U.S. patent application number 14/120300 was filed with the patent office on 2014-11-20 for fuel additive composition.
The applicant listed for this patent is BASF SE. Invention is credited to Alex ATTLESEY, Thomas E. HAYDEN, Alfred K. JUNG, Peter SCHREYER, Ludwig VOELKEL, Marc WALTER, Stephen M. ZELD.
Application Number | 20140338253 14/120300 |
Document ID | / |
Family ID | 50933472 |
Filed Date | 2014-11-20 |
United States Patent
Application |
20140338253 |
Kind Code |
A1 |
JUNG; Alfred K. ; et
al. |
November 20, 2014 |
Fuel additive composition
Abstract
A fuel additive composition includes a polyalkenylsuccinimide, a
mono or polyfunctional polyisobutene amine, and a carrier oil
selected from the group of mineral oils, polyethers,
polyetheramines, esters, and combinations thereof. The
polyalkenylsuccinimide includes the reaction product of a
hydrocarbyl dicarboxylic acid producing reaction intermediate and a
nucleophilic reactant. The hydrocarbyl dicarboxylic acid producing
reaction intermediate includes the reaction product of a polyolefin
comprising C.sub.2 to C.sub.18 olefin units and having a number
average molecular weight (M.sub.n) of about 500 to 5,000 g/mol and
a C.sub.4 to C.sub.10 monounsaturated acid reactant. The
hydrocarbyl dicarboxylic acid producing reaction intermediate
includes from 0.5 to 10 dicarboxylic acid producing moieties per
molecule of the polyolefin. The nucleophilic reactant is selected
from the group of amines, alcohols, amino alcohols, and
combinations thereof.
Inventors: |
JUNG; Alfred K.; (Carmel,
NY) ; WALTER; Marc; (Frankenthal, DE) ;
VOELKEL; Ludwig; (Limburgerhof, DE) ; SCHREYER;
Peter; (Weinheim, DE) ; ZELD; Stephen M.;
(Wyandotte, MI) ; ATTLESEY; Alex; (Bad Duerkheim,
DE) ; HAYDEN; Thomas E.; (Wappingers Falls,
NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Family ID: |
50933472 |
Appl. No.: |
14/120300 |
Filed: |
May 14, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61823083 |
May 14, 2013 |
|
|
|
Current U.S.
Class: |
44/347 |
Current CPC
Class: |
C10L 1/224 20130101;
C10L 1/232 20130101; C10L 1/14 20130101; C10L 2230/22 20130101;
C10L 1/2437 20130101; C10L 2250/08 20130101; C10L 2270/023
20130101; C10L 1/1985 20130101; C10L 1/2383 20130101; C10L 2290/24
20130101 |
Class at
Publication: |
44/347 |
International
Class: |
C10L 1/232 20060101
C10L001/232 |
Claims
1. A fuel additive composition comprising: (A) a
polyalkenylsuccinimide comprising the reaction product of; (1) a
hydrocarbyl dicarboxylic acid producing reaction intermediate
comprising the reaction product of; (a) a polyolefin comprising
C.sub.2 to C.sub.18 olefin units and having a number average
molecular weight (M.sub.n) of about 500 to 5,000 g/mol, and (b) a
C.sub.4 to C.sub.10 monounsaturated acid reactant, wherein said
hydrocarbyl dicarboxylic acid producing reaction intermediate
includes from 0.5 to 10 dicarboxylic acid producing moieties per
molecule of said polyolefin; and (2) a nucleophilic reactant
selected from the group of amines, alcohols, amino alcohols, and
combinations thereof; (B) a mono or polyfunctional polyisobutene
amine; and (C) a carrier oil selected from the group of mineral
oils, polyethers, polyetheramines, esters, and combinations
thereof.
2. A fuel additive composition as set forth in claim 1 further
comprising (D) a demulsifier package.
3. A fuel additive composition as set forth in claim 2 wherein said
demulsifier package (D) comprises a demulsifier selected from a
salt of a fatty acid, an alkyl amino carboxylic acid, an organo
sulfur compound, a polyetherol, and combinations thereof.
4. A fuel additive composition as set forth in claim 3 wherein said
polyetherol is selected from alkoxylated alkyl phenol resins,
alkoxylated alkyl phenol formaldehyde resins, alkoxylated epoxy
resins, alkoxylated polyethyleneimines, amine alkoxylates,
ethoxlyated polyetherols, propoxylated polyetherols,
ethoxylated-propoxylated polyetherols, and combinations
thereof.
5. A fuel additive composition as set forth in claim 4 wherein said
polyetherol is a block copolymer.
6. A fuel additive composition as set forth in claim 4 wherein said
polyetherol is a random copolymer.
7. A fuel additive composition as set forth in claim 2 wherein said
demulsifier package (D) is substantially free of sulfur.
8. A fuel additive composition as set forth in claim 2 wherein said
organo sulfur compound comprises a sulfonic acid.
9. A fuel additive composition as set forth in claim 1 wherein said
polyolefin (a) is a first reactive polyisobutene having a content
of terminal double bonds of greater than 50 mol %.
10. A fuel additive composition as set forth in claim 1 wherein
said C4 to C10 monounsaturated acid reactant (b) is selected from
the group of maleic acid, maleic anhydride, functional derivatives
thereof, and combinations thereof.
11. A fuel additive composition as set forth in claim 1 wherein
said hydrocarbyl dicarboxylic acid producing reaction intermediate
(1) is a polyalkenylsuccinic anhydride.
12. A fuel additive composition as set forth in claim 1 wherein
said hydrocarbyl dicarboxylic acid producing reaction intermediate
(1) is a polyisobutenylsuccinic anhydride.
13. A fuel additive composition as set forth in claim 1 wherein
said nucleophilic reactant (2) comprises
tetraethylenepentamine.
14. A fuel additive composition as set forth in claim 1 wherein
said nucleophilic reactant (2) is a C.sub.2 to C.sub.40
polyalkylene polyamine which includes from 2 to 9 nitrogen atoms
per molecule and wherein 0.1 to 3.0 mol of dicarboxylic acid
moieties are reacted per equivalent of nucleophilic reactant to
form said polyalkenylsuccinimide (A).
15. A fuel additive composition as set forth in claim 1 wherein
said polyalkenylsuccinimide (A) is the reaction product of said
reaction intermediate (1) which is further defined as a
polyisobutylene of having a number average molecular weight
(M.sub.n) of about 500 to 5,000 molecular weight substituted with
succinic anhydride moieties, and said nucleophilic reactant (2)
which is further defined as a C.sub.2 to C.sub.40 polyalkylene
polyamine which includes from 3 to 9 nitrogen atoms per
molecule.
16. A fuel additive composition as set forth in claim 1 wherein
said polyalkenylsuccinimide (A) comprises the reaction product of:
(1) a polyisobutenylsuccinic anhydride; and (2) a first amine;
wherein said polyisobutenylsuccinic anhydride is first reacted with
an alcohol, then reacted with said first amine to form said
polyisobutenylsuccinimide, and wherein said alcohol, which is
either unreacted or cleaved, is optionally removed.
17. A fuel additive composition as set forth in claim 16 wherein
said alcohol is selected from the group consisting of monohydric
alcohols of the formula R.sup.1OH, where R.sup.1 is straight-chain
or branched, cyclic or branched cyclic alkyl of 1 to 16 carbon
atoms, and combinations thereof.
18. A fuel additive composition as set forth in claim 16 wherein
said first amine has the following formula:
H.sub.2N(CH.sub.2).sub.x--NH--[(CH.sub.2).sub.y--NH].sub.z--(CH.sub.2).su-
b.x--NH.sub.2 where x and y are each independently an integer from
1 to 5 and z is an integer from 0 to 8, or mixtures thereof.
19. A fuel additive composition as set forth in claim 1 wherein
said polyalkenylsuccinimide (A) has the following general
structure: (A) a polyisobutenylsuccinimide having the following
structure; ##STR00004## wherein m is an integer of from 2-80.
20. A fuel additive composition as set forth in claim 1 wherein
said mono or polyfunctional polyisobutene amine (B) comprises a
reaction product formed via hydroformylation of a second reactive
polyisobutene having a content of terminal double bonds of greater
than 50 mol % to form an oxo intermediate and subsequent reductive
amination of said oxo intermediate.
21. A fuel additive composition as set forth in claim 1 wherein
said mono or polyfunctional polyisobutene amine (B) comprises the
reaction product of a second reactive polyisobutene having a
content of terminal double bonds of greater than 50 mol % and a
second amine having the following formula; HNR.sup.2R.sup.3 wherein
R.sup.2 and R.sup.3 are each independently H, a
C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.4-C.sub.18-cycloalkyl, C.sub.1-C.sub.18-alkylaryl,
hydroxy-C.sub.1-C.sub.18-alkyl, poly(oxyalkyl), polyalkylene
polyamine or a polyalkylene amine radical; or, together with the
nitrogen atom to which they are bonded, form a heterocyclic
ring.
22. A fuel additive composition as set forth in claim 20 wherein
said second reactive polyisobutene has a dispersity of less than
6.
23. A fuel additive composition as set forth in claim 20 wherein
said second reactive polyisobutene has a number average molecular
weight (M.sub.n) of from 500 to 5,000 g/mol.
24. A fuel additive composition as set forth in claim 1 wherein
said carrier oil (C) comprises a propoxylate carrier oil having the
following formula: R.sup.4-[O--CH.sub.2--CH(CH.sub.3)].sub.n--OH
wherein n is an integer of from 8 to 35, and R.sup.4 is
straight-chain or branched C.sub.8-C.sub.18-alkyl or
C.sub.8-C.sub.18-alkenyl.
25. A fuel additive composition as set forth in claim 1 wherein
said carrier oil (C) comprises propoxylated isotridecanol.
26. A fuel additive composition as set forth in claim 2 comprising
1 to 75 parts by weight of said polyalkenylsuccinimide (A), 5 to 70
parts by weight of said polyisobutene amine (B), 2 to 94 parts by
weight of said carrier oil (C), and less than 5 parts by weight of
said demulsifier package (D), based on 100 parts by weight of said
fuel additive composition.
27. An additivated fuel comprising 10 to 10,000 mg of said fuel
additive composition set forth in claim 1 per 1 kg of fuel.
28. An additivated fuel as set forth in claim 27 in which less than
1.5 mg of sulfur per kg of additivated fuel is contributed by the
fuel additive composition to the additivated fuel.
29. A method of reducing fuel consumption of an internal combustion
engine comprising the step of adding the fuel additive composition
of claim 1 to fuel.
Description
FIELD OF THE DISCLOSURE
[0001] The present disclosure generally relates to a fuel additive
composition for improving the fuel economy of engines and reducing
deposits within these engines. The fuel additive composition
includes a polyalkenylsuccinimide, a polyisobutene amine, and a
carrier oil.
DESCRIPTION OF THE RELATED ART
[0002] Modern vehicles include sophisticated combustion engines,
which optimize combustion, emissions, performance, durability, and
fuel economy. Fuel additive compositions (e.g. gasoline performance
packages), which include fuel economy and additional fuel
additives, such as detergents, can be added to fuel to further
optimize combustion, emissions, performance, durability, and fuel
economy of such engines.
[0003] These engines typically include one or more pistons which
are located inside a cylinder. Fuel and air is introduced into the
cylinder and ignited to move the piston and power the engine. Fuel
economy additives reduce friction between the piston and the
cylinder and thus reduce fuel consumption and improve the fuel
economy of the engine.
[0004] Fuel additive compositions may include fuel additives such
as the reaction products of a carbonic acid or a derivative thereof
and a polyalcohol and/or alkanol amine, and fatty acid amides and
propoxylated fatty acid amides. Fuel additive compositions may also
include various fuel additives such as polyalkene amines and
polyalkenylsuccinimides. Fuel additive compositions may further
include various carrier oils known in the art, including mineral
oils and synthetic oils.
[0005] However, fuel additive compositions comprising fuel
additives such as those set forth above, e.g.
polyalkenylsuccinimide, etc., are generally immiscible with one
another. As such, fuel additive compositions that include such fuel
additives can often be non-homogeneous and non-pumpable or may even
form precipitates, separate into two phases, and/or solidify over
various times and at various temperatures.
[0006] Because it is technically and commercially desirable that
such fuel additive compositions be homogeneous and pumpable over a
broad range of temperatures, even at temperatures as low as
-20.degree. C., solubilizers have been used to improve miscibility
of additives and the homogeneity of fuel additive compositions
formed therefrom. However, these solubilizers are costly and do not
typically contribute to performance improvement of engines. In some
cases these solubilizers can even cause negative side effects such
as poor seal compatibility, oil dilution, and higher levels of
combustion chamber deposits. Such deposits can cause enrichment of
fuel to air ratios in engines which result in increased hydrocarbon
and carbon monoxide emissions, driving problems such as rough
idling and frequent stalling, reduced fuel economy, and decreased
engine life.
[0007] As such, there remains an opportunity to develop improved
fuel additives which are miscible with additional fuel additives,
and also an opportunity to develop fuel additive compositions
formed with the improved fuel additives that are stable over a
broad range of temperatures and conditions and that improve fuel
economy of internal combustion engines.
SUMMARY OF THE DISCLOSURE AND ADVANTAGES
[0008] In some aspects, a fuel additive composition includes a
polyalkenylsuccinimide, a mono or polyfunctional polyisobutene
amine, and a carrier oil selected from the group of mineral oils,
polyethers, polyetheramines, esters, and combinations thereof. The
polyalkenylsuccinimide itself includes the reaction product of a
hydrocarbyl dicarboxylic acid producing reaction intermediate and a
nucleophilic reactant. The hydrocarbyl dicarboxylic acid producing
reaction intermediate includes the reaction product of a polyolefin
comprising C.sub.2 to C.sub.18 olefin units and having a number
average molecular weight (M.sub.n) of about 500 to 5,000 g/mol and
a C.sub.4 to C.sub.10 monounsaturated acid reactant. The
hydrocarbyl dicarboxylic acid producing reaction intermediate
includes from 0.5 to 10 dicarboxylic acid producing moieties per
molecule of the polyolefin. The nucleophilic reactant is selected
from the group of amines, alcohols, amino alcohols, and
combinations thereof.
[0009] The polyalkenylsuccinimide improves the fuel economy of
internal combustion engines when added to fuel yet is miscible with
the polyisobutene amine and the carrier oil included in the fuel
additive compositions. As such, the fuel additive compositions
possess excellent storage stability and remain homogenous over a
wide range of times and temperatures and do not require inclusion
of a solubilizer. Further, the fuel additive compositions can be
added to fuel in minimal amounts to improve fuel economy and reduce
engine deposits and emissions.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0010] In some aspects, the present disclosure provides fuel
additive compositions ("compositions"). The compositions include:
(A) a polyalkenylsuccinimide, (B) a mono or polyfunctional
polyisobutene amine, and (C) a carrier oil. The compositions can be
used in fuels, such as diesel fuels, gasoline, kerosene or middle
distillates, and heating oil, and can also be used as an additive
in lubricants. The compositions can be used as a fully formulated
fuel additive composition, which can be added to fuel to reduce
fuel consumption and thus improve fuel economy of an internal
combustion engine. As a fuel additive, the compositions also reduce
deposits in carburetors, fuel intake systems, and engines, reduce
emissions, and improve engine performance.
The Polyalkenylsuccinimide (A)
[0011] In some embodiments, the polyalkenylsuccinimide (A) includes
the reaction product of: (1) a hydrocarbyl dicarboxylic acid
producing reaction intermediate and (2) a nucleophilic
reactant.
The Hydrocarbyl Dicarboxylic Acid Producing Reaction Intermediate
(A.1)
[0012] In some embodiments, the reaction intermediate (A.1)
includes the reaction product of: (A.1.a) a polyolefin comprising
C.sub.2 to C.sub.18 olefin units and having a number average
molecular weight (M.sub.n) of about 500 to 5,000 g/mol and (A.1.b)
a C.sub.4 to C.sub.10 monounsaturated acid reactant. The polyolefin
(A.1.a) and the C.sub.4 to C.sub.10 monounsaturated acid reactant
(A.1.b) can be reacted by way of various reaction mechanisms under
various conditions to form the reaction intermediate (A.1).
[0013] For example, the reaction intermediate (A.1) can be formed
via an "ene" reaction by heating a mixture of the polyolefin
(A.1.a) and the C.sub.4 to C.sub.10 monounsaturated acid reactant
(A.1.b). In such an "ene" reaction, the polyolefin (A.1.a)
undergoes an addition of the C.sub.4 to C.sub.10 monounsaturated
acid reactant (A.1.b) at a double bond. As another example, the
polyolefin (A.1.a) can be first halogenated, for example,
chlorinated or brominated with from 1 to 8, alternatively from 3 to
7, weight % chlorine or bromine, based on the weight of polyolefin
(A.1.a). By passing the chlorine or bromine through the polyolefin
(A.1.a) at a temperature of from 60 to 160, alternatively from 110
to 130, .degree. C. for from 0.5 to 10, alternatively from 1 to 7,
hours to form a halogenated polyolefin. The halogenated polyolefin
is then reacted with the C.sub.4 to C.sub.10 monounsaturated acid
reactant (A.1.b) at a temperature of from 100 to 250, alternatively
from 180 to 235, .degree. C. for a time of from 0.5 to 10,
alternatively from 3 to 8, hours, to form the reaction intermediate
(A.1).
[0014] The hydrocarbyl dicarboxylic acid producing reaction
intermediate (A.1) can include a polyolefin substituted with
dicarboxylic acid producing moieties. Specifically, the reaction
intermediate (A.1) is, for example, an acid, an anhydride, or ester
which includes a long chain hydrocarbon (polyolefin (A.1.a))
substituted with an average of from 0.5 to 10.0, alternatively from
0.5 to 5, alternatively from 0.7 to 2.0, alternatively from 0.7 to
1.7, alternatively from 0.9 to 1.7, mol of the C.sub.4 to C.sub.10
monounsaturated acid reactant (A.1.b), i.e., dicarboxylic acid
producing moieties, per mol of polyolefin (A.1.a). In one
embodiment, the reaction intermediate (A.1) is a
polyalkenylsuccinic anhydride, e.g. a polyisobutenylsuccinic
anhydride. These functionality ratios of dicarboxylic acid
producing moieties to polyolefin, e.g. 1.2 to 2.0, etc., are based
upon the total amount of polyolefin (A.1.a) that is present in the
resulting product formed in the aforementioned reactions.
The Polyolefin (A.1.a)
[0015] The polyolefin (A.1.a) of the subject disclosure includes
C.sub.2 to C.sub.18, alternatively C.sub.2 to C.sub.10,
alternatively C.sub.2 to C.sub.8, alternatively C.sub.2 to C.sub.6,
olefin units. Non-limiting examples of olefin units include
ethylene, propylene, butylene, isobutylene, pentene, octene-1, and
styrene. In some embodiments, the polyolefin (A.1.a) is a
polyalkene. The polyolefin (A.1.a) can be homopolymer, such as
polyisobutylene, or copolymer of two or more of different olefin
units. Non-limiting examples of copolymers which can be used to
form the polyolefin (A.1.a) include ethylene and propylene,
butylene and isobutylene, propylene and isobutylene. Additional
non-limiting examples of copolymers include copolymers that include
a minor molar amount of olefin units, e.g. 1 to 10 mol %, are
C.sub.4 to C.sub.18 non-conjugated diolefin units such as a
copolymer of isobutylene and butadiene or a copolymer of ethylene,
propylene, and 1,4-hexadiene.
[0016] The polyolefin (A.1.a) can be linear or branched. In some
embodiments, the polyolefin (A.1.a) has a number average molecular
weight (M.sub.n) of from 500 to 5,000, alternatively from 750 to
4,000, alternatively from 1,000 to 3,000, alternatively from 1,000
to 2,000, g/mol.
[0017] The polyolefin (A.1.a) can be saturated or unsaturated. One
non-limiting example of the polyolefin (A.1.a) which is saturated
is an ethylene-propylene copolymer made by a Ziegler-Natta
synthesis using hydrogen as a moderator to control molecular
weight. In some embodiments, the polyolefin (A.1.a) is unsaturated.
In some embodiments, the polyolefin (A.1.a) includes a terminal
double bond.
[0018] To this end, in one embodiment, the polyolefin (A.1.a) is a
first reactive polyisobutene. The first reactive polyisobutene is a
highly reactive polyisobutene which has a high content of terminal
ethylenic double bonds. Terminal double bonds are alpha-olefinic
double bonds, e.g. vinylidene double bonds. The first reactive
polyisobutene can have a content of terminal double bonds of
greater than 50, alternatively greater than 70, alternatively
greater than 75, alternatively greater than 80, alternatively
greater than 85, mol %. The first reactive polyisobutene can have a
uniform polymer backbone which includes greater than 85,
alternatively greater than 90, alternatively greater than 95, % by
weight of isobutene units.
[0019] The first reactive polyisobutene can have a number average
molecular weight (M.sub.n) of from 500 to 5,000, alternatively from
800 to 4,000, alternatively from 800 to 3,000, alternatively from
800 to 2,000, g/mol. The dispersity D (M.sub.w/M.sub.n), i.e., the
quotient of the weight average molecular weight M.sub.w divided
M.sub.n, of the first reactive polyisobutene is less than 7,
alternatively less than 3, alternatively from 1.05 to 7. In some
embodiments, the dispersity D (M.sub.w/M.sub.n) of the first
reactive polyisobutene is less than 3. In some embodiments, the
first reactive polyisobutene has a dispersity of less than 2.0 for
M.sub.n less than or equal to 2,000, and a dispersity of less than
1.5 for M.sub.n less than or equal to 1,000. In some embodiments,
the first reactive polyisobutene is free of organic and inorganic
bases, water, alcohols, ethers, acids and peroxides.
[0020] Suitable non-limiting examples of the first reactive
polyisobutene are commercially available from BASF SE under the
GLISSOPAL.RTM. brand of polyisobutenes.
The C.sub.4 to C.sub.10 Monounsaturated Acid Reactant (A.1.b)
[0021] The C.sub.4 to C.sub.10 monounsaturated acid reactant
(A.1.b) reacts with the polyolefin (A.1.a) to form the reaction
intermediate (A.1). The C.sub.4 to C.sub.10 monounsaturated acid
reactant (A.1.b) is can be an alpha or beta unsaturated C.sub.4 to
C.sub.10 dicarboxylic acid, anhydride or ester thereof.
Non-limiting examples of the C.sub.4 to C.sub.10 monounsaturated
acid reactant (A.1.b) include fumaric acid, itaconic acid, maleic
acid, maleic anhydride, chloromaleic acid, dimethyl fumarate,
chloromaleic an-hydride, and combinations thereof.
[0022] In one embodiment, the C.sub.4 to C.sub.10 monounsaturated
acid reactant (A.1.b) is selected from the group of maleic acid,
maleic anhydride, functional derivatives thereof, and combinations
thereof. As used in the above sentence, the term functional
derivative describes derivatives of maleic acid or maleic anhydride
which react with the polyolefin (A.1.a) to form the same or a
comparable result or product, i.e., the reaction intermediate
(A.1). In the case of maleic acid, functional derivatives include,
for example, monoalkyl maleates, dialkyl maleates, maleyl
dichloride, maleyl dibromide, maleic acid monoalkyl ester
monochloride, or maleic acid monoalkyl ester monobromide. The
alcohol components, in the case of the maleates are, for example,
lower alkyl radicals of, for example, 1 to 6, in particular 1 to 4,
carbon atoms, for example methyl or ethyl. In some embodiments, the
C.sub.4 to C.sub.10 monounsaturated acid reactant (A.1.b) is maleic
anhydride. In one embodiment, maleic anhydride is reacted with the
first reactive polyisobutene to form the reaction intermediate
(A.1) comprising polyisobutenylsuccinic anhydride.
The Nucleophilic Reactant (A.2)
[0023] As set forth above, the polyalkenylsuccinimide (A) includes
the reaction product of the hydrocarbyl dicarboxylic acid producing
reaction intermediate (A.1) and the nucleophilic reactant (A.2). In
some embodiments, the polyalkenylsuccinimide (A) is formed via a
neutralization reaction of the nucleophilic reactant (A.2) with the
hydrocarbyl dicarboxylic acid producing reaction intermediate
(A.1). The nucleophilic reactant (A.2) can be selected from the
group of amines, alcohols, amino alcohols, and combinations
thereof.
[0024] The nucleophilic reactant (A.2) can be a monoamine, an
oligoamine or a polyamine. Since tertiary amines are generally
unreactive with anhydrides, it is desirable to have at least one
primary or secondary amine group on the amine.
[0025] The nucleophilic reactant (A.2) can include an amine having
Formula Ia or Ib immediately below:
##STR00001##
wherein R, R', and R'' are independently selected from the group
consisting of hydrogen, C.sub.1 to C.sub.25 straight or branched
chain alkyl radicals, C.sub.1 to C.sub.12 alkoxy C.sub.2 to C.sub.6
alkylene radicals, C.sub.2 to C.sub.12 hydroxy amino alkylene
radicals, and C.sub.1 to C.sub.12 alkylamino C.sub.2 to C.sub.6
alkylene radicals; each X can be the same or a different number of
from 2 to 6, alternatively from 2 to 4; and Y is a number from 0 to
10, alternatively from 2 to 7, alternatively from 3 to 7.
[0026] In a some embodiments, the nucleophilic reactant (A.2)
includes an amine having Formula II:
H.sub.2N(CH.sub.2).sub.x--NH--[(CH2).sub.y-NH].sub.z--(CH.sub.2).sub.x---
NH.sub.2 (II)
where x and y are each independently an integer from 1 to 5,
alternatively from 2 to 4, and z is an integer from 0 to 8, or
mixtures thereof.
[0027] The nucleophilic reactant (A.2) can include an alkylene
polyamine, such as a methylenepolyamine, ethylenepolyamine,
butylenepolyamine, propylenepolyamine and pentylenepolyamine. In
various embodiments, the alkylene polyamine from 2 to 40,
alternatively from 2 to 20, alternatively from 2 to 12,
alternatively from 2 to 6, total carbon atoms and from 1 to 12,
alternatively from 2 to 12, alternatively from 2 to 9,
alternatively from 3 to 9, nitrogen atoms per molecule. To form the
polyalkenylsuccinimide (A) of such embodiments, from 0.1 to 3.0,
alternatively from 0.1 to 2.0, alternatively from 0.2 to 1.0,
alternatively from 0.2 to 0.6, mol of succinic moieties can be
reacted per equivalent of the nucleophilic reactant (A.2), e.g.
amine, to form the polyalkenylsuccinimide (A).
[0028] The nucleophilic reactant (A.2) can also include a
polyoxyalkylene polyamine, e.g. polyoxyalkylene amines,
polyoxyalkylene diamines, and polyoxyalkylene triamines which have
a number average molecular weight (M.sub.n) of from 200 to about
4000, alternatively from 400 to 2000, g/mol. Non-limiting examples
of polyoxyalkylene polyamines include the polyoxyethylene,
polyoxypropylene diamines, and the polyoxypropylene triamines
having a number average molecular weight (M.sub.n) of from 200 to
2000 g/mol.
[0029] The nucleophilic reactant (A.2) can also include a
hydrocarbyl amine or a hydrocarbyl amine which includes other
functional groups, e.g. hydroxy groups, alkoxy groups, amide
groups, nitriles, imidazoline groups, etc. For example, in one
embodiment, the nucleophilic reactant (A.2) includes a hydrocarbyl
amine with from 1 to 6, alternatively from 1 to 3, hydroxy groups.
Such amines are capable of reacting with the acid or anhydride
groups of the reaction intermediate (A.1) via their amine
functional groups or the other functional groups (described
immediately above). Specific, non-limiting examples of the
nucleophilic reactant (A.2) include hydroxyamines such as
2-amino-1-butanol, 2-amino-2-methyl-1-propanol,
p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol,
3-amino-1-propanol, 2-amino-2-methyl-1,3-propane-diol,
2-amino-2-ethyl-1,3-propanediol,
N-(beta-hydroxy-propyl)-N'-(beta-amino-ethyl)-piperazine,
tris(hydroxy-methyl)amino-methane (also known as
trismethylol-aminomethane), 2-amino-1-butanol, ethanolamine,
beta-(beta-hydroxyethoxy)-ethylamine, and the like.
[0030] The nucleophilic reactant (A.2) can also include an
unsaturated alcohol such as allyl alcohol, cin-namyl alcohol,
propargyl alcohol, 1-cyclohexane-3-ol, and oleyl alcohol. Still
other classes of the alcohols capable of yielding the
polyalkenylsuccinimide (A) of this disclosure include
ether-alcohols and amino-alcohols, e.g. the oxy-alkylene,
oxy-arylene-, amino-alkylene-, and amino-arylene-substituted
alcohols having one or more oxy-alkylene, amino-alkylene or
amino-arylene oxy-arylene radicals exemplified by
N,N,N',N'-tetrahydroxy-trimethylene diamine, and ether-alcohols
having up to about 150 oxy-alkylene radicals in which the alkylene
radical includes from 1 to about 8 carbon atoms.
[0031] Additional non-limiting examples of the nucleophilic
reactant (A.2) include alicyclic diamines such as
1,4-di(aminomethyl)cyclo-hexane, and heterocyclic nitrogen
compounds such as imidazolines, and N-aminoalkyl piperazines.
Specific, non-limiting examples of such amines include 2-pentadecyl
imidazoline, N-(2-aminoethyl) piperazine, combinations thereof.
[0032] In one embodiment, the nucleophilic reactant (A.2) includes
a polyamine selected from the group of ethylenediamine,
triethylenetetramine, propylenediamine, trimethylenediamine,
tripropylenetetramine, tetraethylenepentamine,
hexaethyleneheptamine, pentaethylenehexamine, and combinations
thereof. In this embodiment, the nucleophilic reactant (A.2) can be
the reaction product of ethylene dichloride and ammonia or the
reaction product of an ethyleneimine with a ring-opening agent, for
example water or ammonia.
[0033] In another embodiment, the nucleophilic reactant (A.2)
includes an ethylene polyamine, such as diethylene triamine,
triethylene tetramine, tetraethylene pentamine and pentaethylene
hexamine. In this embodiment, the ethylene polyamine can be the
reaction product of an alkylene chloride with ammonia or an
ethylene imine with ammonia. These reactions result in a mixture of
alkylene polyamines, including cyclic products such as
piperazines.
[0034] Combinations of the various types and embodiments and
examples of the nucleophilic reactant (A.2) referenced above can be
reacted with the reaction intermediate (A.1) to form the
polyalkenylsuccinimide (A).
The Polyalkenylsuccinimide (A)
[0035] The polyalkenylsuccinimide (A) of the subject disclosure is
broadly defined herein to include polyalkenylsuccinimides (e.g.
polyisobutenylsuccinimides), diesters of succinic acids or acidic
esters (e.g. partially esterified succinic acids), and also
partially esterified polyhydric alcohols or phenols, e.g. esters
having free alcohols or phenolic hydroxyl radicals.
[0036] The polyalkenylsuccinimide (A) can be, or include a
polyisobutenylsuccinimide which includes monosuccinimides and
bissuccinimides. A ratio of monosuccinimides to bissuccinimides in
the polyisobutenylsuccinimide can be influenced, for example, by
the varying the molar ratio of the reaction intermediate (A.1),
e.g. polyisobutenylsuccinic anhydride, to the nucleophilic reactant
(A.2), e.g. amine, reacted to form the polyalkenylsuccinimide (A),
e.g. polyisobutenylsuccinimide. The larger the molar amount of the
reaction intermediate (A.1), e.g. polyisobutenylsuccinic, anhydride
in relation to the nucleophilic reactant (A.2), e.g. amine, the
larger the resulting amounts of monosuccinimide, and vice versa. In
order to obtain a higher proportion of monosuccinimide, a molar
ratio of the reaction intermediate (A.1), e.g.
polyisobutenylsuccinic anhydride, to the nucleophilic reactant
(A.2), e.g. amine, of from 0.7 to 1.3, alternatively from 0.9 to
1.1, can be employed. In order to obtain a higher proportion of
bissuccinimide, a molar ratio of the reaction intermediate (A.1),
e.g. polyisobutenylsuccinic anhydride, to the nucleophilic reactant
(A.2), e.g. amine, of from 3 to 18, alternatively from 2.3 to 1.9,
is can be employed. A polyalkenylsuccinimide (A), e.g.
polyisobutenylsuccinimide, having a higher monosuccinimide content
is particularly suitable as an additive for fuels (diesel fuel,
heating oil, gasoline fuel), while a polyalkenylsuccinimide (A),
e.g. polyisobutenylsuccinimide, having a higher content of
bissuccinimides is particularly suitable as an additive for
lubricants.
[0037] To form the polyalkenylsuccinimide (A), the nucleophilic
reactant (A.2), e.g. amines described above, can be reacted with
the reaction intermediate (A.1), e.g. alkenylsuccinic anhydride, by
heating an oil solution including 5 to 95 weight % of the reaction
intermediate (A.1) to a temperature of from 100 to 200,
alternatively from 125 to 175, .degree. C., for a time of from 0.5
to 10, alternatively 1 to 6 hours to remove any residual water and
adding the nucleophilic reactant (A.2). The step of heating the
reaction intermediate (A.1) can facilitate formation of imides or
mixtures of imides and amides, rather than amides and salts. The
reaction ratios of the reaction intermediate (A.1) to equivalents
of amine as well as the other nucleophilic reactants (A.2)
described herein can vary considerably, depending upon the
reactants and type of bonds formed. In some embodiments, from 0.1
to 2.0, alternatively from 0.1 to 2.0, alternatively from 0.2 to
0.6, mol of dicarboxylic acid moiety content (e.g. grafted maleic
anhydride content) is used, per equivalent of nucleophilic reactant
(A.2), e.g. amine. For example, about 0.8 mol of a pentamine
(having two primary amino groups and 5 equivalents of nitrogen per
molecule) can be used to form a mixture of amides and imides, the
product formed by reacting one mol of olefin with sufficient maleic
anhydride to add 1.6 mol of succinic anhydride groups per mol of
olefin, i.e., the pentamine can be used in an amount sufficient to
provide about 0.4 mol (that is 1.6/(0.8.times.5) mol) of succinic
anhydride moiety per nitrogen equivalent of the amine.
[0038] In one embodiment, the polyalkenylsuccinimide (A) is formed
from polyisobutylene substituted with succinic anhydride groups and
reacted with polyethylene amines, e.g. tetraethylene pentamine,
pentaethylene hexamine, polyoxyethylene and polyoxy-propylene
amines, e.g. polyoxypropylene diamine, trismethylolaminomethane and
pentaerythritol, and combinations thereof. As one example, the
polyalkenylsuccinimide (A) can be formed by reacting a
polyisobutene substituted with succinic anhydride groups with a
hydroxy compound, e.g. pentaerythritol, a polyoxyalkylene
polyamine, e.g. polyoxypropylene diamine, and a polyalkylene
polyamine, e.g. polyethylene diamine and tetraethylene
pentamine.
[0039] In another embodiment, the polyalkenylsuccinimide (A)
includes the reaction product of a polyisobutenylsuccinic
anhydride, a first amine, and an alcohol. In this embodiment, the
polyisobutenylsuccinic anhydride, the first amine, and the alcohol
are reacted at a temperature of from 50 to 200, alternatively 80 to
180, alternatively 80 to 160, alternatively 100 to 160, .degree. C.
to form the polyisobutenylsuccinimide.
[0040] The first amine can have the following formula:
H.sub.2N(CH.sub.2).sub.x--NH--[(CH2).sub.y-NH].sub.z--(CH.sub.2).sub.xNH-
.sub.2
where x and y are each independently an integer from 1 to 5,
alternatively from 2 to 4, and z is an integer from 0 to 8, or
mixtures thereof.
[0041] The alcohol is selected from the group consisting of
monohydric alcohols of the formula R.sup.4OH, where R.sup.4 is
straight-chain or branched, cyclic or branched cyclic alkyl of 1 to
16 carbon atoms, and combinations thereof. In many embodiments, the
alcohol is a monohydric alcohol, but polyhydric alcohol is also
suitable. The alcohol is can be a monohydric alcohol of the formula
R.sup.4OH, where R.sup.4 is straight-chain or branched, cyclic or
branched cyclic alkyl of 1 to 16, alternatively 6 to 16, carbon
atoms.
[0042] Specific, non-limiting examples of the alcohol include
methanol, ethanol, n-propanol, isopropanol, cyclopropylcarbinol,
n-butanol, sec-butanol, isobutanol, tert-butanol,
2-hydroxymethylfuran, amyl alcohol, isoamyl alcohol, vinylcarbinol,
cyclohexanol, n-hexanol, 4-methyl-2-pentanol, 2-ethylbutyl alcohol,
sec-capryl alcohol, 2-ethylhexanol, n-decanol, lauryl alcohol,
isocetyl alcohol and mixtures thereof. In one embodiment, the
alcohol is 2-ethylhexanol. Additional specific, non-limiting
examples of the alcohol include phenol, naphthol,
(o,p)-alkylphenols, e.g. di-tert-butylphenol, and salicylic
acid.
[0043] The molar ratio of the polyisobutenylsuccinic anhydride to
the alcohol can vary. It is not necessary to use stoichiometric
amounts of the alcohol, and even comparatively small molar amounts
of the alcohol can be sufficient to form the
polyisobutenylsuccinimide. A example molar ratio of the
polyisobutenylsuccinic anhydride to alcohol is from 10 to 0.5,
alternatively from 4 to 0.8.
[0044] In this embodiment, the polyisobutenylsuccinic anhydride can
be first reacted with the alcohol, then reacted with the first
amine to form the polyisobutenylsuccinimide. More specifically, the
polyisobutenylsuccinic anhydride can be first reacted with the
alcohol to form a second reaction intermediate comprising a
monoester of polyisobutenylsuccinic acid, which is then reacted
with the first amine. In this embodiment, the
polyisobutenylsuccinic anhydride and the alcohol are combined in a
reaction vessel. After the polyisobutenylsuccinic anhydride and the
alcohol react, the first amine can be introduced into the reaction
vessel. After the reaction, any alcohol, which is either unreacted
or cleaved, can be removed in a conventional manner.
[0045] In an embodiment, the second reaction intermediate includes
the reaction product of (1) the first reactive polyisobutene having
a molecular weight M.sub.n of from 500 to 5,000 g/mol and a content
of terminal double bonds of greater than 50, alternatively greater
than 70, mol %, (2) maleic anhydride, and (3) the alcohol selected
from the group consisting of monohydric alcohols of the formula
R.sup.4OH, where R.sup.4 is straight-chain or branched, cyclic or
branched cyclic alkyl of 1 to 16 carbon atoms.
[0046] The second reaction intermediate which is formed during the
formation of the polyisobutenylsuccinimide can, if desired, also be
isolated. The reaction intermediate is not only useful in the
formation of the polyalkenylsuccinimide (A) but, alone or in
combination with other additives, can also be used as additives for
fuels or lubricants.
[0047] Alternatively in this embodiment, isolation of the second
reaction intermediate is not necessary. That is, the
polyisobutenylsuccinic anhydride, the first amine and the alcohol
are reacted simultaneously, i.e., in a single step to from the
polyisobutenylsuccinimide. After the reaction, any alcohol, which
is either unreacted or cleaved, can be removed in a conventional
manner.
[0048] In another embodiment, the polyalkenylsuccinimide (A) can be
the reaction product of (1) the first reactive polyisobutene having
a molecular weight (M.sub.n) of from 500 to 5,000 g/mol and a
content of terminal double bonds of greater than 50, alternatively
greater than 75, mol %, (2) maleic anhydride, and (3) the first
amine (A.2) having the formula:
H.sub.2N(CH.sub.2).sub.x--NH--[(CH2).sub.y-NH].sub.z--(CH.sub.2).sub.xNH-
.sub.2
where x and y are each independently an integer from 1 to 5,
alternatively from 2 to 4, and z is an integer from 0 to 8, or
mixtures thereof.
[0049] In another embodiment, the polyalkenylsuccinimide (A)
includes the reaction product of (1) the first reactive
polyisobutene having a number average molecular weight (M.sub.n) of
from 500 to 5,000 g/mol and a content of terminal double bonds of
greater than 50, alternatively greater than 70, mol %, (2) maleic
anhydride, and (3) a linear, branched, cyclic or cyclic branched
alkylenepolyamine having 1 to 10, alternatively 2 to 4, carbon
atoms in each alkylene group and 1 to 12, alternatively 2 to 12,
alternatively 2 to 9, alternatively 3 to 9, nitrogen atoms, of
which at least one nitrogen atom is present as a primary amino
group, or mixtures thereof, including less than 30% by weight,
based on the total weight of the product, of the corresponding
polyisobutenylsuccinamide.
[0050] In another embodiment, the polyalkenylsuccinimide (A)
includes the reaction product of the reaction intermediate (A.1),
e.g. polyisobutenylsuccinic anhydride, and the nucleophilic
reactant (A.2) comprising a C.sub.2 to C.sub.40, alternatively
C.sub.2 to C.sub.20, alternatively C.sub.2 to C.sub.12 polyalkylene
polyamine which includes from 2 to 12, alternatively 2 to 9,
alternatively 3 to 9, nitrogen atoms per molecule an amine. To form
the polyalkenylsuccinimide (A), e.g. polyisobutenylsuccinimide, of
this embodiment, 0.1 to 3.0, alternatively 0.2 to 1.0,
alternatively 0.2 to 0.6, mol of succinic moieties are reacted per
equivalent of the nucleophilic reactant (A.2), e.g. amine, to form
the polyalkenylsuccinimide (A).
[0051] In some embodiments, the polyalkenylsuccinimide (A) has the
following structure:
##STR00002##
wherein m is an integer of from 2 to 80, alternatively from 2 to
40, alternatively from 2 to 20, alternatively from 6 to 16.
[0052] In some embodiments, the polyalkenylsuccinimide (A) of the
subject disclosure includes a minimal amount of corresponding
amides (polyisobutenylsuccinimide or polyisobutenylsuccinic acid
monoamide). More specifically, the polyalkenylsuccinimide (A) can
include less than 30, alternatively less than 25, alternatively
less than 20, alternatively less than 15, % by weight corresponding
amides, based on the total weight of the polyalkenylsuccinimide
(A), of the corresponding amides. In addition, the
polyalkenylsuccinimide (A) can include no ester fractions, even
when the polyalkenylsuccinimide (A) includes the reaction product
of the reaction intermediate (A.1), the nucleophilic reactant
(A.2), and the alcohol (A.3) and the reaction with the alcohol
(A.3) is carried out in an intermediate stage. Increased purity
(minimal corresponding amides/amide bi-products and lack of ester
fractions) of the polyalkenylsuccinimide (A) can be attributed to
the process by which the polyalkenylsuccinimide (A) is formed.
[0053] In some embodiments the polyalkenylsuccinimide (A) has a
number average molecular weight (M.sub.n) of greater than 500,
alternatively greater than 800, alternatively greater than 1,000,
alternatively from 500 to 5,000, alternatively from 750 to 5,000,
alternatively from 1,000 to 4,000, alternatively from 1,000 to
3,000, g/mol. The higher molecular weight (e.g. M.sub.n>1,000
g/mol) polyalkenylsuccinimide (A) reduces fuel consumption in
internal combustion engines when added to the fuel combusted. That
is, the polyalkenylsuccinimide (A) is an effective fuel economy
additive. In contrast, it is thought that lower molecular weight
(e.g. M.sub.n 300 to 500 g/mol) molecules do not reduce fuel
consumption in internal combustion engines when added to the fuel
combusted. IN some embodiments, a hydrophobic moiety of such
molecules known in the art is typically derived from synthetic or
natural mono or oligo fatty acids with a chain length of typically
C.sub.12 to C.sub.20. In contrast, polyalkenylsuccinimide (A), as
is described above, can be formed from the first reactive
polyisobutene having a chain length of C.sub.40 to C.sub.400,
alternatively from C.sub.40 to C.sub.200 and a number average
molecular weight (M.sub.n) of from 500 to 5,000 g/mol.
[0054] The compositions can be added to fuel in an amount such that
the polyalkenylsuccinimide (A) can be present in the fuel in an
amount of from 10 to 500, alternatively from 20 to 200,
alternatively from 25 to 75, mg/kg of fuel. Further, the
polyalkenylsuccinimide (A) can be present in the compositions in an
amount of from 1 to 75, alternatively 1 to 50, alternatively 5 to
40, alternatively 4 to 40, alternatively 6 to 45, alternatively 2
to 20, alternatively 4 to 15, alternatively from 5 to 12,
alternatively from 15 to 45, alternatively from 20 to 35, parts by
weight per 100 parts by weight of the composition.
The Polyisobutene Amine (B)
[0055] Referring back, in some embodiments, the compositions also
include the polyisobutene amine (B). The polyisobutene amine (B) as
described herein includes mono and polyfunctional polyisobutene
amines. In some embodiments, the polyisobutene amine (B) includes
the reaction product of (B.1) a second polyolefin and (B.2) a
second amine.
The Second Polyolefin (B.1)
[0056] The second polyolefin (B.1) of the subject disclosure
includes C.sub.2 to C.sub.18, alternatively C.sub.2 to C.sub.10,
alternatively C.sub.2 to C.sub.5, olefin units. Non-limiting
examples of olefin units include ethylene, propylene, butylene,
isobutylene, pentene, octene-1, and styrene. In some embodiments,
the second polyolefin (B.1) is a polyalkene. The second polyolefin
(B.1) can be homopolymer, such as polyisobutylene, or copolymer of
two or more of different olefin units. Non-limiting examples of
copolymers which can be used to form the second polyolefin (B.1)
include ethylene and propylene, butylene and isobutylene, propylene
and isobutylene. Additional non-limiting examples of copolymers
include copolymers that include a minor molar amount of olefin
units, e.g. 1 to 10 mol %, are C.sub.4 to C.sub.18 non-conjugated
diolefin units such as a copolymer of isobutylene and butadiene or
a copolymer of ethylene, propylene, and 1,4-hexadiene.
[0057] The second polyolefin (B.1) can be linear or branched. In
some embodiments, the second polyolefin (B.1) has a number average
molecular weight (M.sub.n) of from 500 to 5,000, alternatively from
750 to 4,000, alternatively from 1,000 to 3,000, alternatively from
1,000 to 2,000, g/mol.
[0058] In some embodiments, the second polyolefin (B.1) is
unsaturated. In a some embodiments, the second polyolefin (B.1)
includes a terminal double bond.
[0059] To this end, in one embodiment, the second polyolefin (B.1)
is a second reactive polyisobutene. The second reactive
polyisobutene can be a highly reactive polyisobutene which has a
high content of terminal ethylenic double bonds. In some
embodiments, the second reactive polyisobutene has a content of
terminal double bonds of greater than 50, alternatively greater
than 70, alternatively greater than 75, alternatively greater than
80, alternatively greater than 85, mol %. The second reactive
polyisobutene can have a uniform polymer backbone which includes
greater than 85, alternatively greater than 90, alternatively
greater than 95, % by weight of isobutene units.
[0060] In some embodiments, the second reactive polyisobutene has a
number average molecular weight (M.sub.a) of from 500 to 5,000,
alternatively from 750 to 4,000, alternatively from 1,000 to 3,000,
alternatively from 1,000 to 2,000, g/mol. The dispersity D
(M.sub.w/M.sub.n), i.e., the quotient of the weight average
molecular weight M.sub.w divided M.sub.n, of the second reactive
polyisobutene is less than 7, alternatively from 1.05 to 7. In one
embodiment, the dispersity D (M.sub.w/M.sub.n) of the second
reactive polyisobutene is less than 3. In some embodiments, a
second reactive polyisobutene has a dispersity of less than 2.0 for
M.sub.n less than or equal to 2,000, and a dispersity of less than
1.5 for M.sub.n less than or equal to 1,000. In some embodiments,
the second reactive polyisobutene is free of organic and inorganic
bases, water, alcohols, ethers, acids and peroxides.
[0061] Suitable non-limiting examples of the second reactive
polyisobutene are commercially available from BASF SE under the
GLISSOPAL.RTM. brand of polyisobutenes.
The Second Amine (B.2)
[0062] As described above, the second polyolefin (B.1) reacts with
the second amine (B.2) to form the polyisobutene amine (B). In some
embodiments, the second amine (B.2) has the following formula:
HNR.sup.1R.sup.2
wherein R.sup.1 and R.sup.2 are each independently H, a
C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.4-C.sub.18-cycloalkyl, C.sub.1-C.sub.18-alkylaryl,
hydroxy-C.sub.1-C.sub.18-alkyl, poly(oxyalkyl), polyalkylene
polyamine, a polyalkylene amine radical, a polyalkylene imine
radical; or, together with the nitrogen atom to which they are
bonded, form a heterocyclic ring.
[0063] Non-limiting examples of C.sub.1-C.sub.18-alkyl radicals
include straight-chain or branched radicals having from 1 to 18
carbon atoms such as methyl, ethyl, iso- or n-propyl, n-, iso-,
sec- or tert-butyl, n- or isopentyl; and also n-hexyl, n-heptyl,
n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl,
n-pentadecyl and n-hexadecyl and n-octadecyl, and also the mono- or
polybranched analogs thereof; and also corresponding radicals in
which the hydrocarbon chain has one or more ether bridges.
[0064] Non-limiting examples of C.sub.2-C.sub.18-alkenyl radicals
include the mono- or polyunsaturated, alternatively mono- or
diunsaturated analogs of the above-mentioned alkyl radicals having
from 2 to 18 carbon atoms, in which the double bonds can be in any
position in the hydrocarbon chain.
[0065] Non-limiting examples of C.sub.4-C.sub.18-cycloalkyl
radicals includes cyclobutyl, cyclopentyl and cyclohexyl, and also
the analogs thereof substituted by from 1 to 3
C.sub.1-C.sub.4-alkyl radicals; the C.sub.1-C.sub.4-alkyl radicals
are, for example, selected from methyl, ethyl, iso- or n-propyl,
n-, iso-, sec- or tert-butyl.
[0066] Non-limiting examples of C.sub.1-C.sub.18-alkylaryl radicals
include the C.sub.1-C.sub.18-alkyl group is as defined above and
the aryl group is derived from a monocyclic or bicyclic fused or
nonfused 4- to 7-membered, in particular 6-membered aromatic or
heteroaromatic group such as phenyl, pyridyl, naphthyl and
biphenyl.
[0067] Non-limiting examples of C.sub.2-C.sub.18-alkenylaryl
radicals include radicals where the C.sub.2-C.sub.18-alkenyl group
is as defined above and the aryl group is as defined above.
Non-limiting examples of hydroxy-C.sub.1-C.sub.18-alkyl radical
include the analogs of the above C.sub.1-C.sub.18-alkyl radicals
which have been mono- or polyhydroxylated, alternatively
monohydroxylated, in particular monohydroxylated in the terminal
position; for example 2-hydroxyethyl and 3-hydroxypropyl.
[0068] Non-limiting examples of a poly(oxyalkyl) radical, e.g. that
can be hydroxylated, include radicals which are obtainable by
alkoxylating the nitrogen atom with from 2 to 10
C.sub.1-C.sub.4-alkoxy groups in which individual carbon atoms can
include hydroxyl groups. Exemplary alkoxy groups include methoxy,
ethoxy and n-propoxy groups.
[0069] Non-limiting examples of a polyalkylene polyamine radical
include radicals of the formula:
Z--(NH--C.sub.1-C.sub.6-alkylene-NH).sub.m--C.sub.1-C.sub.6-alkylene
where m is an integer from 0 to 5, Z is H or a
C.sub.1-C.sub.6-alkyl. The C.sub.1-C.sub.6-alkyl represents
radicals such as methyl, ethyl, iso- or n-propyl, n-, iso-, sec- or
tert-butyl, n- or isopentyl, and also n-hexyl, and
C.sub.1-C.sub.6-alkylene represents the corresponding bridged
analogs of these radicals.
[0070] Non-limiting examples of the polyalkylene imine radical
include radicals comprising from 1 to 10 C.sub.1-C.sub.4-alkylene
imine groups, in particular ethylene imine groups. Examples of a
heterocyclic ring include an optionally substituted 5- to
7-membered heterocyclic ring which is optionally substituted by
from one to three C.sub.1-C.sub.4-alkyl radicals and optionally
bears one further ring heteroatom such as 0 or N.
[0071] Non-limiting examples of compounds of the formula
HNR.sup.1R.sup.2 include: ammonia primary amines such as
methylamine, ethylamine, n-propylamine, isopropylamine,
n-butylamine, isobutylamine, sec-butylamine, tert-butylamine,
pentylamine, hexylamine, cyclopentylamine and cyclohexylamine; and
also primary amines of the formula
CH.sub.3--O--C.sub.2H.sub.4--NH.sub.2,
C.sub.2H.sub.5--O--C.sub.2H.sub.4--NH.sub.2,
CH.sub.3--O--C.sub.3H.sub.6--NH.sub.2,
C.sub.2H.sub.5--O--C.sub.3H--NH.sub.2,
n-C.sub.4H.sub.9--O--C.sub.4H.sub.8--NH.sub.2,
HO--C.sub.2H.sub.4--NH.sub.2, HO--C.sub.3H.sub.6--NH.sub.2 and
HO--C.sub.4H.sub.8--NH.sub.2; secondary amines, for example
dimethylamine, diethylamine, methylethylamine, di-n-propylamine,
diisopropylamine, diisobutylamine, di-sec-butylamine,
di-tert-butylamine, dipentylamine, dihexylamine,
dicyclopentylamine, dicyclohexylamine and diphenylamine; and also
secondary amines of the formula
(CH.sub.3--O--C.sub.2H.sub.4).sub.2NH,
(C.sub.2H.sub.5--O--C.sub.2H.sub.4).sub.2NH,
(CH.sub.3--O--C.sub.3H.sub.6).sub.2NH,
(C.sub.2H.sub.5--O--C.sub.3H.sub.6).sub.2NH,
(n-C.sub.4H.sub.9--O--C.sub.4H.sub.8).sub.2NH,
(HO--C.sub.2H.sub.4).sub.2NH, (HO--C.sub.3H.sub.6).sub.2NH and
(HO--C.sub.4H.sub.8).sub.2NH; heterocyclic amines such as
pyrrolidine, piperidine, morpholine and piperazine, and also their
substituted derivatives such as N--C.sub.1-C.sub.6-alkylpiperazines
and dimethylmorpholine. polyamines, for example
C.sub.1-C.sub.4-alkylenediamines,
di-C.sub.1-C.sub.4-alkylenetriamines,
tri-C.sub.1-C.sub.4-alkylenetetramines and higher analogs;
polyethylene imines, alternatively oligoethylene imines, consisting
of from 1 to 10, alternatively from 2 to 6 ethylene imine units.
Non-limiting examples of polyamines and polyimines are
n-propylenediamine, 1,4-butanediamine, 1,6-hexanediamine,
diethylenetriamine, triethylenetetramine and polyethylene imines,
and also their alkylation products, for example
3-(dimethylamino)-n-propylamine, N,N-dimethylethylenediamine,
N,N-diethylethylenediamine and
N,N,N',N'-tetramethyldiethylenetriamine. Ethylenediamine is yet
another non-limiting example.
The Polyisobutene Amine (B)
[0072] The the mono or polyfunctional polyisobutene amine (B) can
be formed via various reactions under various reaction
conditions.
[0073] For example, in one embodiment, the mono or polyfunctional
polyisobutene amine (B) includes the reaction product of a
halogenated hydrocarbon, e.g. halogenated polyisobutene, and the
second amine described above. More specifically, the halogen atoms
of the hydrocarbon chain are replaced by a polyamine group, while a
hydrogen halide is formed. The hydrogen halide can then be removed
in any suitable way, for example, as a salt with excess polyamine.
The reaction between halogenated hydrocarbon and the second amine
can be effected at elevated temperature in the presence of a
solvent, e.g. a solvent having a boiling point of at least
160.degree. C.
[0074] As another example, the polyisobutene amine (B) can be
formed via alkylation of aliphatic polyamines. For example, the
second amine, e.g. a polyamine, can be reacted with an alkyl or
alkenyl halide. The formation of the alkylated polyamine is
accompanied by the formation of hydrogen halide, which is removed,
for example, as a salt of the starting polyamine which is present
in excess.
[0075] As yet another example, a polyalkene having a terminal
double bond whose beta carbon atoms carries a methyl group, e.g.
the second reactive polyisobutene, can be chlorinated with a
theoretical quantity of chlorine to yield an alpha-polyisobutyl
allyl chloride and beta-polyisobutyl methyallyl chloride, while
hydrochloric acid is split off. During chlorination, side reactions
also produce a quantity of dichloro compound. The second amine,
e.g. a polyamine, is then alkylated with the chlorination compounds
obtained to form polyisobutene amine (B). For example, the first
reactive polyisobutylene is treated with chlorine in an inert
solvent at room temperature and the resulting polyisobutenyl
chloride is converted with tetraethylenepentamine into
monoisobuitenyltetraethyleliepentamine or
diisobutenyltetraethylenepentamine.
[0076] In another embodiment, the polyisobutene amine (B) includes
the reaction product of the second reactive polyisobutene, a second
amine having the following formula;
HNR.sup.2R.sup.3
[0077] wherein R.sup.2 and R.sup.3 are each independently H, a
C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.4-C.sub.18-cycloalkyl, C.sub.1-C.sub.18-alkylaryl,
hydroxy-C.sub.1-C.sub.18-alkyl, poly(oxyalkyl), polyalkylene
polyamine or a polyalkylene amine radical; or, together with the
nitrogen atom to which they are bonded, form a heterocyclic
ring.
[0078] For example, the mono or polyfunctional polyisobutene amine
(B) includes a reaction product formed via hydroformylation of the
second reactive polyisobutene to form an oxo intermediate and
subsequent reductive amination of the oxo intermediate in the
presence of ammonia.
[0079] Specifically, the polyisobutene amine (B) can be formed via
hydroformylation of an appropriate polyalkene, e.g. the second
reactive polyisobutene, with a rhodium or cobalt catalyst in the
presence of CO and H.sub.2 at a temperature of from 80 to
200.degree. C. and CO/H.sub.2 pressures of up to 600 bar and then
subjecting the oxo product to a Mannich reaction or amination under
hydrogenating conditions. The amination reaction can be carried out
at 80 to 200.degree. C. and pressures of equal to or less than 600,
alternatively from 80 to 300, bar.
[0080] In this formation process, it is advantageous to use a
suitable, inert solvent in order to reduce the viscosity of the
reaction mixture. Non-limiting examples of such solvents include
aliphatic, cycloaliphatic, and aromatic hydrocarbons having low
sulfur content. In one embodiment, an aliphatic solvent which is
free of sulfur compounds and include less than 1% of aromatics is
used. Such solvents have the advantage that, at high amination
temperatures, no heat of hydrogenation is liberated and no hydrogen
is consumed. In the amination and hydroformulation reaction, the
solvent content can be from 0 to 70% by weight, depending on the
viscosity of the polymer and of the solvent.
[0081] In this formation process, polybutene conversions of 80 to
90% can readily be achieved. In one embodiment, the second reactive
polybutene comprising equal to or greater than 80% by weight
isobutene and having a number average molecular weight (M.sub.n) of
from 300 to 5000, alternatively from 500 to 2500, g/mol is used. In
this embodiment, the second reactive polybutene has a mean degree
of polymerization P of from 10 to 100 and a content E of double
bonds which are capable of reacting with maleic anhydride is from
60 to 90%. A value E of 100% corresponds to the calculated
theoretical value where each molecule of the butene or isobutene
polymer includes one reactive double bond of this type. The value
is calculated for a reaction of polyisobutene with maleic anhydride
in a weight ratio of 5:1, the stirred mixture being heated for 4
hours at 200.degree. C.
[0082] Independent of how the polyisobutene amine (B) is formed,
the polyisobutene amine (B) of the compositions has excellent low
temperature properties, e.g. a low cloud point, a low pour point,
and is stable when stored at low temperatures. Further, the
polyisobutene amine (B) can function as a detergent in internal
combustion engines when added to the fuel combusted.
[0083] To this end, the compositions can be added to fuel in an
amount such that the polyisobutene amine (B) can be present in the
fuel in an amount of from 20 to 2,000, alternatively from 50 to
1,000, alternatively from 100 to 500, mg/kg of fuel. Further, the
polyisobutene amine (B) can be present in the compositions in an
amount of from 5 to 70, alternatively from 10 to 60, alternatively
from 10 to 40, alternatively from 30 to 60, alternatively from 5 to
35, alternatively from 15 to 25, parts by weight per 100 parts by
weight of the composition.
The Carrier Oil (C)
[0084] Referring back, the compositions also include the carrier
oil (C). One or more different carrier oils can be added to the
compositions, i.e., the carrier oil (C) can include a mixture of
one or more different types of carrier oil. The carrier oil (C) can
include mineral carrier oil, synthetic carrier oil, and
combinations thereof. The carrier oil (C) can include one or more
different carrier oils selected from the group of mineral oils,
polyethers, polyetheramines, and esters. The compositions can
include any carrier oil known in the art, including those carrier
oils not specifically described herein.
[0085] As is set forth above, the compositions can include one or
more mineral carrier oils. Non-limiting examples of mineral carrier
oils include fractions obtained in mineral oil processing, such as
kerosine or naphtha, or brightstock or base oils. Non-limiting
examples of suitable mineral carrier oils include naphthenic or
paraffinic mineral oils having a viscosity of from 2 to 25
mm.sup.2/s at 100.degree. C.
[0086] As is set forth above, the compositions can include one or
more polyether carrier oils. Non-limiting examples of polyether
carrier oils include polyalkylene oxides having a number average
molecular weight (M.sub.n) of equal to or greater than 500 g/mol
and propoxylates. Generally, the polyalkylene oxide carrier oils
are formed by polymerizing one or more alkylene oxides, such as
ethylene oxide (EO), propylene oxide (PO), and/or butylene oxide
(BO) with an initiator in the presence of a catalyst. The initiator
used to form the polyalkylene oxide can be an alkanol, an
alkanediol, an amine, or an alkylphenol. For example, the initiator
can be 1,6-hexanediol, 1,8-octanediol, 2-ethylhexanol,
2-propylhexanol, isotridecanol, isononylphenol, isodecylphenol,
and/or isotridecylamine. The polyalkylene oxides can be linear or
branched and can have a random, repeating, or block structure. One
non-limiting example of a suitable polyether carrier oil is a
polyalkylene oxide formed from 50, alternatively from 8 to 30, mol
of propylene oxide or butylene oxide or of a mixture thereof, per
initiator molecule. Another non-limiting example of a suitable
polyether carrier oil is a propoxylate having the following
formula:
R.sup.4-[O--CH.sub.2--CH(CH.sub.3)].sub.n--OH
wherein n is an integer of from 14 to 17, and R.sup.4 is
straight-chain or branched C.sub.8-C.sub.18-alkyl or
C.sub.8-C.sub.18-alkenyl.
[0087] As is set forth above, the compositions can include one or
more polyetheramine carrier oils. Non-limiting examples of
polyetheramine carrier oils include polyetheramines based on EO,
PO, and/or BO and ammonia or primary or secondary mono- or
polyamines having a number average molecular weight (M.sub.n) of
equal to or greater than 500 g/mol. Such polyetheramines can be
prepared from polyethers by an amination reaction wherein the
terminal hydroxyl group is replaced by an amino group with
elimination of water.
[0088] As is set forth above, the compositions can include one or
more esters of mono- or polycarboxylic acids with alkanols or
polyols carrier oils. Non-limiting examples of such ester carrier
oils include esters of mono- or polycarboxylic acids with alkanols
or polyols having a minimum viscosity of 2 mm.sup.2/s at
100.degree. C., aliphatic or aromatic mono- or polycarboxylic
acids, and C.sub.6 to C.sub.24 ester alcohols or ester polyols,
adipates, phthalates, isophthalates, terephthalates, and
trimellitates of isooctanol, isononanol, isodecanol and of
isotridecanol.
[0089] In some embodiments, the compositions include a propoxylate
carrier oil having the following formula:
R.sup.4-[O--CH.sub.2--CH(CH.sub.3)].sub.n--OH
wherein n is an integer of from 8 to 35, alternatively from 14 to
17, and R.sup.4 is straight-chain or branched
C.sub.8-C.sub.18-alkyl or C.sub.8-C.sub.18-alkenyl.
[0090] In one embodiment, R.sup.4 is straight-chain or branched
alkyl of 10 to 16 carbon atoms, or mixtures thereof. In another
embodiment, R.sup.4 is alkyl of 12 to 14 carbon atoms or is a
mixture of such alkyl radicals. In yet another embodiment, R.sup.4
has 13 carbon atoms.
[0091] In one embodiment, n is an integer from 12 to 18. In another
embodiment, n is an integer from 14 to 17. In yet another
embodiment, n is an integer from 14 to 16. In still yet another
embodiment, n is 15. Of course, the above numerical data for n is
an average value since many preparation methods produce a mixture
of compounds with varying molecular weight distribution.
[0092] In one embodiment, the propoxylate carrier oil has the
formula above wherein n is an integer from 14 to 16, alternatively
15, and R.sup.4 is a branched C.sub.13-alcohol, in particular
C.sub.13-monoalcohol. Branched C.sub.13-alcohols can be obtainable
by oligomerization of C.sub.2-C.sub.6-olefins, in particular
C.sub.3- or C.sub.4-olefins, and subsequent hydroformylation.
[0093] The propoxylate carrier oil of this embodiment is prepared
by reacting an alcohol, as an initiator molecule, with propylene
oxide in the presence of an alkali, e.g. sodium hydroxide solution,
potassium hydroxide solution, sodium methylate, potassium
methylate, or another alkali metal alkoxide, at from 120 to 160,
alternatively from 130 to 160, .degree. C., to give the desired
adducts. After alkoxylation is complete, the propoxylate carrier
oil is freed from the catalyst, for example by treatment with
magnesium silicate. In one embodiment, the propoxylate carrier oil
is propoxylated isotridecanol.
[0094] In a another embodiment, the compositions include a
dialkylphenol-initiated propoxylate carrier oil having the
following formula:
##STR00003##
where R.sup.5 and R.sup.6 independently of one another are each
branched or straight-chain C.sub.6 to C.sub.30 alkyl groups, one of
the two radicals R.sup.7 is methyl and the other is hydrogen and q
is from 1 to 100. This embodiment can also include a
monoalkylphenol-initiated propoxylate carrier oil, this propoxylate
carrier oil represented by the formula above with the proviso that
R.sup.6 is omitted.
[0095] In general, any mixture of the carrier oils described above
can be included in the carrier oil (C) of the compositions. To this
end, in another embodiment, the carrier oil (C) includes a mixture
of polyether carrier oil and ester carrier oil.
[0096] Suitable polyether carrier oils include polyalkylene oxides
having a number average molecular weight (M.sub.n) of equal to or
greater than 500 g/mol. The polyalkylene oxides of this embodiment
can be formed from initiators such as aliphatic and aromatic mono-,
di- or polyalcohols or even amines or amides and alkylphenols. The
polyalkylene oxides of this embodiment can be formed from alkylene
oxides such EO, PO, and BO, but it is also possible to use higher
oxides for forming these polyalkylene oxides.
[0097] Suitable esters carrier oils include esters of aliphatic or
aromatic mono- or polycarboxylic acids with long-chain alcohols,
polyol esters (based for example on neopentyl glycol,
pentaerythritol or trimethylolpropane with corresponding
monocarboxylic acids) and oligomer or polymer esters, for example
those based on dicarboxylic acid, a polyol and a monoalcohol, and
esters of aromatic di-, tri- and tetracarboxylic acids with
long-chain aliphatic alcohols composed solely of carbon, hydrogen
and oxygen, the total number of carbon atoms of the esters being 22
or more and the molecular weight being from 370 to 1500,
alternatively from 414 to 1200, g/mol. Suitable esters can have a
minimum viscosity of 2 mm.sup.2/s at 100.degree. C. In one
embodiment, the ester is an adipate, phthalate, isophthalate,
terephthalate and trimellitate of isooctanol, isononanol,
isodecanol and isotridecanol, and combinations thereof.
[0098] The carrier oil (C) functions to carry the components ((A),
(B), etc.) of the compositions and can also function to reduce
deposits in the region of the intake valves of an engine. To this
end, the compositions can be added to fuel in an amount such that
the carrier oil (C) is typically added to the fuel in an amount of
from 10 to 2,000, alternatively, from 20 to 1,000, alternatively
from 50 to 500, mg/kg of fuel. Further, the carrier oil (C) can be
present in the compositions in an amount of from 2 to 94,
alternatively from 2 to 80, alternatively from 5 to 60,
alternatively from 10 to 30, alternatively from 12 to 18,
alternatively from 5 to 15, alternatively from 2 to 20, parts by
weight per 100 parts by weight of the composition.
Additives
[0099] The compositions can include one or more additives,
differing from components (A) and (B) and (C) described above,
selected from the group of detergents, lubricity additives,
corrosion inhibitors, antioxidants, demulsifiers, metal
deactivators, dehazers, markers, solvents, cetane number improvers,
antifoams, solubilizers, deodorants, dehazers, and other additives.
The compositions can include, but do not require solubilizers.
Solubilizers are materials, known in the art, which improve
miscibility of the components included in the fuel additive
compositions and thus improve the homogeneity of the fuel additive
compositions.
Detergents
[0100] One or more detergents, differing from components (A) and
(B) described above, can be added to the compositions. Suitable
examples include detergents, other than the polyisobutene amine
(B), which have detergent action and/or have valve seat
wear-inhibiting action. Suitable, non-limiting examples of the one
or more detergents include neutral metal sulphonates, phenates and
salicylates, and combinations thereof, which are described
below.
[0101] One suitable detergent is a compound having at least one
hydrophobic hydrocarbon radical having a number average molecular
weight (M.sub.n) of from 85 to 20,000 and at least one polar moiety
selected from: (a) mono- or polyamino groups having up to 6
nitrogen atoms, of which at least one nitrogen atom has basic
properties; (b) nitro groups which can be in combination with
hydroxyl groups; (c) hydroxyl groups in combination with mono- or
polyamino groups, in which at least one nitrogen atom has basic
properties; (d) carboxyl groups or their alkali metal or their
alkaline earth metal salts; (e) sulfonic acid groups or their
alkali metal or alkaline earth metal salts; (f) polyoxy-C.sub.2- to
-C.sub.4-alkylene groups which are terminated by hydroxyl groups,
mono- or polyamino groups, in which at least one nitrogen atom has
basic properties, or by carbamate groups; (g) carboxylic ester
groups; and/or (h) moieties obtained by Mannich reaction of
substituted phenols with aldehydes and mono- or polyamines.
[0102] The hydrophobic hydrocarbon radical in the aforementioned
detergents that improves the solubility of the compositions in the
fuel can have a number average molecular weight (M.sub.n) of from
85 to 20,000, alternatively from 113 to 5,000, alternatively from
300 to 5,000. Example hydrophobic hydrocarbon radicals, especially
in conjunction with the polar moieties (a), (c), (h) and (i),
include polypropenyl, polybutenyl and polyisobutenyl radical each
having number average molecular weight (M.sub.n) of from 300 to
5,000, alternatively from 500 to 2,500, alternatively from 700 to
2,300, g/mol.
[0103] Detergents comprising mono- or polyamino groups (a) can be
polyalkenemono- or polyalkenepolyamines based on polypropene or
conventional, i.e., having predominantly internal double bonds,
polybutene or polyisobutene having number average molecular weight
(M.sub.n) from 300 to 5,000. When polybutene or polyisobutene
having predominantly internal double bonds (usually in the beta and
gamma position) are used as starting materials in the preparation
of the detergents, a possible preparative route is by chlorination
and subsequent amination or by oxidation of the double bond with
air or ozone to give the carbonyl or carboxyl compound and
subsequent amination under reductive (hydrogenating) conditions.
The amines used for the amination can be, for example, ammonia,
monoamines or polyamines, such as dimethylaminopropylamine,
ethylenediamine, diethylenetriamine, triethylenetetramine or
tetraethylenepentamine.
[0104] Detergents comprising monoamino groups (a) can also be the
hydrogenation products of the reaction products of polyisobutenes
having an average degree of polymerization P of from 5 to 100 with
nitrogen oxides or mixtures of nitrogen oxides and oxygen.
Detergents comprising monoamino groups (a) can also be compounds
obtainable from polyisobutene epoxides by reaction with amines and
subsequent dehydration and reduction of the amino alcohols.
[0105] Detergents comprising nitro groups (b) which can be in
combination with hydroxyl groups, can be reaction products of
polyisobutenes having an average degree of polymerization P of from
5 to 100 or from 10 to 100 with nitrogen oxides or mixtures of
nitrogen oxides and oxygen. These reaction products are generally
mixtures of pure nitropolyisobutenes (e.g.
alpha,beta-dinitropolyisobutene) and mixed
hydroxynitropolyisobutenes (e.g.
alpha-nitro-beta-hydroxypolyisobutene).
[0106] Detergents comprising hydroxyl groups in combination with
mono- or polyamino groups (c) can be reaction products of
polyisobutene epoxides obtainable from polyisobutene having
terminal double bonds and number average molecular weight (M.sub.n)
from 300 to 5,000, with ammonia or mono- or polyamines.
[0107] Detergents comprising carboxyl groups or their alkali metal
or alkaline earth metal salts (d) can be copolymers of C.sub.2 to
C.sub.40 olefins with maleic anhydride which have a total molar
mass of from 500 to 20,000 and of whose carboxyl groups some or all
have been converted to the alkali metal or alkaline earth metal
salts and any remainder of the carboxyl groups has been reacted
with alcohols or amines. Such detergents can prevent valve seat
wear and can be used in combination with the polyisobutene amine
(B).
[0108] Detergents comprising sulfonic acid groups or their alkali
metal or alkaline earth metal salts (e) can be alkali metal or
alkaline earth metal salts of an alkyl sulfosuccinate. Such
detergents also can prevent valve seat wear and can be used in
combination with the polyisobutene amine (B).
[0109] Detergents comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties (f) can be polyethers or polyether amines which are
obtainable by reaction of C.sub.2- to C.sub.60-alkanols, C.sub.6-
to C.sub.30-alkanediols, mono- or di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group and, in the case of the polyether amines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. In the case of polyethers, such products can also have
carrier oil properties. Examples of these detergents include
tridecanol butoxylates, isotridecanol butoxylates, isononylphenol
butoxylates and polyisobutenol butoxylates and propoxylates and
also the corresponding reaction products with ammonia.
[0110] Detergents comprising carboxylic ester groups (g) can be
esters of mono-, di- or tricarboxylic acids with long-chain
alkanols or polyols, in particular those having a minimum viscosity
of 2 mm.sup.2/s at 100.degree. C. The mono-, di- or tricarboxylic
acids used can be aliphatic or aromatic acids, and particularly
suitable ester alcohols or ester polyols are long-chain
representatives having, for example, from 6 to 24 carbon atoms.
Example esters include adipates, phthalates, isophthalates,
terephthalates and trimellitates of isooctanol, of isononanol, of
isodecanol and of isotridecanol. Such products can also have
carrier oil properties.
[0111] Detergents comprising moieties obtained by Mannich reaction
of substituted phenols with aldehydes and mono- or polyamines (h)
can be reaction products of polyisobutene-substituted phenols with
formaldehyde and mono- or polyamines such as ethylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine or
dimethylaminopropylamine.
Lubricity Additives
[0112] One or more lubricity additives can also be added to the
compositions. Non-limiting examples of lubricity additives include
certain carboxylic acids or fatty acids, alkenylsuccinic esters,
bis(hydroxyalkyl) fatty amines, hydroxyacetoamides or castor oil.
The aforementioned carboxylic acids or fatty acids can be present
as monomer and/or dimeric species.
Corrosion Inhibitors
[0113] One or more corrosion inhibitors can also be included in the
compositions. Non-limiting examples of corrosion inhibitors include
ammonium salts of organic carboxylic acids, which tend to form
films. Heterocyclic aromatics can also be included as corrosion
inhibitors for nonferrous metals. Amines for reducing the pH can
also be included with corrosion inhibitors.
Antioxidants
[0114] One or more antioxidants or stabilizers can also be included
in the compositions. Non-limiting examples of antioxidants or
stabilizers include amines, such as para-phenylenediamine,
dicyclohexylamine, morpholine or derivatives of these amines,
phenolic antioxidants, such as 2,4-di-tert-butylphenol or
3,5-di-tert-butyl-4-hydroxyphenyl-propionic acid and derivatives
thereof.
[0115] Non-limiting examples of antioxidants include alkylated
monophenols, for example 2,6-di-tert-butyl-4-methylphenol,
2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol,
2,6-di-nonyl-4-methylphenol,
2,4-dimethyl-6(1'-methylundec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1
`-methyltridec-1`-yl)phenol, and combinations thereof.
[0116] Other non-limiting examples of suitable antioxidants include
alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonylphenol, and combinations thereof;
hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and combinations
thereof; hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis-(3,6-d
i-sec-amylphenol),
4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide, and combinations
thereof; alkyl idenebisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydr oxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl) butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercapto
butane, ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane-
, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methyl phenyl)pentane,
and combinations thereof can be utilized as antioxidants; O-, N-
and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol
terephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,
isooctyl-3,5di-tert-butyl-4-hydroxy benzylmercaptoacetate, and
combinations thereof; hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,
di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malona-
te,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hy-
droxybenzyl)malonate, and combinations thereof; triazine compounds,
for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3-
,5-triazine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin-
e,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triaz-
ine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl
propionyl)-hexahydro-1,3,5-triazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, and
combinations thereof; aromatic hydroxybenzyl compounds, for example
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and
combinations thereof; benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy 3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and combinations
thereof; acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate; esters of
[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or
polyhydric alcohols, e.g. with methanol, ethanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,
neopentyl glycol, thiodiethylene glycol, diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof; esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof; esters of
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,
neopentyl glycol, thiodiethylene glycol, diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof; esters of 3,5-di-tert-butyl-4-hydroxyphenyl
acetic acid with mono- or polyhydric alcohols, e.g. with methanol,
ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
combinations thereof; compounds including nitrogen, such as amides
of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine;
aminic compounds such as N,N'-diisopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated
diphenylamine, for example p,p'-di-tert-octyldiphenylamine,
4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino
methylphenol, 2,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated isopropyl/isohexyldiphenylamines, mixtures of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,
N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,
bis(2,2,6,6-tetramethyl piperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethyl
piperidin-4-ol, and combinations thereof; aliphatic or aromatic
phosphites, esters of thiodipropionic acid or of thiodiacetic acid,
or salts of dithiocarbamic or dithiophosphoric acid,
2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,1trithiatridecane and
2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane,
and combinations thereof; and sulfurized fatty esters, sulfurized
fats and sulfurized olefins, and combinations thereof.
Demulsifiers
[0117] One or more demulsifiers can also be included in the
compositions. Although a single demulsifier can be included in the
compositions, more than one demulsifier is can be included in the
compositions. Each demulsifier can include one or more solvents
which facilitate dispersion of the demulsifier in the compositions.
As such, the one or more demulsifiers and one or more solvents
included therewith are collectively referred to herein as (D) a
demulsifier package. When added to the compositions, the
demulsifier package (D) prevents the fuel, additivated with the
compositions, from forming an emulsion with water. Specifically,
when water and the additivated fuel are mixed, the demulsifier
package (D) increases the rate at which water and additivated fuel
separate into layers, decreases the amount of water in the fuel
layer, decreases the amount of non-aqueous components in the water,
and prevents the formation of an emulsion layer. The properties
imparted by the demulsifier package (D) on the additivated fuel are
collectively referred to as the demulsification properties of the
demulsifier package (D).
[0118] ASTM Test Method D 1094-07 and ExxonMobil Analytical Method
AM-S 529-08 can be used to test the demulsification properties of
the demulsifier package (D). In such tests, the compositions,
including the demulsifier package (D), is mixed with fuel to form
additivated fuel. In turn, the additivated fuel is mixed with water
and tested in accordance with methods such as those set forth above
to determine the extent to which the additivated fuel and water
emulsify.
[0119] As is set forth in the background, fuel additive
compositions including polyalkenylsuccinimides and other additives
can phase separate over time, especially at lower temperatures
(e.g. temperatures below 23.degree. C.). ExxonMobil Analytical
Method FWI-013 can be used to test the storage stability (i.e. the
homogeneity and resistance to phase separation) of the
compositions. The compositions disclosed herein are homogenous and
resistant to phase separation when stored "neat", i.e., not in
additivated fuel. Although demulsifiers can provide demulsification
properties to additivated fuel, demulsifiers can also cause phase
separation of the compositions over time or upon exposure to lower
temperatures. The demulsifier package (D) used with the
compositions disclosed herein provides the compositions with robust
demulsification properties, and does not cause phase separation of
the compositions during storage.
[0120] The demulsifier package (D) can include a demulsifier
selected from salts of fatty acids, alkylamino carboxylic acids,
organo sulfur compounds (e.g. sulfonic acids, alkylaryl sulfonate),
polyetherols, and combinations thereof. The demulsifier package (D)
can include any combination of demulsifiers selected from the
chemical genera set forth in the previous sentence, and can include
more than one chemical species from each chemical genus.
[0121] Polyetherols include the reaction product of a base molecule
(also known as an initiator) and an alkylene oxide, in a chemical
reaction known as alkoxylation. The base molecule is selected to
impart certain physical properties to the polyetherol, for example,
a base molecule including N or a cyclic hydrocarbon can be used to
form the polyetherol. The alkylene oxide can be selected from the
group of EO, PO, BO, and combinations thereof. Alkoxylation enables
control of hydrophilic-lipophilic balance value ("HLB value"),
M.sub.n, and various other properties of the resulting polyetherol.
Alkoxylation can be carried out to form polyetherols having a
"block" structure (block polyetherols) and/or a "random" structure.
In some embodiments, the polyetherol can have a heteric structure.
For example, the polyetherol can have a totally heteric (or random)
EO, PO structure. As another example, the polyetherol can have
heteric, but uniform blocks, e.g. blocks comprising EO and blocks
comprising PO. As yet another example, the polyetherol can have
heteric blocks and uniform blocks, e.g. blocks comprising all EO
and blocks comprising random EO, PO. As such, the base molecule and
the type and amount of alkylene oxide used for alkoxylating the
base molecule can be varied to achieve certain properties, such as
calculated HLB value and M.sub.n, which improve the demulsification
properties the of the particular demulsifier in the compositions in
additivated fuel.
[0122] The demulsifier package (D) can include a polyetherol
demulsifier selected from alkoxylated butyl, amyl, and nonyl phenol
resins, alkoxylated alkyl phenol formaldehyde resins, alkoxylated
epoxy resins, alkoxylated polyethyleneimines, oxyalklyated alkyl
phenols, amine alkoxylates, EO polyetherols (e.g. nonylphenol
ethoxylate), PO polyetherols, EO/PO block polyetherols, and
combinations thereof. The polyetherol can be a block copolymer, a
random copolymer, or a hybrid thereof. In one embodiment, the
demulsifier package (D) includes a combination of the exemplary
polyetherols set forth above.
[0123] As set forth above, the demulsifier package (D) can also
include one or more organo sulfur compounds. Specific, non-limiting
examples of suitable organo sulfur compounds include sulfonic
acids, alkylaryl sulfonates, and combinations thereof. Specific,
non-limiting examples of suitable sulfonic acids include dodecyl
benzene sulfonic acid and other alkylbenzene sulphonic acids. In
one embodiment, the demulsifier package (D) includes a sulfonic
acid.
[0124] In some embodiments, the demulsifier package (D) includes
less than 2,000, alternatively less than 1,500, alternatively from
100 to 1,000, ppm of sulfur. Accordingly, in various embodiments,
the demulsifier package (D), when used in the compositions set
forth herein, delivers an amount of sulfur to fuel which is less
than an amount which can be detected by instruments and test
methods commonly used to detect sulfur content in additivated
fuel.
[0125] In one embodiment, the demulsifier package (D) is
substantially free of sulfur. "Substantially free" as used herein
in relation to the demulsifier package (D) being substantially free
of sulfur means that the demulsifier package (D) includes sulfur
containing compounds in an amount less than about 25, alternatively
less than about 10, alternatively less than 5, alternatively less
than about 1, alternatively less than about 0.5, alternatively less
than about 0.2, alternatively less than about 0.15, alternatively 0
parts by weight, based on 100 parts by weight of the demulsifier
package (D). Alternatively, in one embodiment, the demulsifier
package (D) contributes less than 50, alternatively less than 25,
alternatively less than 1.5, alternatively less than 1,
alternatively less than 0.5, alternatively less than 0.2,
alternatively less than 0.1, alternatively less than 0.05,
alternatively less than 0.01, mg of sulfur/kg of fuel at the treat
rates set forth herein.
[0126] The compositions can be added to fuel in an amount such that
the demulsifier (or demulsifier package (D)) can be present in the
fuel in an amount of from 0.5 to 500, alternatively from 0.5 to
200, alternatively from 0.5 to 100, alternatively from 0.5 to 50,
alternatively from 1 to 25, mg/kg of fuel. Further, the demulsifier
package (D) can be present in the compositions in an amount of less
than 5, alternatively less than 4, alternatively less than 3,
alternatively less than 2.5, alternatively less than 2,
alternatively less than 1.5, alternatively less than 1,
alternatively less than 0.8, alternatively from 0.1 to 5,
alternatively from 0.2 to 2.5, alternatively from 0.2 to 2,
alternatively from 0.2 to 1, alternatively from 0.2 to 2,
alternatively from 0.2 to 0.8, parts by weight per 100 parts by
weight of the composition.
Metal Deactivators
[0127] One or more metal deactivators can also be included in the
compositions. Non-limiting examples of the one or more metal
deactivators include benzotriazoles and derivatives thereof, for
example 4- or 5-alkylbenzotriazoles (e.g. triazole) and derivatives
thereof, 4,5,6,7-tetrahydrobenzotriazole and
5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole or
triazole, e.g. 1-[bis(2-ethylhexyl)aminomethyl)triazole and
1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and
alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)benzotriazole,
1-(1-butoxyethyl)benzotriazole and
1-(1-cyclohexyloxybutyl)triazole, and combinations thereof.
[0128] Additional non-limiting examples of the one or more metal
deactivators include 1,2,4-triazoles and derivatives thereof, for
example 3-alkyl(or aryl)-1,2,4-triazoles, and Mannich bases of
1,2,4-triazoles, such as
1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole;
alkoxyalkyl-1,2,4-triazoles such as
1-(1-butoxyethyl)-1,2,4-triazole; and acylated
3-amino-1,2,4-triazoles, imidazole derivatives, for example
4,4'-methylenebis(2-undecyl-5-methylimidazole) and
bis[(N-methyl)imidazol-2-yl]carbinol octyl ether, and combinations
thereof.
[0129] Further non-limiting examples of the one or more metal
deactivators include sulfur-containing heterocyclic compounds, for
example 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole
and derivatives thereof; and
3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one, and
combinations thereof. Even further non-limiting examples of the one
or more metal deactivators include amino compounds, for example
salicylidenepropylenediamine, salicylaminoguanidine and salts
thereof, and combinations thereof.
Dehazers
[0130] One or more dehazers can also be included in the
compositions. Non-limiting examples of dehazers include alkoxylated
phenol-formaldehyde condensates.
Markers
[0131] One or more markers can also be included in the
compositions. The marker can be used to color the compositions
and/or for traceability. Markers can also allow for the
quantitative analysis of additivated fuel at the refinery, on the
roadside, or in the laboratory. That is, markers can allow for a
determination of the amount of composition included in the
additivated fuel.
Solvents
[0132] One or more solvents can also be included in the
compositions. The solvents used in the compositions can be inert
stable oleophilic (i.e., dissolves in fuel) organic solvents
boiling in the range of about 65.degree. C. to 205.degree. C. For
example, an aliphatic or an aromatic hydrocarbon solvent is used,
such as benzene, toluene, xylene or higher-boiling aromatics or
aromatic thinners. Aliphatic alcohols of about 3 to 8 carbon atoms,
such as isopropanol, isobutylcarbinol, n-butanol, 2-ethylhexanol,
and the like, in combination with hydrocarbon solvents, are also
suitable for use in the compositions.
The Compositions
[0133] The compositions are not particularly limited in this
disclosure so long as it includes the polyalkenylsuccinimide (A),
the polyisobutene amine (B), and the carrier oil (C).
[0134] In various embodiments, the compositions consist essentially
of, or consist of, the polyalkenylsuccinimide (A), the
polyisobutene amine (B), and the carrier oil (C). In embodiments
that consist essentially of the polyalkenylsuccinimide (A), the
polyisobutene amine (B), and the carrier oil (C), the compositions
are typically free of materials or material compounds that affect
the basic properties of the compositions including, but not limited
to, additional solubilizers.
[0135] In various embodiments, the compositions consist essentially
of, or consists of, the polyalkenylsuccinimide (A), the
polyisobutene amine (B), the carrier oil (C), the demulsifier
package (D), and solvent. In embodiments that consist essentially
of the polyalkenylsuccinimide (A), the polyisobutene amine (B), the
carrier oil (C), the demulsifier package (D), and solvent, the
compositions are free of other materials or material compounds that
affect the basic properties of the compositions.
[0136] In various other embodiments, the compositions are
substantially free of sulfur. "Substantially free" as used herein
in relation to the compositions being substantially free of sulfur
means that the compositions includes sulfur containing compounds in
an amount less than about 5, alternatively less than about 4,
alternatively less than about 3, alternatively less than about 2,
alternatively less than about 1, alternatively less than about 0.5,
alternatively less than about 0.25, alternatively 0 parts by
weight, based on 100 parts by weight of the composition.
[0137] Sulfur limits in fuels in many regions of the globe are less
than 30, less than 20, or even less than 10 ppm (mg/kg fuel)
sulfur. Generally, sulfur limits in fuels are moving towards less
than 10 ppm sulfur across the globe. In some embodiments, the
compositions deliver an amount of sulfur to the fuel which is less
than an amount which can be detected by instruments and test
methods commonly used to detect sulfur content in fuel. In various
embodiments, the compositions deliver no more sulfur to the fuel
than an amount which would "round up" the sulfur content of the
unadditivated fuel to the nearest ppm limit. In some embodiments,
the compositions contribute less than 50, alternatively less than
25, alternatively less than 1.5, alternatively less than 1,
alternatively less than 0.5, alternatively less than 0.2,
alternatively less than 0.1, alternatively less than 0.05,
alternatively less than 0.01, mg of sulfur/kg of fuel at the treat
rates set forth herein.
[0138] In some embodiments, the compositions include 1 to 75 parts
by weight of the polyalkenylsuccinimide (A), 15 to 25 parts by
weight of the polyisobutene amine (B), 5 to 70 parts by weight of
the carrier oil (C), 2 to 94 parts by weight solvents, and less
than 5 parts by weight of the demulsifier package (D), based on 100
parts by weight of the composition.
[0139] In other embodiments, the compositions include 20 to 35
parts by weight of the polyalkenylsuccinimide (A), 15 to 25 parts
by weight of the polyisobutene amine (B), 5 to 15 parts by weight
of the carrier oil (C), 28 to 55 parts by weight solvents, less
than 5 parts by weight of the demulsifier package (D), and less
than 0.5 parts by weight of the marker, based on 100 parts by
weight of the composition.
[0140] In other embodiments, the compositions include 4 to 15 parts
by weight of the polyalkenylsuccinimide (A), 30 to 60 parts by
weight of the polyisobutene amine (B), 12-18 parts by weight of the
carrier oil (C), 16 to 20 parts by weight solvents, 0.35 to 0.5
parts by weight corrosion inhibitors, 0.5 to 3.5 parts by weight
dehazers, and 0.5 to 1.5 parts by weight marker, based on 100 parts
by weight of the composition. In one embodiment, the compositions
include the polyalkenylsuccinimide (A) in an amount of about 6
parts by weight, the polyisobutene amine (B) in an amount of about
34.67 parts by weight, and the carrier oil (C) in an amount of
about 15 parts by weight, each based on the total weight of the
composition.
[0141] The subject disclosure also includes a method of forming the
compositions comprising the step of mixing the components, e.g.
mixing a polyalkenylsuccinimide (A), a polyisobutene amine (B), a
carrier oil (C), and a demulsifier package (D), and solvents and
other additives. In various embodiments, the step of mixing is
conducted with no particular order of addition. For example, all of
the components can be mixed in a single, simultaneous step to form
the compositions. In other embodiments, the step of mixing is
conducted with an order of addition. For example, in one
embodiment, the fatty alcohol solvent, the demulsifier package (D),
and the marker are mixed together. Then, the aromatic solvent is
added to the mixture and mixed in, the polyisobutene amine (B) is
added to the mixture and mixed in, and the carrier oil (C) is added
to the mixture and mixed in. Finally, the polyisobutenylsuccinimide
(A) is added to the mixture and mixed in to form the
compositions.
[0142] The composition can be used as an additive in fuels, such as
diesel fuel, gasoline fuel, heating oil, and kerosene or middle
distillates. When the compositions are used as an additive in
diesel fuel, they can be used in any effective amount,
alternatively in an amount of from 10 to 10,000, alternatively from
10 to 5,000, alternatively from 50 to 1,000, mg/kg of diesel fuel.
When the compositions are used as an additive in gasoline fuel,
they can be used in any effective amount, alternatively in an
amount of from 10 to 10,000, alternatively from 10 to 5,000,
alternatively from 50 to 2,000, mg/kg of gasoline fuel. When the
compositions are used as an additive in heating oil, they can be
used in any effective amount, alternatively in an amount of from 10
to 1,000, alternatively from 50 to 500, mg/kg of heating oil.
[0143] The subject disclosure also includes a method of improving
the fuel economy of an internal combustion engine. The method
includes the step of adding the compositions to fuel. The
compositions can be added to fuel in the amounts set forth in the
preceding paragraph. For example, in one embodiment of the method,
10 to 10,000 mg of the compositions is added per kg of fuel.
[0144] The subject disclosure also includes a fuel including the
compositions. The compositions can be included in the fuel in the
amounts set forth above. For example, one kg of the fuel can
include 10 to 10,000 mg of the composition.
[0145] The following examples are meant to illustrate the
disclosure and are not to be viewed in any way as limiting to the
scope of the disclosure.
EXAMPLES
[0146] A polyisobutenylsuccinimide is formed in accordance with the
instant disclosure. Specifically, the polyisobutenylsuccinimide is
the reaction product of (1) a polyisobutene having a chain length
of C.sub.40 to C.sub.200 and an number average molecular weight
(M.sub.n) of greater than 1,000 g/mol and a content of terminal
double bonds of greater than 75 mol %, (2) maleic anhydride, and
(3) tetraethylenepentamine wherein each mol of polyisobutene is
functionalized with 1 to 2 moles of maleic anhydride.
[0147] The polyisobutenylsuccinimide was added to fuel and the
additivated fuel was tested to determine fuel economy in accordance
with the US Federal Test Procedure--Highway Fuel Economy Test (U.S.
Environmental Protection Agency Test Protocol, C.F.R. Title 40,
Part 600, Subpart B) for five different automobiles. Standard U.S.
regular unleaded gasoline was used in the testing. For each
automobile, fuel consumption was determined first with
unadditivated fuel and then with additivated fuel formed with a
dosage of 190 mg/kg. The results of the fuel economy testing are
set forth in Table 1 below.
TABLE-US-00001 TABLE 1 Fuel Economy Vehicle Model Model Year Engine
Improvement (%) Dodge Caravan 2008 3.3 L V-6 2.50 Mercury Marquis
2007 4.6 L V-8 0.69 Chevrolet 2008 3.9 L V-6 1.14 Uplander Dodge
Journey 2009 3.5 L V-6 3.61 Dodge Caravan 2008 3.8 L V-6 3.57 Base
Fuel: Unadditivated U.S. regular unleaded gasoline Additive: PIBSI
(100%) based on GLISSOPAL .RTM. 1000, MSA, and TEPA Dosage of
Additivated Fuel: 190 mg/kg Crankcase Oil: 10W-30 Test protocol:
U.S. Environmental Protection Agency Test Protocol, C.F.R. Title
40, Part 600, Subpart B Note: Fuel economy determined by carbon
balance.
[0148] Referring now to Table 1, use of the
polyisobutenylsuccinimide in the additivated fuel resulted in an
average fuel savings of 2.3% for the five automobiles tested.
Further, the fuel economy benefit of the polyisobutenylsuccinimide
is even more astonishing since it demonstrates almost no activity
in any type of High Frequency Reciprocating Rig (HFRR) testing and,
as is set forth below with Example 1, is miscible with additional
fuel additives.
[0149] Example 1 is a fuel additive composition which includes the
polyisobutenylsuccinimide and is in accordance with the instant
disclosure. Comparative Examples 1 and 2 are fuel additive
compositions which include fuel economy additives know in the art.
Specifically, the fuel additive composition of Comparative Example
1 includes a fatty acid amide and the fuel additive composition of
Comparative Example 2 includes a propoxylated fatty acid amide. The
fuel additive compositions of Example 1 and Comparative Examples 1
and 2 are set forth in Table 2 below. The amounts set forth in
Table 2 are parts by weight based on 100 parts by weight of the
fuel additive composition.
[0150] Further, the fuel additive compositions of Example 1 and
Comparative Examples 1 and 2 were stored at -20.degree. C. for 6
weeks and then examined for any evidence of phase separation. The
phase separation test results are also set forth in Table 2
below.
TABLE-US-00002 TABLE 2 Comparative Comparative Example 1 Example 1
Example 2 Polyisobutenylsuccinimide 11.1 -- -- (according to the
subject disclosure) Fatty Acid Amide -- 11.1 -- (according to WO
2009/050256) Propoxylated Fatty -- -- 11.1 Acid Amide (according to
WO 2010/005720) Polyisobutene Amine 10.9 10.9 10.9 (according to
the subject disclosure) Propoxylate Carrier Oil 26.7 26.7 26.7
(according to the subject disclosure) Paraffinic Solvent 5.8 5.8
5.8 Aromatic Solvent 45.5 45.5 45.5 Total 100.0 100.0 100.0 Phase
Separation Test One clear Two phases - Two phases - Results (After
6 weeks phase - pass failure failure of storage at -20.degree.
C.)
[0151] Referring now to Table 2, the fuel additive composition of
Example 1, which includes the polyisobutenylsuccinimide, the
polyisobutene amine, and the propoxylate carrier oil, remains clear
and in a single phase even after 6 weeks of storage at -20.degree.
C. However, the fuel additive compositions of Comparative Examples
1 and 2 form separate phases after 6 weeks of storage at
-20.degree. C.
[0152] Example 2 is a fuel additive composition in accordance with
the instant disclosure which includes the
polyisobutenylsuccinimide, the polyisobutene amine, the polyether
carrier oil, and a demulsifier package. The fuel additive
composition of Example 2 is forth in Table 3 below. To form the
fuel additive composition of Example 2, the fatty alcohol solvent,
the demulsifier components, and the marker are mixed together.
Then, the aromatic solvent was added to the mixture and mixed in,
the polyisobutene amine was added to the mixture and mixed in, and
the polyether carrier oil was added to the mixture and mixed in.
Finally, the polyisobutenylsuccinimide was added to the mixture and
mixed in to form the fuel additive composition of Example 2.
TABLE-US-00003 TABLE 3 Example 2 % by weight (based on 100 parts by
Ratio weight of the Additivated (Demulsifier fuel additive Fuel
Component: Generic Name composition) (PPM) PIBSI, by wt.)
Polyisobutenyl- 20-35% 130-303 ppm -- succinimide Polyisobutene
Amine 15-25% 97-217 ppm -- Polyether Carrier Oil 5-15% 32-130 ppm
-- Marker <0.5% <5 ppm -- First Demulsifier .sup. <3%
<26 ppm <1:8 Component Second Demulsifier .sup. <1% <9
ppm <1:14 Component Third Demulsifier .sup. <2% <17 ppm
<0.13 Component Fatty Alcohol Solvent 8-10% 52-104 ppm --
Aromatic Solvent 20-45% 130-390 ppm --
[0153] Fuel additivated with the fuel additive composition of
Example 2 was tested in accordance with ASTM D 1094-07. The test
method of ASTM D 1094-07 determines the miscibility of components
in additivated gasoline with water and the effect of these
components on volume change and on the fuel-water interface. In
this test method, a sample of fuel was shaken at room temperature
with a phosphate buffer solution in a graduated cylinder. The
cleanliness of the glass cylinder as well as the change in volume
of the aqueous layer and the appearance of the interface between
layers were taken as the water reaction of the fuel. The fuel
additivated with the fuel additive composition of Example 2 was
tested and yields a separation rating of (1) (which is the complete
absence of all emulsions and/or precipitates within either the
water layer the treated fuel layer), and has minimal lacing at the
interface between the fuel and water layers. As such, the fuel
additive composition of Example 2, which includes a
polyisobutenylsuccinimide, a polyisobutene amine, a polyether
carrier oil, and a demulsifier package, was resistant to
emulsification upon exposure to water.
[0154] Referring now to Table 4, the miscibility of the fuel
additivated with the fuel additive composition of Example 2 with
water was also tested over a repetitive timing cycle in a
multi-contact test. In this test, each individual cycle is referred
to as a contact. Specifically, 200 ml of fuel additivated with the
fuel additive composition of Example 2 was mixed with 20 ml of
water in a glass container and shaken for 5 minutes at the highest
setting on a mechanical reciprocating shaker. The sample is then
held, with no agitation, for 24 hours and observations regarding
the fuel layer, the water layer, and any interface therebetween are
made. The fuel is then decanted from the glass container, and 200
ml of fresh fuel additivated with the fuel additive composition of
Example 2 are added to the glass container and the cycle was
repeated 10 times, with the results set forth in Table 4. The
contact number is the number of times the additivated fuel and the
water have come into contact, thus there are 10 contacts per test,
with each contact 24 hours apart.
[0155] Emulsion observations regarding the mixture of the fuel
additive composition of Example 2 and water were made as
follows:
[0156] 0) Both the water layer and the fuel layer are clean with no
lacing skin, or bubbles;
[0157] 1) Slight skin at the interface between the water and the
fuel layer that does not break on tilting the bottle;
[0158] 2) Slight skin at the oil-water interface, heavier than 1)
and usually accompanied by dirt and bubbles on the skin (no
evidence of emulsion);
[0159] 3) Minimal amounts of emulsion at the bottom and in the
center of the bottle. It is circular in shape and approximately 1/4
to 1 inch in diameter;
[0160] 4) Emulsion at the interface between the water and the fuel
layer (approximately the same amount of emulsion on the bottom of
the bottle as 3);
[0161] 5) Emulsion at bottom on the bottle expands upward and the
thickness of the emulsion at the interface slightly thicker than
4).
[0162] 6) Emulsion amounts increase with an emulsion film forming
on sides of bottle surrounding the water layer;
[0163] 7) Emulsion on bottom of water layer is almost solid and the
water layer is barely visible;
[0164] 8) Emulsion with bubbles and the water layer is non longer
visible;
[0165] 9) Emulsion with fewer greater than 75% of the emulsion is
solid;
[0166] 10) Emulsion is almost completely solid, with only a few air
bubbles visible; and
[0167] 11) Emulsion is completely solid.
[0168] Further, observations regarding the water layer and the fuel
layer were made with "C" for clear and "H" for hazy.
TABLE-US-00004 TABLE 4 Contact Number The Water Layer The Fuel
Layer Interface 1 C C 0 2 C C 0 3 C C 0 4 C C 1 5 C C 2 6 C C 2 7 C
C 2 8 C C 1 9 C C 1 10 C C 2 7 Days Later C C 2
[0169] Referring now to Table 4, the fuel additive composition of
Example 2, which includes the polyisobutenylsuccinimide, the
polyisobutene amine, the polyether carrier oil, and the demulsifier
package, was resistant to emulsification upon exposure to
multi-contact exposure to water.
[0170] Referring now to Table 5, the storage stability of the fuel
additive composition of Example 2 was also tested at 23.degree. C.
and -15.degree. C. To test storage stability, 100 ml the fuel
additive composition of Example 2 was added to a centrifuge
container which has a conical bottom end. The centrifuge container
is typically clear, and has amount marks on the side thereof. The
conical portion of the centrifuge container is about the size of a
sharpened pencil tip. The samples were held for 4 weeks, with
weekly observations made regarding the amount of phase separation
and sediment formed. After testing a digital photo of the conical
tip of the centrifuge container was taken.
TABLE-US-00005 TABLE 5 23.degree. C. -15.degree. C. Phase Phase
Week Separation Sediment Separation Sediment 1 None None None None
2 None None None None 3 None None None None 4 None None None
None
[0171] Referring now to Table 5, the fuel additive composition of
Example 2, which includes a polyisobutenylsuccinimide, a
polyisobutene amine, a polyether carrier oil, and a demulsifier
package, remained clear and in a single phase even after 4 weeks of
storage at 23.degree. C. and -15.degree. C. Further, little (less
than 0.05 ml per 100 ml of composition) or no sediment forms on the
bottom of the clear centrifuge container.
[0172] It is to be understood that the appended claims are not
limited to express and particular compounds, compositions, or
methods described in the detailed description, which may vary
between particular embodiments which fall within the scope of the
appended claims. With respect to any Markush groups relied upon
herein for describing particular features or aspects of various
embodiments, it is to be appreciated that different, special,
and/or unexpected results may be obtained from each member of the
respective Markush group independent from all other Markush
members. Each member of a Markush group may be relied upon
individually and or in combination and provides adequate support
for specific embodiments within the scope of the appended
claims.
[0173] It is also to be understood that any ranges and subranges
relied upon in describing various embodiments of the present
disclosure independently and collectively fall within the scope of
the appended claims, and are understood to describe and contemplate
all ranges including whole and/or fractional values therein, even
if such values are not expressly written herein. One of skill in
the art readily recognizes that the enumerated ranges and subranges
sufficiently describe and enable various embodiments of the present
disclosure, and such ranges and subranges may be further delineated
into relevant halves, thirds, quarters, fifths, and so on. As just
one example, a range "of from 0.1 to 0.9" may be further delineated
into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e.,
from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which
individually and collectively are within the scope of the appended
claims, and may be relied upon individually and/or collectively and
provide adequate support for specific embodiments within the scope
of the appended claims. In addition, with respect to the language
which defines or modifies a range, such as "at least," "greater
than," "less than," "no greater than," and the like, it is to be
understood that such language includes subranges and/or an upper or
lower limit. As another example, a range of "at least 10"
inherently includes a subrange of from at least 10 to 35, a
subrange of from at least 10 to 25, a subrange of from 25 to 35,
and so on, and each subrange may be relied upon individually and/or
collectively and provides adequate support for specific embodiments
within the scope of the appended claims. Finally, an individual
number within a disclosed range may be relied upon and provides
adequate support for specific embodiments within the scope of the
appended claims. For example, a range "of from 1 to 9" includes
various individual integers, such as 3, as well as individual
numbers including a decimal point (or fraction), such as 4.1, which
may be relied upon and provide adequate support for specific
embodiments within the scope of the appended claims.
[0174] In addition, it is contemplated that the weight percents or
other numerical values or ranges of values described above may vary
and may be further defined as any value or range of values, both
whole and fractional, within those ranges and values described
above and/or may vary from the values and/or range of values above
by .+-.5%, .+-.10%, .+-.15%, .+-.20%, .+-.25%, .+-.30%, etc, so
long as the variations remain within the scope of the disclosure.
As one example, any of the numerical values or ranges described
herein may be further defined as "about" and, as such, may vary in
accordance with this paragraph. As used in the preceding sentence
the word about means reasonably close to.
[0175] The disclosure has been described in an illustrative manner,
and it is to be understood that the terminology which has been used
is intended to be in the nature of words of description rather than
of limitation. Many modifications and variations of the present
disclosure are possible in light of the above teachings, and the
disclosure may be practiced otherwise than as specifically
described.
* * * * *