U.S. patent application number 10/751809 was filed with the patent office on 2005-07-07 for lubricating composition substantially free of zddp.
This patent application is currently assigned to The Lubrizol Corporation. Invention is credited to Cressey, David, Friend, Christopher L., McAtee, Rodney J., Sutton, Michael Robert.
Application Number | 20050148477 10/751809 |
Document ID | / |
Family ID | 34711508 |
Filed Date | 2005-07-07 |
United States Patent
Application |
20050148477 |
Kind Code |
A1 |
Friend, Christopher L. ; et
al. |
July 7, 2005 |
Lubricating composition substantially free of ZDDP
Abstract
The present invention provides a composition comprising: (a) a
metal salixarate; (b) at least one additive selected from the group
consisting of (1) an antioxidant; (2) a friction modifier; (3) a
dispersant; (4) a viscosity modifier; (5) a dispersant viscosity
modifier; and (6) an antiwear agent other than a metal hydrocarbyl
dithiophosphate; and (c) an oil of lubricating viscosity, wherein
the composition contains 400 ppm or less of phosphorus derived from
a metal hydrocarbyl dithiophosphate. The invention further provides
a process for preparing the composition and its use.
Inventors: |
Friend, Christopher L.;
(Nottingham, GB) ; McAtee, Rodney J.; (Derbyshire,
GB) ; Sutton, Michael Robert; (Derbyshire, GB)
; Cressey, David; (Derbyshire, GB) |
Correspondence
Address: |
THE LUBRIZOL CORPORATION
ATTN: DOCKET CLERK, PATENT DEPT.
29400 LAKELAND BLVD.
WICKLIFFE
OH
44092
US
|
Assignee: |
The Lubrizol Corporation
Wickliffe
OH
|
Family ID: |
34711508 |
Appl. No.: |
10/751809 |
Filed: |
January 5, 2004 |
Current U.S.
Class: |
508/291 ;
508/479 |
Current CPC
Class: |
C10M 2209/086 20130101;
C10M 163/00 20130101; C10M 2207/028 20130101; C10M 2217/06
20130101; C10M 2207/144 20130101; C10M 2215/02 20130101; C10N
2030/50 20200501; C10M 2215/064 20130101; C10M 2207/262 20130101;
C10N 2030/06 20130101; C10M 2207/027 20130101; C10M 2207/026
20130101; C10N 2030/04 20130101; C10M 2215/28 20130101; C10M 159/22
20130101; C10N 2030/42 20200501; C10N 2040/25 20130101; C10M
2207/288 20130101; C10N 2030/43 20200501 |
Class at
Publication: |
508/291 ;
508/479 |
International
Class: |
C10M 141/12 |
Claims
What is claimed is:
1. A composition comprising: (a) a metal salixarate; (b) at least
one additive selected from the group consisting of (1) an
antioxidant; (2) a friction modifier; (3) a dispersant; (4) a
viscosity modifier; (5) a dispersant viscosity modifier; and (6) an
antiwear agent other than a metal hydrocarbyl dithiophosphate; and
(c) an oil of lubricating viscosity, wherein the composition
contains about 400 ppm or less of phosphorus derived from a metal
hydrocarbyl dithiophosphate.
2. The composition of claim 1, wherein the metal salixarate is
represented by one or a mixture of substantially linear compounds
comprising at least one unit of the formulae (I) or (II): 10each
end of the compound having a terminal group of formulae (III) or
(IV): 11such groups being linked by divalent bridging groups, which
may be the same or different for each linkage; wherein in formulas
(I)-(IV) f is 1, 2 or 3, preferably 1 or 2; U is --OH, --NH.sub.2
--NHR.sup.1, --N(R.sup.1).sub.2 or mixtures thereof, R.sup.1 is a
hydrocarbyl group containing 1 to 5 carbon atoms; R.sup.2 is
hydroxyl or a hydrocarbyl group and j is 0, 1, or 2; R.sup.3 is
hydrogen or a hydrocarbyl group; R.sup.4 is a hydrocarbyl group or
a substituted hydrocarbyl group; g is 1, 2 or 3, provided at least
one R.sup.4 group contains 8 or more carbon atoms; and wherein the
molecules on average contain at least one of unit (I) or (III) and
at least one of unit (II) or (IV) and the ratio of the total number
of units (I) and (III) to the total number of units of (II) and
(IV) in the composition overall is about 0.1:1 to about 2:1,
although individual molecules within the composition may fall
outside this range.
3. The composition of claim 1, wherein the metal of the metal
salixarate is an alkali metal or alkaline earth metal.
4. The composition of claim 1, wherein the total sulphur content is
below about 0.5 weight percent and the total phosphorus content is
below about 0.07 weight percent.
5. The composition of claim 1, wherein the total sulphated ash
content is below about 1.5 weight percent.
6. The composition of claim 1, wherein the dispersant is a
N-substituted long chain alkenyl succinimide.
7. The composition of claim 1, wherein the antioxidant is a
diphenylamine, a hindered phenol or mixtures thereof.
8. The composition of claim 7 wherein the diphenylamine is
represented by the formula: 12wherein each R.sup.6 and R.sup.7 are
independently a hydrocarbyl group; and z is zero or higher,
provided that on at least one ring, z is non-zero.
9. The composition of claim 7 wherein the hindered phenol is
represented by the formulae: 13wherein R.sup.8 and R.sup.9 are
independently branched or linear alkyl groups containing 1 to 24
carbon atoms; Y is a bridging group; and E is hydrogen, a
hydrocarbyl group, a bridging group linking to a second aromatic
group, an ester-containing group, or mixtures thereof.
10. The composition of claim 1, wherein the friction modifier
comprises a monoester of a polyol and an aliphatic carboxylic
acid.
11. The composition of claim 1, wherein the viscosity modifier
comprises an olefin copolymer.
12. The composition of claim 11, wherein the olefin copolymer
contains an ethylene monomer and at least one other comonomer
derived from an alpha-olefin having the formula
H.sub.2C.dbd.CHR.sup.10, wherein R.sup.10 is a hydrocarbyl
group.
13. The composition of claim 1, wherein the dispersant viscosity
modifier is selected from the group consisting of (a) an olefin
copolymer grafted with an unsaturated dicarboxylic acid anhydride
or derivatives thereof and an amine; (b) a polymethacrylate
functionalised with an amine; (c) an esterified copolymer
comprising (i) styrene, (ii) an unsaturated dicarboxylic acid
anhydride or derivatives thereof, optionally functionalised with an
amine; and mixtures thereof.
14. The composition of claim 1, wherein the oil of lubricating
viscosity is selected from the group consisting of API Group II,
III, IV or V oil and mixtures thereof.
15. The composition of claim 1, wherein the metal salixarate is
present on an oil free basis at about 0.01 to about 20 weight
percent of the composition; wherein the additives (1)-(6) of
component (b) are each present on an oil free basis at 0 to 25
weight percent of the composition, with the proviso that at least
one additive is present at 0.1 or more weight percent of the
composition; and wherein the oil of lubricating viscosity is
present at up to 99.89 weight percent of the composition.
16. A process for the preparation of a composition comprising
mixing: (a) a metal salixarate; (b) at least one additive selected
from the group consisting of (1) an antioxidant; (2) a friction
modifier; (3) a dispersant; (4) a viscosity modifier; (5) a
dispersant viscosity modifier; and (6) an antiwear agent other than
a metal hydrocarbyl dithiophosphate; and (c) an oil of lubricating
viscosity, wherein the composition contains about 400 ppm or less
of phosphorus derived from a metal hydrocarbyl dithiophosphate.
17. A product prepared by the process of claim 16.
18. A method for lubricating an internal combustion engine,
comprising supplying thereto a lubricant comprising the composition
claim 1.
19. The use of the composition of claim 1 for imparting one or more
of the group selected from improved engine cleanliness, decreased
wear, decreased NO, emissions and decreased particulate emissions.
Description
FIELD OF INVENTION
[0001] The present invention relates to a lubricating oil
composition containing a metal salixarate and other performance
additives. The lubricating oil composition has antiwear and
detergency performance in the absence of a metal hydrocarbyl
dithiophosphate.
BACKGROUND OF THE INVENTION
[0002] It is well known for lubricating oils to contain a number of
additives used to protect the engine from wear, the accumulation of
sludge and filter plugging. Common additives for engine lubricating
oils are zinc dialkyldithiophosphate (ZDDP) as an antiwear
additive, and overbased calcium sulphonate detergents. It is
believed that ZDDP antiwear additives protect the engine by forming
a protective film on metal surfaces. Typical treatment quantities
of ZDDP range from 1 to 2 weight percent based on the total weight
of the lubricant. Detergents such as overbased calcium sulphonate
help keep the engine parts clean of soot and other deposits, and
offer an alkalinity reserve. Typical treatment quantities of
detergents range from 0.05 to 10 weight percent based on the total
weight of the lubricant.
[0003] In recent years phosphates and sulphonates derived from
engine lubricants have been shown to contribute in part to
particulate emissions. Further, sulphur and phosphorus tend to
poison the NO, catalysts used in catalytic converters, resulting in
a reduction in performance of said catalysts. Any reduction in the
performance of catalytic converters tends to result in increased
amounts of greenhouse gases such as nitric oxide and/or sulphur
oxides. However, reducing the amount of ZDDP will increase the
amount of wear in an engine. Also reducing the amount of detergent
will decrease engine cleanliness and result in increased soot
deposits.
[0004] International Publication WO03/18728 (Cressey et al.)
discloses additives for lubricants containing linear compounds
containing phenolic and salicylic units in the form of oligomers or
polymers. The linear compounds can be salted with calcium and
optionally cosalted with boric acid. The additives have detergency
and/or antiwear properties. Lubricant examples contain an ashless
dispersant and a zinc dithiophosphate.
[0005] U.S. Pat. NO. 6,200,936 (Moreton) discloses compounds
containing phenolic units and salicylic units in a lubricating
composition. The compounds can be salted with calcium. The examples
of lubricating compositions contain phenolic units with a dodecyl
alkyl group. The compounds of the invention can be used as a
detergent in gasoline or diesel fuel. They also stabilise gasoline
or diesel compositions against thermal decomposition.
[0006] International Publication WO99/25793 (Taylor) discloses a
fuel composition containing kerosene and compounds containing
phenolic units and salicylic units. The compounds can be salted
with calcium. The examples of lubricating compositions contain
phenolic units with a dodecyl alkyl group.
[0007] International Publication WO01/56968 (Taylor et al.)
discloses a cyclic compound containing phenolic units and salicylic
units. The salicylic units can be salted with a metal or an
ammonium cation.
[0008] European Patent Application 1 262 538 A2 (Locke et al.)
discloses a metal detergent derived from an aromatic carboxylic
acid, a metal detergent derived from phenol capable of imparting
oxidation resistance in a lubricating oil composition. In a
preferred embodiment the aromatic carboxylic acid is a salicylic
acid substituted with an alkyl group.
[0009] It has now been found that the composition of the present
invention provides detergency and antiwear performance to an oil of
lubricating viscosity often used in an engine oil and said
composition is substantially free of a metal hydrocarbyl
dithiophosphate.
SUMMARY OF THE INVENTION
[0010] The present invention provides a composition comprising:
[0011] (a) a metal salixarate;
[0012] (b) at least one additive selected from the group consisting
of (1) an antioxidant; (2) a friction modifier; (3) a dispersant;
(4) a viscosity modifier; (5) a dispersant viscosity modifier; and
(6) an antiwear agent other than a metal hydrocarbyl
dithiophosphate; and
[0013] (c) an oil of lubricating viscosity, wherein the composition
contains about 400 ppm or less of phosphorus derived from a metal
hydrocarbyl dithiophosphate.
[0014] The invention further provides a process for the preparation
of a composition comprising mixing:
[0015] (a) a metal salixarate;
[0016] (b) at least one additive selected from the group consisting
of (1) an antioxidant; (2) a friction modifier; (3) a dispersant;
(4) a viscosity modifier; (5) a dispersant viscosity modifier; and
(6) an antiwear agent other than a metal hydrocarbyl
dithiophosphate; and
[0017] (c) an oil of lubricating viscosity, wherein the composition
contains about 400 ppm or less of phosphorus derived from a metal
hydrocarbyl dithiophosphate.
[0018] The use of the composition of the invention imparts one or
more of improved engine cleanliness, decreased wear, decreased NO,
emissions and decreased particulate emissions.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention provides a composition as described
above. Often the composition has a total sulphur content below 0.5
wt %, preferably below 0.3 wt %, more preferably 0.1 wt % and most
preferably near 0 wt %. Often the major source of sulphur in the
composition of the invention is derived from diluent oil. Usually
the diluent oil is used in the manufacturing processes used for
preparing many of the component (b) additives. Excluding the
diluent oil, the composition of the invention often have a sulphur
content of 700 ppm or less, preferably 600 ppm or less, more
preferably 300 ppm or less, even more preferably 100 ppm or less
and most preferably 50 ppm or less such as less than 30 ppm, 25 ppm
or less, 20 ppm or less and 15 ppm or less. When sulphur from the
diluent oil is included, the sulphur content of the composition is
often increased by up to 800 ppm, preferably up to 600 ppm and most
preferably up to 400 ppm, for instance about 200 ppm or about 300
ppm.
[0020] Often the composition has a total phosphorus content below
0.1 wt %, preferably equal to or less than 0.085 wt %, more
preferably equal to or less than 0.07 wt %, even more preferably
equal to or less than 0.055 wt % and most preferably equal to or
less than 0.05 wt % of the composition, such as 200 ppm or less,
preferably 100 ppm or less, more preferably 50 ppm or less and most
preferably 10 ppm or less. In one embodiment the phosphorus is
present from 1 ppm or 10 ppm to 50 ppm or 200 ppm.
[0021] Often the composition has a total ash content as determined
by ASTM D-874 is below 1.5 wt %, preferably equal to or less than
1.1 wt %, more preferably equal to or less than 1.0 wt %, even more
preferably equal to or less than 0.8 wt % and most preferably equal
to or less than 0.5 wt % of the composition. In one embodiment the
total ash content is present from 0.1 wt % or 0.2 wt % to 0.6 wt %
or 0.7 wt %.
[0022] Salixarate Salt Detergent
[0023] The substrate of the metal salixarate of the invention is
often represented by one or a mixture of substantially linear
compounds comprising at least one unit of the formulae (I) or (II):
1
[0024] each end of the compound having a terminal group of formulae
(III) or (IV): 2
[0025] such groups being linked by divalent bridging groups, which
may be the same or different for each linkage; wherein in formulas
(I)-(IV) f is 1, 2 or 3, preferably 1 or 2; U is --OH, --NH.sub.2
--NHR.sup.1, --N(R.sup.1).sub.2 or mixtures thereof, R.sup.1 is a
hydrocarbyl group containing 1 to 5 carbon atoms; R.sup.2 is
hydroxyl or a hydrocarbyl group and j is 0, 1, or 2; R.sup.3 is
hydrogen or a hydrocarbyl group; R.sup.4 is a hydrocarbyl group or
a substituted hydrocarbyl group; g is 1, 2 or 3, provided at least
one R.sup.4 group contains 8 or more carbon atoms; and wherein the
molecules on average contain at least one of unit (I) or (III) and
at least one of unit (II) or (IV) and the ratio of the total number
of units (I) and (III) to the total number of units of (II) and
(IV) in the composition overall is about 0.1:1 to about 2:1,
although individual molecules within the composition may fall
outside this range.
[0026] The U group in formulae (i) and (iii) may be located in one
or more positions ortho, meta, or para to the --COOR.sup.3 group.
Preferably the U group is located ortho to the --COOR.sup.3 group.
When the U group is a --OH group, formulae (i) and (iii) are
derived from 2-hydroxybenzoic acid (often called salicylic acid),
3-hydroxybenzoic acid, 4-hydroxybenzoic acid or mixtures thereof.
When U is a --NH.sub.2 group, formulae (i) and (iii) are derived
from 2-aminobenzoic acid (often called anthranilic acid),
3-aminobenzoic acid, 4-aminobenzoic acid or mixtures thereof.
[0027] The divalent bridging group, which may be the same or
different in each occurrence, includes --CH.sub.2-- (methylene
bridge) and --CH.sub.2OCH.sub.2-- (ether bridge), either of which
may be derived from an aldehyde such as formaldehyde or a
formaldehyde equivalent (e.g., paraform, formalin), ethanal or
propanal.
[0028] The metal of the metal salixarate is often mono-valent,
di-valent or mixtures thereof. Preferably the metal is selected
from an alkali metal or alkaline earth metal such as magnesium,
calcium, potassium or sodium, although magnesium, calcium,
potassium or mixtures thereof are most preferred.
[0029] It is believed that a significant fraction of salixarate
molecules (prior to neutralisation) may be represented on average
by the following formula: 3
[0030] wherein each R.sup.5 can be the same or different, and are
hydrogen or an alkyl group, provided at least one R.sup.5 is alkyl.
In a preferred embodiment, R.sup.5 is a polyisobutene group
(especially of molecular weight 200 to 1,000, or about 550).
Significant amounts of di-or trinuclear species may also be present
containing one salicylic end group of formula (III). The salixarate
detergent may be used alone or with other detergents.
[0031] Salixarate derivatives and methods of their preparation are
described in greater detail in U.S. Pat. No. 6,200,936 and PCT
Publications WO 01/56968 and WO 03/18728. It is believed that the
salixarate derivatives have a predominantly linear, rather than
macrocyclic, structure, although both structures are intended to be
encompassed by the term "salixarate." Additionally "Linear" does
not exclude branching or other structures in the substituent R
groups.
[0032] The metal salixarate is often present on an oil free basis
at 0.01 to 20, preferably 0.1 to 10, more preferably 0.2 to 8 and
most preferably 0.5 to 5 weight percent of the composition.
[0033] Component (b) Additives
[0034] The present invention contains at least one additive
selected from the group consisting of (1) an antioxidant; (2) a
friction modifier; (3) a dispersant; (4) a viscosity modifier; (5)
a dispersant viscosity modifier; and (6) an antiwear agent other
than a metal hydrocarbyl dithiophosphate; and
[0035] The present invention contains at least one additive
selected from the group consisting of (1) an antioxidant; (2) a
friction modifier; (3) a dispersant; (4) a viscosity modifier; (5)
a dispersant viscosity modifier; and (6) an antiwear agent other
than a metal hydrocarbyl dithiophosphate. Often 2 or more and most
preferably 3 or more of additives (1)-(6) are present in the
invention.
[0036] Often the amount of each of the additives (1)-(6) are
present on an oil free basis at 0 to 25, preferably 0.1 to 20, more
preferably 0.3 to 15 and most preferably 1 to 10 weight percent of
the composition, with the proviso that at least one additive is
present at 0.1 or more weight percent of the composition.
[0037] Antioxidant
[0038] When present in the invention the antioxidant often includes
a diphenylamine antioxidant, a hindered phenol antioxidant, or
mixtures thereof.
[0039] Other antioxidant additives such as a molybdenum
dithiocarboamate or a sulphurised olefin may also be added to the
composition of the invention, although preferably the composition
is substantially free of a molybdenum dithiocarboamate or a
sulphurised olefin. As used herein the term "substantially free of
a molybdenum dithiocarboamate or a sulphurised olefin" means the
composition will contain a molybdenum dithiocarboamate or a
sulphurised olefin present at less than 100 ppm, preferably less
than 20 ppm and most preferably 1 ppm or less.
[0040] When present, the diphenylamine suitable for the invention
is often represented by the formula: 4
[0041] wherein are independently a hydrocarbyl group; and z is zero
or higher, provided that on at least one ring, z is non-zero. Often
the hydrocarbyl group contains 1 to 24, preferably 2 to 18 and most
preferably 4 to 12 carbon atoms.
[0042] Examples of suitable diphenylamine antioxidants include
octyl diphenylamine, nonyl diphenylamine, bis-octyl diphenylamine,
bis-nonyl diphenylamine or mixtures thereof.
[0043] When present, the diphenylamine is often present on an oil
free basis at 0.01 to 20, preferably 0.05 to 10, more preferably
0.1 to 5 and most preferably 0.2 to 3 weight percent of the
composition.
[0044] When present, the hindered phenol suitable for the invention
is often represented by the formula: 5
[0045] wherein R.sup.8 and R.sup.9 are independently branched or
linear alkyl groups containing 1 to 24, preferably 4 to 18, and
most preferably 4 to 12 carbon atoms; and E is hydrogen, a
hydrocarbyl group, a bridging group linking to a second aromatic
group, an ester-containing group, or mixtures thereof.
[0046] R.sup.8 and R.sup.9 may be either straight or branched
chain; branched is preferred. Suitable examples of R.sup.8 and
R.sup.9 include secondary butyl and tertiary butyl.
[0047] In one embodiment, the hindered phenol of formula (VII)
suitable for the invention are esters or acids represented by the
formula: 6
[0048] wherein R.sup.8 and R.sup.9 are as defined above and
R.sup.10 is hydrogen, a hydrocarbyl group or mixtures thereof.
[0049] When R.sup.10 is a hydrocarbyl group, R.sup.10 is preferably
selected from the group consisting of butyl, sec-butyl, isobutyl,
tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl,
nonyl, decyl, undecyl, dodecyl and mixtures thereof.
[0050] In one embodiment, the hindered phenol of formula (VII)
suitable for the invention contains a bridging group. Examples of
suitable bridging groups include an alkylene bridge or an ether
bridge, often containing 1 to 8, preferably 1 to 6, more preferably
1 to 4 and most preferably 1 to 2 carbon atoms. Examples of a
suitable bridge group include --CH.sub.2--, --CH.sub.2CH.sub.2--,
--CH.sub.2OCH.sub.2-- and
--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2--.
[0051] When present, the hindered phenol with a bridging group is
often represented by the formula: 7
[0052] wherein R.sup.11 and R.sup.12 are defined above and Y is a
bridging group. Examples of a methylene-bridged hindered phenol
include 4,4 -methylene-bis-(6-tert-butyl-o-cresol), 4,4
-methylene-bis-(2-tert-amyl-o- -cresol) and
4,4'-methylene-bis-(2,6-di-tertbutylphenol).
[0053] The hindered phenol of the invention also includes compounds
represented by the formula: 8
[0054] wherein R.sup.8, E and Y are defined above. Examples of a
suitable methylene-bridged hindered phenol of formula (VIII)
include 2,2 -methylene-bis-(4-methyl-6-tert-butylphenol), and
2,2'-methylene-bis-(4-e- thyl-6-tert-butylphenol),
2,2'-methylene-bis-(4-propyl-6-tert-butylphenol)- .
[0055] When present, the hindered phenol is often present on an oil
free basis at 0.01 to 25, preferably 0.1 to 20, more preferably 0.5
to 15 and most preferably 1 to 10 weight percent of the
composition.
[0056] Dispersant
[0057] When present, the invention further includes a dispersant
often derived from N-substituted long chain alkenyl succinimide or
mixtures thereof. The dispersants can be used alone or in
combination with other dispersants.
[0058] The N-substituted long chain alkenyl succinimides have a
variety of chemical structures and include a mono-succinimide
and/or a di-succinimide. Often the long chain alkenyl group will
have number average molecular weight of 350 to 10,000, preferably
400 to 7000, more preferably 500 to 5000 and most preferably 500 to
4000. In one embodiment the long chain alkenyl group is a
polyisobutylene group, which has a number average molecular weight
from 800 to 1600 and in another embodiment from 1600 to 3000. The
succinimide is often prepared by the condensation of a
hydrocarbyl-substituted acylating agent (e.g.,
hydrocarbyl-substituted succinic anhydride) with a polyamine or an
amino alcohol, often a polyalkylene polyamine or
poly(ethyleneamine) such as triethylene tetramine, tetraethylene
pentamine, pentaethylene hexamine or, in one embodiment, polyamine
still bottoms.
[0059] N-substituted long chain alkenyl succinimides dispersant
additives and their preparation are disclosed, for instance, in
U.S. Pat. Nos. 3,361,673, 3,401,118 and 4,234,435.
[0060] Another class of suitable dispersants include Mannich bases,
which are the reaction products of alkyl phenols in which the alkyl
group typically contains at least 30 carbon atoms with aldehydes
(especially formaldehyde) and amines (especially polyalkylene
polyamines) and are described in more detail in U.S. Pat. No.
3,634,515.
[0061] Another class of ashless dispersant is high molecular weight
esters. These materials are similar to the above-described
succinimides except that they may be seen as having been prepared
by reaction of a hydrocarbyl acylating agent and a polyhydric
aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol.
Such materials are described in more detail in U.S. Pat. No.
3,381,022.
[0062] Other dispersants include polymeric dispersant additives,
which are generally hydrocarbon-based polymers which contain polar
functionality to impart dispersancy characteristics to the
polymer.
[0063] Dispersants may also be post-treated by reaction with any of
a variety of agents. Among these are urea, thiourea,
dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones,
carboxylic acids, hydrocarbon-substituted succinic anhydrides,
nitriles, epoxides, boron compounds, and phosphorus compounds.
References detailing such treatment are listed in U.S. Pat. No.
4,654,403.
[0064] When present, the dispersant is often present on an oil free
basis at 0.01 to 20, preferably 0.1 to 15, more preferably 0.2 to
10 and most preferably 0.5 to 6 weight percent of the
composition.
[0065] Friction Modifiers
[0066] When present in the invention, the friction modifier can be
a monoester of a polyol and an aliphatic carboxylic acid, often an
acid containing 12 to 24 carbon atoms. Often the monoester of a
polyol and an aliphatic carboxylic acid is in the form of a mixture
with a sunflower oil or the like, which may be present in the
friction modifier mixture from 5 to 95, preferably 10 to 90, more
preferably 20 to 85 and most preferably 20 to 80 weight percent of
said mixture.
[0067] Polyols include diols, triols, and alcohols with higher
numbers of alcoholic OH groups. Polyhydric alcohols include
ethylene glycols, including di--, tri-- and tetraethylene glycols;
propylene glycols, including di--, tri-- and tetrapropylene
glycols; glycerol; butane diol; hexane diol; sorbitol; arabitol;
mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol;
and pentaerythritols, including di-- and tripentaerythritol;
preferably, diethylene glycol, triethylene glycol, glycerol,
sorbitol, pentaerythritol and dipentaerythritol.
[0068] The aliphatic carboxylic acids which form the esters are
those acids containing 12 to 24 carbon atoms. Acids containing
straight chain hydrocarbyl groups containing 12 to 24 carbon atoms
are preferred, for instance, 14 to 20 or 16 to 18 carbon atoms.
Such acids can be used in combination with acids with more or fewer
carbon atoms as well.
[0069] Generally the acid is a monocarboxylic acid. Examples of
carboxylic acids include dodecanoic acid, stearic acid, lauric
acid, behenic acid, and oleic acid.
[0070] The esters used in the present invention are in particular
the monoesters of such polyols and such carboxylic acids. A
preferred ester is glycerol monooleate. It is to be understood that
glycerol monooleate, as is the case with other such materials, in
its commercially available grade, is a mixture which includes such
materials as glycerol, oleic acid, other long chain acids, glycerol
dioleate, and glycerol trioleate. The commercial material is
believed to include about 60.+-.5 percent by weight of the chemical
species "glycerol monooleate," along with 35.+-.5 percent glycerol
dioleate, and less than about 5 percent trioleate and oleic acid.
The amounts of the monoesters, described below, are calculated
based on the actual, corrected, amount of polyol monoester present
in any such mixture.
[0071] Other friction modifiers that are suitable for the invention
include fatty amines, fatty phosphites, fatty acid amides, fatty
epoxides, alkoxylated fatty amines, metal salts of fatty acids,
sulfurised olefins, fatty imidazolines, condensation products of
carboxylic acids and polyalkylene-polyamines, amine salts of
alkylphosphoric acids. Preferably the friction modifier is free of
sulphur and/or phosphorus.
[0072] When present, the friction modifier is often present on an
oil free basis at 0.01 to 20, preferably 0.05 to 10, more
preferably 0.1 to 5 and most preferably 0.2 to 3 such as 0.5 to 2
weight percent of the composition.
[0073] Viscosity Modifiers
[0074] When present in the invention the viscosity modifier is
often an olefin copolymer. The olefin copolymer backbone often
contains two to four, preferably two to three and most preferably
two different olefin monomers. The olefin monomers often contain 2
to 20, preferably 2 to 10, more preferably 2 to 6 and most
preferably 2 to 4 carbon atoms.
[0075] When present, the viscosity modifiers are often present on
an oil free basis at of 0.01 to 15, preferably 0.05 to 10, more
preferably 0.1 to 5 and most preferably 0.2 to 3 weight percent of
the composition.
[0076] The olefin copolymer preferably contains an ethylene monomer
and at least one other comonomer derived from an alpha-olefin
having the formula H.sub.2C.dbd.CHR.sup.10, wherein R.sup.10 is a
hydrocarbyl group, preferably an alkyl radical containing 1 to 18,
preferably 1 to 10, more preferably 1 to 6 and most preferably 1 to
3 carbon atoms. The hydrocarbyl group includes an alkyl radical
that has a straight chain, a branched chain or mixtures
thereof.
[0077] Examples of suitable comonomers include propylene, 1-butene,
1-hexene, 1-octene, 4-methylpentene-1, 1-decene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
1-heptadecene, 1-octadecene, 1-nonadecene or mixtures thereof.
Preferably the comonomer is 1-butene, propylene or mixtures
thereof. Example of olefin copolymers include ethylene-propylene
copolymers or ethylene-butene-1 copolymers.
[0078] Other viscosity modifiers suitable for the invention include
polymeric materials including hydrogenated styrene-butadiene
rubbers, hydrogenated styrene-isoprene polymers, hydrogenated
radical isoprene polymers, polymethacrylate acid esters,
polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl
conjugated diene copolymers, polyalkylmethacrylates, esters of
maleic anhydride-styrene copolymers or mixtures thereof.
[0079] Optionally the olefin copolymer of the invention is further
grafted with an unsaturated dicarboxylic acid anhydride or
derivatives thereof and an amine to form a dispersant viscosity
modifier (often referred to as DVM), thus named because they also
exhibit dispersant properties. DVM additives and their preparation
are disclosed, for instance, in U.S. Pat. Nos. 6,107,258 and
6,107,257.
[0080] Examples of olefin copolymer DVM's include those
commercially available from DSM as PA1250.TM., PA1260.TM. and
PA1274.TM. as well as Hitec 5777.TM. (commercially available from
Ethyl Corporation).
[0081] Often the dispersant viscosity modifier is selected from the
group consisting of (a) an olefin copolymer grafted with an
unsaturated dicarboxylic acid anhydride or derivatives thereof and
an amine; (b) a polymethacrylate functionalised with an amine; (c)
an esterified copolymer comprising (i) styrene, (ii) an unsaturated
dicarboxylic acid anhydride or derivatives thereof, optionally
functionalised with an amine; and mixtures thereof. Often DVM's
derived from a polymethacrylate and/or a styrene copolymer are
prepared by reacting with an amine as described in U.S. Pat. Nos.
6,107,258 and 6,107,257. The DVM can be used alone or in
combination with other DVM's.
[0082] When present, the dispersant viscosity modifier is often
present on an oil free basis at 0.01 to 10, preferably 0.05 to 6,
more preferably 0.08 to 4 and most preferably 0.1 to 2 weight
percent of the composition.
[0083] Antiwear Agents
[0084] The composition of the invention may additionally contain an
antiwear agent other than a metal hydrocarbyl dithiophosphate.
Suitable antiwear agents include phosphoric acid esters or salt
thereof; phosphites; and phosphorus-containing carboxylic esters,
ethers, and amides or mixtures thereof. Preferably the composition
of the invention is substantially free of phosphorus-- and/or
sulphur-containing antiwear agents. In one embodiment of the
invention the composition is free of antiwear agents.
[0085] As used herein the term "substantially free of antiwear
agents containing sulphur and/or phosphorus" means the composition
will contain antiwear agents present at less than 50 ppm,
preferably less than 10 ppm and most preferably 1 ppm or less. In
one embodiment of the invention no antiwear agents containing
sulphur and/or phosphorus are present. In one embodiment of the
invention 1 ppm to 15 ppm of antiwear agents containing sulphur
and/or phosphorus are present.
[0086] Oils of Lubricating Viscosity
[0087] The lubricating oil composition of the present invention may
be added to an oil of lubricating viscosity. The oil includes
natural and synthetic oils, oil derived from hydrocracking,
hydrogenation, hydrofinishing, unrefined, refined and re-refined
oils, or mixtures thereof.
[0088] Unrefined oils are those obtained directly from a natural or
synthetic source generally without (or with little) further
purification treatment.
[0089] 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. Purification techniques are known
in the art and include solvent extraction, secondary distillation,
acid or base extraction, filtration, percolation and the like.
[0090] Re-refined oils are also known as reclaimed or reprocessed
oils, and are obtained by processes similar to those used to obtain
refined oils and often are additionally processed by techniques
directed to removal of spent additives and oil breakdown
products.
[0091] Natural oils useful in making the inventive lubricants
include animal oils, vegetable oils (e.g., castor oil, lard oil),
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 and
oils derived from coal or shale or mixtures thereof.
[0092] Synthetic lubricating oils are useful and include
hydrocarbon oils such as polymerised and interpolymerised olefins
(e.g., polybutylenes, polypropylenes, propyleneisobutylene
copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and
mixtures thereof; alkyl-benzenes (e.g. dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes);
polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls);
alkylated diphenyl ethers and alkylated diphenyl sulphides and the
derivatives, analogs and homologs thereof or mixtures thereof.
Preferably the synthetic lubricating oils are free of alkylated
diphenyl sulphides.
[0093] Other synthetic lubricating oils include but are not limited
to polyol esters, liquid esters of phosphorus-containing acids
(e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl
ester of decane phosphonic acid), and polymeric tetrahydrofurans.
Synthetic oils may be produced by Fischer-Tropsch reactions and
typically may be hydroisomerised Fischer-Tropsch hydrocarbons or
waxes. Preferably the synthetic lubricating oils are free of
phosphorus-containing esters.
[0094] Oils of lubricating viscosity may also be defined as
specified in the American Petroleum Institute (API) Base Oil
Interchangeability Guidelines. The five base oil groups are as
follows: Group I (sulphur content >0.03 wt %, and/or <90 wt %
saturates, viscosity index 80-120); Group II (sulphur content
<0.03 wt %, and >90 wt % saturates, viscosity index 80-120);
Group III (sulphur content <0.03 wt %, and >90 wt %
saturates, viscosity index >120); Group IV (all polyalphaolefins
(PAO's)); and Group V (all others not included in Groups I, II,
III, or IV). The oil of lubricating viscosity is selected from the
group consisting of an API Group I, II, III, IV, V oil and mixtures
thereof; preferably an API Group II, III, IV or V oil and mixtures
thereof; and most preferably an API Group III, IV or V oil and
mixtures thereof. If the oil of lubricating viscosity is an API
Group II, III, IV or V oil there may be up to a maximum of 20 wt %,
preferably up to a maximum of 10 wt %, more preferably up to a
maximum of 5 wt % and most preferably up to a maximum of 1.5 wt %
of the lubricating oil an API Group I oil.
[0095] Examples of suitable API Group III oils include Nexbase.TM.
3050, Nexbase.TM. 3043, Yubase.TM. 4, Yubase.TM. 6, and Shell.TM.
XHVI 5.2.
[0096] The oil of lubricating viscosity is often present at up to
99.98, preferably up to 99.8, more preferably up to 99.65 and most
preferably up to 99.3 weight percent of the composition.
[0097] If the present invention is in the form of a concentrate
(which can be combined with additional oil to form, in whole or in
part, a finished lubricant), the ratio of each of the
above-mentioned dispersant, as well as other components, to diluent
oil is often 80:20 to 10:90 by weight.
[0098] Metal Hydrocarbyl Dithiophosphate
[0099] The invention is substantially free of to free of a metal
hydrocarbyl dithiophosphate often represented by the formula: 9
[0100] wherein R.sup.11 and R.sup.12 are independently hydrogen,
hydrocarbyl groups or mixtures thereof, provided that at least one
of R.sup.11 and R.sup.12 is a hydrocarbyl group, preferably alkyl
or cycloalkyl with 1 to 30, preferably 2 to 20 and most preferably
2 to 15 carbon atoms.
[0101] The term "substantially free of" means that the composition
contains 400 ppm or less of phosphorus, preferably 300 ppm or less
of phosphorus, more preferably 200 ppm or less of phosphorus, even
more preferably 100 ppm or less of phosphorus and most preferably
100 ppm or less of phosphorus such as 50 ppm, 20 ppm or 1 ppm or
less, derived from a metal hydrocarbyl dithiophosphate. In one
embodiment of the invention the composition contains 0.5 ppm or 10
ppm to 50 ppm of phosphorus derived from a metal hydrocarbyl
dithiophosphate. In one embodiment of the invention the composition
is free of a metal hydrocarbyl dithiophosphate.
[0102] M' is a metal, and n is an integer equal to the available
valence of M'. M' is mono- or di- or tri-valent, preferably
divalent, more preferably a divalent transition metal. In one
embodiment M' is zinc. In one embodiment M' is calcium. In one
embodiment M' is barium. Examples of a metal hydrocarbyl
dithiophosphate include zinc dihydrocarbyl dithiophosphates (often
referred to as ZDDP, ZDP or ZDTP).
[0103] Other Performance Additives
[0104] The composition of the invention optionally further includes
other performance additives. The other performance additives
selected from the group consisting of detergents other than those
of component (a) of the invention, corrosion inhibitors,
antiscuffing agents, foam inhibitors, demulsifiers, pour point
depressants seal swelling agents and mixtures thereof.
[0105] The total combined amount of the other performance additives
present on an oil free basis is often from 0 to 20, preferably 0.01
to 15, more preferably 0.05 to 10 and most preferably 0.1 to 5
weight percent of the composition. Although one or more of the
other performance additives may be present, it is common for the
other performance additives to be present in different amounts
relative to each other.
[0106] Detergents other than those of component (a) of the
invention are known and include neutral or overbased, Newtonian or
non-Newtonian, basic salts of alkali, alkaline earth and transition
metals with one or more of a phenate, a sulphonate, a carboxylic
acid, a phosphorus acid, a mono- and/or a di-thiophosphoric acid, a
saligenins, an alkylsalicylate or mixtures thereof. Commonly used
metals include sodium, potassium, calcium, magnesium lithium or
mixtures thereof. Most commonly used metals include sodium,
magnesium and calcium. Preferably the composition of the invention
is free of detergents containing sulphur and/or phosphorus.
[0107] Other performance additives such as corrosion inhibitors
including octylamine octanoate, condensation products of dodecenyl
succinic acid or anhydride and a fatty acid such as oleic acid with
a polyamine; metal deactivators including derivatives of
benzotriazoles, 1,2,4-triazoles, benzimidazoles,
2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazole- s; foam
inhibitors including copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including trialkyl phosphates, polyethylene glycols, polyethylene
oxides, polypropylene oxides and (ethylene oxide-propylene oxide)
polymers; pour point depressants including esters of maleic
anhydride-styrene, polymethacrylates, polyacrylates or
polyacrylamides; and seal swell agents including Exxon
Necton-37.TM. (FN 1380) and Exxon Mineral Seal Oil (FN 3200); may
also be used in the composition of the invention.
[0108] Process
[0109] The invention further provides a process for the preparation
of a composition as described above.
[0110] Components (a)-(c) are often mixed sequentially, separately
for the composition of the invention. The mixing conditions are
often 15.degree. C. to 130.degree. C., preferably 20.degree. C. to
120.degree. C. and most preferably 25.degree. C. to 110.degree. C.;
and for a period of time in the range 30 seconds to 48 hours,
preferably 2 minutes to 24 hours, more preferably 5 minutes to 16
hours and most preferably 10 minutes to 5 hours; and at pressures
in the range 86 kPa to 266 kPa (650 mm Hg to 2000 mm Hg),
preferably 91 kPa to 200 kPa (690 mm Hg to 1500 mm Hg), and most
preferably 95 kPa to 133 kPa (715 mm Hg to 1000 mm Hg).
[0111] The process optionally includes mixing other optional
performance additives as described above. The optional performance
additives are often added sequentially, separately or as a
concentrate.
[0112] Industrial Application
[0113] The composition of the present invention is useful in an
internal combustion engines, for example diesel fuelled engines,
gasoline fuelled engines, natural gas fuelled engines or a mixed
gasoline/alcohol fuelled engines.
[0114] In one embodiment of the invention provides a method for
lubricating an internal combustion engine, comprising supplying
thereto a lubricant comprising the composition as described herein.
The use of the composition of the invention is capable of imparting
one or more of the group selected from improved engine cleanliness,
decreased wear, decreased NO.sub.x emissions and decreased
particulate emissions.
[0115] The following examples provide an illustration of the
invention. These examples are non exhaustive and are not intended
to limit the scope of the invention.
EXAMPLES
Preparative Example 1
Preparation of Salixarate Substrate--Salixarene
[0116] A sample of a salixarene substrate is prepared using a
flange flask approximately 2 litres in volume, a flange and clip,
overhead stirrer with paddle and polytetrafluoroethylene (PTFE)
stirrer gland, Dean Stark trap and double surface condenser, an
electric mantle/thermocouple/Euroth- erm.TM. temperature controller
system, the glassware from just above the mantle to just below the
condenser being covered with glass wool. The flask is filled with
475 g polyisobutenyl phenol derived from high vinylidene
polyisobutylene with a number average molecular weight of 550
(GLISSOPAL.RTM.550 commercially available from BASF) and 330 g of
mineral oil (SN 150) and heated to 30.degree. C. via a pressure
equalizing dropping funnel 3.4 g of 50% aqueous KOH is added. The
contents of the flask are heated to 75.degree. C. and the
temperature is kept constant for 30 minutes while 81.6 g of 37%
aqueous formaldehyde (formalin) is added. The reaction is charged
with 51.6 g of salicylic acid and heated to 140.degree. C. while
controlling reflux. Water is removed using Dean Stark trap. The
product is vacuum stripped at 140.degree. C./13 kPa (equivalent to
100 mm Hg) for 30 minutes. A more detailed description of the
reaction process is given in Examples 1 and 5 of International
Publication WO03/018728, pages 22 and 23.
Preparative Example 2
Calcium Salixarate
[0117] A vessel is charged with 1200 g of the salixarene from
Preparative Example 1, 25 g of ethylene glycol, 130 g of calcium
hydroxide and 410 g of 2-ethylhexanol. The vessel and contents are
heated to 95.degree. C. and stirred under vacuum (64 kPa, which is
equivalent to 480 mm Hg). The vessel and contents are then subject
to vacuum at 6.7 kPa (equivalent to 50 mm Hg) for 15 minutes and
heated to 130.degree. C.. The vessel is then charged with an
additional 120 g of ethylene glycol added dropwise over 10 minutes
before carbon dioxide is added via a dip tube under a slight
negative pressure at 1.0 g/minute or less until 48g are added. Upon
completion of carbon dioxide addition, the dip tube is removed and
the temperature is increased to 200.degree. C. under a vacuum of
6.7 kPa (equivalent to 50 mm Hg) to remove solvents. The residue is
vacuum filtered through a 12 mm diatomaceous earth pad in a
sintered funnel yielding a viscous brown liquid.
Preparative Example 3
Magnesium Salixarate
[0118] A vessel is charged with 560.5 g of the salixarene from
Preparative Example 1 with 433 g of xylene. The vessel and contents
are heated to 35.degree. C. under a nitrogen atmosphere where 53 g
of magnesium oxide is added. The vessel is then charged with 20.2 g
of glacial acetic acid and then a mixture of methanol (42 g) and
water (30 g) is added. The vessel and contents are heated to
61.degree. C. and carbonated. The vessel and contents are held at
61.degree. C. for a further 2 hours and a further mixture of
methanol (36 g) and water (26.2 g) is added. The vessel heated to
150.degree. C. and held for 1 hour. The product is vacuum
stripped.
Preparative Example 4
Potassium Salixarate
[0119] A vessel is charged with 313 g of the salixarene from
Preparative Example 1, and heated under a nitrogen atmosphere to
80.degree. C. where 12.1 g of potassium hydroxide in 7 g of water
is added dropwise followed by the addition of 85 g of a diluent
oil. The vessel and contents are heated to 110.degree. C. for 10
minutes, then heated to 120.degree. C. for 90 minutes and heated to
140.degree. C. for 3 hours. A dark brown product is formed.
Reference Example 1
[0120] A composition is prepared by mixing (a) 42.5 g of
Nexbase.TM.3050 oil, (b) 34.4 g of Nexbase.TM.3043 oil, (c) on a an
oil free basis 0.4 g of an amine dispersant viscosity modifier, (d)
on a an oil free basis 2.8 g of polyisobutylene succinimide
dispersants, (e) 5 g of antioxidants including a diphenylamine and
a hindered phenol, (f) 0.7 g of an olefin copolymer viscosity
modifier and (g) a glycerol monooleate friction modifier. The
composition contains 0 wt % of calcium, 0 wt % of phosphorus, 190
ppm of sulphur and 0 wt % of zinc. The composition has a KV100 of
13.11 mm.sup.2/s (cSt) and a sulphated ash content of 0 wt %.
Reference Example 2
Top Tier European Passenger Car Oil Formulation
[0121] Reference Example 2 is a successful European top tier
passenger car oil formulation containing zinc dithiophosphate. The
elemental analysis of the oil formulation indicates a calcium
content of 3307 ppm, a phosphorus content of 889 ppm, a sulphur
content of 2645 ppm and a zinc content of 889 ppm. The oil
formulation has a KV100 of 11.3 mm.sup.2/s (cSt) and sulphated ash
content of 1.26 wt %.
Example 1
[0122] Example 1 has the same composition as Reference Example 1
except 2.5 g (on an oil free basis) of the product of Preparative
Example 2 is also added. The phosphorus content is 0 wt % and the
sulphur content is 190 ppm (all derived from diluent oil).
Example 2
[0123] Example 2 has the same composition as Reference Example 1
except 2.5 g (on an oil free basis) of the product of Preparative
Example 3 is also added. The phosphorus content is 0 wt % and the
sulphur content is 190 ppm (all derived from diluent oil).
Example 3
[0124] Example 3 has the same composition as Reference Example 1
except 2.5 g (on an oil free basis) of the product of Preparative
Example 4 is also added. The phosphorus content is 0 wt % and the
sulphur content is 190 ppm (all derived from diluent oil).
[0125] A number of lubricating oil compositions are formed using
Reference Example 1 and adding examples 1-3 at 2.5 g on a oil free
basis to the oil thus forming "Lubricating Oil Composition with
Example 1", Example 2 is titled "Lubricating Oil Composition with
Example 2" and "Lubricating Oil Composition with Example 3."
Reference example 1 and the corresponding Lubricating Oil
Composition with examples 1-3 have a KV100 of 13.11 mm.sup.2/s (or
cSt).
[0126] Test 1: HFRR of Examples 1-3 and Reference Examples 1-2
[0127] Lubricating Oil Composition with Example 1-3 are and
Reference Example 1-2 are evaluated for wear performance in a
programmed temperature high frequency reciprocating rig (HFRR)
available from PCS Instruments. HFRR conditions for the evaluations
are 200 g load, 75 minute duration, 1000 micrometer stroke, 20
hertz frequency, and temperature profile of 15 minutes at
40.degree. C. followed by an increase in temperature to 160.degree.
C. at a rate of 2.degree. C. per minute. Wear scar in micrometers
and film formation as percent film thickness are measured with
lower wear scar values and higher film formation values indicating
improved wear performance.
[0128] The percent film thickness is based on the measurement of
electrical potential between an upper and a lower metal test plate
in the HFRR. When the film thickness is 100%, there is a high
electrical potential for the full length of the 1000 micrometre
stroke, suggesting no metal to metal contact. Conversely for a film
thickness of 0% there is no electrical potential suggesting
continual metal to metal contact between the plates. For
intermediate film thicknesses, there is an electrical potential
suggesting the upper and lower metal test plate have a degree of
metal to metal contact as well as other areas with no metal to
metal contact. The wear scar and film formation results obtained
are presented in Table 1:
1TABLE 1 HFRR Wear Scar and Film Formation Data Example Wear Scar
Film Formation Lubricating Oil Composition Example 1 128 70
Lubricating Oil Composition Example 2 174 19 Lubricating Oil
Composition Example 3 169 30 Reference Example 1 189 12 Reference
Example 2 126 88
[0129] Test 2: Cameron Print of Example 1 and Reference Examples
1-2
[0130] The Cameron Plint TE-77.TM. is a reciprocating wear tester.
In this test a steel ball upper specimen is reciprocated against a
steel flat lower specimen. The Cameron Plint is charged with 10 ml
of sample and heated to 50.degree. C. and held for 1 minute. The
sample is then subject to a load of 100N over two minutes while at
the same time the reciprocation is started at 10 Hz over 15mm
stroke length. The sample is then heated to 250.degree. C. at
3.degree. C. per minute. At the end of-the test the average
diameter of the wear scar (in micrometers) on the ball (measured in
the X and Y directions) is measured using a calibrated microscope.
The results obtained are:
2TABLE 2 Cameron Plint Wear Scar Data Example Wear Scar Lubricating
Oil Composition Example 1 396 Reference Example 1 753 Reference
Example 2 517
[0131] Test 3: 4 Ball Wear Test Using ASTM D4172
[0132] The "Lubricating Oil Composition Example 4" and "Lubricating
Oil Composition Example 5" used in this test are the same as the
"Lubricating Oil Composition Example 1" except "Example 4" contains
2 g on a oil free basis of the product of Preparative Example 2 and
delivering about 1900 ppm of calcium and a TBN of about 146; and
"Example 5" contains 1.2 g on a oil free basis of the product of
preparative Example 2 and delivering about 1300 ppm of calcium and
a TBN of about 146. Reference Example 3 has the same oil
composition as Reference Example 1, except a calcium
alkylsalicylate (commercially available from AC60C.TM. range of
products from Infineum) is added in sufficient quantity to deliver
about 1300 ppm of calcium and a TBN of about 146. Reference Example
4 has the same oil composition as Reference Example 1, except a
magnesium saligenin (commercially available from The Lubrizol
Corporation) is added in sufficient quantity to deliver about 1300
ppm of magnesium and a TBN of about 146.
[0133] The ASTM D4172 test is run on a number of examples using the
modified B conditions indicated on page Section 8 of ASTM D 4172-94
(reapproved 1999). The wear scar is measured in micrometers. The
results obtained are:
3TABLE 2 ASTM D4172 Wear Scar Data Example Wear Scar Lubricating
Oil Composition Example 4 416 Lubricating Oil Composition Example 5
433 Reference Example 1 583 Reference Example 4 483 Reference
Example 5 482
[0134] Overall the analysis of the data from Test 1 and Test 2
shows the compositions of the invention produce good antiwear and
film formation results compared with reference example 1. The
analysis also indicates that the lubricating oil composition
example 1 has antiwear and film formation results comparable with a
successful European top tier passenger car oil formulation
containing zinc dithiophosphate.
[0135] In this specification the terms "hydrocarbyl substituent" or
"hydrocarbyl group," as used herein are used in its ordinary sense,
which is well-known to those skilled in the art. Specifically, it
refers to a group primarily composed of carbon and hydrogen atoms
and is attached to the remainder of the molecule through a carbon
atom and does not exclude the presence of other atoms or groups in
a proportion insufficient to detract from the molecule having a
predominantly hydrocarbon character. In general, no more than two,
preferably no more than one, non-hydrocarbon substituent will be
present for every ten carbon atoms in the hydrocarbyl group;
typically, there will be no non-hydrocarbon substituents in the
hydrocarbyl group. A more detailed definition of the terms
"hydrocarbyl substituent" or "hydrocarbyl group," is described in
U.S. Pat. No. 6, 583,092.
[0136] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicated, each
chemical or composition referred to herein should be interpreted as
being a commercial grade material which may contain the isomers,
by-products, derivatives, and other such materials which are
normally understood to be present in the commercial grade. However,
the amount of each chemical component is presented exclusive of any
solvent or diluent oil, which may be customarily present in the
commercial material, unless otherwise indicated. It is to be
understood that the upper and lower amount, range, and ratio limits
set forth herein may be independently combined. Similarly, the
ranges and amounts for each element of the invention can be used
together with ranges or amounts for any of the other elements. As
used herein, the expression "consisting essentially of" permits the
inclusion of substances that do not materially affect the basic and
novel characteristics of the composition under consideration.
* * * * *