U.S. patent application number 16/649442 was filed with the patent office on 2020-08-27 for polyacrylate antifoam components for use in fuels.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to James H. Bush, Kevin J. Hughes, Rochelle L. Kovach, David M. Nickerson, Jayasooriya Sujith Perera, Kamalakumari K. Salem, Elizabeth A. Schiferl.
Application Number | 20200270537 16/649442 |
Document ID | / |
Family ID | 1000004844461 |
Filed Date | 2020-08-27 |
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United States Patent
Application |
20200270537 |
Kind Code |
A1 |
Bush; James H. ; et
al. |
August 27, 2020 |
POLYACRYLATE ANTIFOAM COMPONENTS FOR USE IN FUELS
Abstract
There is disclosed an antifoam component which includes at least
one poly(acrylate) copolymer for use in a fuel. Poly(acrylate)
polymers prepared by polymerizing a (meth)acrylate monomer
comprising C.sub.1 to C.sub.30 alkyl esters of (meth)acrylic acid
("multifunctional monomer") are also disclosed. Other
poly(acrylate) polymers prepared by polymerizing (i) a
(meth)acrylate monomer comprising C.sub.1 to C.sub.4 alkyl esters
of (meth)acrylic acid ("solubility monomer"); (ii) a (meth)acrylate
monomer comprising C.sub.5 to C.sub.12 alkyl esters of
(meth)acrylic acid ("surface tension monomer"); and (iii)
optionally at least one additional monomer comprising a solubility
monomer, a surface tension monomer, a monomer comprising C.sub.1 to
C.sub.30 alkyl esters of (meth)acrylic acid ("multifunctional
monomer"), or combinations thereof are also disclosed.
Inventors: |
Bush; James H.; (Mentor,
OH) ; Nickerson; David M.; (Concord Township, OH)
; Kovach; Rochelle L.; (Cleveland, OH) ; Perera;
Jayasooriya Sujith; (Twinsburg, OH) ; Schiferl;
Elizabeth A.; (Chagrin Falls, OH) ; Hughes; Kevin
J.; (Sammamish, WO) ; Salem; Kamalakumari K.;
(Mentor, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
1000004844461 |
Appl. No.: |
16/649442 |
Filed: |
September 21, 2018 |
PCT Filed: |
September 21, 2018 |
PCT NO: |
PCT/US2018/052168 |
371 Date: |
March 20, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62653621 |
Apr 6, 2018 |
|
|
|
62646127 |
Mar 21, 2018 |
|
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62561342 |
Sep 21, 2017 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 220/1804 20200201;
C10L 1/1963 20130101; C10L 2200/0446 20130101; C10L 1/2222
20130101; C10L 1/1983 20130101; C10L 2230/082 20130101 |
International
Class: |
C10L 1/196 20060101
C10L001/196; C08F 220/18 20060101 C08F220/18; C10L 1/222 20060101
C10L001/222; C10L 1/198 20060101 C10L001/198 |
Claims
1-11. (canceled)
12. A composition comprising at least one poly(acrylate) polymer
prepared by polymerizing: a (meth)acrylate monomer comprising
tertiary butyl (meth)acrylate, ethyl (meth)acrylate or combinations
thereof ("solubility monomer"); and (ii) a (meth)acrylate monomer
comprising trimethylhexyl (meth)acrylate. 2-ethylhexyl
(meth)acrylate or combinations thereof ("surface tension monomer");
and wherein the ratio of the solubility monomer to the surface
tension monomer ranges from 98:2 to 80:10.
13. The composition of claim 12, wherein the at least one
poly(acrylate) polymer is is prepared by polymerizing: (i) a
(meth)acrylate monomer comprising tertiary butyl (meth)acrylate
("solubility monomer"); (ii) a (meth)acrylate monomer comprising
trimethylhexyl (meth)acrylate ("surface tension monomer"); and
(iii) at least one additional monomer; and wherein the ratio of the
solubility monomer to the surface tension monomer to the at least
one additional monomer ranges from 85:5:10 to 80:15:5.
14. The composition of claim 13, wherein the at least one
additional monomer comprises 2-ethylhexyl (meth)acrylate.
15-23. (canceled)
24. The composition of claim 12, wherein the at least one
poly(acrylate) polymer has a weight average molecular weight
("M.sub.w") from 10,000 to 350,000 Da.
25. The composition of claim 12, further comprising a fuel and
wherein the at least one poly(acrylate) polymer is present in the
fuel in an amount from 0.1 ppm to 3000 ppm by weight, based on a
total weight of the fuel and composition.
26. The composition of claim 25, wherein the at least one
poly(acrylate) polymer is present in the fuel in an amount from 1
ppm to 100 ppm by weight, based on a total weight of the of the
fuel and composition.
27. (canceled)
28. A method of reducing foam in a fuel, said method comprising
adding the composition of claim 12 to a fuel.
29-30. (canceled)
31. A method of reducing the amount of foam produced while filling
the fuel tank of a vehicle, said method comprising adding the
composition of claim 12 to a fuel.
32-36. (canceled)
37. A fuel additive package comprising: (i) at least one quaternary
ammonium salt; (ii) at least one hydrolyzed polyisobutylene
succinic anhydride (PIBSA), polyisobutylene succinic acid, or
combinations thereof; (iii) at least one demulsifier; (iv) at least
one antifoam component comprising the composition of claim.
38. A method of reducing foam in a fuel, said method comprising
adding the fuel additive package of claim 37 to a fuel.
39. (canceled)
Description
BACKGROUND
[0001] The disclosed technology relates to compounds that are
useful as antifoam components in diesel fuels. In particular,
diesel fuel compositions and concentrates comprising said antifoam
components and the use of same are disclosed.
[0002] Diesel fuel has a tendency to foam and is particularly
problematic at point of sale applications when diesel fuel is
pumped into the tank of a vehicle ("fill-ups"). As the diesel fuel
is pumped into the tank, a large amount of foam is quickly
generated thereby greatly reducing the amount of diesel that can be
pumped into a tank at each fill-up.
[0003] Reducing the amount of foam produced during fill-ups would
greatly increase the volume capacity of diesel tanks, but there are
no viable antifoam options for the North American market.
Currently, only nitrogen, oxygen, carbon and/or hydrogen ("NOCH")
based chemistries are allowed in North American diesel
applications. This precludes known silicone antifoams as a viable
option. Some fluorinated (poly)acrylate antifoams have been shown
to function as antifoams in diesel fuel, however fluorine is also
prevented in diesel additives. Thus, there is a need for
non-silicone, fluorine-free antifoam for diesel fuel.
SUMMARY OF THE INVENTION
[0004] Compositions comprising poly(acrylate) polymers prepared by
polymerizing certain (meth)acrylate monomers have surprisingly
shown to be effective antifoams in fuels. These (meth)acrylate
monomers include (meth)acrylate monomers comprising C.sub.1 to
C.sub.30 alkyl esters of (meth)acrylic acid ("multifunctional
monomers"). In some embodiments, the multifunctional monomer may
comprise C.sub.2 to C.sub.27 alkyl esters of (meth)acrylic acid.
The poly(acrylate) polymer may have a weight average molecular
weight ("M.sub.w") ranging from 10,000 to 350,000 Daltons ("Da") or
20,000 to 200,000 Da. In yet other embodiments, the poly(acrylate)
polymers may be homopolymers.
[0005] In other embodiments, the multifunctional monomers may
comprise C.sub.2 to C.sub.12 alkyl esters of (meth)acrylic acid.
Exemplary multifunctional monomers include, but are not limited to,
monomers comprising tertiary butyl (meth)acrylate.
[0006] In some embodiments, a composition comprising at least one
poly(acrylate) polymer is prepared by polymerizing: (i) a
(meth)acrylate monomer comprising C.sub.1 to C.sub.4 alkyl esters
of (meth)acrylic acid ("solubility monomer"); (ii) a (meth)acrylate
monomer comprising C.sub.5 to C.sub.12 alkyl esters of
(meth)acrylic acid ("surface tension monomer"); and (iii)
optionally at least one additional monomer that may comprise a
solubility monomer, surface tension monomer, a monomer having
C.sub.1 to C.sub.30 alkyl esters of (meth)acrylic acid
("multifunctional monomer"), or combinations thereof. In other
embodiments, poly(acrylate) polymer may be polymerized using: (i)
from 5 wt % to 95 wt % of the solubility monomer; (ii) from 95 wt %
to 5 wt % of the surface tension monomer; and (iii) optionally from
2 wt % to 10 wt % of the at least one additional monomer.
[0007] In some embodiments, the poly(acrylate) polymer may be at
least one of a copolymer, block polymer, random polymer,
terpolymer, or combinations thereof. In some embodiments, the
poly(acrylate) polymer may have a M.sub.w of from 20,000 to 200,000
Da, 20,000 to 80,000 Da, or 30,000 to 40,000 Da.
[0008] In some embodiments, the composition may comprise a
poly(acrylate) polymer comprising units with the structure of
formula (I):
##STR00001##
wherein R.sup.1 is H or CH.sub.3; R.sup.2 is a C.sub.2 to C.sub.10
linear, branched or cyclic hydrocarbyl group; R.sup.3 is a C.sub.2
to C.sub.4 linear or branched hydrocarbyl group; R.sup.4 is H, OH,
or CH.sub.3; n.sub.1 is an integer ranging from 75 to 3000; and
n.sub.2 is an integer ranging from 0 to 3. In some embodiments,
R.sup.2 and/or R.sup.3 is branched. In other embodiments, R.sup.2
is linear and R.sup.3 is branched.
[0009] In some embodiments, the multifunctional monomer and/or
solubility monomer may comprise C.sub.1-C.sub.4 alkyl esters of
(meth)acrylic acid. In other embodiments the multifunctional
monomer and/or surface tension monomer may comprise
C.sub.5-C.sub.12 alkyl esters of (meth)acrylic acid. In some
embodiments, the multifunctional monomer and/or solubility monomer
may comprise tertiary butyl (meth)acrylate, ethyl (meth)acrylate,
or combinations thereof. In other embodiments, the multifunctional
monomer and/or the surface tension monomer may comprise tertiary
butyl (meth)acrylate. In yet other embodiments, the solubility
monomer may comprise tertiary butyl (meth)acrylate, ethyl
(meth)acrylate, or combinations thereof, and the surface tension
monomer may comprise trimethylhexyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, or combinations thereof. In one embodiment, the
solubility monomer may comprise tertiary butyl (meth)acrylate and
the surface tension monomer may comprise 2-ethylhexyl
(meth)acrylate.
[0010] The poly(acrylate) polymers described above may be added to
a fuel to reduce the amount of foam produced in the fuel. The
poly(acrylate) polymer may be present in the fuel in an amount from
0.1 ppm to 2000 ppm by weight, or 2 ppm to 100 ppm, based on a
total weight of the fuel composition. Accordingly, methods of
reducing foam in a diesel are also disclosed. In some embodiments,
the fuel may be a diesel fuel. The use of at least one
poly(acrylate) polymer to reduce a foam in a fuel, typically
diesel, is also disclosed.
[0011] Methods of reducing the amount of foam produced while filing
the diesel tank of a vehicle are also disclosed. The method may
comprise adding at least one poly(acrylate) polymer prepared by
polymerizing a (meth)acrylate monomer to a fuel. The poly(acrylate)
polymer may be as described above.
[0012] Fuel additive packages and their uses are also disclosed
herein. The fuel additive package may comprise: (i) at least one
quaternary ammonium salt; (ii) at least one hydrolyzed
polyisobutylene succinic anhydride (PIBSA), polyisobutylene
succinic acid, or combinations thereof; (iii) at least one
demulsifier; (iv) at least one antifoam component as described
above; (v) optionally, at least one cetane improver; and (vi)
optionally, at least one solvent comprising an aromatic solvent,
ethyl hexyl alcohol, or combinations thereof. Methods of reducing
foam in a fuel comprising adding the fuel additive package
described above to a fuel are also disclosed.
BRIEF DESCRIPTION OF THE FIGURES
[0013] FIG. 1 is a graph showing the surface tensions of various
poly(acrylates) having different carbon chain lengths.
[0014] FIG. 2 is a graph showing the foam collapse time at
different treat rates of various antifoam components.
[0015] FIG. 3 is a graph showing the foam collapse time, Max
Height, and Max Foam of Additive Package A with a TBAT:EHAT
antifoam at different ratios.
[0016] FIG. 4 is a graph illustrating the synergistic effect a
TBAT:EHAT antifoam has with in an additive package (Additive
Package A) on foam collapse time.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Various preferred features and embodiments will be described
below by way of non-limiting illustration.
[0018] The disclosed technology provides a composition including an
antifoam component which includes a poly(acrylate) copolymer.
Without limiting this disclosure to the theory of operation
disclosed herein, it is believed that antifoam components break
foam bubbles by adsorbing on the surface of the bubbles and
lowering their surface tension. It is further believed the
effectiveness of antifoam components in a given fluid is a function
of two factors relative to the bulk fluid. The first factor is the
component's solubility in the bulk fluid. Generally, antifoams that
have poor solubility (insoluble or almost insoluble) in a fluid
will have improved performance than easily soluble antifoams. The
second factor is the component's surface tension. Generally,
antifoam components having a lower surface tension are more
effective as antifoam components than components having a higher
surface tension. FIG. 1 is a graph showing the surface tensions of
various poly(acrylates) having different carbon chain lengths.
[0019] Traditionally, copolymers of 2-ethylhexyl (meth)acrylate
(EHAT or EHMA) and ethyl (meth)acrylate (EAT or EMA) have been used
to prepare poly(acrylate) polymers in many organic fluids. This
two-monomer system can be tailored for the fluid at hand by
adjusting the monomer ratio as follows: a greater percentage of EAT
leads to decreased solubility while a greater percentage of EHAT
leads to decreased surface tension.
[0020] For diesel fuels, however, EHAT/EAT based poly(acrylate)
polymers having a molecular weight (M.sub.w) of 40,000 to 100,000
Da were not effective antifoam components because there was no
combination that provided both the required surface tension as well
as the required solubility properties. For example, the minimum EAT
content needed in the poly(acrylate) polymer to impart diesel fuel
insolubility was 55 wt %. At this level, however, the antifoam's
surface tension properties are incompatible with diesel fuel.
Similarly, at 100 wt %, EHAT based polymers formulations have
sufficiently low surface tension to be active in diesel but are too
soluble and fail to form the necessary antifoam droplets.
[0021] It was surprisingly found, however, that the solubility and
surface tension poly(acrylate) polymers could be varied not only by
the amount of (meth)acrylate monomers used, but by the
(meth)acrylate monomer type. The selection of certain
(meth)acrylate monomers could help drive the solubility properties
or surface tension properties of a resulting poly(acrylate) polymer
in a desired direction.
[0022] As used herein, the term "poly(acrylate) polymers" are
polymers derived from monomers comprising alkyl esters of
(meth)acrylic acids. Poly(acrylate) polymers are commonly referred
to as polyacrylates or acrylics. The terms "(meth)acrylic acid",
"(meth)acrylate" and related terms include both acrylate and
methacrylate groups, i.e. the methyl group is optional. For
example, the term (meth) acrylic acid includes acrylic acid and
methacrylic acid. Accordingly, in some embodiments, a
(meth)acrylate or acrylate may comprise at least one acrylate,
acrylic acid, methacrylate, methacrylic acid, or combinations
thereof.
[0023] When referring to a specified monomer(s) that is
incorporated or used to prepare a poly(acrylate) polymer disclosed
herein, the ordinarily skilled person will recognize that the
monomer(s) will be incorporated as at least one unit into the
poly(acrylate) polymer.
[0024] It was surprisingly found that (meth)acrylate monomers
having C.sub.1 to C.sub.30 alkyl esters of (meth)acrylic acid
resulted in poly(acrylate) polymers having both solubility and
surface tension properties to make them effective antifoam
components in fuels, such as diesel fuels. As such, these
(meth)acrylate monomers having C.sub.1 to C.sub.30 alkyl esters of
(meth)acrylic acid are referred to herein as "multifunctional
monomers". Accordingly, compositions comprising a fuel and at least
one poly(acrylate) polymer prepared by polymerizing (meth)acrylate
monomers comprising C.sub.1 to C.sub.30 alkyl esters of
(meth)acrylic acid ("multifunctional monomers") are disclosed.
Exemplary multifunction monomers include tertiary butyl
(meth)acrylate, ethyl (meth)acrylate.
[0025] As used herein, C.sub.x to C.sub.y, when used to describe
the alkyl esters of (meth)acrylic acid, refers to the number of
carbon atoms in the alkyl group connected to the oxygen on the
(meth)acrylate moiety and does not include the number of carbon
atoms in the (meth)acrylate moiety itself.
[0026] In some embodiments, the multifunctional monomer may
comprise C.sub.2 to C.sub.27 alkyl esters of (meth)acrylic acid. In
other embodiments, the multifunctional monomers may comprise
C.sub.2 to C.sub.12, or C.sub.2, C.sub.3, C.sub.4, C.sub.5,
C.sub.6, C.sub.7, C.sub.8, C.sub.9, C.sub.10, C.sub.11, or C.sub.12
alkyl esters of (meth)acrylic acid. Exemplary multifunctional
monomers include, but are not limited to, monomers comprising
tertiary butyl (meth)acrylate or 3,3-dimethylbutyl(meth)acrylate,
neopentyl(meth)acrylate, or combinations thereof. In yet other
embodiments, the poly(acrylate) polymers made from the
multifunctional monomers may be homopolymers. The compositions may
comprise at least 80 wt %, 85 wt %, 90 wt %, 95 wt %, 98 wt % or
100 wt % of a multifunctional monomer. In some embodiments the
compositions may comprise at least 80 wt % of a multifunctional
monomer and 20 wt % or less of a solubility monomer, surface
tension monomer, or combinations thereof. In yet other embodiments,
the ratio of the multifunctional monomer to the solubility monomer,
surface tension monomer, or combinations thereof may be 85:15,
90:10, 95:05, or 98:02.
[0027] Yet other (meth)acrylate monomers were found to affect
primarily only one factor of the resulting poly(acrylate) polymers.
The (meth)acrylate monomers that primarily affect the solubility of
the resulting poly(acrylate) polymers are referred to herein as
"solubility" monomers. These solubility monomers are (meth)acrylate
monomers comprising C.sub.1 to C.sub.4 alkyl esters of
(meth)acrylic acid Exemplary solubility monomers include, but are
not limited to, methyl (meth)acrylate, ethyl (meth)acrylate,
(meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, polyalkylene
glycol ("PAG") (meth)acrylate, and combinations thereof.
[0028] Similarly, (meth)acrylate monomers that primarily affect the
surface tension of the resulting poly(acrylate) polymers are
referred to herein as "surface tension" monomers. These surface
tension monomers are (meth)acrylate monomers comprising C.sub.5 to
C.sub.12 alkyl esters of (meth)acrylic acid. Exemplary surface
tension monomers include, but are not limited to, 2-ethylhexyl
(meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, and
combinations thereof.
[0029] Accordingly, compositions comprising at least one
poly(acrylate) polymer prepared by polymerizing both solubility
monomers and surface tension monomers are also disclosed. In some
embodiments, the poly(acrylate) polymer may be prepared by
polymerizing (i) a (meth)acrylate monomer comprising C.sub.1 to
C.sub.4 alkyl esters of (meth)acrylic acid ("solubility monomer");
(ii) a (meth)acrylate monomer comprising C.sub.5 to C.sub.12 alkyl
esters of (meth)acrylic acid ("surface tension monomer"); and (iii)
optionally at least one additional monomer that may comprise a
solubility monomer, surface tension monomer, a monomer having
C.sub.1 to C.sub.30 alkyl esters of (meth)acrylic acid
("multifunctional monomer"), or combinations thereof.
[0030] In other embodiments, poly(acrylate) polymer may be
polymerized using: (i) from 5 wt % to 95 wt % of the solubility
monomer; (ii) from 95 wt % to 5 wt % of the surface tension
monomer; and (iii) optionally from 2 wt % to 10 wt % of the at
least one additional monomer. Exemplary ratios of the
solubility:surface tension:additional monomer include, but are not
limited to, 80:15:5; 80:10:10, 80:5:15, 85:10:5, 85:5:10, and
combinations in between. In some embodiments, the ratios may be
85:11:4 or 85:4:11.
[0031] The poly(acrylate) polymer may be at least one of a
copolymer, block polymer, random polymer, terpolymer, or
combinations thereof. In some embodiments, the poly(acrylate)
polymer antifoam component employed herein generally will have a
weight average molecular weight (M.sub.w) of at least 13,000 Da. In
some embodiments, the poly(acrylate) polymer may have a M.sub.w of
from 10,000 to 350,000 Da, or 20,000 to 200,000 Da. In yet other
embodiments, the poly(acrylate) polymer may have a M.sub.w of from
20,000 to 80,000 Da or 30,000 to 40,000 Da.
[0032] As used herein, the weight average molecular weight
(M.sub.w) is measured using gel permeation chromatography ("GPC")
(Waters Alliance e2695) based on polystyrene standards. The
instrument is equipped with a refractive index detector and Waters
Empower.TM. data acquisition and analysis software. The columns are
polystyrene/divinylbenzene (PLgel, (3 "Mixed-C" and one 100
Angstrom, 5 micron particle size), available from Agilent
Technologies). For the mobile phase, individual samples are
dissolved in tetrahydrofuran and filtered with PTFE filters before
they are injected into the GPC port. [0033] Waters Alliance e2695
Operating Conditions: [0034] Column Temperature: 40.degree. C.
[0035] Autosampler Control: Run time: 45 minutes [0036] Injection
volume: 300 microliter [0037] Flow rate: 1.0 ml/minute [0038]
Differential Refractometer (RI) (2414): Sensitivity: 16; Scale
factor: 20
[0039] Persons ordinarily skilled in the art will understand that
the number average molecular weight ("M.sub.n") may be measured
using a similar technique to the one described above.
[0040] The poly(acrylate) polymer antifoam components disclosed
herein can be prepared by methods generally known in the art. The
polymerization may be affected in mass, emulsion or solution in the
presence of a free-radical liberating agent as catalyst and in the
presence or absence of known polymerization regulators. In one
embodiment, the antifoam can be polymerized in the presence of a
solvent. The solvent may be aliphatic (such as heptanes) or
aromatic (such as xylene or toluene). In another embodiment, the
antifoam can be polymerized in a hydrocarbon oil. In yet other
embodiments, the antifoam may be polymerized in light aromatic
petroleum naphtha, heavy aromatic naphtha, or combinations
thereof.
[0041] In some embodiments, the poly(acrylate) polymer may comprise
units with the structure of formula (I):
##STR00002##
wherein R.sup.1 is H or CH.sub.3; R.sup.2 is a C.sub.2 to C.sub.10
linear, branched, or cyclic hydrocarbyl group; R.sup.3 is a C.sub.2
to C.sub.4 linear or branched hydrocarbyl group; R.sup.4 is H, OH,
or CH.sub.3; n.sub.1 is an integer ranging from 75 to 3000; and
n.sub.2 is an integer ranging from 0 to 3.
[0042] In some embodiments, R.sup.2 and/or R.sup.3 is branched. In
other embodiments, R.sup.2 is linear and R.sup.3 is branched.
[0043] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: [0044] hydrocarbon
substituents, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and
aromatic-, aliphatic-, and alicyclic-substituted aromatic
substituents, as well as cyclic substituents wherein the ring is
completed through another portion of the molecule (e.g., two
substituents together form a ring); [0045] substituted hydrocarbon
substituents, that is, substituents containing non-hydrocarbon
groups which, in the context of this invention, do not alter the
predominantly hydrocarbon nature of the substituent (e.g., halo
(especially chloro and fluoro), hydroxy, alkoxy, mercapto,
alkylmercapto, nitro, nitroso, and sulfoxy); [0046] hetero
substituents, that is, substituents which, while having a
predominantly hydrocarbon character, in the context of this
invention, contain other than carbon in a ring or chain otherwise
composed of carbon atoms and encompass substituents as pyridyl,
furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen,
and nitrogen. In general, no more than two, or no more than one,
non-hydrocarbon substituent will be present for every ten carbon
atoms in the hydrocarbyl group; alternatively, there may be no
non-hydrocarbon substituents in the hydrocarbyl group. In one
embodiment, there are no halo substituents in the hydrocarbyl
group.
[0047] The surface tension of the poly(acrylate) polymer varies
with the number of carbon atoms in the (meth)acrylate monomer used
to make the polymer. In some embodiments, the surface tension
monomer may comprise C.sub.7, C.sub.8, C.sub.9, C.sub.10, C.sub.11,
or C.sub.12 alkyl esters of (meth)acrylic acid. In some
embodiments, the surface tension monomer may comprise C.sub.9 alkyl
esters of (meth)acrylic acid. It was further found that the surface
tension monomers having branched alkyl groups tended to result in
poly(acrylate) polymers with lower surface tension properties than
monomers having the same number of carbon atoms in a linear
configuration. Accordingly, in some embodiments, R.sup.2 and/or
R.sup.3 may be branched. In other embodiments, R.sup.2 may be
linear and R.sup.3 may be branched. The (meth)acrylate monomers
having the lowest surface tension for a given carbon number tended
to comprise a neopentyl group having the structure of formula
(II):
##STR00003##
[0048] Accordingly, in some embodiments (meth)acrylate monomers
comprising a terminal neopentyl group are disclosed. Exemplary
monomers include, but are not limited to, monomers comprising
2,2-dimethylheptane, 2,2,4-trimethylhexane,
2,2,4,4-tetramethylpentane, 2,2,5-trimethylhexane, and combinations
thereof as terminal neopentyl groups. In yet another embodiment,
the surface tension monomer may comprise C.sub.9 alkyl esters of
(meth)acrylic acid having a terminal neopental group.
[0049] In some embodiments, the multifunctional monomer and/or
solubility monomer may comprise C.sub.1-C.sub.4 alkyl esters of
(meth)acrylic acid. In other embodiments the multifunctional
monomer and/or surface tension monomer may comprise
C.sub.5-C.sub.12 alkyl esters of (meth)acrylic acid. In some
embodiments, the multifunctional monomer and/or solubility monomer
may comprise tertiary butyl (meth)acrylate. In other embodiments,
the multifunctional monomer and/or the surface tension monomer may
comprise tertiary butyl (meth)acrylate. In yet other embodiments,
the solubility monomer may comprise tertiary butyl (meth)acrylate
and the surface tension monomer may comprise trimethylhexyl
(meth)acrylate. In one embodiment, the solubility monomer may
comprise tertiary butyl (meth)acrylate and the surface tension
monomer may comprise 2-ethylhexyl (meth)acrylate. The ratio of the
multifunctional and/or solubility monomer to the surface tension
monomer is not overly limited. In some embodiments, the ratio may
range from 98:2, 95:5, 90:10, 85:15, or 80:10.
[0050] In yet other embodiments, a composition comprising at least
two poly(acrylate) polymers is disclosed. The composition may
comprise a first poly(acrylate) polymer prepared by polymerizing a
(meth)acrylate monomer comprising C.sub.1 to C.sub.30 alkyl esters
of (meth)acrylic acid ("multifunctional monomer") and a second
poly(acrylate) polymer prepared by polymerizing: (i) a
(meth)acrylate monomer comprising C.sub.1 to C.sub.4 alkyl esters
of (meth)acrylic acid ("solubility monomer"); (ii) a (meth)acrylate
monomer comprising C.sub.5 to C.sub.12 alkyl esters of
(meth)acrylic acid ("surface tension monomer"); and (iii)
optionally at least one additional monomer comprising a solubility
monomer, a surface tension monomer, a monomer comprising C.sub.1 to
C.sub.30 alkyl esters of (meth)acrylic acid ("multifunctional
monomer"), or combinations thereof.
[0051] The poly(acrylate) polymers described above may be added to
a fuel to reduce the amount of foam produced in the fuel. In some
embodiments, the fuel may comprise diesel. The poly(acrylate)
polymer may be present in the fuel in an amount from 0.1 ppm to
3000 ppm by weight, or 1 ppm to 100 ppm, or 75 to 1500 ppm, or even
500 to 3000 ppm by weight, based on a total weight of the fuel
composition. Accordingly, methods of reducing foam in a fuel are
also disclosed. The use of a poly(acrylate) polymer to reduce a
foam in a fuel is also disclosed.
[0052] Methods of reducing the amount of foam produced while filing
the fuel tank of a vehicle are also disclosed. The method may
comprise adding a poly(acrylate) polymer prepared by polymerizing a
(meth)acrylate monomer to a fuel. The poly(acrylate) polymer may be
as described above.
Fuel and Fuel Compositions
[0053] The fuel compositions described herein can comprise a fuel
which is liquid at room temperature and is useful in fueling an
engine. The fuel is normally a liquid at ambient conditions e.g.,
room temperature (20 to 30.degree. C.). The fuel can be a
hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture thereof. The
hydrocarbon fuel can be a diesel fuel as defined by EN590 or ASTM
specification D975. The hydrocarbon fuel can be a hydrocarbon
prepared by a gas to liquid process to include for example
hydrocarbons prepared by a process such as the Fischer-Tropsch
process. Accordingly, in some embodiments, the fuel may be a gas to
liquid ("GTL") diesel, biomass to liquid ("BTL") fuel, or
combinations thereof.
[0054] The nonhydrocarbon fuel can include, transesterified oils
and/or fats from plants and animals such as rapeseed methyl ester
and soybean methyl ester. Mixtures of hydrocarbon and
nonhydrocarbon fuels can include for example, diesel fuel and
ethanol, and diesel fuel and a transesterified plant oil such as
rapeseed methyl ester. In an embodiment of the invention the liquid
fuel is an emulsion of water in a hydrocarbon fuel, a
nonhydrocarbon fuel, or a mixture thereof.
[0055] In some embodiments, the fuel may comprise a hydro-treated
vegetable oil ("HVO"), commonly called a renewable diesel. In other
embodiments, the fuel may comprise mixtures of diesel and HVO. In
yet other embodiments the fuel can comprise blends of biodiesel and
diesel, blends of HVO and diesel, or blends of HVO and
biodiesel.
[0056] In several embodiments, the fuel can have a sulfur content
on a weight basis that is 5000 ppm or less, 1000 ppm or less, 300
ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less. In
another embodiment the fuel can have a sulfur content on a weight
basis of 1 to 100 ppm.
[0057] The fuel is present in a fuel composition in a major amount
that is generally greater than 50 percent by weight, and in other
embodiments is present at greater than 90 percent by weight,
greater than 95 percent by weight, greater than 99.5 percent by
weight, or greater than 99.8 percent by weight. The fuel
composition may comprise one or more fuel additives as described
below.
[0058] In some embodiments, the fuel composition may comprise at
least one combustion improver. Combustion improvers include for
example octane and cetane improvers. Suitable cetane number
improvers are, for example, aliphatic nitrates such as 2-ethylhexyl
nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl
peroxide.
[0059] In a yet another embodiment, the fuel composition comprises
antifoam components of the disclosed technology as described above
and at least one demulsifier. Suitable demuslifiers can include,
but are not limited to arylsulfonates and polyalkoxylated alcohol,
such as, for example, polyethylene and polypropylene oxide
copolymers and the like. The demulsifiers can also comprise
nitrogen containing compounds such as oxazoline and imidazoline
compounds and fatty amines, as well as Mannich compounds. Mannich
compounds are the reaction products of alkylphenols and aldehydes
(especially formaldehyde) and amines (especially amine condensates
and polyalkylenepolyamines). The materials described in the
following U.S. Patents are illustrative: U.S. Pat. Nos. 3,036,003;
3,236,770; 3,414,347; 3,448,047; 3,461,172; 3,539,633; 3,586,629;
3,591,598; 3,634,515; 3,725,480; 3,726,882; and 3,980,569 herein
incorporated by reference. Other suitable demulsifiers are, for
example, the alkali metal or alkaline earth metal salts of
alkyl-substituted phenol- and naphthalenesulfonates and the alkali
metal or alkaline earth metal salts of fatty acids, and also
neutral compounds such as alcohol alkoxylates, e.g. alcohol
ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate
or tert-pentylphenol ethoxylate, fatty acids, alkylphenols,
condensation products of ethylene oxide (EO) and propylene oxide
(PO), for example including in the form of EO/PO block copolymers,
polyethyleneimines or else polysiloxanes. Any of the commercially
available demulsifiers may be employed, suitably in an amount
sufficient to provide a treat level of from 5 to 50 ppm in the
fuel. In one embodiment the fuel composition of the invention does
not comprise a demulsifier. The demulsifiers may be used alone or
in combination. Some demulsifiers are commercially available, for
example from Nalco or Baker Hughes. Typical treat rates of the
demulsifiers to a fuel may range from 0 to 50 ppm by total weight
of the fuel, or 5 to 50 ppm, or 5 to25 ppm, or 5 to 20 ppm.
[0060] The disclosed technology may also be used with demulsifiers
comprising a hydrocarbyl-substituted dicarboxylic acid in the form
of the free acid, or in the form of the anhydride which may be an
intramolecular anhydride, such as succinic, glutaric, or phthalic
anhydride, or an intermolecular anhydride linking two dicarboxylic
acid molecules together. The hydrocarbyl substituent may have from
12 to 2000 carbon atoms and may include polyisobutenyl substituents
having a number average molecular weight of 300 to 2800. Exemplary
hydrocarbyl-substituted dicarboxylic acids include, but are not
limited to, hydrocarbyl-substituted acids derived from malonic,
succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic,
undecanedioic, dodecanedioic, phthalic, isophthalic, terphthalic,
ortho, meta, or paraphenylene diacetic, maleic, fumaric, or
glutaconic acids.
[0061] In another embodiment, the fuel compositions further
comprise at least one detergent/dispersant. Customary
detergent/dispersant additives are amphiphilic substances which
possess at least one hydrophobic hydrocarbon radical with a number
average molecular weight of 100 to 10000 and at least one polar
moiety selected from (i) Mono- or polyamino groups having up to 6
nitrogen atoms, at least one nitrogen atom having basic properties;
(ii) Hydroxyl groups in combination with mono or polyamino groups,
at least one nitrogen atoms having basic properties; (iii) Carboxyl
groups or their alkali metal or alkaline earth metal salts; (iv)
Sulfonic acid groups or their alkali metal or alkaline earth metal
salts; (v) Polyoxy-C.sub.2 to C.sub.4 alkylene moieties terminated
by hydroxyl groups, mono- or polyamino groups, at least one
nitrogen atom having basic properties, or by carbamate groups; (vi)
Carboxylic ester groups; (vii) Moieties derived from succinic
anhydride and having hydroxyl and/or amino and/or amido and/or
imido groups; and/or (viii) Moieties obtained by Mannich reaction
of substituted phenols with aldehydes and mono- or polyamines.
[0062] The hydrophobic hydrocarbon radical in the above
detergent/dispersant additives which ensures the adequate
solubility in the fuel, has a number average molecular weight
(M.sub.n) of 85 to 20,000, or 100 to 10,000, or 300 to 5000. In yet
another embodiment, the detergent/dispersant additives have a
M.sub.n of 300 to 3000, of 500 to 2500, of 700 to 2500, or 800 to
1500. Typical hydrophobic hydrocarbon radicals, may be
polypropenyl, polybutenyl and polyisobutenyl radicals, with a
number average molecular weight M.sub.n, of 300 to 5000, of 300 to
3000, of 500 to 2500, or 700 to 2500. In one embodiment the
detergent/dispersant additives have a M.sub.n of 800 to 1500.
[0063] The additional performance additives may comprise a high TBN
nitrogen containing detergent/dispersant, such as a succinimide,
that is the condensation product of a hydrocarbyl-substituted
succinic anhydride with a poly(alkyleneamine). Succinimide
detergents/dispersants are more fully described in U.S. Pat. Nos.
4,234,435 and 3,172,892. Another class of ashless dispersant is
high molecular weight esters, prepared by reaction of a hydrocarbyl
acylating agent and a polyhydric aliphatic alcohol such as
glycerol, pentaerythritol, or sorbitol. Such materials are
described in more detail in U.S. Pat. No. 3,381,022.
[0064] Nitrogen-containing detergents may be the reaction products
of a carboxylic acid-derived acylating agent and an amine. The
acylating agent can vary from formic acid and its acylating
derivatives to acylating agents having high molecular weight
aliphatic substituents of up to 5,000, 10,000 or 20,000 carbon
atoms. The amino compounds can vary from ammonia itself to amines
typically having aliphatic substituents of up to 30 carbon atoms,
and up to 11 nitrogen atoms. Acylated amino compounds suitable for
use in the present invention may be those formed by the reaction of
an acylating agent having a hydrocarbyl substituent of at least 8
carbon atoms and a compound comprising at least one primary or
secondary amine group. The acylating agent may be a mono- or
polycarboxylic acid (or reactive equivalent thereof) for example a
substituted succinic, phthalic or propionic acid and the amino
compound may be a polyamine or a mixture of polyamines, for example
a mixture of ethylene polyamines. Alternatively, the amine may be a
hydroxyalkyl-substituted polyamine. The hydrocarbyl substituent in
such acylating agents may comprise at least 10 carbon atoms. In one
embodiment, the hydrocarbyl substituent may comprise at least 12,
for example 30 or 50 carbon atoms. In yet another embodiment, it
may comprise up to 200 carbon atoms. The hydrocarbyl substituent of
the acylating agent may have a number average molecular weight
(M.sub.n) of 170 to 2800, for example from 250 to 1500. In other
embodiments, the substituent's M.sub.n may range from 500 to 1500,
or alternatively from 500 to 1100. In yet another embodiment, the
substituent's M.sub.n may range from 700 to 1300. In another
embodiment, the hydrocarbyl substituent may have a number average
molecular weight of 700 to 1000, or 700 to 850, or, for example,
750.
[0065] Another class of ashless dispersant is Mannich bases. These
are materials which are formed by the condensation of a higher
molecular weight, alkyl substituted phenol, an alkylene polyamine,
and an aldehyde such as formaldehyde and are described in more
detail in U.S. Pat. No. 3,634,515.
[0066] A useful nitrogen containing dispersant includes the product
of a Mannich reaction between (a) an aldehyde, (b) a polyamine, and
(c) an optionally substituted phenol. The phenol may be substituted
such that the Mannich product has a molecular weight of less than
7500. Optionally, the molecular weight may be less than 2000, less
than 1500, less than 1300, or for example, less than 1200, less
than 1100, less than 1000. In some embodiments, the Mannich product
has a molecular weight of less than 900, less than 850, or less
than 800, less than 500, or less than 400. The substituted phenol
may be substituted with up to 4 groups on the aromatic ring. For
example, it may be a tri or di-substituted phenol. In some
embodiments, the phenol may be a mono-substituted phenol. The
substitution may be at the ortho, and/or meta, and/or para
position(s). To form the Mannich product, the molar ratio of the
aldehyde to amine is from 4:1 to 1:1 or, from 2:1 to 1:1. The molar
ratio of the aldehyde to phenol may be at least 0.75:1; preferably
from 0.75 to 1 to 4:1, preferably 1:1 to 4;1 more preferably from
1:1 to 2:1. To form the preferred Mannich product, the molar ratio
of the phenol to amine is preferably at least 1.5:1, more
preferably at least 1.6:1, more preferably at least 1.7:1, for
example at least 1.8:1, preferably at least 1.9:1. The molar ratio
of phenol to amine may be up to 5:1; for example it may be up to
4:1, or up to 3.5:1. Suitably it is up to 3.25:1, up to 3:1, up to
2.5:1, up to 2.3:1 or up to 2.1:1.
[0067] Other dispersants include polymeric dispersant additives,
which are generally hydrocarbon-based polymers which contain polar
functionality to impart dispersancy characteristics to the polymer.
An amine is typically employed in preparing the high TBN
nitrogen-containing dispersant. One or more poly(alkyleneamine)s
may be used, and these may comprise one or more
poly(ethyleneamine)s having 3 to 5 ethylene units and 4 to 6
nitrogen units. Such materials include triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA).
Such materials are typically commercially available as mixtures of
various isomers containing a range number of ethylene units and
nitrogen atoms, as well as a variety of isomeric structures,
including various cyclic structures. The poly(alkyleneamine) may
likewise comprise relatively higher molecular weight amines known
in the industry as ethylene amine still bottoms.
[0068] In an embodiment, the fuel composition can additionally
comprise quaternary ammonium salts. The quaternary ammonium salts
can comprise (a) a compound comprising (i) at least one tertiary
amino group as described above, and (ii) a hydrocarbyl-substituent
having a number average molecular weight of 100 to 5000, or 250 to
4000, or 100 to 4000 or 100 to 2500 or 3000; and (b) a quaternizing
agent suitable for converting the tertiary amino group of (a)(i) to
a quaternary nitrogen, as described above. The other quaternary
ammonium salts are more thoroughly described in U.S. Pat. No.
7,951,211, issued May 31, 2011, and U.S. Pat. No. 8,083814, issued
Dec. 27, 2011, and U.S. Publication Nos. 2013/0118062, published
May 16, 2013, 2012/0010112, published Jan. 12, 2012, 2013/0133243,
published May 30, 2013, 2008/0113890, published May 15, 2008, and
2011/0219674, published Sep. 15, 2011, US 2012/0149617 published
May 14, 2012, US 2013/0225463 published Aug. 29, 2013, US
2011/0258917 published Oct. 27, 2011, US 2011/0315107 published
Dec. 29, 2011, US 2013/0074794 published Mar. 28, 2013, US
2012/0255512 published Oct. 11, 2012, US 2013/0333649 published
Dec. 19, 2013, US 2013/0118062 published May 16, 2013, and
international publications WO Publication Nos. 2011/141731,
published Nov. 17, 2011, 2011/095819, published Aug. 11, 2011, and
2013/017886, published Feb. 7, 2013, WO 2013/070503 published May
16, 2013, WO 2011/110860 published Sep. 15, 2011, WO 2013/017889
published Feb. 7, 2013, WO 2013/017884 published Feb. 7, 2013.
[0069] The quaternary ammoniums salts can be prepared from
hydrocarbyl substituted acylating agents, such as, for example,
polyisobutyl succinic acids or anhydrides, having a hydrocarbyl
substituent with a number average molecular weight of greater than
1200 M.sub.n, polyisobutyl succinic acids or anhydrides, having a
hydrocarbyl substituent with a number average molecular weight of
300 to 750, or polyisobutyl succinic acids or anhydrides, having a
hydrocarbyl substituent with a number average molecular weight of
1000 M.sub.n.
[0070] In an embodiment, the additional salts may be an imide
prepared from the reaction of a nitrogen containing compound and a
hydrocarbyl substituted acylating agent having a hydrocarbyl
substituent with a number average molecular weight of 1300 to 3000.
In an embodiment, the quaternary ammonium salts prepared from the
reaction of nitrogen containing compound and a hydrocarbyl
substituted acylating agent having a hydrocarbyl substituent with a
number average molecular weight of greater than 1200 M.sub.n or,
having a hydrocarbyl substituent with a number average molecular
weight of 300 to 750 is an amide or ester.
[0071] In an embodiment the nitrogen containing compound of the
additional quaternary ammonium salts is an imidazole or nitrogen
containing compound of either of formulas:
##STR00004##
wherein R may be a C.sub.1 to C.sub.6 alkylene group; each of
R.sub.1 and R.sub.2, individually, may be a C.sub.1 to C.sub.6
hydrocarbylene group; and each of R.sub.3, R.sub.4, R.sub.5, and
R.sub.6, individually, may be a hydrogen or a C.sub.1 to C.sub.6
hydrocarbyl group.
[0072] In other embodiments, the quaternizing agent used to prepare
the additional quaternary ammonium salts can be a dialkyl sulfate,
an alkyl halide, a hydrocarbyl substituted carbonate, a hydrocarbyl
epoxide, a carboxylate, alkyl esters, or mixtures thereof. In some
cases, the quaternizing agent can be a hydrocarbyl epoxide. In some
cases, the quaternizing agent can be a hydrocarbyl epoxide in
combination with an acid. In some cases, the quaternizing agent can
be a salicylate, oxalate or terephthalate. In an embodiment, the
hydrocarbyl epoxide is an alcohol functionalized epoxides or
C.sub.4 to C.sub.14 epoxides.
[0073] In some embodiments, the quaternizing agent is
multi-functional resulting in the additional quaternary ammonium
salts being a coupled quaternary ammoniums salts.
[0074] Typical treat rates of additional detergents/dispersants to
a fuel of the invention is 0 to 500 ppm, or 0 to 250 ppm, or 0 to
100 ppm, or 5 to 250 ppm, or 5 to 100 ppm, or 10 to 100 ppm.
[0075] In a yet another embodiment, a fuel composition comprises
further comprises a cold flow improver. The cold flow improver is
typically selected from (1) copolymers of a C.sub.2- to
C.sub.40-olefin with at least one further ethylenically unsaturated
monomer; (2) comb polymers; (3) polyoxyalkylenes; (4) polar
nitrogen compounds; and (5) poly(meth)acrylic esters made from
linear alcohols having 10 to 22 carbon atoms. It is possible to use
either mixtures of different representatives from one of the
particular classes (1) to (5) or mixtures of representatives from
different classes (1) to (5).
[0076] Suitable C.sub.2- to C.sub.40-olefin monomers for the
copolymers of class (1) are, for example, those having 2 to 20 and
especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2
carbon-carbon double bonds, especially having one carbon-carbon
double bond. In the latter case, the carbon-carbon double bond may
be arranged either terminally (.alpha.-olefins) or internally.
However, preference is given to .alpha.-olefins, more preferably
.alpha.-olefins having 2 to 6 carbon atoms, for example propene,
1-butene, 1-pentene, 1-hexene and in particular ethylene. The at
least one further ethylenically unsaturated monomer of class (1) is
preferably selected from alkenyl carboxylates; for example,
C.sub.2- to C.sub.14-alkenyl esters, for example the vinyl and
propenyl esters, of carboxylic acids having 2 to 21 carbon atoms,
whose hydrocarbon radical may be linear or branched among these,
preference is given to the vinyl esters, examples of suitable
alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl
butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl
hexanoate, vinyl neononanoate, vinyl neodecanoate and the
corresponding propenyl esters, (meth)acrylic esters; for example,
esters of (meth)acrylic acid with C.sub.1- to C.sub.20-alkanols,
especially C.sub.1- to C.sub.10-alkanols, in particular with
methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol,
isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol,
2-ethylhexanol, nonanol and decanol, and structural isomers thereof
and further olefins; preferably higher in molecular weight than the
abovementioned C.sub.2- to C.sub.40-olefin base monomer for
example, the olefin base monomer used is ethylene or propene,
suitable further olefins are in particular C.sub.10- to
C.sub.40-.alpha.-olefins.
[0077] Suitable copolymers of class (1) are also those which
comprise two or more different alkenyl carboxylates in
copolymerized form, which differ in the alkenyl function and/or in
the carboxylic acid group. Likewise, suitable are copolymers which,
as well as the alkenyl carboxylate(s), comprise at least one olefin
and/or at least one (meth)acrylic ester in copolymerized form.
[0078] Terpolymers of a C.sub.2- to C.sub.40-.alpha.-olefin, a
C.sub.1- to C.sub.20-alkyl ester of an ethylenically unsaturated
monocarboxylic acid having 3 to 15 carbon atoms and a C.sub.2- to
C.sub.14-alkenyl ester of a saturated monocarboxylic acid having 2
to 21 carbon atoms are also suitable as copolymers of class (K1).
Terpolymers of this kind are described in WO 2005/054314. A typical
terpolymer of this kind is formed from ethylene, 2-ethylhexyl
acrylate and vinyl acetate.
[0079] The at least one or the further ethylenically unsaturated
monomer(s) are copolymerized in the copolymers of class (1) in an
amount of preferably 1 to 50% by weight, especially 10 to 45% by
weight and in particular 20 to 40% by weight, based on the overall
copolymer. The main proportion in terms of weight of the monomer
units in the copolymers of class (1) therefore originates generally
from the C.sub.2 to C.sub.40 base olefins. The copolymers of class
(1) may have a number average molecular weight M.sub.n of 1000 to
20,000, or 1000 to 10,000 or 1000 to 8000.
[0080] Typical comb polymers of component (2) are, for example,
obtainable by the copolymerization of maleic anhydride or fumaric
acid with another ethylenically unsaturated monomer, for example
with an .alpha.-olefin or an unsaturated ester, such as vinyl
acetate, and subsequent esterification of the anhydride or acid
function with an alcohol having at least 10 carbon atoms. Further
suitable comb polymers are copolymers of .alpha.-olefins and
esterified comonomers, for example esterified copolymers of styrene
and maleic anhydride or esterified copolymers of styrene and
fumaric acid. Suitable comb polymers may also be polyfumarates or
polymaleates. Homo- and copolymers of vinyl ethers are also
suitable comb polymers. Comb polymers suitable as components of
class (2) are, for example, also those described in WO 2004/035715
and in "Comb-Like Polymers. Structure and Properties", N. A. Plate
and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117
to 253 (1974). Mixtures of comb polymers are also suitable.
[0081] Polyoxyalkylenes suitable as components of class (3) are,
for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed
polyoxyalkylene ester/ethers and mixtures thereof. These
polyoxyalkylene compounds preferably comprise at least one linear
alkyl group, preferably at least two linear alkyl groups, each
having 10 to 30 carbon atoms and a polyoxyalkylene group having a
number average molecular weight of up to 5000. Such polyoxyalkylene
compounds are described, for example, in EP-A 061 895 and also in
U.S. Pat. No. 4,491,455. Particular polyoxyalkylene compounds are
based on polyethylene glycols and polypropylene glycols having a
number average molecular weight of 100 to 5000. Additionally,
suitable are polyoxyalkylene mono- and diesters of fatty acids
having 10 to 30 carbon atoms, such as stearic acid or behenic
acid.
[0082] Polar nitrogen compounds suitable as components of class (4)
may be either ionic or nonionic and may have at least one
substituent, or at least two substituents, in the form of a
tertiary nitrogen atom of the general formula >NR.sup.7 in which
R.sup.7 is a C.sub.8- to C.sub.40-hydrocarbon radical. The nitrogen
substituents may also be quaternized i.e. be in cationic form. An
example of such nitrogen compounds is that of ammonium salts and/or
amides which are obtainable by the reaction of at least one amine
substituted by at least one hydrocarbon radical with a carboxylic
acid having 1 to 4 carboxyl groups or with a suitable derivative
thereof. The amines may comprise at least one linear C.sub.8- to
C.sub.40-alkyl radical. Primary amines suitable for preparing the
polar nitrogen compounds mentioned are, for example, octylamine,
nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine
and the higher linear homologs. Secondary amines suitable for this
purpose are, for example, dioctadecylamine and methylbehenylamine.
Also suitable for this purpose are amine mixtures, in particular
amine mixtures obtainable on the industrial scale, such as fatty
amines or hydrogenated tallow amines, as described, for example, in
Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition,
"Amines, aliphatic" chapter. Acids suitable for the reaction are,
for example, cyclohexane-1,2-dicarboxylic acid,
cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic
acid, naphthalene dicarboxylic acid, phthalic acid, isophthalic
acid, terephthalic acid, and succinic acids substituted by
long-chain hydrocarbon radicals.
[0083] Poly(meth)acrylic esters suitable as cold flow improvers of
class (5) are either homo- or copolymers of acrylic and methacrylic
esters. Preference is given to copolymers of at least two different
(meth)acrylic esters which differ with regard to the esterified
alcohol. The copolymer optionally comprises another different
olefinically unsaturated monomer in copolymerized form. The
weight-average molecular weight of the polymer is preferably 50,000
to 500,000. The polymer may be a copolymer of methacrylic acid and
methacrylic esters of saturated C.sub.14 and C.sub.15 alcohols, the
acid groups having been neutralized with hydrogenated tallow amine.
Suitable poly(meth)acrylic esters are described, for example, in WO
00/44857.
[0084] The cold flow improver or the mixture of different cold flow
improvers is added to the middle distillate fuel or diesel fuel in
a total amount of preferably 0 to 5000 ppm by weight, or 10 to 5000
ppm by weight, or 20 to 2000 ppm by weight, or 50 to 1000 ppm by
weight, or 100 to 700 ppm by weight, for example of 200 to 500 ppm
by weight.
[0085] Additional antifoams and/or foam inhibitors may be used in
addition to the poly(acrylate) polymer antifoam components
disclosed herein. These additional foam inhibitors include
polysiloxanes, copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including fluorinated polysiloxanes, trialkyl phosphates,
polyethylene glycols, polyethylene oxides, polypropylene oxides and
(ethylene oxide-propylene oxide) polymers. The disclosed technology
may also be used with a silicone-containing antifoam agent in
combination with a C.sub.5-C.sub.17 alcohol. In yet other
embodiments, the additional antifoams may include organic silicones
such as polydimethyl siloxane, polyethylsiloxane,
polydiethylsiloxane, polyacrylates and polymethacrylates,
trimethyl-triflouro-propylmethyl siloxane and the like.
[0086] The compositions disclosed herein may also comprise
lubricity improvers or friction modifiers typically based on fatty
acids or fatty acid esters. Typical examples are tall oil fatty
acid, as described, for example, in WO 98/004656, and glyceryl
monooleate. The reaction products, described in U.S. Pat. No.
6,743,266 B2, of natural or synthetic oils, for example
triglycerides, and alkanolamines are also suitable as such
lubricity improvers. Additional examples include commercial tall
oil fatty acids containing polycyclic hydrocarbons and/or rosin
acids.
[0087] The compositions disclosed herein may also comprise
additives to reduce the amount of metal solubilized in the fuel
(reduces "metal pick-up"). These additives may be a hydrocarbon
substituted with at least two carboxy functionalities in the form
of acids or at least one carboxy functionality in the form an
anhydride. Suitable metal pick-up additives include di-acid
polymers derived from fatty acids and/or polyolefins, including
polyalkenes. Exemplary polyolefins include C.sub.10 to C.sub.20
polyolefins, C.sub.12 to C.sub.18 polyolefins, and/or C.sub.16 to
C.sub.18 polyolefins. The polyalkene may be characterized by a
(number average molecular weight) of at least about 300. In some
embodiments, the metal-pick-up additive comprises more hydrocarbyl
substituted succinic anhydride groups. In some embodiments the
hydrocarbyl substituted acylating agent comprises one or more
hydrolyzed hydrocarbyl substituted succinic anhydride groups (i.e.,
hydrocarbyl substituted succinic acid). In some embodiments the
hydrocarbyl substituents are derived from homopolymers and/or
copolymers containing 2 to 10 carbon atoms. In some embodiments the
hydrocarbyl substituents above are derived from polyisobutylene. In
one embodiment, the metal pick-up additive comprises hydrolyzed
polyisobutylene succinic anhydride (PIBSA) or polyisobutylene
succinic acid.acid.acid.
[0088] The fuel compositions disclosed herein may also comprise one
or more antistatic agents, also commonly referred to as static
dissipators or conductivity improvers. Suitable antistatic agents
include but are not limited to alkyl benzene sulfonic acid.
Additive Packages
[0089] Fuel additive packages and their uses are also disclosed
herein. The fuel additive packages may comprise one or more of the
fuel additives described above. In one embodiment, the fuel
additive package may comprise: (i) at least one quaternary ammonium
salt; (ii) at least one hydrolyzed polyisobutylene succinic
anhydride (PIBSA), polyisobutylene succinic acid, or combinations
thereof; (iii) at least one demulsifier; (iv) at least one antifoam
component as described above; (v) optionally, at least one cetane
improver; and (vi) optionally, at least one solvent. Suitable
solvents include paraffinic solvents, aromatic solvents, aliphatic
solvents, protic solvents, or combinations thereof. In one
embodiment, the at least one solvent may comprise an aromatic
solvent (such as heavy aromatic naphtha), ethyl hexyl alcohol, or
combinations thereof. The poly(acrylate) polymer antifoam
components disclosed herein may be provided with one or more
additives described above in an additive package composition. The
additive package composition may comprise one or more additives in
a concentrated solution suitable for adding to a diesel fuel.
Exemplary additive package compositions are included in Table 1.
The amounts shown are in weight percents, based on a total weight
of the additive package.
TABLE-US-00001 TABLE 1 Additive Package A B C D E F G Quaternary
ammonium salts 5 to 20 5 to 20 15 to 35 15 to 35 10 to 20 10 to 30
10 to 40 Hydrolyzed PIBSA 1 to 10 1 to 10 5 to 15 5 to 15 1 to 5 3
to 12 5 to 15 Demulsifier 0.2 to 3.sup. 0.2 to 3 1 to 6 0.2 to
3.sup. 0.1 to 1.sup. 1 to 5 2 to 4 Antifoam component 1 to 5 1 to
10 3 to 10 2.5 to 7.5 0.5 to 5.sup. 1 to 10 7 to 15 Cetane improver
0 60-90 0 0 0 0 0 Aromatic solvent 40 to 60 0 0 to 30 35 to 60 40
to 80 30 to 60 30 to 70 Ethyl hexyl alcohol 15 to 30 0 40 to 80 15
to 30 10 to 40 10 to 35 5 to 30
INDUSTRIAL APPLICATION
[0090] In one embodiment, the invention is useful in a liquid fuel
in an internal combustion engine. The internal combustion engine
may be a diesel engine. Exemplary internal combustion engines
include, but are not limited to, compression ignition engines;
4-stroke cycles; liquid fuel supplied via direct injection,
indirect injection, common rail and unit injector systems; light
(e.g. passenger car) and heavy duty (e.g. commercial truck)
engines; and engines fueled with hydrocarbon and non-hydrocarbon
fuels and mixtures thereof. The engines may be part of integrated
emissions systems incorporating such elements as; EGR systems;
aftertreatment including three-way catalyst, oxidation catalyst,
NO.sub.x absorbers and catalysts, catalyzed and non-catalyzed
particulate traps optionally employing fuel-borne catalyst;
variable valve timing; and injection timing and rate shaping.
[0091] In one embodiment, the technology may be used with diesel
engines having direct fuel injection systems wherein the fuel is
injected directly into the engine's combustion chamber. The
ignition pressures may be greater than 1000 bar and, in one
embodiment, the ignition pressure may be greater than 1350 bar.
Accordingly, in another embodiment, the direct fuel injection
system maybe a high-pressure direct fuel injection system having
ignition pressures greater than 1350 bar. Exemplary types of
high-pressure direct fuel injection systems include, but are not
limited to, unit direct injection (or "pump and nozzle") systems,
and common rail systems. In unit direct injection systems, the
high-pressure fuel pump, fuel metering system and fuel injector are
combined into one apparatus. Common rail systems have a series of
injectors connected to the same pressure accumulator, or rail. The
rail in turn, is connected to a high-pressure fuel pump. In yet
another embodiment, the unit direct injection or common rail
systems may further comprise an optional turbocharged or
supercharged direct injection system.
[0092] Methods reducing the amount of foam produced while filing
the fuel tank of a vehicle are also disclosed. The method may
comprise adding a poly(acrylate) polymer made from a (meth)acrylate
monomer to a fuel. The poly(acrylate) polymer may be as described
above. Methods of reducing foam in a fuel comprising adding the
fuel additive package described above to a fuel are also
disclosed.
[0093] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. For instance, metal ions (of, e.g., a detergent) can migrate
to other acidic or anionic sites of other molecules. The products
formed thereby, including the products formed upon employing the
composition of the present invention in its intended use, may not
be susceptible of easy description. Nevertheless, all such
modifications and reaction products are included within the scope
of the present invention; the present invention encompasses the
composition prepared by admixing the components described
above.
[0094] The following examples provide illustrations of the
disclosed technology. These examples are non-exhaustive and are not
intended to limit the scope of the disclosed technology.
EXAMPLES
Preparation of Inventive Composition 1 (TBAT:TMHAT, 95:05 by
Wt)--In Toluene Process:
[0095] Inventive Composition 1 is prepared by thoroughly mixing
tert-butyl acrylate (TBAT) (190.0 g), 3,5,5-trimethylhexyl acrylate
(TMHAT) (10.0 g), and tert-butyl peroxy-2-ethylhexanoate (TBPE)
(0.22 g) in a glass bottle to prepare a monomer mixture. Then,
66.67 g of the monomer mixture along with 100.0 g of toluene are
transferred to a 1 L round bottom flask equipped with a mechanical
stirrer, Claisen adapter with water-cooled condenser and nitrogen
inlet (set at 0.2 standard cubic feet per hours (scfh)), a
thermocouple and stopper ("reaction vessel"). This mixture is
heated to 90.degree. C. The remaining 133.3 g of the monomer
mixture is added over 180 minutes via peristaltic pump and
maintained at 90.degree. C. for the duration of the addition. After
all the monomer mixture is transferred to the reaction vessel, the
reaction temperature is maintained at 90.degree. C. for 180 min.
Then the temperature is adjusted to 100.degree. C., and TBPE (0.06
g) is added to the reaction vessel and held for 60 min. Similarly,
three more TBPE (0.06 g) aliquots are charged and allowed to react
for 60 min after each addition. Once complete monomer consumption
is observed, 100.0 g toluene is added and stirred for 30 min. The
reaction vessel contents are cooled and a colorless liquid having a
M.sub.w of 146,746 Da is obtained. A portion of the colorless
liquid (50 g) is transferred to a 25 ml single neck round-bottom
flask and the toluene is removed via rotavapor. The purified
bottoms comprise the poly(acrylate) polymer.
Preparation of Inventive Composition 2 (TBAT:TMHAT, 90:10 by
Wt)--In Toluene Process:
[0096] Inventive Composition 2 is prepared by thoroughly mixing
tert-butyl acrylate (TBAT) (180.0 g), 3,5,5-trimethylhexyl acrylate
(TMHAT) (20.0 g), and tert-butyl peroxy-2-ethylhexanoate (TBPE)
(0.22 g) in a glass bottle to prepare a monomer mixture. Then,
66.67 g of the monomer mixture along with 100.0 g of toluene are
transferred to a 1 L round bottom flask equipped with a mechanical
stirrer, Claisen adapter with water-cooled condenser and nitrogen
inlet (set at 0.2 standard cubic feet per hours (scfh)), a
thermocouple and stopper ("reaction vessel"). This mixture is
heated to 90.degree. C. The remaining 133.3 g of the monomer
mixture is added over 180 minutes via peristaltic pump and
maintained at 90.degree. C. for the duration of the addition. After
all the monomer mixture is transferred to the reaction vessel, the
reaction temperature is maintained at 90.degree. C. for 180 min.
Then the temperature is adjusted to 100.degree. C., and TBPE (0.06
g) is added to the reaction vessel and held for 60 min. Similarly,
three more TBPE (0.06 g) aliquots are charged and allowed to react
for 60 min after each addition. Once complete monomer consumption
is observed, 100.0 g toluene is added and stirred for 30 min. The
reaction vessel contents are cooled and a colorless liquid having a
M.sub.w of 155,702 Da is obtained. A portion of the colorless
liquid (50 g) is transferred to a 25 ml single neck round-bottom
flask and the toluene is removed via rotavapor. The purified
bottoms comprise the poly(acrylate) polymer.
Preparation of Inventive Composition 3 (TBAT:TMHAT:EAT, 75:20:05 by
Wt)--In Toluene Process: (Prophetic Example)
[0097] Inventive Composition 3 is prepared by thoroughly mixing
tert-butyl acrylate (TBAT) (150.0 g), 3,5,5-trimethylhexyl acrylate
(TMHAT) (40.0 g), ethyl acrylate (EAT) (10.0 g) and tert-butyl
peroxy-2-ethylhexanoate (TBPE) (0.22 g) in a glass bottle. Then,
66.67 g of the monomer mixture along with 100.0 g of toluene are
transferred to a 1 L round bottom flask equipped with a mechanical
stirrer, Claisen adapter with water-cooled condenser and nitrogen
inlet (set at 0.2 standard cubic feet per hours (scfh)), a
thermocouple and stopper ("reaction vessel"). This mixture is
heated to 90.degree. C. The remaining 133.3 g of the monomer
mixture is added over 180 minutes via peristaltic pump and
maintained at 90.degree. C. for the duration of the addition. After
all the monomer mixture is transferred to the reaction vessel, the
reaction temperature is maintained at 90.degree. C. for 180 min.
Then the temperature is adjusted to 100.degree. C., and TBPE (0.06
g) is added to the reaction vessel and held for 60 min. Similarly,
three more TBPE (0.06 g) aliquots are charged and allowed to react
for 60 min after each addition. Once complete monomer consumption
is observed, 100.0 g toluene is added and stirred for 30 min. The
reaction vessel contents are cooled and have a calculated M.sub.w
of 95,000 Da. A portion of the colorless liquid (50 g) is
transferred to a 25 ml single neck round-bottom flask and the
toluene is removed via rotavapor. The purified bottoms comprise the
poly(acrylate) polymer.
Preparation of Inventive Composition 3a (TBAT:TMHAT:EAT, 85:11:04
by Wt)--In Toluene Process:
[0098] Inventive Composition 3a is prepared by reacting Tert-Butyl
acrylate (TBAT), 3,5,5-trimethylhexyl acrylate (TMHAT), ethyl
acrylate (EAT) and tert-butyl peroxy-2-ethylhexanoate (TBPE) in
toluene. TBAT, (170.0 g), TMHAT (22.0 g), EAT (8.0 g) and
tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g) are thoroughly
mixed in a glass bottle. A 1 L round bottom flask equipped with a
mechanical stirrer, Claisen adapter with water-cooled condenser and
nitrogen inlet set at 0.2 standard cubic feet per hours (scfh),
thermocouple and stopper are charged with 66.67 g of the above
reaction mixture along with a 100.0 g of toluene. This mixture is
heated to 90.degree. C. The remaining 133.3 g of the reaction
mixtures is added over 180 minutes via peristaltic pump and
maintained at 90.degree. C. for the duration of the addition. After
complete, the monomer addition reaction temperature is maintained
at 90.degree. C. for 180 min. Then the temperature is adjusted to
100.degree. C., and TBPE (0.06 g) is added to the reaction vessel
and held for 60 min. Similarly, three more TBPE (0.06 g) aliquots
are charged and allowed to react 60 min at each addition. Once
complete monomer consumption is observed, 100.0 g toluene is added
and started for 30 min, then the reaction contents are cooled and
having a M.sub.w of 168063 Da. A 50 g of toluene diluted mixture is
transferred to a 25 ml single neck round-bottom flask. Toluene is
removed via rotavapor, attained a viscous colorless liquid and use
for foam testing.
Preparation of Inventive Composition 4 (TBAT:TMHAT:PEGA, 78:20:02
by Wt)--In Toluene Process: (Prophetic Example)
[0099] Inventive Composition 4 is prepared by thoroughly mixing
tert-butyl acrylate (TBAT) (156.0 g), 3,5,5-trimethylhexyl acrylate
(TMHAT) (40.0 g), poly(ethylene glycol) acrylate (PEGAT) (4.0 g),
and tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g) in a glass
bottle. Then, 66.67 g of the monomer mixture along with 100.0 g of
toluene are transferred to a 1 L round bottom flask equipped with a
mechanical stirrer, Claisen adapter with water-cooled condenser and
nitrogen inlet (set at 0.2 standard cubic feet per hours (scfh)), a
thermocouple and stopper ("reaction vessel"). This mixture is
heated to 90.degree. C. The remaining 133.3 g of the monomer
mixture is added over 180 minutes via peristaltic pump and
maintained at 90.degree. C. for the duration of the addition. After
all the monomer mixture is transferred to the reaction vessel, the
reaction temperature is maintained at 90.degree. C. for 180 min.
Then the temperature is adjusted to 100.degree. C., and TBPE (0.06
g) is added to the reaction vessel and held for 60 min. Similarly,
three more TBPE (0.06 g) aliquots are charged and allowed to react
for 60 min after each addition. Once complete monomer consumption
is observed, 100.0 g toluene is added and stirred for 30 min. The
reaction vessel contents are cooled and have a calculated M.sub.w
of 150,000 Da. A portion of the colorless liquid (50 g) is
transferred to a 25 ml single neck round-bottom flask and the
toluene is removed via rotavapor. The purified bottoms comprise the
poly(acrylate) polymer.
Preparation of Inventive Composition 5 (TBAT:TMHAT, 95:05 by
Wt)--In Oil Process: (Prophetic Example)
[0100] Inventive Composition 5 is prepared by prepared by
thoroughly mixing tert-butyl acrylate (TBAT) (190.0 g),
3,5,5-trimethylhexyl acrylate (TMHAT) (10.0 g), and tert-butyl
peroxy-2-ethylhexanoate (TBPE) (0.22 g) in a glass bottle. Then,
66.67 g of the monomer mixture along with 100.0 g of mineral oil
(SFNF) having a kinematic viscosity at 100.degree. C. of .about.3.7
cSt. are transferred to a 1 L round bottom flask equipped with a
mechanical stirrer, Claisen adapter with water-cooled condenser and
nitrogen inlet (set at 0.2 standard cubic feet per hours (scfh)), a
thermocouple and stopper ("reaction vessel"). This mixture is
heated to 90.degree. C. The remaining 133.3 g of the monomer
mixture is added over 180 minutes via peristaltic pump and
maintained at 90.degree. C. for the duration of the addition. After
all the monomer mixture is transferred to the reaction vessel, the
reaction temperature is maintained at 90.degree. C. for 180 min.
Then the temperature is adjusted to 100.degree. C., and a first
finishing dose of TBPE (0.06 g) is added and the reaction is
stirred for an additional 60 min. A second finishing dose of TBPE
(0.06 g) is added and the reaction stirred for an additional 60 min
at 100.degree. C. A third and fourth dose of TBPE (0.06 g each) is
added followed by stirring for 60 min at 100.degree. C. after each
dose. Gas chromatography is used to monitor monomer conversion to a
target monomer level of less than 1% for tert-butyl acrylate and
less than 0.1% for 3,5,5-trimethylhexyl acrylate. After the desired
monomer conversion is achieved, an additional 100.0 g of SFNF is
added to the reaction vessel and the reaction mixture allowed to
stir for 30 minutes at 100.degree. C. The reaction vessel contents
are cooled. The resulting contents comprise a poly(acrylate)
polymer having a calculated M.sub.w of 150,000 Da in SFNF
(approximately 50% actives).
[0101] Preparation of Inventive Composition 6 (TBAT:EHAT, 95:05 by
Wt)--In Toluene Process:
[0102] Inventive composition 6 is prepared by reacting tent-Butyl
acrylate (TBAT), 2-ethylhexyl acrylate (EHAT) and tert-butyl
peroxy-2-ethylhexanoate (TBPE) in toluene. TBAT, (190.0 g), EHAT
(10.0 g) and tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g) are
thoroughly mixed in a glass bottle. A 1 L round bottom flask
equipped with a mechanical stirrer, Claisen adapter with
water-cooled condenser and nitrogen inlet set at 0.2 standard cubic
feet per hours (scfh), thermocouple and stopper are charged with
66.67 g of the above reaction mixture along with a 100.0 g of
toluene. This mixture is heated to 90.degree. C. The remaining
133.3 g of the reaction mixtures is added over 180 minutes via
peristaltic pump and maintained at 90.degree. C. for the duration
of the addition. After the monomer addition is complete, the
reaction temperature is maintained at 90.degree. C. for 180 min.
Then the temperature is adjusted to 100.degree. C., and TBPE (0.06
g) is added to the reaction vessel and held for 60 min. Similarly,
three more TBPE (0.06 g) aliquots are charged and allowed to react
60 min at each addition. Once complete monomer consumption is
observed, 100.0 g toluene is added and stirred for 30 min. The
reaction contents are cooled to obtain a solution containing a
(poly)acrylate polymer having a M.sub.w of 165932 Da.
Preparation of Inventive Composition 7 (TBAT:EHAT, 90:10 by Wt)--In
Toluene Process:
[0103] Inventive composition 7 is prepared by reacting Tert-Butyl
acrylate (TBAT), 2-ethylhexyl acrylate (EHAT) and tert-butyl
peroxy-2-ethylhexanoate (TBPE) in toluene. TBAT, (180.0 g), TMHAT
(20.0 g) and tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g) are
thoroughly mixed in a glass bottle. A 1 L round bottom flask
equipped with a mechanical stirrer, Claisen adapter with
water-cooled condenser and nitrogen inlet set at 0.2 standard cubic
feet per hours (scfh), thermocouple and stopper is charged with
66.67 g of the above reaction mixture along with a 100.0 g of
toluene. This mixture is heated to 90.degree. C. The remaining
133.3 g of the reaction mixtures is added over 180 minutes via
peristaltic pump and maintained at 90.degree. C. for the duration
of the addition. After the monomer addition is complete, the
reaction temperature is maintained at 90.degree. C. for 180 min.
Then the temperature is adjusted to 100.degree. C., and TBPE (0.06
g) is added to the reaction vessel and held for 60 min. Similarly,
three more TBPE (0.06 g) aliquots are charged and allowed to react
60 min at each addition. Once complete monomer consumption is
observed, 100.0 g toluene is added and started for 30 min, then the
reaction contents are cooled and obtained a colorless liquid, and
having a M.sub.w of 161957 Da.
Preparation of Inventive Composition 8 (TBAT:EHAT, 90:10 by Wt)--In
Heavy Aromatic Naphtha Process:
[0104] Inventive composition 8 is prepared by reacting Tert-Butyl
acrylate (TBAT), 2-ethylhexyl acrylate (EHAT) and tert-butyl
peroxy-2-ethylhexanoate (TBPE) in heavy aromatic naphtha. TBAT,
(180.0 g), EHAT (20.0 g) and tert-butyl peroxy-2-ethylhexanoate
(TBPE) (0.22 g) are thoroughly mixed in a glass bottle. A 1 L round
bottom flask (equipped with a mechanical stirrer, Claisen adapter
with water-cooled condenser and nitrogen inlet set at 0.2 standard
cubic feet per hours (scfh), thermocouple and stopper) is charged
with 66.67 g of the above reaction mixture along with a 100.0 g of
heavy aromatic naphtha. This mixture is heated to 90.degree. C. The
remaining 133.33 g of the reaction mixtures and 60.0 g of heavy
aromatic naphtha are added over 180 minutes via peristaltic pump
and maintained at 90.degree. C. for the duration of the addition.
After the addition is complete, the reaction temperature is
maintained at 90.degree. C. for 180 minutes ("min"). The
temperature is then adjusted to 100.degree. C., and TBPE (0.06 g)
is added to the reaction vessel and held for 60 min. Similarly,
three more TBPE (0.06 g) aliquots are charged and allowed to react
60 min at each addition. Once complete monomer consumption is
observed, 40.0 g heavy aromatic naphtha is added and started for 30
min. The reaction contents are cooled to give a solution containing
a (poly)acrylate polymer with M.sub.w of 44570 Da.
Preparation of Inventive Composition 9 (TBAT:EHAT, 85:15 by Wt)--In
Heavy Aromatic Naphtha Process:
[0105] Inventive composition 9 is prepared by reacting Tert-Butyl
acrylate (TBAT), 2-ethylhexyl acrylate (EHAT) and tert-butyl
peroxy-2-ethylhexanoate (TBPE) in heavy aromatic naphtha. TBAT,
(170.0 g), EHAT (30.0 g) and tert-butyl peroxy-2-ethylhexanoate
(TBPE) (0.22 g) are thoroughly mixed in a glass bottle. A 1 L round
bottom flask (equipped with a mechanical stirrer, Claisen adapter
with water-cooled condenser and nitrogen inlet set at 0.2 standard
cubic feet per hours (scfh), thermocouple and stopper) is charged
with 66.67 g of the above reaction mixture along with a 100.0 g of
heavy aromatic naphtha. This mixture is heated to 90.degree. C. The
remaining 133.3 g of the reaction mixtures and 60 g of heavy
aromatic naphtha are added over 180 minutes via peristaltic pump
and maintained at 90.degree. C. for the duration of the addition.
After the addition is complete, the reaction temperature is
maintained at 90.degree. C. for 180 minutes ("min"). Then the
temperature is adjusted to 100.degree. C., and TBPE (0.06 g) is
added to the reaction vessel and held for 60 min. Similarly, five
more TBPE (0.06 g) aliquots are charged and allowed to react 60 min
at each addition. Once complete monomer consumption is observed,
40.0 g heavy aromatic naphtha is added and started for 30 min. The
reaction contents are cooled to give a solution containing a
(poly)acrylate polymer with M.sub.w of 34670 Da.
Preparation of Inventive Composition 10 (TBMAC:EHMAC, 90:10 by
Wt)--In Heavy Aromatic Naphtha Process:
[0106] Inventive composition 10 is prepared by reacting Tert-Butyl
methacrylate (TBMAC), 2-ethylhexyl methacrylate (EHMAC) and
tert-butyl peroxy-2-ethylhexanoate (TBPE) in heavy aromatic
naphtha. TBMAC, (180.0 g), EHMAC (20.0 g) and tert-butyl
peroxy-2-ethylhexanoate (TBPE) (0.22 g) are thoroughly mixed in a
glass bottle. A 1 L round bottom flask (equipped with a mechanical
stirrer, Claisen adapter with water-cooled condenser and nitrogen
inlet set at 0.2 standard cubic feet per hours (scfh), thermocouple
and stopper) is charged with 66.67 g of the above reaction mixture
along with a 100.0 g of heavy aromatic naphtha. This mixture is
heated to 90.degree. C. The remaining 133.3 g of the reaction
mixtures and 60 g of heavy aromatic naphtha are added over 180
minutes via peristaltic pump and maintained at 90.degree. C. for
the duration of the addition. After the addition is complete, the
reaction temperature is maintained at 90.degree. C. for 180 minutes
("min"). Then the temperature is adjusted to 100.degree. C., and
TBPE (0.06 g) is added to the reaction vessel and held for 60 min.
Similarly, three more TBPE (0.06 g) aliquots are charged and
allowed to react 60 min at each addition. Once complete monomer
consumption is observed, 40.0 g heavy aromatic naphtha is added and
started for 30 min. The reaction contents are cooled to give a
solution containing a (poly)methacrylate polymer with M.sub.w of
128573 Da.
[0107] The effectiveness of the poly(acrylate) polymers disclosed
herein at reducing foam in diesel fuels is tested by observing the
amount of foam generated and the time it takes for the foam to
collapse.
[0108] For the test, 100 ml of the additized diesel is transferred
to a graduated cylinder using a pressurized injector nozzle placed
245 mm above the graduated cylinder. As the additized diesel is
transferred to the cylinder, the volume of foam generated is
monitored and immediately after the transfer is complete, the
maximum volume of the foam is recorded in milliliters ("Max
Height"). The foam volume immediately after the transfer is
complete is also recorded in milliliters ("Max Foam"). The surface
of the additized diesel is then visually monitored. A stop watch is
used to measure the time it takes the foam to visually disappear
from the surface of the additized diesel and the time is recorded
in seconds ("Collapse Time").
[0109] The test is repeated 5 times and the average Max Foam,
Settle Foam, and Collapse Time is calculated. The average foam test
results of various poly(acrylate) polymers at different treat rates
in a diesel fuel are shown in Table 2 below.
TABLE-US-00002 TABLE 2 Weight Polymer Treat Rate ppm Max Height Max
Foam Collapse Example Monomer Units Ratio Mw (Da) (actives basis)
(ml) (ml) Time (s) Control N/A 106 96 32 Comp 1 Si 5 102 92 13.8
antifoam Ex A TBAT 100 76,699 400 104 94 18.4 Ex B TBAT 100 151,611
100 101 90 15.2 Ex C TBAT 100 151,611 10 103 87 13.3 Ex D TMHAT:EAT
85:15 181,419 800 60 10 13.8 Ex E TBAT 100 76,699 400 76 34 12.2
TMHAT:EAT 85:15 181,419 800 Ex F TBAT:TMHAT 95:05 146,746 100 99 89
8.8 Ex G TBAT:TMHAT 95:05 146,746 10 102 92 8.5 Ex H TBAT:TMHAT
90:10 155,702 100 92 89 6.4 Ex I TBAT:TMHAT 90:10 155,702 10 99 90
8.1 Ex J TBAT:TMHAT:EAT* 85:11:04 168,063 2.5 100 90 13.0 Ex K
TBAT:TMHAT:EAT* 85:11:04 168,063 5 99 88 11.1 Ex L TBAT:TMHAT:EAT*
85:11:04 168,063 10 99 89 10.2 Ex M TBAT:TMHAT:EAT* 85:11:04
168,063 50 98 88 9.2 Ex N TBAT:TMHAT:EAT* 85:11:04 168,063 100 98
88 8.6 Ex O TBAT:EHAT 95:05 165,932 2.5 106 91 17.9 Ex P TBAT:EHAT
95:05 165,932 5 105 94 13.7 Ex Q TBAT:EHAT 95:05 165,932 10 104 94
12.8 Ex R TBAT:EHAT 95:05 165,932 50 104 93 11.7 Ex S TBAT:EHAT
95:05 165,932 100 102 92 10.5 Ex T TBAT:EHAT 90:10 161,957 2.5 97
86 11.3 Ex U TBAT:EHAT 90:10 161,957 5 97 87 11.0 Ex V TBAT:EHAT
90:10 161,957 10 97 87 9.9 Ex W TBAT:EHAT 90:10 161,957 50 98 88
8.8 Ex X TBAT:EHAT 90:10 161,957 100 98 88 8.4 Ex Y TBAT:EHAT 90:10
39,392 5 102 87 9.8 *A terpolymer made from three different
acrylates, not a blend of polymers.
[0110] The results show that the poly(acrylate) polymers are
effective antifoams and have at least the same, or even improved
performance when compared to known silicon-containing
antifoams.
[0111] FIG. 2 is a graph showing the foam collapse time at
different treat rates of various antifoam components.
[0112] Applicants also surprisingly discovered that the antifoams
have a synergistic effect with mixed with one or more fuel
additives in a fuel additive package. FIG. 3 is a graph showing the
foam collapse time, Max Height, and Max Foam of Additive Package A
with a TBAT:EHAT antifoam at different ratios. FIG. 4 is a graph
illustrating the synergistic effect a TBAT:EHAT antifoam has with
in an additive package (Additive Package A) on foam collapse
time.
[0113] Additional suitable test methods for measuring the
effectiveness of the poly(acrylate) polymers disclosed herein at
reducing foam in diesel fuels include the "Determination of the
foaming tendency of diesel fuels" NF M 07-075, published and
distributed by l'Association Francaise de Normalisation
(AFNOR--www.afnor.org).
[0114] Each of the documents referred to above is incorporated
herein by reference, including any prior applications, whether or
not specifically listed above, from which priority is claimed. The
mention of any document is not an admission that such document
qualifies as prior art or constitutes the general knowledge of the
skilled person in any jurisdiction. Except in the Examples, or
where otherwise explicitly indicated, all numerical quantities in
this description specifying amounts of materials, reaction
conditions, molecular weights, number of carbon atoms, and the
like, are to be understood as modified by the word "about." It is
to be understood that the upper and lower amount, range, and ratio
limits set forth herein may be independently combined. Similarly,
the ranges and amounts for each element of the invention can be
used together with ranges or amounts for any of the other elements.
As used herein, the term "comprising" is intended also to encompass
as alternative embodiments "consisting essentially of" and
"consisting of." "Consisting essentially of" permits the inclusion
of substances that do not materially affect the basic and novel
characteristics of the composition under consideration.
* * * * *