W-30 even though the former grades are
not specifically referenced. This aspec~ of thé invention can
be better understood by reference to the following table wherein
viscosity rec,uirements for multigrade engine oils described by
the SAE Engine Oil Viscosity Classification --- SAE'J300 APR84
are provided.
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-9 - ~ 3 ~
1MAXIMUM VISCOSITYVISCOSITYBORDERLINE STABLE
SAE (CENTIPOISE) ATl ATPUMPING 3 POUR4
GRADE TEMPE~TURE (C)100C~TEMP~RATURE POINT
Min. Max.
. =
50W 3250 at -30 3.8 ~ -35C
5W 3500 at -25 3~8/ - -30C -35C
10W 3500 at -20 4.1 - 25C -30~C
15W 3500 at -15 5.6 - -20C
20W 4500 at -10 5.6 - -15C
lO 25W 6000 at -59.3 - -10C
5.6 9.3
9-3 12~5
12.5 16.3
16.3 21.g
ASTM D-2602
ASTM D-445
3 ASTM D-3829
4 FTMS 791b-203
,
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-lo- ~3~
l In one embodiment of the invention SAE 10W-30 engine
oils which do not contain polymeric viscosity index improvers
and which meet the appropriate API "S" Service Classificatio~
for gasoline engines are provided. These Service Categories
5 include, most notably, SC, SD, SE, and SF. Oils meeting API
Service Classification SF are the most important since they may
be used where API Service Categories SE, SD or SC are
recommended. Thus, where a specific Service Category is
referred to herein, all prior Ser~ice Categories which have less
lO stringent engine test requiremen~s are also included. The SAE
10W-30 engine oils suitable for use in gasoline engines contain
5~ to 10~ by weight gasoline engine performance additives so
that the oil meets the ~PI "S" Service requirements and 90% to
95% by weight of a hydrogenated decene-l oligomer mi~ture
15 containing 0.5~ to 20~ C30 oligomer, 43% to 66% C40 oligomer,
16~ to 26% C50 oligomer, 5~ to 11% C60 oligomer and 5% to 11~
C70+ oligomers. Percentages reported herein for oligomers are
area percentages determined by conventional gas-liquid
chromatographic methods.
Generally, these engine oils are formulated with a
performance additive package which meets the desired API l'S"
Service Rating, most typically, API Service Rating S~.
Performance additive packages are commercially available and
widely used in the manufacture of engine oils~ These packages
25 are formulated to contain the necessary corrosion inhibitors,
detergents, dispersants, antiwear additives, defoamers~
antioxidants, metal passivators and other adjuvants required to
obtain a useful motor oil of the desired quality, i.e., meeting
the desired API Service Rating. The use of these additive
3 packages greatly simplifies the task of the formulator. Highly
useful SAE 10W-3Q engine oils suitable for use in gasoline
engines are obtained when`the oligomer composite contains 2g to
17% C30 oligomer, 45% to 63% C40 oligomer, 18% to 24% C50
oligomer, 6g to 10% C60 oligomer, and 6% to 10% C70+ oligomers.
L3~.146
l In another embodi~ent of ~his invention non-polymer
thickened SAE lOW-30 englne oils suitable for use in diesel
engines, i.e., meeting the appropriatP API "C" Col~mercial
Classification~ are also provided. The most common oils of this
type are those having API Service Ratings CC and CD. In addition
to mecting the service requirements for diesel engines, these
SAE 10~-30 oils can also meet API "S" Service requirements.
Tnese latter types of "dual service" or "universal" engine oils
have API Service Designations CD/SD, CD/SE, CC/5E, CC/SF, and
lO CD/SF. Such universal oils are widely used by individuals with
mixed fleets, i.e~, gasoline engine vehicles and lighter duty - -
diesel engine vehicles, such as automobile diesel engines. This
acilitates servicing since only one engine oil suitable for use
in both types of vehicles need be inventoried. The SAE lOhl-30
15 diesel and universal engine oils contain 10% to 20% by weight
performance additives so that the formulated oil meets the
appropriate API Service requirements and 80% to 90% by weight of
a hydrogenated decene-l oligomer mixture containing 0.5% to 16
C30 oligomer, 55% to 68% C40 oligomer, 143 to 23% C50 oligomer,
3% to 9% C60 oligomerj and 3% to 9% C70+ oligomers. Most
advantageously, the oligomer composite will contain 2% to 13%
C3~ oligomer, 57% to 65% C40 oligomer, 16~ to 21% C50 oligomer,
4% to 8% C6o oligomer, and 4% to a% C70+ oligomers.
In yet another embodiment of this invention,
non-polymer thickened SAE 15W-40 diesel and uni~ersal engine
oils are contemplated. These oils, which are typically
recommended for heavier duty usage, contain from 10% to 20% by
weight of the appropriate performance additives so that the
formulated oil meets the desired API Service Rating with 80~ to
90% by weiyht of a hydrogenated decene-l oligomer mixture
containing up to 2.5~ C30 oligomer, 44% to 56~ C40 oligomer, 23~ !
to 34% C50 oligomer, 7% to 16% C60 oligomer, and 7% to 16% C70~
ollgomers. Most generally, the oligomer composite contains from
1% to 2.5~ C30 oligomer, 45~ to 55~ C40 oligomer, 25% to 33% C50
oligomer, 8% to 15~ C60 oligomer~ and 8% to 15~ C7n+ oligomers.
-12- ~3~
l As previously indicated, the performance additives are
most generally incorporated into the oil by the addition of an
available additive package. The oil may, however, be formulated
by the addition of the individual additive components~ In
5 either case the result is the same, that is, the engine oil
contains the requisite amount of the necessary additives to
achieve the desired API Services RatingO The useful additive
packages and the individual additives are known and commercially
available~
Commercial additive packages are formulated to contain
the necessary detergents, dispersants, corrosion/rust
inhibitors, antioxidants, antiwear additives, defoamers, metal
passivators, set point reducers, and the like to meet a specific
API Service Rating when employed at the recommended usage level.
5 They do not, however, contain viscosity index improvers. ~lhile
it is not generally necessary, additional additives may be
employed ln conjunction with these additive packages.
Most additive manufacturers supply a line of additive
2 packages to meet the full range of service re~uirements for
gasoline engine oils, diesel engine oils, and universal oils.
For example, Ethyl Petroleum Additives Division provides a
complete line of products which are sold under the trademar~
HiTEC. The following is a list of the various HiTEC additive
pac~ages and the recommended API Service Rating for each: HiTEC
918 - SF, HiTEC 850C - CD, HiTEC 909 - SF/CC, HiTEC 910 - SF/CC,
HiTEC 914 - SF/CC, HiTEC 920 ~ SF/CC, HiTEC 2000 - SF/CCt HiTEC
2001 - SF/GD, HiTEC 854 - SF/CD, HiTEC 861 - SF/CD, HiTEC 862 -
SF/CD, HiTEC 865 - SF/CD. Similar additive package~ are
available from other manufacturers~ For example, the following
are representative universal additive packages: TLA-654A
(SF/CD), TLA-668 tsF/cc~ and TLA-679 (SF/C~) manufactured by
Texaco Chemical Company; OLA 81SOA (SF/CD), OLA 8363C (SF/CC),
OLA 8373 (SF/CC), OLA 8718 (SF/CD), and OLA 8730 (SF~CD)
-13- ~3~
manufactured by Chevron Chemical Company, Oronite Additives
Division7 Lubrizol (trademark) 7574 ~SF/CC) and Lubrizol 3978
(SF/CD) manufactured by The Lubrizol Corporation; and Amoco
~trademark) 6688 (SF/CD), 6689 (SF/CD), 6817 (SF/CC), and 6831
(SF/CC) manufactured by Amoco Petroleum Additives Company.
Other additive packages with different A~I service ratings are
available from the aforementioned manufacturers and other
suppliers.
The dosage level employed will vary depending on the
particular additive package used. For example, optimal usage
levels for SAE 15~-40 engine oils with the five HiTEC SF/CD
rated packages range from about 11.5 percent to 14.7 percent.
Variations in oligomer distribution may require adjustments of
the dosage level even within the same SAE grade. Even when an
additive package is employed for the formulation, one or more
other additives may still be employed.
If desired, individual additive components including
known antioxidants, dispersants, detergents, metal passivators,
rust/corrosion inhibitors, setting point reducers, friction
reducing agents and the like can be compounded with the oligomer
composite to obtain the engine oil. Useful antioxidants include
substituted aromatic amlnes, such as dioctyldiphenylamine,
mono-t-octylphenylnaphthylamines, dioctylphenothiazine,
phenyl- -naphthylamine, N,N'-di-butyl-p-phenylenediamine and the
like; hindered phenols, such as 2,6 di-t-butyl-p-cresol,
4,4'-bis-(2,6-diisopropylphenol),
2,2'-thio-bis-~4-methyl-6-t-butylphenol),
4,4'-methylene-bis-(2,6-di-t-butylphenol); organic phosphites,
such as trinonyl phosphite, triphenyl phosphite, and the like;
esters of thiodipropionic acid, such as dilauryl
thiodiproplonate; and the like.
Representative detergents and dispersants include
polyalkenylsuccinimides and oil-soluble metal soaps, such as Ca,
Ba, M~ and Al carboxylates, phenates and sulfonates.
~ .
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-14~ 6~ --
1 Useful metal passivators include benzotriazole,
2-mercaptobenzotriazole, 2,5-dimercaptothiadiazole, salts of
salicylaminoguanidine, quinizarin, propyl gallate, and the like.
Useful rust/corrosion inhibitors include primary,
5 secondary or tertiary aliphatic or cycloaliphatic amines and
amine salts of organic and inorganic acids; oil-soluble
alkylammonium carboxylates; substituted imidazolines and
oxazolines; alkali metal and alkaline earth metal carbonates;
alkali metal and alkaline earth metal salts of alkylbenzene
sulfonic acids, such as ~arium dinonylnaphthalenesulfonates,
calcium petroleumsulfonates, and the like, esters, anhydrides,
and metal salts of organic acids, such as sorbitan monooleate,
lead naphthenate, and dodecylsuccinic anhydride; and the like.
Set point reducers can include al~ylated naphthalenes,
alkylated phenols, polymethacrylates and the like. Anti-wear
additives can include sulfur, phosphorus, and halogen-containing
compounds, such as sulfurised vegetable oils, zinc dialkyl
dithiophosphates, chlorinated paraffins, alkyl and aryl
disulfides, and the like. Multifunctional additives such as
those described in U.S. Patent Nos. 3,652,410, 4,162,224, and
4,534,872 can also be utilized for the formulation of these
engine oils.
The amount of the individual additives will ~ary and
is dictated by the particular application and the service
requirement desired. The total amount of the additivesl ~
however, falls within the above-prescribed weight percent limits
specified for each of the engine oils.
~ he following examples illustrate the engine oil
formulations of the present invention more fully. In these
3 examples all parts are on a weight basis. Hydrogenated decene-1
oligomer mixtures were employed throughout as the basestocks for
the formulations. Oligomer distributions were determined by
conventional gas-liquid chromatographic (GLC) methods using a
.. .. . ~
-15 ~3~
1 glass column [3' x 2mm 1 percent SP-2100 on 100 120 Superlcoport
(trademark)]. Oligomer distributions are reported throughout as
area percentages. The injector temperature was maintained at
300C and the flame ionization detector at 375C. Nitrogen was
5 used as the carrier gas at a rate of 30 cm3/min. The oven
temperature was increased at a rate of 15C/min over the rang2
140C to 350C and then maintainecl at 350C for 10 minutes.
Separation of decene-l oligomers above C70 is not possible
employin~ this technique. FQr this reason, the last oligomer
lO fraction is reported as C70+ since it may also contain small
amounts of oligomers higher than C70, primarily C80 and CgO
oligomers.
Viscosities reported in the examples and identified as
the Cold Crank Simulator (CCS) viscosity and 100C viscosity are
15 determined in accordance with ASTM D-2602 and AST~ D-445 per
SAE J300 APR84 specifications. CCS viscosities are reported in
centipoise at the specified temperatures (C) whereas 100C
viscosities are reported in centistokes.
- :
.
.: ' . : . :
-16~
1 E~AMPLE I
A non-polymer thickened SAE lOw-30 gasoline ~ngine oil
having an API Ser~ice Rating SF was prepared using a mixture of
hydrogenated decene-l oligomers. The oligomer composite
employed as the basestock was obtained by blending two different
polyalphaolefin synthetic hydrocarbon fluids. The first fluid
contained 4.8 percent C30 oligomer, 63.7 percent C40 oligomer,
18.7 percent C50 oligomer, 6.5 percent C60 oliyomer, and 6.3
percent C70~ oligomer. The second fluid, which contained
significantly higher amounts of the higher oligomers, contained
54.7 percent C~0 oligomer, 24.5 percent C50 oligomer, 10.0
percent C60 oligomer, and 10.8 percent C70+ oligomers. The
first and second fractions were blended at a 1:1 ratic to
produce an oligomer composite containing 2.~0 percent C30
oligomer, 59.2 percent C40 oligomerl 21.6 percent C50 oligomer,
8.3 percent C60 oligomer, and 8.6 percent C70+ oligomer. The
oligomer composite (92.20 parts) was combined with 7.80 parts
low ash gasoline engine performance additive package (Lubrizol
(trademark) 75741 meeting API SF requirements. The resulting
formulated oil had a 100C viscosity of 10.09 centistokes and
CCS viscosity at -20C of 3290 centipoise. The oil also met the
Borderline Pumping Temperature requirements and stable pour
point requirements of SAE J300 APR84 for SAE grade lOW, thus
fully qualifying it as a cross-graded lOW-30 SF engine oil.
3
.
.
- ~ ,
.
.
-17- ~3~
1 EXAMPLE II
To further demonstrate the ability to obtain an SAE
lOW-30 engine oil an oligomer composite was prepared by blending
the polyalphaolefin synthetic hydrocarbon fluids of Example I.
The first and second hydrocarbon fluids were combined in a ratio
of 3.5:1 and 90 parts of the resulting oligomer composite (3.73
C30 oligomer, 61.40~ C40 oligomer, 19.70% C50 oligomer, 7.06%
C60 oligomer, and 8.58% C70+ oligomer~ was formulated with 1.36
parts of a calcium alkylphenate detersent, 5.40 parts alkenyl
succinimide ashless dispersant, 1.57 parts alkyl zinc
dithiophosphate antioxidant/antiwear additive, 0.30 part
thiodiethylene bis-(3,5-di-t-butyl-4-hydxoxyhydrocinnamate
antioxidant, 0.30 part alkylated phenyl-naphthylamine
antioxidant, 0.05 part copper deactivator, 0.02 part antifoaming
agent (10~ silicon in toluene) and 1.00 part overbased calcium
sulfonate detergent/rust inhibitor. The resulting formulated
oil had a 100C viscosity of 9.30 centistokes and CCS viscosity
at -20C of 3000 centipoise. The non-polymer thickened oil met
all of the SAE J300 APR34 requirements for lOW-30 oils.
A basestock obtained by blending the first and second
polyalphaolein synthetic hydrocarbon fluids at a ratio of
approximately 1:1.25 was also identically formulated to provide
an SAE lOW-30 engine oil. The 100C and CCS (-20C) viscosities
for the formulated oil were 10.0 and 3500, respectively,
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1 EXAMPLE III
In accordance with the general procedure of Example I,
an SAE lOW-30 SF engine oil was obtained using a polyalphaolefin
synthetic hydrocarbon basestoc~ without the addition of
polymeric viscosity index improvers. The oil contained 92.20
parts polyalphaolefin basestock and 7.80 parts of the API SF
gasoline engine performance additive package. The oligomer
distribution of the basestock and 100C viscosity and CCS
viscosity at -20C of the resulting formulated en~ine oil were
as follows:
% C30 oligomer 4.1
40 oligomer 62.4
~~ C50 oligomer 19.6
~ C60 oligomer 7.0
g C70+ oligomex 7.0
Viscosity:
100C 9.39
CCS ~-20C) 2690
The formulation fully met the viscosity re~uirements of SAE J300
APR84 for lOW-30 oils.
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1E~PLES IV AND V
Additional non-polymer thickened SAE 101~-30 SF engine
oils were prepared using basestocX. comprised of mixtures of
decene-l oligomers. The basestocks were obtained by blending
t~o polyalphaolefin synthetic hydrocarbon fluids. The first
- fluid contained 84.9 percent C30 oligomer and 14.8 percent C40
oligomer. The second fl~id was the same as that described in
Example I. The API SF performance additive package was also the
same as used in Example I. Compositions of the engine oils,
including the overall oligomer distribution of the resulting
synthetic hydrocarbon blends, were as follows:
` EX. IV EX. V ?
First Hydrocarbon Fluid (Parts~ l8.44 ll.53
15Second Hydrocarbon Fluid (Parts) 73.76 80.68
Oligomer Distribution of Blend:
30 oligomer 17.0 lO.6
40 oligomer 46.7 49.4
% C50 oligomer 18.6 21.3
20~ C60 oligomer 8.Q 8.7
~ C70+ oligomer 8.6 9.4
Additive Package (Parts) 7.80 7.80
The formulated oil of Example IV had a 100C viscosity of 9.31
centistokes and CCS (-20C) viscosity of 2810 centipoise~ The
formulated oil of EY.ample V had a 100C viscosity of lO.00
centistokes and CCS (-20C) viscosity of 3200 centipoise.
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1 EXAMPLES VI-X
~ ~ .
Non-polymer thickened SAE 10~-30 SF/CD universzl
engine oils suitable for use in both gasoline and die~el engines
were prepared. For these formulations, 86.31 parts
polyalphaolefin synthetic hydrocarbon basestocks comprised of
mixtures of decene-1 oligomers were combined with 13.69 parts
performance additive pac~age meeting API SF/CD service
requirements [Lubrizol (trademark) 3978]. The oligomer
distribution of each basestock and the 100C and CCS (-20C~
viscosities for the resulting formulated engine oils were as
~ollows:
EX. VI EX. VII E. VIII EX. IX EX. X
% C3Q oligomer 3.8 4O0 4.3 4.8 11.7
15 % C40 oligomer 61.9 62.3 62.7 63.7 59.9
% C50 oligomer 19.9 19.6 19.3 18.7 17.7
C60 oligomer 7.2 7.1 6.9 6.5 6.0
% C70+ oligomer 7.2 7.0 6.8 6.3 4.7
Viscosity:
100C10.36 10.25 10.14 9.92 9.39
CCS ~-20C)3400 3220 3130 3270 ~300
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EXA~1PLES XI AND_XII
SA~ 15W-40 engine oils suitable for use in diesel
engines were prepared which did not contain polymeric viscosity
index improvers. The basestock employed were mixtures of
h~drogenated oligomers obtained from the oligomerization of
decene-l. The amount of basestock and the distribution of
decene-1 oligomers in the basestock are set forth below. The
amount of the performance additive package employed is also
indicated. For the formulation of Example XI, a low ash
universal SF/CD performance pac~age ~Lubrizol (trademark) 3978]
was used whereas the formulation of Example XII employed a high
ash premium SF/CD performance package EOLOA 8718 manufactured by
Chevron Chemical Companyl. Compositional details and
viscosities of the resulting formulated engine oils were as
follows:
. EX. XIEX. XII
Basestock (Parts) 86.31 83.70
Oligomer Distribution of Blend:
% C40 oligomer 51.2 - 51.2
% C50 oligomer 27.6 27.6
% C60 oligomer 11.7 11.7
% C70+ oligomer 9.5 9.5
Additive Package ~Parts) 13.69 16.30
Viscosity:
100C 12.77 12.52
CCS (-15C) 2g70 3380
Both oils also met the Borderline Pumping Temperature
3 requirements of SAE J300 APR84 for grade SAE 15W, thus fully
qualifying these oils as cross-graded 15W-4~ SF/CD motor oils
without the addition of polymeric viscosity index improvers.
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