U.S. patent application number 15/315050 was filed with the patent office on 2017-04-20 for epoxide quaternized quaternary ammonium salts.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Paul E. Adams, James H. Bush, Hannah Greenfield, David J. Moreton, Paul R. Stevenson.
Application Number | 20170107441 15/315050 |
Document ID | / |
Family ID | 53434462 |
Filed Date | 2017-04-20 |
United States Patent
Application |
20170107441 |
Kind Code |
A1 |
Adams; Paul E. ; et
al. |
April 20, 2017 |
EPOXIDE QUATERNIZED QUATERNARY AMMONIUM SALTS
Abstract
The present technology is related to quaternary ammonium salts
prepared with alcohol functionalized and/or C.sub.4 to C.sub.20
epoxide quaternizing agents, such as, for example, glycidol and
1,2-butylene oxide, and the use of such quaternary ammonium salts
in fuel compositions to improve the water shedding performance of
the fuel composition.
Inventors: |
Adams; Paul E.; (Willoughby,
OH) ; Bush; James H.; (Mentor, OH) ;
Greenfield; Hannah; (Derby, GB) ; Stevenson; Paul
R.; (Belper, GB) ; Moreton; David J.;
(Milford, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
53434462 |
Appl. No.: |
15/315050 |
Filed: |
May 29, 2015 |
PCT Filed: |
May 29, 2015 |
PCT NO: |
PCT/US2015/033210 |
371 Date: |
November 30, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62005114 |
May 30, 2014 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 133/56 20130101;
C10L 2270/023 20130101; C10M 2215/02 20130101; C10M 2215/042
20130101; C10L 2200/0259 20130101; C10L 10/18 20130101; C10N
2040/252 20200501; C10N 2040/26 20130101; C10L 10/04 20130101; C10M
2215/04 20130101; C10L 2200/0423 20130101; C10L 1/2383 20130101;
C10N 2040/253 20200501; C10M 2207/127 20130101; C10M 2217/043
20130101; C10N 2040/25 20130101; C10N 2070/00 20130101; C10M
2215/28 20130101; C10M 133/06 20130101; C10N 2030/06 20130101; C10N
2040/04 20130101; C10N 2030/04 20130101; C10N 2020/04 20130101;
C10L 2200/0446 20130101; C10N 2040/255 20200501; C10L 1/1883
20130101; C10L 2270/026 20130101; C10L 1/2222 20130101 |
International
Class: |
C10M 133/06 20060101
C10M133/06; C10L 10/18 20060101 C10L010/18; C10L 1/222 20060101
C10L001/222 |
Claims
1. A composition comprising at least one hydrocarbyl-substituted
succinic acid wherein the hydrocarbyl-substituent is a
polyisobutylene having a number average molecular weight ranging
from 100 to 5000 and an epoxide quaternary ammonium salt ("epoxide
quat"), wherein the epoxide quat comprises the reaction product of:
a. a quaternizable compound that is the reaction product of: (i) a
hydrocarbyl-substituted acylating agent, wherein the
hydrocarbyl-substituent has a number average molecular weight
ranging from 100 to 5000, and (ii) a nitrogen containing compound
having an oxygen or nitrogen atom capable of reacting with said
hydrocarbyl-substituted acylating agent, and further having at
least one quaternizable amino group; and b. a quaternizing agent
comprising alcohol functionalized epoxides; C.sub.4 to C.sub.20
epoxides; and mixtures thereof.
2. The composition of claim 1, wherein the hydrocarbyl-substituent
of said acylating agent has a number average molecular weight of
550.
3. The composition of claim 1, wherein the quaternizable amino
group is a primary, secondary or tertiary amino group.
4. The composition of claim 1, wherein the hydrocarbyl-substituted
acylating agent comprises at least one polyisobutenyl succinic
anhydride or polyisobutenyl succinic acid.
5. The composition of claim 1, wherein the reaction in a) is
carried out at a temperature of greater than 80, 90, or 100.degree.
C.
6. The composition of claim 1, wherein the reaction in a) is
carried out at a temperature of less than 80.degree. C.
7. The composition of claim 1, wherein the quaternizing agent
comprises a C.sub.4 to C.sub.14 epoxide.
8. The composition of claim 1, wherein the quaternizing agent
comprises an alcohol functionalized epoxide.
9. The composition of claim 8, wherein the quaternizing agent is
glycidol.
10. The composition of claim 7, wherein the quaternizing agent is
1,2-epoxyhexadecane.
11. The composition of claim 7, wherein the quaternizing agent
comprises butylene oxide.
12. The composition of claim 1, wherein the quaternizing agent is
employed in the presence of a protic solvent.
13. The composition of claim 12, wherein the protic solvent
comprises 2-ethylhexanol, water, and mixtures thereof.
14. The composition of claim 1, wherein the quaternizing agent is
employed in the presence of an acid.
15. The composition of claim 14, wherein the acid is present in the
structure of the acylating agent.
16. The composition of claim 1, further comprising at least one
other additive.
17. The composition of claim 16, wherein the at least one other
additive comprises a detergent, a dispersant, a demulsifier, a
lubricity agent, a cold flow improver, an antioxidant, or a mixture
thereof.
18. The composition of claim 16, wherein the at least one other
additive comprises at least one hydrocarbyl-substituted quaternary
ammonium salt.
19. The composition of claim 16, wherein the at least one other
additive comprises at least one detergent/dispersant that is an
amphiphilic substance which possess at least one hydrophobic
hydrocarbon radical with a number average molecular weight of 100
to 10000 and at least one polar moiety selected from (i) Mono- or
polyamino groups having up to 6 nitrogen atoms, at least one
nitrogen atom having basic properties; (ii) Hydroxyl groups in
combination with mono or polyamino groups, at least one nitrogen
atoms having basic properties; (v) Polyoxy-C.sub.2 to C.sub.4
alkylene moieties terminated by hydroxyl groups, mono- or polyamino
groups, at least one nitrogen atom having basic properties, or by
carbamate groups; (vii) Moieties derived from succinic anhydride
and having hydroxyl and/or amino and/or amido and/or imido groups;
and/or (viii) Moieties obtained by Mannich reaction of substituted
phenols with aldehydes and mono- or polyamines.
20. The composition of claim 18, wherein the
hydrocarbyl-substituent is a polyisobutylene having a number
average molecular weight ranging from 100 to 5000.
21. The composition of claim 16, wherein the at least one other
additive comprises at least one Mannich compound.
22. The composition of claim 1, further comprising a fuel that is
liquid at room temperature.
23. The composition of claim 22, wherein the fuel is gasoline or
diesel.
24. The composition of claim 1 further comprising an oil of
lubricating viscosity.
25. A method of operating an internal combustion engine comprising:
a. supplying to said engine: (i) a fuel, wherein said fuel 1. is
liquid at room temperature; and 2. has a composition comprising an
epoxide quat according to claim 1 therein; and b. operating said
engine.
26. A method of operating an internal combustion engine comprising:
a. supplying to a crankcase of said engine: (i) an oil of
lubricating viscosity; having a composition comprising an epoxide
quat according to claim 1 therein, and b. operating said
engine.
27. The method of claim 26 wherein the oil of lubricating viscosity
has total sulfated ash of less than 1 wt % and/or a phosphorus
content of less than 0.11 wt %.
28. A method of improving water shedding performance of a fuel
composition comprising adding a composition comprising an epoxide
quat according to claim 1 to said fuel composition.
29. A method of reducing and/or preventing injector deposits
comprising: c. supplying to a fuel injector of said engine: (i) a
fuel, wherein said fuel 1. is liquid at room temperature; and 2.
has a composition comprising an epoxide quat according to claim 1
therein; and b. operating said engine.
Description
FIELD OF THE INVENTION
[0001] The present technology is related to quaternary ammonium
salts prepared with alcohol functionalized epoxide and/or C.sub.4
to C.sub.20 epoxide quaternizing agents, and the use of such
quaternary ammonium salts in fuel and lubricant compositions to
improve to improve the water shedding performance of the
composition. The invention further relates to a method of
lubricating an internal combustion engine with the lubricant
composition for at least one of antiwear, friction, detergency,
dispersancy, and/or corrosion control performance.
BACKGROUND OF THE INVENTION
[0002] Deposit formation in diesel fuel injector nozzles is highly
problematic, resulting in incomplete diesel combustion, and
therefore power loss and misfiring. Traditionally, polyisobutylene
succinimide detergents have been used to inhibit injector fouling,
but these materials have shown poor efficacy in modern engines. A
new class of compounds based on quaternized polyisobutylene
succinimides has been shown to provide improved detergency
performance in both the traditional and modern diesel engines.
[0003] Although deposit control is the main function required of
detergent molecules, there are a number of additional performance
attributes which are desired. One of these is the ability of the
detergent to shed water, or resolve water in oil emulsions. The
entrainment of water in, for example, crude oil or downstream fuel
pipelines, and during product transfer, can result in the formation
of stable emulsions and suspended matter in the crude or fuel. Such
emulsions can plug filters or otherwise make such emulsion
containing fuels unacceptable. This could also result in corrosion
issues downstream.
[0004] In order to assist in the water shedding process, a class of
molecules known as demulsifiers can be added to fuel or crude oil
formulations, whether in the pipeline, at the pump or as an
aftermarket additive. While demulsifiers can assist in the water
shedding process, it would be desirable to provide a new detergent
molecule that provides improved demulsification or water shedding
performance.
SUMMARY OF THE INVENTION
[0005] We have now found that quaternary ammoniums salts prepared
with alcohol functionalized epoxides, C.sub.4 to C.sub.14 epoxides,
and mixtures thereof (herein referred to as "epoxide quats") result
in quaternary ammonium salts that, when blended into diesel fuel,
provide improved demulsification performance compared to quaternary
ammonium salts prepared with other epoxides.
[0006] Thus, in one aspect the present technology provides a
composition comprising an epoxide quat prepared with alcohol
functionalized epoxides, C.sub.4 to C.sub.14 epoxides, and mixtures
thereof. The epoxide quat itself can be the reaction product of (a)
a quaternizable compound and (b) a quaternizing agent comprising
alcohol functionalized epoxides, C.sub.4 to C.sub.14 epoxides, and
mixtures thereof.
[0007] The quaternizable compound can be the reaction product of
(i) a hydrocarbyl-substituted acylating agent, and (ii) a nitrogen
containing compound having an oxygen or nitrogen atom capable of
reacting with the hydrocarbyl-substituted acylating agent, and
further having at least one quaternizable amino group. The
hydrocarbyl-substituent can have a number average molecular weight
(M.sub.n) of greater than 100, such as, for example, from 100 to
5000 as measured using gel permeation chromatography (GPC) based on
a polystyrene calibration standard.
[0008] In an embodiment, the quaternizable amino group can be a
primary, secondary or tertiary amino group. In a further
embodiment, the hydrocarbyl-substituted acylating agent can be
polyisobutenyl succinic anhydride or polyisobutenyl succinic
acid.
[0009] In some embodiments, the reaction to prepare the
quaternizable compound of (a) can be carried out at a temperature
of greater than 80 or 90 or 100.degree. C. In some embodiments,
water of reaction can be removed. In some embodiments, the reaction
to prepare the quaternizable compound of (a) can be carried out at
a temperature of less than 80.degree. C.
[0010] In an embodiment, the epoxide quat is an imide containing
quaternary ammonium salt. In an embodiment, the epoxide quat is an
amide or ester containing quaternary ammonium salt.
[0011] In another embodiment, the quaternizing agent can comprise,
consist of, or consist essentially of alcohol functionalized
epoxides. In still further embodiments, the quaternizing agent can
comprise, consist of, or consist essentially of glycidol. In
another embodiment, the quaternizing agent can comprise, consist
of, or consist essentially of C.sub.4 to C.sub.14 epoxides. In
another embodiment, the quaternizing agent can comprise, consist
of, or consist essentially of 1,2-butylene oxide. In another
embodiment, the quaternizing agent can comprise, consist of, or
consist essentially of epoxyhexadecane.
[0012] In some embodiments, the quaternizing agent can be employed
in the presence of a protic solvent. In some embodiments, the
quaternizing agent can be employed in the presence of
2-ethylhexanol, water, or mixtures thereof. In some embodiments,
the quaternizing agent can be employed in the presence of an acid.
In some embodiments, the quaternizing agent can be employed in the
presence of an acid separate from the acid group present on the
acylating agent. In some embodiments, the quaternizing agent can be
employed in the presence of the acid group present in the structure
of the acylating agent.
[0013] In some embodiments, the compositions described above can
further include at least one other additive. In some instances, the
at least one other additive can be a detergent, a demulsifier, or a
mixture thereof. In some instances the at least one other additive
can be at least one hydrocarbyl-substituted succinic acid. In some
instances, the at least one other additive can be at least one
hydrocarbyl-substituted quaternary ammonium salt. In some instances
where the at least one other additive is a non-quaternized or
quaternized hydrocarbyl-substituted succinic acid, the
hydrocarbyl-substituent can be a polyisobutylene having a number
average molecular weight (M.sub.n) of from about 100 to about 5000.
In an embodiment, the at least one other additive can be at least
one Mannich compound.
[0014] A further aspect of the present technology includes a
composition having an epoxide quat as described herein, and further
having a fuel that is liquid at room temperature. In some
embodiments the fuel can be a diesel fuel.
[0015] A further aspect of the present technology includes a
composition having an epoxide quat as described herein, and further
having an oil of lubricating viscosity.
[0016] A still further aspect of the present technology provides a
method of operating an internal combustion engine. The method can
include the steps of (a) supplying to the engine a fuel composition
and (b) operating said engine. The fuel composition employed in the
foregoing method can include (i) a fuel which is liquid at room
temperature, and (ii) a composition comprising epoxide quat as
described herein. In another embodiment, the method of operating an
internal combustion engine can include the steps of (a) supplying a
lubricating oil composition to the crankcase of the engine and (b)
operating said engine. The lubricating oil composition can include
(i) oil of lubricating viscosity, and (ii) the epoxide quat as
described herein.
[0017] Embodiments of the present technology may provide the use of
the epoxide quat for at least one of antiwear performance, friction
modification (particularly for enhancing fuel economy), detergent
performance (particularly deposit control or varnish control),
dispersancy (particularly soot control, or sludge control), or
corrosion control.
[0018] A further embodiment of the present technology provides a
method of improving water shedding, or demulsification, performance
of a fuel composition. The method includes employing in a fuel,
which is liquid at room temperature, a composition containing an
epoxide quat as described herein. Also provided is the use of a
composition containing epoxide quat as described herein, to provide
improved water shedding or demulsification performance in a fuel
that is liquid at room temperature.
[0019] In another embodiment, a composition comprising an epoxide
quaternary ammonium salt ("epoxide quat") is disclosed. The epoxide
quat may comprise the reaction product of a quaternizable compound
and a quaternizing agent comprising alcohol functionalized
epoxides, C.sub.4 to C.sub.14 epoxides, or mixtures thereof. In
other embodiments, the quaternizing agent may be a C.sub.4 to
C.sub.20 epoxide. The quaternizable compound may be the reaction
product of a hydrocarbyl-substituted acylating agent, wherein the
hydrocarbyl-substituent has a number average molecular weight
ranging from 100 to 5000, and a nitrogen containing compound having
an oxygen or nitrogen atom capable of reacting with the
hydrocarbyl-substituted acylating agent, and further having at
least one quaternizable amino group. The quaternizable amino group
may be a primary, secondary or tertiary amino group.
[0020] In one embodiment, the hydrocarbyl-substituted acylating
agent may be a polyisobutenyl succinic anhydride or polyisobutenyl
succinic acid. In yet another embodiment, the reaction in a) may be
carried out at a temperature of greater than 80.degree. C.
Alternatively, the reaction in a) may be carried out at a
temperature of less than 80.degree. C.
[0021] In another embodiment, the quaternizing agent may comprise a
C.sub.4 to C.sub.14 epoxide or an alcohol functionalized epoxide.
Suitable quaternizing agents include, but are not limited to,
glycidol, 1,2-epoxyhexadecane, butylene oxide, or mixtures thereof.
In another embodiment, the quaternizing agent may be employed in
the presence of a protic solvent. Suitable protic solvents include,
but are not limited to, 2-ethylhexanol, water, or mixtures thereof.
In yet another embodiment, the quaternizing agent may be employed
in the presence of an acid, such as acetic acid. The acid may be
present in the structure of the acylating agent.
[0022] The disclosed compositions comprising an epoxide quat may
further comprising at least one other additive. Suitable additive
include, but are not limited to, detergents, dispersants,
demulsifiers, lubricity agents, cold flow improvers, antioxidants,
or mixtures thereof.
[0023] In one embodiment, the at least one other additive comprises
at least one hydrocarbyl-substituted succinic acid or at least one
hydrocarbyl-substituted quaternary ammonium salt. The
hydrocarbyl-substituent may be a polyisobutylene having a molecular
weight ranging from 100 to 5000.
[0024] In another embodiment, the at least one other additive
comprises at least one detergent/dispersant that is an amphiphilic
substance which possess at least one hydrophobic hydrocarbon
radical with a number average molecular weight of 100 to 10000 and
at least one polar moiety selected from (i) Mono- or polyamino
groups having up to 6 nitrogen atoms, at least one nitrogen atom
having basic properties; (ii) Hydroxyl groups in combination with
mono or polyamino groups, at least one nitrogen atoms having basic
properties; (v) Polyoxy-C2 to C4 alkylene moieties terminated by
hydroxyl groups, mono- or polyamino groups, at least one nitrogen
atom having basic properties, or by carbamate groups; (vii)
Moieties derived from succinic anhydride and having hydroxyl and/or
amino and/or amido and/or imido groups; and/or (viii) Moieties
obtained by Mannich reaction of substituted phenols with aldehydes
and mono- or polyamines. In yet another embodiment, the at least
one other additive comprises at least one Mannich compound.
[0025] In another embodiment, the disclosed compositions may
further comprise a fuel that is liquid at room temperature. The
fuel may be gasoline or diesel. The composition of any of claims 1
to 21 further comprising an oil of lubricating viscosity.
[0026] A method of improving water shedding performance of a
gasoline or diesel fuel composition is also disclosed. The method
may comprise employing a composition comprising an epoxide quat as
described above. The epoxide quat may be added to the fuel in an
amount ranging from 5 to 1000 ppm by weight based on a total weight
of the fuel composition.
[0027] In yet another method, the composition comprising an epoxide
quat may further comprise an oil of lubricating viscosity.
[0028] A method of operating an internal combustion engine is also
disclosed. The method may comprise supplying a fuel which is liquid
at room temperature having a composition comprising an epoxide quat
therein to the engine and operating the engine. The epoxide quat
may be added to the fuel in an amount ranging from 5 to 1000 ppm by
weight based on a total weight of the fuel composition.
[0029] In yet another embodiment, the method of operating an
internal combustion engine may comprise supplying an oil of
lubricating viscosity having a composition comprising an epoxide
quat therein to the engine crankcase and operating the engine. The
epoxide quat may be added to the oil on an active basis 1-5 wt %.
The oil of lubricating viscosity may have a total sulfated ash of
less than 1 wt % and/or a phosphorus content of less than 0.11 wt
%.
[0030] A method of reducing and/or preventing injector deposits is
also disclosed. The method may comprise supplying a fuel
composition having a composition comprising an epoxide quat therein
to a fuel injector of the engine and operating the engine.
BRIEF DESCRIPTION OF THE FIGURES
[0031] FIG. 1 shows the demulsification test results of an
embodiment of the disclosed technology.
[0032] FIG. 2 shows the CEC F-23-01 XUD-9 test results at 10 ppm of
an embodiment of the disclosed technology.
[0033] FIG. 3 shows the CEC F-23-01 XUD-9 test results at 30 ppm of
an embodiment of the disclosed technology.
DETAILED DESCRIPTION OF THE INVENTION
[0034] Various preferred features and embodiments will be described
below by way of non-limiting illustration.
[0035] One aspect of the current technology relates to a
composition of an imide containing quaternary ammonium salt. The
quaternary ammonium salt (herein referred to as "epoxide quats")
may be prepared with alcohol functionalized epoxides, C.sub.4 to
C.sub.14 epoxides, and mixtures thereof. In another aspect, the
epoxide quats may be prepared using a C.sub.4 to C.sub.20
epoxides.
Epoxide Quats
[0036] The production of a quaternary ammonium salt generally
results in a mixture of compounds including a quaternary ammonium
salt or salts, and this mixture may be difficult to define apart
from the process steps employed to produce the quaternary ammonium
salt. Further, the process by which a quaternary ammonium salt is
produced can be influential in imparting distinctive structural
characteristics to the final quaternary ammonium salt product that
can affect the properties of the quaternary ammonium salt product.
Thus, in one embodiment, the epoxide quats of the present
technology may be described as a reaction product of (a) a
quaternizable compound, and (b) a quaternizing agent. As used
herein, reference to epoxide quat(s) includes references to the
mixture compounds including a quaternary ammonium salt or salts
prepared with alcohol functionalized epoxides, C.sub.4 to C.sub.14
epoxides, and mixtures thereof, as well as referring to the
quaternary ammonium salt itself.
[0037] The quaternizable compound of (a) employed to prepare the
epoxide quat may itself be the reaction product of (i) a
hydrocarbyl-substituted acylating agent, and (ii) a nitrogen
containing compound. The hydrocarbyl-substituted acylating agent of
(a)(i) can be an acylating agent functionalized with a
hydrocarbyl-substituent having a number average molecular weight of
100 to 5000.
[0038] The number average molecular weight of the materials
described herein is measured using gas permeation chromatography
(GPC) using a Waters GPC 2000 equipped with a refractive index
detector and Waters Empower.TM. data acquisition and analysis
software. The columns are polystyrene (PLgel, 5 micron, available
from Agilent/Polymer Laboratories, Inc.). For the mobile phase,
individual samples are dissolved in tetrahydrofuran and filtered
with PTFE filters before they are injected into the GPC port.
Waters GPC 2000 Operating Conditions:
[0039] Injector, Column, and Pump/Solvent compartment temperatures:
40.degree. C. Autosampler Control: Run time: 40 minutes Injection
volume: 300 microliter Pump: System pressure: .about.90 bars (Max.
pressure limit: 270 bars, Min. pressure limit: 0 psi) Flow rate:
1.0 ml/minute Differential Refractometer (RI): Sensitivity: -16;
Scale factor: 6
[0040] Examples of quaternary ammonium salts and methods for
preparing the same are described in the following patents, which
are hereby incorporated by reference, U.S. Pat. No. 4,253,980, U.S.
Pat. No. 3,778,371, U.S. Pat. No. 4,171,959, U.S. Pat. No.
4,326,973, U.S. Pat. No. 4,338,206, U.S. Pat. No. 5,254,138, and
U.S. Pat. No. 7,951,211.
[0041] Details regarding the quaternizable compound, and
specifically, the hydrocarbyl-substituted acylating agent and the
nitrogen containing compound, as well as the quaternizing agent,
are provided below.
The Hydrocarbyl Substituted Acylating Agent
[0042] The hydrocarbyl substituted acylating agent employed to
prepare the quaternizable compound can be the reaction product of
the precursor to the hydrocarbyl-substituent, which is a long chain
hydrocarbon, generally a polyolefin, 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).
[0043] The hydrocarbyl-substituent is a long chain hydrocarbyl
group. In one embodiment, the hydrocarbyl group can have a number
average molecular weight (M.sub.n) of from about 100 or 300 to
about 5000, or from about 500 to about 2500. The Mn of the
hydrocarbyl group can also be from about 1300 to about 3000. The
M.sub.n of the hydrocarbyl-substituent can also be from 1500 to
2800 or 2900, or from 1700 to 2700, or from 1900 to 2600, or 2000
to 2500. In an embodiment, the M.sub.n can be from about 300 to
about 750. The M.sub.n of the hydrocarbyl-substituent can also be
from about 350 to 700, and in some cases from 400 to 600, or 650.
In yet other embodiments the M.sub.n of the hydrocarbyl-substituent
can also be 550, or 1000, or 2300. In yet another embodiment, the
hydrocarbyl-substituent may have a number average molecular weight
of 1000 to 2300. In an embodiment, the hydrocarbyl-substituent can
be any compound containing an olefinic bond represented by the
general formula:
(R.sup.1)(R.sup.2)C.dbd.C(R.sup.6)(CH(R.sup.7)(R.sup.8)) (I)
wherein each of R.sup.1 and R.sup.2 is, independently, hydrogen or
a hydrocarbon based group. Each of R.sup.6, R.sup.7 and R.sup.8 is,
independently, hydrogen or a hydrocarbon based group; preferably at
least one is a hydrocarbon based group containing at least 20
carbon atoms.
[0044] Olefin polymers for reaction with the monounsaturated
carboxylic acids can include polymers comprising a major molar
amount of C.sub.2 to C.sub.20, e.g. C.sub.2 to C.sub.5 monoolefin.
Such olefins include ethylene, propylene, butylene, isobutylene,
pentene, octene-1, or styrene. The polymers can be homopolymers
such as polyisobutylene, as well as copolymers of two or more of
such olefins such as copolymers of; ethylene and propylene;
butylene and isobutylene; propylene and isobutylene. Other
copolymers include those in which a minor molar amount of the
copolymer monomers e.g., 1 to 10 mole % is a C.sub.4 to C.sub.18
diolefin, e.g., a copolymer of isobutylene and butadiene; or a
copolymer of ethylene, propylene and 1,4-hexadiene.
[0045] In one embodiment, at least one R of formula (I) is derived
from polybutene, that is, polymers of C4 olefins, including
1-butene, 2-butene and isobutylene. C4 polymers can include
polyisobutylene. In another embodiment, at least one R of formula
(I) is derived from ethylene-alpha olefin polymers, including
ethylene-propylene-diene polymers. Ethylene-alpha olefin copolymers
and ethylene-lower olefin-diene terpolymers are described in
numerous patent documents, including European patent publication EP
0 279 863 and the following U.S. Pat. Nos. 3,598,738; 4,026,809;
4,032,700; 4,137,185; 4,156,061; 4,320,019; 4,357,250; 4,658,078;
4,668,834; 4,937,299; 5,324,800 each of which are incorporated
herein by reference for relevant disclosures of these ethylene
based polymers.
[0046] In another embodiment, the olefinic bonds of formula (I) are
predominantly vinylidene groups, represented by the following
formulas:
##STR00001##
wherein R is a hydrocarbyl group
##STR00002##
wherein R is a hydrocarbyl group.
[0047] In one embodiment, the vinylidene content of formula (I) can
comprise at least 30 mole % vinylidene groups, at least 50 mole %
vinylidene groups, or at least 70 mole % vinylidene groups. Such
material and methods for preparing them are described in U.S. Pat.
Nos. 5,071,919; 5,137,978; 5,137,980; 5,286,823, 5,408,018,
6,562,913, 6,683,138, 7,037,999 and U.S. Publication Nos.
20040176552A1, 20050137363 and 20060079652A1, which are expressly
incorporated herein by reference, such products are commercially
available by BASF, under the trade name GLISSOPAL.RTM. and by Texas
PetroChemical LP, under the trade name TPC 1105.TM. and TPC
595.TM..
[0048] In other embodiments, the hydrocarbyl-substituted acylating
agent may be a "conventional" vinylidene polyisobutylene (PIB)
wherein less than 20% of the head groups are vinylidene head groups
as measured by nuclear magnetic resonance (NMR). Alternatively, the
hydrocarbyl-substituted acylating agent may be a mid-vinylidene PIB
or a high-vinylidene PIB. In mid-vinylidene PIBs, the percentage of
head groups that are vinylidene groups can range from greater than
20% to 70%. In high-vinylidene PIBs, the percentage of head groups
that are vinylidene head groups is greater than 70%.
[0049] Methods of making hydrocarbyl substituted acylating agents
from the reaction of the monounsaturated carboxylic acid reactant
and the compound of formula (I) are well known in the art and
disclosed in the following patents: U.S. Pat. Nos. 3,361,673 and
3,401,118 to cause a thermal "ene" reaction to take place; U.S.
Pat. Nos. 3,087,436; 3,172,892; 3,272,746, 3,215,707; 3,231,587;
3,912,764; 4,110,349; 4,234,435; 6,077,909; 6,165,235 and are
hereby incorporated by reference.
[0050] In another embodiment, the hydrocarbyl substituted acylating
agent can be made from the reaction of at least one carboxylic
reactant represented by the following formulas:
##STR00003##
wherein each of R.sup.3, R.sup.5 and R.sup.9 is independently H or
a hydrocarbyl group, R.sup.4 is a divalent hydrocarbylene group and
n is 0 or 1 with any compound containing an olefin bond as
represented by formula (I). Compounds and the processes for making
these compounds are disclosed in U.S. Pat. Nos. 5,739,356;
5,777,142; 5,786,490; 5,856,524; 6,020,500; and 6,114,547.
[0051] In yet another embodiment, the hydrocarbyl substituted
acylating agent can be made from the reaction of any compound
represented by formula (I) with (IV) or (V), and can be carried out
in the presence of at least one aldehyde or ketone. Suitable
aldehydes include formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, isobutyraldehyde, pentanal, hexanal. heptaldehyde,
octanal, benzaldehyde, and higher aldehydes. Other aldehydes,
including monoaldehydes, and dialdehydes, such as glyoxal, may also
be used. In one embodiment, aldehyde is formaldehyde, which can be
supplied as the aqueous solution often referred to as formalin, but
is more often used in the polymeric form as paraformaldehyde, which
is a reactive equivalent of, or a source of, formaldehyde. Other
reactive equivalents include hydrates or cyclic trimers. Suitable
ketones include acetone, butanone, methyl ethyl ketone, and other
ketones. In one embodiment of the disclosed technology, one of the
two hydrocarbyl groups is methyl. Mixtures of two or more aldehydes
and/or ketones are also useful. Compounds and the processes for
making these compounds are disclosed in U.S. Pat. Nos. 5,840,920;
6,147,036; and 6,207,839.
[0052] In another embodiment, the hydrocarbyl substituted acylating
agent can include, methylene bis-phenol alkanoic acid compounds,
the condensation product of (i) aromatic compound of the
formula:
R.sub.m--Ar--Z.sub.c (VI)
wherein R is independently a hydrocarbyl group, Ar is an aromatic
group containing from 5 to 30 carbon atoms and from 0 to 3 optional
substituents such as amino, hydroxy- or alkyl-polyoxyalkyl, nitro,
aminoalkyl, carboxy or combinations of two or more of said optional
substituents, Z is independently OH, lower alkoxy,
(OR.sup.10).sub.bOR.sup.11, or O-- wherein each R.sup.10 is
independently a divalent hydrocarbyl group, R.sup.11 is H or
hydrocarbyl and b is a number ranging from 1 to 30, c is a number
ranging from 1 to 3 and m is 0 or an integer from 1 up to 6 with
the proviso that m does not exceed the number of valences of the
corresponding Ar available for substitution and (ii) at least on
carboxylic reactant such as the compounds of formula (IV) and (V)
described above. In one embodiment, at least one hydrocarbyl group
on the aromatic moiety is derived from polybutene. In one
embodiment, the source of hydrocarbyl groups are above described
polybutenes obtained by polymerization of isobutylene in the
presence of a Lewis acid catalyst such as aluminum trichloride or
boron trifluoride. Compounds and the processes for making these
compounds are disclosed in U.S. Pat. Nos. 3,954,808; 5,336,278;
5,458,793; 5,620,949; 5,827,805; and 6,001,781.
[0053] In another embodiment, the reaction of (i) with (ii),
optionally in the presence of an acidic catalyst such as organic
sulfonic acids, heteropolyacids, and mineral acids, can be carried
out in the presence of at least one aldehyde or ketone. The
aldehyde or ketone reactant employed in this embodiment is the same
as those described above. The ratio of the hydroxyaromatic
compound: carboxylic reactant:aldehyde or ketone can be 2:(0.1 to
1.5):(1.9 to 0.5). In one embodiment, the ratio is 2:(0.8 to
1.1):(1.2 to 0.9). The amounts of the materials fed to the reaction
mixture will normally approximate these ratios, although
corrections may need to be made to compensate for greater or lesser
reactivity of one component or another, in order to arrive at a
reaction product with the desired ratio of monomers. Such
corrections will be apparent to the person skilled in the art.
While the three reactants can be condensed simultaneously to form
the product, it is also possible to conduct the reaction
sequentially, whereby the hydroxyaromatic is reacted first with
either the carboxylic reactant and thereafter with the aldehyde or
ketone, or vice versa. Compounds and the processes for making these
compounds are disclosed in U.S. Pat. No. 5,620,949.
[0054] The hydrocarbyl substituted acylating agent may also be a
copolymer formed by copolymerizing at least one monomer that is an
ethylenically unsaturated hydrocarbon having 2 to 100 carbon atoms.
The monomer may be linear, branched, or cyclic. The monomer may
have oxygen or nitrogen substituents, but will not react with
amines or alcohols. The monomer may be reacted with a second
monomer that is a carboxylic acid or carboxylic acid derivative
having 3 to 12 carbon atoms. The second monomer may have one or two
carboxylic acid functional groups and is reactive with amines or
alcohols. When made using this process, the hydrocarbyl substituted
acylating agent copolymer has a number average molecular weight
M.sub.n of 500 to 20,000.
[0055] Alternatively, the hydrocarbyl substituted acylating agent
may be a terpolymer that is the reaction product of ethylene and at
least one monomer that is an ethylenically unsaturated monomer
having at least one tertiary nitrogen atom, with (i) an alkenyl
ester of one or more aliphatic monocarboxylic acids having 1 to 24
carbon atoms or (ii) an alkyl ester of acrylic or methacrylic
acid.
[0056] In yet another embodiment the hydrocarbyl substituted
acylating agent can include a mono-, dimer or trimer carboxylic
acid with 8 to 54 carbon atoms and is reactive with primary or
secondary amines. Suitable acids include, but are not limited to,
the mono-, dimer, or trimer acids of caprylic acid, capric acid,
lauric acid, myristic acid, palmitic acid, stearic, arachidic acid,
behenic acid, lignoceric acid, cerotic acid, myristoleic acid,
palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic
acid, linoleic acid, linoelaidic acid, .alpha.-linolenic acid,
arachidonic acid, eicosapentaenoic acid, erucic acid, and
docosahexaenoic acid. Other methods of making the hydrocarbyl
substituted acylating agent can be found in the following
reference, U.S. Pat. Nos. 5,912,213; 5,851,966; and 5,885,944 which
are hereby incorporated by reference.
Nitrogen Containing Compound
[0057] The composition of the present invention contains a nitrogen
containing compound having an oxygen or nitrogen atom capable of
reacting with the acylating agent and further having a
quaternizable amino group. A quaternizable amino group is any
primary, secondary or tertiary amino group on the nitrogen
containing compound that is available to react with a quaternizing
agent to become a quaternary amino group.
[0058] In one embodiment, the nitrogen containing compound can be
represented by the following formulas:
##STR00004##
wherein X is an alkylene group containing 1 to 4 carbon atoms;
R.sub.2 may be a H or a hydrocarbyl group; and R.sub.3 and R.sub.4
are hydrocarbyl groups.
##STR00005##
wherein X is a alkylene group containing about 1 to about 4 carbon
atoms; R.sub.3 and R.sub.4 are hydrocarbyl groups.
[0059] Examples of the nitrogen containing compound capable of
reacting with the acylating agent can include, but are not limited
to, dimethylaminopropylamine, N,N-dimethyl-aminopropylamine,
N,N-diethyl-aminopropylamine, N,N-dimethyl-aminoethylamine
ethylenediamine, 1,2-propylenediamine, 1,3-propylene diamine, the
isomeric butylenediamines, pentanediamines, hexanediamines,
heptanediamines, diethylenetriamine, dipropylenetriamine,
dibutylenetriamine, triethylenetetraamine, tetraethylenepentaamine,
pentaethylenehexaamine, hexamethylenetetramine, and
bis(hexamethylene) triamine, the diaminobenzenes, the
diaminopyridines or mixtures thereof. The nitrogen containing
compounds capable of reacting with the acylating agent and further
having a quaternizable amino group can further include aminoalkyl
substituted heterocyclic compounds such as
1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine,
1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine.
Additional nitrogen containing compounds capable of reacting with
the acylating agent and having a quaternizable amino group include
alkanolamines including but not limited to triethanolamine,
trimethanolamine, N,N-dimethylaminopropanol,
N,N-diethylaminopropanol, N,N-diethylaminobutanol,
N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine,
N--N-dimethylethanolamine, N--N-diethylethanolamine,
2-(diisopropylamino)ethanol, 2-(dibutylamino)ethanol,
3-dimethylamino-1-propanol, 3-diethylamino-1-propanol,
1-dimethylamino-2-propanol, 1-diethylamino-2-propanol,
2-dimethylamino-2-methyl-1-1propanol, 5-dimethylamino-2-propanol,
2-[2-(dimethylamino)ethoxy]-ethanol, 4-methyl-2-(piperidino
methyl)phenol, 1-benzyl-3-pyrrolidinol,
1-benzylpyrrolidine-2-methanol,
2,4,6-tri(dimethylaminomethyl)phenol, dialkoxylated amines such as
Ethermeen T12. In some embodiments, the nitrogen containing
compound excludes dimethylaminopropylamine.
[0060] In one embodiment, the nitrogen containing compound can be
an imidazole, for example, as represented by the following
formula:
##STR00006##
wherein R is an amine or alkanol capable of condensing with said
hydrocarbyl-substituted acylating agent and having from 3 to 8
carbon atoms
[0061] In one embodiment, the nitrogen containing compound can be
represented by at least one of formulas X or XI:
##STR00007##
wherein each X can be, individually, a C1 to C6 hydrocarbylene
group, and each R can be, individually, a hydrogen or a C1 to C6
hydrocarbyl group. In one embodiment, X can be, for example, a C1,
C2 or C3 alkylene group. In the same or different embodiments, each
R can be, for example, H or a C1, C2 or C3 alkyl group.
Quaternizable Compound
[0062] The hydrocarbyl substituted acylating agents and nitrogen
containing compounds described above are reacted together to form a
quaternizable compound. Methods and process for reacting the
hydrocarbyl substituted acylating agents and nitrogen containing
compounds are well known in the art.
[0063] In embodiments, the reaction between the hydrocarbyl
substituted acylating agents and nitrogen containing compounds can
be carried out at temperatures of greater than about 80.degree. C.,
or 90.degree. C., or in some cases 100.degree. C., such as between
100 and 150 or 200.degree. C., or 125 and 175.degree. C. In yet
another embodiments the reaction between the hydrocarbyl
substituted acylating agents and the nitrogen containing compounds
may be carried out at temperatures less than 80.degree. C., or
70.degree. C., or 60.degree. C., and in some cases between
40.degree. C. and 80.degree. C. At the foregoing temperatures water
may be produced during the condensation, which is referred to
herein as the water of reaction. In some embodiments, the water of
reaction can be removed during the reaction, such that the water of
reaction does not return to the reaction and further react.
[0064] The hydrocarbyl substituted acylating agents and nitrogen
containing compounds may be reacted at a ratio of 1:1, but the
reaction may also contain the respective reactants (i.e.,
hydrocarbyl substituted acylating agent:nitrogen containing
compound) in ratios from 3:1 to 1:1.2, or from 2.5:1 to 1:1.1, and
in some embodiments from 2:1 to 1:1.05.
Quaternizing Agent
[0065] The quaternary ammonium salt can be formed when the
quaternizable compound, that is, the reaction products of the
hydrocarbyl substituted acylating agent and nitrogen containing
compounds described above, are reacted with a quaternizing agent.
Suitable quaternizing agents can include, for example, alcohol
functionalized epoxides, C.sub.4 to C.sub.14 epoxides, and mixtures
thereof. In yet another embodiment, the quaternizing agents may be
C.sub.4 to C.sub.20 epoxides.
[0066] Epoxides suitable as quaternizing agents for the present
technology include C.sub.4 to C.sub.14 epoxides. Exemplary
epoxides, can be represented by the following formula:
##STR00008##
where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can be independently H,
a C.sub.4 to C.sub.14 hydrocarbyl group, or an alcohol containing
hydrocarbyl group. In an embodiment, the epoxides can be C.sub.4 to
C.sub.14 epoxides. In another embodiment, the epoxides can be
alcohol functionalized epoxides containing from 2 to 32, or from 3
to 28, or even from 3 to 24 carbon atoms. Epoxides suitable as
quaternizing agents in the present technology can include, for
example, C.sub.4 to C.sub.14 epoxides having linear hydrocarbyl
substituents, such as, for example, 2-ethyloxirane,
2-propyloxirane, and the like, and C.sub.4 to C.sub.14 epoxides
having branched and cyclic or aromatic substituents, such as, for
example, styrene oxide. C.sub.4 to C.sub.14 epoxides can also
include epoxidized tri-glycerides, fats or oils; epoxidized alkyl
esters of fatty acids; and mixtures thereof.
[0067] Exemplary alcohol functionalized epoxides can include those
of formula VIII where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can be
independently H or a hydroxyl containing hydrocarbyl group. In an
embodiment, hydroxyl containing hydrocarbyl group can contain from
2 to 32, or from 3 to 28, or even from 3 to 24 carbon atoms.
Exemplary alcohol functionalized epoxide derivatives can include
for example, glycidol and the like.
[0068] In some embodiments the quaternizing agent can be employed
in combination with an acid. The acid used with the quaternizing
agent may be a separate component, such as acetic acid, propionic
acid, 2-ethylhexanoic acid, and the like. In other embodiments, a
small amount of an acid component may be present, such as, about at
<0.2 or even <0.1 moles of acid per mole of hydrocarbyl
acylating agent.
[0069] In certain embodiments the molar ratio of the condensation
compound to quaternizing agent is 1:0.1 to 2, or 1:1 to 1.5, or 1:1
to 1.3.
[0070] In some embodiments, the quaternizing agent can be employed
in the presence of a protic solvent, such as, for example,
2-ethylhexanol, water, and combinations thereof. In some
embodiments, the quaternizing agent can be employed in the presence
of an acid. In yet another embodiment, the quaternizing agent can
be employed in the presence of an acid and a protic solvent. In
some embodiments, the acid can be an acid component in addition to
the acid group present in the structure of the acylating agent. In
further embodiments the reaction can be free of, or essentially
free of, any additional acid component other than the acid group
present in the structure of the acylating agent. By "free of" it is
meant completely free, and by "essentially free" it is meant an
amount that not materially affect the essential or basic and novel
characteristics of the composition, such as, for example, less than
1% by weight.
Structure
[0071] While the process to prepare the epoxide quats can produce a
mixture that is not readily definable apart from the process steps,
certain structural components may be expected in some
circumstances.
[0072] In some embodiments the epoxide quats can comprise, consist
essentially of, or consist of a cation represented by the following
formula:
##STR00009##
wherein: R.sup.21 is a hydrocarbyl group containing from 1 to 10
carbon atoms; R.sup.22 is a hydrocarbyl group containing from 1 to
10 carbon atoms; R.sup.23 is a hydrocarbylene group containing from
1 to 20 carbon atoms; R.sup.24 is a hydrocarbyl group containing
from 5 to 400 carbon atoms, or from 15 or 25 to 300 or 350 carbon
atoms, or from 50 or 120 to 250 carbon atoms, or from 135 to 200
carbon atoms; and X is a group derived from the quaternizing agent.
In some embodiments, R.sup.24 can be a hydrocarbyl group containing
from 92 to 215 carbon atoms, or from 107 to 200 or 210 carbon
atoms, or from 120 to 195 carbon atoms, or from 135 to 190 or from
140 to 180 or 185 carbon atoms, or a hydrocarbyl group containing
from 20 to 55 carbon atoms, or from 25 to 50, or from 28 to 43 or
47 carbon atoms.
[0073] In some embodiments the epoxide quats can comprise, consist
essentially of, or consist of a cation represented by the following
formula:
##STR00010##
wherein: R.sup.21 and R.sup.22 are hydrocarbyl groups containing
from 1 to 10 carbon atoms; R.sup.23 is a hydrocarbylene group
containing from 1 to 20 carbon atoms; R.sup.24 is a hydrocarbyl
group containing from 5 to 400 carbon atoms, or from 15 or 25 to
300 or 350 carbon atoms, or from 50 or 120 to 250 carbon atoms, or
from 135 to 200 carbon atoms; X is a group derived from the
quaternizing agent; and Y is oxygen or nitrogen. In some
embodiments, R.sup.24 can be a hydrocarbyl group containing from 92
to 215 carbon atoms, or from 107 to 200 or 210 carbon atoms, or
from 120 to 195 carbon atoms, or from 135 to 190 or from 140 to 180
or 185 carbon atoms, or a hydrocarbyl group containing from 20 to
55 carbon atoms, or from 25 to 50, or from 28 to 43 or 47 carbon
atoms.
[0074] In some embodiments the epoxide quats can comprise, consist
essentially of, or consist of a cation represented by the following
formulas:
##STR00011##
wherein: R can be a C.sub.1 to C.sub.6 alkyl group; R.sub.1 and
R.sub.2, individually, can be a C.sub.1 to C.sub.6 hydrocarbyl
group, for example a C.sub.1, C.sub.2, or C.sub.3 alkyl group;
R.sub.3, R.sub.4, R.sub.5 and R.sub.6, individually, can be
hydrogen or a C.sub.1 to C.sub.6 hydrocarbyl group, such as, for
example, a C.sub.1, C.sub.2, or C.sub.3 alkyl group; R.sup.24 is a
hydrocarbyl group containing from 5 to 400 carbon atoms, or from 15
or 25 to 300 or 350 carbon atoms, or from 50 or 120 to 250 carbon
atoms, or from 135 to 200 carbon atoms; X.sub.1 and X.sub.2,
individually, can be H or a group derived from the quaternizing
agent, so long as at least one of X.sub.1 and X.sub.2 is a group
derived from the quaternizing agent. In some embodiments, R.sup.24
can be a hydrocarbyl group containing from 92 to 215 carbon atoms,
or from 107 to 200 or 210 carbon atoms, or from 120 to 195 carbon
atoms, or from 135 to 190 or from 140 to 180 or 185 carbon atoms,
or a hydrocarbyl group containing from 20 to 55 carbon atoms, or
from 25 to 50, or from 28 to 43 or 47 carbon atoms.
[0075] In some embodiments the epoxide quats can comprise, consist
essentially of, or consist of a cation represented by the following
formula:
##STR00012##
wherein: R.sup.23 is a hydrocarbylene group containing from 1 to 20
carbon atoms; R.sup.24 is a hydrocarbyl group containing from 5 to
400 carbon atoms, or from 15 or 25 to 300 or 350 carbon atoms, or
from 50 or 120 to 250 carbon atoms, or from 135 to 200 carbon
atoms; and X is a group derived from the quaternizing agent. In
some embodiments, R.sup.24 can be a hydrocarbyl group containing
from 92 to 215 carbon atoms, or from 107 to 200 or 210 carbon
atoms, or from 120 to 195 carbon atoms, or from 135 to 190 or from
140 to 180 or 185 carbon atoms, or a hydrocarbyl group containing
from 20 to 55 carbon atoms, or from 25 to 50, or from 28 to 43 or
47 carbon atoms.
Compositions
[0076] In one embodiment, the present technology provides a
composition comprising an epoxide quat, and the use of the
composition in a fuel composition to improve the water shedding
performance of the fuel composition. In another embodiment, the
present technology provides a composition comprising an epoxide
quat, and the use of the composition in a lubricating composition
with an oil of lubricating viscosity.
Fuel
[0077] The compositions of the present invention can comprise a
fuel which is liquid at room temperature and is useful in fueling
an engine. The fuel is normally a liquid at ambient conditions
e.g., room temperature (20 to 30.degree. C.). The fuel can be a
hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture thereof. The
hydrocarbon fuel can be a petroleum distillate to include a
gasoline as defined by EN228 or ASTM specification D4814, or a
diesel fuel as defined by EN590 or ASTM specification D975. In an
embodiment of the invention the fuel is a gasoline, and in other
embodiments the fuel is a leaded gasoline, or a nonleaded gasoline.
In another embodiment of this invention the fuel is a diesel fuel.
The hydrocarbon fuel can 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 can 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 can 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 can 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 an emulsion of
water in a hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture
thereof. In several embodiments of this invention the fuel can have
a sulfur 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. In another embodiment the fuel can have a sulfur
content on a weight basis of 1 to 100 ppm. In one embodiment the
fuel contains 0 ppm to 1000 ppm, or 0 to 500 ppm, or 0 to 100 ppm,
or 0 to 50 ppm, or 0 to 25 ppm, or 0 to 10 ppm, or 0 to 5 ppm of
alkali metals, alkaline earth metals, transition metals or mixtures
thereof. In another embodiment the fuel contains 1 to 10 ppm by
weight of alkali metals, alkaline earth metals, transition metals
or mixtures thereof. It is well known in the art that a fuel
containing alkali metals, alkaline earth metals, transition metals
or mixtures thereof have a greater tendency to form deposits and
therefore foul or plug common rail injectors. The fuel of the
invention is present in a fuel composition in a major amount that
is generally greater than 50 percent by weight, and in other
embodiments is present at greater than 90 percent by weight,
greater than 95 percent by weight, greater than 99.5 percent by
weight, or greater than 99.8 percent by weight.
[0078] Treat rates of the epoxide quats to fuel range from 5 to
1000 ppm or 5 to 500 ppm, or 10 to 250 ppm, or 10 to 150 ppm, or 15
to 100 ppm. In other embodiments the treat rate range may be from
250 to 1000 ppm, or 250 to 750 ppm, or 500 to 750 ppm or 250 ppm to
500 ppm.
Oil of Lubricating Viscosity
[0079] In lubricating composition embodiments, the compositions of
the present invention can comprise 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 more detailed description of natural and synthetic
lubricating oils is provided in paragraphs [0058] to [0059]
respectively of WO2008/147704. Synthetic oils may also be produced
by Fischer-Tropsch reactions and typically may be hydroisomerized
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.
[0080] Oils of lubricating viscosity may also be selected from any
of the base oils in Groups I-V as specified in the American
Petroleum Institute (API) Base Oil Interchangeability Guidelines.
The five base oil groups are as follow; Group I: >0.03% sulfur
or <90% saturates and viscosity index 80-120; Group II:
<0.03% sulfur and .gtoreq.90% saturates and viscosity index
80-120; Group III: <0.03% sulfur and .gtoreq.90% saturates and
viscosity index .gtoreq.120; Group IV: all polyalphaolefins; Group
V: all others. Groups I, II and III are typically referred to as
mineral oil base stocks.
[0081] Typical treat rates of the epoxide quats of the invention to
lubricating oils is 0.1 to 10 wt % or 0.5 to 5 wt % or 0.5 to 2.5
wt % or 0.5 to 1 wt % or 0.1 to 0.5 wt % or 1 to 2 wt % based on a
total weight of the lubricating oil. 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.
[0082] The lubricating composition may be in the form of a
concentrate and/or 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 from, in whole or in part, a finished lubricant),
the ratio of the of these additive to the oil of lubricating
viscosity and/or diluent oil include the ranged of 1:99 to 99:1 by
weight, or 80:20 to 10:90 by weight.
Miscellaneous
[0083] The fuel and/or lubricant compositions of the present
invention include the epoxide quats described above and may also
include one or more additional additives. Such additional
performance additives can be added to any of the compositions
described depending on the results desired and the application in
which the composition will be used.
[0084] Although any of the additional performance additives
described herein can be used in any of the fuel and/or lubricant
compositions of the invention, the following additional additives
are particularly useful for fuel and/or lubricant compositions:
antioxidants, corrosion inhibitors, detergent and/or dispersant
additives other than those described above, cold flow improvers,
foam inhibitors, demulsifiers, lubricity agents, metal
deactivators, valve seat recession additives, biocides, antistatic
agents, deicers, fluidizers, combustion improvers, seal swelling
agents, wax control polymers, scale inhibitors, gas-hydrate
inhibitors, or any combination thereof.
[0085] Demulsifiers suitable for use with the epoxide quats of the
present technology can include, but not be limited to,
arylsulfonates and polyalkoxylated alcohol, such as, for example,
polyethylene and polypropylene oxide copolymers and the like. The
demulsifiers can also comprise nitrogen containing compounds such
as oxazoline and imidazoline compounds and fatty amines, as well as
Mannich compounds. Mannich compounds are the reaction products of
alkylphenols and aldehydes (especially formaldehyde) and amines
(especially amine condensates and polyalkylenepolyamines). The
materials described in the following U.S. patents are illustrative:
U.S. Pat. Nos. 3,036,003; 3,236,770; 3,414,347; 3,448,047;
3,461,172; 3,539,633; 3,586,629; 3,591,598; 3,634,515; 3,725,480;
3,726,882; and 3,980,569 herein incorporated by reference. Other
suitable demulsifiers are, for example, the alkali metal or
alkaline earth metal salts of alkyl-substituted phenol- and
naphthalenesulfonates and the alkali metal or alkaline earth metal
salts of fatty acids, and also neutral compounds such as alcohol
alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g.
tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty
acids, alkylphenols, condensation products of ethylene oxide (EO)
and propylene oxide (PO), for example including in the form of
EO/PO block copolymers, polyethyleneimines or else polysiloxanes.
Any of the commercially available demulsifiers may be employed,
suitably in an amount sufficient to provide a treat level of from 5
to 50 ppm in the fuel. In an embodiment there is no demulsifier
present in the fuel and/or lubricant composition. The demulsifiers
may be used alone or in combination. Some demulsifiers are
commercially available, for example from Nalco or Baker Hughes.
[0086] Suitable antioxidants include for example hindered phenols
or derivatives thereof and/or diarylamines or derivatives thereof.
Suitable detergent/dispersant additives include for example
polyetheramines or nitrogen containing detergents, including but
not limited to PIB amine detergents/dispersants, succinimide
detergents/dispersants, and other quaternary salt
detergents/dispersants including polyisobutylsuccinimide-derived
quaternized PIB/amine and/or amide dispersants/detergents. Suitable
cold flow improvers include for example esterified copolymers of
maleic anhydride and styrene and/or copolymers of ethylene and
vinyl acetate. Suitable lubricity improvers or friction modifiers
are based typically on fatty acids or fatty acid esters. Typical
examples are tall oil fatty acid, as described, for example, in WO
98/004656, and glyceryl monooleate. The reaction products,
described in U.S. Pat. No. 6,743,266 B2, of natural or synthetic
oils, for example triglycerides, and alkanolamines are also
suitable as such lubricity improvers. Additional examples include
commercial tall oil fatty acids containing polycyclic hydrocarbons
and/or rosin acids. Suitable metal deactivators include for example
aromatic triazoles or derivatives thereof, including but not
limited to benzotriazole. Other suitable metal deactivators are,
for example, salicylic acid derivatives such as
N,N'-disalicylidene-1,2-propanediamine. Suitable valve seat
recession additives include for example alkali metal sulfosuccinate
salts. Suitable foam inhibitors and/or antifoams include for
example organic silicones such as polydimethyl siloxane,
polyethylsiloxane, polydiethylsiloxane, polyacrylates and
polymethacrylates, trimethyl-triflouro-propylmethyl siloxane and
the like. Suitable fluidizers include for example mineral oils
and/or poly(alpha-olefins) and/or polyethers. Combustion improvers
include for example octane and cetane improvers. Suitable cetane
number improvers are, for example, aliphatic nitrates such as
2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as
di-tert-butyl peroxide.
[0087] The additional performance additives, which may be present
in the fuel and/or lubricant compositions of the invention, also
include di-ester, di-amide, ester-amide, and ester-imide friction
modifiers prepared by reacting an .alpha.-hydroxy acid with an
amine and/or alcohol optionally in the presence of a known
esterification catalyst. Examples of .alpha.-hydroxy acids include
glycolic acid, lactic acid, .alpha.-hydroxy dicarboxylic acid (such
as tartaric acid) and/or an .alpha.-hydroxy tricarboxylic acid
(such as citric acid), with an amine and/or alcohol, optionally in
the presence of a known esterification catalyst. These friction
modifiers, often derived from tartaric acid, citric acid, or
derivatives thereof, may be derived from amines and/or alcohols
that are branched, resulting in friction modifiers that themselves
have significant amounts of branched hydrocarbyl groups present
within it structure. Examples of suitable branched alcohols used to
prepare such friction modifiers include 2-ethylhexanol,
isotridecanol, Guerbet alcohols, and mixtures thereof. Friction
modifiers may be present at 0 to 6 wt % or 0.001 to 4 wt %, or 0.01
to 2 wt % or 0.05 to 3 wt % or 0.1 to 2 wt % or 0.1 to 1 wt % or
0.001 to 0.01 wt %.
[0088] The additional performance additives may comprise a
detergent/dispersant comprising a hydrocarbyl substituted acylating
agent. The acylating agent may be, for example, a hydrocarbyl
substituted succinic acid, or the condensation product of a
hydrocarbyl substituted succinic acid with an amine or an alcohol;
that is, a hydrocarbyl substituted succinimide or hydrocarbyl
substituted succinate. In an embodiment, the detergent/dispersant
may be a polyisobutenyl substituted succinic acid, amide or ester,
wherein the polyisobutenyl substituent has a number average
molecular weight of from about 100 to 5000. In some embodiments,
the detergent may be a C.sub.6 to C.sub.18 substituted succinic
acid, amide or ester. A more thorough description of the
hydrocarbyl substituted acylating agent detergents can be found
from paragraph [0017] to [0036] of U.S. Publication 2011/0219674,
published Sep. 15, 2011.
[0089] In one embodiment, the additional detergent/dispersant is a
quaternary ammoniums salt other than that of the present
technology. Additional quaternary ammoniums salts can be quaternary
ammoniums salts prepared from hydrocarbyl substituted acylating
agents, such as, for example, polyisobutyl succinic acids or
anhydrides, having a hydrocarbyl substituent with a number average
molecular weight of greater than 1200 M.sub.n, polyisobutyl
succinic acids or anhydrides, having a hydrocarbyl substituent with
a number average molecular weight of 300 to 750, or polyisobutyl
succinic acids anhydrides, having a hydrocarbyl substituent with a
number average molecular weight of 1000 M.sub.n.
[0090] In an embodiment, the additional quaternary ammonium salts
prepared from the reaction of nitrogen containing compound and a
hydrocarbyl substituted acylating agent having a hydrocarbyl
substituent with a number average molecular weight of 300 to 750 or
1300 to 3000 is an amide or ester. In an embodiment, the quaternary
ammonium salts prepared from the reaction of nitrogen containing
compound and a hydrocarbyl substituted acylating agent having a
hydrocarbyl substituent with a number average molecular weight of
greater than 1200 M.sub.n or having a hydrocarbyl substituent with
a number average molecular weight of from 300 to 750 is an
imide.
[0091] In yet another embodiment the hydrocarbyl substituted
acylating agent can include a mono-, dimer or trimer carboxylic
acid with 8 to 54 carbon atoms and is reactive with primary or
secondary amines. Suitable acids include, but are not limited to,
the mono-, dimer, or trimer acids of caprylic acid, capric acid,
lauric acid, myristic acid, palmitic acid, stearic, arachidic acid,
behenic acid, lignoceric acid, cerotic acid, myristoleic acid,
palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic
acid, linoleic acid, linoelaidic acid, .alpha.-linolenic acid,
arachidonic acid, eicosapentaenoic acid, erucic acid, and
docosahexaenoic acid.
[0092] In an embodiment the nitrogen containing compound of the
additional quaternary ammonium salts is an imidazole or nitrogen
containing compound of either of formulas.
##STR00013##
wherein R may be a C.sub.1 to C.sub.6 alkylene group; each of
R.sub.1 and R.sub.2, individually, may be a C.sub.1 to C.sub.6
hydrocarbylene group; and each of R.sub.3, R.sub.4, R.sub.5, and
R.sub.6, individually, may be a hydrogen or a C.sub.1 to C.sub.6
hydrocarbyl group.
[0093] In other embodiments, the quaternizing agent used to prepare
the additional quaternary ammonium salts can be a dialkyl sulfate,
an alkyl halide, a hydrocarbyl substituted carbonate, a hydrocarbyl
epoxide, a carboxylate, alkyl esters, or mixtures thereof. In some
cases the quaternizing agent can be a hydrocarbyl epoxide. In some
cases the quaternizing agent can be a hydrocarbyl epoxide in
combination with an acid. In some cases the quaternizing agent can
be a salicylate, oxalate or terephthalate. In an embodiment the
hydrocarbyl epoxide is an alcohol functionalized epoxides or
C.sub.4 to C.sub.14 epoxides.
[0094] In some embodiments, the quaternizing agent is
multi-functional resulting in the additional quaternary ammonium
salts being coupled quaternary ammoniums salts.
[0095] Additional quaternary ammonium salts include, but are not
limited to quaternary ammonium salts having a hydrophobic moiety in
the anion. Exemplary compounds include quaternary ammonium
compounds having the formula below:
##STR00014##
wherein R.sup.0, R.sup.1, R.sup.2 and R.sup.3 is each individually
an optionally substituted alkyl, alkenyl or aryl group and R
includes an optionally substituted hydrocarbyl moiety having at
least 5 carbon atoms.
[0096] Additional quaternary ammonium salts may also include
polyetheramines that are the reaction products of a
polyether-substituted amine comprising at least one tertiary
quaternizable amino group and a quaternizing agent that converts
the tertiary amino group to a quaternary ammonium group.
[0097] Dispersants can also be post-treated by reaction with any of
a variety of agents. Among these are urea, thiourea,
dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones,
carboxylic acids, hydrocarbon-substituted succinic anhydrides,
nitriles, epoxides, boron compounds, and phosphorus compounds.
References detailing such treatment are listed in U.S. Pat. No.
4,654,403.
[0098] The fuel and/or lubricant compositions of the invention may
include a detergent additive, different from the disclosed epoxide
quat technology. Most conventional detergents used in the field of
engine lubrication obtain most or all of their basicity or TBN from
the presence of basic metal-containing compounds (metal hydroxides,
oxides, or carbonates, typically based on such metals as calcium,
magnesium, or sodium). Such metallic overbased detergents, also
referred to as overbased or superbased salts, are generally single
phase, homogeneous Newtonian systems characterized by a metal
content in excess 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 typically prepared by reacting an acidic material
(typically an inorganic acid or lower carboxylic acid such as
carbon dioxide) with a mixture of an acidic organic compound (also
referred to as a substrate), a stoichiometric excess of a metal
base, typically in a reaction medium of an one inert, organic
solvent (e.g., mineral oil, naphtha, toluene, xylene) for the
acidic organic substrate. Typically also a small amount of promoter
such as a phenol or alcohol is present, and in some cases a small
amount of water. The acidic organic substrate will normally have a
sufficient number of carbon atoms to provide a degree of solubility
in oil.
[0099] Such conventional overbased materials and their methods of
preparation are well known to those skilled in the art. Patents
describing techniques for making basic metallic salts of sulfonic
acids, carboxylic acids, phenols, phosphonic acids, and mixtures of
any two or more of these include U.S. Pat. Nos. 2,501,731;
2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585;
3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.
Salixarate detergents are described in U.S. Pat. No. 6,200,936. In
certain embodiments, the detergent may contain a metal-containing
salicylate detergent, such as an overbased calcium
hydrocarbyl-substituted salicylate detergent and are described in
U.S. Pat. Nos. 5,688,751 and 4,627,928.
[0100] Viscosity improvers (also sometimes referred to as viscosity
index improvers or viscosity modifiers) may be included in the fuel
and/or lubricant compositions of this invention. Viscosity
improvers are usually polymers, including polyisobutenes,
polymethacrylates (PMA) and polymethacrylic acid esters,
hydrogenated diene polymers, polyalkylstyrenes, esterified
styrene-maleic anhydride copolymers, hydrogenated
alkenylarene-conjugated diene copolymers and polyolefins. PMA's are
prepared from mixtures of methacrylate monomers having different
alkyl groups. The alkyl groups may be either straight chain or
branched chain groups containing from 1 to 18 carbon atoms. Most
PMA's are viscosity modifiers as well as pour point
depressants.
[0101] Multifunctional viscosity improvers, which also have
dispersant and/or antioxidancy properties are known and may
optionally be used in the fuel and/or lubricant compositions.
Dispersant viscosity modifiers (DVM) are one example of such
multifunctional additives. DVM are typically prepared by
copolymerizing a small amount of a nitrogen-containing monomer with
alkyl methacrylates, resulting in an additive with some combination
of dispersancy, viscosity modification, pour point depressancy and
dispersancy. Vinyl pyridine, N-vinyl pyrrolidone and
N,N'-dimethylaminoethyl methacrylate are examples of
nitrogen-containing monomers. Polyacrylates obtained from the
polymerization or copolymerization of one or more alkyl acrylates
also are useful as viscosity modifiers.
[0102] Anti-wear agents may be used in the fuel and/or lubricant
compositions provide herein. Anti-wear agents can in some
embodiments include phosphorus-containing antiwear/extreme pressure
agents such as metal thiophosphates, phosphoric acid esters and
salts thereof, phosphorus-containing carboxylic acids, esters,
ethers, and amides; and phosphites. In certain embodiments a
phosphorus antiwear agent may be present in an amount to deliver
0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08
percent by weight phosphorus. Often the antiwear agent is a zinc
dialkyldithiophosphate (ZDP). For a typical ZDP, which may contain
11 percent P (calculated on an oil free basis), suitable amounts
may include 0.09 to 0.82 percent by weight.
Non-phosphorus-containing anti-wear agents include borate esters
(including borated epoxides), dithiocarbamate compounds,
molybdenum-containing compounds, and sulfurized olefins. In some
embodiments the fuel and/or lubricant compositions of the invention
are free of phosphorus-containing antiwear/extreme pressure
agents.
[0103] Foam inhibitors that may be useful in fuel and/or lubricant
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.
The disclosed technology may also be used with a
silicone-containing antifoam agent in combination with a
C.sub.5-C.sub.17 alcohol.
[0104] Pour point depressants that may be useful in fuel and/or
lubricant compositions of the invention include polyalphaolefins,
esters of maleic anhydride-styrene copolymers, poly(meth)acrylates,
polyacrylates or polyacrylamides.
[0105] Metal deactivators may be chosen from a derivative of
benzotriazole (typically tolyltriazole), 1,2,4-triazole,
benzimidazole, 2-alkyldithiobenzimidazole or
2-alkyldithiobenzothiazole, 1-amino-2-propanol, a derivative of
dimercaptothiadiazole, octylamine octanoate, condensation products
of dodecenyl succinic acid or anhydride and/or a fatty acid such as
oleic acid with a polyamine. The metal deactivators may also be
described as corrosion inhibitors.
[0106] Seal swell agents include sulpholene derivatives Exxon
Necton-37.TM. (FN 1380) and Exxon Mineral Seal Oil.TM. (FN
3200).
Fuel Compositions
[0107] In some embodiments the technology provides fuel
compositions. In some embodiments, the fuel compositions comprise a
majority (>50 wt %) of gasoline or a middle distillate fuel. In
an embodiment, there is provided a fuel composition comprising a
majority of a diesel fuel.
[0108] In yet another embodiment, the fuel composition comprises
the epoxide quats of disclosed herein and a demulsifier.
Demulsifiers suitable for use with the quaternary ammonium salts of
the present technology can include, but not be limited to
arylsulfonates and polyalkoxylated alcohol, such as, for example,
polyethylene and polypropylene oxide copolymers and the like. The
demulsifiers can also comprise nitrogen containing compounds such
as oxazoline and imidazoline compounds and fatty amines, as well as
Mannich compounds. Mannich compounds are the reaction products of
alkylphenols and aldehydes (especially formaldehyde) and amines
(especially amine condensates and polyalkylenepolyamines). The
materials described in the following U.S. patents are illustrative:
U.S. Pat. Nos. 3,036,003; 3,236,770; 3,414,347; 3,448,047;
3,461,172; 3,539,633; 3,586,629; 3,591,598; 3,634,515; 3,725,480;
3,726,882; and 3,980,569 herein incorporated by reference. Other
suitable demulsifiers are, for example, the alkali metal or
alkaline earth metal salts of alkyl-substituted phenol- and
naphthalenesulfonates and the alkali metal or alkaline earth metal
salts of fatty acids, and also neutral compounds such as alcohol
alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g.
tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty
acids, alkylphenols, condensation products of ethylene oxide (EO)
and propylene oxide (PO), for example including in the form of
EO/PO block copolymers, polyethyleneimines or else polysiloxanes.
Any of the commercially available demulsifiers may be employed,
suitably in an amount sufficient to provide a treat level of from 5
to 50 ppm in the fuel. In one embodiment the fuel composition of
the invention does not comprise a demulsifier. The demulsifiers may
be used alone or in combination. Some demulsifiers are commercially
available, for example from Nalco or Baker Hughes. Typical treat
rates of the demulsifiers to a fuel may range from 0 to 50 ppm by
total weight of the fuel, or 5 to 50 ppm, or 5 to 25 ppm, or 5 to
20 ppm.
[0109] The disclosed technology may also be used with demulsifiers
comprising a hydrocarbyl-substituted dicarboxylic acid in the form
of the free acid, or in the form of the anhydride which may be an
intramolecular anhydride, such as succinic, glutaric, or phthalic
anhydride, or an intermolecular anhydride linking two dicarboxylic
acid molecules together. The hydrocarbyl substituent may have from
12 to 2000 carbon atoms and may include polyisobutenyl substituents
having a number average molecular weight of 300 to 2800. Exemplary
hydrocarbyl-substituted dicarboxylic acids include, but are not
limited to, hydrocarbyl-substituted acids derived from malonic,
succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic,
undecanedioic, dodecanedioic, phthalic, isophthalic, terphthalic,
o-, m-, or p-phenylene diacetic, maleic, fumaric, or glutaconic
acids.
[0110] In another embodiment, a fuel composition comprises the
epoxide quats of the present invention and an additional
detergent/dispersant. Customary detergent/dispersant additives are
preferably amphiphilic substances which possess at least one
hydrophobic hydrocarbon radical with a number-average molecular
weight of 100 to 10000 and at least one polar moiety selected from
(i) Mono- or polyamino groups having up to 6 nitrogen atoms, at
least one nitrogen atom having basic properties; (ii) Hydroxyl
groups in combination with mono or polyamino groups, at least one
nitrogen atoms having basic properties; (iii) Carboxyl groups or
their alkali metal or alkaline earth metal salts; (iv) Sulfonic
acid groups or their alkali metal or alkaline earth metal salts;
(v) Polyoxy-C.sub.2 to C.sub.4 alkylene moieties terminated by
hydroxyl groups, mono- or polyamino groups, at least one nitrogen
atom having basic properties, or by carbamate groups; (vi)
Carboxylic ester groups; (vii) Moieties derived from succinic
anhydride and having hydroxyl and/or amino and/or amido and/or
imido groups; and/or (viii) Moieties obtained by Mannich reaction
of substituted phenols with aldehydes and mono- or polyamines.
[0111] The hydrophobic hydrocarbon radical in the above
detergent/dispersant additives which ensures the adequate
solubility in the fuel, has a number-average molecular weight
(M.sub.n) of 85 to 20,000, of 100 to 10,000, or 300 to 5000 In yet
another embodiment, the detergent/dispersant additives have a
M.sub.n of 300 to 3000, of 500 to 2500, of 700 to 2500, or 800 to
1500. Typical hydrophobic hydrocarbon radicals may be polypropenyl,
polybutenyl and polyisobutenyl radicals, with a number average
molecular weight M.sub.n, of 300 to 5000, of 300 to 3000, of 500 to
2500, or 700 to 2500. In one embodiment the detergent/dispersant
additives have a M.sub.n of 800 to 1500.
[0112] The additional performance additives may comprise a high TBN
nitrogen containing detergent/dispersant, such as a succinimide,
that is the condensation product of a hydrocarbyl-substituted
succinic anhydride with a poly(alkyleneamine). Succinimide
detergents/dispersants are more fully described in U.S. Pat. Nos.
4,234,435 and 3,172,892. Another class of ashless dispersant is
high molecular weight esters, prepared by reaction of a hydrocarbyl
acylating agent and a polyhydric aliphatic alcohol such as
glycerol, pentaerythritol, or sorbitol. Such materials are
described in more detail in U.S. Pat. No. 3,381,022.
[0113] Nitrogen-containing detergents are the reaction products of
a carboxylic acid-derived acylating agent and an amine. The
acylating agent can vary from formic acid and its acylating
derivatives to acylating agents having high molecular weight
aliphatic substituents of up to 5,000, 10,000 or 20,000 carbon
atoms. The amino compounds can vary from ammonia itself to amines
typically having aliphatic substituents of up to about 30 carbon
atoms, and up to 11 nitrogen atoms. Acylated amino compounds
suitable for use in the present invention are those formed by the
reaction of an acylating agent having a hydrocarbyl substituent of
at least 8 carbon atoms and a compound comprising at least one
primary or secondary amine group. The acylating agent may be a
mono- or polycarboxylic acid (or reactive equivalent thereof) for
example a substituted succinic, phthalic or propionic acid and the
amino compound may be a polyamine or a mixture of polyamines, for
example a mixture of ethylene polyamines. Alternatively the amine
may be a hydroxyalkyl-substituted polyamine. The hydrocarbyl
substituent in such acylating agents may comprise at least 10
carbon atoms. In one embodiment, the hydrocarbyl substituent may
comprise at least 12, for example 30 or 50 carbon atoms. In yet
another embodiment, it may comprise up to 200 carbon atoms. The
hydrocarbyl substituent of the acylating agent may have a number
average molecular weight (M.sub.n) of 170 to 2800, for example from
250 to 1500. In other embodiments, the substituent's M.sub.n may
range from 500 to 1500, or alternatively from 500 to 1100. In yet
another embodiment, the substituent's M.sub.n may range from 700 to
1300. In another embodiment, the hydrocarbyl substituent may have a
number average molecular weight of 700 to 1000, or 700 to 850, or,
for example, 750.
[0114] Another class of ashless dispersant is Mannich bases. These
are materials which are formed by the condensation of a higher
molecular weight, alkyl substituted phenol, an alkylene polyamine,
and an aldehyde such as formaldehyde and are described in more
detail in U.S. Pat. No. 3,634,515.
[0115] A useful nitrogen containing dispersant includes the product
of a Mannich reaction between (a) an aldehyde, (b) a polyamine, and
(c) an optionally substituted phenol. The phenol may be substituted
such that the Mannich product has a molecular weight of less than
7500. Optionally, the molecular weight may be less than 2000, less
than 1500, less than 1300, or for example, less than 1200, less
than 1100, less than 1000. In some embodiments, the Mannich product
has a molecular weight of less than 900, less than 850, or less
than 800, less than 500, or less than 400. The substituted phenol
may be substituted with up to 4 groups on the aromatic ring. For
example it may be a tri or di-substituted phenol. In some
embodiments, the phenol may be a mono-substituted phenol. The
substitution may be at the ortho, and/or meta, and/or para
position(s). To form the Mannich product, the molar ratio of the
aldehyde to amine is from 4:1 to 1:1 or, from 2:1 to 1:1. The molar
ratio of the aldehyde to phenol may be at least 0.75:1; or 0.75 to
1 to 4:1, or 1:1 to 4:1, or 1:1 to 2:1. To form the preferred
Mannich product, the molar ratio of the phenol to amine can be at
least 1.5:1, at least 1.6:1, at least 1.7:1, for example at least
1.8:1, or at least 1.9:1. The molar ratio of phenol to amine may be
up to 5:1; for example it may be up to 4:1, or up to 3.5:1.
Suitably it is up to 3.25:1, up to 3:1, up to 2.5:1, up to 2.3:1 or
up to 2.1:1.
[0116] Other dispersants include polymeric dispersant additives,
which are generally hydrocarbon-based polymers which contain polar
functionality to impart dispersancy characteristics to the polymer.
An amine is typically employed in preparing the high TBN
nitrogen-containing dispersant. One or more poly(alkyleneamine)s
may be used, and these may comprise one or more
poly(ethyleneamine)s having 3 to 5 ethylene units and 4 to 6
nitrogen units. Such materials include triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA).
Such materials are typically commercially available as mixtures of
various isomers containing a range number of ethylene units and
nitrogen atoms, as well as a variety of isomeric structures,
including various cyclic structures. The poly(alkyleneamine) may
likewise comprise relatively higher molecular weight amines known
in the industry as ethylene amine still bottoms.
[0117] In an embodiment, the fuel composition can additionally
comprise quaternary ammonium salts other than the epoxide quats
disclosed herein. The other quaternary ammonium salts can comprise
(a) a compound comprising (i) at least one tertiary amino group as
described above, and (ii) a hydrocarbyl-substituent having a number
average molecular weight of 100 to 5000, or 250 to 4000, or 100 to
4000, or 100 to 2500, or 3000; and (b) a quaternizing agent
suitable for converting the tertiary amino group of (a)(i) to a
quaternary nitrogen, as described above. The other quaternary
ammonium salts are more thoroughly described in U.S. Pat. No.
7,951,211, issued May 31, 2011, and U.S. Pat. No. 8,083,814, issued
Dec. 27, 2011, and U.S. Publication Nos. 2013/0118062, published
May 16, 2013, 2012/0010112, published Jan. 12, 2012, 2013/0133243,
published May 30, 2013, 2008/0113890, published May 15, 2008, and
2011/0219674, published Sep. 15, 2011, US 2012/0149617 published
May 14, 2012, US 2013/0225463 published Aug. 29, 2013, US
2011/0258917 published Oct. 27, 2011, US 2011/0315107 published
Dec. 29, 2011, US 2013/0074794 published Mar. 28, 2013, US
2012/0255512 published Oct. 11, 2012, US 2013/0333649 published
Dec. 19, 2013, US 2013/0118062 published May 16, 2013, and
international publications WO Publication Nos. 2011/141731,
published Nov. 17, 2011, 2011/095819, published Aug. 11, 2011, and
2013/017886, published Feb. 7, 2013, WO 2013/070503 published May
16, 2013, WO 2011/110860 published Sep. 15, 2011, WO 2013/017889
published Feb. 7, 2013, WO 2013/017884 published Feb. 7, 2013.
[0118] The additional quaternary ammoniums salts other than the
disclosed technology can be quaternary ammoniums salts prepared
from hydrocarbyl substituted acylating agents, such as, for
example, polyisobutyl succinic acids or anhydrides, having a
hydrocarbyl substituent with a number average molecular weight of
greater than 1200 M.sub.n, polyisobutyl succinic acids or
anhydrides, having a hydrocarbyl substituent with a number average
molecular weight of 300 to 750, or polyisobutyl succinic acids or
anhydrides, having a hydrocarbyl substituent with a number average
molecular weight of 1000 M.sub.n.
[0119] In an embodiment, the fuel composition comprising the
epoxide quats disclosed herein can further comprise additional
quaternary ammonium salts that are amides or esters. The additional
amide or ester quats are prepared from the reaction of a nitrogen
containing compound and a hydrocarbyl substituted acylating agent
having a hydrocarbyl substituent with a number average molecular
weight of 300 to 750, or 1300 to 3000. In an embodiment, the fuel
compositions can further can further comprise additional quaternary
ammonium salts that are imides. The imide quats are prepared from
the reaction of nitrogen containing compound and a hydrocarbyl
substituted acylating agent having a hydrocarbyl substituent with a
number average molecular weight of greater than 1200 M.sub.n or,
having a hydrocarbyl substituent with a number average molecular
weight of 300 to 750.
[0120] The hydrocarbyl substituted acylating agent may also be a
copolymer formed by copolymerizing at least one monomer that is an
ethylenically unsaturated hydrocarbon having 2 to 100 carbon atoms.
The monomer may be linear, branched, or cyclic. The monomer may
have oxygen or nitrogen substituents, but will not react with
amines or alcohols. The monomer may be reacted with a second
monomer that is a carboxylic acid or carboxylic acid derivative
having 3 to 12 carbon atoms. The second monomer may have one or two
carboxylic acid functional groups and is reactive with amines or
alcohols. When made using this process, the hydrocarbyl substituted
acylating agent copolymer has a number average molecular weight Mn
of 500 to 20,000.
[0121] Alternatively, the hydrocarbyl substituted acylating agent
may be a terpolymer that is the reaction product of ethylene and at
least one monomer that is an ethylenically unsaturated monomer
having at least one tertiary nitrogen atom, with (i) an alkenyl
ester of one or more aliphatic monocarboxylic acids having 1 to 24
carbon atoms or (ii) an alkyl ester of acrylic or methacrylic
acid.
[0122] In an embodiment the nitrogen containing compound of the
additional quaternary ammonium salts is an imidazole or nitrogen
containing compound of either of formulas.
##STR00015##
wherein R may be a C.sub.1 to C.sub.6 alkylene group; each of
R.sub.1 and R.sub.2, individually, may be a C.sub.1 to C.sub.6
hydrocarbylene group; and each of R.sub.3, R.sub.4, R.sub.5, and
R.sub.6, individually, may be a hydrogen or a C.sub.1 to C.sub.6
hydrocarbyl group. In one embodiment R.sub.1 or R.sub.2 can be, for
example, a C.sub.1, C.sub.2 or C.sub.3 alkylene group. In the same
or different embodiments, each R.sub.3, R.sub.4, R.sub.5, R.sub.6
can be, for example, H or a C.sub.1, C.sub.2 or C.sub.3 alkyl
group.
[0123] In other embodiments, the quaternizing agent used to prepare
the additional quaternary ammonium salts can be a dialkyl sulfate,
an alkyl halide, a hydrocarbyl substituted carbonate, a hydrocarbyl
epoxide, a carboxylate, alkyl esters, or mixtures thereof. In some
cases the quaternizing agent can be a hydrocarbyl epoxide. In some
cases the quaternizing agent can be a hydrocarbyl epoxide in
combination with an acid. In some cases the quaternizing agent can
be a salicylate, oxalate or terephthalate. In an embodiment the
hydrocarbyl epoxide is an alcohol functionalized epoxides or
C.sub.4 to C.sub.14 epoxides.
[0124] In some embodiments, the quaternizing agent is
multi-functional resulting in the additional quaternary ammonium
salts being a coupled quaternary ammoniums salts.
[0125] Typical treat rates of additional detergents/dispersants to
a fuel of the invention is 0 to 500 ppm, or 0 to 250 ppm, or 0 to
100 ppm, or 5 to 250 ppm, or 5 to 100 ppm, or 10 to 100 ppm.
[0126] In a particular embodiment, a fuel composition comprises the
quaternary ammonium salts of the present invention and a cold flow
improver. The cold flow improver is typically selected from (1)
copolymers of a C.sub.2- to C.sub.40-olefin with at least one
further ethylenically unsaturated monomer; (2) comb polymers; (3)
polyoxyalkylenes; (4) polar nitrogen compounds; (5) sulfocarboxylic
acids or sulfonic acids or derivatives thereof; and (6)
poly(meth)acrylic esters. It is possible to use either mixtures of
different representatives from one of the particular classes (1) to
(6) or mixtures of representatives from different classes (1) to
(6).
[0127] Suitable C.sub.2- to C.sub.40-olefin monomers for the
copolymers of class (1) are, for example, those having 2 to 20 and
especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2
carbon-carbon double bonds, especially having one carbon-carbon
double bond. In the latter case, the carbon-carbon double bond may
be arranged either terminally (.alpha.-olefins) or internally.
However, preference is given to .alpha.-olefins, more preferably
.alpha.-olefins having 2 to 6 carbon atoms, for example propene,
1-butene, 1-pentene, 1-hexene and in particular ethylene. The at
least one further ethylenically unsaturated monomer of class (1) is
preferably selected from alkenyl carboxylates; for example,
C.sub.2- to C.sub.14-alkenyl esters, for example the vinyl and
propenyl esters, of carboxylic acids having 2 to 21 carbon atoms,
whose hydrocarbon radical may be linear or branched among these,
preference is given to the vinyl esters, examples of suitable
alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl
butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl
hexanoate, vinyl neononanoate, vinyl neodecanoate and the
corresponding propenyl esters, (meth)acrylic esters; for example,
esters of (meth)acrylic acid with C.sub.1- to C.sub.20-alkanols,
especially C.sub.1- to C.sub.10-alkanols, in particular with
methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol,
isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol,
2-ethylhexanol, nonanol and decanol, and structural isomers thereof
and further olefins; preferably higher in molecular weight than the
abovementioned C.sub.2- to C.sub.40-olefin base monomer for
example, the olefin base monomer used is ethylene or propene,
suitable further olefins are in particular C.sub.10- to
C.sub.40-.alpha.-olefins.
[0128] Suitable copolymers of class (1) are also those which
comprise two or more different alkenyl carboxylates in
copolymerized form, which differ in the alkenyl function and/or in
the carboxylic acid group. Likewise suitable are copolymers which,
as well as the alkenyl carboxylate(s), comprise at least one olefin
and/or at least one (meth)acrylic ester in copolymerized form.
[0129] Terpolymers of a C.sub.2- to C.sub.40-.alpha.-olefin, a
C.sub.1- to C.sub.20-alkyl ester of an ethylenically unsaturated
monocarboxylic acid having 3 to 15 carbon atoms and a C.sub.2- to
C.sub.14-alkenyl ester of a saturated monocarboxylic acid having 2
to 21 carbon atoms are also suitable as copolymers of class (K1).
Terpolymers of this kind are described in WO 2005/054314. A typical
terpolymer of this kind is formed from ethylene, 2-ethylhexyl
acrylate and vinyl acetate.
[0130] The at least one or the further ethylenically unsaturated
monomer(s) are copolymerized in the copolymers of class (1) in an
amount of preferably 1 to 50% by weight, especially 10 to 45% by
weight and in particular 20 to 40% by weight, based on the overall
copolymer. The main proportion in terms of weight of the monomer
units in the copolymers of class (1) therefore originates generally
from the C.sub.2 to C.sub.40 base olefins. The copolymers of class
(1) can have a number-average molecular weight M.sub.n of 1000 to
20,000, or 1000 to 10,000, or 1000 to 8000.
[0131] Typical comb polymers of component (2) are, for example,
obtainable by the copolymerization of maleic anhydride or fumaric
acid with another ethylenically unsaturated monomer, for example
with an a-olefin or an unsaturated ester, such as vinyl acetate,
and subsequent esterification of the anhydride or acid function
with an alcohol having at least 10 carbon atoms. Further suitable
comb polymers are copolymers of .alpha.-olefins and esterified
comonomers, for example esterified copolymers of styrene and maleic
anhydride or esterified copolymers of styrene and fumaric acid.
Suitable comb polymers may also be polyfumarates or polymaleates.
Homo- and copolymers of vinyl ethers are also suitable comb
polymers. Comb polymers suitable as components of class (2) are,
for example, also those described in WO 2004/035715 and in
"Comb-Like Polymers. Structure and Properties", N. A. Plate and V.
P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253
(1974). Mixtures of comb polymers are also suitable.
[0132] Polyoxyalkylenes suitable as components of class (3) are,
for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed
polyoxyalkylene ester/ethers and mixtures thereof. These
polyoxyalkylene compounds preferably comprise at least one linear
alkyl group, preferably at least two linear alkyl groups, each
having 10 to 30 carbon atoms and a polyoxyalkylene group having a
number-average molecular weight of up to 5000. Such polyoxyalkylene
compounds are described, for example, in EP-A 061 895 and also in
U.S. Pat. No. 4,491,455. Particular polyoxyalkylene compounds are
based on polyethylene glycols and polypropylene glycols having a
number-average molecular weight of 100 to 5000. Additionally
suitable are polyoxyalkylene mono- and diesters of fatty acids
having 10 to 30 carbon atoms, such as stearic acid or behenic
acid.
[0133] Polar nitrogen compounds suitable as components of class (4)
may be either ionic or nonionic and may have at least one
substituent, or at least two substituents, in the form of a
tertiary nitrogen atom of the general formula >NR.sup.7 in which
R.sup.7 is a C.sub.8- to C.sub.40-hydrocarbon radical. The nitrogen
substituents may also be quaternized i.e. be in cationic form. An
example of such nitrogen compounds is that of ammonium salts and/or
amides which are obtainable by the reaction of at least one amine
substituted by at least one hydrocarbon radical with a carboxylic
acid having 1 to 4 carboxyl groups or with a suitable derivative
thereof. The amines may comprise at least one linear C.sub.8- to
C.sub.40-alkyl radical. Primary amines suitable for preparing the
polar nitrogen compounds mentioned are, for example, octylamine,
nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine
and the higher linear homologs. Secondary amines suitable for this
purpose are, for example, dioctadecylamine and methylbehenylamine.
Also suitable for this purpose are amine mixtures, in particular
amine mixtures obtainable on the industrial scale, such as fatty
amines or hydrogenated tallamines, as described, for example, in
Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition,
"Amines, aliphatic" chapter. Acids suitable for the reaction are,
for example, cyclohexane-1,2-dicarboxylic acid,
cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic
acid, naphthalene dicarboxylic acid, phthalic acid, isophthalic
acid, terephthalic acid, and succinic acids substituted by
long-chain hydrocarbon radicals.
[0134] Sulfocarboxylic acids, sulfonic acids or derivatives thereof
which are suitable as cold flow improvers of class (5) are, for
example, the oil-soluble carboxamides and carboxylic esters of
ortho-sulfobenzoic acid, in which the sulfonic acid function is
present as a sulfonate with alkyl-substituted ammonium cations, as
described in EP-A 261 957.
[0135] Poly(meth)acrylic esters suitable as cold flow improvers of
class (6) are either homo- or copolymers of acrylic and methacrylic
esters. Preference is given to copolymers of at least two different
(meth)acrylic esters which differ with regard to the esterified
alcohol. The copolymer optionally comprises another different
olefinically unsaturated monomer in copolymerized form. The
weight-average molecular weight of the polymer can be 50,000 to
500,000. The polymer may be a copolymer of methacrylic acid and
methacrylic esters of saturated C.sub.14 and C.sub.15 alcohols, the
acid groups having been neutralized with hydrogenated tallamine.
Suitable poly(meth)acrylic esters are described, for example, in WO
00/44857.
[0136] The cold flow improver or the mixture of different cold flow
improvers is added to the middle distillate fuel or diesel fuel in
a total amount of preferably 0 to 5000 ppm by weight, or 10 to 5000
ppm by weight, or 20 to 2000 ppm by weight, or 50 to 1000 ppm by
weight or 100 to 700 ppm by weight, for example of 200 to 500 ppm
by weight.
Engine Oil Lubricants
[0137] In different embodiments the technology provides engine oil
lubricating compositions that can be employed in internal
combustion engines. The internal combustion engine may be spark
ignition or compression ignition. The internal combustion engine
may be a 2-stroke or 4-stroke engine. The internal combustion
engine may be a passenger car engine, a light duty diesel engine, a
heavy duty diesel engine, a motorcycle engine, or a 2-stroke or
4-stroke marine diesel engine. Typically the internal combustion
engine may be a passenger car engine, or a heavy duty diesel
internal combustion engine.
[0138] In one embodiment an engine oil lubricant composition of the
invention comprises in addition to the quaternary ammonium salts of
the present technology an overbased metal-containing detergent, or
mixtures thereof.
[0139] Overbased detergents are known in the art. Overbased
materials, otherwise referred to as overbased or superbased salts,
are generally single phase, homogeneous systems characterized by a
metal content in excess 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, typically
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.
[0140] The overbased metal-containing detergent may be chosen from
non-sulfur-containing phenates, sulfur-containing phenates,
sulfonates, salixarates, salicylates, carboxylates, and mixtures
thereof, or borated equivalents thereof. The overbased detergent
may be borated with a borating agent such as boric acid.
[0141] The overbased detergent may be non-sulfur containing
phenates, sulfur containing phenates, sulfonates, or mixtures
thereof.
[0142] An engine oil lubricant may further comprise an overbased
sulfonate detergent present at 0.01 wt % to 0.9 wt %, or 0.05 wt %
to 0.8 wt %, or 0.1 wt % to 0.7 wt %, or 0.2 wt % to 0.6 wt %.
[0143] The overbased sulfonate detergent may have a metal ratio of
12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.
[0144] An engine oil lubricant composition may also include one or
more detergents in addition to the overbased sulfonate.
[0145] Overbased sulfonates typically have a total base number of
250 to 600, or 300 to 500 (on an oil free basis). Overbased
detergents are known in the art. In one embodiment the sulfonate
detergent may be a predominantly linear alkylbenzene sulfonate
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 sulfonate detergent may be
particularly useful for assisting in improving fuel economy. In one
embodiment the sulfonate detergent may be a metal salt of one or
more oil-soluble alkyl toluene sulfonate compounds as disclosed in
paragraphs [0046] to [0053] of US Patent Application
2008/0119378.
[0146] In one embodiment the overbased sulfonate detergent
comprises an overbased calcium sulfonate. The calcium sulfonate
detergent may have a metal ratio of 18 to 40 and a TBN of 300 to
500, or 325 to 425.
[0147] The other detergents may have a metal of the
metal-containing detergent may also include "hybrid" detergents
formed with mixed surfactant systems including phenate and/or
sulfonate components, e.g., phenate/salicylates,
sulfonate/phenates, sulfonate/salicylates,
sulfonates/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 sulfonate/phenate detergent is employed, the
hybrid detergent would be considered equivalent to amounts of
distinct phenate and sulfonate detergents introducing like amounts
of phenate and sulfonate soaps, respectively.
[0148] The other detergent may have an alkali metal, an alkaline
earth metal, or zinc counterion. In one embodiment the metal may be
sodium, calcium, barium, or magnesium. Typically other detergent
may be sodium, calcium, or magnesium containing detergent
(typically, calcium, or magnesium containing detergent).
[0149] The other detergent may typically be an overbased detergent
of sodium, calcium or magnesium salt of the phenates,
sulfur-containing phenates, salixarates and salicylates. Overbased
phenates and salicylates typically have a total base number of 180
to 450 TBN (on an oil free basis).
[0150] Phenate detergents are typically derived from p-hydrocarbyl
phenols. Alkylphenols of this type may be coupled with sulfur and
overbased, coupled with aldehyde and overbased, or carboxylated to
form salicylate detergents. Suitable alkylphenols include those
alkylated with oligomers of propylene, i.e. tetrapropenylphenol
(i.e. p-dodecylphenol or PDDP) and pentapropenylphenol. Other
suitable alkylphenols include those alkylated with alpha-olefins,
isomerized alpha-olefins, and polyolefins like polyisobutylene. In
one embodiment, the lubricating composition comprises less than 0.2
wt %, or less than 0.1 wt %, or even less than 0.05 wt % of a
phenate detergent derived from PDDP. In one embodiment, the
lubricant composition comprises a phenate detergent that is not
derived from PDDP.
[0151] The overbased detergent may be present at 0 wt % to 10 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 lubricant composition. For a
passenger car engine the detergent may be present at 0.2 wt % to 1
wt % of the lubricant composition. In one embodiment, an engine oil
lubricant composition comprises at least one overbased detergent
with a metal ratio of at least 3, or at least 8, or at least
15.
[0152] In an embodiment an engine oil lubricant composition
comprising the epoxide quats of the present technology may further
include a dispersant, or mixtures thereof. The dispersant may be
chosen from a succinimide dispersant, a Mannich dispersant, a
succinamide dispersant, a polyolefin succinic acid ester, amide, or
ester-amide, or mixtures thereof.
[0153] In one embodiment an engine oil lubricant composition
includes 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.
[0154] 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 chosen from
ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, polyamine still
bottoms, and mixtures thereof.
[0155] 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).
[0156] 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 may
be 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 U.S. Pat. Nos. 6,165,235,
7,238,650 and EP Patent Application 0 355 895 A.
[0157] 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 may be
reacted with dimercaptothiadiazoles. In one embodiment the
post-treated dispersant may be reacted with phosphoric or
phosphorous acid. In one embodiment the post-treated dispersant may
be reacted with terephthalic acid and boric acid (as described in
US Patent Application US2009/0054278.
[0158] In one embodiment the dispersant may be borated or
non-borated. Typically a borated dispersant may be a succinimide
dispersant. In one embodiment, the ashless dispersant may be
boron-containing, i.e., has incorporated boron and delivers said
boron to the lubricant composition. The boron-containing dispersant
may be present in an amount to deliver at least 25 ppm boron, at
least 50 ppm boron, or at least 100 ppm boron to the lubricant
composition. In one embodiment, the lubricant composition may be
free of a boron-containing dispersant, i.e. delivers no more than
10 ppm boron to the final formulation.
[0159] The dispersant may be prepared/obtained/obtainable from
reaction of succinic anhydride by an "ene" or "thermal" reaction,
by what may be referred to as a "direct alkylation process." The
"ene" reaction mechanism and general reaction conditions are
summarized 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.
[0160] 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.
[0161] 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.
[0162] In one embodiment the dispersant may be a succinimide
dispersant may comprise a polyisobutylene succinimide, wherein the
polyisobutylene from which polyisobutylene succinimide is derived
has a number average molecular weight of 350 to 5000, or 750 to
2500.
[0163] 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 % or 1.5 to
5 wt % of the lubricant composition.
[0164] In one embodiment an engine oil lubricant composition
comprising the epoxide quats of the present technology may be a
lubricant composition further comprising a molybdenum compound. The
molybdenum compound may be an antiwear agent or an antioxidant. The
molybdenum compound may be chosen from molybdenum
dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts
of molybdenum compounds, and mixtures thereof. The molybdenum
compound may provide the lubricant 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.
[0165] In another embodiment an engine oil lubricant composition
comprising the epoxide quats of the present technology may further
comprise an antioxidant. Antioxidants include sulfurized olefins,
diarylamines, alkylated diarylamines, hindered phenols, molybdenum
compounds (such as molybdenum dithiocarbamates), hydroxyl
thioethers, or mixtures thereof. In one embodiment the lubricant
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 lubricant composition.
[0166] In one embodiment an engine oil lubricant composition
comprising the epoxide quats of the present technology further
comprises a phenolic or an aminic antioxidant or mixtures thereof,
and wherein the antioxidant is present at 0.1 wt % to 3 wt %, or
0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt %.
[0167] 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.
[0168] 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-butylphenol. 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.
[0169] Examples of molybdenum dithiocarbamates, which may be used
as an antioxidant, include commercial materials sold under the
trade names such as Molyvan 822.RTM., Molyvan.RTM. A and
Molyvan.RTM. 855 from R. T. Vanderbilt Co., Ltd., and Adeka
Sakura-Lube.TM. 5-100, S-165, S-600 and 525, or mixtures
thereof.
[0170] In one embodiment an engine oil lubricant composition
comprising the epoxide quats of the present technology further
includes a viscosity modifier. The viscosity modifier is known in
the art and may include hydrogenated styrene-butadiene rubbers,
ethylene-propylene copolymers, ethylene copolymers with propylene
and higher olefins, 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. The viscosity modifier may include a block
copolymer comprising (i) a vinyl aromatic monomer block and (ii), a
conjugated diene olefin monomer block (such as a hydrogenated
styrene-butadiene copolymer or a hydrogenated styrene-isoprene
copolymer), a polymethacrylate, an ethylene-alpha olefin copolymer,
a hydrogenated star polymer comprising conjugated diene monomers
such as butadiene or isoprene, or a star polymer of
polymethacrylate, or mixtures thereof.
[0171] In an embodiment the viscosity modifier may be a dispersant
viscosity modifier. The dispersant viscosity modifier may include
functionalized polyolefins, for example, ethylene-propylene
copolymers that have been functionalized with an acylating agent
such as maleic anhydride and an amine.
[0172] In one embodiment the dispersant viscosity modifier
comprises an olefin copolymer further functionalized with a
dispersant amine group. Typically, the olefin copolymer is an
ethylene-propylene copolymer. The olefin copolymer has a number
average molecular weight of 5000 to 20,000, or 6000 to 18,000, or
7000 to 15,000. The olefin copolymer may have a shear stability
index of 0 to 20, or 0 to 10, or 0 to 5 as measured by the Orbahn
shear test (ASTM D6278) as described above.
[0173] The formation of a dispersant viscosity modifier is well
known in the art. The dispersant viscosity modifier may include for
instance those described in U.S. Pat. No. 7,790,661 column 2, line
48 to column 10, line 38.
[0174] In one embodiment the dispersant viscosity modifier may be
prepared by grafting of an olefinic carboxylic acid acylating agent
onto a polymer of 15 to 80 mole percent of ethylene, from 20 to 85
mole percent of C.sub.3-10 .alpha.-monoolefin, and from 0 to 15
mole percent of non-conjugated diene or triene, said polymer having
an average molecular weight ranging from 5000 to 20,000, and
further reacting said grafted polymer with an amine (typically an
aromatic amine).
[0175] The dispersant viscosity modifier may include functionalized
polyolefins, for example, ethylene-propylene copolymers that have
been functionalized with an acylating agent such as maleic
anhydride and an amine; polymethacrylates functionalized with an
amine, or styrene-maleic anhydride copolymers reacted with an
amine. Suitable amines may be aliphatic or aromatic amines and
polyamines. Examples of suitable aromatic amines include
nitroaniline, aminodiphenylamine (ADPA), hydrocarbylene coupled
polyaromatic amines, and mixtures thereof. 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.
[0176] 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.
[0177] In one embodiment an engine oil lubricant composition
comprising the epoxide quats disclosed herein 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 lubricant
composition.
[0178] In one embodiment an engine oil lubricant composition
comprising the epoxide quats of the present technology further
includes a friction modifier. In one embodiment the friction
modifier may be chosen from 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 malic esters and imides, fatty (poly)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 lubricant composition. 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.
[0179] 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 such as
glycerol mono-oleate; 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.
[0180] Friction modifiers may also encompass materials such as
sulfurized fatty compounds and olefins, molybdenum
dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil
or soybean oil monoester of a polyol and an aliphatic carboxylic
acid.
[0181] 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.
[0182] An engine oil lubricant composition comprising the epoxide
quats of the present technology optionally further includes at
least one antiwear agent. Examples of suitable antiwear agents
include titanium compounds, tartaric acid derivatives such as
tartrate esters, amides or tartrimides, malic acid derivatives,
citric acid derivatives, glycolic acid derivatives, oil soluble
amine salts of phosphorus compounds different from that of the
invention, sulfurized 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 thiocarbamates, and bis(S-alkyldithiocarbamyl)
disulphides.
[0183] 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.
[0184] 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.
[0185] In one embodiment, the oil soluble titanium compound is a
titanium carboxylate. In one embodiment the titanium (IV)
carboxylate is titanium neodecanoate.
[0186] An engine oil lubricant composition comprising the epoxide
quats of the present technology may further include a
phosphorus-containing antiwear agent different from that of the
invention. Typically the phosphorus-containing antiwear agent may
be a zinc dialkyldithiophosphate, phosphite, phosphate,
phosphonate, and ammonium phosphate salts, or mixtures thereof.
[0187] In one embodiment an engine oil lubricant composition may
further comprise a phosphorus-containing antiwear agent, typically
zinc dialkyldithiophosphate.
[0188] Zinc dialkyldithiophosphates are known in the art. Examples
of zinc dithiophosphates include zinc isopropyl methylamyl
dithiophosphate, zinc isopropyl isooctyl dithiophosphate, zinc
di(cyclohexyl) dithiophosphate, zinc isobutyl 2-ethylhexyl
dithiophosphate, zinc isopropyl 2-ethylhexyl dithiophosphate, zinc
isobutyl isoamyl dithiophosphate, zinc isopropyl n-butyl
dithiophosphate, and combinations thereof. Zinc
dialkyldithiophosphate may be present in amount to provide 0.01 wt
% to 0.1 wt % phosphorus to the lubricating composition, or to
provide 0.015 wt % to 0.075 wt % phosphorus, or 0.02 wt % to 0.05
wt % phosphorus to the lubricating composition.
[0189] In one embodiment, an engine oil lubricant composition
further comprises one or more zinc dialkyldithiophosphate such that
the amine (thio)phosphate additive of the invention provides at
least 50% of the total phosphorus present in the lubricating
composition, or at least 70% of the total phosphorus, or at least
90% of the total phosphorus in the lubricating composition. In one
embodiment, the lubricant composition is free or substantially free
of a zinc dialkyldithiophosphate.
[0190] 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 lubricant
composition.
[0191] In one embodiment an engine oil lubricant composition
comprising the epoxide quats of the present technology further
comprises 0.01 to 5 wt % or 0.1 to 2 wt % of an ashless antiwear
agent represented by Formula.
##STR00016##
wherein Y and Y' are independently --O--, >NH, >NR.sup.3, or
an imide group formed by taking together both Y and Y' groups and
forming a R.sup.1--N< group between two >C.dbd.O groups; X is
independently --Z--O--Z'--, >CH.sub.2, >CHR.sup.4,
>CR.sup.4R.sup.5, >C(OH)(CO.sub.2R.sup.2),
>C(CO.sub.2R.sup.2).sub.2, or >CHOR.sup.6; Z and Z' are
independently >CH.sub.2, >CHR.sup.4, >CR.sup.4R.sup.5,
>C(OH)(CO.sub.2R.sup.2), or >CHOR.sub.6; n is 0 to 10, with
the proviso that when n=1, X is not >CH.sub.2, and when n=2,
both X's are not >CH.sub.2; m is 0 or 1; R.sup.1 is
independently hydrogen or a hydrocarbyl group, typically containing
1 to 150 carbon atoms, with the proviso that when R.sup.1 is
hydrogen, m is 0, and n is more than or equal to 1; R.sup.2 is a
hydrocarbyl group, typically containing 1 to 150 carbon atoms;
R.sup.3, R.sup.4 and R.sup.5 are independently hydrocarbyl groups;
and R.sup.6 is hydrogen or a hydrocarbyl group, typically
containing 1 to 150 carbon atoms.
[0192] In one embodiment an engine oil lubricant composition
comprising the epoxide quats of the present technology further
comprises 0.01 to 5 wt % or 0.1 to 2 wt % of an ashless antiwear
agent that may be a compound obtained/obtainable by a process
comprising reacting a glycolic acid, a 2-halo-acetic acid, or a
lactic acid, or an alkali or alkaline metal salt thereof,
(typically glycolic acid or a 2-halo-acetic acid) with at least one
member selected from the group consisting of an amine, an alcohol,
and an aminoalcohol. For example the compound may be represented by
formulae:
##STR00017##
wherein Y is independently oxygen or >NH or >NR.sup.1;
R.sup.1 is independently a hydrocarbyl group, typically containing
4 to 30, or 6 to 20, or 8 to 18 carbon atoms; Z is hydrogen or
methyl; Q is the residue of a diol, triol or higher polyol, a
diamine, triamine, or higher polyamine, or an aminoalcohol
(typically Q is a diol, diamine or aminoalcohol) g is 2 to 6, or 2
to 3, or 2; q is 1 to 4, or 1 to 3 or 1 to 2; n is 0 to 10, 0 to 6,
0 to 5, 1 to 4, or 1 to 3; and Ak.sup.1 is an alkylene group
containing 1 to 5, or 2 to 4 or 2 to 3 (typically ethylene) carbon
atoms; and b is 1 to 10, or 2 to 8, or 4 to 6, or 4.
[0193] The compound is known and is described in International
publication WO 2011/022317, and also in granted U.S. Pat. Nos.
8,404,625, 8,530,395, and 8,557,755.
INDUSTRIAL APPLICATION
[0194] In one embodiment the invention is useful in a liquid fuel
or an oil of lubricating viscosity in an internal combustion
engine. The internal combustion engine may be a gasoline or diesel
engine. Exemplary internal combustion engines include, but are not
limited to, spark ignition and compression ignition engines;
2-stroke or 4-stroke cycles; liquid fuel supplied via direct
injection, indirect injection, port injection and carburetor;
common rail and unit injector systems; light (e.g. passenger car)
and heavy duty (e.g. commercial truck) engines; and engines fuelled
with hydrocarbon and non-hydrocarbon fuels and mixtures thereof.
The engines may be part of integrated emissions systems
incorporating such elements as; EGR systems; aftertreatment
including three-way catalyst, oxidation catalyst, NO.sub.x
absorbers and catalysts, catalyzed and non-catalyzed particulate
traps optionally employing fuel-borne catalyst; variable valve
timing; and injection timing and rate shaping.
[0195] In one embodiment, the technology may be used with diesel
engines having direct fuel injection systems wherein the fuel is
injected directly into the engine's combustion chamber. The
ignition pressures may be greater than 1000 bar and, in one
embodiment, the ignition pressure may be greater than 1350 bar.
Accordingly, in another embodiment, the direct fuel injection
system maybe a high-pressure direct fuel injection system having
ignition pressures greater than 1350 bar. Exemplary types of
high-pressure direct fuel injection systems include, but are not
limited to, unit direct injection (or "pump and nozzle") systems,
and common rail systems. In unit direct injection systems the
high-pressure fuel pump, fuel metering system and fuel injector are
combined into one apparatus. Common rail systems have a series of
injectors connected to the same pressure accumulator, or rail. The
rail in turn, is connected to a high-pressure fuel pump. In yet
another embodiment, the unit direct injection or common rail
systems may further comprise an optional turbocharged or
supercharged direct injection system.
[0196] In a further embodiment, the imide quat technology is useful
for providing at least equivalent, if not improved detergency
(deposit reduction and/or prevention) performance in both the
traditional and modern diesel engine compared to a 1000 M.sub.n
quaternary ammonium compound. In addition, the technology can
provide improved water shedding (or demulsifying) performance
compared to 1000 M.sub.n quaternary ammonium compounds in both the
traditional and modern diesel engine. In yet another embodiment,
the disclosed technology may be used to improve the cold
temperature operability or performance of a diesel fuel (as
measured by the ARAL test).
[0197] In yet another embodiment, the lubricating composition
comprising an epoxide quat is useful for lubricating an internal
combustion engine (for crankcase lubrication).
[0198] Embodiments of the present technology may provide at least
one of antiwear performance, friction modification (particularly
for enhancing fuel economy), detergent performance (particularly
deposit control or varnish control), dispersancy (particularly soot
control, or sludge control), or corrosion control.
Deposit Control
[0199] As fuel burns inside an engine, solid carbonaceous
by-products may be produced. The solid by-products may stick to the
interior walls of the engine and are often referred to as deposits.
If left unchecked, engines fouled by deposits may experience a loss
in engine power, fuel efficiency, or drivability.
[0200] In traditional diesel engines operating at low pressures
(i.e., <35 MPa), deposits form on the fuel injector tips and in
the spray holes. These injector tip deposits can disrupt the spray
pattern of the fuel, potentially causing a reduction in power and
fuel economy.
[0201] Deposits may also form inside the injectors in addition to
forming on the tips. These internal deposits are commonly called
internal diesel injector deposits (IDIDs). It is believed that
IDIDs have a minor impact, if any on the operation of traditional
diesel engines operating at low pressures.
[0202] With the introduction of diesel engines equipped with high
pressure common rail fuel injector systems (i.e., >35 MPa),
however, IDIDs may be more problematic than in traditional diesel
engines. In high pressure common rail fuel injector systems, IDIDs
can form on injector moving parts, such as the needle and command
piston or control valve. IDIDs can hinder the movement of the
injector parts, impairing the injection timing and the quantity of
fuel injected. Since modern diesel engines operate on precise
multiple injection strategies in order to maximize efficiency and
performance of combustion, IDIDs can have a serious adverse effect
on engine operation and vehicle drivability.
[0203] High pressure common rail fuel injector systems are both
more susceptible and more prone to IDID formation. These advanced
systems have tighter tolerances due to their extremely high
operating pressures. Likewise, in some cases the clearance between
moving parts in the injectors is only a few microns or less. As
such, advanced diesel fuel systems are more susceptible to IDIDs.
Deposits may be likely to form in these systems because of their
higher operating temperatures which can oxidize and decompose the
chemically unstable components of the diesel fuel. Another factor
that may also contribute to IDID issues in high pressure common
rail systems is that these injectors often have lower activation
forces making them even more prone to sticking than in high
pressure systems. The lower activation forces may also cause some
of the fuel to "leak back" into the injectors, which may also
contribute to IDID.
[0204] Without limiting this specification to one theory of
operation, it is believed that IDIDs are formed from when the
hydrophilic-lipophilic balance (HLB) of sparingly soluble
contaminants moves to a level where the hydrophilic head group
dominates over the lipophilic tail. As the length of the lipophilic
tail decreases, the hydrophilic head group begins to dominate. The
structure of the tail (branched versus linear) and/or may also
affect the solubility of the contaminants. In addition, as the
polarity of the head group sparingly soluble contaminants increase,
its solubility decreases. While there may be multiple causes and
sources of IDID, two types of IDIDs have been identified; 1) metal
(sodium) carboxylate-type IDIDs, often referred to as "metal soaps"
or "sodium soaps", and 2) amide-type IDIDs, often referred to as
"amide lacquers".
[0205] Advanced chemical analysis techniques have been used to
obtain more detailed structural information on IDIDs to help
identify the sources of the problem. Detailed analysis of metal
soap-type IDIDs has helped identify corrosion inhibitors, such as
alkenyl succinic acids, as culprits in IDID formation. The
corrosion inhibitors, for example, dodecenyl succinic acid (DDSA)
and hexadecenyl succinic acid (HDSA) (two commonly used pipeline
corrosion inhibitors in the petroleum industry), pick up trace
levels of sodium and other metals in the fuel left over from the
refinery process. Tests have been conducted using engines compliant
with US Tier 3 emission standards to explore the underlying
structure activity relationships of sodium soap formation. Without
limiting this specification to one theory of operation, it is
believed that the formation of metal soap IDIDs is dependent upon
the size (number of carbons) of the hydrocarbon tail of the "soap"
and the number of carboxylic acids groups (CO.sub.2H) in the head
group of the corrosion inhibitor. It was observed that the tendency
to form deposits increases when the inhibitor had a short tail and
multiple carboxylic acids in the head group. In other words,
dicarboxylic acid corrosion inhibitors with a lower number average
molecular weight (M.sub.n) ranging between 280 and 340, have a
greater tendency to form sodium soap deposits than corrosion
inhibitors with a higher number average molecular weight. Persons
of ordinary skill in the art will understand that there may be some
low molecular weight polymers present in corrosion inhibitors with
a number average molecular weight above 340.
[0206] These laboratory tests have also shown that deposits can
form with as little as 0.5 to 1 ppm of sodium in the fuel along
with 8 to 12 ppm of a corrosion inhibitor, such as DDSA or HDSA,
and it is possible that real world concentrations may be lower with
deposits occurring over longer periods of time, such as 0.01 to 0.5
ppm metal with 1 to 8 ppm corrosion inhibitor.
[0207] These metal soaps can be referred to as low molecular weight
soaps, and can be represented, for example, by structures of:
R*(COOH).sub.x.sup.-M.sup.+
wherein R* is a linear, branched or cyclic hydrocarbyl group having
10 to 36 carbon atoms, or 12 to 18, or 12 to 16 carbon atoms,
M.sup.+ is a metal contaminant, such as sodium, calcium, or
potassium, and x is an integer from 1 to 4, 2 to 3, or 2. One class
of low molecular weight soaps are those represented by formula:
##STR00018##
wherein R* is defined as above. Particular soaps include DDSA or
HDSA soaps. These low molecular weight soaps may have a number
average molecular weight (M.sub.n) ranging between 280 and 340.
[0208] Amide lacquer formation is less certain but it has been
suggested that it is derived from polyisobutylene succinimides
(PIBSIs) with low number average molecular weight (M.sub.n) which
are added to diesel fuel to control nozzle fouling. Low molecular
weight PIBSIs may have an average M.sub.n of 400 or less using gel
permeation chromatography (GPC) and a polystyrene calibration
curve. Alternatively, low M.sub.n PIBSIs may have an average
M.sub.n of 200 to 300. These low molecular weight PIBSIs may be
byproducts formed from low molecular weight PIBS present in the
production process. While generally higher molecular weight
polyisobutylene (PIB) with an average M.sub.n of 1000 is used to
generate the PIBSIs, low molecular weight PIBs may be present as
contaminants. Low molecular weight PIBSIs may also form when
increasing the reaction temperature to remove excess reactants or
catalysts. Again, while completely eliminating low M.sub.n PIBSIs
from anti-foulants might result in reducing IDID formation,
complete elimination might not be practical. Accordingly, low
M.sub.n PIBSIs may be present in an amount of 5 wt % or less of a
total weight of the PIBIs used. It is hypothesized, without
limiting this specification to one theory of operation, that the
low molecular weight portion of the PIBSI is responsible for
deposit formation as it is only sparingly soluble in diesel and
thus deposits on the injector surface. In fact, amide lacquer IDIDs
have been shown to be linked to low molecular weight species by
demonstrating that amide lacquer IDIDs can be produced in US Tier
3-compliant engines using a low molecular weight PIBSI fraction.
Here again, laboratory tests have shown that as little as 5 ppm of
the low molecular weight PIBSI can cause deposit issues and it is
possible that real world concentrations may be lower with deposits
occurring over longer periods of time, such as from 0.01 to 5 ppm
low molecular weight PIBSI.
[0209] Such low molecular weight PIBSI fractions can be
represented, for example, by structure:
##STR00019##
wherein R* is as defined above, and R** is a hydrocarbyl polyamine
such as an ethylene polyamine.
[0210] The degree of bismaleation of the low molecular weight PIBSI
may also affect the polarity of the head group, thereby reducing
the PIBSI's solubility in the fuel.
[0211] Another factor that may contribute to IDID formation is the
change in diesel fuel to sulfur-free diesel fuel. Sulfur-free
diesel fuel is produced by hydrotreating wherein polyaromatics are
reduced, thereby lowering the boiling point of the final fuel. As
the final fuel is less aromatic, it is also less polar and
therefore less able to solubilize sparingly soluble contaminants
such as metal soaps or amide lacquers.
[0212] The formation of IDIDs can be reduced in a fuel containing
low molecular weight soaps or low molecular weight PIBSI fractions
by adding to the fuel the imide quats with a number average
molecular weight ranging from 1300 to 3000 described herein. Thus,
an embodiment of the present technology includes fuel compositions
comprising at least one low molecular weight soap and the imide
quat as described above.
[0213] In another embodiment, a method of reducing and/or
preventing internal diesel injector deposits is disclosed. The
method may comprise employing a fuel composition comprising the
imide quat as described above. The fuel may have a low molecular
weight soap present therein. In an embodiment, the low molecular
weight soap can be derived from the presence of from 0.01 to 5 ppm
of a metal and 1 to 12, or 1 to 8, or 8 to 12 ppm of a corrosion
inhibitor. Exemplary metals include, but are not limited to,
sodium, calcium, and potassium. The corrosion inhibitors may
comprise an alkenyl succinic acid such as dodecenyl succinic acid
(DDSA) or hexadecenyl succinic acid (HDSA). In yet another
embodiment of the present technology the fuel composition may have
a low molecular weight polyisobutylene succinimides (PIBSI) present
therein. The low molecular weight PIBSI may be present in the fuel
at greater than 0.01 ppm, such as, for example, 5 to 25 ppm, or
from 0.01 to 5 ppm of a low molecular weight PIBSI.
[0214] In a further embodiment, the technology may include a method
of cleaning-up deposits in a diesel engine, such as, a diesel
engine having a high pressure (i.e., above 35 MPa) common rail
injector system, by operating the engine with a fuel containing an
imide quat therein. In an embodiment, the clean-up method includes
reducing and/or preventing IDID causing deposits derived from the
presence of a low molecular weight soap. In an embodiment, the
clean-up method includes reducing and/or preventing IDID causing
deposits derived from the presence of a low molecular weight
PIBSI.
[0215] 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,
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);
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);
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.
[0216] 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. For instance, metal ions (of, e.g., a detergent) can migrate
to other acidic or anionic sites of other molecules. 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.
Examples
[0217] The invention will be further illustrated by the following
examples, which sets forth particularly advantageous embodiments.
While the examples are provided to illustrate the present
invention, they are not intended to limit it.
Example 1--Formation of 1000 M.sub.n Polyisobutylene Succinic
Anhydride (PIBSA)
[0218] A 1000 number average molecular weight (M.sub.n)
polyisobutylene (PIB) (2000 g., 2.0 moles, high-vinylidene PIB)
having greater than 70% vinylidene groups is charged to a 5-liter
flange flask equipped with overhead stirrer, air condenser,
nitrogen inlet, thermocouple and Eurotherm.TM. temperature
controller (reaction kit).
[0219] Maleic anhydride (245 g, 2.5 moles) is then charged to the
reaction vessel. The batch is agitated under a nitrogen blanket and
slowly heated to 203.degree. C. over a 90 minute period. The batch
is maintained at 203.degree. C. for 24 hours.
[0220] The reaction kit is then reconfigured for vacuum stripping.
The batch is stripped at 203.degree. C. and 0.05 bar to remove
unreacted maleic anhydride. The batch comprising the formed PIBSA
is then cooled back to 50.degree. C. and decanted into a storage
vessel.
Example 2--Formation of Quaternizable Compound--1000 M.sub.n PIBSA
and Dimethylaminopropylamine (DMAPA)
[0221] A 1000 M.sub.n PIBSA (1950.3 g, 1.86 moles) product of
Example 1 is charged to a 3-liter flask equipped with a water
condenser and Dean Stark trap, a thermocouple, a dropping funnel,
an overhead stirrer and Nitrogen inlet and heated to 90.degree.
C.
[0222] Dimethylaminopropylamine (189.7 g, 1.86 moles) DMAPA is
added to the flask via the dropping funnel over 50 minutes. The
batch temperature is kept below 120.degree. C. while adding the
DMAPA.
[0223] Once all the DMAPA is added, the reaction is slowly heated
to 150.degree. C. and maintained at that temperature for 3 hours.
Approximately 40 g of water is collected in the Dean Stark
apparatus while heating. The remaining product is the 1000 M.sub.n
PIBSA/DMAPA quaternizable compound.
Comparative Example 3--Formation of a 1000 M.sub.n PIBSA/DMAPA
Quaternary Ammonium Salt Using Propylene Oxide (an Imide/Propylene
Oxide Quat)
[0224] A 1000 M.sub.n PIBSA/DMAPA quaternizable compound (551.1 g,
0.54 moles, as prepared in Example 2) is added to a 1-liter flask
equipped with a water condenser, a thermocouple, a syringe pump, an
overhead stirrer and nitrogen inlet.
[0225] 2-ethylhexanol (124.5 g, 0.96 moles), acetic acid (32.4 g,
0.54 moles) and water (5.0 g, 0.287 moles) are also charged to the
1-liter flask. The batch is then heated to 75.degree. C., under
agitation and nitrogen atmosphere. Propylene oxide is added via a
syringe pump over 4 hours. The batch is then held for 4 hours at
75.degree. C. before being cooled back to 50.degree. C. The
imide/propylene oxide quat is then decanted into a storage
vessel.
Comparative Example 4--Formation of a 1000 M.sub.n PIBSA/DMAPA
Quaternary Ammonium Salt Using 1,2-Epoxybutane (an
Imide/Epoxybutane Quat)
[0226] A 1000 M.sub.n PIBSA/DMAPA quaternizable compound (476.2,
0.47 moles, as prepared in Example 2) is added to a 1-liter flask
flange flask equipped with a water condenser, a thermocouple, a
syringe pump, an overhead stirrer and a nitrogen inlet.
[0227] 2-ethylhexanol (136.6 g, 1.05 moles), acetic acid (28.24 g,
0.47 moles) and water (4.76 g, 0.264 moles) are also charged to the
1-liter flask. The batch is then heated to 90.degree. C., under
agitation and nitrogen atmosphere. 1,2-epoxybutane (37.3 g, 0.51
moles) is added via the syringe pump over 2 hours. The batch is
then held for 3 hours at 90.degree. C. before being cooled back to
50.degree. C. The imide/epoxybutane quat is then decanted into a
storage vessel.
Example 5--Formation of a 1000 M.sub.n PIBSA/DMAPA Quaternary
Ammonium Salt Using 1,2-Epoxydodecane (an Imide/Epoxydodecane
Quat)
[0228] A 1000 M.sub.n PIBSA/DMAPA quaternizable compound (791.4 g,
0.776 moles, as prepared in Example 2) is added to a 2-liter flask
flange flask equipped with a water condenser, a thermocouple, an
overhead stirrer and a nitrogen inlet.
[0229] 2-ethylhexanol (315.4 g, 2.43 moles), 1,2-epoxydodecane (146
g, 0.793 moles), acetic acid (46 g, 0.77 moles), and water are also
charged to the 2-liter flask. Agitation is then initiated (200 rpm)
and a slow nitrogen purge is introduced. The batch is then heated
to 75.degree. C. and maintained at temperature for 4 hours. The
imide/epoxydodecane quat is then then cooled before it is
transferred into a storage vessel.
Example 6--Formation of a 1000 M.sub.n PIBSA/DMAPA Quaternary
Ammonium Salt Using 1,2-Epoxyhexadecane (an Imide/Epoxyhexadecane
Quat)
[0230] A 1000 M.sub.n PIBSA/DMAPA quaternizable compound (500 g,
0.495 moles, as prepared in Example 2) is added to a 1-liter flask
flange flask equipped with a water condenser, a thermocouple, an
overhead stirrer and a nitrogen inlet.
[0231] 2-ethylhexanol (163.34 g, 1.26 moles) and water (5 g, 0.27
moles) are added to the flask and heated to 90.degree. C. Acetic
acid (29.65, 0.494 moles) and 1,2-epoxyhexadecane (118.71 g, 0.494
moles) are added to the flask. Agitation is then initiated (200
rpm) and a slow nitrogen purge is introduced. The batch is held at
90.degree. C. for 3 hours. The imide/epoxyhexadecane quat is then
then cooled before it is transferred into a storage vessel.
Example 7--Formation of a 1000 M.sub.n PIBSA/DMAPA Quaternary
Ammonium Salt Using Glycidol (an Imide/Glycidol Quat)
[0232] A 1000 M.sub.n PIBSA/DMAPA quaternizable compound (845 g,
0.78 moles, as prepared in Example 2) is added to a 2-liter flask
flange flask equipped with a water condenser, a thermocouple, an
overhead stirrer and a nitrogen inlet.
[0233] 2-ethylhexanol (315.4 g, 2.43 moles), glycidol (63 g, 0.85
moles), acetic acid (47.3 g, 0.78 moles), and water (8.2 g, 0.45
moles) are also charged to the 2-liter flask. Agitation is then
initiated (200 rpm) and a slow nitrogen purge is introduced. The
batch is then heated to 75.degree. C. and maintained at temperature
for 4 hours. The imide/glycidol quat is then then cooled before it
is transferred into a storage vessel.
Example 8--Formation of 550 M.sub.n Polyisobutylene Succinic
Anhydride (PIBSA)
[0234] A 550 number average molecular weight (M.sub.n)
polyisobutylene (PIB) (2840 g, 5.163 moles, mid-vinylidene PIB
available from Daelim) having greater than 20% vinylidene groups is
charged to a 5-liter flange flask equipped with overhead stirrer,
air condenser, nitrogen inlet, thermocouple and Eurotherm.TM.
temperature controller (reaction kit).
[0235] Maleic anhydride (632.2 g 6.449 moles) is then charged to
the reaction vessel. The batch is agitated under a nitrogen blanket
and slowly heated to 203.degree. C. over a 90 minute period. The
batch is maintained at 203.degree. C. for 24 hours.
[0236] The reaction kit is then reconfigured for vacuum stripping.
The batch is stripped at 203.degree. C. and 0.05 bar to remove
unreacted maleic anhydride. The batch comprising the formed PIBSA
and .about.20% unreacted polyisobutylene is then cooled back to
50.degree. C. and decanted into a storage vessel.
Example 9--Formation of Quaternizable Compound--550 M.sub.n PIBSA
and Dimethylaminopropylamine (DMAPA)
[0237] The 550 M.sub.n PIBSA (1556.2 g, 2.29 moles) (product of
Example 8) is charged to a 3-liter flask equipped with a water
condenser and Dean Stark trap, a thermocouple, a dropping funnel,
an overhead stirrer and Nitrogen inlet and heated to 90.degree.
C.
[0238] DMAPA (233.4 g, 2.29 moles) is added to the flask via the
dropping funnel over 50 minutes. The batch temperature is kept
below 120.degree. C. while adding the DMAPA.
[0239] Once all the DMAPA is added, the reaction is slowly heated
to 150.degree. C. and maintained at that temperature for 3 hours.
Approximately 40 g of water is collected in the Dean Stark
apparatus while heating. The remaining product is the 550 M.sub.n
PIBSA/DMAPA quaternizable compound.
Example 10 (Prophetic)--Formation of a 550 M.sub.n PIBSA/DMAPA
Quaternary Ammonium Salt Using 1,2-Epoxybutane (an
Imide/Epoxybutane Quat)
[0240] The 550 M.sub.n PIBSA/DMAPA quaternizable compound of
Example 9 (475 g, 0.62 moles) is added to a 1-liter flask flange
flask equipped with a water condenser, a thermocouple, a syringe
pump, an overhead stirrer and a nitrogen inlet.
[0241] 2-ethylhexanol (136 g, 1.05 moles), acetic acid (37.3 g,
0.62 moles) and water (4.4 g, 0.24 moles) are also charged to the
1-liter flask. The batch is then heated to 75.degree. C., under
agitation and nitrogen atmosphere. 1,2-epoxybutane (48.9 g, 0.68
moles) is added via the syringe pump over 2 hours. The batch is
then held for 3 hours at 75.degree. C. The imide/epoxybutane quat
is then cooled and discharged into a storage vessel.
Example 11 (Prophetic)--Formation of a 550 M.sub.n PIBSA/DMAPA
Quaternary Ammonium Salt Using 1,2-Epoxydodecane (an
Imide/Epoxydodecane Quat)
[0242] The 550 M.sub.n PIBSA/DMAPA quaternizable compound of
Example 9 (470 g, 0.61 moles) is added to a 1-liter flask flange
flask equipped with a water condenser, a thermocouple, an overhead
stirrer and a nitrogen inlet.
[0243] 2-ethylhexanol (136 g, 1.05 moles), 1,2-epoxydodecane (114.1
g, 0.62 moles), acetic acid (37 g, 0.62 moles), and water (4.4 g,
0.24 moles) are also charged to the 1-liter flask. The batch is
then heated to 75.degree. C. under agitation and nitrogen and
maintained at temperature for 3 hours. The imide/epoxydodecane quat
is then then cooled before it is transferred into a storage
vessel.
Example 12 (Prophetic)--Formation of a 550 M.sub.n PIBSA/DMAPA
Quaternary Ammonium Salt Using 1,2-Epoxyhexadecane (an
Imide/Epoxyhexadecane Quat)
[0244] The 550 M.sub.n PIBSA/DMAPA quaternizable compound of
Example 9 (470 g, 0.61 moles) is added to a 1-liter flask flange
flask equipped with a water condenser, a thermocouple, an overhead
stirrer and a nitrogen inlet.
[0245] 2-ethylhexanol (136 g, 1.05 moles), 1,2-epoxyhexadecane
(148.99 g, 0.62 moles), acetic acid (37.0 g, 0.62 moles), and water
(4.4 g, 0.24 moles) are added to the flask and heated to 75.degree.
C. while agitating under nitrogen. The batch is held at 75.degree.
C. for 3 hours. The imide/epoxyhexadecane quat is then then cooled
before it is transferred into a storage vessel.
Example 13 (Prophetic)--Formation of a 550 M.sub.n PIBSA/DMAPA
Quaternary Ammonium Salt Using Glycidol (an Imide/Glycidol
Quat)
[0246] The 550 M.sub.n PIBSA/DMAPA quaternizable compound of
Example 9 (471 g, 0.62 moles) is added to a 1-liter flask flange
flask equipped with a water condenser, a thermocouple, an overhead
stirrer and a nitrogen inlet.
[0247] 2-ethylhexanol (138.0 g, 1.06 moles), glycidol (48.2 g, 0.65
moles), acetic acid (37.2 g, 0.62 moles), and water (4.1 g, 0.22
moles) are also charged to the 1-liter flask. Agitation is then
initiated (200 rpm) and a slow nitrogen purge is introduced. The
batch is then heated to 75.degree. C. and maintained at temperature
for 4 hours. The imide/glycidol quat is then then cooled before it
is transferred into a storage vessel.
Example 14 (Prophetic)--Formation of 2300 M.sub.n Polyisobutylene
Succinic Anhydride (PIBSA)
[0248] A 2300 number average molecular weight (M.sub.n)
polyisobutylene (PIB) (2000 g., 0.87 moles) high-vinylidene PIB
having greater than 20% vinylidene groups is charged to a 5-liter
flange flask equipped with overhead stirrer, air condenser,
nitrogen inlet, thermocouple and Eurotherm.TM. temperature
controller (reaction kit).
[0249] Maleic anhydride (165.5 g, 1.70 moles) is then charged to
the reaction vessel. The batch is agitated under a nitrogen blanket
and slowly heated to 203.degree. C. over a 90 minute period. The
batch is maintained at 203.degree. C. for 24 hours.
[0250] The reaction kit is then reconfigured for vacuum stripping.
The batch is stripped at 203.degree. C. and 0.05 bar to remove
unreacted maleic anhydride. Diluent oil, such as mineral oil
(1116.8 g), is added to the batch. The batch comprising the formed
PIBSA is then cooled back to 50.degree. C. and decanted into a
storage vessel.
Example 15--Formation of Quaternizable Compound--2300 M.sub.n PIBSA
and Dimethylaminopropylamine (DMAPA)
[0251] A 2300 M.sub.n PIBSA (3000 g, 1.52 moles, as prepared in
Example 14) is charged to a 5-liter flask equipped with a water
condenser and Dean Stark trap, a thermocouple, a dropping funnel,
an overhead stirrer and Nitrogen inlet and heated to 90.degree.
C.
[0252] DMAPA (154.72 g, 1.517 moles) is added to the flask via the
dropping funnel over 40 minutes. An exotherm increasing 6.degree.
C. was observed. Once all the DMAPA is added, the reaction is
slowly heated to 150.degree. C. and maintained at that temperature
for 3 hours, and approximately 25 g water is collected in Dean
Stark trap. The resulting product is a 2300 M.sub.n PIBSA/DMAPA
quaternizable compound.
Example 16 (Prophetic)--Formation of a 2300 M.sub.n PIBSA/DMAPA
Quaternary Ammonium Salt Using 1,2-Epoxydodecane (an
Imide/Epoxydodecane Quat)
[0253] The 2300 M.sub.n PIBSA/DMAPA quaternizable compound of
Example 15 (550.8 g, 0.29 moles) is added to a 1-liter flask flange
flask equipped with a water condenser, a thermocouple, an overhead
stirrer and a nitrogen inlet.
[0254] 2-ethylhexanol (145.4 g, 1.12 moles), 1,2-epoxydodecane
(51.55 g, 0.28 moles), acetic acid (17.4 g, 0.29 moles), and water
(5.6 g, 0.31 moles) are also charged to the 1-liter flask. The
batch is then heated to 75.degree. C. under agitation and nitrogen
and maintained at temperature for 3 hours and 15 minutes. The
imide/epoxydodecane quat is then then cooled before it is
transferred into a storage vessel.
Example 17--Formation of a 2300 M.sub.n PIBSA/DMAPA Quaternary
Ammonium Salt Using 1,2-Epoxyhexadecane (an Imide/Epoxyhexadecane
Quat)
[0255] The 2300 M.sub.n PIBSA/DMAPA quaternizable compound of
Example 15 (550.8 g, 0.29 moles) is added to a 1-liter flask flange
flask equipped with a water condenser, a thermocouple, an overhead
stirrer and a nitrogen inlet.
[0256] 2-ethylhexanol (145.4 g, 1.12 moles), 1,2-epoxyhexadecane
(67.4 g, 0.28 moles), acetic acid (17.4 g, 0.29 moles), and water
(5.6 g, 0.31 moles) are added to the flask and heated to 75.degree.
C. while agitating under nitrogen. The batch is held at 75.degree.
C. for 3 hours and 15 minutes. The imide/epoxyhexadecane quat is
then then cooled before it is transferred into a storage
vessel.
Example 18--Formation of a 2300 M.sub.n PIBSA/DMAPA Quaternary
Ammonium Salt Using Glycidol (an Imide/Glycidol Quat)
[0257] The 2300 M.sub.n PIBSA/DMAPA quaternizable compound of
Example 15 (550 g, 0.25 moles) is added to a 1-liter flask flange
flask equipped with a water condenser, a thermocouple, an overhead
stirrer and a nitrogen inlet.
[0258] 2-ethylhexanol (175.6 g, 1.35 moles), glycidol (18.85 g,
0.25 moles), acetic acid (15.28 g, 0.25 moles), and water (5 g,
0.27 moles) are also charged to the 1-liter flask. Agitation is
then initiated (200 rpm) and a slow nitrogen purge is introduced.
The batch is then heated to 90.degree. C. and maintained at
temperature for 3 hours. The imide/glycidol quat is then then
cooled before it is transferred into a storage vessel.
Demulsification (Water Shedding) Testing
[0259] The demulsification test is performed to measure the epoxide
quats' ability to demulsify fuel and water mixtures as compared to
the 1000 M.sub.n imide/propylene oxide quat of Comparative Example
3. The demulsification test is run according to the procedure in
ASTM D1094-07 ("Standard Test Method for Water Reaction of Aviation
Fuels"). The quaternary ammonium salt is added to room temperature
fuel at 60 ppm actives by weight based on a total weight of the
fuel. A commercially available demulsifier (Tolad 9327 available
from Baker Hughes) is added to the fuel at 18 ppm by weight based
on a total weight of the fuel.
[0260] The fuel (80 mL) is then added to a clean, 100 mL-graduated
cylinder. A phosphate buffer solution with a pH of 7.0 (20 mL) is
then added to the graduated cylinder and the cylinder is stoppered.
The cylinder is shaken for 2 minutes at 2 to 3 strokes per second
and placed on a flat surface. The volume of the aqueous layer, or
water recovery, is then measured at 3, 5, 7, 10, 15, 20, and
30-minute intervals.
[0261] The results of the demulsification tests are shown in Table
1 below and in FIG. 1.
TABLE-US-00001 TABLE 1 3 5 7 10 15 30 Time Example 4 2.5 8.5 14 18
19 20 Water recovered (mL) Example 6 11 18 19 20 20 20 Water
recovered (mL) Example 17 2.5 8.5 14 18 19 20 Water recovered (mL)
Example 5 10.5 18 19 20 20 20 Water recovered (mL) Example 7 0 0 0
2 15 20 Water recovered (mL) Example 18 7 8 13 15 17 19 Water
recovered (mL) Comparative 2 2 4 4 5 10 Water recovered (mL)
Example 3
Deposit Tests--CEC F-23-01 Procedure for Diesel Engine Injector
Nozzle Coking Test
[0262] Deposit tests are performed using Peugeot S.A.'s XUD 9
engine in accordance with the procedure in CEC F-23-01. For the
first deposit test, air flow is measured though clean injector
nozzles of the XUD 9 engine using an air-flow rig. The engine is
then run on a reference fuel (RF79) and cycled through various
loads and speeds for a period of 10 hours to simulate driving and
allow any formed deposits to accumulate. The air-flow through the
nozzles are measured again using the air-flow rig. The percentage
of air flow loss (or flow remaining) is then calculated.
[0263] A set of deposit tests are performed using the same steps
above, except 10 ppm actives of the epoxide quat are added to the
reference fuel. A second set of deposit tests are performed using
the same steps above, except 30 ppm actives are added to the
reference fuel.
[0264] The results of the deposit tests for the first and second
sets are shown in Table 2 and FIG. 2 and in Table 3 and FIG. 3
respectively.
TABLE-US-00002 TABLE 2 10 ppm Actives Flow Loss (%) Flow Remaining
(%) Example 4 65.5 34.5 Example 5 72.1 27.9 Example 7 70.5 29.5
Reference Fuel 80 20
TABLE-US-00003 TABLE 3 30 ppm Actives Flow Loss (%) Flow Remaining
(%) Example 4 25.9 74.1 Example 6 13.0 87.0 Example 7 8.6 91.4
Example 18 19.0 81.0 Reference Fuel 80 20
[0265] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicated, each
chemical or composition referred to herein should be interpreted as
being a commercial grade material which may contain the isomers,
by-products, derivatives, and other such materials which are
normally understood to be present in the commercial grade. However,
the amount of each chemical component is presented exclusive of any
solvent or diluent oil, which may be customarily present in the
commercial material, unless otherwise indicated. It is to be
understood that the upper and lower amount, range, and ratio limits
set forth herein may be independently combined. Similarly, the
ranges and amounts for each element of the invention can be used
together with ranges or amounts for any of the other elements.
[0266] As used herein, the transitional term "comprising," which is
synonymous with "including," "containing," or "characterized by,"
is inclusive or open-ended and does not exclude additional,
un-recited elements or method steps. However, in each recitation of
"comprising" herein, it is intended that the term also encompass,
as alternative embodiments, the phrases "consisting essentially of"
and "consisting of," where "consisting of" excludes any element or
step not specified and "consisting essentially of" permits the
inclusion of additional un-recited elements or steps that do not
materially affect the essential or basic and novel characteristics
of the composition or method under consideration.
[0267] While certain representative embodiments and details have
been shown for the purpose of illustrating the subject invention,
it will be apparent to those skilled in this art that various
changes and modifications can be made therein without departing
from the scope of the subject invention. In this regard, the scope
of the invention is to be limited only by the following claims.
* * * * *