U.S. patent application number 13/988585 was filed with the patent office on 2013-09-19 for polyester quaternary ammonium salts.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. The applicant listed for this patent is Hannah Greenfield, David J. Moreton, Dean Thetford. Invention is credited to Hannah Greenfield, David J. Moreton, Dean Thetford.
Application Number | 20130239468 13/988585 |
Document ID | / |
Family ID | 45094805 |
Filed Date | 2013-09-19 |
United States Patent
Application |
20130239468 |
Kind Code |
A1 |
Greenfield; Hannah ; et
al. |
September 19, 2013 |
Polyester Quaternary Ammonium Salts
Abstract
The invention relates to polyester quaternary ammonium salts,
including amine, amide, and ester salts, processes for making them,
and their use as additives, including their use in fuels, such as
diesel fuel and fuel oils. The invention particularly relates to
the use of polyester quaternary ammonium salts as detergents in
fuels and the methods of making them.
Inventors: |
Greenfield; Hannah; (Derby,
GB) ; Thetford; Dean; (Norden, GB) ; Moreton;
David J.; (Belper, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Greenfield; Hannah
Thetford; Dean
Moreton; David J. |
Derby
Norden
Belper |
|
GB
GB
GB |
|
|
Assignee: |
THE LUBRIZOL CORPORATION
Wickliffe
OH
|
Family ID: |
45094805 |
Appl. No.: |
13/988585 |
Filed: |
November 21, 2011 |
PCT Filed: |
November 21, 2011 |
PCT NO: |
PCT/US11/61620 |
371 Date: |
May 21, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61416767 |
Nov 24, 2010 |
|
|
|
Current U.S.
Class: |
44/419 ;
560/196 |
Current CPC
Class: |
C10L 1/2383 20130101;
C08G 63/912 20130101; C08L 77/12 20130101; C10L 1/224 20130101;
C10L 1/238 20130101; C08G 63/6852 20130101; C10L 1/2222 20130101;
C10L 10/18 20130101; C10L 1/265 20130101 |
Class at
Publication: |
44/419 ;
560/196 |
International
Class: |
C10L 1/224 20060101
C10L001/224 |
Claims
1. A composition comprising a quaternized polyester salt which
comprises the reaction product of: a. a polyester containing a
tertiary amino group; and b. quaternizing agent suitable for
converting the tertiary amino group to a quaternary nitrogen.
2. The composition of claim 1 wherein the polyester comprises the
reaction product of a fatty carboxylic acid containing at least one
hydroxyl group and a compound having an oxygen or nitrogen atom
capable of condensing with said acid where said compound contains a
tertiary amino group.
3. The composition of claim 2 wherein the fatty carboxylic acid is
represented by the formula: ##STR00006## where R.sup.1 is a
hydrogen or a hydrocarbyl group containing from 1 to 20 carbon
atoms and R.sup.2 is a hydrocarbylene group containing from 1 to 20
carbon atoms; and wherein the compound having an oxygen or nitrogen
atom capable of condensing with said acid and further having a
tertiary amino group is represented by the formula: ##STR00007##
where R.sup.3 is a hydrocarbyl group containing from 1 to 10 carbon
atoms; R.sup.4 is a hydrocarbyl group containing from 1 to 10
carbon atoms; R.sup.5 is a hydrocarbylene group containing from 1
to 20 carbon atoms; and X.sup.1 is O or NR.sup.6 where R.sup.6 is a
hydrogen or a hydrocarbyl group containing from 1 to 10 carbon
atoms;
4. The composition of claim 1 wherein the quaternized polyester
salt comprises a quaternized polyester amide salt wherein the
polyester containing a tertiary amino group used to prepare said
quaternized polyester salt comprises a polyester amide containing a
tertiary amino group.
5. The composition of claim 1 wherein the quaternized polyester
salt comprises a cation represented by the following formula:
##STR00008## where R.sup.1 is a hydrogen or a hydrocarbyl group
containing from 1 to 20 carbon atoms and R.sup.2 is a
hydrocarbylene group containing from 1 to 20 carbon atoms; R.sup.3
is a hydrocarbyl group containing from 1 to 10 carbon atoms;
R.sup.4 is a hydrocarbyl group containing from 1 to 10 carbon
atoms; R.sup.5 is a hydrocarbylene group containing from 1 to 20
carbon atoms; R.sup.6 is a hydrogen or a hydrocarbyl group
containing from 1 to 10 carbon atoms; n is a number from 1 to 10;
R.sup.7 is hydrogen, a hydrocarbonyl group containing from 1 to 22
carbon atoms, or a hydrocarbyl group containing from 1 to 22 carbon
atoms; and X.sup.2 is a group derived from the quaternizing
agent.
6. The composition of claim 2 wherein the compound having an oxygen
or nitrogen atom capable of condensing with said acid and further
having a tertiary amino group comprises N,N-diethylethylenediamine,
N,N-dimethylethylenediamine, N,N-dibutylethylenediamine,
N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane,
N,N-dimethylaminoethanol, N,N-diethylaminoethanol, or combinations
thereof.
7. The composition of claim 2 wherein the fatty carboxylic acid
containing at least one hydroxyl group comprises: 12-hydroxystearic
acid; ricinoleic acid; 12-hydroxy dodecanoic acid; 5-hydroxy
dodecanoic acid; 5-hydroxy decanoic acid; 4-hydroxy decanoic acid;
10-hydroxy undecanoic acid; or combinations thereof.
8. The composition of claim 1 wherein the quaternizing agent
comprises ethylene oxide, propylene oxide, butylene oxide, styrene
oxide, or combinations thereof wherein the quaternizing agent is
used in combination with an acid.
9. The composition of claim 1 further comprising a metal
deactivator, a detergent other than those of claim 1, a dispersant,
a viscosity modifier, a friction modifier, a dispersant viscosity
modifier, an extreme pressure agent, an antiwear agent, an
antioxidant, a corrosion inhibitor, a foam inhibitor, a
demulsifier, a pour point depressant, a seal swelling agent, a wax
control polymer, a scale inhibitor, a gas-hydrate inhibitor, or
combinations thereof.
10. The composition of claim 1 further comprising an overbased
metal containing detergent, a zinc dialkyldithiophosphate, or
combinations thereof.
11. The composition of claim 1, further comprising a fuel which is
liquid at room temperature.
12. The method of fueling an internal combustion engine comprising:
A. supplying to said engine: i. a fuel which is liquid at room
temperature; and ii. a composition comprising a quaternized
polyester salt which comprises the reaction product of: (a) a
polyester containing a tertiary amino group; and (b) quaternizing
agent suitable for converting the tertiary amino group to a
quaternary nitrogen.
13. A process of making a quaternary ammonium salt detergent
comprising: I. reacting (a) a polyester containing a tertiary amino
group; and (b) quaternizing agent suitable for converting the
tertiary amino group to a quaternary nitrogen; thereby obtaining
the quaternized dispersant.
14. The process of claim 14 wherein the polyester containing a
tertiary amino group is prepared by a process comprising: I.
reacting (a)(i) a fatty carboxylic acid containing at least one
hydroxyl group and (a)(ii) a compound having an oxygen or nitrogen
atom capable of condensing with said acid and further having a
tertiary amino group; thereby obtaining the polyester containing a
tertiary amino group.
Description
FIELD OF THE INVENTION
[0001] The invention relates to polyester quaternary ammonium
salts, including amine, amide, and ester salts, processes for
making them, and their use as additives, including their use in
fuels, such as diesel fuel and fuel oils. The invention
particularly relates to the use of polyester quaternary ammonium
salts as detergents in fuels and the methods of making them.
BACKGROUND OF THE INVENTION
[0002] Hydrocarbon fuels generally contain numerous deposit-forming
substances. When used in internal combustion engines (ICEs),
deposits tend to form on and around constricted areas of the engine
which are in contact with the fuel. In automobile engines deposits
can build up on engine intake valves leading to progressive
restriction of the gaseous fuel mixture flow into the combustion
chamber and to valve sticking. There are two general types of inlet
valve deposits, heavy deposits and thin deposits. These different
types of deposits affect the performance of the fuel and the engine
in slightly different ways. Heavy deposits are carbonaceous and
oily in appearance. They cause flow restriction past the valves,
which in turn reduces the maximum power of the engine, decreasing
fuel economy and increasing emissions. Thin deposits tend to cause
problems on starting the engine and increasing emissions.
[0003] As engines become more sensitive to deposits, it has become
common practice to incorporate a detergent in the fuel composition
for the purposes of inhibiting the formation, and facilitating the
removal, of engine deposits, thereby improving engine performance
and emissions.
[0004] It is known to use certain polyisobutylsuccinimide-derived
quaternized PIB/amine and/or amide dispersants/detergents as
additives in fuel compositions. Polyisobutylsuccinimides may also
be described as polyisobutylene succinimides. These quaternized
dispersants/detergents are derived from traditional PIB/amine
and/or amide fuel additive compounds that have pendant tertiary
amine sites which can be alkylated, i.e. quaternized, by a
quaternizing agent, such as propylene oxide. Examples of these
additives are disclosed in U.S. patent application US
2008/0307698.
[0005] However there is a need for additives that provide the
benefits described above while also exhibiting improved viscosity
profiles and material handling properties. Such improvements would
allow for the use of less diluent materials in the concentrates and
additive packages generally used in the commercial products that
contain these types of fuel additives, and so in the final fuels as
well. Less diluent would be required if the viscosity profiles and
material handling properties allowed for additive-containing
compositions to be transferred and handled (i.e. pumped, poured,
mixed, etc) without having to heat the material more than typical
and/or without the need of specialized high viscosity equipment.
Improved viscosity profiles and material handling properties would
allow for reduced use of diluents, saving cost, reducing waste and
so and improving the environmental impact of the materials. This
would also allow the use of more concentrated additive packages and
intermediate compositions, which can be transported more
efficiently, again reducing costs and environmental impact.
SUMMARY OF THE INVENTION
[0006] The present invention deals with a new class of detergents
which offer significant improvements over traditional PIB/amine
detergents, including polyisobutylsuccinimide-derived quaternized
detergents. A new class of polyester quaternized salts have now
been discovered. These polyester quaternized salts have
polyester-based hydrocarbyl groups and provide improved viscosity
profiles and material handling properties compared to
polyisobutylsuccinimide-derived quaternized detergents and related
materials. The polyester quaternized salts of the invention provide
equivalent detergency and thermal stability performance as other
quaternized detergents but also provide the improved viscosity
profiles and material handling properties described above
[0007] The present invention provides a composition containing a
quaternized polyester salt derived from the reaction of a polyester
that contains a tertiary amino group and a quaternizing agent
suitable for converting the tertiary amino group to a quaternary
nitrogen. The quaternizing agent may be a dialkyl sulfate, a benzyl
halide, a hydrocarbyl substituted carbonate, a hydrocarbyl epoxide,
or some combination thereof. Any of the quaternizing agents
described, particularly the hydrocarbyl epoxide, may be used in
combination with an acid, for example acetic acid.
[0008] The invention provides for quaternized polyester salts where
the polyester used in their preparation is itself the reaction
product of a fatty carboxylic acid containing at least one hydroxyl
group and a compound having an oxygen or nitrogen atom capable of
condensing with said acid and further having a tertiary amino
group. The invention further provides for the polyester reactant to
be a polyester amide containing a tertiary amino group.
[0009] The invention further provides for fuel compositions that
include the quaternized polyester salts described herein and a fuel
which is liquid at room temperature. Additional fuel additives may
also be present.
[0010] The invention provides for methods of fueling an internal
combustion engine comprising the steps of supplying to the engine a
fuel which is liquid at room temperature and a composition
comprising one or more of the quaternized polyester salts described
herein.
[0011] The invention also provides for a process of making a
quaternary ammonium salt detergent comprising the steps of reacting
(a) a polyester containing a tertiary amino group; and (b) a
quaternizing agent suitable for converting the tertiary amino group
to a quaternary nitrogen. The quaternizing agent may be selected
from the group consisting of dialkyl sulfates, benzyl halides,
hydrocarbyl substituted carbonates; hydrocarbyl epoxides in
combination with an acid or mixtures thereof. The described process
results in the quaternized dispersants described herein.
DETAILED DESCRIPTION OF THE INVENTION
[0012] Various preferred features and embodiments will be described
below by way of non-limiting illustration.
The Polyester Quaternary Ammonium Salt Detergent
[0013] The polyester quaternary salts detergents of the invention
include quaternized polyester amine, amide, and ester salts. The
additives may also be described as quaternary polyester salts. The
additives of the invention may be described as the reaction product
of: a polyester containing a tertiary amino group; and a
quaternizing agent suitable for converting the tertiary amino group
to a quaternary nitrogen. The quaternizing agent may be selected
from the group consisting of dialkyl sulfates, benzyl halides,
hydrocarbyl substituted carbonates; hydrocarbyl epoxides in
combination with an acid or mixtures thereof
a. The Non-Quaternized Polyester
[0014] The polyester containing a tertiary amino group used in the
preparation of the additives of the invention may also be described
as a non-quaternized polyester containing a tertiary amino
group.
[0015] In some embodiments the polyester is the reaction product of
a fatty carboxylic acid containing at least one hydroxyl group and
a compound having an oxygen or nitrogen atom capable of condensing
with said acid and further having a tertiary amino group. Suitable
fatty carboxylic acids that may used in the preparation of the
polyesters described above may be represented by the formula:
##STR00001##
where R.sup.1 is a hydrogen or a hydrocarbyl group containing from
1 to 20 carbon atoms and R.sup.2 is a hydrocarbylene group
containing from 1 to 20 carbon atoms. In some embodiments R.sup.1
contains from 1 to 12, 2 to 10, 4 to 8 or even 6 carbon atoms, and
R.sup.2 contains from 2 to 16, 6 to 14, 8 to 12, or even 10 carbon
atoms.
[0016] In some embodiments the fatty carboxylic acid used in the
preparation of the polyester is 12-hydroxystearic acid, ricinoleic
acid, 12-hydroxy dodecanoic acid, 5-hydroxy dodecanoic acid,
5-hydroxy decanoic acid, 4-hydroxy decanoic acid, 10-hydroxy
undecanoic acid, or combinations thereof.
[0017] In some embodiments the compound having an oxygen or
nitrogen atom capable of condensing with said acid and further
having a tertiary amino group is represented by the formula:
##STR00002##
where R.sup.3 is a hydrocarbyl group containing from 1 to 10 carbon
atoms; R.sup.4 is a hydrocarbyl group containing from 1 to 10
carbon atoms; R.sup.5 is a hydrocarbylene group containing from 1
to 20 carbon atoms; and X.sup.1 is 0 or NR.sup.6 where R.sup.6 is a
hydrogen or a hydrocarbyl group containing from 1 to 10 carbon
atoms. In some embodiments R.sup.3 contains from 1 to 6, 1 to 2, or
even 1 carbon atom, R.sup.4 contains from 1 to 6, 1 to 2, or even 1
carbon atom, R.sup.5 contains from 2 to 12, 2 to 8 or even 3 carbon
atoms, and R.sup.6 contains from 1 to 8, or 1 to 4 carbon atoms. In
some of these embodiments, formula (II) becomes:
##STR00003##
where the various definitions provided above still apply.
[0018] Examples of nitrogen or oxygen containing compounds capable
of condensing with the acylating agents, which also have a tertiary
amino group, or compounds that can be alkylated into such
compounds, include but are not limited to: 1-aminopiperidine,
1-(2-aminoethyl)piperidine , 1-(3-aminopropyl)-2-pipecoline,
1-methyl-(4-methylamino)piperidine, 4-(1-pyrrolidinyl)piperidine,
1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine,
N,N-diethylethylenediamine, N,N-dimethylethylenediamine,
N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane,
N,N-dimethyl-1,3-diaminopropane, N,N,N'-trimethylethylenediamine,
N,N-dimethyl-N'-ethylethylenediamine,
N,N-diethyl-N'-methylethylenediamine,
N,N,N'-triethylethylenediamine, 3-dimethyl aminopropyl amine,
3-diethylaminopropylamine, 3-dibutylaminopropylamine,
N,N,N'-trimethyl-1,3-propanediamine,
N,N,2,2-tetramethyl-1,3-propanediamine,
2-amino-5-diethylaminopentane,
N,N,N',N'-tetraethyldiethylenetriamine,
3,3'-diamino-N-methyldipropylamine,
3,3'-iminobis(N,N-dimethylpropylamine), or combinations thereof. In
such embodiments, the resulting additive includes a quaternary
ammonium amide salt, that is a detergent containing an amide group
and a quaternary ammonium salt.
[0019] The nitrogen or oxygen containing compounds may further
include aminoalkyl substituted heterocyclic compounds such as
1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine.
[0020] Another type of nitrogen or oxygen containing compounds
capable of condensing with the acylating agent and having a
tertiary amino group, in some embodiments after further alkylation,
include alkanolamines including but not limited to triethanolamine,
N,N-dimethylaminopropanol, N,N-diethylaminopropanol,
N,N-diethylaminobutanol, triisopropanolamine,
1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]-ethanol,
N-ethyldiethanolamine, N-methyldiethanol amine,
N-butyldiethanolamine, N,N-diethylaminoethanol,
N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol. In
embodiments where alkanolamines and/or similar materials are used,
the resulting additive includes a quaternary ammonium ester salt,
that is a detergent containing an ester group and a quaternary
ammonium salt.
[0021] In one embodiment the nitrogen or oxygen containing compound
is triisopropanolamine, 1-[2-hydroxyethyl]piperidine,
2-[2-(dimethylamino)ethoxy]-ethanol, N-ethyldiethanolamine,
N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylamino
ethanol, N,N-dimethylaminoethanol,
2-dimethylamino-2-methyl-1-propanol, or combinations thereof.
[0022] In some embodiments the compound having an oxygen or
nitrogen atom capable of condensing with said acid and further
having a tertiary amino group comprises N,N-diethylethylenediamine,
N,N-dimethylethylenediamine, N,N-dibutylethylenediamine,
N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane,
N,N-dimethylaminoethanol, N,N-diethylaminoethanol, or combinations
thereof.
[0023] The quaternized polyester salt can be a quaternized
polyester amide salt. In such embodiments the polyester containing
a tertiary amino group used to prepare the quaternized polyester
salt is a polyester amide containing a tertiary amino group. In
some of these embodiments the amine or amino alcohol is reacted
with a monomer and then the resulting material is polymerized with
additional monomer, resulting in the desired polyester amide which
may then be quaternized.
[0024] In some embodiments the quaternized polyester salt includes
an cation represented by the following formula:
##STR00004##
where R.sup.1 is a hydrogen or a hydrocarbyl group containing from
1 to 20 carbon atoms and R.sup.2 is a hydrocarbylene group
containing from 1 to 20 carbon atoms; R.sup.3 is a hydrocarbyl
group containing from 1 to 10 carbon atoms; R.sup.4 is a
hydrocarbyl group containing from 1 to 10 carbon atoms; R.sup.5 is
a hydrocarbylene group containing from 1 to 20 carbon atoms;
R.sup.6 is a hydrogen or a hydrocarbyl group containing from 1 to
10 carbon atoms; n is a number from 1 to 20 or from 1 to 10;
R.sup.7 is hydrogen, a hydrocarbonyl group containing from 1 to 22
carbon atoms, or a hydrocarbyl group containing from 1 to 22 carbon
atoms; and X.sup.2 is a group derived from the quaternizing agent.
In some embodiments R.sup.6 is hydrogen.
[0025] As above, in some embodiments R.sup.1 contains from 1 to 12,
2 to 10, 4 to 8 or even 6 carbon atoms, and R.sup.2 contains from 1
or even 2 to 16, 6 to 14, 8 to 12, or even 10 carbon atoms, R.sup.3
contains from 1 to 6, 1 to 2, or even 1 carbon atom, R.sup.4
contains from 1 to 6, 1 to 2, or even 1 carbon atom, R.sup.5
contains from 2 to 12, 2 to 8 or even 3 carbon atoms, and R.sup.6
contains from 1 to 8, or 1 to 4 carbon atoms. In any of these
embodiments n may be from 2 to 9, or 3 to 7, and R.sup.7 may
contain from 6 to 22, or 8 to 20 carbon atoms. R.sup.7 may be an
acyl group.
[0026] In these embodiments the quaternized polyester salt is
essentially capped with a C1-22, or a C8-20, fatty acid. Examples
of suitable acids include oleic acid, palmitic acid, stearic acid,
erucic acid, lauric acid, 2-ethylhexanoic acid, 9,11-linoleic acid,
9,12-linoleic acid, 9,12,15-linolenic acid, abietic acid, or
combinations thereof.
[0027] The number average molecular weight (Mn) of the quaternized
polyester salts of the invention may be from 500 to 3000, or from
700 to 2500.
[0028] The polyester useful in the present invention can be
obtained by heating one or more hydroxycarboxylic acids or a
mixture of the hydroxycarboxylic acid and a carboxylic acid,
optionally in the presence of an esterification catalyst. The
hydroxycarboxylic acids can have the formula HO--X--COOH wherein X
is a divalent saturated or unsaturated aliphatic radical containing
at least 8 carbon atoms and in which there are at least 4 carbon
atoms between the hydroxy and carboxylic acid groups, or from a
mixture of such a hydroxycarboxylic acid and a carboxylic acid
which is free from hydroxy groups. This reaction can be carried out
at a temperature in the region of 160 C to 200 C, until the desired
molecular weight has been obtained. The course of the
esterification can be followed by measuring the acid value of the
product, with the desired polyester, in some embodiments, having an
acid value in the range of 10 to 100 mg KOH/g or in the range of 20
to 50 mg KOH/g. The indicated acid value range of 10 to 100 mg
KOH/g is equivalent to a number average molecular weight range of
5600 to 560. The water formed in the esterification reaction can be
removed from the reaction medium, and this can be conveniently done
by passing a stream of nitrogen over the reaction mixture or, by
carrying out the reaction in the presence of a solvent, such as
toluene or xylene, and distilling off the water as it is
formed.
[0029] The resulting polyester can then be isolated in conventional
manner; however, when the reaction is carried out in the presence
of an organic solvent whose presence would not be harmful in the
subsequent application, the resulting solution of the polyester can
be used.
[0030] In the said hydroxycarboxylic acids the radical represented
by X may contain from 12 to 20 carbon atoms, optionally where there
are between 8 and 14 carbon atoms between the carboxylic acid and
hydroxy groups. In some embodiments the hydroxy group is a
secondary hydroxy group.
[0031] Specific examples of such hydroxycarboxylic acids include
ricinoleic acid, a mixture of 9- and 10-hydroxystearic acids
(obtained by sulphation of oleic acid followed by hydrolysis), and
12-hydroxystearic acid, and especially the commercially available
hydrogenated castor oil fatty acid which contains in addition to
12-hydroxystearic acid minor amounts of stearic acid and palmitic
acid.
[0032] The carboxylic acids which can be used in conjunction with
the hydroxycarboxylic acids to obtain these polyesters are
preferably carboxylic acids of saturated or unsaturated aliphatic
compounds, particularly alkyl and alkenyl carboxylic acids
containing a chain of from 8 to 20 carbon atoms. As examples of
such acids there may be mentioned lauric acid, palmitic acid,
stearic acid and oleic acid.
[0033] In one embodiment the polyester is derived from commercial
12-hydroxy-stearic acid having a number average molecular weight of
about 1600. Polyesters such as this are described in greater detail
in U.K. Patent Specification Nos. 1373660 and 1342746.
[0034] In some embodiments the components used to prepare the
additives described above are substantially free of, essentially
free of, or even completely free of, non-polyester-containing
hydrocarbyl substituted acylating agents and/or
non-polyester-containing hydrocarbyl substituted diacylating
agents, such as for example polyisobutylene succinic anhydride. In
some embodiments these excluded agents are the reaction product of
a long chain hydrocarbon, generally a polyolefin reacted with a
monounsaturated carboxylic acid reactant, such as, (i)
.alpha.,.beta.-monounsaturated C.sub.4 to C.sub.10 dicarboxylic
acid, such as, fumaric acid, itaconic acid, maleic acid.; (ii)
derivatives of (i) such as anhydrides or C.sub.1 to C.sub.5 alcohol
derived mono- or di-esters of (i); (iii)
.alpha.,.beta.-monounsaturated C.sub.3 to C.sub.10 monocarboxylic
acid such as acrylic acid and methacrylic acid.; or (iv)
derivatives of (iii), such as, C.sub.1 to C.sub.5 alcohol derived
esters of (iii) with any compound containing an olefinic bond
represented by the general formula
(R.sup.9)(R.sup.10)C.dbd.C(R.sup.11)(CH(R.sup.7)(R.sup.8)) wherein
each of R.sup.9 and R.sup.10 is independently hydrogen or a
hydrocarbon based group; each of R.sup.11, R.sup.7 and R.sup.8 is
independently hydrogen or a hydrocarbon based group and preferably
at least one is a hydrocarbyl group containing at least 20 carbon
atoms. In one embodiment, the excluded hydrocarbyl-substituted
acylating agent is a dicarboxylic acylating agent. In some of these
embodiments, the excluded hydrocarbyl-substituted acylating agent
is polyisobutylene succinic anhydride.
[0035] By substantially free of, it is meant that the components of
the present invention are primarily composed of materials other
than hydrocarbyl substituted acylating agents described above such
that these agents are not significantly involved in the reaction
and the compositions of the invention do not contain significant
amounts of additives derived from such agents. In some embodiments
the components of the invention, or the compositions of the
invention, may contain less than 10 percent by weight of these
agents, or of the additives derived from these agents. In other
embodiments the maximum allowable amount may be 5, 3, 2, 1 or even
0.5 or 0.1 percent by weight. One of the purposes of these
embodiments is to allow the exclusion of agents such as
polyisobutylene succinic anhydrides from the reactions of the
invention and so, to also allow the exclusion of quaternized salt
detergent additive derived from agents such as polyisobutylene
succinic anhydrides. The focus of this invention is on polyester,
or hyperdispersant, quaternary salt detergent additives.
b. The Quaternizing Agent
[0036] The quaternized salt detergents of the present invention are
formed when the non-quaternized detergents described above are
reacted with a quaternizing agent. Suitable quaternizing agents
include selected dialkyl sulfates, benzyl halides, hydrocarbyl
substituted carbonates; hydrocarbyl epoxides in combination with an
acid or mixtures thereof.
[0037] In one embodiment, the quaternizing agent can include alkyl
halides, such as chlorides, iodides or bromides; alkyl sulphonates;
dialkyl sulphates, such as, dimethyl sulphate; sultones; alkyl
phosphates; such as, C1-12 trialkylphosphates; di C1-12
alkylphosphates; borates; C1-12 alkyl borates; alkyl nitrites;
alkyl nitrates; dialkyl carbonates; alkyl alkanoates; O,O-di-C1-12
alkyldithiophosphates; or mixtures thereof.
[0038] In one embodiment, the quaternizing agent may be derived
from dialkyl sulphates such as dimethyl sulphate, N-oxides,
sultones such as propane and butane sultone; alkyl, acyl or
araalkyl halides such as methyl and ethyl chloride, bromide or
iodide or benzyl chloride, and a hydrocarbyl (or alkyl) substituted
carbonates. If the alkyl halide is benzyl chloride, the aromatic
ring is optionally further substituted with alkyl or alkenyl
groups.
[0039] The hydrocarbyl (or alkyl) groups of the hydrocarbyl
substituted carbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1
to 5 carbon atoms per group. In one embodiment, the hydrocarbyl
substituted carbonates contain two hydrocarbyl groups that may be
the same or different. Examples of suitable hydrocarbyl substituted
carbonates include dimethyl or diethyl carbonate.
[0040] In another embodiment, the quaternizing agent can be a
hydrocarbyl epoxide, as represented by the following formula, in
combination with an acid:
##STR00005##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can be independently
H or a hydrocarbyl group contain from 1 to 50 carbon atoms.
Examples of hydrocarbyl epoxides include: ethylene oxide, propylene
oxide, butylene oxide, styrene oxide and combinations thereof. In
one embodiment the quaternizing agent does not contain any styrene
oxide.
[0041] In some embodiments the acid used with the hydrocarbyl
epoxide may be a separate component, such as acetic acid. In other
embodiments, for example when the hydrocarbyl acylating agent is a
dicarboxylic acylating agent, no separate acid component is needed.
In such embodiments, the detergent may be prepared by combining
reactants which are essentially free of, or even free of, a
separate acid component, such as acetic acid, and rely on the acid
group of the hydrocarbyl acylating agent instead. In other
embodiments, a small amount of an acid component may be present,
but at <0.2 or even <0.1 moles of acid per mole of
hydrocarbyl acylating agent. These acids may also be used with the
other quaternizing agents described above, including the
hydrocarbyl substituted carbonates and related materials described
below.
[0042] In some embodiments the quaternizing agent of the invention
does not contain any substituent group that contains more than 20
carbon atoms. In other words, in some embodiments the long
substituent group that allows for the resulting additive to be
organic soluble and thus useful for the purposes of this invention
is not provided by the quaternizing agent but instead is brought to
the additive by the non-quaternized detergents described above.
[0043] In certain embodiments the molar ratio of detergent having
an amine functionality to quaternizing agent is 1:0.1 to 2, or 1:1
to 1.5, or 1:1 to 1.3.
[0044] In another embodiment the quaternizing agent can be an ester
of a carboxylic acid capable of reacting with a tertiary amine to
form a quaternary ammonium salt, or an ester of a polycarboxylic
acid. In a general sense such materials may be described as
compounds having the structure:
R.sup.19--C(.dbd.O)--O--R.sup.20 (IX)
where R.sup.19 is an optionally substituted alkyl, alkenyl, aryl or
alkylaryl group and R.sup.20 is a hydrocarbyl group containing from
1 to 22 carbon atoms.
[0045] Suitable compounds include esters of carboxylic acids having
a pKa of 3.5 or less. In some embodiments the compound is an ester
of a carboxylic acid selected from a substituted aromatic
carboxylic acid, an a-hydroxycarboxylic acid and a polycarboxylic
acid. In some embodiments the compound is an ester of a substituted
aromatic carboxylic acid and thus R.sup.19 is a subsituted aryl
group. R may be a substituted aryl group having 6 to 10 carbon
atoms, a phenyl group, or a naphthyl group. R may be suitably
substituted with one or more groups selected from carboalkoxy,
nitro, cyano, hydroxy, SR' or NR'R'' where each of R' and R'' may
independently be hydrogen, or an optionally substituted alkyl,
alkenyl, aryl or carboalkoxy groups. In some embodiments R' and R''
are each independently hydrogen or an optionally substituted alkyl
group containing from 1 to 22, 1 to 16, 1 to 10, or even 1 to 4
carbon atoms.
[0046] In some embodiments R.sup.19 in the formula above is an aryl
group substituted with one or more groups selected from hydroxyl,
carboalkoxy, nitro, cyano and NH.sup.2. R.sup.19 may be a
poly-substituted aryl group, for example trihydroxyphenyl, but may
also be a mono-substituted aryl group, for example an ortho
substituted aryl group. R.sup.19 may be substituted with a group
selected from OH, NH.sub.2, NO.sub.2, or COOMe. Suitably R.sup.19
is a hydroxy substituted aryl group. In some embodiments R.sup.19
is a 2-hydroxyphenyl group. R.sup.20 may be an alkyl or alkylaryl
group, for example an alkyl or alkylaryl group containing from 1 to
16 carbon atoms, or from 1 to 10, or 1 to 8 carbon atoms. R.sup.20
may be methyl, ethyl, propyl, butyl, pentyl, benzyl or an isomer
thereof. In some embodiments R.sup.2.degree. is benzyl or methyl.
In some embodiments the quaternizing agent is methyl
salicylate.
[0047] In some embodiments the quaternizing agent is an ester of an
alpha-hydroxycarboxylic acid. Compounds of this type suitable for
use herein are described in EP 1254889. Examples of suitable
compounds which contain the residue of an alpha-hydroxycarboxylic
acid include (i) methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-,
benzyl-, phenyl-, and allyl esters of 2-hydroxyisobutyric acid;
(ii) methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-,
phenyl-, and allyl esters of 2-hydroxy-2-methylbutyric acid; (iii)
methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-,
phenyl-, and allyl esters of 2-hydroxy-2-ethylbutyric acid; (iv)
methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-,
phenyl-, and allyl esters of lactic acid; and (v) methyl-, ethyl-,
propyl-, butyl-, pentyl-, hexyl-, allyl-, benzyl-, and phenyl
esters of glycolic acid. In some embodiments the quaternizing agent
comprises methyl 2-hydroxyisobutyrate.
[0048] In some embodiments the quaternizing agent comprises an
ester of a polycarboxylic acid. In this definition we mean to
include dicarboxylic acids and carboxylic acids having more than 2
acidic moieties. In some embodiments the esters are alkyl esters
with alkyl groups that contain from 1 to 4 carbon atoms. Suitable
example include diesters of oxalic acid, diesters of phthalic acid,
diesters of maleic acid, diesters of malonic acid or diesters or
triesters of citric acid.
[0049] In some embodiments the quaternizing agent is an ester of a
carboxylic acid having a pKa of less than 3.5. In such embodiments
in which the compound includes more than one acid group, we mean to
refer to the first dissociation constant. The quaternizing agent
may be selected from an ester of a carboxylic acid selected from
one or more of oxalic acid, phthalic acid, salicylic acid, maleic
acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic
acid and 2,4,6-trihydroxybenzoic acid. In some embodiments the
quaternizing agent includes dimethyl oxalate, methyl
2-nitrobenzoate and methyl salicylate.
[0050] Any of the quaternizing agents described above, including
the hydrocarbyl epoxides, may be used in combination with an acid.
Suitable acids include carboxylic acids, such as acetic acid,
propionic acid, 2-ethylhexanoic acid, and the like.
Polyester Quaternized Detergent Containing Compositions
[0051] The quaternized salt detergents of the present invention may
be used as an additive in various types of compositions, including
fuel compositions and additive concentrate compositions.
a. Fuel Compositions
[0052] The quaternized detergents of the present invention may be
used as an additive in fuel compositions. The fuel compositions of
the present invention comprise the quaternized detergent additive
described above and a liquid fuel, and is useful in fueling an
internal combustion engine or an open flame burner. These
compositions may also contain one or more additional additives.
These optional additives are described below. In some embodiments,
the fuels suitable for use in the present invention include any
commercially available fuel, and in some embodiments any
commercially available diesel fuel and/or biofuel.
[0053] The description that follows of the types of fuels suitable
for use in the present invention refer to the fuel that may be
present in the additive containing compositions of the present
invention as well as the fuel and/or fuel additive concentrate
compositions to which the additive containing compositions may be
added.
[0054] Fuels suitable for use in the present invention are not
overly limited. Generally, suitable fuels are normally liquid at
ambient conditions e.g., room temperature (20 to 30.degree. C.) or
are normally liquid at operating conditions. The fuel can be a
hydrocarbon fuel, non-hydrocarbon fuel, or mixture thereof.
[0055] The hydrocarbon fuel can be a petroleum distillate,
including a gasoline as defined by ASTM specification D4814, or a
diesel fuel, as defined by ASTM specification D975. In one
embodiment the liquid fuel is a gasoline, and in another embodiment
the liquid fuel is a non-leaded gasoline. In another embodiment the
liquid 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, and optionally hydro-isomerized. In some
embodiments, the fuel used in the present invention is a diesel
fuel, a biodiesel fuel, or combinations thereof.
[0056] Suitable fuels also include heavier fuel oils, such as
number 5 and number 6 fuel oils, which are also referred to as
residual fuel oils, heavy fuel oils, and/or furnace fuel oils. Such
fuels may be used alone or mixed with other, typically lighter,
fuels to form mixtures with lower viscosities. Bunker fuels are
also included, which are generally used in marine engines. These
types of fuels have high viscosities and may be solids at ambient
conditions, but are liquid when heated and supplied to the engine
or burner it is fueling.
[0057] The non-hydrocarbon fuel can be an oxygen containing
composition, often referred to as an oxygenate, which includes
alcohols, ethers, ketones, esters of a carboxylic acids,
nitroalkanes, or mixtures thereof. Non-hydrocarbon fuels can
include 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.
[0058] Mixtures of hydrocarbon and non-hydrocarbon 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 and other bio-derived fuels. In one
embodiment the liquid fuel is an emulsion of water in a hydrocarbon
fuel, a non-hydrocarbon fuel, or a mixture thereof.
[0059] In several embodiments of this invention the liquid fuel can
have a sulphur content on a weight basis that is 50,000 ppm or
less, 5000 ppm or less, 1000 ppm or less, 350 ppm or less, 100 ppm
or less, 50 ppm or less, or 15 ppm or less.
[0060] The liquid fuel of the invention is present in a fuel
composition in a major amount that is generally greater than 95% by
weight, and in other embodiments is present at greater than 97% by
weight, greater than 99.5% by weight, greater than 99.9% by weight,
or greater than 99.99% by weight.
b. Additive Concentrate Compositions
[0061] Additive concentrates are compositions that contain one or
more additives and which may also contain some amount of fuel, oil,
or a diluent of some type. These concentrates can then be added to
other compositions as a convenient way to handle and deliver the
additives, resulting in the final compositions such as the fuel
compositions described above.
[0062] The additive concentrate compositions of the present
invention contain one or more of the quaternized detergents
described above and an optional diluent, which may be any of the
fuels described above, a solvent, a diluent oil, or similar
material. These compositions may also contain one or more of the
additional additives described below.
c. Optional Additional Additives
[0063] The compositions of the present invention include the
quaternized detergents 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.
[0064] Although any of the additional performance additives
described herein can be used in any of the compositions of the
invention, the following additional additives are particularly
useful for fuel 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.
[0065] 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 demulsifiers include for example
polyalkoxylated alcohols. Suitable lubricity agents include for
example fatty carboxylic acids. Suitable metal deactivators include
for example aromatic triazoles or derivatives thereof, including
but not limited to benzotriazole. 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-triflouropropylmethyl 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.
[0066] The additional performance additives, which may be present
in the compositions of the invention, also include di-ester,
di-amide, ester-amide, and ester-imide friction modifiers prepared
by reacting a dicarboxylic acid (such as tartaric acid) and/or a
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.
[0067] 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. 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. 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.
[0068] 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.
[0069] The compositions of the invention may include a detergent
additive, different from the quaternized salt additive of the
invention. 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.
[0070] 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.
[0071] Antioxidants encompass phenolic antioxidants, which may
comprise a butyl substituted phenol containing 2 or 3 t-butyl
groups. The para position may also be occupied by a hydrocarbyl
group or a group bridging two aromatic rings. The latter
antioxidants are described in greater detail in U.S. Pat. No.
6,559,105. Antioxidants also include aromatic amines, such as
nonylated diphenylamine. Other antioxidants include sulfurized
olefins, titanium compounds, and molybdenum compounds. U.S. Pat.
No. 4,285,822, for instance, discloses lubricating oil compositions
containing a molybdenum and sulfur containing composition. Typical
amounts of antioxidants will, of course, depend on the specific
antioxidant and its individual effectiveness, but illustrative
total amounts can be 0.01 to 5, or 0.15 to 4.5, or 0.2 to 4 percent
by weight. Additionally, more than one antioxidant may be present,
and certain combinations of these can be synergistic in their
combined overall effect.
[0072] Viscosity improvers (also sometimes referred to as viscosity
index improvers or viscosity modifiers) may be included in the
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.
[0073] Multifunctional viscosity improvers, which also have
dispersant and/or antioxidancy properties are known and may
optionally be used. 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.
[0074] 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 compositions of the invention are free of
phosphorus-containing antiwear/extreme pressure agents.
[0075] Any of the additional performance additives described above
may be added to the compositions of the present invention. Each may
be added directly to the additive and/or the compositions of the
present invention, but they are generally mixed with the additive
to form an additive composition, or concentrate, which is then
mixed with fuel to result in a fuel composition. These various
types of compositions are described in more detail above. The
amount of additional additives in the present composition can
typically be 1 to 10 weight percent, or 1.5 to 9.0 percent, or 2.0
to 8.0 percent, all expressed on an oil-free basis.
The Process of Preparing the Quaternized Salt Detergent
[0076] The present invention provides a process of preparing
quaternized amide and/or ester detergent where the process
includes: reacting (a) a polyester containing a tertiary amino
group; and (b) quaternizing agent suitable for converting the
tertiary amino group to a quaternary nitrogen, thereby obtaining
the quaternized dispersant.
[0077] As described above the quaternizing agent may be selected
from the group consisting of dialkyl sulfates, benzyl halides,
hydrocarbyl substituted carbonates; hydrocarbyl epoxides in
combination with an acid or mixtures thereof.
[0078] The processes of the present invention may also be described
as a process for preparing a quaternized detergent comprising the
steps of: (1) mixing (a) a polyester containing a tertiary amino
group, (b) a quaternizing agent and optionally (c) a protic
solvent; (2) heating the mixture to a temperature between
50.degree. C. to 130.degree. C.; and (3) holding for the reaction
to complete; thereby obtaining the quaternized detergent. In one
embodiment the reaction is carried out at a temperature of less
than 80.degree. C., or less then 70.degree. C. In other embodiments
the reaction mixture is heated to a temperature of about 50.degree.
C. to 120.degree. C., 80.degree. C., or 70.degree. C. In still
other embodiments the reaction temperature may be 70.degree. C. to
130.degree. C. In other embodiments the reaction temperature may be
50.degree. C. to 80.degree. C. or 50.degree. C. to 70.degree.
C.
[0079] In some embodiments the processes of the present invention
are free of the addition of any acid reactant, such as acetic acid.
The salt product is obtained in these embodiments despite the
absence of the separate acid reactant.
[0080] As described above, in some embodiments the non-quaternized
polyester containing a tertiary amino group is the condensation
product of a fatty carboxylic acid containing at least one hydroxyl
group and a compound having an oxygen or nitrogen atom capable of
condensing with said acid and further having a tertiary amino
group, thereby obtaining the polyester containing a tertiary amino
group. In some embodiments the compound having an oxygen or
nitrogen atom capable of condensing with said acid and further
having a tertiary amino group is a diamine containing a tertiary
amino group and a primary or secondary amino group.
[0081] The additives of the present invention may be derived in the
presence of a protic solvent. Suitable protic solvents include
solvents that have dielectric constants of greater than 9. In one
embodiment the protic solvent includes compounds that contain 1 or
more hydroxyl (--OH) functional groups, and may include water.
[0082] In one embodiment, the solvents are glycols and glycol
ethers. Glycols containing from 2 to 12 carbon atoms, or from 4 to
10, or 6 to 8 carbon atoms, and oligomers thereof (e.g., dimers,
trimers and tetramers) are generally suitable for use. Illustrative
glycols include ethylene glycol, propylene glycol, diethylene
glycol, dipropylene glycol, 1,4-butanediol,
2-methyl-1,3-propanediol, neopentyl glycol, triethylene glycol,
polyethylene glycol and the like and oligomers and polymeric
derivative and mixtures thereof. Illustrative glycol ethers include
the C.sub.1-C.sub.6 alkyl ethers of propylene glycol, ethylene
glycol and oligomers thereof such as di-, tri- and tetra glycol
ethers of methyl, ethyl, propyl, butyl or hexyl. Suitable glycol
ethers include ethers of dipropylene glycol, tripropylene glycol
diethylene glycol, triethylene glycol; ethyl diglycol ether, butyl
diethyleneglycol ether, methoxytriethyleneglycol,
ethoxytriethyleneglycol, butoxytriethyleneglycol,
methoxytetraethyleneglycol, butoxytetraethyleneglycol.
[0083] Suitable solvents for use in the invention also include
alcohols from C1-20 including branched hydrocarbyl alcohols.
Examples of suitable alcohols include 2-methylheptanol,
2-methyldecanol, 2-ethylpentanol, 2-ethylhexanol, 2-ethylnonanol,
2-propylheptanol, 2-butylheptanol, 2-butyloctanol, isooctanol,
dodecanol, cyclohexanol, methanol, ethanol, propan-1-ol,
2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-1-ol, butan-2-ol,
pentanol and its isomers, and mixtures thereof. In one embodiment
the solvent of the present invention is 2-ethylhexanol, 2-ethyl
nonanol, 2-propylheptanol, or combinations thereof. In one
embodiment the solvent of the present invention includes
2-ethylhexanol.
[0084] The solvent can be any of the commercially available
alcohols or mixtures of such alcohols and also includes such
alcohols and mixtures of alcohols mixed with water. In some
embodiments water is the only solvent used. In some embodiments the
amount of water present may be above 1 percent by weight of the
solvent mixture. In other embodiments the solvent mixture may
contain traces of water, with the water content being less than 1
or 0.5 percent by weight.
[0085] The alcohols can be aliphatic, cycloaliphatic, aromatic, or
heterocyclic, including aliphatic-substituted cycloaliphatic
alcohols, aliphatic-substituted aromatic alcohols,
aliphatic-substituted heterocyclic alcohols,
cycloaliphatic-substituted aliphatic alcohols,
cycloaliphatic-substituted aromatic alcohols,
cycloaliphatic-substituted heterocyclic alcohols,
heterocyclic-substituted aliphatic alcohols,
heterocyclic-substituted cycloaliphatic alcohols, and
heterocyclic-substituted aromatic alcohols.
[0086] While not wishing to be bound by theory, it is believed that
a polar protic solvent (which may include water) is required in
order to facilitate the dissociation of the acid into ions and
protons. The dissociation is required to protonate the ion formed
when the detergent having an amine functionality initially reacts
with the quaternizing agent. In the case where the quaternizing
agent is an alkyl epoxide the resulting ion would be an unstable
alkoxide ion. The dissociation also provides a counter ion from the
acid group of the additive that acts to stabilize the quaternary
ammonium ion formed in the reaction, resulting in a more stable
product.
INDUSTRIAL APPLICATION
[0087] In one embodiment, the process of the present invention
produces a quaternized salt detergent. The quaternized detergent
can be used as an additive for use in a fuel for use in an internal
combustion engine and/or an open flame burner.
[0088] The internal combustion engine includes 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,
NOx absorbers and catalysts, catalyzed and non-catalyzed
particulate traps optionally employing fuel-borne catalyst;
variable valve timing; and injection timing and rate shaping.
[0089] The open flame burner burning may be any open-flame burning
apparatus equipped to burn a liquid fuel. These include domestic,
commercial and industrial burners. The industrial burners include
those requiring preheating for proper handling and atomization of
the fuel. Also included are oil fired combustion units, oil fired
power plants, fired heaters and boilers, and boilers for use in
ships and marine applications including deep draft vessels.
Included are boilers for power plants, utility plants, and large
stationary and marine engines. The open-flame fuel burning
apparatus may be an incinerator such as rotary kiln incinerator,
liquid injection kiln, fluidized bed kiln, cement kiln, and the
like. Also included are steel and aluminum forging furnaces. The
open-flame burning apparatus may be equipped with a flue gas
recirculation system.
[0090] 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. As used
herein, the term "hydrocarbonyl group" or "hydrocarbonyl
substituent" means a hydrocarbyl group containing a carbonyl
group.
[0091] 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
[0092] The invention will be further illustrated by the following
examples.
[0093] While the Examples are provided to illustrate the invention,
they are not intended to limit it.
Example A
Non-Quaternized Polyester Amide (Preparatory Material)
[0094] A non-quaternized polyester amide is prepared by reacting,
in a jacketed reaction vessel fitted with stirrer, condenser, feed
pump attached to subline addition pipe, nitrogen line and
thermocouple/temperature controller system, 6 moles of
12-hydroxystearic acid and 1 mole of dimethylaminopropylamine where
the reaction is carried out at about 130.degree. C. and held for
about 4 hours. The reaction mixture is then cooled to about
100.degree. C. and zirconium butoxide is added, in an amount so
that the catalyst makes up 0.57 percent by weight of the reaction
mixture. The reaction mixture is heated to about 195.degree. C. and
held for about 12 hours. The resulting product is cooled and
collected.
Example B
Quaternized Polyester Amide Salt Detergent (Inventive Example)
[0095] A quaternized polyester amide salt detergent is prepared by
reacting, in a jacketed reaction vessel fitted with stirrer,
condenser, feed pump attached to subline addition pipe, nitrogen
line and thermocouple/temperature controller system, 600 grams of
the non-quaternized polyester amide of Example A, 120 grams of
2-ethylhexanol, 18.5 grams of acetic acid, and 32.3 ml of propylene
oxide, where the reaction is carried out at about 75.degree. C. and
the propylene oxide is fed in to the reaction vessel over about 3.5
hours. The reaction mixture is then held at temperature for about 3
hours. 760 grams of product is cooled and collected, which TAN,
FTIR and ESI-MS analysis confirms to be about 80% by weight
quaternized polyester amide salt detergent, with the remaining
material being primarily non-quaternized polyester amide. The
collected material has a TAN of 1.26 mg KOH/gram, a TBN of 23.82 mg
KOH/gram, a kinematic viscosity at 100.degree. C. of 28.58 cSt (as
measured by ASTM D445), an acetate peak by IR at 1574 cm.sup.-1,
and is 1.22% nitrogen.
Example C
Non-Quaternized Polyester Amide (Preparatory Material)
[0096] A non-quaternized polyester amide is prepared by reacting,
in a jacketed reaction vessel fitted with stirrer, condenser, feed
pump attached to subline addition pipe, nitrogen line and
thermocouple/temperature controller system, 1300 grams of
ricinoleic acid and 73.5 grams of dimethylaminopropylamine where
the reaction is carried out at about 130.degree. C., the amine is
added dropwise over about 8 minutes, and the reaction mixture held
for about 4 hours. The reaction mixture is then cooled to about
100.degree. C. and 7.8 grams of zirconium butoxide is added. The
reaction mixture is heated to about 195.degree. C. and held for
about 17 hours. The resulting product is filtered, cooled and
collected. 1301 grams of product is collected which has a TAN of 0
mg KOH/gram and shows by IR an ester peak at 1732 cm.sup.-1, an
amide peak at 1654 cm.sup.-1, but no acid peak at 1700
cm.sup.-1.
Example D
Quaternized Polyester Amide Salt Detergent (Inventive Example)
[0097] A quaternized polyester amide salt detergent is prepared by
reacting, in a jacketed reaction vessel fitted with stirrer,
condenser, feed pump attached to subline addition pipe, nitrogen
line and thermocouple/temperature controller system, 600 grams of
the non-quaternized polyester amide of Example C, 123 grams of
2-ethylhexanol, 18.9 grams of acetic acid, and 33.1 ml of propylene
oxide, where the reaction is carried out at about 75.degree. C. and
the propylene oxide is fed in to the reaction vessel over about 3.5
hours. The reaction mixture is then held at temperature for about 3
hours. 751 grams of product is cooled and collected, which TAN,
FTIR and ESI-MS analysis confirms to be about 70% by weight
quaternized polyester amide salt detergent, with the remaining
material being primarily non-quaternized polyester amide. The
collected material has a TAN of 0 mg KOH/gram, a TBN of 23.14 mg
KOH/gram, a kinematic viscosity at 100.degree. C. of 47.0 cSt (as
measured by ASTM D445), an acetate peak by IR at 1574
cm.sup.-1.
Example E
Non-Quaternized Polyisobutylene Detergent (Comparative Example)
[0098] A non-quaternized polyisobutylene monosuccinimide detergent
is prepared by reacting, in a jacketed reaction vessel fitted with
stirrer, condenser, feed pump attached to subline addition pipe,
nitrogen line and thermocouple/temperature controller system, 100
pbw polyisobutylene succinic anhydride (which is itself prepared
from 1000 number average molecular weight high vinylidene
polyisobutylene and maleic anhydride reaction in a 1:1.2 molar
ratio) 13 pbw tetraethylenepentamine, where the anhydride is
preheated to about 80.degree. C., the amine is added to the system
over about 8 hours, where the reaction mixture temperature is kept
below 120.degree. C. The reaction mixture is then heated to
170.degree. C. and then vacuum stripped. The resulting
non-quaternized polyisobutylene monosuccinimide detergent is cooled
and collected.
Example F
Quaternized Polyisobutylene Detergent (Comparative Example)
[0099] A quaternized polyisobutylene succinimide detergent is
prepared by reacting, in a jacketed reaction vessel fitted with
stirrer, condenser, feed pump attached to subline addition pipe,
nitrogen line and thermocouple/temperature controller system, 100
pbw polyisobutylene succinic anhydride (which is itself prepared
from 1000 number average molecular weight high vinylidene
polyisobutylene and maleic anhydride reaction in a 1:1.2 molar
ratio) 10.9 pbw dimethylaminopropylamine, where the anhydride is
preheated to about 80.degree. C., the amine is added to the system
over about 8 hours, where the reaction mixture temperature is kept
below 120.degree. C. The reaction mixture is then heated to
150.degree. C. and held for 3 hours, resulting in a non-quaternized
polyisobutylene succinimide detergent. 40.6 pbw 2-ethylhexanol, 1
pbw water, 5.9 pbw acetic acid is then added to the non-quaternized
polyisobutylene succinimide detergent. After a 3 hour hold 8.5 pbw
propylene oxide is added with the reaction being held at 75.degree.
C. for about 6 hours. The resulting quaternized polyisobutylene
succinimide detergent is cooled and collected.
XUD-9 Engine Testing
[0100] The Peugot XUD-9 engine in an indirect injection engine. In
the test the percent flow remaining in the fuel injector is
measured at the end of the test, with higher percent flow remaining
being desired, as indicative of reduced injector deposit formation.
Separate XUD-9 engine tests were performed on a fuel composition
containing Example B, a fuel composition containing Example F, and
a fuel composition contain Example E. Each composition uses the
same base fuel and contains 71 ppm of the additive being evaluated.
The base fuel is known to give a percent remaining flow of less
than 20% when tested alone. The results obtained are as
follows:
TABLE-US-00001 TABLE 1 XUD-9 Engine Test Results Fuel Percent Flow
Sample Additive Evaluated Remaining 1 Inventive Example B 84 2
Comparative Example F 100 3 Comparative Example E 36
[0101] The results show that the Inventive Example B additive
performs about as well as the quaternized polyisobutylene
succinimide detergent of Example F and much better than the
non-quaternized polyisobutylene succinimide detergent of Example E.
All of the examples perform better than the base fuel alone,
however the additives of Examples B and F perform significantly
better that the base fuel.
[0102] As discussed herein, the comparable XUD-9 engine test
performance delivered by Inventive Example B and Comparative
Example F is important when one then considers the superior
viscosity and materials handling properties of Inventive Example B,
further demonstrated below.
DW-10 Engine Testing
[0103] The DW-10 screen test uses the Coordinating European
Council's (CEC) F-98-08 testing protocol, which utilizes a Peugeot
DW-10 engine. This is a light duty direct injection, common rail
engine test that measures engine power loss, which relates to fuel
detergent additive efficiency. Lower power loss values indicate
better detergent performance. The test engine is representative of
new engines coming into the market.
[0104] Each composition uses the same base fuel and contains 71
ppm, on an actives basis, of the additive being evaluated. The
results obtained are as follows:
TABLE-US-00002 TABLE 2 DW-10 Engine Test Results Fuel Sample
Additive Evaluated Percent Power Change at EOT 4 None - Base Fuel
alone -5.1% 5 Inventive Example B +2.1% 6 Inventive Example D +1.1%
7 Comparative Example E -3.4% 8 Comparative Example F +2.0%
[0105] The results show that the Inventive Example B and D
additives performs about as well as the quaternized polyisobutylene
succinimide detergent of Example F and much better than the
non-quaternized polyisobutylene succinimide detergent of Example E.
All of the examples perform better than the base fuel alone,
however the additives of Examples B, D and F perform significantly
better that the base fuel.
[0106] As discussed herein, the comparable DW-10 engine performance
delivered by Inventive Examples B, D and Comparative Example F is
important when one then considers the superior viscosity and
materials handling properties of Inventive Examples B and D,
further demonstrated below.
Viscometric & Materials Handling Properties
[0107] Material handling properties, which may be evaluated by
considering the kinematic viscosity of a material, significantly
impact how easily a material may be used in commercial products
and/or the amount of diluent that needs to be added to make the
materials sufficiently handle-able, adding cost, complexity and
waste to the overall process. Generally speaking, the lower the
viscosity at 100.degree. C. the better the material handling
properties. For a proper comparison, the kinematic viscosities of
materials should be compared at an equal actives level, that is,
with the same amount of diluent oil and similar materials
present.
[0108] To this end, Examples B, D and F were tested for viscosity
at their original actives levels, about 85% actives for Example B
and D, and about 75% actives for Example F. Examples B and D were
also tested for viscosity at 75% actives, all on a weight basis, to
allow for a better comparison to Example F. The reduced actives
samples are prepared by mixing the example additive with an
appropriate amount of 2-ethylhexanol. The viscosities of these
blends were then determined using ASTM D445. The results obtained
are presented below:
TABLE-US-00003 TABLE 3 Viscometric Data KV100 (cSt) KV100 (cSt) at
about 85% actives at about 75% actives Example (15% diluent) (25%
diluent) B 79 23 D 47 39 F 100
[0109] The results show that Inventive Examples B and D have a
significantly lower kinematic viscosity at 100.degree. C. compared
to Comparative Example F, where the samples are considered at an
actives level of 75%. These results indicate that the Inventive
Samples have significantly better material handling properties and
could be more easily utilized in higher concentrations without
handling problems compared to the additives of Comparative Examples
E and F.
Example G
Quaternized Polyester Amide Salt Detergent (Inventive Example)
[0110] A quaternized polyester amide salt detergent is prepared by
reacting, in a jacketed reaction vessel fitted with stirrer,
condenser, feed pump attached to subline addition pipe, nitrogen
line and thermocouple/temperature controller system, 3501 grams of
the non-quaternized polyester amide of Example A, 80.4 grams of
acetic acid, 24.5 grams of water, and 141.3 ml of propylene oxide,
where the reaction is carried out at about 75.degree. C. and the
propylene oxide is fed in to the reaction vessel over about 4 hours
with moderate stirring. The reaction mixture is then held at
temperature for about 3 hours. 3710.5 grams of product is cooled
and collected, which TAN, FTIR and ESI-MS analysis confirms to be
>90% by weight quaternized polyester amide salt detergent, with
the remaining material being primarily non-quaternized polyester
amide. The collected material has a TAN of 0 mg KOH/gram, a TBN of
27.76 mg KOH/gram, a kinematic viscosity at 100.degree. C. of 327.4
cSt (as measured by ASTM D445), an acetate peak by IR at 1575
cm.sup.-1, and is 1.42% nitrogen.
Example H
Quaternized Polyester Amide Salt Detergent (Inventive Example)
[0111] A quaternized polyester amide salt detergent is prepared by
reacting, in a jacketed reaction vessel fitted with stirrer,
condenser, feed pump attached to subline addition pipe, nitrogen
line and thermocouple/temperature controller system, 3401 grams of
the non-quaternized polyester amide of Example C, 107.3 grams of
acetic acid, 32.0 grams of water, and 1875.1 ml of propylene oxide,
where the reaction is carried out at about 75.degree. C. and the
propylene oxide is fed in to the reaction vessel over about 3.5
hours with moderate stirring. The reaction mixture is then held at
temperature for about 3 hours. 3687.8 grams of product is cooled
and collected, which TAN, FTIR and ESI-MS analysis confirms to be
>90% by weight quaternized polyester amide salt detergent, with
the remaining material being primarily non-quaternized polyester
amide. The collected material has a TAN of 0 mg KOH/gram, a TBN of
26.4 mg KOH/gram, a kinematic viscosity at 100.degree. C. of 201.3
cSt (as measured by ASTM D445), an acetate peak by IR at 1574
cm.sup.-1, and is 1.33% nitrogen.
[0112] 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." Except where otherwise indicated,
all numerical quantities in the description specifying amounts or
ratios of materials are on a weight basis. Unless otherwise
indicated, each chemical or composition referred to herein should
be interpreted as being a commercial grade material which may
contain the isomers, by-products, derivatives, and other such
materials which are normally understood to be present in the
commercial grade. However, the amount of each chemical component is
presented exclusive of any solvent or diluent oil, which may be
customarily present in the commercial material, unless otherwise
indicated. It is to be understood that the upper and lower amount,
range, and ratio limits set forth herein may be independently
combined. Similarly, the ranges and amounts for each element of the
invention can be used together with ranges or amounts for any of
the other elements. As used herein, the expression "consisting
essentially of permits the inclusion of substances that do not
materially affect the basic and novel characteristics of the
composition under consideration.
* * * * *