U.S. patent application number 11/338456 was filed with the patent office on 2006-09-21 for blend comprising group iii and group iv basestocks.
Invention is credited to Charles L. JR. Bullock, Kathleen K. Cooper, Nicole B. Temme, Norman Yang.
Application Number | 20060211581 11/338456 |
Document ID | / |
Family ID | 34956741 |
Filed Date | 2006-09-21 |
United States Patent
Application |
20060211581 |
Kind Code |
A1 |
Bullock; Charles L. JR. ; et
al. |
September 21, 2006 |
Blend comprising group III and group IV basestocks
Abstract
The invention relates to compositions comprising a blend of
Group III basestocks and low volatility, low viscosity PAO
basestocks. The blend is particularly useful for preparing finished
lubricants that meet or even exceed the criteria for SAE Grade 0 W
multi-grade engine oils. The combination of these low volatility,
low viscosity PAOs with Group III basestocks provide, in
embodiments, the necessary performance criteria in automatic
transmission fluids, automotive or industrial gear oils, hydraulic
fluids, or any other high performance lubricant requiring a
combination of excellent low fluidity and low volatility.
Inventors: |
Bullock; Charles L. JR.;
(Cypress, TX) ; Yang; Norman; (Westfield, NJ)
; Cooper; Kathleen K.; (South River, NJ) ; Temme;
Nicole B.; (Rahway, NJ) |
Correspondence
Address: |
ExxonMobil Chemical Company;Law Technology
P.O. Box 2149
Baytown
TX
77522-2149
US
|
Family ID: |
34956741 |
Appl. No.: |
11/338456 |
Filed: |
January 24, 2006 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60662608 |
Mar 17, 2005 |
|
|
|
Current U.S.
Class: |
508/110 ;
208/19 |
Current CPC
Class: |
C10M 2203/1025 20130101;
C10G 69/126 20130101; C10M 169/04 20130101; C10N 2030/76 20200501;
C10N 2040/04 20130101; C10N 2070/00 20130101; C10M 2205/0285
20130101; C10G 2400/10 20130101; C10M 111/04 20130101; C10N 2030/02
20130101; C10N 2020/085 20200501; C10N 2040/042 20200501; C10N
2040/044 20200501; C10M 171/00 20130101; C10M 2205/0265 20130101;
C10N 2040/08 20130101; C10G 50/02 20130101; C10N 2020/02
20130101 |
Class at
Publication: |
508/110 ;
208/019 |
International
Class: |
C10M 169/04 20060101
C10M169/04; C10G 71/00 20060101 C10G071/00 |
Claims
1. A composition comprising: (a) at least one API Group III
basestock; and (b) at least one PAO basestock characterized by a
pour point <-54.degree. C., and at least one of the following
relationships: (i) a Noack volatility versus CCS relationship on or
below curve A in FIG. 1; (ii) a Noack volatility versus CCS
relationship on or below curve B in FIG. 1; (iii) a Noack
volatility to KV relationship on or below the curve A in FIG. 2;
(iv) a Noack volatility to KV relationship on or below the curve B
in FIG. 2; (v) a Noack volatility to KV relationship on or below
the curve A in FIG. 3; (vi) a Noack volatility to KV relationship
on or below the curve B in FIG. 3.
2. The composition according to claim 1, wherein (b) includes at
least one PAO basestock further characterized by at least one of
the relationships (i) and (iii).
3. The composition according to claim 1, wherein (b) includes at
least one PAO basestock further characterized by both of the
relationships (i) and (iii).
4. The composition according to claim 1, wherein (b) includes at
least one PAO basestock further characterized by at least one of
the relationships (ii) and (iv).
5. The composition according to claim 1, wherein (b) includes at
least one PAO basestock further characterized by both of the
relationships (ii) and (iv).
6. The composition according to claim 1, wherein (b) is further
characterized as being obtainable by a process comprising
oligomerizing at least one alphaolefin in the presence of an
oligomerization catalyst and a dual promoter system comprising an
alcohol and an ester.
7. The composition according to claim 1, wherein (b) is further
characterized as being made by a process comprising oligomerizing
at least one alphaolefin in the presence of an oligomerization
catalyst and a dual promoter system comprising an alcohol and an
ester.
8. The composition according to claim 1, wherein (b) is further
characterized as comprised of an oligomerized alphaolefin which has
been subjected to hydrogenation, wherein said oligomerized
alphaolefin is prepared from an olefin feed comprises of 50 to 80
wt. % 1-decene and 50 to 20 weight percent 1-dodecene, and wherein
said oligomerized alphaolefin has been oligomerized in the presence
of BF.sub.3 and a dual promoter comprising at least one alcohol and
at least one alkyl acetate.
9. The composition according to claim 1, wherein (b) is further
characterized as comprising a 5 cSt PAO comprising about 40 to 80
weight percent of 1-decene and from about 60 to about 20 weight
percent of 1-dodecene based on the weight of said 5 cSt PAO.
10. The composition according to claim 1, wherein (b) is further
characterized as being made by a process comprising the
oligomerization of alphaolefins comprising: (a) contacting at least
one alphaolefin, an alphaolefin oligomerization catalyst, an
alcohol promoter, and an ester promoter in at least one
continuously stirred reactor under oligomerization conditions for a
time sufficient to produce a trimer of said at least one
alphaolefin; (b) distilling off unreacted alphaolefin and dimers of
said alphaolefin to obtain a bottoms product comprising said
trimer; (c) hydrogenating said bottoms product to obtain a
hydrogenated bottoms product; and then (d) fractionating said
bottoms product to obtain at least one cut comprising a trimer
product.
11. The composition according to claim 10, wherein step (a)
comprises contacting at least one alphaolefin selected from C8,
C10, C12, C14, and C16 alphaolefins, and mixtures thereof
12. The composition according to claim 1, wherein (b) is further
characterized as being obtainable by or made by an improved process
comprising contacting at least one alphaolefin, an alphaolefin
oligomerization catalyst, an alcohol promoter, and an ester
promoter in at least one continuously stirred reactor under
oligomerization conditions for a time sufficient to produce a
trimer of said at least one alphaolefin, the improvement comprising
distilling off unreacted monomers and promoters in a first
distillation column, taking the bottoms product from said first
distillation column and distilling off dimers in a second
distillation column, taking the bottoms product from said second
distillation column and hydrogenating said product to produce a
hydrogenated product, sending said hydrogenated product to a third
distillation column, and obtaining at least one product from either
the overheads or bottoms of said third distillation column.
13. The composition according to claim 1, wherein (a) is selected
from solvent dewaxed API Group III basestocks, catalytically
dewaxed API Group III basestocks, and wax isomerate API Group III
basestocks.
14. The composition according to claim 1, wherein (a) excludes wax
isomerate API Group III basestocks.
15. The composition according to claim 1, wherein (b) is selected
from at least one of (i) a PAO comprising at least 85 wt. % trimers
of 1-decene and having a viscosity of about 3.6 cSt at 100.degree.
C.; and (ii) a PAO comprising at least 85 wt. % trimers of 1-decene
and 1-dodecene and having a viscosity of about 3.9 cSt at
100.degree. C.
16. A composition comprising: (a) at least one Group III basestock;
and (b) at least one PAO obtainable or made by a process comprising
oligomerizing at least one alphaolefin in the presence of an
oligomerization catalyst and a dual promoter system comprising an
alcohol and an ester.
17. The composition according to claim 16, wherein (a) is selected
from solvent dewaxed API Group III basestocks, catalytically
dewaxed API Group III basestocks, and wax isomerate API Group III
basestocks.
18. The composition according to claim 16, wherein (a) excludes wax
isomerate API Group III basestocks.
19. A composition comprising: (a) at least one Group III basestock;
and (b) at least one PAO characterized by a pour point less than
-54.degree. C., and at least one of the following: (ia) within the
range of 3.5 to 3.95 cSt at 100.degree. C. the Noack
volatility=(50,000)(KV100).sup.-6; and (ib) within the range of
greater than 3.95 to 6 cSt at 100.degree. C. the Noack
volatility=(182)(KV100).sup.-1.9; and within the range of 3.5 to
3.95 cSt at 100.degree. C. the Noack Volatility=(9O0)(KV).sup.-3.2;
and (iib) within the range of greater than 3.95 to 6 cSt at
100.degree. C. the Noack Volatility=(175)(KV).sup.-2.
20. The composition according to claim 19, wherein (a) is selected
from solvent dewaxed API Group III basestocks, catalytically
dewaxed API Group III basestocks, and wax isomerate API Group III
basestocks.
21. The composition according to claim 19, wherein (a) excludes wax
isomerate API Group III basestocks.
22. A composition comprising a 3.6 cSt PAO, said 3.6 cSt PAO
comprising about 99 wt. % C30 linear hydrocarbon, less than 0.5 wt.
% C20 linear hydrocarbon, and less than 0.5 wt. % C40 linear
hydrocarbon.
23. A fully-formulated SAE Grade 0 W multigrade lubricant
composition comprising 30 vol. % or greater of at least one API
Group III basestock and about 1 to 70 vol. % of at least one
PAO.
24. The composition according to claim 23, wherein said at least
one API Group III basestock excludes wax isomerates API Group III
basestocks.
25. The composition according to claim 23, wherein said at least
one API Group III basestock has a CCS @ -35 of greater than
2600.
26. The composition according to claim 23, wherein said at least
one API Group III basestock has a CCS @ -35 of greater than
2700.
27. A product meeting the requirements of at least one of ILSAC
GF-4 specifications and SAE Grade 0 W multigrade lubricant, said
product comprising at least one API Group III basestock and at
least one PAO characterized by at least one of the following
criteria: (a) said PAO is obtainable by or made by a process
comprising oligomerizing at least one alphaolefin in the presence
of an oligomerization catalyst and a dual promoter system
comprising an alcohol and an ester and recovering said PAO as
overheads and/or bottoms product from a process further including
at least two distillation steps; (b) said PAO has a pour point
<-54.degree. C., and at least one of the following
relationships: (i) a Noack volatility versus CCS relationship on or
below curve A in FIG. 1; (ii) a Noack volatility versus CCS
relationship on or below curve B in FIG. 1; (iii) a Noack
volatility to KV relationship on or below the curve A in FIG. 2;
(iv) a Noack volatility to KV relationship on or below the curve B
in FIG. 2; (v) a Noack volatility to KV relationship on or below
the curve A in FIG. 3; (vi) a Noack volatility to KV relationship
on or below the curve B in FIG. 3; and (c) said PAO has a pour
point less than -54.degree. C., and at least one of the following
relationships: (i) a Noack volatility to KV at 100.degree. C.
relationship such that: (ia) within the range of 3.5 to 3.95 cSt at
100.degree. C. the Noack Volatility=(900)KV.sup.-3.2; and (ib)
within the range of greater than 3.95 to 6 cSt at 100.degree. C.
the Noack Volatility=(175)(KV)-.sup.-2.
28. The product according to claim 27, wherein said at least one
API Group III basestocks excludes wax isomerate API Group III
basestocks.
29. The product according to claim 27, wherein said at least one
API Group III basestock includes at least one solvent dewaxed or
catalytically dewaxed API Group III basestock, present in the
amount of at least about 30 vol. % or greater based on the volume
of the solvent dewaxed API Group III basestock, catalytically
dewaxed basestock, or combination thereof, relative to the volume
of the entire product.
30. The product according to claim 27, comprising at least 30 vol.
% or greater of at least one solvent dewaxed API Group III
basestock, based on the volume of the entire product.
31. A product comprising: (a) a composition according to claim 1;
and (b) at least one additive selected from oxidation inhibitors,
metallic and non-metallic dispersants, metallic and non-metallic
detergents, corrosion and rust inhibitors, metal deactivators,
anti-wear agents, extreme pressure additives, anti-seizure agents,
pour point depressants, wax modifiers, viscosity modifiers, seal
compatibility agents, friction modifiers, lubricity agents,
anti-staining agents, chromophoric agents, defoamants,
demulsifiers, emulsifiers, thickeners, fuel stabilizers, and
tackifiers.
32. An automatic transmission fluid, automotive or industrial gear
oils, or hydraulic fluid comprising the composition according to
claim 1.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of Provisional
Application No. 60/662,608 filed Mar. 17, 2005, the disclosure of
which is incorporated by reference.
FIELD OF THE INVENTION
[0002] The invention relates to compositions comprising a blend of
Group III basestocks and low volatility, low viscosity PAO
basestocks. The blend is particularly useful for preparing finished
lubricants that meet or even exceed the criteria for SAE Grade 0 W
multi-grade engine oils.
BACKGROUND OF THE INVENTION
[0003] Current technology requires either catalytically dewaxed,
wax isomerate based Group III basestocks, or polyalphaolefins
(PAOs) as the primary basestock to achieve certain requirements set
by organizations such as ACEA (Association des Constructeurs d'
Automobiles), ATIEL (Association Technique de L'Industrie Europeane
des Lubrifiants), API (American Petroleum Institute), ILSAC
(International Lubricant Standardization and Approval Committee),
ASTM (American Society of Testing and Materials), EOLCS (Engine Oil
Licensing and Certification System), SAE (Society of Automotive
Engineers) for applications requiring excellent low temperature
properties as well as high temperature stability. An example is SAE
Grade 0 W multi-grade engine oils and ILSAC GF-4 specifications.
There is currently a limited supply of both of these relatively
expensive basestocks and development of alternatives is needed to
meet growing demand. Technology to enable the use of more
petroleum-derived basestocks in such formulations is highly
sought-after.
[0004] U.S. Pat. No. 5,693,598 describes a low viscosity oil having
a kinematic viscosity of up to about 4 cSt at 100.degree. C. and a
composition having antiwear properties and comprising said oil. The
feed comprises from about 60 to about 90% C12.
[0005] U.S. Pat. No. 5,789,355 relates to SAE Grade 5 W and higher
multigrade oils including a basestock and a detergent inhibitor
package. The basestock is selected from API Groups I and II. The
detergent inhibitor package includes an ashless dispersant derived
from an ethylene alphaolefin (EAO).
[0006] U.S. Pat. No. 6,303,548 is directed to a base oil for an SAE
Grade 0 W40 lubricant composition comprising a PAO and a synthetic
ester lubricant.
[0007] U.S. Pat. No. 6,824,671 describes a mixture of about 50 to
80 wt. % 1-decene and about 20 to 50 wt. % 1-dodecene are
co-oligomerized in two continuous stirred-tank reactors in series
using BF3 with an ethanol:ethyl acetate promoter. Monomers and
dimers are taken overhead and the bottoms product is hydrogenated
to saturate the trimers/oligomers to create a 5 cSt PAO. This
product is further distilled and the distillation cuts blended to
produce a 4 cSt PAO containing mostly trimers and tetramers, and a
6 cSt PAO containing trimers, tetramers, and pentamers. The
lubricants thus obtained are characterized by a Noack volatility of
about 4% to 12%, a pour point of about -40.degree. C. to
-65.degree. C. See also copending U.S. application Ser. No.
10/959544.
[0008] U.S. Patent Application 2004/0033908 describes a
fully-formulated lubricant comprising PAOs, including a PAO
prepared from an oligomerization process comprising contacting an
alphaolefin feed with a BF.sub.3 catalyst and a promoter (or
cocatalyst) system including an alcohol and an ester.
[0009] U.S. Patent Application 2004/0129603; 2004/0154957; and
2004/0154958 describe formulations using catalytically dewaxed
Group III materials.
[0010] The present inventor has surprisingly discovered that an
appreciable amount of conventional, hydrocracked Group III
basestocks may be included in a blend further comprising a new type
of PAO in order to meet increasingly stringent requirements for
lubricants.
SUMMARY OF THE INVENTION
[0011] The invention is directed to compositions comprising a blend
of (a) Group III basestocks, and (b) low volatility, low viscosity
PAO basestocks characterized by a low kinematic viscosity, a low
Noack volatility, and a low pour point.
[0012] The invention is also related to a process for producing a
blend comprising (a) at least one Group III basestock and (b) a PAO
according to the invention.
[0013] In preferred embodiments, the PAO according to the invention
is characterized as obtainable by a process comprising contacting
at least one alphaolefin with an oligomerization catalyst in the
presence of a dual promoter system comprising at least one alcohol
and at least one ester.
[0014] In preferred embodiments, the PAO according to the invention
is characterized as made by a process comprising contacting at
least one alphaolefin with an oligomerization catalyst in the
presence of a dual promoter system comprising at least one alcohol
and at least one ester.
[0015] In preferred embodiments, the PAO according to the invention
is characterized as having a pour point less than -54.degree. C.,
and at least one of the following relationships: (i) a Noack
volatility versus CCS relationship on or below curve A in FIG. 1;
(ii) a Noack volatility versus CCS relationship on or below curve B
in FIG. 1; (iii) a Noack volatility to KV relationship on or below
the curve A in FIG. 2; (iv) a Noack volatility to KV relationship
on or below the curve B in FIG. 2; (v) a Noack volatility to KV
relationship on or below the curve A in FIG. 3; (vi) a Noack
volatility to KV relationship on or below the curve B in FIG. 3.
Preferably two or more, or three or more, or four or more, or five
or more, or all six of these relationships hold.
[0016] In preferred embodiments, the PAO according to the invention
is characterized by a pour point less than -54.degree. C., and a
Noack volatility to KV at 100.degree. C. relationship such that:
(ia) within the range of 3.5 to 3.95 cSt at 100.degree. C. the
Noack Volatility=(900)(KV).sup.-3.2; and (ib) within the range of
greater than 3.95 to 6 cSt at 100.degree. C. the Noack
Volatility=(175)(KV).sup.-2.
[0017] In preferred embodiments, the Group III basestock used in
the composition or blend according to the invention is not a Group
III basestock obtained by a wax isomerization process.
[0018] In preferred embodiments, the PAO characterizable by a low
kinematic viscosity, low Noack volatility, and a low pour point is
used without blending with other PAOs.
[0019] It is an object of the invention to provide a convenient
method of upgrading conventional petroleum-derived basestock,
specifically Group III basestocks, into premium lubricant
applications capable of meeting new requirements related to cold
temperature performance and high temperature stability.
[0020] It is further an object of the invention to provide an
improved lubricant basestock blend, the improvement comprising an
improved pour point as well as at least one of the properties
defined by (i) through (vi) set forth above.
[0021] These and other objects, features, and advantages will
become apparent as reference is made to the following detailed
description, preferred embodiments, examples, and appended claims.
These and other embodiments, objects, features, and advantages will
become apparent as reference is made to the following drawings,
detailed description, examples, and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 illustrates the relationship of Noack Volatility
versus Cold Crank Simulator (CCS) test @ -35.degree. C. for
compositions according to the present invention compared with prior
art compositions.
[0023] FIG. 2 illustrates the relationship of Noack Volatility
versus Kinematic Viscosity @ 100.degree. C. for compositions
according to the present invention compared with prior art
compositions.
[0024] FIG. 3 is similar to FIG. 2, except that the curves are
idealized using a smaller set of data points.
[0025] In each drawing the top curve is referred to as Curve A and
the bottom curve is referred to as Curve B in the following
description.
DETAILED DESCRIPTION
[0026] According to the invention, a blend is provided comprising
(a) at least one Group III basestock, and (b) at least one PAO
basestock according to the invention, which may be characterized as
a PAO having a low kinematic viscosity, a low Noack volatility, and
a low pour point.
[0027] Group III Basestock
[0028] The first component of the composition according to the
present invention is selected from at least one Group III
basestock.
[0029] As used herein, the term "Group III basestock" refers to the
API Group III basestocks. Group III basestocks are characterized by
a sulfur content of less than 300 ppm, saturates greater than 90
wt. %, and a viscosity index (VI) of 120 cSt or greater. Typically
such basestocks will be petroleum-derived, however, any natural oil
characterizable as a Group III basestock may be used, including
animal oils and vegetable oils (e.g., lard oil, castor oil) as well
as mineral lubricating oils such as liquid petroleum oils and
solvent treated or acid-treated mineral lubricating oils of the
paraffinic, naphthenic or mixed paraffinic/naphthenic types which
may be further refined by hydrocracking and/or hydrofinishing
processes and are dewaxed. Group III basestocks are available from
a wide number of commercial sources.
[0030] Representative useful Group III basestocks in the blend
according to the invention include those mentioned in U.S. Pat.
Nos. 6,503,872; 6,649,576; and 6,713,438.
[0031] Group III basestocks useful in the present invention may
also be characterized as mineral oils that are severely
hydrotreated or hydrocracked and have the aforementioned
characteristics specified by API for Group III basestocks. These
processes expose the mineral oils to very high hydrogen pressures
at elevated temperatures in the presence of hydrogenation
catalysts. Typical processing conditions include hydrogen pressures
of approximately 3000 pounds per square inch (psi) at temperatures
ranging from 300.degree. C. to 450.degree. C. over a
hydrogenation-type catalyst. This processing removes sulfur and
nitrogen from the lubricating oil and saturates any alkylene or
aromatic structures in the feedstock. The result is a base oil with
extremely good oxidation resistance and viscosity index. A
secondary benefit of these processes is that low molecular weight
constituents of the feed stock, such as waxes, can be isomerized
from linear to branched structures thereby providing finished base
oils with significantly improved low temperature properties. These
hydrotreated base oils may then be further de-waxed either
catalytically or by conventional means to reduce their pour point
and improve their low temperature fluidity.
[0032] A particular advantage of the present invention is that wax
isomerate Group III materials are not necessary in a composition
according to the invention in order to achieve certain
specifications discussed in the Background section. Accordingly, in
an embodiment, component (i) excludes wax isomerate materials.
However, such materials are nonetheless contemplated as embodiments
of Group III basestocks useful for blending with the PAO according
to the invention. Likewise, a composition according to the present
invention may include or it may exclude catalytically dewaxed Group
III materials and it may also include or it may exclude solvent
dewaxed Group III materials.
[0033] Representative of Group III basestocks are materials such as
Visom, commercially available from ExxonMobil Lubricants and
Specialties, and XHVI available from Shell, or materials such as
described in U.S. Patent Applications 2004/0129603; 2004/0154957
and 2004/0154958.
[0034] While not critical to the broad invention contemplated,
Group III basestocks may also be characterized by performance on
the Cold Crank Simulator test (CCS), as discussed more fully below.
A fully formulated SAE Grade 0 W engine oil needs to have a CCS at
-35.degree. C. of 6200 or less. Heretofore a fully formulated 0 W
engine oil using an appreciable amount of Group III basestock
(e.g., greater than 30 vol. %) required a Group III basestock
having a CCS at -35.degree. C. of 2600 or less. This could be met
in the prior art by wax isomerate based materials such as Visom.TM.
basestock discussed herein. However, using the PAO according to the
invention, appreciable concentrations of Group III basestocks
having CCS at -35.degree. C. of greater than 2600, or greater than
2700, or greater than 2800, or even greater, can be blended in to
achieve SAE Grade 0 W engine oils. This is a greater advantage of
the present invention.
[0035] Preferred Group III basestocks include Yubase 4 (with
saturate contents of 99.5%) and Yubase 6 (with saturate contents of
97.5%), available from S. K. Corporation.
[0036] Also preferred are Group III materials that are
characterizable by having a viscosity of 3 cSt or greater, or more
preferably greater than 3 cSt.
[0037] Other preferred Group III basestocks are those available
from Fortum, S-Oil, Petro-Canada, ChevronTexaco, and Motiva.
[0038] Low Volatility, Low Viscosity PAO Basestocks
[0039] The second component of a composition according to the
present invention is at least one PAO basestock characterized by a
low kinematic viscosity, a low Noack volatility, and a low pour
point.
[0040] PAOs and methods of making PAOs useful in the present
invention have been described recently in U.S. Pat. No. 6,824,671;
and U.S. Patent Application 2004/0033908 and are also described in
commonly assigned, copending application Ser. No. ______ (Attorney
Docket No. 2005B031).
[0041] In an embodiment, the PAOs useful in the present invention
are made by a process comprising contacting a feed comprising at
least one alphaolefin with an oligomerization catalyst and a dual
promoter (or cocatalyst) system comprising an alcohol and an ester,
and oligomerizing said at least one alphaolefin to obtain a product
comprising substantially a trimer of said at least one
alphaolefin.
[0042] A preferred PAO according to the invention is at least one
trimer rich oligomer produced by controlling the degree of
polymerization with the use of the dual promoter system comprising
ester and alcohol. The process comprises contacting a feed
comprising at least one a-olefin with a catalyst comprising
BF.sub.3 in the presence of a promoter comprising an alcohol and
acid or an ester formed therefrom, in two or more continuously
stirred reactors connected in series, under oligomerization
conditions. Products lighter than trimers are distilled off after
polymerization from the second reactor vessel and the bottoms
product is hydrogenated. The hydrogenation product is then
distilled to yield a trimer-rich product. In an embodiment the
products are narrow cut (narrow molecular weight distribution), low
viscosity, low Noack volatility PAOs. In another embodiment the
bottoms product obtained is used without blending with a second
PAO.
[0043] In an embodiment, the product is a narrow cut (narrow
molecular weight), low viscosity, low Noack volatility PAO. As used
herein, the term "narrow cut" means narrow molecular weight range.
In its most preferred embodiment, for the present invention, narrow
cut, low viscosity, low Noack volatility PAOs will comprise a very
high percentage of trimers of the at least alphaolefin feed,
preferably at least 85 wt. %, more preferably at least 90 wt. %,
still more preferably at least 95 wt. %, yet still more preferably
at least 99 wt. % trimer. The meaning of the term "narrow molecular
weight range" may be understood by one of ordinary skill in the art
in view of the foregoing.
[0044] The feed comprises at least one .alpha.-olefin. The terms
".alpha.-olefin" and "alphaolefin" are used interchangeably herein.
The alphaolefins may be selected from any one or more of C3 to C21
alphaolefins, preferably C6 to C16 alphaolefins and more preferably
at least one species selected from 1-octene, 1-decene, 1-dodecene,
and 1-tetradecene. It is preferred that the alphaolefins are linear
alphaolefins (LAOs). Mixtures of any of these alphaolefins
mentioned may also be used.
[0045] In a preferred embodiment, at least two species selected
from 1-octene, 1-decene, 1-dodecene, and 1-tetradecene are used in
the feed. In another preferred embodiment, the feed comprises
greater than or equal to 40 wt. % 1-decene, or greater than 40 wt.
% 1-decene, or greater than or equal to 50 wt. % 1-decene.
[0046] In another preferred embodiment, the olefin feed consists
essentially of greater than or equal to 40 wt. % 1-decene, or
greater than 40 wt. % 1-decene, or greater than or equal to 50 wt.
% 1-decene, with the remainder of the olefin feed consisting
essentially of one or more of species selected from 1-octene,
1-dodecene, and 1-tetradecene.
[0047] In another preferred embodiment the olefin feed consists
essentially of 1-decene, in yet another preferred embodiment the
olefin feed consists essentially of 1-decene and 1-dodecene, in
still another preferred embodiment the olefin feed consists
essentially of 1-dodecene and 1-tetradecene, and in yet still
another preferred embodiment the feed consists essentially of
1-dodecene .
[0048] In an embodiment, the feed comprises 1-decene. In a
preferred embodiment, the feed consists essentially of 1-decene and
a promoter according to the invention, co-fed into the reactor
comprising an oligomerization catalyst, and the product of the
process according to the invention comprises a distillation cut
characterized by a viscosity of about 3.6 cSt at 100.degree. C.
[0049] In another embodiment, the feed consists essentially of
1-decene, 1-dodecene, and promoter according to the invention,
co-fed into the reactor comprising an oligomerization catalyst, and
the product of the process according to the invention comprises a
distillation cut characterized by a viscosity of about 3.9 cSt at
100.degree. C.
[0050] In an embodiment, the olefins used in the feed are co-fed
into the reactor. In another embodiment, the olefins are fed
separately into the reactor.
[0051] In addition to the presence of a conventional BF.sub.3
oligomerization catalyst, at least two different promoters (or
cocatalysts) are also present. According to the present invention,
the two different promoters are selected from (i) alcohols and (ii)
esters, with at least one alcohol and at least one ester
present.
[0052] Alcohols useful in the process of the invention are selected
from C1-C10 alcohols, more preferably C1-C6 alcohols. They may be
straight-chain or branched alcohols. Preferred alcohols are
methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol,
and mixtures thereof.
[0053] Esters useful in the process of the invention are selected
from the reaction product(s) of at least one alcohol and one acid.
The alcohols useful to make esters according to the invention are
preferably selected from the same alcohols set forth above,
although the alcohol used to make the ester for the promoter used
in (ii) may be different than the alcohol used as promoter in (i),
or it may be the same alcohol. The acid is preferably acetic acid,
although it may be any low molecular weight mono-basic carboxylic
acid, such as formic acid, propionic acid, and the like.
[0054] It will be recognized by one of ordinary skill in the art
that in the case where the alcohol in (i) is different than the
alcohol used in (ii) that there may be some dissociation of the
ester in (ii) so that it may be difficult to say exactly what the
species of alcohol(s) and ester(s) are with precision. Furthermore,
(i) and/or (ii) may be added separately from each other or added
together, and separately or together with one or more of the olefin
feed(s). It is preferred that BF.sub.3 and acid/ester be added in
the feed together with the one or more alphaolefin.
[0055] In this process, it is preferred that the ratio of the group
(i) cocatalysts to group (ii) cocatalysts (i.e., (i):(ii)) range
from about 0.2:1 to 15:1, with 0.5:1 to 7:1 being preferred.
[0056] As to the boron trifluoride, it is preferred that it be
introduced into the reactor simultaneously with cocatalysts and
olefin feed. In the case of more than one continuously stirred
reactor connected in series, it is preferred that BF3, cocatalyst
and olefin feed be introduced only to the first reactor, and
preferably simultaneously. It is further preferred that the
reaction zone(s) contain an excess of boron trifluoride, which is
governed by the pressure and partial pressure of the boron
trifluoride. In this regard, it is preferred that the boron
trifluoride be maintained in the reaction zone at a pressure of
about 2 to about 500 psig, preferably about 2 to 50 psig (1 psi=703
kg/m.sup.2). Alternatively, the boron trifluoride can be sparged
into the reaction mixture, along with other known methods for
introducing the boron trifluoride to the reaction zone.
[0057] Suitable temperatures for the reaction are also conventional
and can vary from about -20.degree. C. to about 90.degree. C., with
a range of about 15.degree. to 70.degree. C. being preferred.
Appropriate residence times in each reactor, and other further
details of processing, are within the skill of the ordinary
artisan, in possession of the present disclosure.
[0058] In an embodiment, after steady-state conditions are achieved
in the final reactor, product from the final or last reactor is
sent to a first distillation column, wherein the unreacted monomers
and promoters are distilled off. Steady-state conditions may be
ascertained by one of ordinary skill in the art in possesson of the
present disclosure, e.g., when QI (as discussed below) of samples
taken from the final reactor does not change. The bottoms product
is then sent to a second distillation column where dimers are
distilled off. In embodiments, for instance in the case where the
dimers are a desired product, the bottoms product is preferably
first hydrogenated prior to distillation of the dimers. A useful
dimer product may be, for instance, a PAO having a nominal 2 cSt
viscosity. In an alternative, dimers are first distilled off and
the bottoms product from the second distillation product is then
hydrogenated.
[0059] The products taken off overhead from this hydrogenated
bottoms product, in a third distillation column, preferably will be
a narrow cut, meaning a high percentage of trimer. In an
embodiment, the product comprises at least 85 wt. % trimer. In
another embodiment, the product comprises at least 95 wt. % trimer.
In still another embodiment, the product comprises about 99 wt. %
trimer and about 1 wt. % tetramer. The actual molecular weight
range will depend on the feed. Thus, with a feed consisting
essentially of 1-decene, a preferred product will be a narrow cut
having, for instance, 85 wt. % C30 PAO. In the case of a feed
consisting essentially of 1-decene and 1-dodecene, a preferred
product will be a narrow cut having, for instance, 85 wt. % C30,
C32, C34, C36 PAO. The percentages of each specific carbon number
can be attenuated by one of ordinary skill in the art in possession
of the present disclosure.
[0060] The bottoms product from this third distillation column also
yields a useful PAO product, e.g., a PAO having a nominal 6 cSt
viscosity.
[0061] In an embodiment, a particular advantage of the present
invention is the surprising discovery that the viscosity can be
controlled by the ratio of alcohol to ester, with the higher
viscosity achieved by having a higher alcohol:ester ratio. The
degree of polymerization may also be attenuated more finely by
controlling the concentration of the alcohol and the ester. This
is, again, within the skill of the ordinary artisan in possession
of the present disclosure.
EXAMPLES
[0062] In the following examples the improvement in the selectivity
of trimer yield is indicated by the parameter QI, which is the
ratio of wt. % trimer to the sum of wt. % of trimers, tetramers and
higher oligomers. The results are set forth in Tables 1 and 2. The
properties of the narrow cut trimers and the co-products made in
the same process are shown in Tables 3 and 4. These are compared to
the conventional PAO's that have similar viscosity. The examples
are meant to illustrate the present invention, and it will be
recognized by one of ordinary skill in the art in possession of the
present disclosure that numerous modifications and variations are
possible. Therefore, it is to be understood that within the scope
of the appended claims, the invention may be practiced otherwise
than as specifically described herein.
Example 1 (Comparative)
[0063] 1-decene was oligomerized in two continuous stirred-tank
reactors in series at 18.degree. C. and 5 psig using a feed
consisting essentially of olefin, BF.sub.3 and BF.sub.3.butanol
(complex of the catalyst and the alcohol). The free BF.sub.3
concentration was 0.1 wt. % (1.8 mmoles/100 parts olefin feed); the
weight ratio of BF.sub.3 to BF.sub.3.alcohol complex in the feed
was 0.2:1. Residence times in the primary and secondary reactors
were 1.4 hrs and 1 hr, respectively. When the system reached
steady-state, a sample was taken from the second reactor and the
composition of the crude polymer was determined by gas
chromatography (GC). The % conversion and QI, shown in Table 1,
were computed from the GC results. The QI obtained was 0.375,
meaning that only 37.5% of the mixture of oligomers (trimers and
higher) were trimers.
Example 2
[0064] As Example 1, except that the promoter system had
BF.sub.3.butanol and BF.sub.3.butyl acetate and the residence times
in the primary and secondary reactors were 0.5 hr and 1.3 hrs,
respectively. The mole ratio of butanol to butyl acetate was 7 to
1; the weight ratio of free to complexed BF.sub.3 is 0.1:1. With
the addition of BF.sub.3.butyl acetate in the promoter system, the
conversion was lower and more trimers were produced as indicated by
the higher QI of Example 2 compared to that of Example 1, as shown
in Table 1.
Example 3
[0065] Same as Example 2, except that the concentration of the
BF.sub.3.butyl acetate complex was increased so that the promoter
system had a BF.sub.3.butanol: BF.sub.3.butyl acetate ratio of 4:1;
the weight ratio of free to complexed BF.sub.3 was 0.08:1. With the
incorporation of more acetate in the promoter system, conversion is
similar to that in Example 2, while the QI of the polymer, also
shown in Table 1, is increased to 0.651.
Example 4
[0066] Same as Example 2, except that the promoter system had a
still further increase in BF.sub.3.butyl acetate so that the ratio
of BF.sub.3-butanol to BF.sub.3-butyl acetate was 2.5:1, the
reaction temperature was at 21.degree. C., and the residence times
in the primary and secondary reactors were 1.7 hrs and 0.7 hr,
respectively. Again, as shown in Table 1, the QI increased still
further with the simultaneous increase in temperature and acetate
content, despite the higher conversion attained. TABLE-US-00001
TABLE 1 1-Decene Feed Residence Time in Primary/ Secondary %
Reaction Reactors Con- Ex. Promoter System Temperature (in hours)
version QI 1 BF3-Butanol 18.degree. C. 1.4/1 80 0.375 2 7:1
BF3-Butanol/ 18.degree. C. 0.5/1.3 76 0.575 BF3-Butyl acetate 3 4:1
BF3-Butanol/ 18.degree. C. 0.5/1.3 76 0.651 BF3 Butyl Acetate 4
2.5:1 BF3-Butanol/ 21.degree. C. 1.7/0.7 90 0.733 BF3-Butyl
Acetate
Example 5 (Comparative).
[0067] Same as Example 1, except that the feed was a mixture
containing 70 wt. % 1-decene and 30 wt. % 1-dodecene, the promoter
system was BF.sub.3.ethanol and the residence times in the primary
and secondary reactors were 1.3 hrs and 0.94 hr, respectively. The
conversion and QI of the polymer are shown in Table 2. By using a
mixture of 1-decene and 1-dodecene and lower molecular weight
alcohol than that used in Example 1, the QI increased to 0.51.
Example 6
[0068] Same as Example 5, except that a dual promoter system of
BF.sub.3.ethanol and BF.sub.3 ethyl acetate was used, in the ratio
of 12:1. The addition of BF.sub.3.ethyl acetate to the promoter
system resulted in a QI that was higher than that of Example 5, as
shown in Table 2, below, even though the conversion of Example 5
lower.
Example 7
[0069] Same as Example 5, except that the promoter system used was
3.5:1 in BF.sub.3.butanol:BF.sub.3.butyl acetate. The QI still
increased even when a higher molecular weight alcohol-alkyl acetate
system was used. The conversion, however, was lower.
Example 8
[0070] Same as Example 7 except that the olefin feed mixture
contained 60 wt. % 1-decene and 40 wt. % 1-dodecene. When the feed
mixture contained more 1-dodecene, the QI was reduced even if the
conversion was similar to that of Example 7. TABLE-US-00002 TABLE 2
1-Decene/1-Dodecene feed Residence Time in Primary/ C10/C12
Reaction Secondary % Ratio Promoter Temper- Reactors Con- Ex.
Wt./Wt. System ature (in hours) version QI 5 70:30 BF3-Ethanol
18.degree. C. 1.3/0.94 88 0.51 6 70:30 12:1 BF3- 18.degree. C.
1.3/0.94 93 0.582 Ethanol/ BF3 Ethyl Acetate 7 70:30 3.5:1 BF3-
18.degree. C. 1.3/0.94 85 0.682 Butanol/ Butyl Acetate 8 60:40
3.5:1 BF3- 18.degree. C. 1.3/0.94 86 0.671 Butanol/ Butyl
Acetate
Example 9 (Comparative)
[0071] A low viscosity mixture containing 7.2 wt. % PAO with a
nominal viscosity of 2 cSt and 92.8 wt. % of PAO with nominal
viscosity of 4 cSt, was made from commercial samples. The
properties are shown in Table 3, below. Although the blend's
viscosity was low, the Noack volatility was high due to the high
dimer content.
[0072] Also shown in Table 3 are two references--Reference A
(SpectraSyn.TM. 4 PAO) and Reference B (Synfluid.RTM. 4 PAO). These
are both commercially-available PAOs from ExxonMobil Chemical
Company and Chevron Phillips, respectively, with nominal viscosity
of 4 cSt. Both references have broad molecular weight distribution
as indicated by oligomer distribution.
Example 10
[0073] This example used the product obtained in Example 4. In
Example 4, a sample was taken from the second reactor when
steady-state condition was attained. This sample was distilled to
remove the monomer and dimer. The bottoms stream was hydrogenated
to saturate the trimer and higher oligomers. The hydrogenated
product was distilled and two cuts of PAO were obtained, one
(overheads) with a nominal viscosity of 4 cSt, shown as Example 10A
in Table 3, below, and one (bottoms product) with a nominal
viscosity of 6 cSt, shown as Example 10B in Table 4, further
below.
[0074] From Example 10A, the PAO that had a nominal viscosity of 4
cSt produced in this process was mostly trimers--greater than 95%
trimers. It had a narrow molecular weight distribution and had a
100.degree. C. and -40.degree. C. viscosities that were lower than
the references. It also had a good Noack volatility.
[0075] The co-product, shown in Table 4, had a nominal viscosity of
6 cSt and better Noack volatility and low temperature viscosity
than conventional, commercially available 1-decene-based PAO that
has a nominal viscosity of 6 cSt (Reference C,
commercially-available, nominal 6 cSt PAO, from ExxonMobil Chemical
Company).
Example 11
[0076] Same as Example 10, except using the product produced in
Example 8 instead of Example 4. The PAO produced that had a nominal
viscosity of 4 cSt, shown as Example 11A in Table 3, was also
narrow cut and had better low temperature viscosity and Noack
volatility than the conventional PAOs that have a nominal viscosity
of 4 cSt (References A and B).
[0077] The co-product cut, Example 11B, had a nominal viscosity of
6 cSt and was also superior to both commercially available
C10-based and mixed olefin-based (C8/C10/C12) references, C and D,
respectively. Reference D is commercially-available, also a nominal
6 cSt PAO, from ExxonMobil Chemical Company. TABLE-US-00003 TABLE 3
Properties of Narrow Cut Trimers (overheads) Oligomer Distribution
100.degree. -40.degree. Noack Dimer/Trimer/ C. C. Vola- Tetramer/
K.V. K.V. tility Pentamer Ex. Feed (cSt) (cSt) VI (wt. %) (wt. %)
Ref A C10 4.00 2728 123 12.4 0.8/77.8/18.3/3.1 Ref B C10 3.81 2387
122 14.2 0.8/87/11.6/0.6 9 C10 3.86 2383 125 17.8 7.5/67.8/20.4/4.3
10A C10 3.62 2057 121 15.5 0/95.2/4.8/0 11A 60:40 3.86 2499 126
11.3 0.8/96.7/2.5/0 C10:C12
[0078] TABLE-US-00004 TABLE 4 Properties of Co-Products of Narrow
Cut Trimers (bottoms product) 100.degree. C. -40.degree. C. Noack
K.V. K.V. Volatility Ex. Feed (cSt) (cSt) VI (wt. %) Ref C C10 5.80
7800 136 7.5 10B C10 5.86 7959 137 6.6 Ref D 10:60:30 5.86 7712 138
6.6 C8:C10:C12 11B 60:40 5.90 7200 143 6.0 C10:C12
[0079] Blends According to the Invention.
[0080] The composition according to the invention comprises: (a) at
least one Group III basestock; and (b) at least one PAO according
to the invention.
[0081] In an embodiment, component (a) of the composition is
present in the amount of about 1 to 99 vol. %, and component (b) is
present in the amount of about 1 to 99 vol. %. In another
embodiment, component (a) is present in the amount of about 30 to
90 vol. %, and component (b) is present in the amount of about 10
vol % to about 70 vol. %. In still another embodiment, component
(a) is present in the amount of greater than 30 to about 80 vol. %,
and component (b) is present in the amount of about 20 vol % to
less than 70 vol. %. Additional embodiments envisioned include
amounts from any lower limit given to any upper limit given, and
thus, by way of further example, component (a) may be present in
the amount of about 1 to 80 vol. %, and component (b) may be
present in the amount of about 20 to 99 vol. %. Percentages are
based on the volume of the entire composition.
[0082] The blend of at least one Group III material and PAO
according to the invention may be used by itself as a functional
fluids, such as a carrier or diluent, or it may be further blended
with other basestocks and/or additives, such as one or more
additives selected from detergents, anti-wear additives, extreme
pressure additives, viscosity index improvers, antioxidants,
dispersants, pour point depressants, corrosion inhibitors, seal
compatibility agents, antifoam agents, and the like, discussed more
fully below. Fully formulated lubricants are useful for lubricating
engines, industrial and automotive gearsets, and the like.
[0083] PAOs suitable for use in the present invention were
synthesized and the Noack volatility vs. CCS @ -35.degree. C. (FIG.
1) and Noack volatility vs. KV at 100.degree. C. (FIGS. 2 and 3)
relationships are shown relative to existing commercial products.
The curves shown were generated using an Excel graphing function,
illustrating approximate boundary functions for PAOs according to
the present invention.
[0084] In FIG. 1, "C10trimer" is a low volatility, low viscosity
PAO according to the invention, taken as overheads from the third
distillation column (i.e., after a first distillation removing
unreacted monomers and promoters, an hydrogenation step, and second
distillation to remove dimers). The "C10/C12 trimer (1)" is taken
in the same fashion, but using a feed of 55 vol. % C10, remainder
C12, and having a KV100=3.9 cSt. The "C10/C12 trimer (2)" is taken
in the same fashion, overhead, but using a feed of 60 vol. % C10,
remainder C12, and having a KV100=4.1 cSt; the "C10/C12 oligomer
(3)" is the bottoms product using this feed and has a KV100 of 5.9
cSt. "C10/C12 oligomer (3)" is referred to in the drawings as
"C10/C12 trimer (3)".
[0085] Also shown on FIGS. 1 and 2 are commercial products as
identified and also a "2/4" mixture of conventional PAOs made
without dual promoter system, having a nominal viscosity of 2 cSt
and 4 cSt, respectively. The top curve (A) in each graph is drawn
through data points representing existing products and the bottom
curve (B) is drawn through data points representing products
according to the present invention. These curves are directly from
Excel graphing/power fit functions. It should be noted that
although certain existing commercial products appear below the "B"
curves, such products do not have pour points less than -54.degree.
C.
[0086] FIG. 3 is similar to FIG. 2 and used to demonstrate a
mathematical relationship between Noack volatility and Kinematic
Viscosity at 100.degree. C. (KV100) for both conventional low
viscosity PAO and the low volatility, low viscosity PAO according
to the present invention. In both sets of PAO data (curves A and
B), the curve is segmented between 3.5 and 3.95 cSt for one
relationship, and then redefined for products between 3.95 and 6
cSt. Curve A, drawn through data points of conventional PAO may be
described by the following equation: (ia) within the range of 3.5
to 3.95 cSt at 100.degree. C. the Noack
volatility=(50,000)(KV100).sup.-6; and (ib) within the range of
greater than 3.95 to 6 cSt at 100.degree. C. the Noack
volatility=(182)(KV100).sup.-1.9. Curve B, drawn through data
points representing PAOs according to the invention, may be
described by the following equation: (iia) within the range of 3.5
to 3.95 cSt at 100.degree. C. the Noack
Volatility=(900)(KV100).sup.-3.2; and (iib) within the range of
greater than 3.95 to 6 cSt at 100.degree. C. the Noack
Volatility=(175)(KV100).sup.-2. These equations closely model the
actual relationship between Noack volatility and kinematic
viscosity at 100.degree. C. for both classes of PAO. The clear
difference in Noack volatility vs. kinematic viscosity at
100.degree. C. for the present invention PAO, combined with its
pour point <-54.degree. C. provides significant advantage in
blending many finished lubricants over prior art PAO.
[0087] In a preferred embodiment, the PAO according to the
invention is characterized as having a pour point less than
-54.degree. C., and at least one of the following: (i) a Noack
volatility (wt. %) versus Cold Crank Simulator test (CCS) at
-35.degree. C. relationship about equal to or better than (below
the curve) described by Curve A or preferably Curve B in FIG. 1,
these curves also characterized by the equations: Noack volatility
(wt. %)=(6473.1)(CCS @ -35.degree. C., in cP).sup.-0.834 and Noack
volatility (wt. %)=(500)(CCS @ -35.degree. C., in cP).sup.-0.83,
respectively; (ii) a Noack volatility (wt. %) versus Kinematic
Viscosity @ 100.degree. C. (KV100) relationship about equal to or
better than (below the curve) described by Curve A or preferably
Curve B in FIG. 2, these curves also characterized by the
equations: Noack volatility (wt. %)=(354.75)(CCS @ -35 C, in
cP).sup.-2.2629 and Noack volatility (wt. %)=(234.58)(CCS @ -35C,
in cP).sup.2.1632, respectively; and (iii) a Noack volatility (wt.
%) versus Kinematic Viscosity relationship about equal to or better
than (below the curve) described by Curve A or preferably Curve B
in FIG. 3.
[0088] In a preferred embodiment, the PAO according to the
invention is characterized by a pour point less than -54.degree.
C., and a Noack volatility to KV at 100.degree. C. (KV100)
relationship such that: in an embodiment (ia) within the range of
3.5 to 3.95 cSt at 100.degree. C. the Noack volatility (wt.
%)=(50,000)(KV100).sup.-6, and (ib) within the range of greater
than 3.95 to 6 cSt at 100.degree. C. the Noack
volatility=(182)(KV100).sup.-1.9 or in another embodiment (iia)
within the range of 3.5 to 3.95 cSt at 100.degree. C. the Noack
Volatility=(900)(KV)-.sup.3.2; and (iib) within the range of
greater than 3.95 to 6 cSt at 100.degree. C. the Noack
Volatility=(175)(KV).sup.-2.
[0089] Blend--Experimental
[0090] As with the previous examples, the following are meant to
illustrate the present invention and also to provide a comparison
with other methods and the products produced therefrom. Numerous
modifications and variations are possible and it is to be
understood that within the scope of the appended claims, the
invention may be practiced otherwise than as specifically described
herein.
[0091] Tables 5a and 5b below illustrate the formulation of PAOs
according to the invention with Group III basestocks that meet SAE
Grade 0 W multigrade engine oil requirements. TABLE-US-00005 TABLE
5a SAE Viscosity Grade Require- 0W-30 0W-30 0W-40 ments Yubase 4
41.6 60.0 50.0 C10 trimer 27.7 18.8 26.3 Infineum P6608 13.7 13.7
13.7 Adpak SV151 Viscosity 17.0 0.0 0.0 Modifier SV301 Viscosity
0.0 7.5 10.0 Modifier 100.0 100.0 100.0 KV @ 10.78 11.06
9.3-<12.4 100.degree. C., cSt KV @ 13.25 12.5-<16.3
100.degree. C., cSt VI 177 185 181 Pour Point, .degree. C. -45 -33
-36 CCS @: -35.degree. C., cP 5,848 6,006 5,978 6,200 Max HTHS @
150.degree. C. Apparent 2.96 3.02 3.34 2.9-3.4 Viscosity, cP
MRV-TP1 @ -40.degree. C.: Apparent 19,120 38,663 40,165 60,000 Max
Viscosity, cP Base Oil 15.6 15.9 15.8 Predicted Noack, %
[0092] TABLE-US-00006 TABLE 5b Viscosity Grade SAE 0W-30 0W-30
0W-30 0W-30 0W-30 Requirements Yubase 4 33.0 40.5 Yubase 6 30.4
24.3 30.2 C10 trimer 45.6 C10/C12 (1) 45.6 56.7 14.3 30.0 C10/C12
(3) 28.5 5.0 Infineum P6026- DDI 12.9 12.9 12.9 12.9 12.9 Infineum
C9440- Friction Modifier 0.5 0.5 0.5 0.5 0.5 Infineum SV201-VII 5.7
5.7 5.7 5.7 6.0 Infineum V351 -PPD -- -- 0.2 0.2 0.2 Esterex NP343
5.0 -- 5.0 5.0 5.0 100.0 100.0 100.0 100.0 100.0 KV @ 100.degree.
C., cSt 10.14 9.82 9.77 10.18 9.60 9.3-<12.4 VI 172 179 171 172
178 Pour Point, .degree. C. CCS @: -35.degree. C., cP 5,772 5,063
5,530 6,143 5,230 6,200 Max HTHS @ 150.degree. C. Apparent
Viscosity, cP 2.93 2.90 3.10 2.90 2.9-3.4 MRV-TP1 @ -40.degree. C.:
Apparent Viscosity, cP 60,000 Max Base Oil Predicted Noack, % 7.4
8.2 9.1 7.8 9.5
[0093] Table 5a and 5b clearly illustrate a blend of significant
concentrations of Yubase 4 and/or Yubase 6 with the low volatility,
low viscosity PAOs according to the invention can be utilized to
meet the low temperature viscosity and high temperature stability
requirements of SAE Grade 0 W multi-grade engine oils. At least one
advantage of the present invention is that availability of
conventional Group III basestocks is much greater than the
availability of PAO and/or wax isomerate based Group III
basestocks. The "C 10 trimer", "C10/C12 (1)" and "C1O/C12 (3)"
materials are the same as those identified in FIGS. 1 and 2,
discussed above. TABLE-US-00007 TABLE 6 5 cSt Blend Estimates Kin.
Visc @ Noack Kin. Visc. @ Noack CCS 100 C. (cSt) Volatility % Each
100 C. (cSt) Volatility @ -35 C. (cP) Grp III 4 cSt 4.2 14.5 58%
Grp III 6 cSt 6.4 7.3 42% Blend 5.1 11.9 4,491 PAO 4 3.9 13.0 44%
PAO 6 5.9 6.8 56% Blend 5.0 9.0 2,525 Grp III 4 cSt 4.2 14.5 44%
Grp IV + 6 cSt 5.9 5.1 56% Blend 5.1 9.5 3,133 Grp IV + 4 cSt 3.9
11.4 44% Grp III 6 cSt 6.4 7.3 56% Blend 5.1 8.9 2,030 Grp IV + 3.6
cSt 3.6 15.2 44% Grp III 6 cSt 6.4 7.3 56% Blend 4.5 12.0 2,329
[0094] Table 6 above illustrates how greater than 50% of
conventional Group III basestocks blended with this new class of
PAO can yield approximately the same low temperature viscosity and
Noack volatility as 100% conventional PAO. "Grp IV+" identifies the
low volatility, low viscosity PAO basestocks according to the
present invention.
[0095] In an embodiment, the mixture of Group III and Group IV
basestocks according to the invention are used with additional
lubricant components in effective amounts to form lubricant
compositions. Additional ingredients may include, for example,
other polar and/or non-polar lubricant base stocks (such as API
Group I, II, V, and mixtures thereof), and performance additives,
such as, for example, but not limited to, oxidation inhibitors,
metallic and non-metallic dispersants, metallic and non-metallic
detergents, corrosion and rust inhibitors, metal deactivators,
anti-wear agents (metallic and non-metallic, phosphorus-containing
and non-phosphorus, sulfur-containing and non-sulfur types),
extreme pressure additives (metallic and non-metallic,
phosphorus-containing and non-phosphorus, sulfur-containing and
non-sulfur types), anti-seizure agents, pour point depressants, wax
modifiers, viscosity modifiers, seal compatibility agents, friction
modifiers, lubricity agents, anti-staining agents, chromophoric
agents, defoamants, demulsifiers, emulsifiers, thickeners
(sometimes also referred to as VI improvers, exemplified by PIB,
some PMAs, and the like), fuel stabilizers, tackifiers, and others,
depending on the use to which the composition is put.
[0096] For example, fuel stabilizers re added to two cycle engines
where the fuel and lube intermix. Demulsifiers are added to
lubricant compositions that are expected to come into contact with
water, while emulsifiers are primarily used in metal working.
[0097] For a review of many commonly used additives see Klamann in
Lubricants and Related Products, Verlag Chemie, Deerfield Beach,
Fla.; ISBN 0-89573-177-0, which gives a good discussion of a number
of the lubricant additives discussed mentioned below. Reference is
also made to "Lubricant Additives" by M. W. Ranney, published by
Noyes Data Corporation of Parkridge, N.J. (1973).
[0098] In preferred embodiments, a lubricant composition according
to the present invention will comprise the Group III/Group IV blend
according to the invention and at least one ingredient selected
from the following.
[0099] Detergents
[0100] Suitable detergents include one or more alkali or alkaline
earth metal salts of sulfates, phenates, carboxylates, phosphates,
and salicylates.
[0101] Sulfonates may be prepared from sulfonic acids that are
typically obtained by sulfonation of alkyl substituted aromatic
hydrocarbons. Hydrocarbon examples include those obtained by
alkylating benzene, toluene, xylene, naphthalene, biphenyl and
their halogenated derivatives (chlorobenzene, chlorotoluene, and
chloronaphthalene, for example). The alkylating agents typically
have about 3 to 70 carbon atoms. The alkaryl sulfonates typically
contain about 9 to about 80 carbon or more carbon atoms, more
typically from about 16 to 60 carbon atoms.
[0102] Ranney in "Lubricant Additives" op cit discloses a number of
overbased metal salts of various sulfonic acids that are useful as
detergents and dispersants in lubricants. The book entitled
"Lubricant Additives", C. V. Smallheer and R. K. Smith, published
by the Lezius-Hiles Co. of Cleveland, Ohio (1967), similarly
discloses a number of overbased sulfonates, which are useful as
dispersants/detergents.
[0103] Alkaline earth phenates are another useful class of
detergent. These detergents are made by reacting alkaline earth
metal hydroxide or oxide [CaO, Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2,
for example] with an alkyl phenol or sulfurized alkylphenol. Useful
alkyl groups include straight chain or branched C1-C30 alkyl
groups, preferably C4-C20. Examples of suitable phenols include
isobutylphenol, 2-ethylhexylphenol, nonylphenol,
1-ethyldecylphenol, and the like. It should be noted that starting
alkylphenols may contain more than one alkyl substituent that are
each independently straight chain or branched. When a
non-sulfurized alkylphenol is used, the sulfurized product may be
obtained by methods well known in the art. These methods include
heating a mixture of alkylphenol and sulfurizing agent (including
elemental sulfur, sulfur halides such as sulfur dichloride, and the
like) and then reacting the sulfurized phenol with an alkaline
earth metal base.
[0104] Metal salts of carboxylic acids other than salicylic acid
are also used as detergents. These carboxylic acid detergents are
prepared by a method analogous to that used for salicylates.
[0105] Alkaline earth metal phosphates are also used as
detergents.
[0106] Detergents may be simple detergents or what is known as
hybrid or complex detergents. The latter detergents can provide the
properties of two detergents without the need to blend separate
materials. See U.S. Pat. No. 6,034,039, for example, which is
incorporated herein by reference in its entirety. In preferred
embodiment, the total detergent concentration is about 0.01 to
about 6.0 weight percent, preferably, 0.1 to 0.4 weight percent,
based on the weight of the entire composition.
[0107] Anti-Wear and Extreme Pressure (EP) Additives
[0108] Internal combustion engine lubricating oils typically
include the presence of anti-wear and/or extreme pressure additives
in order to provide adequate anti-wear protection for the engine.
Increasingly, specifications for engine oil performance have
exhibited a trend for improved anti-wear properties of the oil.
Anti-wear and EP additives perform this role by reducing friction
and wear of metal parts.
[0109] While there are many different types of anti-wear additives,
for several decades the principal anti-wear additive for internal
combustion engine crankcase oils has been a metal
alkylthiophosphate and more particularly a metal
dialkyldithiophosphate in which the primary metal constituent is
zinc, or zinc dialkyldithiophosphate (ZDDP). ZDDP compounds are
generally of the formula Zn[SP(S)(OR1)(OR2)]2 where R1 and R2 are
C1-C18 alkyl groups, preferably C2-C12 alkyl groups. These alkyl
groups may be straight chain or branched and may be derived from
primary and/or secondary alcohols and/or alkylaryl groups such as
alkyl phenols. The ZDDP is typically used in amounts of from about
0.4 to 1.4 weight percent of the total lube oil composition,
although more or less can often be used advantageously.
[0110] However, it has been found that the phosphorus from these
additives has a deleterious effect on the catalyst in catalytic
converters and also on oxygen sensors in automobiles. One way to
minimize this effect is to replace some or all of the ZDDP with
phosphorus-free, anti-wear additives.
[0111] A variety of non-phosphorus additives have also been used as
anti-wear additives. Sulfurized olefins are useful as anti-wear and
EP additives. Sulfur-containing olefins can be prepared by
sulfuirization or various organic materials including aliphatic,
arylaliphatic or alicyclic olefinic hydrocarbons containing from
about 3 to 30 carbon atoms, preferably about 3 to 20 carbon atoms.
The olefinic compounds contain at least one non-aromatic double
bond. Such compounds are defined by the formula
R.sup.3R.sup.4C=CR.sup.5R.sup.6 where each of R.sup.3, R.sup.4,
R.sup.5, R.sup.6 are independently hydrogen or a hydrocarbon
radical. Preferred hydrocarbon radicals are alkyl or alkenyl
radicals. Any two of R.sup.3, R.sup.4, R.sup.5, and R.sup.6 may be
connected so as to form a cyclic ring. Additional information
concerning sulfurized olefins and their preparation can be found in
U.S. Pat. No. 4,941,984, incorporated by reference herein in its
entirety.
[0112] The use of polysulfides of thiophosphorus acids and
thiophosphorus acid esters as lubricant additives is disclosed in
U.S. Pat. Nos. 2,443,264; 2,471,115; 2,526,497; and 2,591,577.
Addition of phosphorothionyl disulfides as anti-wear, antioxidant,
and EP additives is disclosed in U.S. Pat. No. 3,770,854. Use of
alkylthiocarbamoyl compounds [bis(dibutyl)thiocarbamoyl, for
example] in combination with a molybdenum compound (oxymolybdenum
diisopropylphosphorodithioate sulfide, for example) and a
phosphorus ester (dibutyl hydrogen phosphite, for example) as
anti-wear additives in lubricants is disclosed in U.S. Pat. No.
4,501,678. U.S. Pat. No. 4,758,362 discloses use of a carbamate
additive to provide improved anti-wear and extreme pressure
properties. The use of thiocarbamate as an anti-wear additive is
disclosed in U.S. Pat. No. 5,693,598. Thiocarbamate/molybdenum
complexes such as moly-sulfur alkyl dithiocarbamate trimer complex
(R=C8-C18 alkyl) are also useful anti-wear agents.
[0113] Esters of glycerol may be used as anti-wear agents. For
example, mono-, di-, and tri-oleates, mono-palmitates and
mono-myristates may be used.
[0114] ZDDP has been combined with other compositions that provide
anti-wear properties. U.S. Pat. No. 5,034,141 discloses that a
combination of a thiodixanthogen compound (octylthiodi-xanthogen,
for example) and a metal thiophosphate (ZDDP, for example) can
improve anti-wear properties. U.S. Pat. No. 5,034,142 discloses
that use of a metal alkyoxyalkylxanthate (nickel
ethoxy-ethylxanthate, for example) and a dixanthogen (diethoxyethyl
dixanthogen, for example) in combination with ZDDP improves
anti-wear properties.
[0115] Preferred anti-wear additives include phosphorus and sulfur
compounds such as zinc dithiophosphates and/or sulfur, nitrogen,
boron, molybdenum phosphorodithioates, molybdenum dithiocarbamates
and various organo-molybdenum derivatives including heterocyclics
(including dimercaptothia-diazoles, mercaptobenzothiazoles,
triazines and the like), alicyclics, amines, alcohols, esters,
diols, triols, fatty amides and the like can also be used. In
preferred embodiment, such additives may be used in an amount of
about 0.01 to 6 weight percent, preferably about 0.01 to 4 weight
percent, based on the weight of the entire composition.
[0116] Viscosity Index Improvers
[0117] Viscosity index improvers (also known as VI improvers,
viscosity modifiers, and viscosity improvers) provide lubricants
with high and low temperature operability. These additives impart
shear stability at elevated temperatures and acceptable viscosity
at low temperatures.
[0118] Suitable viscosity index improvers include high molecular
weight hydrocarbons, olefin polymers and copolymers, polyesters and
viscosity index improver dispersants that function as both a
viscosity index improver and a dispersant. Typical molecular
weights of these polymers range from about 10,000 to about
1,000,000, more typically about 20,000 to about 500,000, and even
more typically between about 50,000 and about 200,000.
[0119] Examples of suitable viscosity index improvers are polymers
and copolymers of methacrylate, butadiene, olefins, or alkylated
styrenes. Polyisobutylene (PIB) is a commonly used viscosity index
improver. Another suitable viscosity index improver is PMA or
polymethacrylate (copolymers of various chain length alkyl
methacrylates, for example), some formulations of which also serve
as pour point depressants. Other suitable viscosity index improvers
include copolymers of ethylene and propylene, hydrogenated block
copolymers of styrene and isoprene, and polyacrylates (copolymers
of various chain length acrylates, for example). Specific examples
include styrene-isoprene or styrene-butadiene based polymers of
about 50,000 to 200,000 molecular weight.
[0120] In one embodiment of the present invention, viscosity index
improvers are used in an amount of about 0.01 to 6 weight percent,
preferably about 0.01 to 4 weight percent, based on the weight of
the entire composition.
[0121] Antioxidants
[0122] Antioxidants retard the oxidative degradation of base stocks
during service. Such degradation may result in deposits on metal
surfaces, the presence of sludge, or a viscosity increase in the
lubricant. A wide variety of oxidation inhibitors that are useful
in lubricating oil compositions are well known. See, Klamann in
Lubricants and Related Products, op cit., and U.S. Pat. Nos.
4,798,684 and 5,084,197, for example, the disclosures of which are
incorporated by reference herein in their entirety.
[0123] Useful antioxidants include hindered phenols. These phenolic
antioxidants may be ashless (metal-free) phenolic compounds or
neutral or basic metal salts of certain phenolic compounds. Typical
phenolic antioxidant compounds are the hindered phenolics that
contain a sterically hindered hydroxyl group, and these include
those derivatives of dihydroxy aryl compounds in which the hydroxyl
groups are in the o- or p-position to each other. Typical phenolic
antioxidants include the hindered phenols substituted with C6+
alkyl groups and the alkylene coupled derivatives of these hindered
phenols. Examples of phenolic materials of this type
2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol;
2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol;
2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl
phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful
hindered mono-phenolic antioxidants may include, for example,
hindered 2,6-di-alkyl-phenolic propionic ester derivatives.
Bis-phenolic antioxidants may also be advantageously used in
combination with the instant invention. Examples of ortho coupled
phenols include: 2,2'-bis(6-t-butyl-4-heptyl phenol);
2,2'-bis(6-t-butyl-4-octyl phenol); and
2,2'-bis(6-t-butyl-4-dodecyl phenol). Para coupled bis phenols
include, for example, 4,4'-bis(2,6-di-t-butyl phenol) and
4,4'-methylene-bis(2,6-di-t-butyl phenol).
[0124] Non-phenolic oxidation inhibitors that may be used include
aromatic amine antioxidants and these may be used either as such or
in combination with phenolics. Typical examples of non-phenolic
antioxidants include: alkylated and non-alkylated aromatic amines
such as the aromatic monoamines of the formula R8R9R10N where R8 is
an aliphatic, aromatic or substituted aromatic group, R9 is an
aromatic or a substituted aromatic group, and R10is H, alkyl, aryl
or R11S(O)XR12 where R11 is an alkylene, alkenylene, or aralkylene
group, R12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl
group, and x is 0, 1 or 2. The aliphatic group R8 may contain from
1 to about 20 carbon atoms, and preferably contains from 6 to 12
carbon atoms. The aliphatic group is a saturated aliphatic group.
Preferably, both R8 and R9 are aromatic or substituted aromatic
groups, and the aromatic group may be a fused ring aromatic group
such as naphthyl. Aromatic groups R8 and R9 may be joined together
with other groups such as S.
[0125] Typical aromatic amine antioxidants have alkyl substituent
groups of at least about 6 carbon atoms. Examples of aliphatic
groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally,
the aliphatic groups will not contain more than about 14 carbon
atoms. The general types of amine antioxidants useful in the
present compositions include diphenylamines, phenyl naphthylamines,
phenothiazines, imidodibenzyls and diphenyl phenylene diamines.
Mixtures of two or more aromatic amines are also useful. Polymeric
amine antioxidants can also be used. Particular examples of
aromatic amine antioxidants useful in the present invention
include: p,p'-dioctyldiphenylamine;
t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and
p-octylphenyl-alpha-naphthylamine.
[0126] Sulfirized alkyl phenols and alkali or alkaline earth metal
salts thereof also are useful antioxidants. Low sulfur peroxide
decomposers are useful as antioxidants.
[0127] Another class of antioxidant used in lubricating oil
compositions is oil-soluble copper compounds. Any oil-soluble
suitable copper compound may be blended into the lubricating oil.
Examples of suitable copper antioxidants include copper
dihydrocarbyl thio or dithio-phosphates and copper salts of
carboxylic acid (naturally occurring or synthetic). Other suitable
copper salts include copper dithiacarbamates, sulphonates,
phenates, and acetylacetonates. Basic, neutral, or acidic copper
Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or
anhydrides are known to be particularly useful.
[0128] Preferred antioxidants include hindered phenols, arylamines,
low sulfur peroxide decomposers and other related components. These
antioxidants may be used individually by type or in combination
with one another. In preferred embodiments, such additives may be
used in an amount of about 0.01 to 5 weight percent, preferably
about 0.01 to 1.5 weight percent, based on the weight of the entire
composition.
[0129] Dispersants
[0130] During engine operation, oil insoluble oxidation byproducts
are produced. Dispersants help keep these byproducts in solution,
thus diminishing their deposit on metal surfaces. Dispersants may
be ashless or ash-forming in nature. Preferably, the dispersant is
ashless. So-called ashless dispersants are organic materials that
form substantially no ash upon combustion. For example,
non-metal-containing or borated metal-free dispersants are
considered ashless. In contrast, metal-containing detergents
discussed above form ash upon combustion.
[0131] Suitable dispersants typically contain a polar group
attached to a relatively high molecular weight hydrocarbon chain.
The polar group typically contains at least one element of
nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain
about 50 to 400 carbon atoms.
[0132] Chemically, many dispersants may be characterized as
phenates, sulfonates, sulfurized phenates, salicylates,
naphthenates, stearates, carbamates, thiocarbamates, and phosphorus
derivatives. A particularly useful class of dispersants is the
alkenylsuccinic derivatives, typically produced by the reaction of
a long chain substituted alkenyl succinic compound, usually a
substituted succinic anhydride, with a polyhydroxy or polyamino
compound. The long chain group constituting the oleophilic portion
of the molecule, which confers solubility in the oil, is normally a
polyisobutylene group. Many examples of this type of dispersant are
well known commercially and in the literature. Exemplary U.S.
Patents describing such dispersants are U.S. Pat Nos. 3,172,892;
3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607;
3,541,012; 3,630,904; 3,632,511; 3,787,374; and 4,234,435. Other
types of dispersants are described in U.S. Pat. Nos. 3,036,003;
3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804;
3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059;
3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300;
4,100,082; and 5,705,458, which are fully incorporated by
reference. A further description of dispersants may be found, for
example, in European Patent Application 471 071, which is
incorporated by reference.
[0133] Hydrocarbyl-substituted succinic acid compounds are popular
dispersants. In particular, succinimide, succinate esters, or
succinate ester amides prepared by the reaction of a
hydrocarbon-substituted succinic acid compound preferably having at
least 50 carbon atoms in the hydrocarbon substituent, with at least
one equivalent of an alkylene amine are particularly useful.
[0134] Succinimides are formed by the condensation reaction between
alkenyl succinic anhydrides and amines. Molar ratios can vary
depending on the polyamine. For example, the molar ratio of alkenyl
succinic anhydride to TEPA can vary from about 1:1 to about 5:1.
Representative examples are shown in U.S. Pat. Nos. 3,087,936;
3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800;
and Canada Patent 1,094,044, which are incorporated herein in their
entirety by reference.
[0135] Succinate esters are formed by the condensation reaction
between alkenyl succinic anhydrides and alcohols or polyols. Molar
ratios can vary depending on the alcohol or polyol used. For
example, the condensation product of an alkenyl succinic anhydride
and pentaerythritol is a useful dispersant.
[0136] Succinate ester amides are formed by condensation reaction
between alkenyl succinic anhydrides and alkanol amines. For
example, suitable alkanol amines include ethoxylated
polyalkylpolyamines, propoxylated polyalkylpoly-amines and
polyalkenylpolyamines such as polyethylene polyamines. One example
is propoxylated hexamethylenediamine. Representative examples are
shown in U.S. Pat. No. 4,426,305, incorporated herein by
reference.
[0137] The molecular weight of the alkenyl succinic anhydrides used
in the preceding paragraphs will range between about 800 and 2,500
or more. The hydrocarbyl groups may be, for example, a group such
as polyisobutylene having a molecular weight of about 500 to 5,000
or a mixture of such groups. The above products can be post-reacted
with various reagents such as sulfur, oxygen, formaldehyde,
carboxylic acids such as oleic acid, hydrocarbyl dibasic acids or
anhydrides, and boron compounds such as borate esters or highly
borated dispersants. In one embodiment according to the present
invention, the dispersants are borated with from about 0.1 to about
5 moles of boron per mole of dispersant reaction product, including
those derived from mono-succinimide, bis-succinimide (also known as
disuccinimides), and mixtures thereof.
[0138] Mannich base dispersants are made from the reaction of
alkylphenols, formaldehyde, and amines. See U.S. Pat. No.
4,767,551, which is incorporated herein by reference. Process acids
and catalysts, such as oleic acid and sulfonic acids, can also be
part of the reaction mixture. Molecular weights of the alkylphenols
range from 800 to 2,500. Representative examples are shown in U.S.
Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953;
3,798,165; and 3,803,039, which are incorporated herein in their
entirety by reference.
[0139] Typical high molecular weight aliphatic acid modified
Mannich condensation products useful in this invention can be
prepared from high molecular weight alkyl-substituted
hydroxyaromatics or HN(R)2 group-containing reactants.
[0140] Examples of high molecular weight alkyl-substituted
hydroxyaromatic compounds are polypropylphenol, polybutylphenol,
and other polyalkylphenols. These polyalkylphenols can be obtained
by the alkylation, in the presence of an alkylating catalyst, such
as BF3, of phenol with high molecular weight polypropylene,
polybutylene, and other polyalkylene compounds to give alkyl
substituents on the benzene ring of phenol having an average of
from about 600 to about 100,000 molecular weight.
[0141] Examples of HN(R)2 group-containing reactants are alkylene
polyamines, principally polyethylene polyamines. Other
representative organic compounds containing at least one HN(R)2
group suitable for use in the preparation of Mannich condensation
products are well known and include the mono- and di-amino alkanes
and their substituted analogs, e.g., ethylamine and diethanol
amine; aromatic diamines, e.g., phenylene diamine, diamino
naphthalenes; heterocyclic amines, e.g., morpholine, pyrrole,
pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and
their substituted analogs.
[0142] Examples of alkylene polyamide reactants include
ethylenediamine, diethylene triamine, triethylene tetraamine,
tetraethylene pentaamine, pentaethylene hexamine, hexaethylene
heptaamine, heptaethylene octaamine, octaethylene nonaamine,
nonaethylene decamine, and decaethylene undecamine and mixture of
such amines having nitrogen contents corresponding to the alkylene
polyamines, in the formula H2N-(Z-NH-)nH, mentioned before, Z is a
divalent ethylene and n is 1 to 10 of the foregoing formula.
Corresponding propylene polyamines such as propylene diamine and
di-, tri-, tetra-, penta- propylene tri-, tetra-, penta- and
hexaamines are also suitable reactants. The alkylene polyamines are
usually obtained by the reaction of ammonia and dihalo alkanes,
such as dichloro alkanes. Thus the alkylene polyamines obtained
from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of
dichloro alkanes having 2 to 6 carbon atoms and the chlorines on
different carbons are suitable alkylene polyamine reactants.
[0143] Aldehyde reactants useful in the preparation of the high
molecular products useful in this invention include the aliphatic
aldehydes such as formaldehyde (such as paraformaldehyde and
formalin), acetaldehyde and aldol (b-hydroxybutyraldehyde, for
example). Formaldehyde or a formaldehyde--yielding reactant is
preferred.
[0144] Hydrocarbyl substituted amine ashless dispersant additives
are well known to one skilled in the art; see, for example, U.S.
Pat. Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433; 3,822,209;
and 5,084,197, which are incorporated herein in their entirety by
reference.
[0145] Preferred dispersants include borated and non-borated
succinimides, including those derivatives from mono-succinimides,
bis-succinimides, and/or mixtures of mono- and bis-succinimides,
wherein the hydrocarbyl succinimide is derived from a
hydrocarbylene group such as polyisobutylene having a number
average molecular weight (Mn) of from about 500 to about 5,000 or a
mixture of such hydrocarbylene groups. Other preferred dispersants
include succinic acid-esters and amides, alkylphenol-polyamine
coupled Mannich adducts, their capped derivatives, and other
related components. In one embodiment, such additives are used in
an amount of about 0.1 to 20 weight percent, preferably about 0.1
to 8 weight percent.
[0146] Pour Point Depressants
[0147] Conventional pour point depressants (also known as lube oil
flow improvers) may be added to the compositions of the present
invention if desired. The pour point depressant may be added to
lubricating compositions of the present invention to lower the
minimum temperature at which the fluid will flow or can be poured.
Examples of suitable pour point depressants include
polymethacrylates, polyacrylates, polyarylamides, condensation
products of haloparaffin waxes and aromatic compounds, vinyl
carboxylate polymers, and terpolymers of dialkylfumarates, vinyl
esters of fatty acids and allyl vinyl ethers. U.S. Pat. Nos.
1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746;
2,721,877; 2,721,878; and 3,250,715, which are fully incorporated
by reference, describe useful pour point depressants and/or the
preparation thereof. In one embodiment of the present invention,
such additives are used in an amount of about 0.01 to 5 weight
percent, preferably about 0.01 to 1.5 weight percent.
[0148] Corrosion Inhibitors
[0149] Corrosion inhibitors are used to reduce the degradation of
metallic parts that are in contact with the lubricating oil
composition. Suitable corrosion inhibitors include thiadiazoles and
triazoles. See, for example, U.S. Pat. Nos. 2,719,125; 2,719,126;
and 3,087,932, which are incorporated herein by reference in their
entirety. In one embodiment of the present invention, such
additives are used in an amount of about 0.01 to 5 weight percent,
preferably about 0.01 to 1.5 weight percent.
[0150] Seal Compatibility Additives
[0151] Seal compatibility agents help to swell elastomeric seals by
causing a chemical reaction in the fluid or a physical change in
the elastomer. Suitable seal compatibility agents for lubricating
oils include organic phosphates, aromatic esters, aromatic
hydrocarbons, esters (butylbenzyl phthalate, for example), and
polybutenyl succinic anhydride. Additives of this type are
commercially available. In one embodiment of the present invention,
such additives are used in an amount of about 0.01 to 3 weight
percent, preferably about 0.01 to 2 weight percent.
[0152] Anti-Foam Agents
[0153] Anti-foam agents may advantageously be added to lubricant
compositions. These agents retard the formation of stable foams.
Silicones and organic polymers are typical anti-foam agents. For
example, polysiloxanes, such as silicon oil or polydimethyl
siloxane, provide anti-foam properties. Anti-foam agents are
commercially available and may be used in conventional minor
amounts along with other additives such as demulsifiers. Usually
the amount of these additives combined is less than 1 percent and
often less than 0.1 percent.
[0154] Inhibitors and Anti-Rust Additives
[0155] Anti-rust additives (or corrosion inhibitors) are additives
that protect lubricated metal surfaces against chemical attack by
water or other contaminants. A wide variety of these are
commercially available; they are referred to also in Klamann in
Lubricants and Related Products, op cit.
[0156] One type of anti-rust additive is a polar compound that wets
the metal surface preferentially, protecting it with a film of oil.
Another type of anti-rust additive absorbs water by incorporating
it in a water-in-oil emulsion so that only the oil touches the
metal surface. Yet another type of anti-rust additive chemically
adheres to the metal to produce a non-reactive surface. Examples of
suitable additives include zinc dithiophosphates, metal phenolates,
basic metal sulfonates, fatty acids and amines. In one embodiment
of the present invention, such additives are used in an amount of
about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight
percent.
[0157] Typical Additive Amounts
[0158] When lubricating oil compositions contain one or more of the
additives discussed above, the additive(s) are blended into the
composition in an amount sufficient for it to perform its intended
function. Typical amounts of such additives useful in the present
invention are shown in Table 7 below.
[0159] Note that many of the additives are shipped from the
manufacturer and used with a certain amount of processing oil
solvent in the formulation. Accordingly, the weight amounts in
Table 7, as well as other amounts mentioned in this patent, are
directed to the amount of active ingredient (that is the
non-solvent portion of the ingredient). The weight percents
indicated below are based on the total weight of the lubricating
oil composition. TABLE-US-00008 TABLE 7 Typical Amounts of Various
Lubricant Components Approximate Weight Approximate Weight Compound
Percent (Useful) Percent (Preferred) Detergent 0.01-6 0.01-4
Dispersant 0.1-20 0.1-8 Friction Reducer 0.01-5 0.01-1.5 Viscosity
Index 0.01-40 0.01-30, Improver preferably 0.01-15 Antioxidant
0.01-5 0.01-2.0 Corrosion Inhibitor 0.01-5 0.01-1.5 Anti-wear
Additive 0.01-6 0.01-4 Pour Point Depressant 0.01-5 0.01-1.5
Anti-foam Agent 0.001-3 0.001-0.20 Base stock Balance Balance
[0160] Important physical properties set forth herein were
determined in accordance with the following methods.
[0161] Kinematic Viscosity (K.V.) were measured according to ASTM
D445 at the temperature indicated (e.g., 100.degree. C. or
-40.degree. C.).
[0162] Viscosity Index (VI) was determined according to ASTM
D-2270.
[0163] Noack volatility was determined according to the ASTM D5800
method, with the exception that the thermometer calibration is
performed annually rather than biannually.
[0164] Pour point was determined according to ASTM D5950.
[0165] Cold Crank Simulator (CCS) test was determined according to
ASTM D5293.
[0166] Trade names used herein are indicated by a .TM. symbol or
.RTM. symbol, indicating that the names may be protected by certain
trademark rights, e.g., they may be registered trademarks in
various jurisdictions.
[0167] All patents and patent applications, test procedures (such
as ASTM methods, and the like), and other documents cited herein
are fully incorporated by reference to the extent such disclosure
is not inconsistent with this invention and for all jurisdictions
in which such incorporation is permitted.
[0168] When numerical lower limits and numerical upper limits are
listed herein, ranges from any lower limit to any upper limit are
contemplated. While the illustrative embodiments of the invention
have been described with particularity, it will be understood that
various other modifications will be apparent to and can be readily
made by those skilled in the art without departing from the spirit
and scope of the invention. Accordingly, it is not intended that
the scope of the claims appended hereto be limited to the examples
and descriptions set forth herein but rather that the claims be
construed as encompassing all the features of patentable novelty
which reside in the present invention, including all features which
would be treated as equivalents thereof by those skilled in the art
to which the invention pertains.
[0169] The invention has been described above with reference to
numerous embodiments and specific examples. Many variations will
suggest themselves to those skilled in this art in light of the
above detailed description. All such obvious variations are within
the full intended scope of the appended claims.
* * * * *