U.S. patent application number 11/461196 was filed with the patent office on 2007-02-01 for novel dispersants.
This patent application is currently assigned to The Lubrizol Corporation. Invention is credited to David Cressey, Mark Davies, Christopher Friend, Claire Hollingshurst.
Application Number | 20070027046 11/461196 |
Document ID | / |
Family ID | 37440572 |
Filed Date | 2007-02-01 |
United States Patent
Application |
20070027046 |
Kind Code |
A1 |
Friend; Christopher ; et
al. |
February 1, 2007 |
Novel Dispersants
Abstract
The present invention provides a composition comprising: (a) a
hydrocarbon fluid; and (b) a dispersant/detergent comprising the
structure of Formula (1): (E).sub.p-Z Formula (1), wherein Z is a
residue of a polyamine or polyimine; E is (i) a residue of a
polyester having a free carboxylic acid group, or (ii) a residue of
a hydrocarbyl-substituted acylating agent, with the proviso that if
E is the hydrocarbyl-substituted acylating agent, Z is a polyimine,
and wherein when E is the hydrocarbyl-substituted acylating agent,
the composition has a phosphorus content of 0 ppm to 650 ppm. The
invention further provides a use for the composition.
Inventors: |
Friend; Christopher; (Derby,
GB) ; Davies; Mark; (Derby, GB) ;
Hollingshurst; Claire; (Derby, GB) ; Cressey;
David; (Derby, GB) |
Correspondence
Address: |
THE LUBRIZOL CORPORATION;ATTN: DOCKET CLERK, PATENT DEPT.
29400 LAKELAND BLVD.
WICKLIFFE
OH
44092
US
|
Assignee: |
The Lubrizol Corporation
29400 Lakeland Boulevard
Wickliffe
OH
44092
|
Family ID: |
37440572 |
Appl. No.: |
11/461196 |
Filed: |
July 31, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60704301 |
Aug 1, 2005 |
|
|
|
Current U.S.
Class: |
508/545 |
Current CPC
Class: |
C10M 133/56 20130101;
C10M 169/04 20130101; C10N 2030/42 20200501; C10N 2030/54 20200501;
C09K 8/524 20130101; C10N 2030/041 20200501; C10L 10/08 20130101;
C10L 10/02 20130101; C10L 1/224 20130101; C10M 2203/1006 20130101;
C10N 2030/04 20130101; C10N 2030/36 20200501; C10N 2070/00
20130101; C10L 1/2383 20130101; C10M 149/14 20130101; C10L 10/18
20130101; C10M 2217/041 20130101; C10N 2030/52 20200501; C10M
2215/28 20130101; C10N 2040/25 20130101; C10L 1/2381 20130101; C10L
1/238 20130101 |
Class at
Publication: |
508/545 |
International
Class: |
C10M 133/06 20060101
C10M133/06 |
Claims
1. A composition comprising: (a) a hydrocarbon fluid; and (b) a
dispersant/detergent comprising the structure of Formula (1):
(E).sub.p-Z Formula (1) wherein Z is a residue of a polyamine or
polyimine; E is (i) a residue of a polyester having a free
carboxylic acid group, or (ii) a residue of a
hydrocarbyl-substituted acylating agent, with the proviso that if E
is the residue of the hydrocarbyl-substituted acylating agent, Z is
a polyimine and the composition has a phosphorus content of 0 ppm
to 650 ppm; and p is at least 1.
2. The composition of claim 1, wherein the residue of a polyester
having a free carboxylic acid group comprises a residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))--, wherein T is H or a
polymerisation terminating group; A is C2-C40 alkenylene; B is
C2-C40 alkylene; n is 0 to 50; m is 0 to 50, provided the sum of
m+n is 1 or more; and p is at least 1.
3. The composition of claim 2, wherein the sum of m+n is less than
15.
4. The composition of claim 2, wherein A (the alkenylene) contains
8-30 carbon atoms; and wherein B (the alkylene) contains 8-30
carbon atoms.
5. The composition of claim 1, wherein the hydrocarbyl-substituted
acylating agent comprises a polyisobutylene succinic anhydride.
6. The composition of claim 1, wherein the polyimine is a poly
(C.sub.2-6-alkyleneimine).
7. The composition of claim 1, wherein the polyimine has a
number-average molecular weight of not less than 350.
8. The composition of claim 1, wherein the polyamine comprises
polyalkylenepolyamines.
9. The composition of claim 2, wherein the dispersant of Formula
(1) has E defined as the residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))--; and Z is the residue of a
polyamine.
10. The composition of claim 2, wherein the dispersant of Formula
(1) has E defined as the residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))--; and Z is the residue of a
polyimine.
11. The composition of claim 2, wherein E is the residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))-- and the weight ratio of
((T-(O-A-CO).sub.n(O--B--CO).sub.m))-- to Z is 8:1 to 30:1.
12. The composition of claim 1, wherein the hydrocarbon fluid is a
liquid fuel, an oil of lubricating viscosity or an unrefined or
partially refined heterogeneous fluid.
13. The composition of claim 1, wherein the hydrocarbon fluid is an
oil of lubricating viscosity; and wherein the dispersant of Formula
(1) has E defined as the hydrocarbyl-substituted acylating agent;
and Z is the residue of a polyimine.
14. The composition of claim 13, wherein the composition has a
phosphorus content of 0 ppm to 650 ppm; and a sulphur content of
0.5 wt % or less.
15. The composition of claim 13, further comprising a metal
dialkyldithiophosphate present at less than 0.6 wt %.
16. The composition of claim 13, wherein the composition has a
total sulphated ash content of less than 1.0 wt %; a sulphur
content of 1 ppm to 0.1 wt % or less; and a phosphorus content of 0
ppm to 650 ppm.
17. A method for lubricating an internal combustion engine,
comprising supplying thereto a lubricant comprising the composition
of claim 1, wherein the hydrocarbon fluid is an oil of lubricating
viscosity.
18. A method for fuelling an internal combustion engine, comprising
supplying thereto a fuel comprising the composition of claim 1,
wherein the hydrocarbon fluid is a liquid fuel.
19. A method of asphaltene control in an unrefined or partially
refined heterogeneous fluid, the method comprising employing
therein a dispersant/detergent of Formula (1) (E).sub.p-Z Formula
(1) wherein Z is a residue of a polyamine or polyimine; E is (i) a
residue of a polyester having a free carboxylic acid group, or (ii)
a residue of a hydrocarbyl-substituted acylating agent, with the
proviso that if E is the residue of the hydrocarbyl-substituted
acylating agent, Z is a polyimine; and p is at least 1.
20. A process for preparing a composition, comprising: (1) mixing
(a) an aliphatic hydrocarbon solvent; and (b) a
hydrocarbyl-substituted acylating agent to form a mixture; (2)
reacting component (b) of the mixture with a polyimine to form a
dispersant/detergent additive; and (3) adding a hydrocarbon fluid
to the mixture of step (1), to the reactants during step (2), to
the dispersant/detergent additive formed in step (2), or a
combination thereof.
Description
TECHNICAL FIELD
[0001] The present invention relates to a composition containing
novel dispersants. The invention further relates a process for the
preparation of the dispersants and their use in various
applications including in an oil of lubricating viscosity, liquid
fuel or in oil-field applications.
BACKGROUND OF THE INVENTION
[0002] The use of dispersants in a wide variety of lubricants,
fuels and oil field applications is known. Many of the known
dispersants are based on polyisobutylene succinimides derived from
polyalkyleneamines (also known as HPAX.TM.). Typically the
dispersants are useful for soot or sludge control in fuels or
lubricants. In oil field applications, the dispersants are useful
for asphaltene control.
[0003] However, many of the dispersants are not appropriate in
several applications and there are technical difficulties making
the succinimide dispersants because known processes employ aromatic
solvent/diluent systems that have low flash points. The low flash
points typically result in the dispersants being made by processes
that may not be as efficient and/or having increased flammability
risks. This restricts possible processes to prepare succinimide
dispersants. Examples of such systems are taught in International
Publication WO 98/12282 A1, U.S. Pat. Nos. 5,279,626; 3,658,494;
and 6,408,812. In principle higher aromatic compounds with higher
flash points may be used. However, many of these aromatic compounds
have toxicity issues such as carcinogenicity.
[0004] Other dispersant systems contemplated include those
disclosed in International Publication WO 04/090080 and British
patent GB 1,506,786.
[0005] British patent GB 1,506,786 discloses an oil composition
containing a dispersant which is the reaction product of an
alk(en)yl succinic acid or anhydride with an alkylene imine. The
dispersant is prepared in a non-polar solvent including xylene,
toluene, benzene and hexane.
[0006] U.S. Pat. No. 4,938,885 disccloses an antioxidant dispersant
polymer dendrimer derived from succinimide poly(amidoamine)
dendrimers.
[0007] U.S. Pat. No. 6,228,978 discloses lubricant compositions
containing a dispersant derived from reacting a polyolefin with a
diaminoalkane with acrylonitrile.
[0008] International Publication WO 04/090080 discloses a method of
preparing a fuel emulsion containing a hydrocarbon fuel, a
fuel-soluble surfactant with a hydrocarbyl substituent of number
average molecular of at least 590 and a hydrophilic moiety having
acidic or basic functionality. The emulsion further comprises an
aqueous phase complementary to the hydrophilic moiety. A suitable
surfactant includes the reaction product of 12-hydroxystearic acid
with a polyethyleneimine.
[0009] In some applications, for example, in an internal combustion
engine, many of the conventional succinimide dispersants, whilst
providing soot and/or sludge control, are believed to be
detrimental to fuel efficiency and/or seal compatability.
Furthermore it would be useful if a dispersant/detergent additive
could provide dispersant properties in lubricants with various
levels of sulphated ash, phosphorus and sulphur content.
[0010] Therefore it would be advantageous to have a
dispersant/detergent additive capable of providing improved fuel
economy and/or seal compatability. Improving fuel economy will help
to reduce effect of sulphur and/or phosphorus moieties, NO.sub.x
and particulate emissions. Further, as sulphur and/or phosphorus
moieties (known to poison NO.sub.x catalysts or other
after-treatment devices) are reduced, the performance of said
catalysts increases due to less poisoning.
[0011] The present invention overcomes at least one of the
difficulties highlighted in the prior art.
SUMMARY OF THE INVENTION
[0012] The present invention provides a composition comprising:
[0013] (a) a hydrocarbon fluid; and
[0014] (b) a dispersant/detergent comprising the structure of
Formula (1): (E).sub.p-Z Formula (1) wherein
[0015] Z is a residue of a polyamine or polyimine;
[0016] E is (i) a residue of a polyester having a free carboxylic
acid group, or [0017] (ii) a residue of a hydrocarbyl-substituted
acylating agent, with the proviso that if E is the residue of the
hydrocarbyl-substituted acylating agent, Z is a polyimine and the
composition has a phosphorus content of 0 ppm to 650 ppm; and
[0018] p is at least one, typically with upper limits of 2000 or
1000.
[0019] In one embodiment the present invention provides a
composition comprising:
[0020] (a) a hydrocarbon fluid; and
[0021] (b) a dispersant/detergent comprising the structure of
Formula (1):
[0022] (E).sub.p-Z Formula (1)
wherein
[0023] Z is a residue of a polyamine or polyimine;
[0024] E is [0025] (i) a residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))--, or [0026] (ii) a residue of
a hydrocarbyl-substituted acylating agent;
[0027] T is H or a polymerisation terminating group;
[0028] A is C2-C40, or C8-C30 or C16-C20 alkenylene or mixtures
thereof;
[0029] B is C2-C40, or C8-C30 or C10-C20 or C10-C16 alkylene or
mixtures thereof;
[0030] n is 0 to 50 or 2 to 50;
[0031] m is 0 to 25 or 1 to 25, provided the sum of m+n is 1 or
more; and
[0032] p is at least 1, typically with upper limits of 2000 or
1000,
with the proviso that if E is the residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))--, p is at least 2; and if E
is the hydrocarbyl-substituted acylating agent, Z is a polyimine
and the composition has a phosphorus content of 0 ppm to 650
ppm.
[0033] The invention further provides the composition as described
above wherein the hydrocarbon fluid is a liquid fuel (including
gasoline, diesel). The invention further provides the composition
as described above wherein the hydrocarbon fluid is an oil of
lubricating viscosity.
[0034] The invention further provides a method for lubricating or
fuelling an internal combustion engine.
[0035] In another embodiment the invention provides a method of
asphaltene control in an unrefined or partially refined
heterogeneous fluid, the method employing said dispersant of
Formula (1).
[0036] The invention further provides an additive capable of
imparting at least one of detergent/dispersant activity, fuel
economy activity and seal compatability.
DETAILED DESCRIPTION OF THE INVENTION
[0037] The present invention provides a compositions as defined
above.
[0038] The dispersants defined by Formula (1) may have a total base
number (TBN) of at least 2, or at least 10, or in ranges from 5 to
90, 70 to 400, or 80 to 350, or 100 to 300 mg KOH/g.
[0039] In one embodiment the composition comprises:
[0040] (a) a hydrocarbon fluid; and
[0041] (b) a dispersant/detergent comprising the structure of
Formula (1): (E).sub.p-Z Formula (1) wherein
[0042] Z is a residue of a polyamine or polyimine;
[0043] E is the residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))--;
[0044] T is H or a polymerisation terminating group;
[0045] A is C2-C40, or C8-C30 or C16-C20 alkenylene or mixtures
thereof;
[0046] B is C2-C40, or C8-C30 or C10-C20 or C10-C16 alkylene or
mixtures thereof;
[0047] n is 0 to 50 or 1 to 50 or 2 to 50;
[0048] m is 0 to 50 or 1 to 25, provided the sum of m+n is 1 or
more; and
[0049] p is at least 2, typically with upper limits of 2000 or
1000.
[0050] In one embodiment the dispersant of Formula (1) has E
defined as the residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))--; and Z is the residue of a
polyimine.
[0051] In one embodiment the dispersant of Formula (1) has E
defined as the residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))--; and Z is the residue of a
polyamine.
[0052] When E is the residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))-- the weight ratio of
((T-(O-A-CO).sub.n(O--B--CO).sub.m))-- to Z may be 2:1 to 80:1 or
4:1 to 60:1 or 8:1 to 30:1 or 8:1 to 20:1.
[0053] The residue of formula
((T-(O-A-CO).sub.n(O--B--CO).sub.m))-- may be a homopolymer or a
random or block copolymer. In one embodiment the residue is in the
form of a random copolymer.
[0054] In several embodiments the sum of m+n is less than 15, or
less than 10, for example 5, 6, 7, or 8.
[0055] In one embodiment the composition comprises:
[0056] (a) a hydrocarbon fluid; and
[0057] (b) a dispersant/detergent comprising the structure of
Formula (1): (E).sub.p-Z Formula (1) wherein
[0058] Z is a residue of a polyimine;
[0059] E is a hydrocarbyl-substituted acylating agent; and
[0060] p is at least 1,
wherein the composition has a phosphorus content of 0 ppm to 650
ppm; and the composition has a sulphur content of 0.5 wt % or
less.
Hydrocarbyl-Substituted Acylating Agent
[0061] The hydrocarbyl group of the hydrocarbyl-substituted
acylating agent generally contains an average of at least 8, or 30,
or 35 up to 350, or to 200, or to 100 carbon atoms. In one
embodiment, the hydrocarbyl group is derived from a polyalkene
characterised by an {overscore (M)}.sub.n (number average molecular
weight) of at least 500. Generally, the polyalkene is characterised
by a {overscore (M)}.sub.n of 500, or 700, or 750, or even 900 or
up to 5000. Examples of suitable ranges for the {overscore
(M)}.sub.n of polyalkene include 500 to 3000, or to 5000, 750 to
3000 or 900 to 2500. Specific polyalkene may have a {overscore
(M)}.sub.n of 550, 750, 950-1000, 1500, or 2300. Polyolefins which
may form the hydrocarbyl substituent may be prepared by
polymerising olefin monomers by well known polymerisation methods,
as described above, and are also commercially available. The olefin
monomers include monoolefins, including monoolefins having 2 to 10
carbon atoms such as ethylene, propylene, 1-butene, isobutylene,
and 1-decene. An especially useful monoolefin source is a C.sub.4
refinery stream having a 35 to 75 weight percent butene content and
a 30 to 60 weight percent isobutene content. Useful olefin monomers
also include diolefins such as isoprene and 1,3-butadiene. Olefin
monomers may also include mixtures of two or more monoolefins, of
two or more diolefins, or of one or more monoolefins and one or
more diolefins. Useful polyolefins include polyisobutylenes having
a number average molecular weight of 140 to 5000, in another
instance of 400 to 2500, and in a further instance of 140 or 500 to
1500. The polyisobutylene may have a vinylidene double bond content
of 5 to 69%, in a second instance of 50 to 69%, and in a third
instance of 50 to 95% or 70 to 90%. The polyolefin may be a
homopolymer prepared from a single olefin monomer or a copolymer
prepared from a mixture of two or more olefin monomers. Also
possible as the hydrocarbyl substituent source are mixtures of two
or more homopolymers, two or more copolymers, or one or more
homopolymers and one or more copolymers.
[0062] The acylating agent may be an alpha, beta-unsaturated mono-
or poly-carboxylic acid or derivative thereof, to include
anhydrides and esters. Examples of acylating agents include, for
example, acrylic acid, methyl acrylate, methacrylic acid, maleic
acid or anhydride, fumaric acid, and itaconic acid or anhydride. In
one embodiment the hydrocarbyl-substituted acylating agent
comprises a polyisobutylene succinic anhydride.
Polyimine and Polyamine
[0063] When Z is the residue of a polyimine or mixtures thereof,
the polyimine may be a polyalkyleneimine (PAI), such as poly
(C.sub.2-6-alkyleneimine). Specific examples include
polyethyleneimine (often referred to as PEI; and commonly prepared
by acid catalysed ring opening of aziridine) or polypropyleneimine.
The polyimine may be linear or branched. In one embodiment the
polyimine is branched. Linear polyethyleneimine may be prepared by
the hydrolysis of poly(N-acyl) alkyleneimines as described, for
example, by Takeo Saegusa et al. in Macromolecules, 1972, Vol 5,
page 4470. Branched polyethyleneimines of differing molecular
weight are commercially available from BASF and Nippon Shokubai.
Polypropyleneimine dendrimers are commercially available from DSM
Fine Chemicals.
[0064] The number average molecular weight of the polyimine may
range from 300 to 650,000, 350 or 500 to 600,000, 600 to 100,000,
1200 to 70,000 or 2000 to 20,000. In the case of polyethyleneimine,
the number-average molecular weight in one embodiment is not less
than 350, or not less than 600, not less than 1200 or not less than
1800.
[0065] In one embodiment when E is the hydrocarbyl-substituted
acylating agent, the number average molecular weight of the
polyimine may be in range of 300 to 30,000 or 500 to 15,000.
Examples of suitable number average molecular weights for the
polyimine include 350 to 12,000 or 600 and 10,000.
[0066] When Z is a polyamine or mixtures thereof, suitable
materials include a polyamine with 2 to 30 carbon atoms. The
polyamine may include alkylenediamines, N-alkyl alkylenediamines,
and polyalkylenepolyamines. Useful polyamines include
ethylenediamine, 1,2-diaminopropane, N-methyl-ethylenediamine,
N-tallow(C .sub.16-C.sub.18)-1,3-propylenediamine,
N-oleyl-1,3-propylenediamine, polyethylenepolyamines (such as
diethylenetriamine and tri-ethylenetetramine,
tetraethylenepentamine and "polyamine bottoms" (or
"alkylenepolyamine bottoms")). In one embodiment the polyamine
comprises polyalkylenepolyamines.
[0067] In general, alkylenepolyamine bottoms may be characterised
as having less than two, usually less than 1% (by weight) material
boiling below about 200.degree. C. A typical sample of such
ethylene polyamine bottoms obtained from the Dow Chemical Company
of Freeport, Tex. designated "E-100" has a specific gravity at
15.6.degree. C. of 1.0168, a percent nitrogen by weight of 33.15
and a viscosity at 40.degree. C. of 121 centistokes. Gas
chromatography analysis reveals that such a sample contains about
0.93% "Light Ends" (most probably diethylene triamine (DETA), 0.72%
triethylene tetramine (TETA), 21.74% tetraethylene pentamine and
76.61% pentaethylenehexamine and higher (by weight). These
alkylenepolyamine bottoms include cyclic condensation products such
as piperazine and higher analogs of diethylenetriamine or
triethylenetetramine.
Polymerisation Terminating Group
[0068] T is hydrogen or a polymerisation terminating group that may
be attached to either --(O-A-CO).sub.n-- or --(O--B--CO).sub.m--.
When T is a polymerisation terminating group it may include the
residue of a carboxylic acid R--COOH or an alcohol R--OH, where R
is a hydrocarbyl group which is optionally substituted containing 1
to 50, carbon atoms. In other embodiments R contains at least 8, or
at least 12, or at least 14 carbon atoms. The upper range of carbon
atoms present in R may be 30, or 25 or 20. Examples of suitable
ranges for the number of carbon atoms present in R include 12 to 30
or 14 to 25.
[0069] When T is a polymerisation terminating group, it may be a
residue of a carboxylic acid of formula T-COOH, wherein T may be
aromatic, heterocyclic, alicyclic or aliphatic.
(O-A-CO)
[0070] In one embodiment, the residue (O-A-CO) may be derivable
from an unsaturated fatty acid. Examples of unsaturated fatty acids
include undecylenic acid, myristoleic acid, palmitoleic acid, oleic
acid, gadoleic acid, elaidic acid, cis-eicosenoic acid, erucic
acid, nervonic acid, 2,4-hexadienoic acid, linoleic acid,
16-hydroxy icosanic acid 11,14-eicosadienoic acid, linolenic acid,
cis-8,11,14-eicosatrienoic acid, arachidonic acid,
cis-5,8,11,14,17-eicosapentenoic acid,
cis-4,7,10,13,16,19-docosahexenoic acid, all-trans-retinoic acid,
ricinoleic acid lauroleic acid, eleostearic acid, licanic acid,
citronelic acid, nervonic acid, abietic acid, or abscisic acid. In
one embodiment (O-A-CO) is the residue of ricinoleic acid.
(O--B--CO)
[0071] The residue of (O--B--CO) may be derivable from a saturated
hydroxy substituted fatty acid. Examples of saturated fatty acids
include as hydroxycarboxylic acids including 12-hydroxydodecanoic
acid, 5-hydroxydecanoic acid, 4-hydroxydodecanoic acid or
12-hydroxystearic acid.
[0072] In one embodiment A and B as defined in the residue of
formula ((T-(O-A-CO).sub.n(O--B--CO).sub.m))-- may comprise
saturated or unsaturated groups containing less than 8 carbon
atoms, provided that the final product is soluble in the
hydrocarbon fluid.
Hydrocarbon Fluid
[0073] In different embodiments the hydrocarbon fluid is a liquid
fuel, an oil of lubricating viscosity or an unrefined or partially
refined heterogeneous fluid as described below. The hydrocarbon
fluid of the invention typically has a sulphur content of 0.5 wt %
or less or 0.3 wt % or less, or less than 0.1 wt %. The sulphur
content may be as low as 1 ppm or 5 ppm. An example of a suitable
range for sulphur content includes 1 ppm to 0.1 wt %. Some fluids
may have up to 2% or 3% sulphur.
[0074] The dispersant above-described may used in an oil of
lubricating viscosity or a liquid fuel to provide a lubricant or an
additised liquid fuel. The hydrocarbon fluid may also be present in
an amount sufficient for the composition to be an additive
concentrate.
Liquid Fuel
[0075] The fuel composition of the present invention optionally
comprises a liquid fuel and is useful in fueling an internal
combustion engine. The liquid fuel is normally a liquid at ambient
conditions. The liquid fuel may be a hydrocarbon fuel, a
nonhydrocarbon fuel, or a mixture thereof. The hydrocarbon fuel may
be a petroleum distillate to include a gasoline as defined by ASTM
specification D4814 or a diesel fuel as defined by ASTM
specification D975. In an embodiment of the invention the liquid
fuel is a gasoline, and in other embodiments the liquid fuel is a
leaded gasoline, or a nonleaded gasoline. In another embodiment of
this invention the liquid fuel is a diesel fuel. The hydrocarbon
fuel may be a hydrocarbon prepared by a gas to liquid process to
include for example hydrocarbons prepared by a process such as the
Fischer-Tropsch process. The nonhydrocarbon fuel may be an oxygen
containing composition, often referred to as an oxygenate, to
include an alcohol, an ether, a ketone, an ester of a carboxylic
acid, a nitroalkane, or a mixture thereof. The nonhydrocarbon fuel
may include, for example, methanol, ethanol, methyl t-butyl ether,
methyl ethyl ketone, transesterified oils and/or fats from plants
and animals such as rapeseed methyl ester and soybean methyl ester,
and nitromethane. Mixtures of hydrocarbon and nonhydrocarbon fuels
may include, for example, gasoline and methanol and/or ethanol,
diesel fuel and ethanol, and diesel fuel and a transesterified
plant oil such as rapeseed methyl ester. In an embodiment of the
invention, the liquid fuel is a hydrocarbon fuel, a nonhydrocarbon
fuel, or a mixture thereof.
[0076] In several embodiments of this invention the liquid fuel may
have a sulphur content on a weight basis that is 5000 ppm or less,
1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less,
or 10 ppm or less.
[0077] Typically a liquid fuel contains less than 650 ppm of
phosphorus and often less than 50 ppm or even 0 ppm.
[0078] When the invention is in the form of a fuel composition, the
composition in one embodiment excludes a water-in-oil or
oil-in-water emulsion.
[0079] When in the invention is in the form of a liquid fuel, the
amount of liquid fuel present in the composition is generally
greater than 50 wt %, and in other embodiments is present at
greater than 90 wt %, greater than 95 wt %, greater than 99.5 wt %,
or greater than 99.8 wt % of the composition.
Oil of Lubricating Viscosity
[0080] In one embodiment the hydrocarbon fluid is an oil of
lubricating viscosity. Oils of lubricating viscosity may be derived
from a variety of sources, and include natural and synthetic
lubricating oils and mixtures thereof. The source of the oil or
process for preparing the oil is generally not of particular
importance unless that source or process provides some particular
benefit, provided that the oil falls within one or more of the
descriptions, below.
[0081] The natural oils useful in making the inventive lubricants
and functional fluids include animal oils and vegetable oils (e.g.,
lard oil, castor oil) as well as mineral lubricating oils such as
liquid petroleum oils and solvent--treated or acid-treated mineral
lubricating oils of the paraffinic, naphthenic or mixed
paraffinic/naphthenic types which may be further refined by
hydrocracking and hydrofinishing processes and are dewaxed. Oils of
lubricating viscosity derived from coal or shale are also useful.
In several embodiments useful base oils may be those designated by
the American Petroleum Institute (API) as Group I, II, III, IV or V
oils. In several embodiments useful base oils may be those
designated by the American Petroleum Institute (API) as Group II,
III, IV or V oils. Group I oils contain <90% saturates and/or
>0.03% sulfur and have a viscosity index (VI) of .gtoreq.80.
Group II oils contain .gtoreq.90% saturates, .ltoreq.0.03% sulfur,
and have a VI .gtoreq.80. Group III oils are similar to group II
but have a VI .gtoreq.120.
[0082] Upon occasion, highly refined or hydrocracked natural oils
have been referred to as "synthetic" oils. More commonly, however,
synthetic lubricating oils are understood to include hydrocarbon
oils and halo-substituted hydrocarbon oils such as polymerised and
interpolymerised olefins (e.g., polybutylenes, polypropylenes,
propylene-isobutylene copolymers, chlorinated polybutylenes);
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 sulfides and the derivatives, analogs
and homologs thereof and the like. Polyalphaolefin oils are also
referred to as API Group IV oils. (API Group V oils are "all
others.")
[0083] In one embodiment, the oil of lubricating viscosity is a
poly-alpha-olefin (PAO). Typically, the poly-alpha-olefins (PAOs)
are derived from monomers having from 4 to 30, or from 4 to 20, or
from 6 to 16 carbon atoms. Examples of useful PAOs include those
derived from 1-decene. These PAOs may have a viscosity from 2 to
150 or 2 to 50 mm/s (or cSt).
[0084] Suitable base oils include poly-a-olefins such as oligomers
of 1-decene. These synthetic base oils are typically hydrogenated,
resulting in an oil of stability against oxidation. The synthetic
oils may encompass a single viscosity range or a mixture of high
viscosity and low viscosity range oils so long as the mixture
results in a viscosity which is consistent with the requirements
set forth below. Also included as preferred base oils are highly
hydrocracked and dewaxed oils. These petroleum oils are generally
refined to give enhanced low temperature viscosity and
antioxidation performance. Mixtures of synthetic oils with refined
mineral oils may also be employed.
[0085] Another class of oils is known as traction oils, which are
typically synthetic fluids containing a large fraction of highly
branched or cycloaliphatic structures, i.e., cyclohexyl rings.
Traction oils or traction fluids are described in detail, for
example, in U.S. Pat. Nos. 3,411,369 and 4,704,490.
[0086] Other suitable oils may be oils derived from a
Fischer-Tropsch process and hydrogenation.
[0087] When used as a lubricant, the amount of the above-described
dispersant is typically 0.1 to 90, or to 20, or to 10, percent by
weight of the composition, the balance being the oil of lubricating
viscosity and any other components or additives desired for the
application at hand. This broad range encompasses both fully
formulated lubricant and concentrates. When used as an additive
concentrate, (designed to be added to a lubricant to prepare a
fully formulated lubricant) the amount of the present reaction
product may be 20 to 90 percent by weight or 40 to 80 percent by
weight. When the invention is in the form of a lubricant, the
composition has a total sulphur content below 0.5 wt %, or 0.3 wt %
or less, or 1 ppm to 0.1 wt % or less.
[0088] The total phosphorus content of the composition may also be
below 0.1 wt %, or 0.085 wt % or less, or 0.07 wt % or less, or
0.055 wt % or less, or 0.05 wt % or less of the composition. In
several embodiments the phosphorus is present from 1 ppm or 10 ppm
to 50 ppm or to 200 ppm or to 400 ppm.
[0089] The total sulphated ash content as determined by ASTM D-874
is typically below 1.5 wt %, or less than 1.1 wt %, or less than
1.0 wt %, or 0.8 wt % or less, or 0.5 wt % or less of the
composition. In several embodiments the total sulphated ash content
is from 0.1 wt % or 0.2 wt % to 0.6 wt % or to 0.7 wt %.
Heterogeneous Fluid
[0090] The dispersant above-described may used in an unrefined or
partially refined heterogeneous fluid to impart asphaltene control.
The unrefined or partially refined heterogeneous fluid may be
crude, black oil or a non-volatile fraction from a distillation of
a crude oil. The heterogeneous fluid may also be a heavy fuel such
as a heavy distillate heating oil or marine/industrial fuel oil,
including bunker fuel. The heterogeneous fluid may also be any
petrochemical process oil which has a propensity to form
asphaltenic and ultimately coke-like species at surfaces under high
temperature conditions. In one embodiment the heterogeneous fluid
is an oil field product, e.g., a whole well product or a multiphase
mixture in or from a well bore or one at a well head after at least
partial separation of gas and/or water, for instance, an oil export
fraction. In one embodiment the heterogeneous fluid is a refinery
or petrochemical process stream or a heavy distillate or residual
fuel.
[0091] The heterogeneous fluid may contain at least 0.01 wt % of
asphaltene, in another embodiment up to a maximum of 30 wt % of
asphaltene. Examples of suitable ranges of asphaltene present in
the heterogeneous fluid include up to 90 wt %, or 0.001 wt % to 90
wt %, 0.01 wt % to 70 wt % or 0.04 to 50 wt % or 0.06 to 30 wt %.
In one embodiment the asphaltene content is up to 90 wt %.
Generally higher asphaltene content is present in oil shale,
bitumen or asphalt.
[0092] The heterogeneous fluid may further comprise wax, often
present from 0 wt % to 35 wt %, 0.5 wt % to 30 wt % or 1 wt % to 15
wt %; gas, present from 0 wt % to 10 wt % or water (or water
droplets) from 0 wt % to 20 wt %. The heterogeneous fluid in one
embodiment has multiple phases between the oil and gas and/or
water.
[0093] In one embodiment the invention provides a method of
asphaltene control in an unrefined or partially refined
heterogeneous fluid, the method employing the dispersant of Formula
(1), wherein E is defined as the hydrocarbyl-substituted acylating
agent; and Z is the residue of a polyimine.
Other Performance Additives
[0094] The fuel or lubricant compositions optionally comprises one
or more additional/other performance additives. The other
performance additives include metal deactivators, detergents,
dispersants other than component (b) above, viscosity modifiers,
friction modifiers, dispersant viscosity modifiers, extreme
pressure agents, antiwear agents, antioxidants, corrosion
inhibitors, foam inhibitors, demulsifiers, pour point depressants,
seal swelling agents, fuel lubricity improvers, and mixtures
thereof.
[0095] The total combined amount of the additional performance
additive compounds present on an actives basis (i.e. absence of
normal amounts of additive diluent oil) ranges from 0 wt % to 25 wt
% or 0.01 wt % to 20 wt % of the fuel or lubricant 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.
[0096] In one embodiment antiwear agents present include metal
(especially zinc) dialkyldithiophosphates at less than 0.6 wt %, or
less than 0.1 wt % or less than 0.01 wt % of the composition. The
metal dialkyldithiophosphates may be present in ranges from 0 wt %
to less than 0.6 wt %, or 0.001 wt % to less than 0.55 wt %.
[0097] In one embodiment a detergent is present. Suitable
detergents include neutral or overbased, Newtonian or
non-Newtonian, basic salts of alkali, alkaline earth and transition
metals with one or more substrates selected from the group
consisting of phenates, sulphurised phenates, sulphonates,
carboxylic acids, phosphorus acids, mono- and/or di-thiophosphoric
acids, saligenins, alkylsalicylates and salixarates.
[0098] The amount of detergent present may be from 0 wt % to 10 wt
% or 0.5 to 6 wt %.
[0099] In one embodiment a dispersant other than component (b)
above is present.
[0100] In one embodiment the composition is in a concentrate
forming amount. If the present invention is in the form of a
concentrate (which may be combined with additional oil to form, in
whole or in part, a finished lubricant and/or liquid fuel), the
ratio of the additive of the invention and/or other additional
performance additives in an oil of lubricating viscosity and/or
liquid fuel, to diluent oil is typically in the range of 80:20 to
10:90 by weight.
[0101] Antioxidants include molybdenum dithiocarbamates,
sulphurised olefins, hindered phenols, and diphenylamines.
Dispersants include N-substituted long chain alkenyl succinimides
as well as posted treated version thereof. Post-treated dispersants
include those by reaction with urea, thiourea,
dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones,
carboxylic acids, hydrocarbon-substituted succinic anhydrides,
nitriles, epoxides, boron compounds, and phosphorus compounds.
[0102] Antiwear agents include compounds such as metal
thiophosphates, especially zinc dialkyldithiophosphates; phosphoric
acid esters or salts thereof, phosphites; and phosphorus-containing
carboxylic esters, ethers, and amides. Antiscuffing agents
including organic sulphides and polysulphides, such as
benzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl
tetrasulphide, di-tertiary butyl polysulphide,
di-tert-butylsulphide, sulphurised Diels-Alder adducts or alkyl
sulphenyl N'N-dialkyl dithiocarbamates. Extreme Pressure (EP)
agents include chlorinated wax; organic sulphides and polysulphides
such as benzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl
tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised
alkylphenol, sulphurised dipentene, sulphurised terpene, and
sulphurised Diels-Alder adducts; phosphosulphurised hydrocarbons;
metal thiocarbamates such as zinc dioctyldithiocarbamate; and
barium heptylphenol diacid.
[0103] Friction modifiers include fatty amines, esters such as
borated glycerol esters, partial esters of glycerol such as
glycerol monooleate, fatty phosphites, fatty acid amides, fatty
epoxides, borated fatty epoxides, alkoxylated fatty amines, borated
alkoxylated fatty amines, metal salts of fatty acids, fatty
imidazolines, condensation products of carboxylic acids and
polyalkylene-polyamines, and amine salts of alkylphosphoric acids.
Viscosity modifiers include hydrogenated copolymers of
styrene-butadiene, ethylene-propylene polymers, polyisobutenes,
hydrogenated styrene-isoprene polymers, hydrogenated isoprene
polymers, polymethacrylate acid esters, polyacrylate acid esters,
polyalkyl styrenes, alkenyl aryl conjugated diene copolymers,
polyolefins, polyalkylmethacrylates and esters of maleic
anhydride-styrene copolymers. Dispersant viscosity modifiers (often
referred to as DVM) include functionalised polyolefins, for
example, ethylene-propylene copolymers that have been
functionalized with the reaction product of maleic anhydride and an
amine, polymethacrylates functionalised with an amine, or
esterified styrene-maleic anhydride copolymers reacted with an
amine.
[0104] Corrosion inhibitors include octylamine octanoate,
condensation products of dodecenyl succinic acid or anhydride and a
fatty acid such as oleic acid with a polyamine. Metal deactivators
include derivatives of benzotriazoles, 1,2,4-triazoles,
benzimidazoles, 2-alkyldithiobenzimidazoles or
2-alkyldithiobenzothiazoles. Foam inhibitors include copolymers of
ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl
acetate. Demulsifiers include 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. Seal swell agents include Exxon Necton-37.TM. (FN
1380) and Exxon Mineral Seal Oil (FN 3200).
Process
[0105] The invention further provides a process for preparing a
composition, comprising:
[0106] (1) mixing [0107] (a) an aliphatic hydrocarbon solvent; and
[0108] (b) a hydrocarbyl-substituted acylating agent to form a
mixture;
[0109] (2) reacting component (b) of the mixture with a polyimine
to form a dispersant/detergent additive; and
[0110] (3) adding a hydrocarbon fluid to the mixture of step (1),
to the reactants during step (2), to the dispersant/detergent
additive formed in step (2), or a combination thereof.
[0111] In one embodiment the reaction temperature of step (2) is
carried out at elevated temperatures, including 30.degree. C. or
above, or at least 50.degree. C. or at least 100.degree. C. The
reaction temperature may be in ranges from 70.degree. C. to
220.degree. C. or 120.degree. C. to 200.degree. C. or 140.degree.
C. to 190.degree. C.
[0112] Typically the aliphatic hydrocarbon solvent is substantially
free of to free of sulphur and/or aromatic moieties. Typically the
aliphatic hydrocarbon solvent has a boiling point of 150.degree. C.
or higher, or 175.degree. C. or higher, or 200.degree. C. or
higher, or 225.degree. C. or higher. Often the boiling point is
250.degree. C. or 258.degree. C.
[0113] Often the aliphatic hydrocarbon solvent has a flash point of
at least 90.degree. C., or at least 105.degree. C., or at least
120.degree. C., or 130.degree. C. or higher. Often the aliphatic
hydrocarbon solvent flash point is 145.degree. C. or higher or
150.degree. C. or higher. The flash point may be determined by the
Pensky Closed Cup method as described in ASTM Test Method D93.
[0114] In one embodiment the aliphatic hydrocarbon solvent is an
oil of lubricating viscosity, such as, an API Group I, II, III, IV
or V base oil. In one embodiment the aliphatic hydrocarbon solvent
is an oil of lubricating viscosity, such as, an API Group II, III,
IV or V base oil. Examples of commercially available aliphatic
hydrocarbon solvents Pilot.TM. 140 and Pilot.TM. 299 and Pilot.TM.
900 available from Petrochem Carless, Petro-Canada.TM. 100N,
Nexbase.TM., Yubase.TM., and poly(alpha-olefins), such as, PAO-5,
PAO-6, PAO-7 and PAO-8.
INDUSTRIAL APPLICATION
[0115] When in the form of a lubricant 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.
[0116] 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,
improved seal compatibility, improved fuel economy, decreased
NO.sub.x emissions and decreased particulate emissions.
[0117] When the invention is in the form of a lubricant, the amount
of dispersant of Formula (1) present may range from 0.1 wt % to 20
wt %, or 0.5 wt % to 15 wt %, or 1 wt % to 10 wt %, or 1.5 wt % to
8 wt % of the composition.
[0118] When in the form of a liquid fuel, the invention is useful
for imparting to a fuel composition at least one of improved fuel
economy, a homogeneous air/fuel mix, nozzle cleanliness and
injector cleanliness. In one embodiment the invention provides a
method for fuelling an internal combustion engine, comprising
supplying thereto a fuel comprising the composition of disclosed
herein, wherein the hydrocarbon fluid is a liquid fuel.
[0119] When the invention is in the form of a liquid fuel, the
dispersant defined by Formula (1) may be present in ranges from
0.01 wt % to 20 wt %, or 0.05 wt % to 15 wt %, or 0.1 wt % to 10 wt
%, or 0.15 wt % to 8 wt % of the composition.
[0120] When in the form of a unrefined or partially refined
heterogeneous fluid, the composition of the invention is useful the
reduction and/or inhibition of asphaltene deposit formation and/or
flocculation in an subterranean oil reservoir, oil pipe line or
storage vessel or other relevant equipment that a hydrocarbon
fluid, e.g., a crude oil, may come in contact with. The method and
composition of the invention are also useful in the reduction
and/or inhibition of deposit formation and settling in industrial
and marine hydrocarbon fuel systems, including where fuel stream
mixing may occur and give rise to asphaltenic destabilization,
agglomeration and settling or deposition. The method and
composition of the invention are also useful in the inhibition of
deposition of asphaltenic species at surfaces in refinery and
petrochemical processes.
[0121] In one embodiment the invention provides a method of
asphaltene control in an unrefined or partially refined
heterogeneous fluid, the method employing said dispersant of
Formula (1).
[0122] For asphaltene control, the composition comprising a
dispersant of Formula (I) may be present in an oil reservoir in an
amount including 1 ppm to 30 wt % of the dispersant, in another
embodiment 5 ppm to 10 wt % of the dispersant, in another
embodiment 20 ppm to 3 wt % of the dispersant and in another
embodiment 40 ppm to 1 wt % of the dispersant. For example the
dispersant may be present from 60 ppm to 500 ppm or 80 ppm to 350
ppm.
[0123] 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:
[0124] hydrocarbon substituents, that is, aliphatic (e.g., alkyl or
alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents,
and aromatic-, aliphatic-, and alicyclic-substituted aromatic
substituents, as well as cyclic substituents wherein the ring is
completed through another portion of the molecule (e.g., two
substituents together form a ring);
[0125] (i) 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 (e.g., halo (especially
chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto,
nitro, nitroso, and sulfoxy);
[0126] (ii) hetero substituents, that is, substituents which, while
having a predominantly hydrocarbon character, in the context of
this invention, contain other than carbon in a ring or chain
otherwise composed of carbon atoms. Heteroatoms include sulfur,
oxygen, nitrogen, and encompass substituents as pyridyl, furyl,
thienyl and imidazolyl. 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.
[0127] 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 the 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 the composition prepared by admixing the
components described above.
[0128] 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.
[0129] 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
Dispersants 1 to 43
[0130] Dispersants 1-14 (formation of PIBSA:PEI) are prepared by
the following process. A flange flask is charged with
polyisobutylene succinic anhydride and Pilot.TM.900. The flask is
equipped with a lid and clip. A nitrogen inlet is added and a
stirrer with stirrer guide. A 250 ml pressure equalising funnel
with dog leg adaptor is added. A nitrogen blanket is switched on.
The contents are stirred at .about.200 rpm and the content warmed
to 90.degree. C. polyethylyeneimine (PEI) is charged to a pressure
equalising dropping funnel and added drop wise over 1 hour. After
addition of the PEI the temperature is increased to 120.degree. C.
and the reaction vessel lagged with glass wool. The reaction
temperature is held at 120.degree. C. (or 175.degree. C. as noted)
for 4 hours. The reaction is then cooled to ambient temperature.
Dispersant 1 has polyisobutylene with a number average molecular
weight of about 1500 and a ratio of polyisobutylene to maleic
anhydride of 1:2.24. Dispersants 2-10 have polyisobutylene with a
number average molecular weight of 950-1000; Dispersants 11-14 have
polyisobutylene with a number average molecular weight of 2300; and
a ratio of polyisobutylene to maleic anhydride of 1:1.2. Other
characteristics of Dispersants 1 to 14 are summarised in Table 1.
TABLE-US-00001 TABLE 1 Reaction % PEI Temperature of Pilot .TM.
Example Mn C.dbd.O:N (.degree. C.) 900 Oil TBN Dispersant 1 600
1:4.71 120 28 219 Dispersant 2 600 1:3.45 120 40 205 Dispersant 3
600 1:3.45 175 40 100 Dispersant 4 600 1:1.79 120 40 48 Dispersant
5 600 1:1.79 175 40 33 Dispersant 6 600 1:2.5 120 40 77 Dispersant
7 400 1:1.79 120 40 54 Dispersant 8 400 1:2.5 120 40 82 Dispersant
9 400 1:3.45 120 40 145 Dispersant 10 10,000 1:1.79 120 40 54
Dispersant 11 600 0.85:1 120 40 12.5 Dispersant 12 10,000 0.85:1
120 40 8.7 Dispersant 13 600 1.6:1 120 40 20.6 Dispersant 14 10,000
1.6:1 120 40 23.1
[0131] Dispersant 15 is prepared in a similar process to Dispersant
1, except 200 g of polyricinoleic acid is used instead of
polyisobutylene succinic anhydride; and polyethyleneimine is
replaced with 57 g of a polyamine, specifically HPA-X.TM.. Further
the reaction temperature is held at 140.degree. C. for 5 hours
before cooling to ambient. The resultant product has a C.dbd.O:N
ratio of 1:3.5.
[0132] Dispersants 16 to 27 are prepared as described in Examples 1
to 12 respectively of WO 02/077111.
[0133] Dispersant 28 is prepared by the same methodology as Example
1 of WO 00/024503, except the polyricinoleic acid is replaced by
polyhydroxystearic acid with weight average molecular weight of
1600 (derived from 12-hydroxystearic acid); and polyethyleneimine
has a molecular weight of 600. The product formed has a C.dbd.O:N
ratio of 1:3.5.
[0134] Dispersants 29 to 37 are prepared as described in Examples 1
to 12 respectively of WO 00/024503.
[0135] Dispersants 38 to 41 are prepared in a similar process to
Dispersant 1, except polyhydroxystearic acid is used instead of
polyisobutylene succinic anhydride and the amine used is shown in
Table 2. Dispersants 38 to 41 are characterised as shown in Table
2. TABLE-US-00002 TABLE 2 Nitrogen Example Amine CO:N ratio content
(wt %) TBN Dispersant 38 TETA 1:1.3 0.66 20.0 Dispersant 39 TETA
1:2.6 1.58 9.2 Dispersant 40 HPAX .TM. 1:1.3 0.67 22.3 Dispersant
41 HPAX .TM. 1:2.6 1.40 6.9 Footnote to Table 2: TETA is
Tetraethylene triamine.
[0136] Dispersants 42 and 43 are prepared by the same methodology
as Dispersant 24, except the dispersant products formed have a
C.dbd.O:N ratio of 1:1.3 and 1:2.6 respectively.
Test 1: Deposit Control
[0137] A soot (or deposit)-dispersive screen test is performed on
several of the dispersants prepared above. In this test, a
specified amount (e.g., 0.2 wt % or 1 wt %) of the candidate
chemistry is added to a used oil sample from the end of a test
drain from a Mack.TM. T-11 engine test that exhibited a relatively
high degree of viscosity increase. The sample is subjected to
oscillation and the ability of the candidate to reduce the buildup
of associations between molecules of soot is measured as a modulus,
by a method described in Society of Automotive Engineers (SAE)
Technical Paper 2001-01-1967, "Understanding Soot Mediated Oil
Thickening: Rotational Rheology Techniques to Determine Viscosity
and Soot Structure in Peugot XUD-11 BTE Drain Oils," M. Parry, H.
George, and J. Edgar, presented at International Spring Fuels &
Lubricants Meeting & Exhibition, Orlando, Fla., May 7-9, 2001.
The calculated parameter is referred to as G'. The G' of the sample
treated with the experimental chemistry is compared to the G' of
the drain oil without the additive, the latter of which is defined
as 1.00. Values of G' less than 1.00 indicate increasing
effectiveness at soot dispersion. The results obtained are:
TABLE-US-00003 TABLE 3 Example (Treat Example (Treat Rate 1 wt %)
G'.sub.add/G'.sub.oil Rate 1 wt %) G'.sub.add/G'.sub.oil
Comparative Example 1* 1 Dispersant 10 0.78 Comparative Example 2**
0.56 Dispersant 11 0.64 Dispersant 1 0.37 Dispersant 12 0.92
Dispersant 2 0.23 Dispersant 13 0.06 Dispersant 3 0.36 Dispersant
14 0.23 Dispersant 4 0.58 Dispersant 38 0.48 Dispersant 5 0.57
Dispersant 39 0.14 Dispersant 6 0.52 Dispersant 40 0.35 Dispersant
7 0.71 Dispersant 41 0.09 Dispersant 8 0.56 Dispersant 42 0.37
Dispersant 9 0.40 Dispersant 43 0.16 Footnote to Table 3:
*indicates that Comparative Example 1 is a base oil without a
dispersant/detergent additive; and **indicates Comparative Example
2 is polyisobutylene succinimide (derived from tetraethylene
pentamine).
[0138] TABLE-US-00004 TABLE 4 Example Treat Rate 0.2 wt %)
G'.sub.add/G'.sub.oil Comparative Example 3*** 0.56 Dispersant 15
0.52 Dispersant 28 0.29 Footnote to Table 4: ***indicates that
Comparative Example 3 is same as Comparative Example 2, except the
treat rate is 0.2 wt %.
Test 2: Sludge Handling
[0139] A number of dispersants prepared above are dissolved in a
tube at 6 different concentrations ranging from 0.125 wt % to 0.004
wt % in Exxon 100 N base oil forming a mixture (of 10 cm.sup.3).
Each mixture is then added to an artificial sludge solution and
allowed to stand for one day. The tubes are examined to determine
the amount of sludge deposited and the tube rating. The tube rating
results reported are rated on a scale from 1 to 6. Typically better
results are obtained for a sample with a higher tube rating and for
samples with ability to suspend higher amounts of deposit. The
results obtained for a number of dispersants prepared above are
shown in Table 5. TABLE-US-00005 TABLE 5 Example (Treat Rate
Deposits Suspended 0.2 wt %) Tube Rating (mg) Dispersant 11 7* 350
Dispersant 13 7* 500 Dispersant 14 7* 500 Dispersant 38 5 63
Dispersant 39 5 63 Dispersant 40 3 32 Dispersant 41 4 32 Dispersant
42 3 32 Dispersant 43 4 65 Footnote to Table 5: *indicates that the
samples performed sufficiently that a 7.sup.th tube is tested.
Test 3: Seal Compatibility
[0140] Seal compatibility tests are designed to evaluate the effect
of motor oils on Parker-Pradifa.TM. FKM E-281 seal elastomers
(fluoroelastomer). Six dumbbells of elastomer are suspended using a
micro wire and glass separators are covered by at least 10 ml of
oil. The test vessel is covered with aluminium foil and stored at
150.degree. C. for 96 hours. The elastomer is removed from the oil
and tested for percentage change in tensile strength (T/S), rupture
elongation (R/E), and cracking (by bending). The results obtained
samples are presented in Table 6. TABLE-US-00006 TABLE 6 Example
T/S Final (N/m.sup.2) R/E Final (%) Dispersant 40 11.4 251
Dispersant 41 9.5 212
[0141] Overall the results indicate the composition and dispersants
of the invention are suitable for providing dispersant properties,
providing improved fuel economy and/or seal compatibility.
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