Note: Descriptions are shown in the official language in which they were submitted.
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QUATERNARY AMMONIUM SALTS IN HEATING OILS
Field of the Invention
[0001] The invention relates to heating oils continuing quaternary ammoni-
um salts, including succinimide, Mannich, polyalkylene substituted amine,
quaternary ammonium salts. The invention also relates to the use of such salts
in heating oil compositions and the use of such heating oil compositions in
heating systems such as furnaces.
Background of the Invention
[0002] Home heating systems can use a variety of fuels, ranging from
coal to
natural gas. One commonly used fuel is heating oil. This fuel is easily deliv-
ered and can be stored in tanks on site near the equipment using the heating
oil,
for example a furnace.
[0003] Home heating applications typically use open flame burners, which
are significantly different from combustion chambers utilized in other applica-
tions. Thus home heating applications present unique problems and challenges
that are often different from the problems seen in other applications. Some
problems are seen in both home heating applications and other application that
use a different type of combustion chamber, however, due to the different in
design and operation of home heating applications, solutions for problems do
not generally carry over from one application to the other. In other words,
home
heating applications have different equipment and modes of operation than
other
applications that utilize combustion chambers, and home heating applications
present unique problems and require unique solutions to address those
problems.
[0004] In home heating applications, burning home heating oil over time
can
leave deposits on the nozzle tip where the heating oil composition is
delivered
to the burner. These deposits can disrupt the spray pattern, causing
incomplete
combustion and increased emissions. It is therefore desirable to prevent the
soot
from forming on the nozzle tip.
[0005] Additives based on the reaction product of polyisobutenyl
succinic
anhydride (PIBSA) and polyamines have been shown to reduce the level of soot
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on nozzle tips. One way of evaluating such additive performance is with the
XUD-9 engine test. The XUD-9 test measures an additives ability to prevent the
buildup of soot deposits on tips of injectors. It has been found that those
addi-
tives that work comparatively better in the XUD-9 test also perform compara-
tively better in preventing nozzle deposit buildup in home heating
applications.
[0006] However, there is demand for improved soot and deposit control
in
home heating applications and there is also demand for good performance
provided at lower costs, which effectively means lower additive treat rate, in
home heating applications. Thus there is a need for additives that provide
improved soot control and/or deposit reduction in home heating applications.
Summary of the Invention
[0007] The present invention deals with a heating oil composition
compris-
ing: (A) a heating oil; and (B) a quaternary ammonium salt; where the quater-
nary ammonium salt comprises the reaction product of: (i) a compound compris-
ing at least one tertiary amino group; and (ii) a quaternizing agent suitable
for
converting the tertiary amino group of compound (i) to a quaternary nitrogen.
[0008] The invention provides for various embodiments of component (i),
the compound comprising at least one tertiary amino group, including: (a) the
condensation product of a hydrocarbyl-substituted acylating agent and a com-
pound having an oxygen or nitrogen atom capable of condensing the acylating
agent wherein the condensation product has at least one tertiary amino group;
(b) a polyalkene-substituted amine having at least one tertiary amino group;
(c)
a Mannich reaction product having at least one tertiary amino group, wherein
the Mannich reaction product is derived from a hydrocarbyl-substituted phenol,
an aldehyde, and an amine; or (d) any combination thereof.
[0009] The invention provides for various embodiments of component
(ii),
the quaternizing agent suitable for converting the tertiary amino group of
compound, including: (a) dialkyl sulfates; (b) benzyl halides; (c) hydrocarbyl
substituted carbonates; (d) hydrocarbyl epoxides optionally in combination
with
an acid; (e) esters of polycarboxylic acids; or (f) any combination thereof.
[0010] The invention further provides for a method of operating a
heating
device comprising the steps of: supplying to said heating device a heating oil
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composition comprising (A) a heating oil; and (B) a quaternary ammonium salt;
wherein the quaternary ammonium salt comprises the reaction product of: (i) a
compound comprising at least one tertiary amino group; and (ii) a quaternizing
agent suitable for converting the tertiary amino group of compound (i) to a
quaternary nitrogen. The quaternary ammonium salt may be any of the com-
pounds described herein, made from any of the components described herein.
[0011] The invention further provides for the use of a quaternary
ammonium
salt as a soot modifier in a heating oil composition; wherein the quaternary
ammonium salt comprises the reaction product of: (i) a compound comprising at
least one tertiary amino group; and (ii) a quaternizing agent suitable for
convert-
ing the tertiary amino group of compound (i) to a quaternary nitrogen. The
quaternary ammonium salt may be any of the compounds described herein and
can be made from any of the components described herein.
Detailed Description of the Invention
[0012] Various preferred features and embodiments will be described below
by way of non-limiting illustration.
[0013] The invention provides a heating oil composition comprising: (A)
a
heating oil; and (B) a quaternary ammonium salt; wherein the quaternary am-
monium salt detergent comprises the reaction product of: (i) a compound com-
prising at least one tertiary amino group; and (ii) a quaternizing agent
suitable
for converting the tertiary amino group of compound (i) to a quaternary nitro-
gen. The various components are described in greater detail below.
The Heating Oil
[0014] The heating oils, which in some embodiments may be referred to
as
home heating oils (HHO) and/or furnace fuel oils (FFO), suitable for use in
the
present invention are not overly limited and may include all heating oil
suitable
for use in home heating applications. In general heating oils are relatively
low
viscosity, flammable liquid petroleum products used as fuel for furnaces or
boilers in homes and other buildings.
[0015] Heating oil is commonly delivered by tank truck to customers in
residential, commercial and municipal buildings. The heating oil is typically
stored in underground storage tanks (UST) or above-ground storage tanks
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(AST). AST are generally located in garages or outside the buildings, but may
also be located in the basements of the buildings. Heating oil is generally
not
used as an industrial fuel or for power generation, but rather is more common
for smaller scale applications such as home heating.
[0016] In some
embodiments the heating oil of the invention consists of a
mixture of petroleum-derived hydrocarbons containing from 14 to 20 carbon
atoms with a condensation/distillation point between 250 and 350 C. Heating
oil generally distills at a lower temperature than the heavy hydrocarbons
(those
that contain more than 20 carbon atoms) such as petroleum jelly, bitumen,
candle wax, and lubricating oils, which typically distills between 340 and
400 C, while it generally distills at a higher temperature than kerosene,
which
distills between 160 and 250 C.
[0017] The
fuel may also be a blend of petroleum-derived hydrocarbons and
fuels derived from a bio source. In some embodiments the fuel may contain a
portion derived from a bio source such as biodiesel. The biodiesel portion of
the fuel may be up to 20%. Suitable biodiesel is typically in the form of, but
not
limited to, methyl esters of the fatty acids from soybean, rapeseed, or palm
oils.
[0018] The
heating oil compositions of the present invention may include
one or more additives other than the quaternary ammonium salt described
below. Such performance additives can be added to any of the compositions
described depending on the results desired and the application in which the
composition will be used. Although any of the additional performance additives
described herein can be used in any of the compositions of the invention, the
following additional additives are particularly useful for heating oil composi-
tions: antioxidants, corrosion inhibitors, detergent and/or dispersant
additives
other than those described above, cold flow improvers, foam inhibitors, demul-
sifiers, lubricity agents, metal deactivators, biocides, antistatic agents,
deicers,
fluidizers, combustion improvers, wax control polymers, scale inhibitors, or
any
combination thereof.
[0019] Suitable antioxidants include for example hindered phenols or deriva-
tives thereof and/or diarylamines or derivatives thereof.
Suitable deter-
gent/dispersant additives include for example polyetheramines or nitrogen
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containing detergents, including but not limited to PIB amine deter-
gents/dispersants, succinimide detergents/dispersants, and other quaternary
salt
detergents/dispersants including polyisobutylsuccinimide-derived quaternized
PIB/amine and/or amide dispersants/detergents. Suitable cold flow improvers
include for example esterified copolymers of maleic anhydride and styrene
and/or copolymers of ethylene and vinyl acetate. Suitable demulsifiers include
for example polyalkoxylated alcohols. Suitable lubricity agents include for
example fatty carboxylic acids. Suitable metal deactivators include for
example
aromatic triazoles or derivatives thereof, including but not limited to
benzotria-
zole. Suitable foam inhibitors and/or antifoams include for example organic
silicones such as polydimethylsiloxane, polyethylsiloxane,
polydiethylsiloxane,
polyacrylates and polymethacrylates, trimethyl-triflouro-propylmethylsiloxane
and the like. Suitable fluidizers include for example mineral oils and/or
poly(alpha-olefins) and/or polyethers. Combustion improvers include for exam-
ple iron, cerium or platinum compounds.
[0020] The additional performance additives, which may be present in
the
compositions of the invention, also include di-ester, di-amide, ester-amide,
and
ester-imide friction modifiers prepared by reacting a dicarboxylic acid (such
as
tartaric acid) and/or a tricarboxylic acid (such as citric acid), with an
amine
and/or alcohol, optionally in the presence of a known esterification catalyst.
These friction modifiers, often derived from tartaric acid, citric acid, or
deriva-
tives thereof, may be derived from amines and/or alcohols that are linear or
branched, but in some embodiments are derived from branched alcohols result-
ing in friction modifiers that themselves have significant amounts of branched
hydrocarbyl groups present within it structure. Examples of suitable branched
alcohols used to prepare such friction modifiers include 2-ethylhexanol,
isotride-
canol, Guerbet alcohols, and mixtures thereof
[0021] 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 de-
scribed in U.S. patents 4,234,435 and 3,172,892. Another class of ashless
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dispersant is high molecular weight esters, prepared by reaction of a
hydrocarbyl
acylating agent and a polyhydric aliphatic alcohol such as glycerol,
pentaerythri-
tol, or sorbitol. Such materials are described in more detail in U.S. Patent
3,381,022. Another class of ashless dispersant is Mannich bases. These are
materials which are formed by the condensation of a higher molecular weight,
alkyl substituted phenol, an alkylene polyamine, and an aldehyde such as
formal-
dehyde and are described in more detail in U.S. Patent 3,634,515. Other disper-
sants include polymeric dispersant additives, which are generally hydrocarbon-
based polymers which contain polar functionality to impart dispersancy charac-
teristics 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
triethylenetet-
ramine (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.
[0022] Dispersants can also be post-treated by reaction with any of a
variety
of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon
disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted
succinic
anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds.
References detailing such treatment are listed in U.S. Patent 4,654,403.
[0023] The compositions of the invention may include a detergent additive,
different from the quaternized salt additive of the invention.
[0024] Antioxidants encompass phenolic antioxidants, which may comprise
a
butyl substituted phenol containing 2 or 3 t-butyl groups. The para position
may
also be occupied by a hydrocarbyl group or a group bridging two aromatic
rings.
The latter antioxidants are described in greater detail in U.S. Patent
6,559,105.
Antioxidants also include aromatic amines, such as nonylated diphenylamine.
Other antioxidants include sulfurized olefins, titanium compounds, and molyb-
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denum compounds. U.S. Pat. No. 4,285,822, for instance, discloses lubricating
oil compositions containing a molybdenum and sulfur containing composition.
Typical amounts of antioxidants will, of course, depend on the specific
antioxi-
dant and its individual effectiveness, but illustrative total amounts can be
0.01 to
5, or 0.15 to 4.5, or 0.2 to 4 percent by weight. Additionally, more than one
antioxidant may be present, and certain combinations of these can be
synergistic
in their combined overall effect.
[0025]
Viscosity improvers (also sometimes referred to as viscosity index
improvers or viscosity modifiers) may be included in the compositions of this
invention. Viscosity improvers are usually polymers, including polyisobutenes,
polymethacrylates (PMA) such as polymethacrylic acid esters, hydrogenated
diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copoly-
mers, hydrogenated alkenylarene-conjugated diene copolymers and polyolefins.
PMA's are prepared from mixtures of methacrylate monomers having different
alkyl groups. The alkyl groups may be either straight chain or branched chain
groups containing from 1 to 18 carbon atoms. Most PMA's are viscosity modi-
fiers as well as pour point depressants.
[0026]
Multifunctional viscosity improvers, which also have dispersant and/or
antioxidancy properties are known and may optionally be used. Dispersant
viscosity modifiers (DVM) are one example of such multifunctional additives.
DVM are typically prepared by copolymerizing a small amount of a nitrogen-
containing monomer with alkyl methacrylates, resulting in an additive with
some combination of dispersancy, viscosity modification, pour point depressan-
cy and dispersancy.
Vinyl pyridine, N-vinyl pyrrolidone and N,N'-
dimethylaminoethyl methacrylate are examples of nitrogen-containing mono-
mers. Polyacrylates obtained from the polymerization or copolymerization of
one or more alkyl acrylates also are useful as viscosity modifiers.
[0027] Any
of the additional performance additives described above may be
added to the compositions of the present invention. The amount of additional
additives in the present composition can typically be 1 to 10 weight percent,
or
1.5 to 9.0 percent, or 2.0 to 8.0 percent, all expressed on an oil-free basis.
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[0028] In some embodiments the heating oil compositions of the
invention
includes one or more of the following additional additives: an alcohol, a
phenolic
antioxidant, an alkaryl amine antioxidant, a triazole metal deactivator, a
polyisobu-
tylene succinic acid, a demulsifier, a petroleum naphtha solvent, and an
addition-
al antioxidant booster.
The Quaternary Ammonium Salt
[0029] The quaternary ammonium salts of the present invention include
the
reaction product of: (i) a compound comprising at least one tertiary amino
group; and (ii) a quaternizing agent suitable for converting the tertiary
amino
group of compound (i) to a quaternary nitrogen. Various embodiments of
suitable quaternary ammonium salts are described herein and the invention
contemplates the use of any one of them or combination thereof.
[0030] The compositions of the present invention comprise a quaternary
ammonium salt. The quaternary ammonium salt may be the reaction product of:
(i) at least one compound which may include: (a) the condensation product of a
hydrocarbyl-substituted acylating agent and a compound having an oxygen or
nitrogen atom capable of condensing the acylating agent where the condensation
product has at least one tertiary amino group; (b) a polyalkene-substituted
amine
having at least one tertiary amino group; and (c) a Mannich reaction product
having at least one tertiary amino group, where the Mannich reaction product
is
derived from a hydrocarbyl-substituted phenol, an aldehyde, and an amine; and
(ii) a quaternizing agent suitable for converting the tertiary amino group of
compound (i) to a quaternary nitrogen. The quaternizing agent may include
dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, and
hydro-
carbyl epoxides, any of which may be used in combination with an acid.
[0031] The compounds of component (i)(a), (i)(b) and (i)(c), described
in
greater detail below, contain at least one tertiary amino group and include
compounds that may be alkylated to contain at least one tertiary amino group
after an alkylation step. In some embodiments the quaternary ammonium salt
may be the reaction product of a polyalkene chloride, for example polyisobutyl-
ene chloride and a compound with a tertiary amine. In such embodiments the
polyisobutylene chloride is the quaternizing agent and the compound with a
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tertiary amine is component (i). Suitable example of component (i) for such
embodiments includes tertiary amines such as trimethylamine.
[0032] Examples of quaternary ammonium salt and methods for preparing
the same are described in United States patents: 4,253,980; 3,778,371;
4,171,959; 4,326,973; 4,338,206; and 5,254,138.
[0033] The quaternary ammonium salts may be prepared in the presence of
a
solvent, which may or may not be removed once the reaction is complete.
Suitable solvents include, but are not limited to, diluent oil, petroleum
naphtha,
and certain alcohols. In one embodiment, these alcohols contain at least 2
carbon atoms, and in other embodiments at least 4, at least 6 or at least 8
carbon
atoms. In another embodiment, the solvent of the present invention contains 2
to 20 carbon atoms, 4 to 16 carbon atoms, 6 to 12 carbon atoms, 8 to 10 carbon
atoms, or just 8 carbon atoms. These alcohols often have a 2-(C1_4 alkyl) sub-
stituent, namely, methyl, ethyl, or any isomer of propyl or butyl. Examples of
suitable alcohols include 2-methylheptano1, 2-methyldecanol, 2-ethylpentanol,
2-ethylhexanol, 2-ethylnonanol, 2-propylheptanol, 2-butylheptanol, 2-
butyloctanol, isooctanol, dodecanol, cyclohexanol, methanol, ethanol, propan-l-
ol, 2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-l-ol, butan-2-ol, pentanol
and its isomers, and mixtures thereof In one embodiment the solvent of the
present invention is 2-ethylhexanol, 2-ethyl nonanol, 2-methylheptanol, or
combinations thereof In one embodiment the solvent of the present invention
includes 2-ethylhexanol.
Succinimide Quaternary Ammonium Salts
[0034] In one embodiment the quaternary salt detergent comprises the
reac-
tion product of (i)(a) the condensation product of a hydrocarbyl-substituted
acylating agent and a compound having an oxygen or nitrogen atom capable of
condensing with said acylating agent where the condensation product has at
least one tertiary amino group; and (ii) a quaternizing agent suitable for
convert-
ing the tertiary amino group of compound (i) to a quaternary nitrogen.
[0035] Hydrocarbyl substituted acylating agents useful in the present inven-
tion include the reaction product of a long chain hydrocarbon, generally a
polyolefin, with a monounsaturated carboxylic acid or derivative thereof.
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[0036] Suitable monounsaturated carboxylic acids or derivatives thereof
include: (i) a,13-monounsaturated C4 to C10 dicarboxylic acids, such as
fumaric
acid, itaconic acid, maleic acid; (ii) derivatives of (i), such as anhydrides
or Ci
to C5 alcohol derived mono- or di- esters of (i); (iii) a,13-monounsaturated
C3 to
C10 monocarboxylic acids, such as acrylic acid and methacrylic acid; or (iv)
derivatives of (iii), such as C1 to C5 alcohol derived esters of (iii).
[0037] Suitable long chain hydrocarbons for use in preparing the
hydrocarbyl
substituted acylating agents include any compound containing an olefinic bond
represented by the general Formula I, shown here:
(R1)(R2¨=
)k, C(R3)(CH(R4)(R5)) (I)
wherein each of R1, R2, R3, R4 and R5 is, independently, hydrogen or a hydro-
carbon based group. In some embodiments at least one of R3, R4 or R5 is a
hydrocarbon based group containing at least 20 carbon atoms.
[0038] These long chain hydrocarbons, which may also be described as
polyolefins or olefin polymers, are reacted with the monounsaturated
carboxylic
acids and derivatives described above to form the hydrocarbyl substituted
acylating agents used to prepare the nitrogen-containing detergent of the
present
invention. Suitable olefin polymers include polymers comprising a major molar
amount of C2 to C20, or C2 to C5 mono-olefins. Such olefins include ethylene,
propylene, butylene, isobutylene, pentene, octene-1, or styrene. The polymers
may be homo-polymers, such as polyisobutylene, as well as copolymers of two
or more of such olefins. Suitable copolymers include copolymers of ethylene
and propylene, butylene and isobutylene, and propylene and isobutylene. Other
suitable copolymers include those in which a minor molar amount of the copol-
ymer monomers, e.g. 1 to 10 mole %, is a C4 to C18 di-olefin. Such copolymers
include: a copolymer of isobutylene and butadiene; and a copolymer of eth-
ylene, propylene and 1,4-hexadiene.
[0039] In one embodiment, at least one of the ¨R groups of Formula (I)
shown above is derived from polybutene, that is, polymers of C4 olefins,
includ-
ing 1-butene, 2-butene and isobutylene. C4 polymers include polyisobutylene.
In another embodiment, at least one of the ¨R groups of Formula I is derived
from ethylene-alpha olefin polymers, including ethylene-propylene-diene
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polymers. Examples of documents that described ethylene-alpha olefin copoly-
mers and ethylene-lower olefin-diene ter-polymers include United States pa-
tents: 3,598,738; 4,026,809; 4,032,700; 4,137,185; 4,156,061; 4,320,019;
4,357,250; 4,658,078; 4,668,834; 4,937,299; and 5,324,800.
[0040] In another embodiment, the olefinic bonds of Formula (I) are predom-
inantly vinylidene groups, represented by the following formula:
HR
C=C
/\
H \R (II)
wherein each R is a hydrocarbyl group; which in some embodiments may be:
H2
C CH
61'113
(III)
wherein R is a hydrocarbyl group.
[0041] In one embodiment, the vinylidene content of Formula (I) may
comprise at least 30 mole % vinylidene groups, at least 50 mole % vinylidene
groups, or at least 70 mole % vinylidene groups. Such materials and methods of
preparation are described in United States patents: 5,071,919; 5,137,978;
5,137,980; 5,286,823, 5,408,018, 6,562,913, 6,683,138, 7,037,999; and United
States publications: 2004/0176552A1; 2005/0137363; and 2006/0079652A1.
Such products are commercially available from BASF, under the trade name
GLISSOPALTM and from Texas PetroChemical LP, under the trade name TPC
11O5TM and TPC 595TM
[0042] Methods of making hydrocarbyl substituted acylating agents from the
reaction of monounsaturated carboxylic acid reactants and compounds of For-
mula (I) are well known in the art and disclosed in: United States patents:
3,361,673; 3,401,118; 3,087,436; 3,172,892; 3,272,746, 3,215,707; 3,231,587;
3,912,764; 4,110,349; 4,234,435; 6,077,909; and 6,165,235.
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[0043] In another embodiment, the hydrocarbyl substituted acylating
agent
can be made from the reaction of a compound represented by Formula (I) with
at least one carboxylic reactant represented by the following formulas:
0 0
R6A¨(R7),,A¨OR8
(IV)
and
OR9 0
R6¨¨(R7)A¨OR8
L
(V)
wherein each of R6, R8 and R9 is independently H or a hydrocarbyl group, R7 is
a divalent hydrocarbylene group, and n is 0 or 1. Such compounds and the
processes for making them are disclosed in United States patents: 5,739,356;
5,777,142; 5,786,490; 5,856,524; 6,020,500; and 6,114,547.
[0044] In yet another embodiment, the hydrocarbyl substituted acylating
agent may be made from the reaction of any compound represented by Formula
(I) with any compound represented by Formula (IV) or Formula (V), where the
reaction is carried out in the presence of at least one aldehyde or ketone.
Suita-
ble aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyralde-
hyde, isobutyraldehyde, pentanal, hexanal. heptaldehyde, octanal,
benzaldehyde,
as well as higher aldehydes. Other aldehydes, such as dialdehydes, especially
glyoxal, are useful, although monoaldehydes are generally preferred. In one
embodiment, the aldehyde is formaldehyde, which may be supplied in the
aqueous solution often referred to as formalin, but which is more often used
in
the polymeric form referred to as paraformaldehyde. Paraformaldehyde is
considered a reactive equivalent of and/or source of formaldehyde. Other
reactive equivalents include hydrates or cyclic trimers. Suitable ketones
include
acetone, butanone, methyl ethyl ketone, as well as other ketones. In some
embodiments, one of the two hydrocarbyl groups of the ketone is a methyl
group. Mixtures of two or more aldehydes and/or ketones are also useful. Such
hydrocarbyl substituted acylating agents and the processes for making them are
disclosed in United States patents: 5,840,920; 6,147,036; and 6,207,839.
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[0045] In another embodiment, the hydrocarbyl substituted acylating
agent
may include methylene bis-phenol alkanoic acid compounds. Such compounds
may be the condensation product of (i) an aromatic compound of the formula:
Rrn-Ar-Z, (VI)
and (ii) at least on carboxylic reactant such as the compounds of formula (IV)
and (V) described above, wherein, in Formula (VI): each R is independently a
hydrocarbyl group; m is 0 or an integer from 1 up to 6 with the proviso that m
does not exceed the number of valences of the corresponding Ar group available
for substitution; Ar is an aromatic group or moiety containing from 5 to 30
carbon atoms and from 0 to 3 optional substituents such as amino, hydroxy- or
alkyl- polyoxyalkyl, nitro, aminoalkyl, and carboxy groups, or combinations of
two or more of said optional substituents; Z is independently -OH, -0, a lower
alkoxy group, or -(ORio)bo¨ x1 1 wherein each R1 is independently a divalent
hydrocarbyl group, b is a number from 1 to 30, and R11 is -H or a hydrocarbyl
group; and c is a number ranging from 1 to 3.
[0046] In one embodiment, at least one hydrocarbyl group on the
aromatic
moiety is derived from polybutene. In one embodiment, the source of the
hydrocarbyl groups described above are polybutenes obtained by polymerization
of isobutylene in the presence of a Lewis acid catalyst such as aluminum
trichlo-
ride or boron trifluoride. Such compounds and the processes for making them
are disclosed in United States patents: 3,954,808; 5,336,278; 5,458,793;
5,620,949; 5,827,805; and 6,001,781.
[0047] In another embodiment, the reaction of (i) with (ii), optionally
in the
presence of an acidic catalyst such as organic sulfonic acids,
heteropolyacids,
and mineral acids, can be carried out in the presence of at least one aldehyde
or
ketone. The aldehyde or ketone reactant employed in this embodiment is the
same as those described above. Such compounds and the processes for making
them are disclosed in United States patent: 5,620,949. Still other methods of
making suitable hydrocarbyl substituted acylating agents can be found in
United
States patents: 5,912,213; 5,851,966; and 5,885,944.
[0048] The succinimide quaternary ammonium salt detergents are derived
by
reacting the hydrocarbyl substituted acylating agent described above with a
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compound having an oxygen or nitrogen atom capable of condensing with the
acylating agent. In one embodiment, suitable compounds contain at least one
tertiary amino group or may be alkylated until they contain a tertiary amino
group, so long as the hydrocarbyl substituted acylating agent has at least one
tertiary amino group when it is reacted with the quaternizing agent.
[0049] In
one embodiment, this compound may be represented by one of the
following formulas:
H R
\I-X-11
/ \
R' R
(VII)
and
R
HO-X-II
\
(VIII)
Wherein, for both Formulas (VII) and (VIII), each X is independently a
alkylene
group containing 1 to 4 carbon atoms; and each R is independently a
hydrocarbyl group and R' is a hydrogen or a hydrocarbyl group.
[0050] Suitable compounds include but are not limited to: 1-
aminopiperidine, 1- (2 -amino ethyl)p ip eri dine , 1 -(3 - aminopropy1)-2 -
pip e coline,
1 -methyl-(4 -methylamino)pip eri din e, 1-amino -2,6 -dim ethylp ip eri dine
, 4 -(1 -
p yrroli dinyl)p ip eri din e, 1 -
(2 -amino ethyl)p yrroli din e, 2 -(2 - amino ethyl) - 1-
methylpyrrolidine, N,N-diethylethylenediamine, N,N-dimethylethylenediamine,
N,N-dibutylethylenediamine, N,N,N' -trimethylethylenediamine, N,N-dimethyl-
N'-ethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N,N' -
triethylethylenediamine, 3-dimethylaminopropylamine, 3-diethylaminopropyl-
amine, 3 -dibutylaminopropylamine, N,N,N ' -trimethyl- 1 ,3 -prop anediamine,
N,N,2,2 -tetramethyl- 1,3 -prop anediamine, 2 -amino -5 - di ethyl aminop
entan e,
N,N,N',N'-tetraethyldiethylenetriamine, 3,3 '-diamino-N-methyldipropylamine,
3,3'-iminobis(N,N-dimethylpropylamine), or combinations thereof. In some
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embodiments the amine used is 3-dimethylaminopropylamine, 3-diethylamino-
propylamine, 1-(2-aminoethyl)pyrrolidine, N,N-dimethylethylenediamine, or
combinations thereof.
[0051]
Suitable compounds further include aminoalkyl substituted heterocy-
clic compounds such as 1 -(3 -
aminopropyl)imidazole and 4 -(3 -
aminopropyl)morpholine, 1 -(2 -amino ethyl)p ip eri dine , 3,3 -
diamino -N-
methyldipropylamine, 3,3 '-aminobis(N,N-dimethylpropylamine) These have
been mentioned in previous list.
[0052] Still
further nitrogen or oxygen containing compounds capable of
condensing with the acylating agent which also have a tertiary amino group
include: alkanolamines, including but not limited to triethanolamine, N,N-
dim ethylaminoprop anol, N,N-diethylaminopropanol, and N,N-
diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine.
[0053] The
succinimide quaternary ammonium salt detergents of the present
invention are formed by combining the reaction product described above (the
reaction product of a hydrocarbyl-substituted acylating agent and a compound
having an oxygen or nitrogen atom capable of condensing with said acylating
agent and further having at least one tertiary amino group) with a
quaternizing
agent suitable for converting the tertiary amino group to a quaternary
nitrogen.
Suitable quaternizing agents are discussed in greater detail below. In some
embodiments these preparations may be carried out neat or in the presence of a
solvent, as described above. By way of non-limiting example, preparations of
succinimide quaternary ammonium salts are provided below.
[0054] In
some embodiments the compositions of the invention are substan-
tially free of, or even completely free of, the succinimide quaternary
ammonium
salts described above.
Polyalkene-Substituted Amine Quaternary Ammonium Salts
[0055] In
one embodiment the quaternary ammonium salt is the reaction
product of: (i)(b) a polyalkene-substituted amine having at least one tertiary
amino group; and (ii) a quaternizing agent suitable for converting the
tertiary
amino group of compound (i) to a quaternary nitrogen.
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[0056]
Suitable polyalkene-substituted amines may be derived from an olefin
polymer and an amine, such as ammonia, monoamines, polyamines or mixtures
thereof They may be prepared by a variety of methods. Suitable polyalkene-
substituted amines or the amines from which they are derived either contain a
tertiary amino group or may be alkylated until they contain a tertiary amino
group, so long as the polyalkene-substituted amine has at least one tertiary
amino group when it is reacted with the quaternizing agent.
[0057] One
method of preparation of a polyalkene-substituted amine in-
volves reacting a halogenated olefin polymer with an amine, as disclosed in
United States patents: 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433;
and 3,822,289. Another method of preparation of a polyalkene-substituted
amine involves reaction of a hydro-formylated olefin with a polyamine and
hydrogenating the reaction product, as disclosed in United States patents:
5,567,845 and 5,496,383.
Another method for preparing a polyalkene-
substituted amine involves converting a polyalkene, by means of a conventional
epoxidation reagent, with or without a catalyst, into the corresponding
epoxide
and converting the epoxide into the polyalkene substituted amine by reaction
with ammonia or an amine under the conditions of reductive amination, as
disclosed in United States patent: 5,350,429. Another method for preparing a
polyalkene-substituted amine involves hydrogenation of a 13-aminonitrile, made
by reacting an amine with a nitrile, as disclosed in United States patent:
5,492,641. Yet another method for preparing a polyalkene-substituted amine
involves hydroformylating polybutene or polyisobutylene, with a catalyst, such
as rhodium or cobalt, in the presence of CO, H2 and NH3 at elevated pressures
and temperatures, as disclosed in United States patents: 4,832,702; 5,496,383
and 5,567,845. The above methods for the preparation of polyalkene substituted
amine are for illustrative purposes only and are not meant to be an exhaustive
list. The polyalkene-substituted amines of the present invention are not
limited
in scope to the methods of their preparation disclosed hereinabove.
[0058] The polyalkene-substituted amine may be derived from olefin poly-
mers. Suitable olefin polymers for preparing the polyalkene-substituted amines
of the invention are the same as those described above.
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[0059] The polyalkene-substituted amine may be derived from ammonia,
monoamines, polyamines, or mixtures thereof, including mixtures of different
monoamines, mixtures of different polyamines, and mixtures of monoamines
and polyamines (which include diamines). Suitable amines include aliphatic,
aromatic, heterocyclic and carbocyclic amines.
[0060] In one embodiment, the amines may be characterized by the
formula:
Ri2Ri3NH
(IX)
wherein R12 and R13 are each independently hydrogen, hydrocarbon, amino-
substituted hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy- substituted
hydrocarbon, or acylimidoyl groups provided that no more than one of R12 and
R13 is hydrogen. The amine may be characterized by the presence of at least of
at least one primary (H2N-) or secondary amino (H-N<) group. These amines,
or the polyalkene-substituted amines they are used to prepare may be alkylated
as needed to ensure they contain at least one tertiary amino group. Examples
of
suitable monoamines include ethylamine, dimethylamine, diethylamine, n-
butylamine, dibutylamine, allylamine, isobutylamine, cocoamine, stearylamine,
laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecyl-
amine, diethanolamine, morpholine, and octadecylamine.
[0061] The polyamines from which the detergent is derived include
princi-
pally alkylene amines conforming, for the most part, to the formula:
HN¨(Alkylene-N)n_R14
it14 it14
(X)
wherein n is an integer typically less than 10, each R14 is independently
hydrogen or a hydrocarbyl group typically having up to 30 carbon atoms, and
the alkylene group is typically an alkylene group having less than 8 carbon
atoms. The alkylene amines include principally, ethylene amines, hexylene
amines, heptylene amines, octylene amines, other polymethylene amines. They
are exemplified specifically by: ethylenediamine, diethylenetriamine,
triethylene
tetramine, propylene diamine, decamethylene diamine, octamethylene diamine,
di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine,
trimethylene diamine, pentaethylene hexamine, di(-trimethylene) triamine,
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aminopropylmorpholine and dimethylaminopropylamine. Higher homologues
such as are obtained by condensing two or more of the above-illustrated
alkylene amines likewise are useful. Tetraethylene pentamine is particularly
useful.
[0062] The ethylene amines, also referred to as polyethylene polyamines,
are
especially useful. They are described in some detail under the heading "Eth-
ylene Amines" in Encyclopedia of Chemical Technology, Kirk and Othmer,
Vol. 5, pp. 898-905, Interscience Publishers, New York (1950).
[0063] Any of the above polyalkene-substituted amines, or the amines
from
which they are derived, which are secondary or primary amines, may be alkylat-
ed to tertiary amines using alkylating agents before or while they are reacted
with the quaternizing agents to form the quaternary ammonium salt additives of
the present invention. Suitable alkylating agents include the quaternizing
agents
discussed below.
[0064] The polyalkene-substituted amine quaternary ammonium salts of the
present invention are formed by combining the reaction product described above
(the polyalkene-substituted amine, having at least one tertiary amino group)
with a quaternizing agent suitable for converting the tertiary amino group to
a
quaternary nitrogen. Suitable quaternizing agents are discussed in greater
detail
below. By way of non-limiting example, a preparation of a polyalkene-
substituted amine quaternary ammonium salt is provided below.
[0065] In some embodiments the compositions of the invention are
substan-
tially free of, or even completely free of, the polyalkene-substituted amine
quaternary ammonium salts described above.
Mannich Quaternary Ammonium Salts
[0066] In one embodiment the quaternary ammonium salt is the reaction
product of: (i)(c) a Mannich reaction product; and (ii) a quaternizing agent
suitable for converting the tertiary amino group of compound (i) to a
quaternary
nitrogen. Suitable Mannich reaction products have at least one tertiary amino
group and are prepared from the reaction of a hydrocarbyl-substituted phenol,
an aldehyde, and an amine.
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[0067] The hydrocarbyl substituent of the hydrocarbyl-substituted
phenol
can have 10 to 400 carbon atoms, in another instance 30 to 180 carbon atoms,
and in a further instance 10 or 40 to 110 carbon atoms. This hydrocarbyl sub-
stituent can be derived from an olefin or a polyolefin. Useful olefins include
alpha-olefins, such as 1-decene, which are commercially available. Suitable
polyolefins include those described in the sections above. The hydrocarbyl-
substituted phenol can be prepared by alkylating phenol with one of these
suitable olefins or polyolefins, such as a polyisobutylene or polypropylene,
using well-known alkylation methods.
[0068] The aldehyde used to form the Mannich detergent can have 1 to 10
carbon atoms, and is generally formaldehyde or a reactive equivalent thereof,
such as formalin or paraformaldehyde.
[0069] The amine used to form the Mannich detergent can be a monoamine
or a polyamine. Amines suitable for preparing the Mannich reaction product of
the invention are the same as those are described in the sections above.
[0070] In one embodiment, the Mannich detergent is prepared by reacting
a
hydrocarbyl-substituted phenol, an aldehyde, and an amine, as described in
United States patent 5,697,988. In one embodiment, the Mannich reaction
product is prepared from: an alkylphenol derived from a polyisobutylene;
formaldehyde; and a primary monoamine, secondary monoamine, or alkylenedi-
amine. In some of such embodiments the amine is ethylenediamine or dime-
thylamine. Other methods of preparing suitable Mannich reaction products can
be found in United States patents: 5,876,468 and 5,876,468.
[0071] As discussed above, it may be necessary, with some of the
amines, to
further react the Mannich reaction product with an epoxide or carbonate, or
other alkylating agent, in order to obtain the tertiary amino group.
[0072] The Mannich quaternary ammonium salts of the present invention
are
formed by combining the reaction product described above (the Mannich reac-
tion product with at least one tertiary amino group) with a quaternizing agent
suitable for converting the tertiary amino group to a quaternary nitrogen.
Suitable quaternizing agents are discussed below.
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[0073] In some embodiments the compositions of the invention are
substan-
tially free of, or even completely free of, the Mannich quaternary ammonium
salts described above.
Amide and/or Ester Quaternary Ammonium Salts
[0074] In some embodiments the quaternary ammonium salts used in the
invention are quaternary amide and/or ester detergents which may be described
as the reaction product of: (i) a non-quaternized amide and/or ester detergent
having a tertiary amine functionality; and (ii) a quaternizing agent. In some
embodiments the non-quaternized detergent is the condensation product of (a) a
hydrocarbyl-substituted acylating agent and (b) a compound having an oxygen
or nitrogen atom capable of condensing with said acylating agent and further
having at least one tertiary amino group.
[0075] The non-quaternized amide and/or ester detergents suitable for
use in
the present invention include the condensation product of (i) a hydrocarbyl-
substituted acylating agent and (ii) a compound having an oxygen or nitrogen
atom capable of condensing with said acylating agent and further having at
least
one tertiary amino group, where the resulting detergent has at least one
tertiary
amino group and also contains an amide group and/or an ester group. Typically,
the compound having an oxygen or nitrogen atom capable of condensing with
said acylating agent determined whether the resulting detergent contains an
amide group or an ester group. In some embodiments, the non-quaternized
detergent, and so the resulting quaternized detergent is free of any imide
groups.
In some embodiments, the non-quaternized detergent, and so the resulting
quaternized detergent is free of any ester groups. In these embodiments the
detergent contains at least one, or just one, amide group.
[0076] The hydrocarbyl substituted acylating agent can be any of the
materi-
als described in section above provided that the material contains an amide
group and/or an ester group.
[0077] The non-quaternized amide and/or ester detergent used to prepare
the
additives of the present invention are themselves formed when the acylating
agents described above are reacted with a compound having an oxygen or
nitrogen atom capable of condensing with the acylating agent which further has
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at least one tertiary amino group. Any of these compounds described above
may be used here as well.
[0078] The quaternary amide and/or ester detergents are prepared by
reacting
(a) the non-quaternized amide and/or ester detergent having a tertiary amine
functionality with (b) the quaternizing agent; thereby obtaining the
quaternized
detergent. The processes of the present in invention may also be described as
a
process for preparing a quaternized amide and/or ester detergent comprising
the
steps of: (1) mixing (a) a non-quaternized amide and/or ester detergent having
an amine functionality, (b) a quaternizing agent and optionally with (c) a
protic
solvent, which in some embodiments is free of methanol; (2) heating the mix-
ture to a temperature between 50 C to 130 C; and (3) holding for the reaction
to
complete; thereby obtaining the quaternized amide and/or ester detergent. In
one embodiment the reaction is carried out at a temperature of less than 80 C,
or
less than 70 C. In other embodiments the reaction mixture is heated to a tem-
perature of about 50 C to 120 C, 80 C, or 70 C. In still other embodiments
where the hydrocarbyl acylating agent is derived from a monocarboxylic acid,
the reaction temperature may be 70 C to 130 C. In other embodiments where
the hydrocarbyl acylating agent is derived from a dicarboxylic acid, the
reaction
temperature may be 50 C to 80 C or 50 C to 70 C. In some embodiments the
processes of the present invention are free of the addition of any acid
reactant,
such as acetic acid. The salt product is obtained in these embodiments despite
the absence of the separate acid reactant.
[0079] As described above, in some embodiments the non-quaternized
amide
and/or ester detergent is the condensation product of hydrocarbyl-substituted
acylating agent and a compound having an oxygen or nitrogen atom capable of
condensing with said acylating agent and further having at least one tertiary
amino group. Suitable quaternizing agents and compounds having an oxygen or
nitrogen atom are also described above.
[0080] The additives of the present invention may be derived in the
presence
of a protic solvent. In some embodiments the process used to prepare these
additives is substantially free of to free of methanol. Substantially free of
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methanol can mean less than 0.5, 0.1 or 0.05 percent by weight methanol in the
reaction mixture, and may also mean completely free of methanol.
[0081] Suitable protic solvents include solvents that have dielectric
constants
of greater than 9. In one embodiment the protic solvent includes compounds
that contain 1 or more hydroxyl functional groups, and may include water.
[0082] In one embodiment, the solvents are glycols and glycol ethers.
Glycols containing from 2 to 12 carbon atoms, or from 4 to 10, or 6 to 8
carbon
atoms, and oligomers thereof (e.g., dimers, trimers and tetramers) are
generally
suitable for use. Illustrative glycols include ethylene glycol, propylene
glycol,
diethylene glycol, dipropylene glycol, 1,4-butanediol, 2-methyl-1,3-
propanediol,
neopentyl glycol, triethylene glycol, polyethylene glycol and the like and
oligomers and polymeric derivative and mixtures thereof Illustrative glycol
ethers include the C1-C6 alkyl ethers of propylene glycol, ethylene glycol and
oligomers thereof such as di-, tri- and tetra glycol ethers of methyl, ethyl,
propyl, butyl or hexyl. Suitable glycol ethers include ethers of dipropylene
glycol, tripropylene glycol diethylene glycol, triethylene glycol; ethyl
diglycol
ether, butyl diglycol ether, methoxytriglycol, ethoxytriglycol,
butoxytriglycol,
methoxytetraglycol, butoxytetraglycol.
[0083] Suitable solvents for use in the invention also include certain
alco-
hols. In one embodiment, these alcohols contain at least 2 carbon atoms, and
in
other embodiments at least 4, at least 6 or at least 8 carbon atoms. In
another
embodiment, the solvent of the present invention contains 2 to 20 carbon
atoms,
4 to 16 carbon atoms, 6 to 12 carbon atoms, 8 to 10 carbon atoms, or just 8
carbon atoms. These alcohols normally have a 2-(C1_4 alkyl) substituent, name-
ly, methyl, ethyl, or any isomer of propyl or butyl. Examples of suitable alco-
hols include 2-methylheptanol, 2-methyldecanol, 2-ethylpentanol, 2-
ethylhexanol, 2-ethylnonanol, 2-propylheptanol, 2-butylheptanol, 2-
butyloctanol, isooctanol, dodecanol, cyclohexanol, methanol, ethanol, propan-l-
ol, 2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-l-ol, butan-2-ol, pentanol
and its isomers, and mixtures thereof In one embodiment the solvent of the
present invention is 2-ethylhexanol, 2-ethyl nonanol, 2-propylheptanol, or
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combinations thereof In one embodiment the solvent of the present invention
includes 2-ethylhexanol.
[0084] The solvent can be any of the commercially available alcohols or
mixtures of such alcohols and also includes such alcohols and mixtures of
alcohols mixed with water. In some embodiments the amount of water present
may be above 1 percent by weight of the solvent mixture. In other embodiments
the solvent mixture may contain traces of water, with the water content being
less than 1 or 0.5 percent by weight.
[0085] The alcohols can be aliphatic, cycloaliphatic, aromatic, or
heterocy-
clic, including aliphatic-substituted cycloaliphatic alcohols, aliphatic-
substituted
aromatic alcohols, aliphatic-substituted heterocyclic alcohols, cycloaliphatic-
substituted aliphatic alcohols, cycloaliphatic-substituted aromatic alcohols,
cycloaliphatic-substituted heterocyclic alcohols, heterocyclic-substituted ali-
phatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, and
heterocy-
clic-substituted aromatic alcohols.
[0086] While not wishing to be bound by theory, it is believed that a
polar
protic solvent is required in order to facilitate the dissociation of the acid
into
ions and protons. The dissociation is required to protonate the ion formed
when
the detergent having an amine functionality initially reacts with the
quaternizing
agent. In the case where the quaternizing agent is an alkyl epoxide the
resulting
ion would be an unstable alkoxide ion. The dissociation also provides a
counter
ion from the acid group of the additive that acts to stabilize the quaternary
ammonium ion formed in the reaction, resulting in a more stable product.
[0087] The solvent may be present such that the weight ratio of the
amount
of detergent having an amine functionality to the amount of polar solvent is
in
one set of embodiments from 20:1 to 1:20; or from 10:1 to 1:10. In additional
embodiments, the detergent to solvent weight ratio can be from 1:10 to 1:15;
from 15:1 to 10:1; or from 5:1 to 1:1.
[0088] In some embodiments the compositions of the invention are
substan-
tially free of, or even completely free of, the quaternary amide and/or ester
detergents described above.
Polyester Quaternary Ammonium Salts
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[0089] In some embodiments the quaternary ammonium salt is a polyester
quaternary salt, which may include quaternized polyester amine, amide, and
ester salts. Such additives may also be described as quaternary polyester
salts.
The additives of the invention may be described as the reaction product of: a
polyester containing a tertiary amino group; and a quaternizing agent suitable
for converting the tertiary amino group to a quaternary nitrogen. The
quaternary
agents may be any of the agents described herein.
[0090] The polyester containing a tertiary amino group used in the
prepara-
tion of the additives of the invention may also be described as a non-
quaternized
polyester containing a tertiary amino group.
[0091] In some embodiments the polyester is the reaction product of a
fatty
carboxylic acid containing at least one hydroxyl group and a compound having
an oxygen or nitrogen atom capable of condensing with said acid further having
a tertiary amino group. Suitable fatty carboxylic acids to use in the
preparation
of the polyesters described above may be represented by the formula:
OH 0
R1R2OH (XI)
where R1 is a hydrogen or a hydrocarbyl group containing from 1 to 20 carbon
atoms and R2 is a hydrocarbylene group containing from 1 to 20 carbon atoms.
In some embodiments R1 contains from 1 to 12, 2 to 10, 4 to 8 or even 6 carbon
atoms, and R2 contains from 2 to 16, 6 to 14, 8 to 12, or even 10 carbon
atoms.
[0092] In some embodiments the fatty carboxylic acid used in the
prepara-
tion of the polyester is 12-hydroxystearic acid, ricinoleic acid, 12-hydroxy
dodecanoic acid, 5-hydroxy dodecanoic acid, 5-hydroxy decanoic acid, 4-
hydroxy decanoic acid, 10-hydroxy undecanoic acid, or combinations thereof.
[0093] In some embodiments the compound having an oxygen or nitrogen
atom capable of condensing with said acid and further having a tertiary amino
group is represented by the formula:
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R3 H
111 I
Xi
R4 R5
(XII)
where R3 is a hydrocarbyl group containing from 1 to 10 carbon atoms; R4 is a
hydrocarbyl group containing from 1 to 10 carbon atoms; R5 is a hydrocarbylene
group containing from 1 to 20 carbon atoms; and X1 is 0 or NR6 where R6 is a
hydrogen or a hydrocarbyl group containing from 1 to 10 carbon atoms. In
some embodiments R3 contains from 1 to 6, 1 to 2, or even 1 carbon atom, R4
contains from 1 to 6, 1 to 2, or even 1 carbon atom, R5 contains from 2 to 12,
2
to 8 or even 3 carbon atoms, and R6 contains from 1 to 8, or 1 to 4 carbon
atoms. In some of these embodiments, formula (XII) becomes:
R3 R6 R3
NI
NI H NI
NH2
R4 R5 (XII-a) or R4 R5 (XII-b)
where the various definitions provided above still apply.
[0094]
Examples of nitrogen or oxygen containing compounds capable of
condensing with the acylating agents, which also have a tertiary amino group,
or
compounds that can be alkylated into such compounds, include any of the
materials described in the sections above.
[0095] The
nitrogen or oxygen containing compounds may further include
aminoalkyl substituted heterocyclic compounds such as 1-(3-
aminopropyl)imidazole and 4-(3-aminopropyl)morpholine.
[0096] In
one embodiment the nitrogen or oxygen containing compound is
triisopropanolamine, 1- [2 -hydro xyethyl] pip
eridine, 2 - [2 -(dimethylamino)
ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-
butyldiethanolamine, N,N-diethylamino ethanol, N,N-dimethylaminoethanol, 2-
dimethylamino -2 -methyl-1 -prop anol, or combinations thereof
[0097] In
some embodiments the compound having an oxygen or nitrogen
atom capable of condensing with said acid and further having a tertiary amino
group comprises N,N-diethylethylenediamine, N,N-dimethylethylenediamine,
N,N-dibutylethyl enedi amine, N,N-dimethy1-1,3 -di aminoprop ane, N,N-diethyl-
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1,3 -di aminoprop ane, N,N-dimethylamino ethanol, N,N-di ethylamino ethanol,
or
combinations thereof.
[0098] The quaternized polyester salt can be a quaternized polyester
amide
salt. In such embodiments the polyester containing a tertiary amino group used
to prepare the quaternized polyester salt is a polyester amide containing a
tertiary amino group. In some of these embodiments the amine or amino alcohol
is reacted with a monomer and then the resulting material is polymerized with
additional monomer, giving the polyester amide which may then be quaternized.
[0099] In some embodiments the quaternized polyester salt includes a
cation
represented by the following formula:
R1 0
R5 e X2
R7 ____________________________________ 0-R2.N N
- - n I / \
R3 4
R6 (XIII)
where R1 is a hydrogen or a hydrocarbyl group containing from 1 to 20 carbon
atoms and R2 is a hydrocarbylene group containing from 1 to 20 carbon atoms;
R3 is a hydrocarbyl group containing from 1 to 10 carbon atoms; R4 is a hydro-
carbyl group containing from 1 to 10 carbon atoms; R5 is a hydrocarbylene
group containing from 1 to 20 carbon atoms; R6 is a hydrogen or a hydrocarbyl
group containing from 1 to 10 carbon atoms; n is a number from 1 to 20 or from
1 to 10; R7 is hydrogen, a hydrocarbonyl group containing from 1 to 22 carbon
atoms, or a hydrocarbyl group containing from 1 to 22 carbon atoms; and X2 is
a
group derived from the quaternizing agent. In some embodiments R6 is hydro-
gen.
[0100] As above, in some embodiments R1 contains from 1 to 12, 2 to 10,
4
to 8 or even 6 carbon atoms, and R2 contains from 1 or even 2 to 16, 6 to 14,
8
to 12, or even 10 carbon atoms, R3 contains from 1 to 6, 1 to 2, or even 1
carbon
atom, R4 contains from 1 to 6, 1 to 2, or even 1 carbon atom, R5 contains from
2
to 12, 2 to 8 or even 3 carbon atoms, and R6 contains from 1 to 8, or 1 to 4
carbon atoms. In any of these embodiments n may be from 2 to 9, or 3 to 7, and
R7 may contain from 6 to 22, or 8 to 20 carbon atoms. R7 may be an acyl group.
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[01 0 1] In these embodiments the quaternized polyester salt is
essentially
capped with a C1-22, or a C8-20, fatty acid. Examples of suitable acids
include
oleic acid, palmitic acid, stearic acid, erucic acid, lauric acid, 2-
ethylhexanoic
acid, 9,11-linoleic acid, 9,12-linoleic acid, 9,12,15-linolenic acid, abietic
acid,
or combinations thereof
[0102] The number average molecular weight (Mn) of the quaternized
polyester salts of the invention may be from 500 to 3000, or from 700 to 2500.
[0103] The polyester useful in the present invention can be obtained by
heating one or more hydroxycarboxylic acids or a mixture of the hydroxycar-
boxylic acid and a carboxylic acid, optionally in the presence of an
esterification
catalyst. The hydroxycarboxylic acids can have the formula HO-X-COOH
wherein X is a divalent saturated or unsaturated aliphatic radical containing
at
least 8 carbon atoms and in which there are at least 4 carbon atoms between
the
hydroxy and carboxylic acid groups, or from a mixture of such a hydroxycar-
boxylic acid and a carboxylic acid which is free from hydroxy groups. This
reaction can be carried out at a temperature in the region of 160 C to 200 C,
until the desired molecular weight has been obtained. The course of the
esterifi-
cation can be followed by measuring the acid value of the product, with the
desired polyester, in some embodiments, having an acid value in the range of
10
to 100 mg KOH/g or in the range of 20 to 50 mg KOH/g. The indicated acid
value range of 10 to 100 mg KOH/g is equivalent to a number average molecu-
lar weight range of 5600 to 560. The water formed in the esterification
reaction
can be removed from the reaction medium, and this can be conveniently done by
passing a stream of nitrogen over the reaction mixture or, by carrying out the
reaction in the presence of a solvent, such as toluene or xylene, and
distilling off
the water as it is formed.
[0104] The resulting polyester can then be isolated in conventional
manner;
however, when the reaction is carried out in the presence of an organic
solvent
whose presence would not be harmful in the subsequent application, the result-
ing solution of the polyester can be used.
[0105] In the said hydroxycarboxylic acids the radical represented by X
may
contain from 12 to 20 carbon atoms, optionally where there are between 8 and
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14 carbon atoms between the carboxylic acid and hydroxy groups. In some
embodiments the hydroxy group is a secondary hydroxy group.
[0106] Specific examples of such hydroxycarboxylic acids include
ricinoleic
acid, a mixture of 9- and 10-hydroxystearic acids (obtained by sulphation of
oleic acid and then hydrolysis), and 12-hydroxystearic acid, and the commer-
cially available hydrogenated castor oil fatty acid which contains in addition
to
12-hydroxystearic acid minor amounts of stearic acid and palmitic acid.
[0107] The carboxylic acids which can be used in conjunction with the
hydroxycarboxylic acids to obtain these polyesters are preferably carboxylic
acids of saturated or unsaturated aliphatic compounds, particularly alkyl and
alkenyl carboxylic acids containing a chain of from 8 to 20 carbon atoms. As
examples of such acids there may be mentioned lauric acid, palmitic acid,
stearic acid and oleic acid.
[0108] In one embodiment the polyester is derived from commercial 12-
hydroxy-stearic acid having a number average molecular weight of about 1600.
Polyesters such as this are described in greater detail in U.K. Patent
Specifica-
tion Nos. 1373660 and 1342746.
[0109] In some embodiments the components used to prepare the additives
described above are substantially free of, essentially free of, or even
completely
free of, non-polyester-containing hydrocarbyl substituted acylating agents
and/or non-polyester-containing hydro carbyl substituted diacylating agents,
such as for example polyisobutylene. In some embodiments these excluded
agents are the reaction product of a long chain hydrocarbon, generally a
polyole-
fin reacted with a monounsaturated carboxylic acid reactant, such as, (i) a,I3-
monounsaturated C4 to C10 dicarboxylic acid, such as, fumaric acid, itaconic
acid, maleic acid.; (ii) derivatives of (i) such as anhydrides or Ci to C5
alcohol
derived mono- or di-esters of (i); (iii) a,13-monounsaturated C3 to C10
monocar-
boxylic acid such as acrylic acid and methacrylic acid.; or (iv) derivatives
of
(iii), such as, C1 to C5 alcohol derived esters of (iii) with any compound con-
taming an olefinic bond represented by the general formula
(R9)(R10)c c,¨
11( )(CH(R7)(R8)) wherein each of R9 and R1 is independently
hydrogen or a hydrocarbon based group; each of R11, R7 and R8 is independently
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hydrogen or a hydrocarbon based group and preferably at least one is a hydro-
carbyl group containing at least 20 carbon atoms. In one embodiment, the
excluded hydrocarbyl-substituted acylating agent is a dicarboxylic acylating
agent. In some of these embodiments, the excluded hydrocarbyl-substituted
acylating agent is polyisobutylene succinic anhydride.
[0110] By substantially free of, it is meant that the components of the
pre-
sent invention are primarily composed of materials other than hydrocarbyl
substituted acylating agents described above such that these agents are not
significantly involved in the reaction and the compositions of the invention
do
not contain significant amounts of additives derived from such agents. In some
embodiments the components of the invention, or the compositions of the
invention, may contain less than 10 percent by weight of these agents, or of
the
additives derived from these agents. In other embodiments the maximum
allowable amount may be 5, 3, 2, 1 or even 0.5 or 0.1 percent by weight. One
of
the purposes of these embodiments is to allow the exclusion of agents such as
polyisobutylene succinic anhydrides from the reactions of the invention and
so,
to also allow the exclusion of quaternized salt detergent additive derived
from
agents such as polyisobutylene succinic anhydrides. The focus of this embodi-
ment is on polyester, or hyperdispersant, quaternary salt detergent additives.
[0111] In some embodiments the compositions of the invention are substan-
tially free of, or even completely free of, the polyester quaternary salts de-
scribed above.
The Quaternizing Agent
[0112] Suitable quaternizing agents for preparing any of the quaternary
ammonium salt detergents described above include dialkyl sulfates, benzyl
halides, hydrocarbyl substituted carbonates, hydrocarbyl epoxides used in
combination with an acid, esters of polycarboxylic acids, or mixtures thereof.
[0113] In one embodiment the quaternizing agent includes: halides such
as
chloride, iodide or bromide; hydroxides; sulphonates; alkyl sulphates such as
dimethyl sulphate; sultones; phosphates; C1_12 alkylphosphates; di-C1_12 al-
kylphosphates; borates; C1_12 alkylborates; nitrites; nitrates; carbonates;
bicar-
bonates; alkanoates; 0,0-di-C1_12 alkyldithiophosphates; or mixtures thereof.
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[0114] In one embodiment the quaternizing agent may be: a dialkyl
sulphate
such as dimethyl sulphate; N-oxides; sultones such as propane or butane sul-
tone; alkyl, acyl or aralkyl halides such as methyl and ethyl chloride,
bromide or
iodide or benzyl chloride; hydrocarbyl (or alkyl) substituted carbonates; or
combinations thereof. If the aralkyl halide is benzyl chloride, the aromatic
ring
is optionally further substituted with alkyl or alkenyl groups.
[0115] The hydrocarbyl (or alkyl) groups of the hydrocarbyl substituted
carbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atoms per
group. In one embodiment the hydrocarbyl substituted carbonates contain two
hydrocarbyl groups that may be the same or different. Examples of suitable
hydrocarbyl substituted carbonates include dimethyl or diethyl carbonate.
[0116] In another embodiment the quaternizing agent can be a
hydrocarbyl
epoxides, as represented by the following formula:
R15 0 R17
R' R'8
(XIV)
wherein R15, R165 R17
and R18 can be independently H or a C1_50 hydrocarbyl
group. Examples of suitable hydrocarbyl epoxides include: styrene oxide,
ethylene oxide, propylene oxide, butylene oxide, stilbene oxide, C2_50
epoxides,
or combinations thereof
[0117] In another embodiment the quaternizing agent can be an ester of
a
carboxylic acid capable of reacting with a tertiary amine to form a quaternary
ammo-
nium salt, or an ester of a polycarboxylic acid. In a general sense such
materials
may be described as compounds having the structure:
R19-C(=0)-0-R2 (XV)
where R19 is an optionally substituted alkyl, alkenyl, aryl or alkylaryl group
and R2
is a hydrocarbyl group containing from 1 to 22 carbon atoms.
[0118] Suitable compounds include esters of carboxylic acids having a
pKa of
3.5 or less. In some embodiments the compound is an ester of a carboxylic acid
selected from a substituted aromatic carboxylic acid, an a-hydroxycarboxylic
acid
and a polycarboxylic acid. In some embodiments the compound is an ester of a
substituted aromatic carboxylic acid and thus R19 is a substituted aryl group.
R may
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be a substituted aryl group having 6 to 10 carbon atoms, a phenyl group, or a
naph-
thyl group. R may be suitably substituted with one or more groups selected
from
carboalkoxy, nitro, cyano, hydroxy, SR' or NRµR¨ where each of R' and R¨ may
independently be hydrogen, or an optionally substituted alkyl, alkenyl, aryl
or
carboalkoxy groups. In some embodiments R' and R¨ are each independently
hydrogen or an optionally substituted alkyl group containing from 1 to 22, 1
to 16, 1
to 10, or even 1 to 4 carbon atoms.
[0119] In some embodiments R19 in the formula above is an aryl group
substitut-
ed with one or more groups selected from hydroxyl, carboalkoxy, nitro, cyano
and
[0120] In some embodiments the quaternizing agent is an ester of an
alpha-
[0121] In some embodiments the quaternizing agent comprises an ester of
a
polycarboxylic acid. In this definition we mean to include dicarboxylic acids
and
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carboxylic acids having more than 2 acidic moieties. In some embodiments the
esters are alkyl esters with alkyl groups that contain from 1 to 4 carbon
atoms.
Suitable example include diesters of oxalic acid, diesters of phthalic acid,
diesters of
maleic acid, diesters of malonic acid or diesters or triesters of citric acid.
[0122] In some
embodiments the quaternizing agent is an ester of a carboxylic
acid having a pKa of less than 3.5. In such embodiments in which the compound
includes more than one acid group, we mean to refer to the first dissociation
constant.
The quaternizing agent may be selected from an ester of a carboxylic acid
selected
from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid,
malonic
acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2, 4, 6-
trihydroxybenzoic
acid. In some embodiments the quaternizing agent includes dimethyl oxalate,
methyl 2-nitrobenzoate and methyl salicylate.
[0123] Any
of the quaternizing agents described above, including the hydro-
carbyl epoxides, may be used in combination with an acid. Suitable acids
include carboxylic acids, such as acetic acid, propionic acid, 2-ethylhexanoic
acid, and the like.
[0124] In
some embodiments the quaternary ammonium salt includes the
reaction product of: (i) a compound comprising at least one tertiary amino
group; and (ii) a quaternizing agent suitable for converting the tertiary
amino
group of compound (i) to a quaternary nitrogen, where component (i), the
compound comprising at least one tertiary amino group, comprises: (a) the
condensation product of a hydrocarbyl-substituted acylating agent and a com-
pound having an oxygen or nitrogen atom capable of condensing the acylating
agent wherein the condensation product has at least one tertiary amino group.
[0125] In some embodiments the hydrocarbyl-substituted acylating agent
may be polyisobutylene succinic anhydride and the compound having an oxygen
or nitrogen atom capable of condensing with said acylating agent may be dime-
thylaminopropylamine, N-m ethyl- 1,3 - di aminoprop ane, N,N-
dimethyl-
aminopropylamine, N,N-diethyl-aminopropylamine, N,N-
dimethyl-
aminoethylamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine,
triethylenetetraamine, tetraethylenepentaamine, p
entaethylenehexaamine,
hexamethylenetetramine, and bis(hexamethylene) triamine.
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[0126] In some embodiments the quaternary ammonium salt comprises an
cation represented by the following formula:
0
R23 e x
N
/
R24 R21 \22.-------
0 (XVI)
wherein: R21 is a hydrocarbyl group containing from 1 to 10 carbon atoms; R22
is a hydrocarbyl group containing from 1 to 10 carbon atoms; R23 is a hydro-
carbylene group containing from 1 to 20 carbon atoms; R24 is a hydrocarbyl
group containing from 50 to 150 carbon atoms; and X is a group derived from
the quaternizing agent.
[0127] In some embodiments the quaternary ammonium salt includes the
reaction product of: (i) a compound comprising at least one tertiary amino
group; and (ii) a quaternizing agent suitable for converting the tertiary
amino
group of compound (i) to a quaternary nitrogen, where component (i), the
compound comprising at least one tertiary amino group, comprises: (b) a poly-
alkene-substituted amine having at least one tertiary amino group.
[0128] In some embodiments the polyalkene substituent of the polyalkene-
substituted amine is derived from polyisobutylene and the polyalkene-
substituted amine has a number average molecular weight of about 500 to about
3000.
[0129] In some embodiments the quaternary ammonium salt includes the
reaction product of: (i) a compound comprising at least one tertiary amino
group; and (ii) a quaternizing agent suitable for converting the tertiary
amino
group of compound (i) to a quaternary nitrogen, where component (i), the
compound comprising at least one tertiary amino group, comprises: (c) a Man-
nich reaction product having at least one tertiary amino group, wherein the
Mannich reaction product is derived from a hydrocarbyl-substituted phenol, an
aldehyde, and an amine.
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[0130] In some embodiments component (i), the compound comprising at
least one tertiary amino group, comprises a Mannich reaction product having a
tertiary amino group, said Mannich reaction product being prepared from the
reaction of a hydrocarbyl-substituted phenol, an aldehyde, and an amine; and
wherein the hydrocarbyl substituent of the hydrocarbyl-substituted phenol of
component (a) is derived from a polyolefin having a number average molecular
weight of 400 to 3,000; wherein the aldehyde of component (a) is a formalde-
hyde or a reactive equivalent thereof; and wherein the amine of component (a)
is
selected from the group consisting of dimethylamine, ethylenediamine, dime-
thylaminopropylamine, diethylenetriamine, dibutylamine, and mixtures thereof.
[0131] In any of these embodiments described above, any of one or
combina-
tion of quaternizing agents described above may be used.
Industrial Application
[0132] As noted above, home heating applications use specially designed
burners, sometimes referred to as open air burners. Such burners are highly
designed to increase burner efficiency in forced air furnaces and other
similar
home heating applications. These burners are very different from those seen on
other application, especially the equipment designed for use in internal
combus-
tion engines, and present special problems and challenges unique to home
heating applications.
[0133] In a forced-air furnace a pump may be used to drawn the heating
oil
from a storage tank and pressurize it to 1,034 kPa, forcing it through a
nozzle to
form an atomized spray. A pair of metal electrodes is typically used to ignite
the heating oil, with the electrodes positioned near the heating oil spray
nozzle
such that high voltage formed across the electrode gap produces a spark approx-
imately 6 mm long. With the airflow coming from a fan or similar source, the
spark ignites the oil droplets in the spray. A combustion chamber is used to
contain the flame and flue gases are directed through a heat exchanger to a
chimney or similar exhaust. The heat of the flue gases is transferred in heat
exchanger and a fan circulates a separate stream of air through the heat ex-
changer and throughout the building, such as a house, that the furnace is sued
to
heat, typically through a network of duct piping. Colder air in the building
is
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returned to the furnace either through an air return system, typically a
separate
network of cold air ducts or a central return duct located near the center of
the
building or house, which is then passed through the heat exchanger to again to
be warmed and circulated back through the living space of the house.
[0134] The invention provides a method of operating a heating device, such
as those described above, comprising the steps of: (I) supplying to said
heating
device any of the heating oil compositions, including any of the quaternary
ammonium salts, described above.
[0135] The invention also provides for the use of any of the quaternary
ammonium salts described above as a soot modifiers and/or depositor control
additives in any of the heating oil compositions described above and/or in any
heating oil application.
[0136] 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. Specifi-
cally, it refers to a group having a carbon atom directly attached to the
remainder of
the molecule and having predominantly hydrocarbon character. Examples of hydro-
carbyl groups include: hydrocarbon substituents, that is, aliphatic (e.g.,
alkyl or
alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and
aromatic-, ali-
phatic-, and alicyclic-substituted aromatic substituents, as well as cyclic
substituents
wherein the ring is completed through another portion of the molecule (e.g.,
two
substituents together form a ring); substituted hydrocarbon substituents, that
is,
substituents containing non-hydrocarbon groups which, in the context of this
inven-
tion, do not alter the predominantly hydrocarbon nature of the substituent
(e.g., halo
(especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto,
nitro,
nitroso, and sulfoxy); hetero substituents, that is, substituents which, while
having a
predominantly hydrocarbon character, in the context of this invention, contain
other
than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms
include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl,
furyl, thienyl
and imidazolyl. In general, no more than two, preferably no more than one, non-
hydrocarbon substituent will be present for every ten carbon atoms in the
hydro-
carbyl group; typically, there will be no non-hydrocarbon substituents in the
hydro-
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carbyl group. As used herein, the term "hydrocarbonyl group" or "hydrocarbonyl
substituent" means a hydrocarbyl group containing a carbonyl group.
[0137] It is known that some of the materials described above may
interact in the
final formulation, so that the components of the final formulation may be
different
from those that are initially added. For instance, metal ions (of, e.g., a
detergent) can
migrate to other acidic or anionic sites of other molecules. The products
formed
thereby, including the products formed upon employing the composition of the
present invention in its intended use, may not be susceptible of easy
description.
Nevertheless, all such modifications and reaction products are included within
the
scope of the present invention; the present invention encompasses the
composition
prepared by admixing the components described above.
Examples
[0138] The invention will be further illustrated by the following
examples.
While the Examples are provided to illustrate the invention, they are not
intended to
limit it.
[0139] A set of quaternary ammonium salts are prepared as described in
the
examples below.
Example Q-1
[0140] Polyisobutylene succinic anhydride (100 pbw), (which itself is
prepared by reacting 1000 number average molecular weight high vinylidene
polyisobutylene and maleic anhydride at elevated temperatures), is heated to
80 C and is charged to a jacketed reaction vessel fitted with stirrer,
condenser,
feed pump attached to subline addition pipe, nitrogen line and thermocou-
ple/temperature controller system. The reaction vessel is heated to 100 C.
Dimethylaminopropylamine (10.9 pbw) is charged to the reaction, maintaining
the batch temperature below 120 C, over an 8 hour period. The reaction mix-
ture is then heated to 150 C and maintained at temperature for 4 hours,
resulting
in a non-quaternized succinimide detergent.
[0141] A portion of the non-quaternized succinimide detergent (100 pbw)
is
then charged to a similar reaction vessel. Acetic acid (5.8 pbw) and 2-
ethylhexanol (38.4 pbw) are added to the vessel and the mixture is stirred and
heated to 75 C. Propylene oxide (8.5 pbw) is added to the reaction vessel over
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4 hours, holding the reaction temperature at 75 C. The batch is held at
tempera-
ture for 4 hours. The resulting product contains a quaternized succinimide
detergent.
Example Q-2
[0142] A non-
quaternized succinimide detergent is prepared from a mixture of
polyisobutylene succinic anhydride, as described above, (100 pbw) and diluent
oil ¨ pilot 900 (17.6 pbw) which are heated with stirring to 110 C under a
nitrogen atmosphere. Dimethylaminopropylamine (DMAPA, 10.8 pbw) is added
slowly over 45 minutes maintaining batch temperature below 115 C. The
reaction temperature is increased to 150 C and held for a further 3 hours. The
resulting compound is a DMAPA succinimide non-quaternized detergent. A
portion of this non-quaternized succinimide detergent (100 pbw) is heated with
stirring to 90 C. Dimethyl sulfate (6.8 pbw) is charged to the reaction vessel
and stirring is resumed at 300rpm under a nitrogen blanket. The resulting
exotherm raises the batch temperature to ¨100 C. The reaction is maintained at
100 C for 3 hours before cooling back and decanting. The resulting product
contains a dimethyl sulfate derived quaternary ammonium salt.
Example Q-3
[0143] An
apparatus suitable to handle chlorine and hydrogen chloride gas
(glass reactor, glass stirrer, PTFE joints, glass thermowell for thermocouple)
is
connected to sodium hydroxide scrubbers. The glass vessel is charged with low
vinylidene 1000 Mn polyisobutylene (PIB, 100 grams) and is heated to 110-
120 C. Chlorine (70 grams) is bubbled into the reactor over 7 hours. The
reaction mixture is then sparged with nitrogen at 110-120 C overnight to
remove
HC1.
[0144] The
resultant PIB chloride is transferred to an autoclave and the
autoclave is sealed. For every mole (-1030g) of PIB chloride, 1 mole of
gaseous
dimethylamine (DMA, 45g) is added and the reaction is heated to 160-170 C
and held for 8 hours, or until no further reduction in pressure is seen. The
reaction is cooled to room temperature and the pressure is released. Enough
SolvessoTM 150 solvent is added to make a 70% w/w actives solution and the
reaction is stirred until homogenous. The
resultant polyisobutene-
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dimethylamine (PIB-DMA) solution is transferred to a separating funnel and
washed twice with 2M sodium hydroxide solution, to remove HC1 and NaCl.
After separation, the product is dried over MgSO4 and is filtered through a
Celite TM pad.
[0145] The resultant
PIB-DMA solution (41 grams of the 70% active solu-
tion) is charged to a glass reaction vessel and stirred at room temperature.
Dimethyl sulphate (3.3 grams) is added dropwise over one minute to provide the
quaternary ammonium salt. The mixture is stirred at room temperature for 1
hour under a nitrogen blanket and is sampled and titrated against bromocresol
green indicator. The resulting compound is a quaternary ammonium salt
detergent of a polyalkene-substituted amine.
Example Q-4
[0146]
Alkylated phenol (800 grams), which itself is prepared from 1000 Mn
polyisobutylene, and SO-44 diluent oil (240 grams) is charged to a reaction
vessel matching the description above. A nitrogen blanket is applied to the
vessel and the mixture is stirred at 100 rpm. To this mixture, Formalin (55.9
grams) is added (dropwise) over 50 minutes. After which, dimethylamine
(DMA, 73.3 grams) is added (dropwise) over the next 50 minutes. The mixture
is heated to 68 C and held for one hour. The mixture is then heated to 106 C
and held for a further 2 hours. The temperature of the mixture is then
increased
to 130 C and held for 30 minutes before allowing the mixture to cool to
ambient
temperature. The mixture is purified by vacuum distillation (at 130 C and -0.9
bar) to remove any remaining water, resulting in a DMA Mannich.
[0147] The
DMA Mannich (1700 grams) is added to a reaction vessel.
Styrene oxide (263 grams), acetic acid (66 grams) and methanol (4564 grams)
are added to the vessel and the mixture is heated with stirring to reflux (-75
C)
for 6.5 hours under a nitrogen blanket. The reaction is purified by vacuum
distillation (at 30 C and -0.8bar). The resulting compound is a Mannich quater-
nary ammonium salt detergent.
Example Q-5
[0148]
Polyisobutylene succinic anhydride (500 g), which itself is prepared by
reacting 1000 number average molecular weight high vinylidene polyisobutylene
and
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maleic anhydride, is heated to 70 C and charged to a jacketed reaction vessel
fitted with stirrer, condenser, feed pump attached to subline addition pipe,
nitrogen line and thermocouple/temperature controller system. Heptane (76.9
grams) is added to the reaction vessel and then dimethylaminopropylamine (52.3
g)
is added over time, holding the reaction temperature at 70 C. Once the
addition is
complete, the reaction vessel is held at 70 C for 1 hour. The resulting
product, a
non-quaternized succinamide detergent, is cooled and collected.
[0149] The resulting non-quaternized succinamide detergent (470 g), is
charged to a 2-liter round bottom flange flask with water condenser attached.
2-
ethylhexanol (180.6 g) is added to the flask and the mixture is stirred with
an
overhead stirrer and heated to 55 C under a nitrogen blanket. Propylene oxide
(40.2 g) is then added to the reaction vessel via syringe pump over 4 hours,
holding the reaction temperature at 55 C. The batch is held at temperature for
16 hours. The product, which is primarily a quaternized succinamide detergent,
is cooled and collected.
Example Q-6
[0150] A non-quaternized polyester amide is prepared by reacting, in a
jacketed
reaction vessel fitted with stirrer, condenser, feed pump attached to subline
addition pipe, nitrogen line and thermocouple/temperature controller system, 6
moles of 12-hydroxystearic acid and 1 mole of dimethylaminopropylamine where
the
reaction is carried out at about 130 C and held for about 4 hours. The
reaction
mixture is then cooled to about 100 C and zirconium butoxide is added, in an
amount
so that the catalyst makes up 0.57 percent by weight of the reaction mixture.
The
reaction mixture is heated to about 195 C and held for about 12 hours. The
resulting
product is cooled and collected.
[0151] A quaternized polyester amide salt detergent is prepared by
reacting, in a
jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to
subline addition pipe, nitrogen line and thermocouple/temperature controller
system, 600 grams of the non-quaternized polyester amide described above, 120
grams of 2-ethylhexanol, 18.5 grams of acetic acid, and 32.3 ml of propylene
oxide,
where the reaction is carried out at about 90 C and the propylene oxide is fed
in to
the reaction vessel over about 3.5 hours. The reaction mixture is then held at
temper-
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ature for about 3 hours. 760 grams of product is cooled and collected, which
TAN,
FTIR and ESI-MS analysis confirms to be about 80% by weight quaternized polyes-
ter amide salt detergent, with the remaining material being primarily non-
quaternized
polyester amide. The collected material has a TAN of 1.26 mg KOH/gram, a TBN
of
23.82 mg KOH/gram, a kinematic viscosity at 100 C of 28.58 cSt (as measured by
ASTM D445), an acetate peak by IR at 1574 cm-1, and is 1.22% nitrogen.
Example Q-7
[0152] A non-quaternized polyester amide is prepared by reacting, in a
jacketed
reaction vessel fitted with stirrer, condenser, feed pump attached to subline
addition pipe, nitrogen line and thermocouple/temperature controller system,
1300 grams of ricinoleic acid and 73.5 grams of dimethylaminopropylamine where
the reaction is carried out at about 130 C, the amine is added dropwise over
about 8
minutes, and the reaction mixture held for about 4 hours. The reaction mixture
is
then cooled to about 100 C and 7.8 grams of zirconium butoxide is added. The
reaction mixture is heated to about 195 C and held for about 17 hours. The
resulting
product is filtered, cooled and collected. 1301 grams of product is collected
which
has a TAN of 0 mg KOH/gram and shows by IR an ester peak at 1732 cm-1, an
amide
peak at 1654 cm-1, but no acid peak at 1700 cm-1.
[0153] A quaternized polyester amide salt detergent is prepared by
reacting, in a
jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to
subline addition pipe, nitrogen line and thermocouple/temperature controller
system, 600 grams of the non-quaternized polyester amide described above, 123
grams of 2-ethylhexanol, 18.9 grams of acetic acid, and 33.1 ml of propylene
oxide,
where the reaction is carried out at about 90 C and the propylene oxide is fed
in to
the reaction vessel over about 3.5 hours. The reaction mixture is then held at
temper-
ature for about 3 hours. 751 grams of product is cooled and collected, which
TAN,
FTIR and ESI-MS analysis confirms to be about 70% by weight quaternized polyes-
ter amide salt detergent, with the remaining material being primarily non-
quaternized
polyester amide. The collected material has a TAN of 0 mg KOH/gram, a TBN of
23.14 mg KOH/gram, a kinematic viscosity at 100 C of 47.0 cSt (as measured by
ASTM D445), an acetate peak by IR at 1574 cm-1.
Example Set/
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[0154] A set of compositions are prepared for evaluation in the DGMK
570-2
Light Box Test. This test method is used to evaluate the storage stability of
a heating
oil composition.
[0155] For storage stability the sample is passed through a membrane
filter, and
then the oil sample is exposed to five artificial light sources (light box)
for 24 hours
in the presence of a copper wire, and subsequently again filtered through a
membrane
filter. The filter residue is washed, dried, and weighed in mg/kg as
"filtratable ageing
residue". The residue, which remained in the ageing vessel and on the copper
wire,
is dissolved in a solvent (4.5) and transferred into a vessel for evaporation.
After
evaporation of the solvent and drying, this residue is weighed in mg/kg as
"not
filtratable ageing residue". The sum of filtratable and not filtratable ageing
residues
is reported in mg/kg as "storage sediment". The lower the storage sediment,
the
better the storage stability of the composition.
[0156] A set of additive packages are prepared using a conventional
additive
package. Two of the packages also contain a conventional succinimide
dispersant
made from polyisobutylene succinic anhydride, which itself is prepared by
reacting 1000 number average molecular weight high vinylidene polyisobutyl-
ene and maleic anhydride, and a polyalkylene polyamine. Two of the packages
also contain a succinimide quaternary ammonium salt similar to that described
in
Example Q-1 above. All of the additive packages contain identical amounts of
an
alcohol, a phenolic antioxidant, an alkaryl amine antioxidant, a triazole
metal deacti-
vator, a polyisobutylene succinic acid, and a demulsifier, with the balance
being
made up with a petroleum naphtha solvent. One set of examples also includes an
additional antioxidant booster. The formulations of the additive packages are
sum-
marized below.
Table 1 ¨ Additive Package Sample]
Ex A Ex B Ex C Ex D
Comparative Inventive Comparative
Inventive
Additive Package2 85% 85% 85% 85%
Conventional Succinimide 15% 0% 15% 0%
Quaternary Ammonium Salt 0% 4.5% 0% 4.5%
Additional Solvent3 0% 10.5% 0% 10.5%
Antioxidant Booster 0% 0% 2% 2%
1 ¨All values are percent by weight.
2 ¨ The additive package used in each of the examples is identical.
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3 ¨ The additional solvent added here is petroleum naphtha solvent to make up
for the reduced
treat rate of the quaternary ammonium salt.
[0157] Each of the additive package examples were treated into fuels
for testing
in the DGMK 570-2 Light Box Test described above. One set of samples was
treated
at 500 ppm into an un-additized reference home heating oil (Fuel A). One set
of
samples was treated at 500 ppm into a fuel mixture that was 5 percent by
weight soy
methyl ester (SME) and 95 percent by weight of the same un-additized reference
home heating oil used in the other example set (Fuel B). The results obtained
are
summarized below.
Table 2¨ Test Results'
Ex A Ex B Ex C Ex D
Comparative Inventive Comparative
Inventive
In Fuel A at 500 ppm 177 119 92 82
In Fuel B at 500 ppm 113 80 26 24
1 ¨ Reported values are storage sediment, measured in mg/kg, which is the sum
of filtratable and not
filtratable ageing residues.
[0158] The results show that the heating oil compositions of the invention
give
improved storage stability over the comparative heating oil compositions that
use a
conventional additive in place of the described quaternary ammonium salts.
[0159] Each of the documents referred to above is incorporated herein
by refer-
ence. Except in the Examples, or where otherwise explicitly indicated, all
numerical
quantities in this description specifying amounts of materials, reaction
conditions,
molecular weights, number of carbon atoms, and the like, are to be understood
as
modified by the word "about." Except where otherwise indicated, all numerical
quantities in the description specifying amounts or ratios of materials are on
a weight
basis. Unless otherwise indicated, each chemical or composition referred to
herein
should be interpreted as being a commercial grade material which may contain
the
isomers, by-products, derivatives, and other such materials which are normally
understood to be present in the commercial grade. However, the amount of each
chemical component is presented exclusive of any solvent or diluent oil, which
may
be customarily present in the commercial material, unless otherwise indicated.
It is
to be understood that the upper and lower amount, range, and ratio limits set
forth
herein may be independently combined. Similarly, the ranges and amounts for
each
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element of the invention can be used together with ranges or amounts for any
of the
other elements. As used herein, the expression "consisting essentially of'
permits the
inclusion of substances that do not materially affect the basic and novel
characteris-
tics of the composition under consideration.
43
