U.S. patent application number 14/345320 was filed with the patent office on 2014-11-27 for quaternary ammonium salts in heating oils.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to David C. Arters, James H. Bush, Sarah J. Harrison.
Application Number | 20140345191 14/345320 |
Document ID | / |
Family ID | 46846004 |
Filed Date | 2014-11-27 |
United States Patent
Application |
20140345191 |
Kind Code |
A1 |
Bush; James H. ; et
al. |
November 27, 2014 |
Quaternary Ammonium Salts In Heating Oils
Abstract
The invention relates to heating oils continuing quaternary
ammonium 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.
Inventors: |
Bush; James H.; (Mentor,
OH) ; Harrison; Sarah J.; (Ashborne, GB) ;
Arters; David C.; (Wicklifffe, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
46846004 |
Appl. No.: |
14/345320 |
Filed: |
August 29, 2012 |
PCT Filed: |
August 29, 2012 |
PCT NO: |
PCT/US2012/052784 |
371 Date: |
March 17, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61538169 |
Sep 23, 2011 |
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|
Current U.S.
Class: |
44/347 ;
44/422 |
Current CPC
Class: |
C10L 1/198 20130101;
C10L 1/2387 20130101; C10L 1/1616 20130101; C10L 2200/0438
20130101; C10L 1/238 20130101; C10L 1/232 20130101; C10L 2230/14
20130101; C10L 10/00 20130101; C10L 1/143 20130101; C10L 1/2222
20130101; C10L 1/223 20130101; C10L 10/18 20130101; C10L 10/06
20130101; C10L 1/2383 20130101; C10L 1/1832 20130101 |
Class at
Publication: |
44/347 ;
44/422 |
International
Class: |
C10L 1/222 20060101
C10L001/222; C10L 10/06 20060101 C10L010/06; C10L 1/232 20060101
C10L001/232 |
Claims
1. A heating oil composition comprising: (A) a heating oil; and (B)
a quaternary ammonium salt detergent; wherein the detergent
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.
2. The composition of claim 1 wherein component (i), the compound
comprising at least one tertiary amino group, comprises: (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 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; (d) a
compound containing at least one amide group and at least one
tertiary amine functionality; (e) a compound containing at least
one ester group and at least one tertiary amino group; or (f) any
combination thereof.
3. The composition of claim 1 wherein component (i), the compound
comprising at least one tertiary amino group, comprises 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 and further having at least
one tertiary amino group; and wherein the hydrocarbyl-substituted
acylating agent is polyisobutylene succinic anhydride and the
compound having an oxygen or nitrogen atom capable of condensing
with said acylating agent is dimethylaminopropylamine,
N-methyl-1,3-diaminopropane, N,N-dimethyl-aminopropylamine,
N,N-diethylaminopropylamine, N,N-dimethyl-aminoethylamine,
diethylenetriamine, dipropylenetriamine, dibutylenetriamine,
triethylenetetraamine, tetraethylenepentaamine,
pentaethylenehexaamine, hexamethylenetetramine, and
bis(hexamethylene)triamine.
4. The composition of claim 1 wherein component (i), the compound
comprising at least one tertiary amino group, comprises a
polyalkene-substituted amine having at least one tertiary amino
group; wherein the polyalkene substituent of the
polyalkene-substituted amine is derived from polyisobutylene; and
wherein the polyalkene-substituted amine has a number average
molecular weight of about 500 to about 3000.
5. The composition of claim 1 wherein 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; wherein
the hydrocarbyl substituent of the hydrocarbyl-substituted phenol
of component (a) is a polyolefin having a number average molecular
weight of 400 to 3,000; wherein the aldehyde of component (a) is a
formaldehyde or a reactive equivalent thereof; and wherein the
amine of component (a) is selected from the group consisting of
dimethylamine, ethylenediamine, dimethylaminopropylamine,
diethylenetriamine, dibutylamine, and mixtures thereof.
6. The composition of claim 1 wherein the quaternary ammonium salt
comprises a cation represented by the following formula:
##STR00012## wherein: R.sup.21 is a hydrocarbyl group containing
from 1 to 10 carbon atoms; R.sup.22 is a hydrocarbyl group
containing from 1 to 10 carbon atoms; R.sup.23 is a hydrocarbylene
group containing from 1 to 20 carbon atoms; R.sup.24 is a
hydrocarbyl group containing from 50 to 150 carbon atoms; and X is
a group derived from the quaternizing agent.
7. The composition of claim 1 wherein component (ii), the
quaternizing agent suitable for converting the tertiary amino group
of compound (i) to a quaternary nitrogen, comprises: (a) dialkyl
sulfates; (b) benzyl halides; (c) hydrocarbyl substituted
carbonates; (d) hydrocarbyl epoxides; (e) esters of carboxylic
acids and/or polycarboxylic acids; (f) any combination thereof;
wherein the quaternizing agent may optionally be used in
combination with an acid.
8. A method of operating a heating device comprising the steps of:
I. Supplying to said heating device a heating oil composition
comprising (A) a heating oil; and (B) a quaternary ammonium salt;
wherein the quaternary ammonium salt detergent 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.
9. The method of claim 8 wherein component (i), the compound
comprising at least one tertiary amino group, comprises: (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 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; (d) a
compound containing at least one amide group and at least one
tertiary amine functionality; (e) a compound containing at least
one ester group and at least one tertiary amino group; or (f) any
combination thereof.
10. The method of claim 9 wherein component (ii), the quaternizing
agent suitable for converting the tertiary amino group of compound
(i) to a quaternary nitrogen, comprises: (a) dialkyl sulfates; (b)
benzyl halides; (c) hydrocarbyl substituted carbonates; (d)
hydrocarbyl epoxides; (e) esters of carboxylic acids and/or
polycarboxylic acids; (f) any combination thereof; wherein the
quaternizing agent may optionally be used in combination with an
acid.
11. 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 converting the tertiary amino group of compound (i) to
a quaternary nitrogen.
12. The use of claim 11 wherein component (i), the compound
comprising at least one tertiary amino group, comprises: (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 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; (d) a
compound containing at least one amide group and at least one
tertiary amine functionality; (e) a compound containing at least
one ester group and at least one tertiary amino group; or (f) any
combination thereof.
13. The use of claim 11 wherein component (ii), the quaternizing
agent suitable for converting the tertiary amino group of compound
(i) to a quaternary nitrogen, comprises: (a) dialkyl sulfates; (b)
benzyl halides; (c) hydrocarbyl substituted carbonates; (d)
hydrocarbyl epoxides; (e) esters of carboxylic acids and/or
polycarboxylic acids; (f) any combination thereof; wherein the
quaternizing agent may optionally be used in combination with an
acid.
Description
FIELD OF THE INVENTION
[0001] The invention relates to heating oils continuing quaternary
ammonium 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 delivered 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 applications. 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 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
additives that work comparatively better in the XUD-9 test also
perform comparatively 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
comprising: (A) a heating oil; and (B) a quaternary ammonium salt;
where 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.
[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 compound 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 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 compounds 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 converting 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 ammonium salt detergent 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 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 (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.degree. 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.degree. C., while it generally distills at a higher temperature
than kerosene, which distills between 160 and 250.degree. 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
compositions: antioxidants, corrosion inhibitors, detergent and/or
dispersant additives other than those described above, cold flow
improvers, foam inhibitors, demulsifiers, 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 derivatives thereof and/or diarylamines or derivatives thereof.
Suitable detergent/dispersant additives include for example
polyetheramines or nitrogen containing detergents, including but
not limited to PIB amine detergents/dispersants, succinimide
detergents/dispersants, and other quaternary salt
detergents/dispersants including polyisobutylsuccinimide-derived
quaternized PIB/amine and/or amide dispersants/detergents. Suitable
cold flow improvers include for example esterified copolymers of
maleic anhydride and styrene and/or copolymers of ethylene and
vinyl acetate. Suitable demulsifiers include for example
polyalkoxylated alcohols. Suitable lubricity agents include for
example fatty carboxylic acids. Suitable metal deactivators include
for example aromatic triazoles or derivatives thereof, including
but not limited to benzotriazole. Suitable foam inhibitors and/or
antifoams include for example organic silicones such as
polydimethylsiloxane, polyethylsiloxane, polydiethylsiloxane,
polyacrylates and polymethacrylates,
trimethyl-trifluoro-propylmethylsiloxane and the like. Suitable
fluidizers include for example mineral oils and/or
poly(alpha-olefins) and/or polyethers. Combustion improvers include
for example 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 derivatives thereof, may be derived from
amines and/or alcohols that are linear or branched, but in some
embodiments are derived from branched alcohols resulting in
friction modifiers that themselves have significant amounts of
branched hydrocarbyl groups present within it structure. Examples
of suitable branched alcohols used to prepare such friction
modifiers include 2-ethylhexanol, isotridecanol, Guerbet alcohols,
and mixtures thereof.
[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 described in U.S. Pat. Nos.
4,234,435 and 3,172,892. Another class of ashless dispersant is
high molecular weight esters, prepared by reaction of a hydrocarbyl
acylating agent and a polyhydric aliphatic alcohol such as
glycerol, pentaerythritol, or sorbitol. Such materials are
described in more detail in U.S. Pat. No. 3,381,022. Another class
of ashless dispersant is Mannich bases. These are materials which
are formed by the condensation of a higher molecular weight, alkyl
substituted phenol, an alkylene polyamine, and an aldehyde such as
formaldehyde and are described in more detail in U.S. Pat. No.
3,634,515. Other dispersants include polymeric dispersant
additives, which are generally hydrocarbon-based polymers which
contain polar functionality to impart dispersancy characteristics
to the polymer. An amine is typically employed in preparing the
high TBN nitrogen-containing dispersant. One or more
poly(alkyleneamine)s may be used, and these may comprise one or
more poly(ethyleneamine)s having 3 to 5 ethylene units and 4 to 6
nitrogen units. Such materials include triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA).
Such materials are typically commercially available as mixtures of
various isomers containing a range number of ethylene units and
nitrogen atoms, as well as a variety of isomeric structures,
including various cyclic structures. The poly(alkyleneamine) may
likewise comprise relatively higher molecular weight amines known
in the industry as ethylene amine still bottoms.
[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. Pat. No.
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. Pat. No.
6,559,105. Antioxidants also include aromatic amines, such as
nonylated diphenylamine. Other antioxidants include sulfurized
olefins, titanium compounds, and molybdenum compounds. U.S. Pat.
No. 4,285,822, for instance, discloses lubricating oil compositions
containing a molybdenum and sulfur containing composition. Typical
amounts of antioxidants will, of course, depend on the specific
antioxidant and its individual effectiveness, but illustrative
total amounts can be 0.01 to 5, or 0.15 to 4.5, or 0.2 to 4 percent
by weight. Additionally, more than one antioxidant may be present,
and certain combinations of these can be synergistic in their
combined overall effect.
[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 copolymers,
hydrogenated alkenylarene-conjugated diene copolymers and
polyolefins. PMA's are prepared from mixtures of methacrylate
monomers having different alkyl groups. The alkyl groups may be
either straight chain or branched chain groups containing from 1 to
18 carbon atoms. Most PMA's are viscosity modifiers as well as pour
point depressants.
[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
depressancy and dispersancy. Vinyl pyridine, N-vinyl pyrrolidone
and N,N'-dimethylaminoethyl methacrylate are examples of
nitrogen-containing monomers. Polyacrylates obtained from the
polymerization or copolymerization of one or more alkyl acrylates
also are useful as viscosity modifiers.
[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.
[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 polyisobutylene
succinic acid, a demulsifier, a petroleum naphtha solvent, and an
additional 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 hydrocarbyl 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 polyisobutylene
chloride and a compound with a tertiary amine. In such embodiments
the polyisobutylene chloride is the quaternizing agent and the
compound with a 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 U.S. Pat. Nos. 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-(C.sub.1-4 alkyl) substituent,
namely, methyl, ethyl, or any isomer of propyl or butyl. Examples
of suitable alcohols include 2-methylheptanol, 2-methyldecanol,
2-ethylpentanol, 2-ethylhexanol, 2-ethylnonanol, 2-propylheptanol,
2-butylheptanol, 2-butyloctanol, isooctanol, dodecanol,
cyclohexanol, methanol, ethanol, propan-1-ol, 2-methylpropan-2-ol,
2-methylpropan-1-ol, butan-1-ol, butan-2-ol, pentanol and its
isomers, and mixtures thereof. In one embodiment the solvent of the
present invention is 2-ethylhexanol, 2-ethyl nonanol,
2-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 reaction 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 converting
the tertiary amino group of compound (i) to a quaternary
nitrogen.
[0035] Hydrocarbyl substituted acylating agents useful in the
present invention include the reaction product of a long chain
hydrocarbon, generally a polyolefin, with a monounsaturated
carboxylic acid or derivative thereof.
[0036] Suitable monounsaturated carboxylic acids or derivatives
thereof include: (i) .alpha.,.beta.-monounsaturated C.sub.4 to
C.sub.10 dicarboxylic acids, such as fumaric acid, itaconic acid,
maleic acid; (ii) derivatives of (i), such as anhydrides or C.sub.1
to C.sub.5 alcohol derived mono- or di-esters of (i); (iii)
.alpha.,.beta.-monounsaturated C.sub.3 to C.sub.10 monocarboxylic
acids, such as acrylic acid and methacrylic acid; or (iv)
derivatives of (iii), such as C.sub.1 to C.sub.5 alcohol derived
esters of (iii).
[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:
(R.sup.1)(R.sup.2)C.dbd.C(R.sup.3)(CH(R.sup.4)(R.sup.5)) (I)
wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 is,
independently, hydrogen or a hydrocarbon based group. In some
embodiments at least one of R.sup.3, R.sup.4 or R.sup.5 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 C.sub.2 to C.sub.20, or C.sub.2 to C.sub.5 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 copolymer monomers, e.g. 1 to 10 mole %,
is a C.sub.4 to C.sub.18 di-olefin. Such copolymers include: a
copolymer of isobutylene and butadiene; and a copolymer of
ethylene, 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
C.sub.4 olefins, including 1-butene, 2-butene and isobutylene.
C.sub.4 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
polymers. Examples of documents that described ethylene-alpha
olefin copolymers and ethylene-lower olefin-diene ter-polymers
include U.S. Pat. Nos. 3,598,738; 4,026,809; 4,032,700; 4,137,185;
4,156,061; 4,320,019; 4,357,250; 4,658,078; 4,668,834; 4,937,299;
and 5,324,800.
[0040] In another embodiment, the olefinic bonds of Formula (I) are
predominantly vinylidene groups, represented by the following
formula:
##STR00001##
wherein each R is a hydrocarbyl group; which in some embodiments
may be:
##STR00002##
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 U.S. Pat.
Nos. 5,071,919; 5,137,978; 5,137,980; 5,286,823, 5,408,018,
6,562,913, 6,683,138, 7,037,999; and United States publications:
2004/0176552A1; 2005/0137363; and 2006/0079652A1. Such products are
commercially available from BASF, under the trade name
GLISSOPAL.TM. and from Texas PetroChemical LP, under the trade name
TPC 1105.TM. and TPC 595.TM..
[0042] Methods of making hydrocarbyl substituted acylating agents
from the reaction of monounsaturated carboxylic acid reactants and
compounds of Formula (I) are well known in the art and disclosed
in: U.S. Pat. Nos. 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.
[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:
##STR00003##
wherein each of R.sup.6, R.sup.8 and R.sup.9 is independently H or
a hydrocarbyl group, R.sup.7 is a divalent hydrocarbylene group,
and n is 0 or 1. Such compounds and the processes for making them
are disclosed in U.S. Pat. Nos. 5,739,356; 5,777,142; 5,786,490;
5,856,524; 6,020,500; and 6,114,547.
[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. Suitable aldehydes
include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,
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 U.S. Pat. Nos. 5,840,920; 6,147,036; and
6,207,839.
[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:
R.sub.m--Ar--Z.sub.c (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, --O, a lower alkoxy group,
or --(OR.sup.10).sub.bOR.sup.11 wherein each R.sup.10 is
independently a divalent hydrocarbyl group, b is a number from 1 to
30, and R.sup.11 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 trichloride or boron
trifluoride. Such compounds and the processes for making them are
disclosed in U.S. Pat. Nos. 3,954,808; 5,336,278; 5,458,793;
5,620,949; 5,827,805; and 6,001,781.
[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 U.S. Pat. No. 5,620,949. Still other
methods of making suitable hydrocarbyl substituted acylating agents
can be found in U.S. Pat. Nos. 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 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:
##STR00004##
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-aminoethyl)piperidine,
1-(3-aminopropyl)-2-pipecoline, 1-methyl-(4-methylamino)piperidine,
1-amino-2,6-dimethylpiperidine, 4-(1-pyrrolidinyl)piperidine,
1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-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-diethylaminopropylamine, 3-dibutylaminopropylamine,
N,N,N'-trimethyl-1,3-propanediamine,
N,N,2,2-tetramethyl-1,3-propanediamine,
2-amino-5-diethylaminopentane,
N,N,N',N'-tetraethyldiethylenetriamine,
3,3'-diamino-N-methyldipropylamine,
3,3'-iminobis(N,N-dimethylpropylamine), or combinations thereof. In
some embodiments the amine used is 3-dimethylaminopropylamine,
3-diethylaminopropylamine, 1-(2-aminoethyl)pyrrolidine,
N,N-dimethylethylenediamine, or combinations thereof.
[0051] Suitable compounds further include aminoalkyl substituted
heterocyclic compounds such as 1-(3-aminopropyl)imidazole and
4-(3-aminopropyl)morpholine, 1-(2-amino ethyl)piperidine,
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-dimethylaminopropanol,
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
substantially 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.
[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
involves reacting a halogenated olefin polymer with an amine, as
disclosed in U.S. Pat. Nos. 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 U.S. Pat. Nos. 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 U.S.
Pat. No. 5,350,429. Another method for preparing a
polyalkene-substituted amine involves hydrogenation of a
.beta.-aminonitrile, made by reacting an amine with a nitrile, as
disclosed in U.S. Pat. No. 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, H.sub.2 and NH.sub.3 at elevated
pressures and temperatures, as disclosed in U.S. Pat. Nos.
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
polymers. Suitable olefin polymers for preparing the
polyalkene-substituted amines of the invention are the same as
those described above.
[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:
R.sup.12R.sup.13NH (IX)
wherein R.sup.12 and R.sup.13 are each independently hydrogen,
hydrocarbon, amino-substituted hydrocarbon, hydroxy-substituted
hydrocarbon, alkoxy-substituted hydrocarbon, or acylimidoyl groups
provided that no more than one of R.sup.12 and R.sup.13 is
hydrogen. The amine may be characterized by the presence of at
least of at least one primary (H.sub.2N--) 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, dodecylamine,
diethanolamine, morpholine, and octadecylamine.
[0061] The polyamines from which the detergent is derived include
principally alkylene amines conforming, for the most part, to the
formula:
##STR00005##
wherein n is an integer typically less than 10, each R.sup.14 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, 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 "Ethylene 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 alkylated 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
substantially 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.
[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 substituent 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 U.S. Pat. No. 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 alkylenediamine. In some of such
embodiments the amine is ethylenediamine or dimethylamine. Other
methods of preparing suitable Mannich reaction products can be
found in U.S. Pat. Nos. 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 reaction 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.
[0073] In some embodiments the compositions of the invention are
substantially 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 materials 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 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 mixture to a temperature
between 50.degree. C. to 130.degree. 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.degree. C., or less than
70.degree. C. In other embodiments the reaction mixture is heated
to a temperature of about 50.degree. C. to 120.degree. C.,
80.degree. C., or 70.degree. C. In still other embodiments where
the hydrocarbyl acylating agent is derived from a monocarboxylic
acid, the reaction temperature may be 70.degree. C. to 130.degree.
C. In other embodiments where the hydrocarbyl acylating agent is
derived from a dicarboxylic acid, the reaction temperature may be
50.degree. C. to 80.degree. C. or 50.degree. C. to 70.degree. 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 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 C.sub.1-C.sub.6 alkyl ethers of propylene glycol, ethylene
glycol and oligomers thereof such as di-, tri- and tetra glycol
ethers of methyl, ethyl, propyl, butyl or hexyl. Suitable glycol
ethers include ethers of dipropylene glycol, tripropylene glycol
diethylene glycol, triethylene glycol; ethyl diglycol ether, butyl
diglycol ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol,
methoxytetraglycol, butoxytetraglycol.
[0083] Suitable solvents for use in the invention also include
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 normally have a 2-(C.sub.1-4 alkyl)
substituent, namely, methyl, ethyl, or any isomer of propyl or
butyl. Examples of suitable alcohols include 2-methylheptanol,
2-methyldecanol, 2-ethylpentanol, 2-ethylhexanol, 2-ethylnonanol,
2-propylheptanol, 2-butylheptanol, 2-butyloctanol, isooctanol,
dodecanol, cyclohexanol, methanol, ethanol, propan-1-ol,
2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-1-ol, butan-2-ol,
pentanol and its isomers, and mixtures thereof. In one embodiment
the solvent of the present invention is 2-ethylhexanol, 2-ethyl
nonanol, 2-propylheptanol, or combinations thereof. In one
embodiment the solvent of the present invention includes
2-ethylhexanol.
[0084] The solvent can be any of the commercially available
alcohols or mixtures of such alcohols and also includes such
alcohols and mixtures of alcohols mixed with water. In some
embodiments the amount of water present may be above 1 percent by
weight of the solvent mixture. In other embodiments the solvent
mixture may contain traces of water, with the water content being
less than 1 or 0.5 percent by weight.
[0085] The alcohols can be aliphatic, cycloaliphatic, aromatic, or
heterocyclic, including aliphatic-substituted cycloaliphatic
alcohols, aliphatic-substituted aromatic alcohols,
aliphatic-substituted heterocyclic alcohols,
cycloaliphatic-substituted aliphatic alcohols,
cycloaliphatic-substituted aromatic alcohols,
cycloaliphatic-substituted heterocyclic alcohols,
heterocyclic-substituted aliphatic alcohols,
heterocyclic-substituted cycloaliphatic alcohols, and
heterocyclic-substituted aromatic alcohols.
[0086] While not wishing to be bound by theory, it is believed that
a polar protic solvent 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
substantially free of, or even completely free of, the quaternary
amide and/or ester detergents described above.
Polyester Quaternary Ammonium Salts
[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
preparation 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:
##STR00006##
where R.sup.1 is a hydrogen or a hydrocarbyl group containing from
1 to 20 carbon atoms and R.sup.2 is a hydrocarbylene group
containing from 1 to 20 carbon atoms. In some embodiments R.sup.1
contains from 1 to 12, 2 to 10, 4 to 8 or even 6 carbon atoms, and
R.sup.2 contains from 2 to 16, 6 to 14, 8 to 12, or even 10 carbon
atoms.
[0092] In some embodiments the fatty carboxylic acid used in the
preparation of the polyester is 12-hydroxystearic acid, ricinoleic
acid, 12-hydroxy dodecanoic acid, 5-hydroxy dodecanoic acid,
5-hydroxy decanoic acid, 4-hydroxy decanoic acid, 10-hydroxy
undecanoic acid, or combinations thereof.
[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:
##STR00007##
where R.sup.3 is a hydrocarbyl group containing from 1 to 10 carbon
atoms; R.sup.4 is a hydrocarbyl group containing from 1 to 10
carbon atoms; R.sup.5 is a hydrocarbylene group containing from 1
to 20 carbon atoms; and X.sup.1 is O or NR.sup.6 where R.sup.6 is a
hydrogen or a hydrocarbyl group containing from 1 to 10 carbon
atoms. In some embodiments R.sup.3 contains from 1 to 6, 1 to 2, or
even 1 carbon atom, R.sup.4 contains from 1 to 6, 1 to 2, or even 1
carbon atom, R.sup.5 contains from 2 to 12, 2 to 8 or even 3 carbon
atoms, and R.sup.6 contains from 1 to 8, or 1 to 4 carbon atoms. In
some of these embodiments, formula (XII) becomes:
##STR00008##
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-hydroxyethyl]piperidine,
2-[2-(dimethylamino) ethoxy]-ethanol, N-ethyldiethanolamine,
N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylamino
ethanol, N,N-dimethylaminoethanol,
2-dimethylamino-2-methyl-1-propanol, or combinations thereof.
[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-dibutylethylenediamine,
N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane,
N,N-dimethylaminoethanol, N,N-diethylaminoethanol, 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:
##STR00009##
where R.sup.1 is a hydrogen or a hydrocarbyl group containing from
1 to 20 carbon atoms and R.sup.2 is a hydrocarbylene group
containing from 1 to 20 carbon atoms; R.sup.3 is a hydrocarbyl
group containing from 1 to 10 carbon atoms; R.sup.4 is a
hydrocarbyl group containing from 1 to 10 carbon atoms; R.sup.5 is
a hydrocarbylene group containing from 1 to 20 carbon atoms;
R.sup.6 is a hydrogen or a hydrocarbyl group containing from 1 to
10 carbon atoms; n is a number from 1 to 20 or from 1 to 10;
R.sup.7 is hydrogen, a hydrocarbonyl group containing from 1 to 22
carbon atoms, or a hydrocarbyl group containing from 1 to 22 carbon
atoms; and X.sup.2 is a group derived from the quaternizing agent.
In some embodiments R.sup.6 is hydrogen.
[0100] As above, in some embodiments R.sup.1 contains from 1 to 12,
2 to 10, 4 to 8 or even 6 carbon atoms, and R.sup.2 contains from 1
or even 2 to 16, 6 to 14, 8 to 12, or even 10 carbon atoms, R.sup.3
contains from 1 to 6, 1 to 2, or even 1 carbon atom, R.sup.4
contains from 1 to 6, 1 to 2, or even 1 carbon atom, R.sup.5
contains from 2 to 12, 2 to 8 or even 3 carbon atoms, and R.sup.6
contains from 1 to 8, or 1 to 4 carbon atoms. In any of these
embodiments n may be from 2 to 9, or 3 to 7, and R.sup.7 may
contain from 6 to 22, or 8 to 20 carbon atoms. R.sup.7 may be an
acyl group.
[0101] 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 hydroxycarboxylic acid and a carboxylic acid,
optionally in the presence of an esterification catalyst. The
hydroxycarboxylic acids can have the formula HO--X--COOH wherein X
is a divalent saturated or unsaturated aliphatic radical containing
at least 8 carbon atoms and in which there are at least 4 carbon
atoms between the hydroxy and carboxylic acid groups, or from a
mixture of such a hydroxycarboxylic acid and a carboxylic acid
which is free from hydroxy groups. This reaction can be carried out
at a temperature in the region of 160 C to 200 C, until the desired
molecular weight has been obtained. The course of the
esterification can be followed by measuring the acid value of the
product, with the desired polyester, in some embodiments, having an
acid value in the range of 10 to 100 mg KOH/g or in the range of 20
to 50 mg KOH/g. The indicated acid value range of 10 to 100 mg
KOH/g is equivalent to a number average molecular weight range of
5600 to 560. The water formed in the esterification reaction can be
removed from the reaction medium, and this can be conveniently done
by passing a stream of nitrogen over the reaction mixture or, by
carrying out the reaction in the presence of a solvent, such as
toluene or xylene, and distilling off the water as it is
formed.
[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 resulting 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 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 commercially 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 Specification 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 hydrocarbyl 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 polyolefin reacted with a monounsaturated
carboxylic acid reactant, such as, (i)
.alpha.,.beta.-monounsaturated C.sub.4 to C.sub.10 dicarboxylic
acid, such as, fumaric acid, itaconic acid, maleic acid; (ii)
derivatives of (i) such as anhydrides or C.sub.1 to C.sub.5 alcohol
derived mono- or di-esters of (i); (iii)
.alpha.,.beta.-monounsaturated C.sub.3 to C.sub.10 monocarboxylic
acid such as acrylic acid and methacrylic acid; or (iv) derivatives
of (iii), such as, C.sub.1 to C.sub.5 alcohol derived esters of
(iii) with any compound containing an olefinic bond represented by
the general formula
(R.sup.9)(R.sup.10)C.dbd.C(R.sup.11)(CH(R.sup.7)(R.sup.8)) wherein
each of R.sup.9 and R.sup.10 is independently hydrogen or a
hydrocarbon based group; each of R.sup.11, R.sup.7 and R.sup.8 is
independently hydrogen or a hydrocarbon based group and preferably
at least one is a hydrocarbyl group containing at least 20 carbon
atoms. In one embodiment, the excluded hydrocarbyl-substituted
acylating agent is a dicarboxylic acylating agent. In some of these
embodiments, the excluded hydrocarbyl-substituted acylating agent
is polyisobutylene succinic anhydride.
[0110] By substantially free of, it is meant that the components of
the present invention are primarily composed of materials other
than hydrocarbyl substituted acylating agents described above such
that these agents are not significantly involved in the reaction
and the compositions of the invention do not contain significant
amounts of additives derived from such agents. In some embodiments
the components of the invention, or the compositions of the
invention, may contain less than 10 percent by weight of these
agents, or of the additives derived from these agents. In other
embodiments the maximum allowable amount may be 5, 3, 2, 1 or even
0.5 or 0.1 percent by weight. One of the purposes of these
embodiments is to allow the exclusion of agents such as
polyisobutylene succinic anhydrides from the reactions of the
invention and so, to also allow the exclusion of quaternized salt
detergent additive derived from agents such as polyisobutylene
succinic anhydrides. The focus of this embodiment is on polyester,
or hyperdispersant, quaternary salt detergent additives.
[0111] In some embodiments the compositions of the invention are
substantially free of, or even completely free of, the polyester
quaternary salts described 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;
C.sub.1-12 alkylphosphates; di-C.sub.1-12 alkylphosphates; borates;
C.sub.1-12 alkylborates; nitrites; nitrates; carbonates;
bicarbonates; alkanoates; O,O-di-C.sub.1-12 alkyldithiophosphates;
or mixtures thereof.
[0114] In one embodiment the quaternizing agent may be: a dialkyl
sulphate such as dimethyl sulphate; N-oxides; sultones such as
propane or butane sultone; 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:
##STR00010##
wherein R.sup.15, R.sup.16, R.sup.17 and R.sup.18 can be
independently H or a C.sub.1-50 hydrocarbyl group. Examples of
suitable hydrocarbyl epoxides include: styrene oxide, ethylene
oxide, propylene oxide, butylene oxide, stilbene oxide, C.sub.2-50
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 ammonium salt, or an ester of a polycarboxylic
acid. In a general sense such materials may be described as
compounds having the structure:
R.sup.19--C(.dbd.O)--O--R.sup.20 (XV)
where R.sup.19 is an optionally substituted alkyl, alkenyl, aryl or
alkylaryl group and R.sup.20 is a hydrocarbyl group containing from
1 to 22 carbon atoms.
[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 R.sup.19 is a substituted aryl
group. R may be a substituted aryl group having 6 to 10 carbon
atoms, a phenyl group, or a naphthyl group. R may be suitably
substituted with one or more groups selected from carboalkoxy,
nitro, cyano, hydroxy, SR' or NR'R'' where each of R' and R'' may
independently be hydrogen, or an optionally substituted alkyl,
alkenyl, aryl or carboalkoxy groups. In some embodiments R' and R''
are each independently hydrogen or an optionally substituted alkyl
group containing from 1 to 22, 1 to 16, 1 to 10, or even 1 to 4
carbon atoms.
[0119] In some embodiments R.sup.19 in the formula above is an aryl
group substituted with one or more groups selected from hydroxyl,
carboalkoxy, nitro, cyano and NH.sup.2. R.sup.19 may be a
poly-substituted aryl group, for example trihydroxyphenyl, but may
also be a mono-substituted aryl group, for example an ortho
substituted aryl group. R.sup.19 may be substituted with a group
selected from OH, NH.sub.2, NO.sub.2, or COOMe. Suitably R.sup.19
is a hydroxy substituted aryl group. In some embodiments R.sup.19
is a 2-hydroxyphenyl group. R.sup.20 may be an alkyl or alkylaryl
group, for example an alkyl or alkylaryl group containing from 1 to
16 carbon atoms, or from 1 to 10, or 1 to 8 carbon atoms. R.sup.20
may be methyl, ethyl, propyl, butyl, pentyl, benzyl or an isomer
thereof. In some embodiments R.sup.20 is benzyl or methyl. In some
embodiments the quaternizing agent is methyl salicylate.
[0120] In some embodiments the quaternizing agent is an ester of an
alpha-hydroxycarboxylic acid. Compounds of this type suitable for
use herein are described in EP 1254889. Examples of suitable
compounds which contain the residue of an alpha-hydroxycarboxylic
acid include (i) methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-,
benzyl-, phenyl-, and allyl esters of 2-hydroxyisobutyric acid;
(ii) methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-,
phenyl-, and allyl esters of 2-hydroxy-2-methylbutyric acid; (iii)
methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-,
phenyl-, and allyl esters of 2-hydroxy-2-ethylbutyric acid; (iv)
methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-,
phenyl-, and allyl esters of lactic acid; and (v) methyl-, ethyl-,
propyl-, butyl-, pentyl-, hexyl-, allyl-, benzyl-, and phenyl
esters of glycolic acid. In some embodiments the quaternizing agent
comprises methyl 2-hydroxyisobutyrate.
[0121] In some embodiments the quaternizing agent comprises an
ester of a polycarboxylic acid. In this definition we mean to
include dicarboxylic acids and carboxylic acids having more than 2
acidic moieties. In some embodiments the esters are alkyl esters
with alkyl groups that contain from 1 to 4 carbon atoms. Suitable
example include diesters of oxalic acid, diesters of phthalic acid,
diesters of maleic acid, diesters of malonic acid or diesters or
triesters of citric acid.
[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 hydrocarbyl epoxides, may be used in combination with an acid.
Suitable acids include carboxylic acids, such as acetic acid,
propionic acid, 2-ethylhexanoic acid, and the like.
[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 compound 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 dimethylaminopropylamine,
N-methyl-1,3-diaminopropane, N,N-dimethylaminopropylamine,
N,N-diethyl-aminopropylamine, N,N-dimethylaminoethylamine,
diethylenetriamine, dipropylenetriamine, dibutylenetriamine,
triethylenetetraamine, tetraethylenepentaamine,
pentaethylenehexaamine, hexamethylenetetramine, and
bis(hexamethylene)triamine.
[0126] In some embodiments the quaternary ammonium salt comprises
an cation represented by the following formula:
##STR00011##
wherein: R.sup.21 is a hydrocarbyl group containing from 1 to 10
carbon atoms; R.sup.22 is a hydrocarbyl group containing from 1 to
10 carbon atoms; R.sup.23 is a hydrocarbylene group containing from
1 to 20 carbon atoms; R.sup.24 is a hydrocarbyl group containing
from 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 polyalkene-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 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.
[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 formaldehyde or a reactive
equivalent thereof; and wherein the amine of component (a) is
selected from the group consisting of dimethylamine,
ethylenediamine, dimethylaminopropylamine, diethylenetriamine,
dibutylamine, and mixtures thereof.
[0131] In any of these embodiments described above, any of one or
combination 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 combustion
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
approximately 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 exchanger
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 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. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: hydrocarbon substituents,
that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g.,
cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-,
and alicyclic-substituted aromatic substituents, as well as cyclic
substituents wherein the ring is completed through another portion
of the molecule (e.g., two substituents together form a ring);
substituted hydrocarbon substituents, that is, substituents
containing non-hydrocarbon groups which, in the context of this
invention, do not alter the predominantly hydrocarbon nature of the
substituent (e.g., halo (especially chloro and fluoro), hydroxy,
alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
hetero substituents, that is, substituents which, while having a
predominantly hydrocarbon character, in the context of this
invention, contain other than carbon in a ring or chain otherwise
composed of carbon atoms. Heteroatoms include sulfur, oxygen,
nitrogen, and encompass substituents as pyridyl, furyl, thienyl and
imidazolyl. In general, no more than two, preferably no more than
one, non-hydrocarbon substituent will be present for every ten
carbon atoms in the hydrocarbyl group; typically, there will be no
non-hydrocarbon substituents in the hydrocarbyl group. As used
herein, the term "hydrocarbonyl group" or "hydrocarbonyl
substituent" means a hydrocarbyl group containing a carbonyl
group.
[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.degree. C. and is charged to a
jacketed reaction vessel fitted with stirrer, condenser, feed pump
attached to subline addition pipe, nitrogen line and
thermocouple/temperature controller system. The reaction vessel is
heated to 100.degree. C. Dimethylaminopropylamine (10.9 pbw) is
charged to the reaction, maintaining the batch temperature below
120.degree. C., over an 8 hour period. The reaction mixture is then
heated to 150.degree. 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.degree. C. Propylene oxide (8.5
pbw) is added to the reaction vessel over 4 hours, holding the
reaction temperature at 75.degree. C. The batch is held at
temperature 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.degree. C. under a nitrogen atmosphere.
Dimethylaminopropylamine (DMAPA, 10.8 pbw) is added slowly over 45
minutes maintaining batch temperature below 115.degree. C. The
reaction temperature is increased to 150.degree. 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.degree. C. Dimethyl sulfate (6.8 pbw) is charged to the reaction
vessel and stirring is resumed at 300 rpm under a nitrogen blanket.
The resulting exotherm raises the batch temperature to
.about.100.degree. C. The reaction is maintained at 100.degree. 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.degree.
C. Chlorine (70 grams) is bubbled into the reactor over 7 hours.
The reaction mixture is then sparged with nitrogen at
110-120.degree. C. overnight to remove HCl.
[0144] The resultant PIB chloride is transferred to an autoclave
and the autoclave is sealed. For every mole (.about.1030 g) of PIB
chloride, 1 mole of gaseous dimethylamine (DMA, 45 g) is added and
the reaction is heated to 160-170.degree. 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
Solvesso.TM. 150 solvent is added to make a 70% w/w actives
solution and the reaction is stirred until homogenous. The
resultant polyisobutene-dimethylamine (PIB-DMA) solution is
transferred to a separating funnel and washed twice with 2M sodium
hydroxide solution, to remove HCl 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
solution) 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.degree. C. and held for one hour. The mixture is then
heated to 106.degree. C. and held for a further 2 hours. The
temperature of the mixture is then increased to 130.degree. C. and
held for 30 minutes before allowing the mixture to cool to ambient
temperature. The mixture is purified by vacuum distillation (at
130.degree. 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 (.about.75.degree. C.) for 6.5 hours under a
nitrogen blanket. The reaction is purified by vacuum distillation
(at 30.degree. C. and -0.8 bar). The resulting compound is a
Mannich quaternary 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 maleic anhydride, is heated to
70.degree. 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.degree. C. Once the addition is
complete, the reaction vessel is held at 70.degree. 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.degree. 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.degree. 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.degree. C. and held for
about 4 hours. The reaction mixture is then cooled to about
100.degree. C. and zirconium butoxide is added, in an amount so
that the catalyst makes up 0.57 percent by weight of the reaction
mixture. The reaction mixture is heated to about 195.degree. C. and
held for about 12 hours. The resulting product is cooled and
collected.
[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.degree. C. and
the propylene oxide is fed in to the reaction vessel over about 3.5
hours. The reaction mixture is then held at temperature for about 3
hours. 760 grams of product is cooled and collected, which TAN,
FTIR and ESI-MS analysis confirms to be about 80% by weight
quaternized polyester amide salt detergent, with the remaining
material being primarily non-quaternized polyester amide. The
collected material has a TAN of 1.26 mg KOH/gram, a TBN of 23.82 mg
KOH/gram, a kinematic viscosity at 100.degree. C. of 28.58 cSt (as
measured by ASTM D445), an acetate peak by IR at 1574 cm.sup.-1,
and is 1.22% nitrogen.
Example 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.degree. C., the amine is
added dropwise over about 8 minutes, and the reaction mixture held
for about 4 hours. The reaction mixture is then cooled to about
100.degree. C. and 7.8 grams of zirconium butoxide is added. The
reaction mixture is heated to about 195.degree. C. and held for
about 17 hours. The resulting product is filtered, cooled and
collected. 1301 grams of product is collected which has a TAN of 0
mg KOH/gram and shows by IR an ester peak at 1732 cm.sup.-1, an
amide peak at 1654 cm.sup.-1, but no acid peak at 1700
cm.sup.-1.
[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.degree. C. and
the propylene oxide is fed in to the reaction vessel over about 3.5
hours. The reaction mixture is then held at temperature for about 3
hours. 751 grams of product is cooled and collected, which TAN,
FTIR and ESI-MS analysis confirms to be about 70% by weight
quaternized polyester amide salt detergent, with the remaining
material being primarily non-quaternized polyester amide. The
collected material has a TAN of 0 mg KOH/gram, a TBN of 23.14 mg
KOH/gram, a kinematic viscosity at 100.degree. C. of 47.0 cSt (as
measured by ASTM D445), an acetate peak by IR at 1574
cm.sup.-1.
Example Set 1
[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 polyisobutylene 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 deactivator, 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 summarized below.
TABLE-US-00001 TABLE 1 Additive Package Sample.sup.1 Ex A Ex B Ex C
Ex D Comparative Inventive Comparative Inventive Additive
Package.sup.2 85% 85% 85% 85% Conventional 15% 0% 15% 0%
Succinimide Quaternary 0% 4.5% 0% 4.5% Ammonium Salt Additional
Solvent.sup.3 0% 10.5% 0% 10.5% Antioxidant Booster 0% 0% 2% 2%
.sup.1All values are percent by weight. .sup.2The additive package
used in each of the examples is identical. .sup.3The 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-US-00002 TABLE 2 Test Results.sup.1 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 .sup.1Reported
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 reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Except where otherwise indicated,
all numerical quantities in the description specifying amounts or
ratios of materials are on a weight basis. Unless otherwise
indicated, each chemical or composition referred to herein should
be interpreted as being a commercial grade material which may
contain the isomers, by-products, derivatives, and other such
materials which are normally understood to be present in the
commercial grade. However, the amount of each chemical component is
presented exclusive of any solvent or diluent oil, which may be
customarily present in the commercial material, unless otherwise
indicated. It is to be understood that the upper and lower amount,
range, and ratio limits set forth herein may be independently
combined. Similarly, the ranges and amounts for each element of the
invention can be used together with ranges or amounts for any of
the other elements. As used herein, the expression "consisting
essentially of" permits the inclusion of substances that do not
materially affect the basic and novel characteristics of the
composition under consideration.
* * * * *