U.S. patent application number 11/465278 was filed with the patent office on 2008-02-21 for fuel additive compounds and method of making the compounds.
Invention is credited to Abbas Kadkhodayan, Dennis J. Malfer, May Thomas.
Application Number | 20080040968 11/465278 |
Document ID | / |
Family ID | 39094177 |
Filed Date | 2008-02-21 |
United States Patent
Application |
20080040968 |
Kind Code |
A1 |
Malfer; Dennis J. ; et
al. |
February 21, 2008 |
FUEL ADDITIVE COMPOUNDS AND METHOD OF MAKING THE COMPOUNDS
Abstract
The present application is directed to detergent base products
and processes for forming the detergent base products. One
embodiment of the process comprises forming a bis-Mannich
intermediate compound by reacting (i) at least one hydroxyl
substituted aromatic ring compound having on the ring an aliphatic
hydrocarbyl substituent derived from a polyolefin having a number
average molecular weight of about 500 to about 3000; (ii) at least
one primary amine; and (iii) at least one aldehyde. The resulting
bis-Mannich intermediate compound is then reacted with at least one
second amine compound chosen from primary and secondary amines to
form the detergent base product.
Inventors: |
Malfer; Dennis J.; (Glen
Allen, VA) ; Kadkhodayan; Abbas; (Collinsville,
IL) ; Thomas; May; (Richmond, VA) |
Correspondence
Address: |
MH2 TECHNOLOGY LAW GROUP (Cust. No. w/NewMarket)
1951 KIDWELL DRIVE, SUITE 550
TYSONS CORNER
VA
22182
US
|
Family ID: |
39094177 |
Appl. No.: |
11/465278 |
Filed: |
August 17, 2006 |
Current U.S.
Class: |
44/415 ;
508/542 |
Current CPC
Class: |
C10L 1/238 20130101;
C10N 2030/04 20130101; C10L 10/06 20130101; C10M 159/16 20130101;
C08F 8/32 20130101; C10L 1/221 20130101; C10L 10/18 20130101; C08F
8/32 20130101; C08F 110/08 20130101; C08F 8/32 20130101; C08F
110/00 20130101 |
Class at
Publication: |
44/415 ;
508/542 |
International
Class: |
C10L 1/22 20060101
C10L001/22; C10M 159/16 20060101 C10M159/16 |
Claims
1. A process for forming a detergent base product, the process
comprising: forming a bis-Mannich intermediate compound by reacting
(i) at least one hydroxyl substituted aromatic ring compound having
on the ring an aliphatic hydrocarbyl substituent derived from a
polyolefin having a number average molecular weight of about 500 to
about 3000; (ii) at least one primary amine; and (iii) at least one
aldehyde; and reacting the bis-Mannich intermediate compound with
at least one second amine compound chosen from primary and
secondary amines to form the detergent base product.
2. The process of claim 1, wherein at least one hydroxyl
substituted aromatic ring compound has a formula 1, ##STR00012##
where R.sup.1, R.sup.2 and R.sup.3 are substituents independently
chosen from a hydrogen radical, C.sub.1-6 alkyls and hydrocarbyl
substituents having a number average molecular weight in the range
of about 500 to about 3000, with the proviso that at least one of
R.sup.1, R.sup.2 and R.sup.3 is a hydrocarbyl substitutent.
3. The process of claim 2, wherein one of R.sup.1, R.sup.2 and
R.sup.3 is a C.sub.1-6 alkyl chosen from methyl, ethyl, propyl,
isopropyl, butyl, and isobutyl.
4. The process of claim 2, wherein the hydrocarbyl substituent is a
group chosen from polypropylene groups, polybutylene groups,
polyalpha-olefin groups, and ethylene/alpha-olefin copolymer
groups.
5. The process of claim 2, wherein the hydrocarbyl substituent is a
copolymer group having at least one monomer chosen from butylene,
isobutylene, and propylene, and at least one monomer chosen from
mono-olefinic comonomers.
6. The process of claim 2, wherein the hydrocarbyl substituent is a
polyisobutylene group.
7. The process of claim 2, wherein R.sup.1 is methyl, R.sup.2 is a
hydrogen radical and R.sup.3 is a polyisobutylene group.
8. The process of claim 1, wherein the at least one primary amine
is a compound of formula (II), ##STR00013## where R.sup.4 is a
substituent chosen from alkyl, aryl, alkenyl, alkyl amino, dialkyl
amino, alkylaminoalkyl, and dialkylaminoalkyl groups.
9. The process of claim 8, wherein R.sup.4 is a -C.sub.1-8NR'R''
group, where the C.sub.1-8 portion of the group is a straight or
branched chain alkyl, and R' and R'' are independently chosen from
hydrogen radicals, methyl, ethyl, propyl and butyl groups.
10. The process of claim 1, wherein at least one primary amine is
chosen from dimethylaminopropyl amine, diethylaminopropyl amine,
and dimethylaminobutyl amine.
11. The process of claim 1, wherein the at least one aidehyde is
chosen from formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde,
stearaldehyde, benzaldehyde, salicylaldehyde, furfural aldehyde,
thiophene aldehyde, and paraformaldehyde.
12. The process of claim 1, wherein at least one hydroxyl
substituted aromatic ring compound, the at least one primary amine
and the at least one aldehyde are mixed in a ratio of about 1 mole
of hydroxyl substituted aromatic ring compound; about 0.3 to about
0.7 moles of primary amine; and from about 0.8 to about 1.5 moles
aldehyde.
13. The process of claim 1, wherein at least one second amine is a
compound of formula (IV), ##STR00014## wherein R.sup.5 and R.sup.6
are each independently chosen from a hydrogen radical, alkyl,
cycloalkyl, aryl, alkaryl, and aralkyl groups, with the proviso
that at least one of R.sup.5 and R.sup.6 is not a hydrogen
radical.
14. The process of claim 1, wherein at least one second amine is a
compound of formula (V): ##STR00015## where R.sup.7 is a linear,
branched, or cyclic alkyl group having from 1 to 10 carbon
atoms.
15. The process of claim 14, where R.sup.7 is a saturated, straight
chain hydrocarbon having 1 to 6 carbon atoms.
16. The process of claim 14, where R.sup.7 is a substituted or
unsubstituted cycloalkane having a 4 to 8 carbon member ring that
is optionally substituted with one or more methyl, ethyl or propyl
groups.
17. The process of claim 1, wherein the at least one second amine
is chosen from dimethylamine, diethylamine, dipropylamine,
dibutylamine, and dipentylamine.
18. The process of claim 1, wherein the at least one second amine
is chosen from cyclohexaneamine; 1,3-propanediamine; 1,2 ethane
diamine; 1,4-butanediamine; 1,6-hexanediamine;
1,2-diaminocyclohexane; 1,2-amino-3 methyl cyclohexane; 1,2 amino 4
methyl cyclohexane; N-methylamine methanediamine and 3,3 dimethyl
amino propyl amine.
19. A detergent base product formed by the method of claim 1.
20. A process for forming a Mannich reaction product, the process
comprising: reacting at least one amine compound chosen from
primary and secondary amines with a bis-Mannich compound having a
formula III, ##STR00016## where R.sup.1 is chosen from a hydrogen
radical and C.sub.1-6 alkyl; R.sup.3 is a hydroxyaromatic compound
having on the ring an aliphatic hydrocarbyl substituent derived
from a polyolefin having a number average molecular weight of about
500 to about 3000; and R.sup.4 is a linear, branched, or cyclic,
substituted or unsubstituted, saturated or unsaturated alkyl amine
group.
21. A fuel composition comprising: a base fuel; and a detergent
base product comprising a mixture of formulae (VI) and (VII),
##STR00017## where R.sup.1and R.sup.3 are substituents
independently chosen from a hydrogen radical, C.sub.1-6 alkyls and
hydrocarbyl substituents having a number average molecular weight
in the range of about 500 to about 3000, with the proviso that at
least one of R.sup.1and R.sup.3 is a hydrocarbyl substitutent,
R.sup.4 is a substituent chosen from alkyl, aryl, alkenyl, alkyl
amino, dialkyl amino, alkylaminoalkyl, and dialkylaminoalkyl
groups, R.sup.5 and R.sup.6 are each independently chosen from a
hydrogen radical, alkyl, cycloalkyl, aryl, alkaryl, and aralkyl
groups, with the proviso that at least one of R.sup.5 and R.sup.6
is not a hydrogen radical.
Description
FIELD OF THE DISCLOSURE
[0001] The present application is directed to a novel process for
making detergents and fuel compositions comprising the
detergents.
BACKGROUND OF THE DISCLOSURE
[0002] Over the years considerable work has been devoted to
additives for controlling (preventing or reducing) deposit
formation in the fuel induction systems of spark-ignition internal
combustion engines. In particular, additives that can effectively
control fuel injector deposits, intake valve deposits and
combustion chamber deposits represent the focal point of
considerable research activities in the field, and despite these
efforts, further improvements are desired.
[0003] Conventional port-fuel injection (PFI) engines form a
homogeneous pre-mixture of gasoline and air by injecting gasoline
into the intake port. Direct injection gasoline (DIG) engines
inject gasoline directly into the combustion chamber like a diesel
engine so that it becomes possible to form a stratified fuel
mixture which contains greater than the stoichiometric amount of
fuel in the neighborhood of the spark plug but highly lean in the
entire combustion chamber.
[0004] The major fuel-related deposit problem areas for PFI and DIG
engines are injectors, intake valves, and the combustion chamber.
Mannich base fuel additives are well known in the petroleum
industry for controlling such deposit problems. However, while
Mannich base additives traditionally provide excellent control for
intake valve deposits, they may not control deposits to a desired
degree for injectors in PFI and/or DIG engines. There is,
therefore, a desire in the petroleum industry to produce fuel
additives suitable for use in PFI and/or DIG engines that can
provide improved control of engine deposits, and to develop methods
for producing such fuel additives.
SUMMARY OF THE DISCLOSURE
[0005] In accordance with the disclosure, an embodiment of the
present application is directed to a process for forming a
detergent base product. The process comprises forming a bis-Mannich
intermediate compound by reacting (i) at least one hydroxyl
substituted aromatic ring compound having on the ring an aliphatic
hydrocarbyl substituent derived from a polyolefin having a number
average molecular weight of about 500 to about 3000; (ii) at least
one primary amine; and (iii) at least one aldehyde. The resulting
bis-Mannich intermediate compound is then reacted with at least one
second amine compound chosen from primary and secondary amines to
form the detergent base product.
[0006] Another embodiment of the present application is directed to
a process for forming a Mannich reaction product, The process
comprises reacting at least one amine compound chosen from primary
and secondary amines with a bis-Mannich compound having a formula
III,
##STR00001##
where R.sup.1 is chosen from a hydrogen radical and C.sub.1-6
alkyl; R.sup.3 is a hydroxyaromatic compound having on the ring an
aliphatic hydrocarbyl substituent derived from a polyolefin having
a number average molecular weight of about 500 to about 3000; and
R.sup.4 is a linear, branched, or cyclic, substituted or
unsubstituted, saturated or unsaturated alkyl amine group.
[0007] Another embodiment of the present application is directed to
a fuel composition comprising: a base fuel; and a detergent base
product comprising a mixture of formulae (VI) and (Vl),
##STR00002##
where R.sup.1and R.sup.3 are substituents independently chosen from
a hydrogen radical, C.sub.1-6 alkyls and hydrocarbyl substituents
having a number average molecular weight in the range of about 500
to about 3000, with the proviso that at least one of R.sup.1 and
R.sup.3 is a hydrocarbyl substitutent; R.sup.4 is a substituent
chosen from alkyl, aryl, alkenyl, alkyl amino, dialkyl amino,
alkylaminoalkyl, and dialkylaminoalkyl groups; R.sup.5 and R.sup.6
are each independently chosen from a hydrogen radical, alkyl,
cycloalkyl, aryl, alkaryl, and aralkyl groups, with the proviso
that at least one of R.sup.5 and R.sup.6 is not a hydrogen
radical.
[0008] Additional objects and advantages of the disclosure will be
set forth in part in the description which follows, and can be
learned by practice of the disclosure. The objects and advantages
of the disclosure will be realized and attained by means of the
elements and combinations particularly pointed out in the appended
claims.
[0009] It is to be understood that both the foregoing general
description and the following detailed description are exemplary
and explanatory only and are not restrictive of the disclosure, as
claimed.
DESCRIPTION OF THE EMBODIMENTS
[0010] The process of the present application involves formation of
a detergent base product using a bis-Mannich intermediate. In
embodiments, the reaction mechanism can include a two stage
process, wherein the bis-Mannich intermediate is formed during the
first stage, and then reacted with an amine during the second stage
to form the detergent base product. The reactions of the first and
second stage will now be described.
Formation of the Bis-Mannich Intermediate
[0011] In embodiments of the present application, the bis-Mannich
intermediate compounds can be formed by reacting (i) at least one
hydroxyl substituted aromatic ring compound having on the ring an
aliphatic hydrocarbyl substituent derived from a polyolefin having
a number average molecular weight of about 500 to about 3000; (ii)
at least one primary amine; and (iii) at least one aldehyde. Any
hydroxyl substituted aromatic ring compound readily reactive in the
Mannich condensation reaction may be employed. Representative
hydroxyl substituted aromatic ring compounds used in forming the
bis-Mannich intermediates of the present application are
represented by the following formula I:
##STR00003##
where R.sup.1, R.sup.2 and R.sup.3 can each be independently chosen
from a hydrogen radical, a C.sub.1-6 alkyl, or a hydrocarbyl
substitutent having a number average molecular weight in the range
of about 500 to about 3000, with the proviso that at least one of
R.sup.1, R.sup.2 and R3 is a hydrocarbyl substitutent.
Representative C.sub.1-6 alkyl groups include methyl, ethyl,
propyl, isopropyl, butyl, isobutyl.
[0012] Representative hydrocarbyl substituents can include
polypropylene groups; polybutene groups, polyisobutylene groups;
polyalpha-olefin groups, such as poly 1-octene groups; and
ethylene/alpha-olefin copolymer groups. Other similar long-chain
hydrocarbyl substituents may also be used. Examples include
copolymer groups having at least one monomer chosen from butylene,
isobutylene, and propylene, and at least one monomer chosen from
mono-olefinic comonomers copolymerizable therewith, such as
ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc., where the
copolymer molecule contains at least 50% by weight, of butylene
and/or isobutylene and/or propylene units. The comonomers
polymerized with propylene or such butenes may be aliphatic and can
also contain non-aliphatic groups, e.g., styrene, o-methylstyrene,
p-methylstyrene, divinyl benzene and the like. The resulting
polymers and copolymers used in forming the compound of formula (I)
are substantially aliphatic hydrocarbon polymers. In some
embodiments, the hydrocarbyl substituents may be substantially
saturated, containing only residual unsaturation.
[0013] In one embodiment, the hydrocarbyl substituent is a
polybutylene group. Unless otherwise specified herein, the term
"polybutylene" is used in a generic sense to include polymers made
from "pure" or "substantially pure" 1 -butene or isobutene, and
polymers made from mixtures of two or all three of 1-butene,
2-butene and isobutene. Commercial grades of such polymers may also
contain insignificant amounts of other olefins.
[0014] In some embodiments, high reactivity polyisobutenes having
relatively high proportions of polymer molecules with a terminal
vinylidene group can be used to form the hydrocarbyl substituent.
In embodiments, at least 20% of the total terminal oletinic double
bonds in such high reactivity polyisobutenes can comprise an
alkylvinylidene isomer. For example, at least 50%, and in other
examples, at least 70%, of the total terminal olefinic double bonds
can comprise an alkylvinylidene isomer. Suitable high reactivity
polyisobutenes are disclosed, for example, in U.S. Pat. No.
4,152,499 and W. German Offenlegungsschrift 29 04 314, the
disclosures of which are herein incorporated by reference in their
entirety. In other embodiments, ethylene alpha-oletin copolymers
having a number average molecular weight of 500 to 3000, wherein at
least about 30% of the polymer's chains contain terminal ethylidene
unsaturation, can be used to form the hydrocarbyl substituent.
[0015] In one embodiment the compound of formula (I) can be
obtained by alkylating o-cresol with the high molecular weight
hydrocarbyl polymers described above. For example, an o-cresol,
such as ortho methyl phenol, can be reacted with polyisobutylene
(PIB) to form an ortho methyl phenol substituted at the para
position with a PIB group. Suitable methods of alkylating the
hydroxyaromatic compounds of the present disclosure are well known
in the art. Examples of some suitable well known methods for
forming hydroxyl substituted aromatic ring compounds are taught in
GB 1,159,368 and U.S. Pat. Nos. 4,238,628; 5,300,701, 5,876,468,
and 6,800,103, the disclosures of all of which are herein
incorporated by reference in their entirety.
[0016] In one embodiment, R.sup.1 of the hydroxyl substituted
aromatic ring compound of formula I can be a C.sub.1-4 alkyl,
R.sup.2 can be a hydrogen radical, and R.sup.3 can be a hydrocarbyl
substituent chosen from the hydrocarbyl substituents described
above. For example, R.sup.1 can be methyl, R.sup.2 can be a
hydrogen radical, and R.sup.3 can be a polyisobutylene group. In
other embodiments, both R.sup.1 and R.sup.2 are hydrogen radicals,
and R.sup.3 is a hydrocarbyl substituent chosen from the
hydrocarbyl substituents described above.
[0017] Amines which may be employed in the first stage of the
reaction include any primary amines suitable for use in Mannich
reactions for forming the bis-Mannich intermediate. In embodiments,
the primary amine can have the formula (II):
##STR00004##
where R.sup.4 can be any substituent chosen from alkyl, aryl,
alkenyl, alkyl amine, dialkyl amine, alkylaminoalkyl, and
dialkylaminoalkyl groups.
[0018] Representative examples of suitable secondary amines include
dimethylamine, diethylamine, dipropylamine, dibutylamine, and
dipentylamine. Representative examples of suitable primary amines
include cyclohexaneamine; 1,3-propanediamine; 1,2-ethane diamine;
1,4-butanediamine; 1,6-hexanediamine; 1,2-cyclohexanediamine;
1,2-diamino-3-methyl cyclohexane; 1,2-diamino-4-methyl cyclohexane;
N-aminomethyl-11-methanediamine and 3,3-dimethyl amino propyl
amine.
[0019] In some embodiments, the amine of formula (II) may be a
hydrocarbon chain substituted at one end with a primary amino
group, and substituted at the other end with a primary, secondary,
or tertiary amino group. For example, R.sup.4 of the compound of
formula (II) can be --C.sub.1-8NNR'R'', where the C.sub.1-8 portion
of the substituent is a straight or branched chain alkyl, and R'
and R'' can be independently chosen from H, methyl, ethyl, propyl
and butyl substituents. Examples of such compounds include
dialkylaminoalkyl amines, such as dimethylaminopropyl amine,
diethylaminopropyl amine, and dimethylaminobutyl amine.
[0020] Any aldehydes suitable for use in a Mannich reaction can be
employed in the preparation of the bis-Mannich intermediate.
Non-limiting examples of suitable aldehydes include aliphatic
aldehydes; such as formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, and
stearaldehyde. Aromatic aldehydes which may be used include
benzaldehyde and salicylaldehyde. Illustrative heterocyclic
aldehydes for use herein are furfural and thiophene aldehyde, etc.
Also useful are formaldehyde-producing reagents such as
paraformaldehyde. In one embodiment, the chosen aldehyde is
formaldehyde.
[0021] Any suitable proportions of the reactants that will result
in formation of the bis-Mannich intermediate can be used. In one
embodiment, the reactants can be mixed in a ratio of about: 1 mole
of hydroxyl substituted aromatic ring compound; about 0.3 to about
0.7 moles of primary amine; and from about 0.8 to about 1.5 moles
aldehyde. For example, the reactants can be mixed in a ratio of
about: 1 mole of hydroxyl substituted aromatic ring compound; about
0.5 moles of primary amine; and about 1 mole aldehyde.
[0022] The condensation reaction among the hydroxyl substituted
aromatic ring compounds, the primary amines and the aldehydes is
conducted at a temperature in the range of about 40.degree. C. to
about 200.degree. C. The reaction can be conducted with or without
a diluent or solvent. Examples of suitable solvents include
aromatic solvents, such as xylenes, toluene, mesitylene, Aromatic
100, and heptane, or mixtures of such solvents. Water is evolved
during the reaction and can be removed by azeotropic distillation
during the course of the reaction. Typical reaction times range
from 2 to 4 hours, although longer or shorter times can be used as
necessary.
[0023] The resulting bis-Mannich intermediate compound is a
compound of formula (Ill):
##STR00005##
where R.sup.1, R.sup.3 and R.sup.4 are defined as above. As seen
from formula (Ill), the bis-Mannich intermediate includes two
hydroxyl substituted aromatic ring groups formed from the reactant
compounds of formula (I) above, which are bridged together with a
tertiary amine group. The bis-Mannich intermediate can be used to
form the desired detergent base products in a second stage
reaction, which will be described below.
Formation of a Detergent Base from the Bis-Mannich Intermediate
[0024] In the second stage of the reaction process, the bis-Mannich
intermediate of formula (III) can be reacted with a primary or
secondary amine to form a desired detergent base product. The
primary or secondary amine can be an amine of formula (IV):
##STR00006##
wherein R.sup.5 and R.sup.6 are each independently chosen from a
hydrogen radical, alkyl, cycloalkyl, aryl, alkaryl, and aralkyl
groups, with the proviso that at least one of R.sup.5 and R.sup.6
is not a hydrogen radical. The alkyl, cycloalkyl, aryl, alkaryl,
and aralkyl groups can be unsubstituted, or substituted with
suitable functional groups, such as carbonyl groups, hydroxyl
groups and amino groups. The alkyl, cycloalkyl, aryl, alkaryl, and
aralkyl groups can have, for example, from 1 to 30 carbon atoms,
such as from 1 to 18 carbon atoms, or in other examples, from 1 to
6 carbon atoms.
[0025] In some embodiments, R.sup.6 is chosen to be a hydrogen
radical, and R.sup.5 is an alkyl group substituted with a primary
amine. The resulting amine is a diamine of formula (V):
##STR00007##
where R.sup.7 is a linear, branched, or cyclic alkyl group having
from 1 to 10 carbon atoms. For example, R.sup.7 can be a saturated,
straight chain hydrocarbon having 1 to 6 carbon atoms. In another
embodiment, R.sup.7 can be a substituted or unsubstituted
cycloalkane having a 4 to 8 carbon member ring, which can
optionally be substituted with one or more methyl, ethyl or propyl
groups.
[0026] Representative examples of suitable secondary amines include
dimethylamine, diethylamine, dipropylamine, dibutylamine, and
dipentylamine. Representative examples of suitable primary amines
include cyclohexaneamine; 1,3-propanediamine; 1,2-ethane diamine;
1,4-butanediamine; 1,6-hexanediamine; 1,2-diaminocyclohexane
(DACH); 1,2-diamino-3-methyl cyclohexane; 1,2-diamino-4-methyl
cyclohexane; N-aminomethyl-1,1-methanediamine and 3,3-dimethyl
amino propyl amine.
[0027] The bis-Mannich intermediate of formula (III) is mixed and
reacted with the primary or secondary amines of formula (IV). Any
suitable proportions of the reactants that will result in formation
of the desired final products can be used. In one embodiment, the
reactants can be mixed in a ratio of about 1 mole of primary or
secondary amine for each mole of bis-Mannich intermediate.
[0028] The reaction can be conducted in the range of about
125.degree. C. to about 200.degree. C., such as about 150.degree.
C. Reaction times can range from 2 to 4 hours, although longer or
shorter times can be used as necessary. Solvents from the first
state of the reaction can be present during the second stage of the
reaction, and/or additional suitable solvents may be added during
the second stage, if desired.
[0029] The second stage of the reaction results in the following
products of formulae (VI) and (VIl):
##STR00008##
where R.sup.1, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are defined as
set forth above. As seen from formulae (VI) and (VII), the reaction
cleaves the bis-Mannich intermediate of Formula (III) to form two
hydroxyl substituted aromatic ring compounds that are each
substituted with an amine group, in addition to the R.sup.1,
R.sup.3 and hydroxyl substituents. Formula (VI) is substituted with
an amine group formed from the primary amine reactant of the first
stage of the reaction, while formula (VIl) is substituted with an
amine group formed from the primary or secondary amine reactant of
the second stage of the reaction.
[0030] In an embodiment where a primary amine of formula (V) is
used as the amine in the second stage, the products of the reaction
include an amine substituted compound of formula (VI) as described
above. However, in this embodiment, the product also comprises a
primary amine substituent on one of the hydroxyl substituted
aromatic ring compounds, as shown below in formula (VIII):
##STR00009##
where R.sup.1, R.sup.3, R.sup.4 and R.sup.7 are defined as set
forth above. The ratio of the compound of formula VI to the
compound of formula VIII in the product mixture may vary depending
on such things as reaction conditions and/or the reactants
employed. For example, the ratio of the compound of formula VI to
the compound of formula VIII may range from about 1:4 to about 4:1.
In some embodiments, the ratio may be about 1:1.
[0031] The amine substituted products of the present application
can be used as a detergent base in fuel compositions. In some
embodiments, the detergent base can be used in fuel additive
concentrates, which can be packaged and sold to consumers
separately from the base fuel. The additive concentrates of this
invention can contain, for example, from about 12 to about 69 wt %,
and for example from about 22 to about 50 wt % of the detergent on
an active ingredient basis. The additive concentrates may also
contain carrier fluid, the level of which is determined by the
desired carrier to detergent base ratio.
[0032] The carrier fluid can be of various types, such as for
example liquid poly-.alpha.-olefin oligomers, liquid polyalkene
hydrocarbons (e.g., polypropene, polybutene, polyisobutene, or the
like), liquid hydrotreated polyalkene hydrocarbons (e.g.,
hydrotreated polypropene, hydrotreated polybutene, hydrotreated
polyisobutene, or the like), mineral oils, hydrotreated mineral
oils, liquid poly(oxyalkylene) compounds, liquid alcohols or
polyols, liquid esters, and similar liquid carriers or solvents.
Mixtures of two or more such carriers or solvents can be
employed.
[0033] When formulating fuel compositions according to the present
application, the detergent base and carrier fluid (with or without
other additives) are employed in amounts sufficient to reduce or
inhibit deposit formation in an internal combustion engine. Thus,
the fuels can contain minor amounts of the detergent base and of
the liquid carrier fluid proportioned as above that control or
reduce formation of engine deposits, such as intake valve and
injector deposits.
[0034] In some embodiments, the fuels of this disclosure can
contain on an active ingredient basis, an amount of the Mannich
base detergent in a range of about 5 to about 300 ptb (pounds by
weight of additive per thousand barrels by volume of fuel), such
as, for example, in the range of about 10 to about 200 ptb. The
active ingredient basis excludes the weight of (i) unreacted
components such as polyalkylene compounds associated and remaining
in the product as produced and used, and (ii) diluents or solvents,
if any, used in the manufacture of the detergent either during or
after its formation, but before addition of a carrier, if a carrier
is employed.
[0035] Other optional additives, such as one or more fuel-soluble
antioxidants, demulsifying agents; antioxidants, such as hindered
phenols and amines; rust or corrosion inhibitors, metal
deactivators, combustion modifiers, alcohol cosolvents, octane
improvers, emission reducers, friction modifiers, lubricity
additives, ancillary detergent/dispersant additives, markers, dyes
and multifunctional additives (e.g., methylcyclopentadienyl
manganese tricarbonyl and/or other cyclopentadienyl manganese
tricarbonyl compounds) can also be included in the fuels and
additive concentrates. These components can be present in the
composition in any desired concentrations. For example, each
component can be present in an amount at least sufficient for it to
exert its intended function or functions in the finished fuel
composition.
[0036] The base fuels used in formulating the fuels disclosed
herein can be any and all base fuels suitable for use in the
operation of spark ignition internal combustion engines, such as
unleaded motor and aviation gasolines, and so-called reformulated
gasolines which often contain both hydrocarbons of the gasoline
boiling range and fuel-soluble oxygenated blending components
("oxygenates"). Examples of suitable oxygenates which may be used
include alcohols, such as methanol and ethanol; fuel-soluble
ethers, such as methyl tertiary butyl ether, ethyl tertiary butyl
ether, and methyl tertiary amyl ether; and mixtures of such
materials. Oxygenates, when used, can be present in the base fuel
in any desired amount. Choosing an effective amount of oxygenates
is within the ordinary skill of the art.
EXAMPLES
Example 1
Process of Preparing the Intermediate
[0037] Exact quantities of the starting materials were
pre-determined and calculated based upon a mole ratio of 2:1:2 of
2-methyl-4-polyisobutyl phenol, dimethylaminepropylamine (DMAPA),
and formaldehyde, respectfully. The 2-methyl-4-polyisobutyl phenol
was added to a round bottom flask, followed by the addition of
approximately 75% of the total calculated amount of Aromatic 100
solvent to be used during the process. The mixture was stirred
under a nitrogen blanket. Once the mixture was homogeneous, the
calculated amount of DMAPA was added. The temperature of the
mixture was about 40 to 45.degree. C. Formaldehyde was added, and
the temperature of the mixture increased to about 45 to 50.degree.
C. The mixture was heated and distilled under nitrogen using a Dean
Stark trap set to 150.degree. C. During distillation, the
temperature of 150.degree. C. was maintained for about 2 to 2.5
hours. After distillation, sufficient Aromatic 100 solvent was
added to the intermediate product to bring the final package
composition to 25% solvent, taking into consideration the loss of
water.
[0038] The above procedure theoretically resulted in the BIS
product shown in the reaction below:
##STR00010##
Example 2
Process of Preparing the Final Product
[0039] Using the intermediate BIS product of Example 1 as a
starting material, 1,2-diaminocyloohexane (DACH) was added at a 1:1
molar ratio while stirring at room temperature under a nitrogen
blanket. The temperature was set to 90.degree. C. and held for 2
hours. The temperature was then set to 145.degree. C. with
increased nitrogen flow and held for 2.5 hours. The process
theoretically resulted in the following reaction.
##STR00011##
Example 3
[0040] Gasoline fuel compositions employing the final product of
Example 2 were subjected to engine tests whereby the substantial
effectiveness of these compositions in reducing intake valve
deposit weight was demonstrated. The above reaction products of
Example 2 were compared with several other detergent compounds,
including a first comparative compound formed by a mannich reaction
of a 1:1:1 mole ratio of 2-methyl-4-polyisobutyl phenol,
dibutylamine, and formaldehyde ("Mannich 1 additive"); a second
comparative compound formed by a mannich reaction of a 1:1:1 mole
ratio of 2-methyl-4-polyisobutyl phenol, DMAPA, and formaldehyde
("Mannich 2 additive"); and a third comparative compound that was a
PIB Amine. The compounds of example 2 and the comparative compounds
were each blended with a base fuel to form fuel compositions that
are referred to in Table 1 and Table 2 by the additive compound
employed (Example 2 Compounds, Mannich 1, Mannich 2, and PIB
Amine).
[0041] A first comparative IVD Engine test of the compounds of
Example 1, Mannich 1, Mannich 2 and the base fuel without additive
was run using a Ford 2.3-liter engine operated on a test stand
under standard operating conditions for determination of deposit
formation on intake valves. The results are reported in Table 1
below.
TABLE-US-00001 TABLE 1 2.3 L IVD Engine Test Results Example
Composition IVD (mg) Fuel Without Additive 478 527 mg Mannich 1 53
56 mg Mannich 2 67.9 mg Example 2 Compound 64.6
Example 4
[0042] A second comparative IVD Engine test of the compounds of
Example 2; Mannich 1, Mannich 2, PIB Amine and the base fuel
without additive was run using an IVD Bench Simulator (Model L-2),
which can be used to test gasoline detergent IVD performance. The
test simulates the IVD deposition in an engine. During the test,
the fuel compositions with detergent additives were run through an
injector. A separate air flow was run through an air flow line to
the injector. The air flow and gasoline flow were mixed at the tip
of the injector, and the mixture was directed against a heated
metal plate. Plate temperatures were controlled at around
174.degree. C. Gasoline evaporated on the surface of the hot plate,
leaving a deposit and stain behind.
[0043] At the end of the IVD Bench Simulator test, the deposit on
the metal plate was weighted. The results are reported in Table 2
below.
TABLE-US-00002 TABLE 2 IVD Bench Test From China Example
Composition IVD (mg) Fuel Without Additive 14 15 mg Comparative
Example 1 7.7 mg Comparative Example 2 1.3 mg Example 2 1.0 PIB
Amine 1.4 mg
[0044] It is clear, upon examination of the above Tables 1 and 2,
that the reaction products of Example 2 exhibit improved
performance over the base fuel without additive, and comparable
performance to the additives of Comparative Examples 1 and 2, as
demonstrated by the reduced amount of deposits in the Ford 2.3L
Test. In addition, the reaction product of Example 2 exhibits
improved performance over the base fuel without additive and the
additives of Comparative Examples 1 and 2, as demonstrated by the
reduced amount of deposits in the IVD Bench Test From China.
[0045] For the purposes of this specification and appended claims,
unless otherwise indicated, all numbers expressing quantities,
percentages or proportions, and other numerical values used in the
specification and claims, are to be understood as being modified in
all instances by the term "about." Accordingly, unless indicated to
the contrary, the numerical parameters set forth in the following
specification and attached claims are approximations that can vary
depending upon the desired properties sought to be obtained by the
present disclosure. At the very least, and not as an attempt to
limit the application of the doctrine of equivalents to the scope
of the claims, each numerical parameter should at least be
construed in light of the number of reported significant digits and
by applying ordinary rounding techniques.
[0046] It is noted that, as used in this specification and the
appended claims, the singular forms "a," "an," and "the," include
plural referents unless expressly and unequivocally limited to one
referent. Thus, for example, reference to "an acid" includes two or
more different acids. As used herein, the term "include" and its
grammatical variants are intended to be non-limiting, such that
recitation of items in a list is not to the exclusion of other like
items that can be substituted or added to the listed items.
[0047] While particular embodiments have been described,
alternatives, modifications, variations, improvements, and
substantial equivalents that are or can be presently unforeseen can
arise to applicants or others skilled in the art. Accordingly, the
appended claims as filed and as they can be amended are intended to
embrace all such alternatives, modifications variations,
improvements, and substantial equivalents.
* * * * *