U.S. patent application number 14/123645 was filed with the patent office on 2014-04-17 for lubricating composition containing a dispersant.
The applicant listed for this patent is Matthew D. Gieselman, Hannah Greenfield, Joanne L. Jones, David J. Moreton, Dean Thetford. Invention is credited to Matthew D. Gieselman, Hannah Greenfield, Joanne L. Jones, David J. Moreton, Dean Thetford.
Application Number | 20140107003 14/123645 |
Document ID | / |
Family ID | 46397647 |
Filed Date | 2014-04-17 |
United States Patent
Application |
20140107003 |
Kind Code |
A1 |
Gieselman; Matthew D. ; et
al. |
April 17, 2014 |
Lubricating Composition Containing a Dispersant
Abstract
The invention provides a lubricating composition containing a
lubricating composition comprising an oil of lubricating viscosity
and a quaternised polyester salt. The invention further relates to
a method of lubricating a mechanical device (such as an internal
combustion engine) with the lubricating composition. The invention
further relates to the use of the quaternised polyester salt as a
dispersant.
Inventors: |
Gieselman; Matthew D.;
(Wickliffe, OH) ; Jones; Joanne L.; (Nottingham,
GB) ; Moreton; David J.; (Belper, GB) ;
Thetford; Dean; (Norden, GB) ; Greenfield;
Hannah; (Derby, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Gieselman; Matthew D.
Jones; Joanne L.
Moreton; David J.
Thetford; Dean
Greenfield; Hannah |
Wickliffe
Nottingham
Belper
Norden
Derby |
OH |
US
GB
GB
GB
GB |
|
|
Family ID: |
46397647 |
Appl. No.: |
14/123645 |
Filed: |
June 18, 2012 |
PCT Filed: |
June 18, 2012 |
PCT NO: |
PCT/US12/42882 |
371 Date: |
December 3, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61499333 |
Jun 21, 2011 |
|
|
|
Current U.S.
Class: |
508/291 |
Current CPC
Class: |
C10M 133/06 20130101;
C10M 133/08 20130101; C10M 149/14 20130101; C10M 2205/022 20130101;
C10N 2030/04 20130101; C10M 2229/02 20130101; C10M 2219/046
20130101; C10N 2040/25 20130101; C10M 2203/1025 20130101; C10M
133/44 20130101; C10M 2223/045 20130101; C10M 2215/064 20130101;
C10M 2207/028 20130101; C10N 2040/252 20200501; C10M 2223/045
20130101; C10N 2010/04 20130101; C10M 2205/022 20130101; C10M
2205/024 20130101; C10M 2219/046 20130101; C10N 2010/02 20130101;
C10M 2219/046 20130101; C10N 2010/04 20130101; C10M 2219/046
20130101; C10N 2010/02 20130101; C10M 2223/045 20130101; C10N
2010/04 20130101; C10M 2219/046 20130101; C10N 2010/04
20130101 |
Class at
Publication: |
508/291 |
International
Class: |
C10M 149/14 20060101
C10M149/14; C10M 133/44 20060101 C10M133/44 |
Claims
1. A lubricating composition comprising an oil of lubricating
viscosity 0.1 wt % to 15 wt % of a dispersant, wherein the
dispersant is a polyisobutylene succinimide, wherein the
polyisobutylene from which the polyisobutylene succinimide is
derived has a number average molecular weight in the range of 350
to 5000. and 0.1 wt % to 10 wt % of a quaternised polyester salt
which comprises a product obtained/obtainable by reaction of (i) a
polyester containing a tertiary amino group; and (ii) a
quaternising agent suitable for converting the tertiary amino group
to a quaternary nitrogen, wherein the quaternising agent is
selected from the group consisting of a dialkyl sulphate, a benzyl
halide, an organic carbonate, an ester of a polycarboxylic acid, an
organic epoxide in combination with an acid, and mixtures
thereof.
2. The lubricating composition of claim 1 wherein the polyester
comprises the reaction product of a fatty carboxylic acid
containing at least one hydroxyl group and a compound having an
oxygen or nitrogen atom capable of condensing with said acid and
further having a tertiary amino group.
3. The lubricating composition of claim 2 wherein the fatty
carboxylic acid is represented by the formula: ##STR00006## where
R.sup.1 is a hydrogen or a hydrocarbyl group containing from 1 to
20 carbon atoms and R.sup.2 is a hydrocarbylene group containing
from 1 to 20 carbon atoms, with the proviso that the total number
of carbon atoms present from R.sup.1 and R.sup.2 is 6 or more, or 8
or more; and wherein the compound having an oxygen or nitrogen atom
capable of condensing with said acid and further having a tertiary
amino group is represented by the formula: ##STR00007## where
R.sup.3 is a hydrocarbyl group containing from 1 to 10 carbon
atoms; R.sup.4 is a hydrocarbyl group containing from 1 to 10
carbon atoms; R.sup.5 is a hydrocarbylene group containing from 1
to 20 carbon atoms; and X.sup.1 is O or NR.sup.6 where R.sup.6 is a
hydrogen or a hydrocarbyl group containing from 1 to 10 carbon
atoms.
4-15. (canceled)
16. The lubricating composition of claim 1, wherein the quaternised
polyester salt comprises a quaternised polyester amide salt wherein
the polyester containing a tertiary amino group used to prepare
said quaternised polyester salt comprises a polyester amide
containing a tertiary amino group.
17. The lubricating composition of claim 1, wherein the quaternised
polyester salt comprises a cation represented by the following
formula: ##STR00008## where R.sup.1 is a hydrogen or a hydrocarbyl
group containing from 1 to 20 carbon atoms and R.sup.2 is a
hydrocarbylene group containing from 1 to 20 carbon atoms; R.sup.3
is a hydrocarbyl group containing from 1 to 10 carbon atoms;
R.sup.4 is a hydrocarbyl group containing from 1 to 10 carbon
atoms; R.sup.5 is a hydrocarbylene group containing from 1 to 20
carbon atoms; R.sup.6 is a hydrogen or a hydrocarbyl group
containing from 1 to 10 carbon atoms; n is a number from 1 to 10;
R.sup.7 is hydrogen, a hydrocarbyl-substituted carbonyl group
containing from 1 to 22 carbon atoms, or a hydrocarbyl group
containing from 1 to 22 carbon atoms; and X.sup.2 is a group
derived from the quaternising agent.
18. The lubricating composition of claim 2, wherein the compound
having an oxygen or nitrogen atom capable of condensing with said
acid and further having a tertiary amino group comprises
N,N-diethylethylenediamine, N,N-dimethylethylenediamine,
N,N-dibutylethylenediamine, N,N-dimethyl-1,3-diaminopropane,
N,N-diethyl-1,3-diaminopropane, N,N-dimethylamino ethanol,
N,N-diethylaminoethanol, or combinations thereof.
19. The lubricating composition of claim 2, wherein the fatty
carboxylic acid containing at least one hydroxyl group comprises:
12-hydroxystearic acid; ricinoleic acid; 12-hydroxy dodecanoic
acid; 5-hydroxy dodecanoic acid; 5-hydroxy decanoic acid; 4-hydroxy
decanoic acid; 10-hydroxy undecanoic acid; or combinations
thereof.
20. The lubricating composition of claim 1, wherein the
quaternising agent comprises ethylene oxide, propylene oxide,
butylene oxide, styrene oxide, or combinations thereof in
combination with an acid.
21. The lubricating composition of claim 1, wherein the quaternised
polyester salt is present at 1 wt % to 8 wt % of the lubricating
composition.
22. The lubricating composition of claim 1, wherein the quaternised
polyester salt is present at 2 wt % to 6.5 wt % of the lubricating
composition.
23. The lubricating composition of claim 1, wherein the
polyisobutylene from which the polyisobutylene succinimide is
derived has a number average molecular weight in the range of 750
to 2200.
24. The lubricating composition of claim 1, wherein the dispersant
is a polyisobutylene succinimide derived from an aliphatic
polyamine selected from ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, polyamine still bottoms, and mixtures
thereof.
25. The lubricating composition of claim 23, wherein the dispersant
is present at 0.5 wt % to 9 wt % of the lubricating
composition.
26. The lubricating composition of claim 23, wherein the dispersant
is present at 1 wt % to 8.5 wt % of the lubricating
composition.
27. A method of lubricating an internal combustion engine
comprising supplying to the internal combustion engine a
lubricating composition of claim 1.
28. The method of claim 27, wherein the internal combustion engine
has a steel surface on a cylinder bore, cylinder block, or piston
ring.
29. The method of claim 27, wherein the internal combustion engine
has a surface of steel, or an aluminium alloy, or an aluminium
composite.
Description
FIELD OF INVENTION
[0001] The invention provides a lubricating composition containing
a lubricating composition comprising an oil of lubricating
viscosity and a quaternised polyester salt. The invention further
relates to a method of lubricating a mechanical device (such as an
internal combustion engine) with the lubricating composition. The
invention further relates to the use of the quaternised polyester
salt as a dispersant.
BACKGROUND OF THE INVENTION
[0002] In order to reduce deposit formation, detergents and
dispersants are known to assist in maintaining reduced amounts of
deposits on engine components. The lubricant industry has a number
of tests used to evaluate a lubricant's ability to handle deposits
and sludge including the Sequence VG, Sequence IIIG, TDi, Cat 1N,
and OM501LA.
[0003] With recent changes to engine specifications there is an
increasing demand on the lubricant to reduce deposits. For
instance, the new ILSAC GF-5 specification will require a 4.0
piston merit rating in the Sequence IIIG (vs. 3.5 for GF-4).
[0004] International Application WO2007/128740 (published 15 Nov.,
2007) discloses the use of one or more poly (hydroxycarboxylic
acid) amide salt in combination with one or more antiwear additive.
Such compositions were useful for dispersing preformed sludge
deposits.
[0005] International Application WO2009/053413 (published 30 Apr.
2009) and European Patent Application EP2055729 (published 6 May
2009) both disclose compositions comprising base oil and one or
more poly (hydroxycarboxylic acid) amide salt derivatives. The
lubricating oils were useful for reducing wear and friction.
[0006] International Application WO2009/156393 (published 30 Dec.
2009) discloses a lubricant with one or more poly
(hydroxycarboxylic acid) amide salt with TBN less than 10. The
Lubricant ameliorated piston deposits in fired engine tests such as
the TU5 and Sequence IIIF.
[0007] International Application WO2010/012756 (published 4 Feb.
2010) and US Patent Application US2010/0024286 (published 4 Feb.
2010) both disclose a fuel composition comprising a fuel and one or
more poly (hydroxycarboxylic acid) amide salts. Such fuels offered
benefits such as improved lubricity by HFRR, Improved inlet valve
deposits in fired engine tests and improved sludge dispersancy in
the Sequence VG engine test.
[0008] International Application WO2010/014678 (published 4 Feb.
2010) discloses a poly (hydroxycarboxylic acid) amide salt
derivative wherein the anionic portion of the salt does not contain
sulphur. The molecules described showed lower phosphorus volatility
in Selby NOACK testing in fully formulated fluids than similar
materials that had sulphur-containing anions.
[0009] International Application WO2010/015706 (published 11 Feb.
2010) discloses a lubricant comprising base oil, a poly
(hydroxycarboxylic acid) amide salt and one or more detergents. The
composition is useful for dispersing preformed sludge deposits.
[0010] International Application WO2010/012763 (published 4 Feb.
2010) and US Patent Application US2010/0024287 (published 4 Feb.
2010) both disclose a fuel composition comprising a fuel and one or
more poly (hydroxycarboxylic acid) derivative having a terminal
acid group. The fuels of the disclosed composition demonstrated
some improved lubricity characteristics.
[0011] International publication WO 2011/095819 (published 11 Aug.
2011) discloses a diesel fuel composition comprising, as a fuel
additive, a quaternary ammonium salt wherein the quaternising agent
is an ester of a polycarboxylic acid such as dimethyl oxalate. The
fuel composition disclosed has reduced occurrence of deposits in a
diesel engine.
SUMMARY OF THE INVENTION
[0012] The objectives of the present invention include providing at
least one of (i) dispersancy, (ii) cleanliness, or (iii) a
lubricant with reduced sludge formation.
[0013] As used herein reference to the amounts of additives present
in the lubricating composition disclosed are quoted on an oil free
basis, i.e., amount of actives, unless otherwise indicated.
[0014] In one embodiment the present invention provides a
lubricating composition comprising an oil of lubricating viscosity
and a quaternised polyester salt which comprises a product
obtained/obtainable by reaction of (i) a polyester containing a
tertiary amino group; and (ii) a quaternising agent suitable for
converting the tertiary amino group to a quaternary nitrogen,
wherein the quaternising agent is selected from the group
consisting of a dialkyl sulphate, a benzyl halide, an organic
carbonate, an ester of a polycarboxylic acid, an organic epoxide in
combination with an acid, and mixtures thereof.
[0015] In one embodiment the present invention provides a
lubricating composition comprising a dispersant (typically a
succinimide dispersant), an oil of lubricating viscosity and a
quaternised polyester salt which comprises a product
obtained/obtainable by reaction of (that is to say, which may be
the reaction product of) (i) a polyester containing a tertiary
amino group; and (ii) a quaternising agent suitable for converting
the tertiary amino group to a quaternary nitrogen, wherein the
quaternising agent is selected from the group consisting of a
dialkyl sulphate, a benzyl halide, an organic carbonate (such as an
alkylene carbonate or a dialkyl carbonate), an ester of a
polycarboxylic acid, an organic epoxide (such as a hydrocarbyl
epoxide, or ethylene oxide) in combination with an acid, and
mixtures thereof.
[0016] In one embodiment the present invention provides a
lubricating composition comprising:
an oil of lubricating viscosity; 0.1 wt % to 10 wt %, or 1 wt % to
8 wt % of a quaternised polyester salt which comprises a product
obtained/obtainable by reaction of (i) a polyester containing a
tertiary amino group; and (ii) a quaternising agent suitable for
converting the tertiary amino group to a quaternary nitrogen,
wherein the quaternising agent is selected from the group
consisting of a dialkyl sulphate, a benzyl halide, an organic
carbonate; an organic epoxide in combination with an acid or
mixtures thereof; and 0.1 wt % to 15 wt %, or 0.5 wt % to 9 wt % of
a dispersant (typically a succinimide dispersant).
[0017] In one embodiment the present invention provides a
lubricating composition comprising:
an oil of lubricating viscosity; 2 wt % to 6.5 wt % of a
quaternised polyester salt which comprises a product
obtained/obtainable by reaction of (i) a polyester containing a
tertiary amino group; and (ii) a quaternising agent suitable for
converting the tertiary amino group to a quaternary nitrogen,
wherein the quaternising agent is selected from the group
consisting of a dialkyl sulphate, a benzyl halide, an organic
carbonate, an ester of a polycarboxylic acid, an organic epoxide in
combination with an acid, and mixtures thereof; and 2 wt % to 8.5
wt % of a dispersant (typically a succinimide dispersant).
[0018] In one embodiment the invention provides for a method of
lubricating a mechanical device with a lubricating composition
disclosed herein. The mechanical device may be an internal
combustion engine.
[0019] The internal combustion engine may have a steel surface on
at least one of a cylinder bore, cylinder block, or piston
ring.
[0020] The internal combustion engine may have an aluminium alloy,
or aluminium composite surface on at least one of a cylinder bore,
cylinder block, or piston ring.
[0021] In one embodiment the invention provides for the use of the
polyester quaternary salt of the invention as a dispersant in a
lubricant for use in an internal combustion engine.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The present invention provides a detergent, a process to
prepare a detergent, a lubricating composition, a method for
lubricating a mechanical device and a use as disclosed above.
The Polyester Quaternary Ammonium Salt
[0023] The polyester quaternary salt of the invention includes
quaternised polyester amine, amide, and ester salts. The additives
may also be described as quaternary polyester salts. The additives
of the invention may be described as the reaction product of: a
polyester containing a tertiary amino group; and a quaternising
agent suitable for converting the tertiary amino group to a
quaternary nitrogen. The quaternising agent may be selected from
the group consisting of a dialkyl sulphate, a benzyl halide, an
organic carbonate, an ester of a polycarboxylic acid, an organic
epoxide in combination with an acid, and mixtures thereof.
The Non-Quaternised Polyester
[0024] The polyester containing a tertiary amino group used in the
preparation of the additives of the invention may also be described
as a non-quaternised polyester containing a tertiary amino
group.
[0025] As used herein the term "fatty carboxylic acid" used in
relation to the polyester means an acid with a carbon chain of 8 to
22, or 10 to 22 carbon atoms.
[0026] In some embodiments the polyester may be a reaction product
of a fatty carboxylic acid containing at least one hydroxyl group
and a compound having an oxygen or nitrogen atom capable of
condensing with said acid and further having a tertiary amino
group. The reaction product may be formed by adding the fatty
carboxylic acid and the compound having an oxygen or nitrogen atom
capable of condensing with said acid in any order. Suitable fatty
carboxylic acids that may used in the preparation of the polyesters
described above may be represented by the formula:
##STR00001##
wherein R.sup.1 may be a hydrogen or a hydrocarbyl group containing
from 1 to 20 carbon atoms and R.sup.2 may be a hydrocarbylene group
containing from 1 to 20 carbon atoms, with the proviso that the
total number of carbon atoms present from R.sup.1 and R.sup.2 may
be 6 or more, or 8 or more. In some embodiments R.sup.1 contains
from 1 to 12, 2 to 10, 4 to 8 or even 6 carbon atoms R.sup.2 may
contain from 2 to 16, 6 to 14, 8 to 12, or even 10 carbon
atoms.
[0027] In some embodiments the fatty carboxylic acid used in the
preparation of the polyester may be 12-hydroxystearic acid,
ricinoleic acid, 12-hydroxy dodecanoic acid, 5-hydroxy dodecanoic
acid, 5-hydroxy decanoic acid, 4-hydroxy decanoic acid, 10-hydroxy
undecanoic acid, or combinations thereof.
[0028] In some embodiments the compound having an oxygen or
nitrogen atom capable of condensing with said acid and further
having a tertiary amino group may be represented by the
formula:
##STR00002##
wherein R.sup.3 may be a hydrocarbyl group containing from 1 to 10
carbon atoms; R.sup.4 may be a hydrocarbyl group containing from 1
to 10 carbon atoms; R.sup.5 may be a hydrocarbylene group
containing from 1 to 20 carbon atoms; and X.sup.1 may be O or
NR.sup.6 where R.sup.6 may be a hydrogen or a hydrocarbyl group
containing from 1 to 10 carbon atoms. In some embodiments R.sup.3
contains from 1 to 6, 1 to 2, or even 1 carbon atom, R.sup.4
contains from 1 to 6, 1 to 2, or even 1 carbon atom, R.sup.5
contains from 2 to 12, 2 to 8 or even 3 carbon atoms, and R.sup.6
contains from 1 to 8, or 1 to 4 carbon atoms. In some of these
embodiments, formula (II) becomes:
##STR00003##
wherein the various definitions provided above still apply.
[0029] Examples of nitrogen or oxygen containing compounds capable
of condensing with the acylating agents, which also have a tertiary
amino group, or compounds that may be alkylated into such
compounds, include: 1-aminopiperidine, 1-(2-aminoethyl)piperidine,
1-(3-aminopropyl)-2-pipecoline, 1-methyl-(4-methylamino)piperidine,
4-(1-pyrrolidinyl)piperidine, 1-(2-amino-ethyl)pyrrolidine,
2-(2-aminoethyl)-1-methylpyrrolidine, N,N-diethylethylene-diamine,
N,N-dimethylethylenediamine, N,N-dibutylethylenediamine,
N,N-diethyl-1,3-diaminopropane, N,N-dimethyl-1,3-diaminopropane,
N,N,N'-trimethylethylenediamine,
N,N-dimethyl-N'-ethylethylenediamine,
N,N-diethyl-N'-methylethylenediamine,
N,N,N'-triethylethylenediamine, 3-dimethylamino-propylamine,
3-diethylaminopropylamine, 3-dibutylaminopropylamine,
N,N,N'-trimethyl-1,3-propanediamine,
N,N,2,2-tetramethyl-1,3-propanediamine,
2-amino-5-diethylaminopentane,
N,N,N',N'-tetraethyldiethylenetriamine,
3,3'-diamino-N-methyldipropylamine,
3,3'-iminobis(N,N-dimethylpropylamine), or combinations thereof. In
such embodiments, the resulting additive includes a quaternary
ammonium amide salt, containing an amide group and a quaternary
ammonium salt.
[0030] The nitrogen or oxygen containing compounds may further
include aminoalkyl substituted heterocyclic compounds such as
1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine.
[0031] Another type of nitrogen or oxygen containing compounds
capable of condensing with the acylating agent and having a
tertiary amino group, in some embodiments after further alkylation,
includes alkanolamines including but not limited to
triethanolamine, N,N-dimethylaminopropanol,
N,N-diethyl-aminopropanol, N,N-diethylaminobutanol,
triisopropanolamine, 1-[2-hydroxy-ethyl]piperidine,
2-[2-(dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine,
N-methyldiethanol amine, N-butyldiethanolamine, N,N-diethylamino
ethanol, N,N-dimethylamino ethanol,
2-dimethylamino-2-methyl-1-propanol. In embodiments where
alkanolamines and/or similar materials are used, the resulting
additive includes a quaternary ammonium ester salt, containing an
ester group and a quaternary ammonium salt.
[0032] In one embodiment the nitrogen or oxygen containing compound
may be triisopropanolamine, 1-[2-hydroxyethyl]piperidine,
2-[2-(dimethylamino) ethoxy]-ethanol, N-ethyldiethanolamine,
N-methyldiethanolamine, N-butyldiethanolamine,
N,N-diethylaminoethanol, N,N-dimethylaminoethanol,
2-dimethylamino-2-methyl-1-propanol, or combinations thereof.
[0033] In some embodiments the compound having an oxygen or
nitrogen atom capable of condensing with said acid and further
having a tertiary amino group comprises N,N-diethylethylenediamine,
N,N-dimethylethylenediamine, N,N-dibutylethylenediamine,
N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane,
N,N-dimethylaminoethanol, N,N-diethylamino ethanol, or combinations
thereof.
[0034] The quaternised polyester salt may be a quaternised
polyester amide salt. In such embodiments the polyester containing
a tertiary amino group used to prepare the quaternised polyester
salt may be a polyester amide containing a tertiary amino group. In
some of these embodiments the amine or aminoalcohol may be reacted
with a monomer and then the resulting material may be polymerised
with additional monomer, resulting in the desired polyester amide
which may then be quaternised.
[0035] In some embodiments the quaternised polyester salt includes
an cation represented by the following formula:
##STR00004##
wherein R.sup.1 may be a hydrogen or a hydrocarbyl group containing
from 1 to 20 carbon atoms and R.sup.2 may be a hydrocarbylene group
containing from 1 to 20 carbon atoms; R.sup.3 may be a hydrocarbyl
group containing from 1 to 10 carbon atoms; R.sup.4 may be a
hydrocarbyl group containing from 1 to 10 carbon atoms; R.sup.5 may
be a hydrocarbylene group containing from 1 to 20 carbon atoms;
R.sup.6 may be a hydrogen or a hydrocarbyl group containing from 1
to 10 carbon atoms; n may be a number from 1 to 10; R.sup.7 may be
hydrogen, a hydrocarbyl-substituted carbonyl group containing from
1 to 22 carbon atoms (i.e., a hydrocarbyl-substituted carbonyl
group may be a hydrocarbyl group containing a carbonyl group that
bonds to the --O-- within [ ].sub.n), or a hydrocarbyl group
containing from 1 to 22 carbon atoms; and X.sup.2 may be a group
derived from the quaternising agent. In some embodiments R.sup.6
may be hydrogen.
[0036] As above, in some embodiments R.sup.1 contains from 1 to 12,
2 to 10, 4 to 8 or even 6 carbon atoms, and R.sup.2 contains from 2
to 16, 6 to 14, 8 to 12, or even 10 carbon atoms, R.sup.3 contains
from 1 to 6, 1 to 2, or even 1 carbon atom, R.sup.4 contains from 1
to 6, 1 to 2, or even 1 carbon atom, R.sup.5 contains from 2 to 12,
2 to 8 or even 3 carbon atoms, and R.sup.6 contains from 1 to 8, or
1 to 4 carbon atoms. In any of these embodiments n may be from 2 to
9, or 3 to 7, and R.sup.7 may contain from 6 to 22, or 8 to 20
carbon atoms.
[0037] In these embodiments the quaternised polyester salt may be
capped with a C1-22, or a C8-20, fatty acid. Examples of suitable
acids include oleic acid, palmitic acid, stearic acid, erucic acid,
lauric acid, 2-ethylhexanoic acid, 9,11-linoleic acid,
9,12-linoleic acid, 9,12,15-linolenic acid, abietic acid, or
combinations thereof.
[0038] The number average molecular weight (Mn) of the quaternised
polyester salts of the invention may be from 500 to 3000, or from
700 to 2500.
[0039] The polyester useful in the present invention may be
obtained/obtainable by heating one or more hydroxycarboxylic acids
or a mixture of the hydroxycarboxylic acid and a carboxylic acid,
optionally in the presence of an esterification catalyst. The
hydroxycarboxylic acids may, in certain embodiments, have the
formula HO--X--COOH wherein X may be a divalent saturated or
unsaturated aliphatic radical containing at least 8 carbon atoms
and in which there are at least 4 carbon atoms between the hydroxy
and carboxylic acid groups, or from a mixture of such a
hydroxycarboxylic acid and a carboxylic acid which is free from
hydroxy groups. This reaction may be carried out at a temperature
in the region of 160.degree. C. to 200.degree. C., until the
desired molecular weight has been obtained. The course of the
esterification may be followed by measuring the acid value of the
product, with the desired polyester, in some embodiments, having an
acid value in the range of 10 to 100 mg KOH/g or in the range of 20
to 50 mg KOH/g. The indicated acid value range of 10 to 100 mg
KOH/g is equivalent to a number average molecular weight range of
5600 to 560. The water formed in the esterification reaction may be
removed from the reaction medium, and this may be conveniently done
by passing a stream of nitrogen over the reaction mixture or by
carrying out the reaction in the presence of a solvent, such as
toluene or xylene, and distilling off the water as it is
formed.
[0040] The resulting polyester may then be isolated in conventional
manner; however, when the reaction is carried out in the presence
of an organic solvent whose presence would not be harmful in the
subsequent application, the resulting solution of the polyester may
be used.
[0041] In the said hydroxycarboxylic acids the radical represented
by X may contain from 12 to 20 carbon atoms, optionally where there
are between 8 and 14 carbon atoms between the carboxylic acid and
hydroxy groups. In some embodiments the hydroxycarboxylic acid may
contain a second hydroxy group. Typically, the hydroxycarboxylic
acid may contain one hydroxy group, and one carboxylic acid
group.
[0042] Specific examples of such hydroxycarboxylic acids include
ricinoleic acid, a mixture of 9- and 10-hydroxystearic acids
(obtained by sulphation of oleic acid followed by hydrolysis), and
12-hydroxystearic acid, and especially the commercially available
hydrogenated castor oil fatty acid which contains in addition to
12-hydroxystearic acid minor amounts of stearic acid and palmitic
acid.
[0043] The carboxylic acids which may be used in conjunction with
the hydroxycarboxylic acids to obtain these polyesters are
preferably carboxylic acids of saturated or unsaturated aliphatic
compounds, particularly alkyl and alkenyl carboxylic acids
containing a chain of from 8 to 20 carbon atoms. As examples of
such acids there may be mentioned lauric acid, palmitic acid,
stearic acid and oleic acid.
[0044] In one embodiment the polyester may be derived from
commercial 12-hydroxy-stearic acid and may have a number average
molecular weight of about 1600. Polyesters such as this are
described in greater detail in U.K. Patent Specification Nos.
1373660 and 1342746.
[0045] In some embodiments the components used to prepare the
additives described above are substantially free of, essentially
free of, or even completely free of, non-polyester-containing
hydrocarbyl substituted acylating agents and/or
non-polyester-containing hydrocarbyl substituted diacylating
agents, such as for example polyisobutylene succinic anhydride. In
some embodiments these excluded agents are the reaction product of
a long chain hydrocarbon, generally a polyolefin, reacted with a
monounsaturated carboxylic acid reactant, such as, (i)
.alpha.,.beta.-monounsaturated C.sub.4 to C.sub.10 dicarboxylic
acid, such as fumaric acid, itaconic acid, maleic acid; (ii)
derivatives of (i) such as anhydrides or C.sub.1 to C.sub.5 alcohol
derived mono- or di-esters of (i); (iii)
.alpha.,.beta.-monounsaturated C.sub.3 to C.sub.10 monocarboxylic
acid such as acrylic acid and methacrylic acid; or (iv) derivatives
of (iii), such as C.sub.1 to C.sub.5 alcohol derived esters of
(iii) with any compound containing an olefinic bond represented by
the general formula
(R.sup.9)(R.sup.10)C.dbd.C(R.sup.11(CH(R.sup.7)(R.sup.8)) wherein
each of R.sup.9 and R.sup.10 may be independently hydrogen or a
hydrocarbon based group; each of R.sup.11, R.sup.7 and R.sup.8 may
be independently hydrogen or a hydrocarbon based group and
preferably at least one may be a hydrocarbyl group containing at
least 20 carbon atoms. In one embodiment, the excluded
hydrocarbyl-substituted acylating agent may be a dicarboxylic
acylating agent. In some of these embodiments, the excluded
hydrocarbyl-substituted acylating agent is polyisobutylene succinic
anhydride.
[0046] By substantially free of, it is meant that the components of
the present invention are primarily composed of materials other
than hydrocarbyl substituted acylating agents described above such
that these agents are not significantly involved in the reaction
and the compositions of the invention do not contain significant
amounts of additives derived from such agents.
The Quaternising Agent
[0047] The quaternised salt of the present invention are formed
when the non-quaternised polyester described above are reacted with
a quaternising agent. Suitable quaternising agents include a
dialkyl sulphate, a benzyl halide, an organic carbonate; an ester
of a polycarboxylic acid, an organic epoxide in combination with an
acid, and mixtures thereof.
[0048] In one embodiment, the quaternising agent may include an
ester of a polycarboxylic acid. The ester of a polycarboxylic acid
is described in international publication WO 2011/095819 (published
11 Aug. 2011).
[0049] In this definition we mean to include dicarboxylic acids and
carboxylic acids having more than 2 acidic moieties. In some
embodiments the esters are alkyl esters with alkyl groups that
contain from 1 to 4 carbon atoms. Suitable examples include
diesters of oxalic acid, diesters of phthalic acid, diesters of
maleic acid, diesters of malonic acid, diesters of tartaric acid,
or diesters or triesters of citric acid.
[0050] In some embodiments the quaternizing agent is an ester of a
carboxylic acid having a pKa of less than 3.5. In such embodiments
in which the compound includes more than one acid group, we mean to
refer to the first dissociation constant. The quaternizing agent
may be selected from an ester of a carboxylic acid selected from
one or more of oxalic acid, phthalic acid, salicylic acid, maleic
acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic
acid and 2,4,6-trihydroxybenzoic acid. In some embodiments the
quaternizing agent includes dimethyl oxalate, methyl
2-nitrobenzoate and methyl salicylate.
[0051] In one embodiment, the quaternising agent may include an
alkyl halide, such as a chloride, an iodide or a bromide; an alkyl
sulphonate; a dialkyl sulphate, such as dimethyl sulphate;
sultones; alkyl a phosphate such as, C1-12 trialkylphosphates; di
C1-12 alkylphosphates; a borate; a C1-12 alkyl borate; an alkyl
nitrite; an alkyl nitrate; a dialkyl carbonate; an alkyl alkanoate;
an O,O-di-C1-12 alkyldithiophosphate; or mixtures thereof.
[0052] In one embodiment, the quaternising agent may be derived
from a dialkyl sulphate such as dimethyl sulphate, N-oxides,
sultones such as propane and butane sultone; alkyl, acyl or
araalkyl halides such as methyl and ethyl chloride, bromide or
iodide or benzyl chloride, and a hydrocarbyl (or alkyl) substituted
carbonates. If the alkyl halide may be benzyl chloride, the
aromatic ring may be optionally further substituted with alkyl or
alkenyl groups.
[0053] The hydrocarbyl (or alkyl) groups of the hydrocarbyl
substituted carbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1
to 5 carbon atoms per group. In one embodiment, the hydrocarbyl
substituted carbonates contain two hydrocarbyl groups that may be
the same or different. Examples of suitable hydrocarbyl substituted
carbonates include dimethyl or diethyl carbonate.
[0054] In another embodiment, the quaternising agent may be an
organic epoxide, as represented by the following formula, in
combination with an acid:
##STR00005##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be independently
H or a hydrocarbyl group contain from 1 to 50 carbon atoms.
Examples of an organic epoxide include ethylene oxide, propylene
oxide, butylene oxide, styrene oxide and combinations thereof. In
one embodiment the quaternising agent does not contain styrene
oxide.
[0055] In some embodiments the acid used with the hydrocarbyl
epoxide may be a separate component, such as acetic acid. In other
embodiments, for example when the hydrocarbyl acylating agent may
be a dicarboxylic acylating agent, no separate acid component is
needed. In such embodiments, the detergent may be prepared by
combining reactants which are essentially free of, or even free of,
a separate acid component, such as acetic acid, and rely on the
acid group of the hydrocarbyl acylating agent instead. In other
embodiments, a small amount of an acid component may be present,
but at <0.2 or even <0.1 moles of acid per mole of
hydrocarbyl acylating agent.
[0056] In some embodiments the quaternising agent of the invention
does not contain any substituent group that contains more than 20
carbon atoms. In other words, in some embodiments the long
substituent group that allows for the resulting additive to be
organic soluble and thus useful for the purposes of this invention
is not provided by the quaternising agent but instead is brought to
the additive by the non-quaternised polyester having an amine
functionality to quaternising agent ratio of 1:0.1 to 2, or 1:1 to
1.5, or 1:1 to 1.3.
[0057] In certain embodiments the quaternised polyester salt may be
present at 0.1 wt % to 10 wt %, or 1 wt % to 8 wt %, or 2 wt % to
6.5 wt % of the lubricating composition.
Dispersant
[0058] The lubricating composition may further include a
dispersant, or mixtures thereof. The dispersant may be a
succinimide dispersant, a Mannich dispersant, a succinamide
dispersant, a polyolefin succinic acid ester, amide, or
ester-amide, or mixtures thereof. In one embodiment the invention
does include a dispersant or mixtures thereof. The dispersant may
be present as a single dispersant. The dispersant may be present as
a mixture of two or more (typically two or three) different
dispersants, wherein at least one may be a succinimide
dispersant.
[0059] The succinimide dispersant may be derived from an aliphatic
polyamine, or mixtures thereof. The aliphatic polyamine may be
aliphatic polyamine such as an ethylenepolyamine, a
propylenepolyamine, a butylenepolyamine, or mixtures thereof. In
one embodiment the aliphatic polyamine may be ethylenepolyamine. In
one embodiment the aliphatic polyamine may be selected from the
group consisting of ethylenediamine, diethylenetriamine,
triethylenetetramine, tetra-ethylenepentamine,
pentaethylenehexamine, polyamine still bottoms, and mixtures
thereof.
[0060] In one embodiment the dispersant may be a polyolefin
succinic acid ester, amide, or ester-amide. For instance, a
polyolefin succinic acid ester may be a polyisobutylene succinic
acid ester of pentaerythritol, or mixtures thereof. A polyolefin
succinic acid ester-amide may be a polyisobutylene succinic acid
reacted with an alcohol (such as pentaerythritol) and an amine
(such as a diamine, typically diethyleneamine).
[0061] The dispersant may be an N-substituted long chain alkenyl
succinimide. An example of an N-substituted long chain alkenyl
succinimide is polyisobutylene succinimide. Typically the
polyisobutylene from which polyisobutylene succinic anhydride is
derived has a number average molecular weight of 350 to 5000, or
550 to 3000 or 750 to 2500. Succinimide dispersants and their
preparation are disclosed, for instance in U.S. Pat. Nos.
3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022,
3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743,
3,632,511, 4,234,435, Re 26,433, and 6,165,235, 7,238,650 and EP
Patent Application 0 355 895 A.
[0062] The dispersants may also be post-treated by conventional
methods by a reaction with any of a variety of agents. Among these
are boron compounds (such as boric acid), urea, thiourea,
dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones,
carboxylic acids such as terephthalic acid, hydrocarbon-substituted
succinic anhydrides, maleic anhydride, nitriles, epoxides, and
phosphorus compounds. In one embodiment the post-treated dispersant
is borated. In one embodiment the post-treated dispersant is
reacted with dimercaptothiadiazoles. In one embodiment the
post-treated dispersant is reacted with phosphoric or phosphorous
acid. In one embodiment the post-treated dispersant is reacted with
terephthalic acid and boric acid (as described in US Patent
Application US2009/0054278.
[0063] In one embodiment the dispersant may be borated or
non-borated. Typically a borated dispersant may be a succinimide
dispersant.
[0064] The dispersant may be prepared/obtained/obtainable from
reaction of succinic anhydride by an "ene" or "thermal" reaction,
by what is referred to as a "direct alkylation process." The "ene"
reaction mechanism and general reaction conditions are summarised
in "Maleic Anhydride", pages, 147-149, Edited by B. C. Trivedi and
B. C. Culbertson and Published by Plenum Press in 1982. The
dispersant prepared by a process that includes an "ene" reaction
may be a polyisobutylene succinimide having a carbocyclic ring
present on less than 50 mole %, or 0 to less than 30 mole %, or 0
to less than 20 mole %, or 0 mole % of the dispersant molecules.
The "ene" reaction may have a reaction temperature of 180.degree.
C. to less than 300.degree. C., or 200.degree. C. to 250.degree.
C., or 200.degree. C. to 220.degree. C.
[0065] The dispersant may also be obtained/obtainable from a
chlorine-assisted process, often involving Diels-Alder chemistry,
leading to formation of carbocyclic linkages. The process is known
to a person skilled in the art. The chlorine-assisted process may
produce a dispersant that is a polyisobutylene succinimide having a
carbocyclic ring present on 50 mole % or more, or 60 to 100 mole %
of the dispersant molecules. Both the thermal and chlorine-assisted
processes are described in greater detail in U.S. Pat. No.
7,615,521, columns 4-5 and preparative examples A and B.
[0066] The dispersant may have a carbonyl to nitrogen ratio (CO:N
ratio) of 5:1 to 1:10, 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1:2.
In one embodiment the dispersant may have a CO:N ratio of 2:1 to
1:10, or 2:1 to 1:5, or 2:1 to 1:2, or 1:1.4 to 1:0.6.
[0067] The dispersant may be present at 0 wt % to 20 wt %, 0.1 wt %
to 15 wt %, or 0.5 wt % to 9 wt %, or 1 wt % to 8.5 wt % of the
lubricating composition.
Oils of Lubricating Viscosity
[0068] The lubricating composition comprises an oil of lubricating
viscosity. Such oils include natural and synthetic oils, oil
derived from hydrocracking, hydrogenation, and hydrofinishing,
unrefined, refined, re-refined oils or mixtures thereof. A more
detailed description of unrefined, refined and re-refined oils is
provided in International Publication WO2008/147704, paragraphs
[0054] to [0056] (a similar disclosure is provided in US Patent
Application 2010/197536, see [0072] to [0073]). A more detailed
description of natural and synthetic lubricating oils is described
in paragraphs [0058] to [0059] respectively of WO2008/147704 (a
similar disclosure is provided in US Patent Application
2010/197536, see [0075] to [0076]). Synthetic oils may also be
produced by Fischer-Tropsch reactions and typically may be
hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one
embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid
synthetic procedure as well as other gas-to-liquid oils.
[0069] Oils of lubricating viscosity may also be defined as
specified in April 2008 version of "Appendix E--API Base Oil
Interchangeability Guidelines for Passenger Car Motor Oils and
Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock
Categories". The API Guidelines are also summarised in U.S. Pat.
No. 7,285,516 (see column 11, line 64 to column 12, line 10). In
one embodiment the oil of lubricating viscosity may be an API Group
II, Group III, Group IV oil, or mixtures thereof.
[0070] The amount of the oil of lubricating viscosity present is
typically the balance remaining after subtracting from 100 wt % the
sum of the amount of the compound of the invention and the other
performance additives.
[0071] The lubricating composition may be in the form of a
concentrate and/or a fully formulated lubricant. If the lubricating
composition of the invention (comprising the additives disclosed
herein) is in the form of a concentrate which may be combined with
additional oil to form, in whole or in part, a finished lubricant),
the ratio of the of these additives to the oil of lubricating
viscosity and/or to diluent oil include the ranges of 1:99 to 99:1
by weight, or 80:20 to 10:90 by weight.
Other Performance Additives
[0072] A lubricating composition may be prepared by adding the
product of the process described herein to an oil of lubricating
viscosity, optionally in the presence of other performance
additives (as described herein below).
[0073] The lubricating composition of the invention optionally
comprises other performance additives. The other performance
additives include at least one of metal deactivators, viscosity
modifiers, detergents, friction modifiers, antiwear agents,
corrosion inhibitors, dispersant viscosity modifiers, extreme
pressure agents, antioxidants, foam inhibitors, demulsifiers, pour
point depressants, seal swelling agents and mixtures thereof.
Typically, fully-formulated lubricating oil will contain one or
more of these performance additives.
[0074] The lubricating composition of the invention may further
include other additives. In one embodiment the invention provides a
lubricating composition further comprising at least one of a
dispersant, an antiwear agent, a dispersant viscosity modifier, a
friction modifier, a viscosity modifier, an antioxidant, an
overbased detergent, or mixtures thereof. In one embodiment the
invention provides a lubricating composition further comprising at
least one of a polyisobutylene succinimide dispersant, an antiwear
agent, a dispersant viscosity modifier, a friction modifier, a
viscosity modifier (typically an olefin copolymer such as an
ethylene-propylene copolymer), an antioxidant (including phenolic
and aminic antioxidants), an overbased detergent (including
overbased sulphonates and phenates), or mixtures thereof.
[0075] In one embodiment the lubricating composition may be a
lubricating composition further comprising a molybdenum compound.
The molybdenum compound may be an antiwear agent or an antioxidant.
The molybdenum compound may be selected from the group consisting
of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates,
amine salts of molybdenum compounds, and mixtures thereof. The
molybdenum compound may provide the lubricating composition with 0
to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 300 ppm,
or 20 ppm to 250 ppm of molybdenum.
[0076] Antioxidants include sulphurised olefins, diarylamines,
alkylated diarylamines, hindered phenols, molybdenum compounds
(such as molybdenum dithiocarbamates), hydroxyl thioethers, or
mixtures thereof. In one embodiment the lubricating composition
includes an antioxidant, or mixtures thereof. The antioxidant may
be present at 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt
% to 5 wt %, or 0.5 wt % to 3 wt %, or 0.3 wt % to 1.5 wt % of the
lubricating composition.
[0077] The diarylamine or alkylated diarylamine may be a
phenyl-.alpha.-naphthylamine (PANA), an alkylated diphenylamine, or
an alkylated phenylnapthylamine, or mixtures thereof. The alkylated
diphenylamine may include di-nonylated diphenylamine, nonyl
diphenylamine, octyl diphenylamine, di-octylated diphenylamine,
di-decylated diphenylamine, decyl diphenylamine and mixtures
thereof. In one embodiment the diphenylamine may include nonyl
diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl
diphenylamine, or mixtures thereof. In one embodiment the alkylated
diphenylamine may include nonyl diphenylamine, or dinonyl
diphenylamine. The alkylated diarylamine may include octyl,
di-octyl, nonyl, di-nonyl, decyl or di-decyl
phenylnapthylamines.
[0078] 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
or 4-butyl-2,6-di-tert-butylphenol, or
4-dodecyl-2,6-di-tert-butyl-phenol. In one embodiment the hindered
phenol antioxidant may be an ester and may include, e.g.,
Irganox.TM. L-135 from Ciba. A more detailed description of
suitable ester-containing hindered phenol antioxidant chemistry is
found in U.S. Pat. No. 6,559,105.
[0079] Examples of molybdenum dithiocarbamates, which may be used
as an antioxidant, include commercial materials sold under the
trade names such as Vanlube 822.TM. and Molyvan.TM. A from R. T.
Vanderbilt Co., Ltd., and Adeka Sakura-Lube.TM. S-100, S-165, S-600
and 525, or mixtures thereof.
[0080] In one embodiment the lubricating composition further
includes a viscosity modifier. The viscosity modifier is known in
the art and may include hydrogenated styrene-butadiene rubbers,
ethylene-propylene copolymers, polymethacrylates, polyacrylates,
hydrogenated styrene-isoprene polymers, hydrogenated diene
polymers, polyalkyl styrenes, polyolefins, esters of maleic
anhydride-olefin copolymers (such as those described in
International Application WO 2010/014655), esters of maleic
anhydride-styrene copolymers, or mixtures thereof.
[0081] The dispersant viscosity modifier may include functionalised
polyolefins, for example, ethylene-propylene copolymers that have
been functionalised with an acylating agent such as maleic
anhydride and an amine; polymethacrylates functionalised with an
amine, or styrene-maleic anhydride copolymers reacted with an
amine. More detailed description of dispersant viscosity modifiers
are disclosed in International Publication WO2006/015130 or U.S.
Pat. Nos. 4,863,623; 6,107,257; 6,107,258; 6,117,825; and U.S. Pat.
No. 7,790,661. In one embodiment the dispersant viscosity modifier
may include those described in U.S. Pat. No. 4,863,623 (see column
2, line 15 to column 3, line 52) or in International Publication
WO2006/015130 (see page 2, paragraph [0008] and preparative
examples are described paragraphs [0065] to [0073]). In one
embodiment the dispersant viscosity modifier may include those
described in U.S. Pat. No. 7,790,661 column 2, line 48 to column
10, line 38.
[0082] In one embodiment the lubricating composition of the
invention further comprises a dispersant viscosity modifier. The
dispersant viscosity modifier may be present at 0 wt % to 5 wt %,
or 0 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.2 wt % to 1.2 wt
% of the lubricating composition.
[0083] In one embodiment the invention provides a lubricating
composition further comprising an overbased metal-containing
detergent. The metal of the metal-containing detergent may be zinc,
sodium, calcium, barium, or magnesium. Typically the metal of the
metal-containing detergent may be sodium, calcium, or
magnesium.
[0084] The overbased metal-containing detergent may be selected
from the group consisting of non-sulphur containing phenates,
sulphur containing phenates, sulphonates, salixarates, salicylates,
and mixtures thereof, or borated equivalents thereof. The overbased
detergent may be borated with a borating agent such as boric
acid.
[0085] The overbased metal-containing detergent may also include
"hybrid" detergents formed with mixed surfactant systems including
phenate and/or sulphonate components, e.g., phenate/salicylates,
sulphonate/phenates, sulphonate/salicylates,
sulphonates/phenates/salicylates, as described; for example, in
U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179.
Where, for example, a hybrid sulphonate/phenate detergent is
employed, the hybrid detergent would be considered equivalent to
amounts of distinct phenate and sulphonate detergents introducing
like amounts of phenate and sulphonate soaps, respectively.
[0086] Typically an overbased detergent may be sodium, calcium or
magnesium salt of the phenates, sulphur containing phenates,
sulphonates, salixarates and salicylates. Overbased phenates and
salicylates typically have a total base number of 180 to 450 TBN.
Overbased sulphonates typically have a total base number of 250 to
600, or 300 to 500. Overbased detergents are known in the art. In
one embodiment the sulphonate detergent may be a predominantly
linear alkylbenzene sulphonate detergent having a metal ratio of at
least 8 as is described in paragraphs [0026] to [0037] of US Patent
Application 2005065045 (and granted as U.S. Pat. No. 7,407,919).
Linear alkyl benzenes may have the benzene ring attached anywhere
on the linear chain, usually at the 2, 3, or 4 position, or
mixtures thereof. The predominantly linear alkylbenzene sulphonate
detergent may be particularly useful for assisting in improving
fuel economy. In one embodiment the sulphonate detergent may be a
metal salt of one or more oil-soluble alkyl toluene sulphonate
compounds as disclosed in paragraphs [0046] to [0053] of US Patent
Application 2008/0119378.
[0087] Typically the overbased metal-containing detergent may be a
calcium or magnesium an overbased detergent.
[0088] Overbased detergents are known in the art. Overbased
materials, otherwise referred to as overbased or superbased salts,
are generally single phase, homogeneous Newtonian systems
characterised by a metal content in of that which would be present
for neutralization according to the stoichiometry of the metal and
the particular acidic organic compound reacted with the metal. The
overbased materials are prepared by reacting an acidic material
(typically an inorganic acid or lower carboxylic acid, preferably
carbon dioxide) with a mixture comprising an acidic organic
compound, a reaction medium comprising at least one inert, organic
solvent (mineral oil, naphtha, toluene, xylene, etc.) for said
acidic organic material, a stoichiometric excess of a metal base,
and a promoter such as a calcium chloride, acetic acid, phenol or
alcohol. The acidic organic material will normally have a
sufficient number of carbon atoms to provide a degree of solubility
in oil. The amount of "excess" metal (stoichiometrically) is
commonly expressed in terms of metal ratio. The term "metal ratio"
is the ratio of the total equivalents of the metal to the
equivalents of the acidic organic compound. A neutral metal salt
has a metal ratio of one. A salt having 4.5 times as much metal as
present in a normal salt will have metal excess of 3.5 equivalents,
or a ratio of 4.5. The term "metal ratio is also explained in
standard textbook entitled "Chemistry and Technology of
Lubricants", Third Edition, Edited by R. M. Mortier and S. T.
Orszulik, Copyright 2010, page 219, sub-heading 7.25.
[0089] The overbased detergent (other than the detergent of the
present invention) may be present at 0 wt % to 15 wt %, or 0.1 wt %
to 10 wt %, or 0.2 wt % to 8 wt %, or 0.2 wt % to 3 wt %. For
example in a heavy duty diesel engine the detergent may be present
at 2 wt % to 3 wt % of the lubricating composition. For a passenger
car engine the detergent may be present at 0.2 wt % to 1 wt % of
the lubricating composition. In one embodiment, an engine
lubricating composition further comprises at least one overbased
detergent with a metal ratio of at least 3, or at least 8, or at
least 15.
[0090] In one embodiment the friction modifier may be selected from
the group consisting of long chain fatty acid derivatives of
amines, long chain fatty esters, or derivatives of long chain fatty
epoxides; fatty imidazolines; amine salts of alkylphosphoric acids;
fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl
tartramides; fatty glycolates; and fatty glycolamides. The friction
modifier may be present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt
%, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the lubricating
composition.
[0091] As used herein the term "fatty alkyl" or "fatty" in relation
to friction modifiers means a carbon chain having 10 to 22 carbon
atoms, typically a straight carbon chain.
[0092] Examples of suitable friction modifiers include long chain
fatty acid derivatives of amines, fatty esters, or fatty epoxides;
fatty imidazolines such as condensation products of carboxylic
acids and polyalkylene-polyamines; amine salts of alkylphosphoric
acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl
tartramides; fatty phosphonates; fatty phosphites; borated
phospholipids, borated fatty epoxides; glycerol esters; borated
glycerol esters; fatty amines; alkoxylated fatty amines; borated
alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines
including tertiary hydroxy fatty amines; hydroxy alkyl amides;
metal salts of fatty acids; metal salts of alkyl salicylates; fatty
oxazolines; fatty ethoxylated alcohols; condensation products of
carboxylic acids and polyalkylene polyamines; or reaction products
from fatty carboxylic acids with guanidine, aminoguanidine, urea,
or thiourea and salts thereof.
[0093] Friction modifiers may also encompass materials such as
sulphurised fatty compounds and olefins, molybdenum
dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil
or soybean oil monoester of a polyol and an aliphatic carboxylic
acid.
[0094] In one embodiment the friction modifier may be a long chain
fatty acid ester. In another embodiment the long chain fatty acid
ester may be a mono-ester and in another embodiment the long chain
fatty acid ester may be a triglyceride.
[0095] The lubricating composition optionally further includes at
least one antiwear agent. Examples of suitable antiwear agents
include titanium compounds, tartrates, tartrimides, oil soluble
amine salts of phosphorus compounds, sulphurised olefins, metal
dihydrocarbyldithiophosphates (such as zinc
dialkyldithiophosphates), phosphites (such as dibutyl phosphite),
phosphonates, thiocarbamate-containing compounds, such as
thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers,
alkylene-coupled thio-carbamates, and bis(S-alkyldithiocarbamyl)
disulphides.
[0096] The antiwear agent may in one embodiment include a tartrate
or tartrimide as disclosed in International Publication WO
2006/044411 or Canadian Patent CA 1 183 125. The tartrate or
tartrimide may contain alkyl-ester groups, where the sum of carbon
atoms on the alkyl groups is at least 8. The antiwear agent may in
one embodiment include a citrate as is disclosed in US Patent
Application 20050198894.
[0097] The lubricating composition may further include a
phosphorus-containing antiwear agent. Typically the
phosphorus-containing antiwear agent may be a zinc
dialkyldithiophosphate, phosphite, phosphate, phosphonate, and
ammonium phosphate salts, or mixtures thereof. Zinc
dialkyldithiophosphates are known in the art. The antiwear agent
may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5
wt % to 0.9 wt % of the lubricating composition.
[0098] Another class of additives includes oil-soluble titanium
compounds as disclosed in U.S. Pat. No. 7,727,943 and
US2006/0014651. The oil-soluble titanium compounds may function as
antiwear agents, friction modifiers, antioxidants, deposit control
additives, or more than one of these functions. In one embodiment
the oil soluble titanium compound is a titanium (IV) alkoxide. The
titanium alkoxide is formed from a monohydric alcohol, a polyol or
mixtures thereof. The monohydric alkoxides may have 2 to 16, or 3
to 10 carbon atoms. In one embodiment, the titanium alkoxide is
titanium (IV) isopropoxide. In one embodiment, the titanium
alkoxide is titanium (IV) 2-ethylhexoxide. In one embodiment, the
titanium compound comprises the alkoxide of a vicinal 1,2-diol or
polyol. In one embodiment, the 1,2-vicinal diol comprises a fatty
acid mono-ester of glycerol, often the fatty acid is oleic
acid.
[0099] In one embodiment, the oil soluble titanium compound is a
titanium carboxylate. In one embodiment the titanium (IV)
carboxylate is titanium neodecanoate.
[0100] Useful corrosion inhibitors for an engine lubricating
composition include those described in paragraphs 5 to 8 of
WO2006/047486, octylamine octanoate, condensation products of
dodecenyl succinic acid or anhydride and a fatty acid such as oleic
acid with a polyamine. In one embodiment the corrosion inhibitors
include the Synalox.RTM. corrosion inhibitor. The Synalox.RTM.
corrosion inhibitor may be a homopolymer or copolymer of propylene
oxide. The Synalox.RTM. corrosion inhibitor is described in more
detail in a product brochure with Form No. 118-01453-0702 AMS,
published by The Dow Chemical Company. The product brochure is
entitled "SYNALOX Lubricants, High-Performance Polyglycols for
Demanding Applications."
[0101] Foam inhibitors that may be useful in the compositions of
the invention include polysiloxanes, copolymers of ethyl acrylate
and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including fluorinated polysiloxanes, trialkyl phosphates,
polyethylene glycols, polyethylene oxides, polypropylene oxides and
(ethylene oxide-propylene oxide) polymers.
[0102] Pour point depressants that may be useful in the
compositions of the invention include polyalphaolefins, esters of
maleic anhydride-styrene copolymers, poly(meth)acrylates,
polyacrylates or polyacrylamides.
[0103] Demulsifiers include trialkyl phosphates, and various
polymers and copolymers of ethylene glycol, ethylene oxide,
propylene oxide, or mixtures thereof.
[0104] Metal deactivators include derivatives of benzotriazoles
(typically tolyltriazole), 1,2,4-triazoles, benzimidazoles,
2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles. The
metal deactivators may also be described as corrosion
inhibitors.
[0105] Seal swell agents include sulpholene derivatives Exxon
Necton37.TM. (FN 1380) and Exxon Mineral Seal Oil.TM. (FN
3200).
[0106] An engine lubricating composition in different embodiments
may have a composition as disclosed in the following table.
TABLE-US-00001 Embodiments (wt %) Additive A B C Quaternised
Polyester Salt 0.01 to 8 0.1 to 6 0.15 to 5 Dispersant 0 to 12 0 to
8 0.5 to 6 Dispersant Viscosity Modifier 0 to 5 0 to 4 0.05 to 2
Overbased Detergent 0.1 to 15 0.1 to 10 0.2 to 8 Antioxidant 0.1 to
13 0.1 to 10 0.5 to 5 Antiwear Agent 0.1 to 15 0.1 to 10 0.3 to 5
Friction Modifier 0.01 to 6 0.05 to 4 0.1 to 2 Viscosity Modifier 0
to 10 0.5 to 8 1 to 6 Any Other Performance 0 to 10 0 to 8 0 to 6
Additive Oil of Lubricating Viscosity Balance to Balance to Balance
to 100% 100% 100%
INDUSTRIAL APPLICATION
[0107] In one embodiment the invention provides a method of
lubricating an internal combustion engine. The engine components
may have a surface of steel or aluminium.
[0108] An aluminium surface may be derived from an aluminium alloy
that may be a eutectic or a hyper-eutectic aluminium alloy (such as
those derived from aluminium silicates, aluminium oxides, or other
ceramic materials). The aluminium surface may be present on a
cylinder bore, cylinder block, or piston ring having an aluminium
alloy, or aluminium composite.
[0109] The internal combustion engine may or may not have an
exhaust gas recirculation system. The internal combustion engine
may be fitted with an emission control system or a turbocharger.
Examples of the emission control system include diesel particulate
filters (DPF), or systems employing selective catalytic reduction
(SCR).
[0110] In one embodiment the internal combustion engine may be a
diesel fuelled engine (typically a heavy duty diesel engine), a
gasoline fuelled engine, a natural gas fuelled engine, a mixed
gasoline/alcohol fuelled engine, or a hydrogen fuelled internal
combustion engine. In one embodiment the internal combustion engine
may be a diesel fuelled engine and in another embodiment a gasoline
fuelled engine. In one embodiment the internal combustion engine
may be a heavy duty diesel engine.
[0111] The internal combustion engine may be a 2-stroke or 4-stroke
engine. Suitable internal combustion engines include marine diesel
engines, aviation piston engines, low-load diesel engines, and
automobile and truck engines. The marine diesel engine may be
lubricated with a marine diesel cylinder lubricant (typically in a
2-stroke engine), a system oil (typically in a 2-stroke engine), or
a crankcase lubricant (typically in a 4-stroke engine).
[0112] The lubricant composition for an internal combustion engine
may be suitable for any engine lubricant irrespective of the
sulphur, phosphorus or sulphated ash (ASTM D-874) content. The
sulphur content of the engine oil lubricant may be 1 wt % or less,
or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In
one embodiment the sulphur content may be in the range of 0.001 wt
% to 0.5 wt %, or 0.01 wt % to 0.3 wt %. The phosphorus content may
be 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or
0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or
less, 0.055 wt % or less, or 0.05 wt % or less. In one embodiment
the phosphorus content may be 0.04 wt % to 0.12 wt %. In one
embodiment the phosphorus content may be 100 ppm to 1000 ppm, or
200 ppm to 600 ppm. The total sulphated ash content may be 0.3 wt %
to 1.2 wt %, or 0.5 wt % to 1.1 wt % of the lubricating
composition. In one embodiment the sulphated ash content may be 0.5
wt % to 1.1 wt % of the lubricating composition.
[0113] In one embodiment the lubricating composition may be an
engine oil, wherein the lubricating composition may be
characterised as having at least one of (i) a sulphur content of
0.5 wt % or less, (ii) a phosphorus content of 0.12 wt % or less,
and (iii) a sulphated ash content of 0.5 wt % to 1.1 wt % of the
lubricating composition.
[0114] The following examples provide illustrations of the
invention. These examples are non-exhaustive and are not intended
to limit the scope of the invention.
EXAMPLES
Example 1
[0115] A non-quaternised polyester amide is prepared by reacting,
in a jacketed reaction vessel fitted with stirrer, condenser, feed
pump attached to sub-line addition pipe, nitrogen line and
thermocouple/temperature controller system, 6 moles of
12-hydroxystearic acid and 1 mole of dimethylaminopropylamine where
the reaction is carried out at about 130.degree. C. and held for
about 4 hours. The reaction mixture is then cooled to about
100.degree. C. and zirconium butoxide is added, in an amount so
that the catalyst makes up 0.57 percent by weight of the reaction
mixture. The reaction mixture is heated to about 195.degree. C. and
held for about 12 hours. The resulting product is cooled and
collected.
Example 2
[0116] A quaternised polyester amide is prepared by placing 511.7 g
of Example 1 in a 1 L flask with 179 g methanol and 18.1 g acetic
acid. The solution is heated with agitation under an atmosphere of
nitrogen to 55.degree. C. 28.2 g propylene oxide is charged
sub-surface over 4 h and the solution is stirred at 55.degree. C.
for 17 h. 184.5 g diluent oil is added and the vessel is placed
under vacuum. The temperature is increased to 70.degree. C. over 2
hours until the methanol is removed. The solution is further
diluted with 181.6 g diluent oil and cooled to 60.degree. C. 111.3
g of a C20-24 benzene sulphonic acid is added and the solution is
agitated for 2 hours at 60.degree. C. Vacuum is applied to the
vessel and the reaction is stripped of acetic acid for 2 h while
the vessel is warmed to 100.degree. C. The isolated material has a
TAN of 13.59 mg KOH/g, a TBN of 0 mg KOH/g, 0.81% N and a kinematic
viscosity at 100.degree. C. of 90.32 mm/s.
Example 3
[0117] Substantially the same procedure is used as in Example 2
except that styrene oxide is used instead of propylene oxide. The
isolated material has a TAN of 5.62 mg KOH/g, a TBN of 25.87 mg
KOH/g, 0.73% N and a kinematic viscosity at 100.degree. C. of 90.9
mm/s.
Example 4
[0118] A mixture of xylene (348 parts) and a commercial grade of
12-hydroxystearic acid (3350 parts; having acid and hydroxyl values
of 182 mg KOH/g and 160 mg KOH/g respectively) is stirred for 22
hours at 190.degree. C. to 200.degree. C., the water formed in the
reaction being separated from the xylene in the distillate which is
then returned to the reaction medium. After 152 parts of water have
been collected, the xylene is removed by heating at 200.degree. C.
in a stream of nitrogen. The resulting pale amber coloured liquid
has an acid value of 35.0 mg KOH/g. The product of this step is
polyester A.
[0119] A mixture of polyester A (320 parts),
3-dimethylaminopropylamine (10.2 parts) and toluene (65 parts) is
stirred under reflux and under a current of nitrogen using a Dean
and Stark head to remove water. The temperature is raised to
165.degree. C. and held at this temperature for 6 hours. After
cooling to 20.degree. C. to 25.degree. C. under nitrogen, an 87.6%
solution of adduct is obtained.
[0120] 226 parts of the adduct is stirred at 40.degree. C. and
dimethyl sulphate (6.7 parts) is added. An exotherm raises the
temperature to about 50.degree. C. which is further raised to
90.degree. C. by external heating. After holding at 90.degree. C.
for a further 90 minutes the reaction mass is cooled to 20.degree.
C. No free dimethyl sulphate is detected by gas/liquid
chromatography.
Example 5
[0121] is similar to Example 4, except ricinoleic acid is used
instead of 12-hydroxystearic acid.
Example 6
[0122] A mixture of 348 parts of xylene and 3350 parts of a
commercial grade of 12-hydroxystearic acid (having acid and
hydroxyl values of 182 mg KOH/g. and 160 mg KOH/g. respectively) is
stirred for 22 hours at 190.degree. C. to 200.degree. C., the water
formed in the reaction being separated from the xylene in the
distillate which is then returned to the reaction medium. After 152
parts of water have been collected, the xylene is removed by
heating at 200.degree. C. in a stream of nitrogen. The resulting
pale amber coloured liquid has an acid value of 35.0 mg KOH/g. This
is polyester B.
[0123] A mixture of 1600 parts of polyester B and 102 parts of
3-dimethylaminopropylamine is stirred for 2 and a half hours at
160.degree. C. under a reflux condenser and in a current of
nitrogen. 10 Parts by volume of the mixture are then distilled off;
the temperature is raised to 190.degree. C. during 20 minutes, and
maintained at 190.degree. C. to 200.degree. C. for 2 hours 45
minutes. The resulting pale amber coloured viscous liquid partially
solidifies on cooling to ambient temperature. The product is then
heated to 44.degree. C. and 183 parts of dimethyl sulphate is
added. The temperature increased to 72.degree. C. The mixture is
then heated to 90.degree. C. to 100 .degree. C. and held for 90
minutes. The product is a pale amber coloured viscous liquid which
forms a gum on cooling
Example 7
[0124] is similar to Example 6, except ricinoleic acid is used
instead of 12-hydroxystearic acid.
Example 8
[0125] A non-quaternised polyester amide is prepared by reacting,
in a jacketed reaction vessel fitted with stirrer, condenser, feed
pump attached to sub-line addition pipe, nitrogen line and
thermocouple/temperature controller system, 6 moles of
12-hydroxystearic acid and 1 mole of dimethylaminopropylamine where
the reaction is carried out at about 130.degree. C. and held for
about 4 hours. The reaction mixture is then cooled to about
100.degree. C. and zirconium butoxide is added, in an amount so
that the catalyst makes up 0.57 percent by weight of the reaction
mixture. The reaction mixture is heated to about 195.degree. C. and
held for about 12 hours. The resulting product is cooled and
collected.
[0126] A quaternised polyester amide is prepared by placing 250 g
(1 mol eq) of the product collected above in a 500 mL flask with
64.68 g dimethyl oxalate (4 mol eq) and 1.48 g octanoic acid (0.075
mol eq). The reaction is heated with agitation under an atmosphere
of nitrogen to 120.degree. C. Once at temperature, the reaction is
held for 5 hours. After the hold, vacuum is applied to the vessel
and the reaction is stripped of excess dimethyl oxalate at
120.degree. C. over a period of about 5 hours. After stripping, the
quaternised polyester amide is cooled and collected without
filtering.
Example 9
[0127] A non-quaternised polyester amide is prepared by reacting,
in a jacketed reaction vessel fitted with stirrer, condenser, feed
pump attached to sub-line addition pipe, nitrogen line and
thermocouple/temperature controller system, 6 moles of ricinoleic
acid and 1 mole of dimethylaminopropylamine where the reaction is
carried out at about 130.degree. C. and held for about 4 hours. The
reaction mixture is then cooled to about 100.degree. C. and
zirconium butoxide is added, in an amount so that the catalyst
makes up 0.57 percent by weight of the reaction mixture. The
reaction mixture is heated to about 195.degree. C. and held for
about 12 hours. The resulting product is cooled and collected.
[0128] A quaternised polyester amide is prepared by placing 250 g
(1 mol eq) of product collected above in a 500 mL flask with 61.71
g dimethyl oxalate (4 mol eq) and 1.41 g octanoic acid (0.075 mol
eq). The reaction is heated with agitation under an atmosphere of
nitrogen to 120.degree. C. Once at temperature, the reaction is
held for 5 hours. Vacuum is then applied and the reaction is
stripped of excess dimethyl oxalate at 120.degree. C. over a period
of about 5 hours. After stripping, the quaternised polyester amide
is cooled and collected without filtering.
[0129] A series of engine lubricants are prepared containing the
products of the examples above. The engine lubricants include both
heavy diesel (HD) and gasoline passenger car (PC) lubricants.
[0130] In the lubricant examples below all amounts are expressed on
an actives basis.
[0131] Comparative Lubricant Example 1 (CLE1) is a passenger car
lubricant. CLE1 is an API SM capable 5W-30 lubricant containing 2
wt % of a succinimide dispersant. The lubricant contains an 1.25 wt
% of antioxidant system (containing a mixture of aminic, phenolic
and sulphur-containing antioxidants), 0.91 wt % of a zinc
dialkyldithiophosphate, 0.62 wt % of an ethylene-propylene
copolymer viscosity modifier, 0.14 wt % of pour point depressant, a
0.79 wt % of detergent system (containing a mixture of a sodium
overbased sulphonate and calcium overbased sulphonate), 11 ppm of
silioxane antifoam agent, and balance API Group II base oil.
[0132] Engine Lubricant 1 (EL1): is the same as CLE1 except it
further contains 3 wt % of Example 4.
[0133] Engine Lubricant 2 (EL2): is the same as CLE1 except it
further contains 3 wt % of Example 6.
[0134] Engine Lubricant 3 (EL3): is the same as CLE1 except it
further contains 3 wt % of Example 5.
[0135] Engine Lubricant 4 (EL4): is the same as CLE1 except it
further contains 3 wt % of Example 7.
[0136] Engine Lubricant 5 (EL5): is the same as CLE1 except it
further contains 3 wt % of Example 2.
[0137] The PC compositions (EL1 to EL5) are tested in a panel coker
apparatus. 210 g of oil to be analysed (Examples EU to EL5) is
placed in a steel sump chamber at 105.degree. C. An agitator
consisting of several metal tongs on a spindle is inserted into the
sump and spun at 1000 rpm. The apparatus is capped with a flat
aluminum plate with a constant surface temperature of 325.degree.
C. The agitator sprays a continuous thin layer of oil onto the
aluminum plate for a period of 4 hours. At the end of test, the
plate is removed and optically rated. A rating scale is applied
with 0 meaning a plate completely covered in black deposits and 100
meaning a plate completely free of deposits. The results obtained
for the test are presented below:
TABLE-US-00002 CLE1 EL1 EL2 EL3 EL4 EL5 Rating 55 79 78 70 79
84
[0138] The data indicates that adding a quaternised polyester salt
of the present invention increases the panel coker rating. This
means that the addition of quaternised polyester salt improves
deposit cleanliness.
[0139] Lubricant Comparative Example 1 (CLE2) is a heavy duty
diesel lubricant. CLE2 is an API CJ-4 capable 15W-40 Lubricant
containing 4.1 wt % of a succinimide dispersant. The lubricant
contains an 1.23 wt % of antioxidant system (containing a mixture
of aminic, phenolic and sulphur-containing antioxidants), 0.99 wt %
of a zinc dialkyldithiophosphate, 1.24 wt % of an
ethylene-propylene copolymer viscosity modifier, 0.08 wt % of pour
point depressant, a 1.71 wt % of detergent system (containing a
mixture of a sodium overbased sulphonate and calcium overbased
sulphonate), 100 ppm of siloxane antifoam agent, 0.12 wt % of
corrosion inhibitor, and balance API Group II base oil.
[0140] Engine Lubricant 6 (EL6): is the same as CLE2 except it
further contains 3 wt % of Example 4.
[0141] Engine Lubricant 7 (EL7): is the same as CLE2 except it
further contains 3 wt % of Example 5.
[0142] Engine Lubricant 8 (EL8): is the same as CLE2 except it
further contains 3 wt % of Example 7.
[0143] Engine Lubricant 9 (EL9): is the same as CLE2 except it
further contains 3 wt % of Example 2.
[0144] CLE2, and EL6 to EL9 are evaluated by panel coker test as
described above. The results obtained for the heavy duty diesel
lubricants are as follows:
TABLE-US-00003 CLE2 EL6 EL7 EL8 EL9 Rating 46 69 67 62 55
[0145] The data indicates that adding a quaternised polyester salt
of the present invention increases the panel coker rating. This
means that the addition of quaternised polyester salt improves
deposit cleanliness.
[0146] The combination of succinimide dispersant and quaternised
polyester salt of the present invention is further evaluated in the
following examples and panel coker analysis. Examples EL10, EL11,
and CLE1 relate to passenger car gasoline engine lubricants, and
CLE2, EL12, and EL13 relate to heavy duty diesel engine
lubricants.
[0147] Engine Lubricant 10 (EL10): is a passenger car gasoline
engine lubricant. EL10 is an API SM capable 5W-30 Lubricant
containing 0 wt % of a succinimide dispersant, and 2 wt % of the
product of Example 4. The lubricant also contains 1.25 wt % of an
antioxidant system (containing a mixture of aminic, phenolic and
sulphur-containing antioxidants), 0.91 wt % of a zinc
dialkyldithiophosphate, 0.62 wt % of an ethylene-propylene
copolymer viscosity modifier, 0.14 wt % of pour point depressant, a
0.91 wt % of detergent system (containing a mixture of a sodium
overbased sulphonate and calcium overbased sulphonate), 11 ppm of
silioxane antifoam agent, and balance API Group II base oil.
[0148] Engine Lubricant 11 (EL11): is a passenger car gasoline
engine lubricant. EL11 is an API SM capable 5W-30 Lubricant
containing 1 wt % of a succinimide dispersant, and 1 wt % of the
product of Example 4. The lubricant also contains 1.25 wt % of an
antioxidant system (containing a mixture of aminic, phenolic and
sulphur-containing antioxidants), 0.91 wt % of a zinc
dialkyldithiophosphate, 0.62 wt % of an ethylene-propylene
copolymer viscosity modifier, 0.14 wt % of pour point depressant, a
0.91 wt % of detergent system (containing a mixture of a sodium
overbased sulphonate and calcium overbased sulphonate), 11 ppm of
silioxane antifoam agent, and balance API Group II base oil.
[0149] Employing the panel coker test described above, CLE1, EL10
and EL11 are evaluated for deposit cleanliness. The results
obtained are as follows:
TABLE-US-00004 CLE1 EL10 EL11 Rating 55 69 77
[0150] The results obtained for CLE1, EL10 and EL11 indicate that
whilst a lubricant containing dispersant of only the quaternised
polyester salt of the present invention (i.e., EL10) does improve
deposit cleanliness over CLE1 (i.e., rating increase from 55 to
69), even better results are obtained when both the succinimide
dispersant and quaternised polyester salt are employed (i.e., as in
EL11) with a rating of 77.
[0151] Engine Lubricant 12 (EL12): is an API CJ-4 capable 15W-40
Lubricant containing 0 wt % of a succinimide dispersant, and 4.1 wt
% of the product of Example 4. The lubricant also contains 1.23 wt
% of an antioxidant system (containing a mixture of aminic,
phenolic and sulphur-containing antioxidants), 0.99 wt % of a zinc
dialkyldithiophosphate, 1.24 wt % of an ethylene-propylene
copolymer viscosity modifier, 0.08 wt % of pour point depressant, a
1.71 wt % of detergent system (containing a mixture of a sodium
overbased sulphonate and calcium overbased sulphonate), 100 ppm of
siloxane antifoam agent, 0.12 wt % of corrosion inhibitor, and
balance API Group II base oil.
[0152] Engine Lubricant 13 (EL13): is an API CJ-4 capable 15W-40
Lubricant containing 2.05 wt % of a succinimide dispersant, and
2.05 wt % of the product of Example 4. The lubricant also contains
1.23 wt % of an antioxidant system (containing a mixture of aminic,
phenolic and sulphur-containing antioxidants), 0.99 wt % of a zinc
dialkyldithiophosphate, 1.24 wt % of an ethylene-propylene
copolymer viscosity modifier, 0.08 wt % of pour point depressant, a
1.71 wt % of detergent system (containing a mixture of a sodium
overbased sulphonate and calcium overbased sulphonate), 100 ppm of
siloxane antifoam agent, 0.12 wt % of corrosion inhibitor, and
balance API Group II base oil.
[0153] Employing the panel coker test described above, CLE2, EL12
and EL13 are evaluated for deposit cleanliness. The results
obtained are as follows:
TABLE-US-00005 CLE2 EL12 EL13 Rating 46 58 66
[0154] The results obtained for CLE2, EL12 and EL13 indicate that
whilst a lubricant containing dispersant of only the quaternised
polyester salt of the present invention (i.e., EL12) does improve
deposit cleanliness over CLE2 (i.e., rating increase from 46 to
58), even better results are obtained when both the succinimide
dispersant and quaternised polyester salt are employed (i.e., as in
EL13) with a rating of 66.
[0155] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. The products formed thereby, including the products formed
upon employing lubricant composition of the present invention in
its intended use, may not be susceptible of easy description.
Nevertheless, all such modifications and reaction products are
included within the scope of the present invention; the present
invention encompasses lubricant composition prepared by admixing
the components described above.
[0156] 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 may be used
together with ranges or amounts for any of the other elements.
[0157] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: hydrocarbon substituents,
including aliphatic, alicyclic, and aromatic substituents;
substituted hydrocarbon substituents, that is, substituents
containing non-hydrocarbon groups which, in the context of this
invention, do not alter the predominantly hydrocarbon nature of the
substituent; and hetero substituents, that is, substituents which
similarly have a predominantly hydrocarbon character but contain
other than carbon in a ring or chain. A more detailed definition of
the term "hydrocarbyl substituent" or "hydrocarbyl group" is
described in paragraphs [0118] to [0119] of International
Publication WO2008147704, or a similar definition in paragraphs
[0137] to [0141] of published application US 2010-0197536.
[0158] While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover
such modifications as fall within the scope of the appended
claims.
* * * * *