U.S. patent application number 16/021213 was filed with the patent office on 2019-01-03 for lubricating oil compositions containing detergent compounds.
The applicant listed for this patent is Chevron Oronite Company LLC, CHEVRON ORONITE TECHNOLOGY B.V. Invention is credited to Alexander Bowman Boffa, Curtis Bay Campbell, Walter Alexander Hartgers, Seyedeh Mahboobeh Hosseini.
Application Number | 20190002791 16/021213 |
Document ID | / |
Family ID | 63080224 |
Filed Date | 2019-01-03 |
United States Patent
Application |
20190002791 |
Kind Code |
A1 |
Boffa; Alexander Bowman ; et
al. |
January 3, 2019 |
LUBRICATING OIL COMPOSITIONS CONTAINING DETERGENT COMPOUNDS
Abstract
The present disclosure generally relates to a lubricating oil
composition comprising: a major amount of an oil of lubricating
viscosity, and one or more detergents wherein at least one
detergent is an alkylhydroxybenzoate compound.
Inventors: |
Boffa; Alexander Bowman;
(Oakland, CA) ; Hartgers; Walter Alexander;
(Rotterdam, NL) ; Hosseini; Seyedeh Mahboobeh;
(Richmond, CA) ; Campbell; Curtis Bay; (Hercules,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chevron Oronite Company LLC
CHEVRON ORONITE TECHNOLOGY B.V |
San Ramon
San Ramon |
CA
CA |
US
US |
|
|
Family ID: |
63080224 |
Appl. No.: |
16/021213 |
Filed: |
June 28, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62527089 |
Jun 30, 2017 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2219/068 20130101;
C10N 2020/071 20200501; C10M 2207/262 20130101; C10M 141/08
20130101; C10M 2219/046 20130101; C10N 2030/12 20130101; C10N
2030/52 20200501; C10M 2223/045 20130101; C10N 2010/12 20130101;
C10M 2207/26 20130101; C10N 2030/06 20130101; C10N 2030/04
20130101; C10M 169/04 20130101; C10N 2030/54 20200501; C10M 129/54
20130101; C10M 135/10 20130101; C10M 129/50 20130101; C10M 2207/262
20130101; C10N 2010/04 20130101; C10M 2223/045 20130101; C10N
2010/04 20130101; C10M 2207/262 20130101; C10N 2010/04 20130101;
C10M 2223/045 20130101; C10N 2010/04 20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04; C10M 129/54 20060101 C10M129/54; C10M 135/10 20060101
C10M135/10; C10M 129/50 20060101 C10M129/50; C10M 141/08 20060101
C10M141/08 |
Claims
1. A lubricating oil composition comprising: (a) a major amount of
an oil of lubricating viscosity, and (b) one or more detergents
comprising at least one alkylhydroxybenzoate compound derived from
isomerized normal alpha olefin (NAO) having from about 10 to about
40 carbon atoms, wherein the TBN of the alkylhydroxybenzoate
compound is at least 600 mgKOH/gm on an actives basis.
2. The lubricating oil composition of claim 1 wherein the TBN of
the alkylhydroxybenzoate compound is 600-800 mgKOH/gm on an actives
basis.
3. The lubricating oil composition as in claim 1 further comprising
one or more detergents selected from an alkali or an alkali earth
metal sulfonate, phenate, or a salixarate, a saligenin, or a
complex detergent, carboxylate or a salicylate, that is derived
from an alkyl group with 20-40 carbon atoms and different from the
alkylhydroxybenzoate detergent compound in claim 1.
4. The lubricating oil composition as in claim 3, wherein the one
more detergent is an alkali or alkali earth metal sulfonate with a
TBN of 10-700 mgKOH/gm.
5. The lubricating oil composition as in claim 3, where the one
more detergent is an alkali or alkali earth metal phenate with TBN
100-600 mgKOH/gm.
6. The lubricating oil composition as in claim 3, where one more
detergent is an alkali or an alkali earth metal
alkylhydroxybenzoate derived from an alkyl group with 20-28 carbon
atoms and having a TBN of 10-590 mgKOH/gm.
7. The lubricating oil composition of claim 1, wherein the
isomerized normal alpha olefin has an isomerization level (I) of
the normal alpha olefin of from about 0.1 to about 0.4.
8. The lubricating oil composition of claim 1, further comprising
an additional detergent.
9. The lubricating oil composition of claim 8, wherein the
additional detergent is an alkylhydroxybenzoate, a phenate, a
sulfonate, or a combination thereof.
10. The lubricating oil composition of claim 9, wherein the
detergent is derived from a NAO, isomerized NAO, or a combination
thereof.
11. The lubricating oil composition of claim 10, wherein the
detergent is a magnesium alkylhydroxybenzoate derived from an
isomerized NAO.
12. The lubricating oil of claim 9, wherein the sulfonate is a
calcium sulfonate or a magnesium sulfonate.
13. A method of lubricating an engine comprising lubricating said
engine with a lubricating oil composition comprising: (a) a major
amount of an oil of lubricating viscosity, (b) one or more
detergents comprising at least one alkylhydroxybenzoate compound
derived from isomerized normal alpha olefin (NAO) having from about
10 to 40 carbon atoms, wherein the TBN of the alkylhydroxybenzoate
compound is at least 600 mgKOH/gm on an actives basis.
14. The method of claim 13 wherein the TBN of the
alkylhydroxybenzoate compound is 600-800 mgKOH/gm on an actives
basis.
15. The method of claim 13 wherein the lubricating oil composition
further comprises one or more detergents selected from an alkali or
an alkali earth metal sulfonate, phenate, or a salixarate, a
saligenin, or a complex detergent, carboxylate or a salicylate,
that is derived from an alkyl group with 20-40 carbon atoms and
different from the alkylhydroxybenzoate detergent compound in claim
1.
16. The method of claim 15 wherein the one more detergent is an
alkali or alkali earth metal sulfonate with a TBN of 10-700
mgKOH/gm.
17. The method of claim 15 wherein the one more detergent is an
alkali or alkali earth metal phenate with a TBN 100-600
mgKOH/gm.
18. The method of claim 15 wherein the where one more detergent is
an alkali or an alkali earth metal alkylhydroxybenzoate derived
from an alkyl group with 20-28 carbon atoms and having a TBN of
10-590 mgKOH/gm.
19. The method of claim 13 wherein the isomerized normal alpha
olefin has an isomerization level (I) of the normal alpha olefin of
from about 0.1 to about 0.4.
20. The method of claim 13 wherein the lubricating oil composition
further comprises an additional detergent.
21. The method of claim 20 wherein the additional detergent is an
alkylhydroxybenzoate, a phenate, a sulfonate, or a combination
thereof.
22. The method of claim 21 wherein the detergent is derived from a
NAO, isomerized NAO, or a combination thereof.
23. The method of claim 22 wherein the detergent is a magnesium
alkylhydroxybenzoate derived from an isomerized NAO.
24. The method of claim 21 wherein the wherein the sulfonate is a
calcium sulfonate or a magnesium sulfonate.
Description
[0001] This application claims the benefit of and priority to U.S.
Provisional Application Ser. No. 62/527,089, filed Jun. 30,
2017.
BACKGROUND OF THE DISCLOSURE
[0002] Overbased detergents are well described to provide
lubricating properties. Often such detergent additives are
proportioned with other lubricating additives to provide
lubricating oil compositions that exhibit certain desired
lubricating properties. Metal-containing detergents function both
as detergents to control deposits, and as acid neutralizers or rust
inhibitors, thereby reducing wear, controlling corrosion, and
extending engine life.
[0003] The present disclosure generally relates to lubricating oil
compositions which simultaneously achieve wear control and
corrosion inhibition, while also achieving improved fuel economy.
The lubricating oil compositions are suitable for automotive
engines, motorcycle engines, natural gas engines, dual fuel
engines, railroad locomotive engines, mobile natural gas engines,
and as functional fluids for automotive and industrial
applications.
[0004] Among other factors, the present invention is based on the
surprising discovery that a lubricating oil composition containing
more highly overbased metal hydroxybenzoate detergent, having a TBN
of 600 mgKOH/g or greater on an actives basis, exhibits improved
lubricating properties such as superior performance at low
temperatures, BN retention, oxidative and thermal stability,
corrosion resistance, and oxidative and thermal stability, in
addition to providing a more cost effective formulating approach
over the use of overbased hydroxybenzoate detergent technology
previously described in the art.
SUMMARY OF THE DISCLOSURE
[0005] In accordance with one embodiment of the present disclosure,
there is provided a lubricating oil composition which comprises:
[0006] (a) a major amount of an oil of lubricating viscosity, and
[0007] (b) one or more detergents comprising at least one
alkylhydroxybenzoate compound derived from isomerized NAO having
from about 10 to about 40 carbon atoms, [0008] wherein the TBN of
the alkylhydroxybenzoate compound is at least 600 mgKOH/gm on an
actives basis.
[0009] Also provided is a method of lubricating an engine
comprising lubricating said engine with a lubricating oil
composition comprising: [0010] (a) a major amount of an oil of
lubricating viscosity, [0011] (b) one or more detergents comprising
at least one alkylhydroxybenzoate compound derived from isomerized
NAO having from about 10 to 40 carbon atoms, [0012] wherein the TBN
of the alkylhydroxybenzoate compound is at least 600 mgKOH/gm on an
actives basis.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0013] While the invention is susceptible to various modifications
and alternative forms, specific embodiments thereof are herein
described in detail. It should be understood, however, that the
description herein of specific embodiments is not intended to limit
the invention to the particular forms disclosed, but on the
contrary, the intention is to cover all modifications, equivalents,
and alternatives falling within the spirit and scope of the
invention as defined by the appended claims.
[0014] To facilitate the understanding of the subject matter
disclosed herein, a number of terms, abbreviations or other
shorthand as used herein are defined below. Any term, abbreviation
or shorthand not defined is understood to have the ordinary meaning
used by a skilled artisan contemporaneous with the submission of
this application.
Definitions
[0015] As used herein, the following terms have the following
meanings, unless expressly stated to the contrary. In this
specification, the following words and expressions, if and when
used, have the meanings given below.
[0016] A "major amount" means in excess of 50 weight % of a
composition.
[0017] A "minor amount" means less than 50 weight % of a
composition, expressed in respect of the stated additive and in
respect of the total mass of all the additives present in the
composition, reckoned as active ingredient of the additive or
additives.
[0018] "Active ingredients" or "actives" or "oil free" refers to
additive material that is not diluent or solvent.
[0019] All percentages reported are weight % on an active
ingredient basis (i.e., without regard to carrier or diluent oil)
unless otherwise stated.
[0020] The abbreviation "ppm" means parts per million by weight,
based on the total weight of the lubricating oil composition.
[0021] Total base number (TBN) was determined in accordance with
ASTM D2896.
[0022] Metal--The term "metal" refers to alkali metals, alkaline
earth metals, or mixtures thereof.
[0023] High temperature high shear (HTHS) viscosity at 150.degree.
C. was determined in accordance with ASTM D4863.
[0024] Kinematic viscosity at 100.degree. C. (KV.sub.100) was
determined in accordance with ASTM D445.
[0025] Cold Cranking Simulator (CCS) viscosity at -35.degree. C.
was determined in accordance with ASTM D5293.
[0026] Olefins--The term "olefins" refers to a class of unsaturated
aliphatic hydrocarbons having one or more carbon-carbon double
bonds, obtained by a number of processes. Those containing one
double bond are called mono-alkenes, and those with two double
bonds are called dienes, alkyldienes, or diolefins. Alpha olefins
are particularly reactive because the double bond is between the
first and second carbons. Examples are 1-octene and 1-octadecene,
which are used as the starting point for medium-biodegradable
surfactants. Linear and branched olefins are also included in the
definition of olefins.
[0027] Normal Alpha Olefins--The term "Normal Alpha Olefins" refers
to olefins which are straight chain, non-branched hydrocarbons with
carbon-carbon double bond present in beginning and end of the
chain.
[0028] Isomerized Normal Alpha Olefin. The term "Isomerized Normal
Alpha Olefin." as used herein refers to an alpha olefin that has
been subjected to isomerization conditions which results in an
alteration of the distribution of the olefin species present and/or
the introduction of branching along the alkyl chain. The isomerized
olefin product may be obtained by isomerizing a linear alpha olefin
containing from about 10 to about 40 carbon atoms, preferably from
about 20 to about 28 carbon atoms, and preferably from about 20 to
about 24 carbon atoms.
[0029] All ASTM standards referred to herein are the most current
versions as of the filing date of the present application.
[0030] In one aspect, the present disclosure is directed to a
lubricating oil composition comprising: [0031] (a) a major amount
of an oil of lubricating viscosity, and [0032] (b) one or more
detergents comprising at least one alkylhydroxybenzoate compound
derived from isomerized normal alpha olefins having from about 10
to 40 carbon atoms, [0033] wherein the TBN of the
alkylhydroxybenzoate compound is at least 600 mgKOH/gm on an
actives basis.
[0034] In another aspect, provided is a method of lubricating an
engine comprising lubricating said engine with a lubricating oil
composition comprising: [0035] (a) a major amount of an oil of
lubricating viscosity, and [0036] (b) one or more detergents
comprising at least one alkylhydroxybenzoate compound derived from
isomerized normal alpha olefins having from about 10 to 40 carbon
atoms, [0037] wherein the TBN of the alkylhydroxybenzoate compound
is at least 600 mgKOH/gm on an actives basis.
[0038] Alkylhydroxybenzoate Detergent compound derived from C10-C40
isomerized Normal Alpha Olefin (NAO)
[0039] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent compound derived from
C.sub.10-C.sub.40 isomerized NAO has a TBN of at least 600, 600 or
greater, from 600-800, 600-750, 600-700 mgKOH/gram on an actives
basis.
[0040] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent derived from C.sub.10-C.sub.40
isomerized NAO with a TBN of 600 mgKOH/gram or greater on an
oil-free basis can be prepared as described in U.S. Pat. No.
8,993,499 which is herein incorporated in its entirety.
[0041] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent derived from C.sub.10-C.sub.40
isomerized NAO is a Ca alkylhydroxybenzoate detergent.
[0042] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent derived from C.sub.10-C.sub.40
isomerized NAO can be an alkylated hydroxybenzoate detergent. In
one embodiment, the detergent can be a salicylate detergent. In
another embodiment, the detergent can be a carboxylate detergent.
In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent with a TBN of 600 mgKOH/gram or greater on an oil-free
basis is made from an alkylphenol having an alkyl group derived
from an isomerized alpha olefin having from about 14 to about 28,
or from about 20 to about 24 carbon atoms per molecule.
[0043] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent derived from C.sub.10-C.sub.40
isomerized NAO with a TBN of 600 mgKOH/gram or greater on an
actives basis is made from one or more alkylphenols with an alkyl
group derived from C.sub.10-C.sub.40 isomerized NAO and one or more
alkylphenols with an alkyl group different from C.sub.10-C.sub.40
isomerized NAO. Preferably the one or more alkylphenols with an
alkyl group different from C.sub.10-C.sub.40 isomerized NAO has a
highly branched alkyl group of at least 9 carbon atoms, from 9 to
24, and from 10-15 carbon atoms. In one aspect of the present
disclosure, the lubricating oil composition comprises about 0.01 to
2 wt. % in terms of Ca content of the alkylhydroxybenzoate
detergent derived from C.sub.10-C.sub.40 isomerized NAO with a TBN
of 600 mgKOH/gram or greater on an actives basis, preferably 0.1 to
1 wt. %, more preferably 0.05 to 0.5 wt. %, more preferably 0.1 to
0.5 wt %. In one aspect of the present disclosure, the lubricating
oil composition comprises the alkylhydroxybenzoate derived from
C.sub.10-C.sub.40 isomerized NAO with TBN 600 or more on an active
basis is an automotive engine oil, a gas engine oil, a motorcycle
oil, a dual fuel engine oil, a mobile gas engine oil, or a
locomotive engine oil.
[0044] In one aspect of the present disclosure, the lubricating oil
composition comprises the alkylhydroxybenzoate derived from
C.sub.10-C.sub.40 isomerized NAO with a TBN of 600 mgKOH/gram or
more on an oil-free basis is a functional fluid for automotive and
industrial applications, such as transmission oil, hydraulic oil,
tractor fluid, gear oil, et. In one aspect of the present
disclosure, the lubricating oil composition comprises the
alkylhydroxybenzoate derived from C.sub.10-C.sub.40 isomerized NAO
with a TBN of 600 mgKOH/gram or more on an actives basis is a
multi-grade oil.
[0045] In one aspect of the present disclosure, the lubricating oil
composition comprises the alkylhydroxybenzoate derived from
C.sub.10-C.sub.40 isomerized NAO with a TBN of 600 mgKOH/gram or
more on an actives basis lubricates crankcase, gear as well as
clutches.
Additional Detergents
[0046] The lubricating oil composition of the present invention can
further contain one or more overbased detergents having a TBN of
10-800, 10-700, 30-690, 100-600, 150-600, 150-500, 200-450 mg KOH/g
on an actives basis.
[0047] Detergents that may be used include oil-soluble overbased
sulfonate, non-sulfur containing phenate, sulfurized phenates,
salixarate, salicylate, saligenin, complex detergents and
naphthenate detergents and other oil-soluble alkylhydroxybenzoates
of a metal, particularly the alkali or alkaline earth metals, e.g.,
barium, sodium, potassium, lithium, calcium, and magnesium. The
most commonly used metals are calcium and magnesium, which may both
be present in detergents used in a lubricant, and mixtures of
calcium and/or magnesium with sodium.
[0048] Overbased metal detergents are generally produced by
carbonating a mixture of hydrocarbons, detergent acid, for example:
sulfonic acid, alkylhydroxybenzoate etc., metal oxide or hydroxides
(for example calcium oxide or calcium hydroxide) and promoters such
as xylene, methanol and water. For example, for preparing an
overbased calcium sulfonate, in carbonation, the calcium oxide or
hydroxide reacts with the gaseous carbon dioxide to form calcium
carbonate. The sulfonic acid is neutralized with an excess of CaO
or Ca(OH).sub.2, to form the sulfonate.
[0049] Overbased detergents may be low overbased, e.g., an
overbased salt having a TBN below 100 on an actives basis. In one
embodiment, the TBN of a low overbased salt may be from about 30 to
about 100. In another embodiment, the TBN of a low overbased salt
may be from about 30 to about 80. Overbased detergents may be
medium overbased, e.g., an overbased salt having a TBN from about
100 to about 250. In one embodiment, the TBN of a medium overbased
salt may be from about 100 to about 200. In another embodiment, the
TBN of a medium overbased salt may be from about 125 to about 175.
Overbased detergents may be high overbased, e.g., an overbased salt
having a TBN above 250. In one embodiment, the TBN of a high
overbased salt may be from about 250 to about 800 on an actives
basis.
[0050] In one embodiment, the detergent can be one or more alkali
or alkaline earth metal salts of an alkyl-substituted
hydroxyaromatic carboxylic acid. Suitable hydroxyaromatic compounds
include mononuclear monohydroxy and polyhydroxy aromatic
hydrocarbons having 1 to 4, and preferably 1 to 3, hydroxyl groups.
Suitable hydroxyaromatic compounds include phenol, catechol,
resorcinol, hydroquinone, pyrogallol, cresol, and the like. The
preferred hydroxyaromatic compound is phenol.
[0051] The alkyl substituted moiety of the alkali or alkaline earth
metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid
is derived from an alpha olefin having from about 10 to about 80
carbon atoms. The olefins employed may be linear, isomerized
linear, branched or partially branched linear. The olefin may be a
mixture of linear olefins, a mixture of isomerized linear olefins,
a mixture of branched olefins, a mixture of partially branched
linear or a mixture of any of the foregoing.
[0052] In one embodiment, the mixture of linear olefins that may be
used is a mixture of normal alpha olefins selected from olefins
having from about 10 to about 40 carbon atoms per molecule. In one
embodiment, the normal alpha olefins are isomerized using at least
one of a solid or liquid catalyst.
[0053] In one embodiment, at least about 50 mole %, at least about
75 mole %, at least about 80 mole %, at least about 85 mole %, at
least about 90 mole %, at least about 95 mole % of the alkyl groups
contained within the alkali or alkaline earth metal salt of an
alkyl-substituted hydroxyaromatic carboxylic acid such as the alkyl
groups of an alkaline earth metal salt of an alkyl-substituted
hydroxybenzoic acid detergent are a C.sub.20 or higher. In another
embodiment, the alkali or alkaline earth metal salt of an
alkyl-substituted hydroxyaromatic carboxylic acid is an alkali or
alkaline earth metal salt of an alkyl-substituted hydroxybenzoic
acid that is derived from an alkyl-substituted hydroxybenzoic acid
in which the alkyl groups are C.sub.20 to about C.sub.28 normal
alpha-olefins. In another embodiment, the alkyl group is derived
from at least two alkylated phenols. The alkyl group on at least
one of the at least two alkyl phenols is derived from an isomerized
alpha olefin. The alkyl group on the second alkyl phenol may be
derived from branched or partially branched olefins, highly
isomerized olefins or mixtures thereof.
[0054] In another embodiment, the alkali or alkaline earth metal
salt of an alkyl-substituted hydroxyaromatic carboxylic acid is a
salicylate derived from an alkyl group with 20-40 carbon atoms,
preferably 20-28 carbon atoms, more preferably, isomerized 20-24
NAO.
[0055] Sulfonates may be prepared from sulfonic acids which are
typically obtained by the sulfonation of alkyl substituted aromatic
hydrocarbons such as those obtained from the fractionation of
petroleum or by the alkylation of aromatic hydrocarbons. Examples
included those obtained by alkylating benzene, toluene, xylene,
naphthalene, diphenyl or their halogen derivatives. The alkylation
may be carried out in the presence of a catalyst with alkylating
agents having from about 3 to more than 70 carbon atoms. The
alkaryl sulfonates usually contain from about 9 to about 80 or more
carbon atoms, preferably from about 16 to about 60 carbon atoms,
preferably about 16 to 30 carbon atoms, and more preferably 20-24
carbon atoms per alkyl substituted aromatic moiety.
[0056] Metal salts of phenols and sulfurized phenols, which are
sulfurized phenate detergents, are prepared by reaction with an
appropriate metal compound such as an oxide or hydroxide and
neutral or overbased products may be obtained by methods well known
in the art. Sulfurized phenols may be prepared by reacting a phenol
with sulfur or a sulfur containing compound such as hydrogen
sulfide, sulfur monohalide or sulfur dihalide, to form products
which are generally mixtures of compounds in which 2 or more
phenols are bridged by sulfur containing bridges.
[0057] Additional details regarding the general preparation of
sulfurized phenates can be found in, for example, U.S. Pat. Nos.
2,680,096; 3,178,368, 3,801,507, and 8,580,717 the contents of
which are incorporated herein by reference.
[0058] Considering now in detail, the reactants and reagents used
in the present process, first all allotropic forms of sulfur can be
used. The sulfur can be employed either as molten sulfur or as a
solid (e.g., powder or particulate) or as a solid suspension in a
compatible hydrocarbon liquid.
[0059] It is desirable to use calcium hydroxide as the calcium base
because of its handling convenience versus, for example, calcium
oxide, and also because it affords excellent results. Other calcium
bases can also be used, for example, calcium alkoxides.
[0060] Suitable alkylphenols which can be used are those wherein
the alkyl substituents contain a sufficient number of carbon atoms
to render the resulting overbased sulfurized calcium alkylphenate
composition oil-soluble. Oil solubility may be provided by a single
long chain alkyl substitute or by a combination of alkyl
substituents. Typically, the alkylphenol used will be a mixture of
different alkylphenols, e.g., C.sub.20 to C.sub.24 alkylphenol.
[0061] In one embodiment, suitable alkyl phenolic compounds will be
derived from isomerized alpha olefin alkyl groups having from about
10 to about 40 carbon atoms per molecule, having an isomerized
level (1) of the alpha olefin between from about 0.1 to about 0.4.
In one embodiment, suitable alkyl phenolic compounds will be
derived from alkyl groups which are branched olefinic propylene
oligomers or mixture thereof having from about 9 to about 80 carbon
atoms. In one embodiment, the branched olefinic propylene oligomer
or mixtures thereof have from about 9 to about 40 carbon atoms. In
one embodiment, the branched olefinic propylene oligomer or
mixtures thereof have from about 9 to about 18 carbon atoms. In one
embodiment, the branched olefinic propylene oligomer or mixtures
thereof have from about 9 to about 12 carbon atoms.
[0062] In one embodiment, suitable alkyl phenolic compounds
comprise distilled cashew nut shell liquid (CNSL) or hydrogenated
distilled cashew nut shell liquid. Distilled CNSL is a mixture of
biodegradable meta-hydrocarbyl substituted phenols, where the
hydrocarbyl group is linear and unsaturated, including cardanol.
Catalytic hydrogenation of distilled CNSL gives rise to a mixture
of meta-hydrocarbyl substituted phenols predominantly rich in
3-pentadecylphenol.
[0063] The alkylphenols can be para-alkylphenols, meta-alkylphenols
or ortho alkylphenols. Since it is believed that p-alkylphenols
facilitate the preparation of highly overbased calcium sulfurized
alkylphenate where overbased products are desired, the alkylphenol
is preferably predominantly a para alkylphenol with no more than
about 45 mole percent of the alkylphenol being ortho alkylphenols;
and more preferably no more than about 35 mole percent of the
alkylphenol is ortho alkylphenol. Alkyl-hydroxy toluenes or
xylenes, and other alkyl phenols having one or more alkyl
substituents in addition to at least one long chained alkyl
substituent can also be used. In the case of distilled cashew nut
shell liquid, the catalytic hydrogenation of distilled CNSL gives
rise to a mixture of meta-hydrocarbyl substituted phenols.
[0064] In one embodiment, the one or more overbased detergent can
be a complex or hybrid detergent which is known in the art as
comprising a surfactant system derived from at least two
surfactants described above.
[0065] In one embodiment, the one or more overbased detergent can
be a salicylate with an alkyl group having 20-28 carbon atoms, more
preferably 20-24C carbon atoms. In another embodiment, the one or
more overbased detergent can be a salicylate with an alkyl group
derived from C.sub.14-18NAO and contribute less than 0.05 wt %,
preferably less than 0.025 wt %, more preferably less than 0.01 wt
% in terms of Ca content to the lubricating oil.
[0066] Generally, the amount of the detergent can be from about
0.001 wt. % to about 50 wt. %, or from about 0.05 wt. % to about 25
wt. %, or from about 0.1 wt. % to about 20 wt. %, or from about
0.01 to 15 wt. % based on the total weight of the lubricating oil
composition.
[0067] Antiwear Agents
[0068] The lubricating oil composition disclosed herein can
comprise one or more antiwear agent. Antiwear agents reduce wear of
metal parts. Suitable anti-wear agents include dihydrocarbyl
dithiophosphate metal salts such as zinc dihydrocarbyl
dithiophosphates (ZDDP) of formula (Formula 1):
Zn[S--P(.dbd.S)(OR.sup.1)(OR.sup.2)].sub.2 Formula 1,
[0069] wherein R.sup.1 and R.sup.2 may be the same of different
hydrocarbyl radicals having from 1 to 18 (e.g., 2 to 12) carbon
atoms and including radicals such as alkyl, alkenyl, aryl,
arylalkyl, alkaryl and cycloaliphatic radicals. Particularly
preferred as R.sup.1 and R.sup.2 groups are alkyl groups having
from 2 to 8 carbon atoms (e.g., the alkyl radicals may be ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl,
isopentyl, n-hexyl, isohexyl, 2-ethylhexyl). In order to obtain oil
solubility, the total number of carbon atoms (i.e.,
R.sup.1+R.sup.2) will be at least 5. The zinc dihydrocarbyl
dithiophosphate can therefore comprise zinc dialkyl
dithiophosphates. The zinc dialkyl dithiophosphate is a primary,
secondary zinc dialkyl dithiophosphate, or a combination thereof.
ZDDP may be present at 3 wt. % or less (e.g., 0.1 to 1.5 wt. %, or
0.5 to 1.0 wt %) of the lubricating oil composition. In one
embodiment, the lubricating oil composition containing the
magnesium salicylate detergent described herein further comprises
an antioxidant compound. In one embodiment, the antioxidant is a
diphenylamine antioxidant. In another embodiment, the antioxidant
is a hindered phenol antioxidant. In yet another embodiment, the
antioxidant is a combination of a diphenylamine antioxidant and a
hindered phenol antioxidant.
[0070] Antioxidants
[0071] The lubricating oil composition disclosed herein can
comprise one or more antioxidant. Antioxidants reduce the tendency
of mineral oils during to deteriorate during service. Oxidative
deterioration can be evidenced by sludge in the lubricant,
varnish-like deposits on the metal surfaces, and by viscosity
growth. Suitable antioxidants include hindered phenols, aromatic
amines, and sulfurized alkylphenols and alkali and alkaline earth
metals salts thereof.
[0072] The hindered phenol antioxidant often contains a secondary
butyl and/or a tertiary butyl group as a sterically hindering
group. The phenol group may be further substituted with a
hydrocarbyl group (typically linear or branched alkyl) and/or a
bridging group linking to a second aromatic group. Examples of
suitable hindered phenol antioxidants include
2,6-di-tert-butylphenol; 4-methyl-2,6-di-tert-butylphenol;
4-ethyl-2,6-di-tert-butylphenol; 4-propyl-2,6-di-tert-butylphenol;
4-butyl-2,6-di-tert-butylphenol; and
4-dodecyl-2,6-di-tert-butylphenol. Other useful hindered phenol
antioxidants include 2,6-di-alkyl-phenolic propionic ester
derivatives such as IRGANOX.RTM. L-135 from Ciba and bis-phenolic
antioxidants such as 4,4'-bis(2,6-di-tert-butylphenol) and
4,4'-methylenebis(2,6-di-tert-butylphenol). Typical aromatic amine
antioxidants have at least two aromatic groups attached directly to
one amine nitrogen. Typical aromatic amine antioxidants have alkyl
substituent groups of at least 6 carbon atoms. Particular examples
of aromatic amine antioxidants useful herein include
4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octyphenyl)-1-naphthylamine,
and N-(4-octylphenyl)-1-naphthylamine. Antioxidants may be present
at 0.01 to 5 wt. % (e.g., 0.1 to 2 wt. %) of the lubricating oil
composition.
Dispersants
[0073] The lubricating oil composition disclosed herein can
comprise one or more dispersant. Dispersants maintain in suspension
materials resulting from oxidation during engine operation that are
insoluble in oil, thus preventing sludge flocculation and
precipitation or deposition on metal parts. Dispersants useful
herein include nitrogen-containing, ashless (metal-free)
dispersants known to effective to reduce formation of deposits upon
use in gasoline and diesel engines.
[0074] Suitable dispersants include hydrocarbyl succinimides,
hydrocarbyl succinamides, mixed ester/amides of
hydrocarbyl-substituted succinic acid, hydroxyesters of
hydrocarbyl-substituted succinic acid, and Mannich condensation
products of hydrocarbyl-substituted phenols, formaldehyde and
polyamines. Also suitable are condensation products of polyamines
and hydrocarbyl-substituted phenyl acids. Mixtures of these
dispersants can also be used. Basic nitrogen-containing ashless
dispersants are well-known lubricating oil additives and methods
for their preparation are extensively described in the patent
literature. Preferred dispersants are the alkenyl succinimides and
succinamides where the alkenyl-substituent is a long-chain of
preferably greater than 40 carbon atoms. These materials are
readily made by reacting a hydrocarbyl-substituted dicarboxylic
acid material with a molecule containing amine functionality.
Examples of suitable amines are polyamines such as polyalkylene
polyamines, hydroxy-substituted polyamines and polyoxyalkylene
polyamines.
[0075] Particularly preferred ashless dispersants are the
polyisobutenyl succinimides formed from polyisobutenyl succinic
anhydride and a polyalkylene polyamine such as a polyethylene
polyamine of formula 2:
NH.sub.2(CH.sub.2CH.sub.2NH).sub.zH Formula 2,
wherein z is 1 to 11. The polyisobutenyl group is derived from
polyisobutene and preferably has a number average molecular weight
(M.sub.n) in a range of 700 to 3000 Daltons (e.g., 900 to 2500
Daltons). For example, the polyisobutenyl succinimide may be a
bis-succinimide derived from a polyisobutenyl group having a
M.sub.n of 900 to 2500 Daltons. As is known in the art, the
dispersants may be post-treated (e.g., with a boronating agent or a
cyclic carbonate, ethylene carbonate etc).
[0076] Nitrogen-containing ashless (metal-free) dispersants are
basic, and contribute to the TBN of a lubricating oil composition
to which they are added, without introducing additional sulfated
ash. Dispersants may be present at 0.1 to 10 wt. % (e.g., 2 to 5
wt. %) of the lubricating oil composition.
[0077] Foam Inhibitors
[0078] The lubricating oil composition disclosed herein can
comprise one or more foam inhibitor that can break up foams in
oils. Non-limiting examples of suitable foam inhibitors or
anti-foam inhibitors include silicone oils or
polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic
acids, polyethers (e.g., polyethylene glycols), branched polyvinyl
ethers, alkyl acrylate polymers, alkyl methacrylate polymers,
polyalkoxyamines and combinations thereof.
[0079] Additional Co-Additives
[0080] The lubricating oil compositions of the present disclosure
may also contain other conventional additives that can impart or
improve any desirable property of the lubricating oil composition
in which these additives are dispersed or dissolved. Any additive
known to a person of ordinary skill in the art may be used in the
lubricating oil compositions disclosed herein. Some suitable
additives have been described in Mortier et al., "Chemistry and
Technology of Lubricants", 2nd Edition, London, Springer, (1996);
and Leslie R. Rudnick, "Lubricant Additives: Chemistry and
Applications", New York, Marcel Dekker (2003), both of which are
incorporated herein by reference. For example, the lubricating oil
compositions can be blended with antioxidants, anti-wear agents,
detergents such as metal detergents, rust inhibitors, dehazing
agents, demulsifying agents, metal deactivating agents, friction
modifiers, pour point depressants, antifoaming agents, co-solvents,
corrosion-inhibitors, ashless dispersants, multifunctional agents,
dyes, extreme pressure agents and the like and mixtures thereof. A
variety of the additives are known and commercially available.
These additives, or their analogous compounds, can be employed for
the preparation of the lubricating oil compositions of the
disclosure by the usual blending procedures.
[0081] In the preparation of lubricating oil formulations it is
common practice to introduce the additives in the form of 10 to 100
wt. % active ingredient concentrates in hydrocarbon oil, e.g.
mineral lubricating oil, or other suitable solvent.
[0082] Usually these concentrates may be diluted with 3 to 100,
e.g., 5 to 40, parts by weight of lubricating oil per part by
weight of the additive package in forming finished lubricants, e.g.
crankcase motor oils. The purpose of concentrates, of course, is to
make the handling of the various materials less difficult and
awkward as well as to facilitate solution or dispersion in the
final blend.
[0083] Each of the foregoing additives, when used, is used at a
functionally effective amount to impart the desired properties to
the lubricant. Thus, for example, if an additive is a friction
modifier, a functionally effective amount of this friction modifier
would be an amount sufficient to impart the desired friction
modifying characteristics to the lubricant.
[0084] In general, the concentration of each of the additives in
the lubricating oil composition, when used, may range from about
0.001 wt. % to about 20 wt. %, from about 0.01 wt. % to about 15
wt. %, or from about 0.1 wt. % to about 10 wt. %, from about 0.005
wt. % to about 5 wt. %, or from about 0.1 wt. % to about 2.5 wt. %,
based on the total weight of the lubricating oil composition.
Further, the total amount of the additives in the lubricating oil
composition may range from about 0.001 wt. % to about 20 wt. %,
from about 0.01 wt. % to about 10 wt. %, or from about 0.1 wt. % to
about 5 wt. %, based on the total weight of the lubricating oil
composition.
[0085] Oil of Lubricating Viscosity
[0086] The oil of lubricating viscosity (sometimes referred to as
"base stock" or "base oil") is the primary liquid constituent of a
lubricant, into which additives and possibly other oils are
blended, for example to produce a final lubricant (or lubricant
composition). A base oil is useful for making concentrates as well
as for making lubricating oil compositions therefrom, and may be
selected from natural and synthetic lubricating oils and
combinations thereof.
[0087] Natural oils include animal and vegetable oils, liquid
petroleum oils and hydrorefined, solvent-treated mineral
lubricating oils of the paraffinic, naphthenic and mixed
paraffinic-naphthenic types. Oils of lubricating viscosity derived
from coal or shale are also useful base oils.
[0088] Synthetic lubricating oils include hydrocarbon oils such as
polymerized and interpolymerized olefins (e.g., polybutylenes,
polypropylenes, propylene-isobutylene copolymers, chlorinated
polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-decenes);
alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di(2-ethylhexyl)benzenes; polyphenols (e.g.,
biphenyls, terphenyls, alkylated polyphenols); and alkylated
diphenyl ethers and alkylated diphenyl sulfides and the
derivatives, analogues and homologues thereof.
[0089] Another suitable class of synthetic lubricating oils
comprises the esters of dicarboxylic acids (e.g., malonic acid,
alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl
succinic acids and alkenyl succinic acids, maleic acid, fumaric
acid, azelaic acid, suberic acid, sebacic acid, adipic acid,
linoleic acid dimer, phthalic acid) with a variety of alcohols
(e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol, ethylene glycol, diethylene glycol monoether, propylene
glycol). Specific examples of these esters include dibutyl adipate,
di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate,
diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl
phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic
acid dimer, and the complex ester formed by reacting one mole of
sebacic acid with two moles of tetraethylene glycol and two moles
of 2-ethylhexanoic acid.
[0090] Esters useful as synthetic oils also include those made from
C.sub.5 to C.sub.12 monocarboxylic acids and polyols, and polyol
ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol and tripentaerythritol.
[0091] The base oil may be derived from Fischer-Tropsch synthesized
hydrocarbons. Fischer-Tropsch synthesized hydrocarbons are made
from synthesis gas containing H2 and CO using a Fischer-Tropsch
catalyst. Such hydrocarbons typically require further processing in
order to be useful as the base oil. For example, the hydrocarbons
may be hydroisomerized; hydrocracked and hydroisomerized; dewaxed;
or hydroisomerized and dewaxed; using processes known to those
skilled in the art.
[0092] Unrefined, refined and re-refined oils can be used in the
present lubricating oil composition. Unrefined oils are those
obtained directly from a natural or synthetic source without
further purification treatment. For example, a shale oil obtained
directly from retorting operations, a petroleum oil obtained
directly from distillation or ester oil obtained directly from an
esterification process and used without further treatment would be
unrefined oil. Refined oils are similar to the unrefined oils
except they have been further treated in one or more purification
steps to improve one or more properties. Many such purification
techniques, such as distillation, solvent extraction, acid or base
extraction, filtration and percolation are known to those skilled
in the art.
[0093] Re-refined oils are obtained by processes similar to those
used to obtain refined oils applied to refined oils which have been
already used in service. Such re-refined oils are also known as
reclaimed or reprocessed oils and often are additionally processed
by techniques for approval of spent additive and oil breakdown
products.
[0094] Hence, the base oil which may be used to make the present
lubricating oil composition may be selected from any of the base
oils in Groups I-V as specified in the American Petroleum Institute
(API) Base Oil Interchangeability Guidelines (API Publication
1509). Such base oil groups are summarized in Table 1 below:
TABLE-US-00001 TABLE 1 Base Oil Properties Group.sup.(a)
Saturates.sup.(b), wt. % Sulfur.sup.(c), wt. % Viscosity
Index.sup.(d) Group I <90 and/or >0.03 80 to <120 Group II
.gtoreq.90 .ltoreq.0.03 80 to <120 Group III .gtoreq.90
.ltoreq.0.03 .gtoreq.120 Group IV Polyalphaolefins (PAOs) Group V
All other base stocks not included in Groups I, II, III or IV
.sup.(a)Groups I-III are mineral oil base stocks.
.sup.(b)Determined in accordance with ASTM D2007.
.sup.(c)Determined in accordance with ASTM D2622, ASTM D3120, ASTM
D4294 or ASTM D4927. .sup.(d)Determined in accordance with ASTM
D2270.
[0095] Base oils suitable for use herein are any of the variety
corresponding to API Group II, Group III, Group IV, and Group V
oils and combinations thereof, preferably the Group III to Group V
oils due to their exceptional volatility, stability, viscometric
and cleanliness features.
[0096] The oil of lubricating viscosity for use in the lubricating
oil compositions of this disclosure, also referred to as a base
oil, is typically present in a major amount, e.g., an amount of
greater than 50 wt. %, preferably greater than about 70 wt. %, more
preferably from about 80 to about 99.5 wt. % and most preferably
from about 85 to about 98 wt. %, based on the total weight of the
composition. The expression "base oil" as used herein shall be
understood to mean a base stock or blend of base stocks which is a
lubricant component that is produced by a single manufacturer to
the same specifications (independent of feed source or
manufacturer's location); that meets the same manufacturer's
specification; and that is identified by a unique formula, product
identification number, or both. The base oil for use herein can be
any presently known or later-discovered oil of lubricating
viscosity used in formulating lubricating oil compositions for any
and all such applications, e.g., engine oils, marine cylinder oils,
functional fluids such as hydraulic oils, gear oils, transmission
fluids, etc. Additionally, the base oils for use herein can
optionally contain viscosity index improvers, e.g., polymeric
alkylmethacrylates; olefinic copolymers, e.g., an
ethylene-propylene copolymer or a styrene-butadiene copolymer; and
the like and mixtures thereof.
[0097] As one skilled in the art would readily appreciate, the
viscosity of the base oil is dependent upon the application.
Accordingly, the viscosity of a base oil for use herein will
ordinarily range from about 2 to about 2000 centistokes (cSt) at
100.degree. Centigrade (C.). Generally, individually the base oils
used as engine oils will have a kinematic viscosity range at
100.degree. C. of about 2 cSt to about 30 cSt, preferably about 3
cSt to about 16 cSt, and most preferably about 4 cSt to about 12
cSt and will be selected or blended depending on the desired end
use and the additives in the finished oil to give the desired grade
of engine oil, e.g., a lubricating oil composition having an SAE
Viscosity Grade of 0W, 0W-8, 0W-12, 0W-16, 0W-20, 0W-26, 0W-30,
0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W,
10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40
and the like.
[0098] Lubricating Oil Compositions
[0099] In general, the level of sulfur in the lubricating oil
compositions of the present invention is less than or equal to
about 0.7 wt. %, based on the total weight of the lubricating oil
composition, e.g., a level of sulfur of about 0.01 wt. % to about
0.70 wt. %, 0.01 to 0.6 wt. %, 0.01 to 0.5 wt. %, 0.01 to 0.4 wt.
%, 0.01 to 0.3 wt. %, 0.01 to 0.2 wt. %, 0.01 wt. % to 0.10 wt. %.
In one embodiment, the level of sulfur in the lubricating oil
compositions of the present invention is less than or equal to
about 0.60 wt. %, less than or equal to about 0.50 wt. %, less than
or equal to about 0.40 wt. %, less than or equal to about 0.30 wt.
%, less than or equal to about 0.20 wt. %, less than or equal to
about 0.10 wt. % based on the total weight of the lubricating oil
composition.
[0100] In one embodiment, the levels of phosphorus in the
lubricating oil compositions of the present invention is less than
or equal to about 0.12 wt. %, based on the total weight of the
lubricating oil composition, e.g., a level of phosphorus of about
0.01 wt. % to about 0.12 wt. %. In one embodiment, the levels of
phosphorus in the lubricating oil compositions of the present
invention is less than or equal to about 0.11 wt. %, based on the
total weight of the lubricating oil composition, e.g., a level of
phosphorus of about 0.01 wt. % to about 0.11 wt. %. In one
embodiment, the levels of phosphorus in the lubricating oil
compositions of the present invention is less than or equal to
about 0.10 wt. %, based on the total weight of the lubricating oil
composition, e.g., a level of phosphorus of about 0.01 wt. % to
about 0.10 wt. %. In one embodiment, the levels of phosphorus in
the lubricating oil compositions of the present invention is less
than or equal to about 0.09 wt. %, based on the total weight of the
lubricating oil composition, e.g., a level of phosphorus of about
0.01 wt. % to about 0.09 wt. %. In one embodiment, the levels of
phosphorus in the lubricating oil compositions of the present
invention is less than or equal to about 0.08 wt. %, based on the
total weight of the lubricating oil composition, e.g., a level of
phosphorus of about 0.01 wt. % to about 0.08 wt. %. In one
embodiment, the levels of phosphorus in the lubricating oil
compositions of the present invention is less than or equal to
about 0.07 wt. %, based on the total weight of the lubricating oil
composition, e.g., a level of phosphorus of about 0.01 wt. % to
about 0.07 wt. %. In one embodiment, the levels of phosphorus in
the lubricating oil compositions of the present invention is less
than or equal to about 0.05 wt. %, based on the total weight of the
lubricating oil composition, e.g., a level of phosphorus of about
0.01 wt. % to about 0.05 wt. %.
[0101] In one embodiment, the level of sulfated ash produced by the
lubricating oil compositions of the present invention is less than
or equal to about 1.60 wt. % as determined by ASTM D 874, e.g., a
level of sulfated ash of from about 0.10 to about 1.60 wt. % as
determined by ASTM D 874. In one embodiment, the level of sulfated
ash produced by the lubricating oil compositions of the present
invention is less than or equal to about 1.00 wt. % as determined
by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to
about 1.00 wt. % as determined by ASTM D 874. In one embodiment,
the level of sulfated ash produced by the lubricating oil
compositions of the present invention is less than or equal to
about 0.80 wt. % as determined by ASTM D 874, e.g., a level of
sulfated ash of from about 0.10 to about 0.80 wt. % as determined
by ASTM D 874. In one embodiment, the level of sulfated ash
produced by the lubricating oil compositions of the present
invention is less than or equal to about 0.60 wt. % as determined
by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to
about 0.60 wt. % as determined by ASTM D 874.
[0102] The following examples are presented to exemplify
embodiments of the invention but are not intended to limit the
invention to the specific embodiments set forth. Unless indicated
to the contrary, all parts and percentages are by weight. All
numerical values are approximate. When numerical ranges are given,
it should be understood that embodiments outside the stated ranges
may still fall within the scope of the invention. Specific details
described in each example should not be construed as necessary
features of the invention.
EXAMPLES
[0103] The following examples are intended for illustrative
purposes only and do not limit in any way the scope of the present
disclosure.
Isomerization Level (I) and NMR Method
[0104] The isomerization level (I) of the olefin was determined by
hydrogen-1 (1H) NMR. The NMR spectra were obtained on a Bruker
Ultrashield Plus 400 in chloroform-d1 at 400 MHz using TopSpin 3.2
spectral processing software.
[0105] The isomerization level (I) represents the relative amount
of methyl groups (--CH3) (chemical shift 0.3-1.01 ppm) attached to
the methylene backbone groups (--CH2-) (chemical shift 1.01-1.38
ppm) and is defined by Equation (1) as shown below,
I=m/(m+n) Equation (I)
where m is NMR integral for methyl groups with chemical shifts
between 0.3.+-.0.03 to 1.01.+-.0.03 ppm, and n is NMR integral for
methylene groups with chemical shifts between 1.01.+-.0.03 to
1.38.+-.0.10 ppm.
[0106] The isomerized level (I) of the alpha olefin is between from
about 0.1 to about 0.4, preferably from about 0.1 to about 0.3,
more preferably from about 0.12 to about 0.3.
[0107] In one embodiment, the isomerization level of the NAO is
about 0.16, and having from about 20 to about 24 carbon atoms.
[0108] In another embodiment, the isomerization level of the NAO is
about 0.26, and having from about 20 to about 24 carbon atoms.
[0109] Baseline Formulation 1
[0110] A 5W-40 lubricating oil composition was prepared that
contained a major amount of a base oil of lubricating viscosity and
the following additives:
[0111] (1) an ethylene carbonate post-treated bis-succinimide;
[0112] (2) a zinc dialkyldithiophosphate;
[0113] (3) a mixture of antioxidants;
[0114] (4) a foam inhibitor.
Example A
[0115] An alkylated phenol and a Ca alkylhydroxybenzoate were
prepared in substantially the same manner as in U.S. Pat. No.
8,993,499 using a C.sub.20-24 isomerized normal alpha olefin. The
isomerization level of the alpha olefin is about 0.16. The
resulting alkylhydroxybenzoate composition has a TBN of about 630
and Ca content of about 22.4 wt. % on an oil-free basis.
Example B
[0116] An alkylated phenol and Ca alkylhydroxybenzoate were
prepared in substantially the same manner as in U.S. Pat. No.
8,993,499 using a C.sub.20-24 isomerized normal alpha olefin. The
isomerization level of the alpha olefin is about 0.16. The
resulting alkylhydroxybenzoate composition has a TBN of about 225
and Ca content of about 8 wt. % on an oil-free basis.
Comparative Example A
[0117] An alkylhydroxybenzoate was prepared from an alkylphenol
with an alkyl group derived from C.sub.14-18 NAO and a TBN about
300 and Ca content about 10.6 wt % on an oil-free basis.
Comparative Example B
[0118] An alkylated phenol and alkylhydroxybenzoate were prepared
in substantially the same manner as in U.S. Pat. No. 8,030,258
using a C.sub.20-28 NAO available from CP Chem. The resulting
alkylhydroxybenzoate composition has a TBN of about 520 and Ca
content of about 18.7 wt. % on an oil-free basis.
Example 1
[0119] To baseline formulation 1 was added 0.13 wt. % in terms of
Ca content of a Ca alkylhydroxybenzoate detergent of Example A and
0.05 wt. % in terms of Ca content of a Ca alkylhydroxybenzoate
detergent of Example B.
Example 2
[0120] To baseline formulation 1 was added 0.13 wt. % in terms of
Ca content of a Ca alkylhydroxybenzoate detergent of Example A and
0.02 wt. % in terms of Ca content of a sulfurized overbased Ca
phenate detergent.
Example 3
[0121] To baseline formulation 1 was added (9.83 mmol Soap) of a Ca
alkylhydroxybenzoate detergent of Example A.
Comparative Example 1
[0122] To baseline formulation 1 was added 0.13 wt. % in terms of
Ca content of a Ca alkylhydroxybenzoate detergent of Comparative
Example B and 0.02 wt. % in terms of Ca content of a sulfurized
overbased Ca phenate detergent.
Comparative Example 2
[0123] To baseline formulation 1 was added (9.83 mmol of Soap) of
Ca alkylhydroxybenzoate detergent of Comparative Example B.
HTCBT Test
[0124] The ASTM D6594 HTCBT test is used to test diesel engine
lubricants to determine their tendency to corrode various metals,
specifically alloys of lead and copper commonly used in cam
followers and bearings. Four metal specimens of copper, lead, tin
and phosphor bronze are immersed in a measured amount of engine
oil. The oil, at an elevated temperature (170.degree. C.), is blown
with air (5 l/h) for a period of time (168 h). When the test is
completed, the copper specimen and the stressed oil are examined to
detect corrosion and corrosion products, respectively. The
concentrations of copper, lead, and tin in the new oil and stressed
oil and the respective changes in metal concentrations are
reported. To be a pass the concentration of lead should not exceed
120 ppm and the copper 20 ppm.
TABLE-US-00002 TABLE 2 HTCBT Change in Concentration Example
Example Comparative (mg/kg) 1 2 Ex 1 Copper 5 4 4 Lead 106 123
124
TABLE-US-00003 TABLE 3 HTCBT (equal soap comparison) Change in
Concentration Example Comparative (mg/kg) 3 Ex. 2 Copper 3 2 Lead
24 44
Baseline Formulation 2
[0125] A heavy duty automotive lubricating oil composition was
prepared that contained a major amount of a base oil of lubricating
viscosity and the following additives, to provide an SAE 15W-40
finished oil: [0126] (1) an ethylene carbonate post-treated
bis-succinimide dispersant; [0127] (2) 990 ppm in terms of
phosphorus content, of a mixture of a primary zinc
dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate;
[0128] (3) Moly succinimide complex providing 50 ppm of molybdenum
[0129] (4) an alkylated diphenylamine antioxidant; [0130] (5) 5 ppm
in terms of silicon content, of a foam inhibitor; [0131] (6) 9.5
wt. % VII (additive) of Non-dispersant OCP and 0.3 wt. % PPD; and
[0132] (7) the remainder, a Group II base oil (Chevron 220R).
Example 4
[0133] To formulation baseline 2 was added 0.2290 wt. % in terms of
calcium content, of a calcium alkylhydroxybenzoate detergent of
Example A and 0.078 wt. % in terms of magnesium content a
C.sub.20-C.sub.24 magnesium alkylhydroxybenzoate detergent, made
from isomerized NAO with isomerization level of 0.16. Properties:
TBN (mgKOH/g)=199 in 35 wt % of diluent oil.
Comparative Example 3
[0134] To formulation baseline 2 was added 0.2290 wt. % in terms of
calcium content, of a calcium alkylhydroxybenzoate detergent of
Example A and 0.075 wt. % in terms of magnesium content a
C.sub.14-C.sub.18 magnesium alkylhydroxybenzoate detergent, made
from alpha olefin. Properties: TBN (mgKOH/g)=236; Mg (wt.
%)=5.34.
Oxidator Bx Test
[0135] A 25 g sample was weighted into a special glass oxidator
cell. A catalyst was added, followed by inserting a glass stirrer.
The cell was then sealed and placed in an oil bath maintained at
340.degree. F. and connected to the oxygen supply. One liter of
oxygen was fed into the cell while the stirrer agitated the oil
sample. The test was run until 1 liter of oxygen was consumed by
the sample and the total time, in hours, of the sample run was
reported. Higher hours to 1 Liter means better oxidation
performance. Results are given in Table 4 below.
TABLE-US-00004 TABLE 4 Comp. Ex. 4 Ex. 3 Hours to 39.3 36.9 1
Ltr.
Example C
[0136] An alkylated phenol and a Ca alkylhydroxybenzoate were
prepared in substantially the same manner as in U.S. Pat. No.
8,993,499 using a C.sub.20-24 isomerized normal alpha olefin. The
isomerization level of the alpha olefin is about 0.16. The
resulting alkylhydroxybenzoate composition has a TBN of about 120
and Ca content of about 4.2 wt. % on an oil-free basis.
Baseline Formulation 3
[0137] A passenger car automotive lubricating oil composition was
prepared that contained a major amount of a base oil of lubricating
viscosity and the following additives, to provide an SAE 5W-30
finished oil: [0138] (1) an ethylene carbonate post-treated
bis-succinimide dispersant and borated dispersant; [0139] (2) 770
ppm in terms of phosphorus content, of a mixture of a primary zinc
dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate;
[0140] (3) Moly succinimide complex providing 180 ppm of molybdenum
[0141] (4) an alkylated diphenylamine antioxidant; [0142] (5) a
borated friction modifier; [0143] (5) 5 ppm in terms of silicon
content, of a foam inhibitor; [0144] (6) 9.5 wt. % VII (additive)
of Non-dispersant OCP and 0.3 wt. % PPD; and [0145] (7) the
remainder, a Group III base oil.
Example 5
[0146] To formulation baseline 3 was added a mixture of both a
calcium alkylhydroxybenzoate of Example A (32.3 mMol) and Example C
(23.3 mMol) in a total amount of 0.2230 wt. %.
Example 6
[0147] To formulation baseline 3 was added a mixture of both a
calcium alkylhydroxybenzoate of Example C (23.3 mMol) and an HOB
sulfonate (31.7 mMol) derived from a C.sub.20-24 NAO in a total
amount of 0.2300 wt. %.
Comparative Example 4
[0148] To formulation baseline 3 was added a mixture of both a
calcium alkylhydroxybenzoate derived from a C.sub.20-28 NAO with a
TBN of 135 on an oil free basis (24.1 mMol) and Comparative Example
B (31.6 mMol) in a total amount of 0.2230 wt. %.
Comparative Example 5
[0149] To formulation baseline 3 was added a mixture of both a
calcium alkylhydroxybenzoate derived from a C.sub.20-28 NAO with a
TBN of 135 on an oil free basis (27.7 mMol) and an HOB sulfonate
(29.6 mMol) derived from a C.sub.20-24 NAO in a total amount of
0.2300 wt. %.
Baseline Formulation 4
[0150] A passenger car automotive lubricating oil composition was
prepared that contained a major amount of a base oil of lubricating
viscosity and the following additives, to provide an SAE 5W-40
finished oil: [0151] (1) an ethylene carbonate post-treated
bis-succinimide dispersant and borated dispersant; [0152] (2) 740
ppm in terms of phosphorus content, of a secondary zinc
dialkyldithiophosphate; [0153] (3) a mixture of a borated
sulfonate, LOB sulfonate, and MOB phenate; [0154] (4) Moly
succinimide complex providing 90 ppm of molybdenum [0155] (5) an
alkylated diphenylamine and hindered phenol antioxidant; [0156] (6)
5 ppm in terms of silicon content, of a foam inhibitor; [0157] (7)
13.5 wt. % VII (additive) of Non-dispersant OCP and 0.3 wt. % PPD;
and [0158] (8) the remainder, a Group III base oil.
Example 7
[0159] To formulation baseline 4 was added a calcium
alkylhydroxybenzoate of Example A (27 mMol).
Comparative Example 6
[0160] To formulation baseline 4 was added a calcium
alkylhydroxybenzoate of Comparative Example B (27 mMol).
ASTM D4684 Mini-Rotary Viscometer Test (MRV)
[0161] In this test, a test oil is first heated, and then cooled to
test temperature, in this case -40.degree. C., in a mini-rotary
viscometer cell. Each cell contains a calibrated rotor-stator set,
in which the rotor is rotated by means of a string wound around the
rotor shaft and attached to a weight. A series of increasing
weights are applied to the string starting with a 10 g weight until
rotation occurs to determine the yield stress. Results are reported
as Yield Stress as the applied force in Pascals. A 150 g weight is
then applied to determine the apparent viscosity of the oil. The
larger the apparent viscosity, the more likely it is that the oil
will not be continuously and adequately supplied to the oil pump
inlet. Results are reported as Viscosity in centipoise.
[0162] The results of the MRV test for each of the lubricating oil
compositions are set forth below in Table 4.
TABLE-US-00005 TABLE 4 Comp. Comp. Ex. 4 Ex. 5 Ex. 5 Ex. 6 Yield
Stress (-40.degree. C.) Pa >350 <140 >350 <140
Viscosity (-40.degree. C.) cP (<60,000) Frozen 33,800 Frozen
43,100
TABLE-US-00006 TABLE 5 Comp. Ex. 6 Ex. 7 Yield Stress (-40.degree.
C.) Pa >35 <35 Viscosity (-40.degree. C.) cP (<60,000)
27,000 20,900
[0163] From these examples it is clear that lubricating oils
formulated with an alkylhydroxybenzoate detergent of the invention
perform as well as or better than formulations containing
alkyhydroxybenzoates which are not derived from isomerized NAO
having from about 10 to about 40 carbon atoms.
* * * * *