USOO846556OB1

12) United States Patent 10) Patent No.: US 8.465,560

9 9 B1
WOf (45) Date of Patent: Jun. 18, 2013
(54) GASOLINE DEPOSIT CONTROL ADDITIVE 5,393,309 A 2/1995 Cherpeck
COMPOSITION 5,567.212 A * 10/1996 Gentry et al. ................... 44,420
5,588,973 A 12/1996 Blackborow et al.
(75) Inventor: Leslie R. Wolf, Naperville, IL (US) 3. A $32, E:
5,669,939 A 9/1997 Cherpeck
(73) Assignee: Butamax Advanced Biofuels LLC, 5,749,929 A 5/1998 Cherpecket al.
Wilmington, DE (US) 5,830,243 A * 1 1/1998 Wolak et al. .................... 44,336
5,851,242 A 12/1998 Cherpecket al.
(*) Notice: Subject to any disclaimer, the term of this E. A gig E:
patent is extended or adjusted under 35 5.993,497 A 1 1/1999 Cherpecket al.
U.S.C. 154(b) by 272 days. 6,114,542 A 9/2000 Cherpeck
6,117,197 A * 9/2000 Houser ........................... 44/389
(21) Appl. No.: 12/697.590 6,203,584 B1 3/2001 Fuentes-Afflicket al.
6,217,624 B1 4/2001 Morris et al.
1-1. 6,652,667 B2 11/2003 Ahmadi et al.
(22) Filed: Feb. 1, 2010 6,660,050 B1* 12/2003 Dieckmann et al. ............ 44/412
O O 2004/O123516 A1* 7/2004 Hull et al. ....................... 44, 349
Related U.S. Application Data 2007/0094922 A1 ck 5/2007 Bergemann et al.
(60) Provisional application No. 61/150,045, filed on Feb. 38.5% A. 3. Ringham . . . . . . . . . . . . . . . . . 435,161
5, 2009.
FOREIGN PATENT DOCUMENTS
(51) Int. Cl. EP 1494.86 1, 1985
CIOL I/22 (2006.01) EP O902O79 3, 1999
(52) USPC
U.S. Cl................................... 44/421; 44/420; 44/340 E.
EP
9,
11324.54
1949.
9, 2001
(58) Field of Classification Search GB 985373 3, 1965
USPC ................... 44/340, 412,420, 421, 434, 451, GB 1083712 9, 1967
44/452 GB 1486144 3, 1975
See application file for complete search history. W8 ge: h 22
WO 9730.103 8, 1997
(56) References Cited WO 2007039488 4/2007
U.S. PATENT DOCUMENTS OTHER PUBLICATIONS
2,622,018. A 12/1952 White et al. Jeffamine M-600 (evidentiary reference).*
3.438,757 A 4, 1969 Honnen et al. Jeffamine M-600.
3,565,804 A 2f1971 Honnen et al. STIC Search 12 2011.
3.6% A 78. As et al. International Search Report and Written Opinion of corresponding
3.845083 A 11/1974 Dubeck PCT/US2010/023027 mailed Jun. 15, 2010.
3,960,515 A 6, 1976 Honnen et al.
4,160,648 A 7, 1979 Lewis et al. * cited by examiner
4,191,537 A 3, 1980 Lewis et al.
13: A
4- - -
1788 Hill, 1CWS ca.
Primary Examiner — Pamela H Weiss
4,236,020 A 1 1/1980 Lewis et al. (74) Attorney, Agent, or Firm — Christine M. Lhulier
4,243,798 A 1/1981 Franklin et al.
4,270,930 A 6/1981 Campbellet al. (57) ABSTRACT
258. A 33. S. A gasoline deposit control additive composition for use in a
4,347,109 A * 8/1982 Meshbesher .................. 568/853 fuel comprising from about 70 to about 95 volume percent of
4,398,921 A 8, 1983 Rifkin et al. hydrocarbons in the gasoline boiling range and from about 5
4,409,000 A 10/1983 LeSuer to about 30 Volume percent of at least one alcohol, comprising
15 A SES SE al the imine or tertiary amine product of the reaction between (a)
4.8 10,263 A 3/1989 Zimmermanet al. at least one aldehyde or ketone or mixture thereof having the
4,832,702 A 5, 1989 Kummer et al. formula R CHO, RCH, CHO, R., (C=O) Rs or R, CH,
4,836,829 A 6, 1989 Zimmerman et al. (C=O) Rs, wherein Re, R7, and Rs are the same or different
4,881,945 A I. 1989 Buckley, III and are each independently a straight or branched chain
2.
www. A lA. Wiello et al. hydrocarbyl or aryl group that contains from 1 to 18 carbon
5,112,364 A 5, 1992 Rath et al. atoms, and (b) a primary or secondary amine functionality.
5,139,534 A 8, 1992 Tomassen et al.
5,197.997 A * 3/1993 MoZdzen et al. ............... 44/386 11 Claims, No Drawings
 US 8,465,560 B1
1. 2
GASOLINE DEPOST CONTROL ADDITIVE Substituted amines by various addition or condensation reac
COMPOSITION tions. For example, fermentation processes can produce
acetone, which during purification of the desired alcohol
CROSS REFERENCE TO RELATED product can form diacetone alcohol, a hydroxylketone and its
APPLICATIONS dehydration product, mesityl oxide, an unsaturated ketone.
Other ketones and aldehydes can produce corresponding con
This application is related to and claims the benefit of densation products. These impurities likewise may ultimately
priority to U.S. Provisional Application No. 61/150,045 filed end up in the fuel induction system of the engine and contrib
Feb. 5, 2009, the entirety of which is herein incorporated by ute to deposit formation. Also the aldehydes and ketones
reference. 10 could react with the amine functionality of the detergent
additive and reduce its effectiveness. Often the amount of
FIELD OF THE INVENTION carbonyl compounds present is more than that which would
be stoichiometrically required to react with all the amine
The invention relates to the field of detergent additive com functionality.
positions, particularly to gasoline deposit control additive 15 Other factors which may contribute to deposit formation
compositions, for use in gasoline containing an alcohol com are phase separation which may occur because commercial
ponent. alcohol has limited solubility in gasoline and the presence of
dissolved mineral salts, such as Sodium sulfate, which may
BACKGROUND OF THE INVENTION find their way into the fuel during production, Storage and
transportation.
Detergent additives are required in fuels in order to control Furthermore, alcohol-gasoline blends have different sol
intake-valve deposits that can cause increased emissions from Vency characteristics than non-oxygenated gasoline. This
vehicles. Generally these additives have amine functionality, change in Solvency can impede the detergent additive perfor
typically primary or secondary amines or both, and a hydro mance because the carefully chosen amine base strength and
carbyl chain that is compatible with the fuel. The amine 25 chain composition described previously behaves differently
functionality binds to the intake-valve deposits, and the chain in this medium. In extreme cases of altered compatibility
allows solubilization either in the liquid fuel or a carrier fluid between the detergent additive and the alcohol gasoline
that may be included in the detergent control additive pack blend, the detergent additive can precipitate from solution or
age. The amine's base strength and the chain's composition insolubilize on the engine's intake valves causing Sticking
are carefully chosen to provide optimum performance. The 30 during start-up at cold temperatures.
importance of controlling intake-valve deposits so that emis For enhanced intake-valve keep-clean and clean-up perfor
sions are not increased has led the United States Environmen mance recent fuel trends have been to use higher concentra
tal Protection Agency (EPA) to mandate the use of detergent tions than the minimum required by the EPA for a particular
additives (also known as deposit control additives or DCA's) detergent additive. For example, each detergent additive or
in all on-road gasoline for use in the United States. 35 deposit control additive, DCA is assigned a “lowest additive
Worldwide concern over the growing shortages of crude oil concentration' or LAC by the EPA based on its ability to
Supplies has promoted the use of many materials as blending prevent intake-valve deposits as measured by a prescribed
agents in gasoline to extend the fuel Supply. From the engine test. To meet EPA regulations a one times (1x) treat rate at this
or motor vehicle manufacturers’ point of view, it seems easi concentration level is required. Auto manufacturers, such as
est to employ alcohol blended with gasoline. Methanol, etha 40 General Motors in its Top Tier Program, have recommended
nol and butanol have emerged as the most widely used alcohol the use of higher levels, for example, 2x (or two times) LAC,
blending agents. A high level of interest has been shown in the to provide improved performance of their engines. At high
use of “gasohol.' defined herein as a blend of gasoline with concentrations, low-temperature valve-sticking becomes a
from about 5 to about 30 volume percent ethanol, as an critical issue because the high concentration can leave a film
automotive fuel. Interest has been especially high in countries 45 of sticky additive on the intake-valve stem causing the valve
Such as Brazil which have an intense cultivation of Sugarcane, to remain open during cold-starting. The formation of the
mandioca and other raw materials of vegetable origin sticky film depends on the compatibility of the additive for
adequate for the production of ethanol. mulation. Good compatibility of an additive formulation cor
The use of a polar oxygenate such as an alcohol in gasoline responds to the formulation being very soluble in fuel (that is,
blends, however, has far reaching consequences. One of these 50 gasoline or alcohol-gasoline blend). However, the change in
is the formation of deposits in the fuel induction system such Solvency of alcohol-gasoline blends can upset this compat
as the carburetor or fuel injector and around the intake valves. ibility. The concentration and type of the alcohols as well as
These deposits interfere with the efficient operation of the the additive's composition influence this compatibility. Fur
engine and can lead to lower mileage and increased exhaust thermore, Some additive formulations contain a high boiling
emissions. It is believed that deposit formation may be caused 55 fluidizer that is very compatible with the additive and that acts
by several factors. One of these may be the loosening of rust to wash the sticky additive off the intake-valve stem.
by the alcohol from the walls in pipelines and storage tanks Thus, there is presently a need for a fuel induction deter
which is then transported through the system until it finds its gent that will either retard or prevent the formation of deposits
way into the fuel induction system of the engine. in the fuel induction system of an internal combustion engine
Another factor may be the presence of trace amounts of 60 operated on an alcohol-gasoline fuel mixture. Further, it is
acetic acid, acetaldehyde, ethyl acetate and n-butanol in alco important that the detergent be effective in very Small quan
hol-gasoline blends which are formed during the production tities in order to minimize cost and to avoid adverse effects,
of the alcohol during fermentation. Biofuels such as ethanol Such as adding to the gum component of the fuel, increasing
and butanols that are made by fermentation processes often combustion chamber deposits, etc. Also it is desirable for the
contain carbonyl compounds, in particular, aldehydes and 65 detergent to be immune to the presence of carbonyl com
ketones, which can react with conventional nitrogen-contain pounds and not to cause valve-sticking during start-up at low
ing deposit control additives, to form imines or more highly temperature.
 US 8,465,560 B1
3 4
Several detergent compositions have been disclosed. For amine functionality in at least one nitrogen-containing com
example, U.S. Pat. No. 4.398,921 discloses a fuel for internal pound selected from the group consisting of aliphatic hydro
combustion engines comprising from about 70 to about 90 carbyl amines, hydrocarbyl-substituted poly (oxyalkylene)
Volume percent of hydrocarbons boiling in the gasoline boil amines, hydrocarbyl-substituted Succinimides, Mannich
ing range, from about 5 to about 30 volume percent of ethanol reaction products, polyalkylphenoxyaminoalkanes, nitro and
and a detergent amount of a mixture of (1) a mononuclear or amino aromatic esters of polyalkylyphenoxyalkanols, a car
dinuclear aromatic hydrocarbon Solvent, (2) a hydrocarbyl buretor/injector detergent additive having a molecular weight
Succinic acid or anhydride corrosion inhibitor (3) a demulsi in the range from 100 to 600 and having a non-polar moiety
fying agent containing at least one oil-soluble polyether and and nitrogen-containing polar moiety, and mixtures thereof.
an oxyalkylated phenol formaldehyde resin, and (4) a Man 10
nich product formed by the reaction between an alkylphenol, DETAILED DESCRIPTION OF THE INVENTION
an aldehyde and an amine having at least one active hydrogen
atom bonded to an amino nitrogen atom. The deposit control additives employed in the present
U. S. Pat. No. 6,652,667 discloses a method for removing invention are reaction products of certain aldehydes or
engine deposits in a gasoline internal combustion engine by 15 ketones with the following conventional unmodified nitro
introducing a cleaning composition into a air-intake manifold gen-containing detergent additives disclosed in U.S. Pat. No.
of a warmed-up and idling gasoline internal combustion 6,652,667: aliphatic hydrocarbyl amines, hydrocarbyl-sub
engine and running the engine while the cleaning composi stituted poly(oxyalkylene) amines, hydrocarbyl-substituted
tion is being introduced. The cleaning composition comprises Succinimides, Mannich reaction products, polyalkylphe
(1) a phenoxy mono- or poly(oxyalkylene) alcohol, (2) at noxyaminoalkanes, nitro and amino aromatic esters of poly
least one solvent selected from an alkoxy mono- or poly alkylphenoxyalkanols, carburetor/injector detergent addi
(oxyalkylene) alcohol and an aliphalic or aromatic solvent, tives having a molecular weight in the range of from 100 to
and (3) at least one nitrogen-containing detergent additive. 600 and having a non-polar moiety and nitrogen-containing
Useful nitrogen-containing detergent additives include all of polar moiety, or mixtures thereof.
the nitrogen-containing compounds that are Suitable for use 25 The aliphatic hydrocarbyl-substituted amines which may
in the formation of the nitrogen-containing detergent compo be employed as reactants in the manufacture of the deposit
sitions of the present invention. control additives of the present invention are typically straight
PCT patent application number PCT/EP2006/066623, or branched chain hydrocarbyl-substituted amines having at
published as WO 2007/039488 A1, discloses hydroxyalkyl least one basic nitrogen atom and wherein the hydrocarbyl
Substituted amino-alkylamides of fatty acids for use as fric 30 group has a number average molecular weight of about 400 to
tion modifying agents for fuels such as gasolines containing 3,000. Preferred aliphatic hydrocarbyl-substituted amines
oxygenated compounds such as ethanol. These amides are include polyisobutenyl and polyisobutyl monoamines and
formed by reacting a specific class of amines with a carboxy polyamines. Such aliphatic hydrocarbyl amines can be pre
lic acid or a carboxylic acid derivative thereof which is pared by conventional procedures known in the art. Suitable
capable of reacting with an amine to form an amide. If the 35 preparations are described in detail in U.S. Pat. Nos. 3,438,
resulting amide product contains an active hydrogen atom 757; 3,565,804: 3,574,576; 3,848,056; 3,960,515; 4,832,702:
bonded to an amino nitrogen atom, the amide product is and 6,203.584, the disclosures of which are incorporated
further reacted with an alkylene oxide. herein by reference.
US2007/0094922 A1 discloses compositions which com The deposit control additives of the present invention are
prise at least one polyalkene amine in a solvent for improving 40 intended for use in automotive fuels containing from about 5.
the intake system-cleaning action of fuels which can contain preferably from about 2, to about 30 volume percent, prefer
up to 25 percent by Volume of oxygen containing materials ably to about 20 volume percent of at least one alcohol. The
Such as alcohols and ethers. The polyalkene amines employed alcohol can be methanol, ethanol, propyl or butyl alcohol and
are those whose polyalkene moiety is the polymerization preferably is a butyl alcohol isomer.
product of identical or different, straight chain or branched C. 45 Another class of deposit control additives suitable for use
- Colefin monomers. as reactants in the manufacture of the detergent additives of
Published U.S. patent application No. US2008/0066377 the present invention are the hydrocarbyl-substituted poly
A1 discloses a biodegradable fuel detergent additive compo (oxyalkylene) amines, also referred to as polyether amines.
sition for use in gasoline and diesel fuel, including fuels Typical hydrocarbyl-substituted poly(oxyalkylene) amines
containing alcohols. The detergent additive can be selected 50 include hydrocarbyl poly(oxyalkylene) monoamines and
from the group consisting of polyamines, polyetheramines, polyamines wherein the hydrocarbyl group contains from 1 to
Succinimides, succinamides, aliphatic polyamines and Man about 30 carbon atoms, the number of oxyalkylene units will
nich detergents. range from about 5 to 100, and the amine moiety is derived
from ammonia, a primary alkyl or secondary dialkyl
SUMMARY OF THE INVENTION 55 monoamine, or a polyamine having a terminal amino nitrogen
atom. Preferably, the oxyalkylene moiety will be oxypropy
The present invention is a deposit control additive for use in lene or oxybutylene or a mixture thereof. Such hydrocarbyl
a liquid automotive fuel comprising from about 70 to about 95 substituted poly(oxyalkylene) amines are described, for
Volume percent of hydrocarbons boiling in the gasoline range example, in U.S. Pat. Nos. 6,217,624 and 5,112.364, the
and from about 5 to about 30 volume percent of at least one 60 disclosures of which are incorporated herein by reference.
alcohol, comprising an imine or tertiary amine product of the A preferred type of hydrocarbyl-substituted poly(oxyalky
reaction between (a) at least one aldehyde or ketone or mix lene) monoamine is an alkylphenyl poly(oxyalkylene)mon
ture thereofhaving the formula R CHO, RCH, CHO, R, oamine wherein the poly(oxyalkylene) moiety contains
(C=O) Rs or R7 CH(CO) Rs, wherein R. R., and Rs oxypropylene units or oxybutylene units or mixtures of
are the same or different and are each independently a straight 65 oxypropylene and oxybutylene units. Preferably, the alkyl
or branched chain hydrocarbyl or aryl group that contains group on the alkylphenyl moiety is a straight or branched
from 1 to 18 carbon atoms, with (b) a primary or secondary chain alkyl of 1 to 24 carbon atoms. An especially preferred
 US 8,465,560 B1
5
alkylphenyl moiety is tetrapropenylphenyl, that is, where the
alkyl group is a branched-chain alkyl group of 12 carbon (I)
atoms derived from propylene tetramer.
An additional type of hydrocarbyl-substituted poly(oxy
alkylene)amine for use as reactants in the manufacture of the
deposit control additives of the present invention is hydrocar
byl-substituted poly(oxyalkylene) aminocarbamates dis
closed, for example, in U.S. Pat. Nos. 4.288,612; 4.236,020; wherein: R is a polyalkyl group having an average molecular
4,160,648; 4,191,537; 4,270,930; 4,233,168; 4,197,409: 10 weight in the range of about 600 to 5,000; R and R are
4,243,798 and 4,881,945, the disclosures of which are incor independently hydrogen or lower alkyl having 1 to 6 carbon
porated herein by reference. These hydrocarbyl poly(oxy atoms; and A is amino, N-alkylamino having about 1 to about
alkylene) aminocarbamates contain at least one basic nitro 20 carbon atoms in the alkyl group, N,N-dialkyl amino hav
gen atom and have an average molecular weight of about 500 ing about 1 to about 20 carbon atoms in each alkyl group, or
to 10,000, preferably about 500 to 5,000, and more preferably 15 a polyamine moiety having about 2 to about 12 amine nitro
about 1,000 to 3,000. A preferred aminocarbamate is alky gen atoms and about 2 to about 40 carbon atoms. The poly
lphenyl poly(oxybutylene) aminocarbamate wherein the alkylphenoxyaminoalkanes of Formula I above and their
amine moiety is derived from ethylene diamine or diethylene preparations are described in detail in U.S. Pat. No. 5,669,
triamine.
A further class of detergent additives suitable for use as 939, the disclosure of which is incorporated herein by refer
ence. Mixtures of polyalkylphenoxyaminoalkanes and poly
reactants in the manufacture of the deposit control additives (oxyalkylene) amines are also Suitable for use as reactants in
of the present invention is the hydrocarbyl-substituted suc the manufacture of the detergent additives of the present
cinimides. Typical hydrocarbyl-substituted Succinimides invention. These mixtures are described in detail in U.S. Pat.
include polyalkyl and polyalkenyl Succinimides wherein the No. 5,851,242, the disclosure of which is incorporated herein
polyalkyl or polyalkenyl group has an average molecular 25
by reference.
weight of about 500 to 5,000, and preferably about 700 to
3,000. The hydrocarbyl-substituted succinimides are typi A preferred class of detergent additives finding use as
cally prepared by reacting a hydrocarbyl-substituted Succinic reactants in the manufacture of the deposit control additives
anhydride with an amine or polyamine having at least one of the present invention are nitro and amino aromatic esters of
reactive hydrogen bonded to an amine nitrogen atom. Pre 30 polyalkylphenoxyalkanols. Preferred nitro and amino aro
ferred hydrocarbyl-substituted succinimides include poly matic esters of polyalkylphenoxyalkanols include those hav
isobutenyl and polyisobutanyl Succinimides, and derivatives ing the formula:
thereof. The hydrocarbyl-substituted succinimides are
described, for example, in U.S. Pat. Nos. 5,393,309: 5,588, 35
973; 5,620,486; 5,916,825; 5,954,843; 5,993,497; and 6,114, (II)
542, and British Patent No. 1,486,144, the disclosures of
which are incorporated herein by reference.
Yet another class of detergent additives which can be
employed as reactants in the manufacture of the deposit con 40
trol additives of the present invention is Mannich reaction
products which are typically obtained from the Mannich con
densation of a high molecular weight alkyl-substituted
hydroxyaromatic compound, an amine containing at least one wherein: R is nitro or —(CH2), NRo Ro, wherein Ro and
reactive hydrogen, and an aldehyde. The high molecular 45
Ro are independently hydrogen or lower alkyl having 1 to 6
weight alkyl-substituted hydroxyaromatic compounds are carbonatoms and n is 0 or 1; Rs is hydrogen, hydroxy, nitro or
preferably polyalkylphenols, such as polypropylphenol and —NR, R2, wherein R and R2 are independently hydro
polybutylphenol, especially polyisobutylphenol, wherein the gen or lower alkyl having 1 to 6 carbonatoms; R and R-7, are
polyakyl group has an average molecular weight of about 600 independently hydrogen or lower alkyl having 1 to 6 carbon
to 3,000. The amine reactant is typically a polyamine. Such as 50
atoms; and Rs is a polyalkyl group having an average molecu
alkylene polyamines, especially ethylene or polyethylene
polyamines, for example, ethylene diamine, diethylene tri lar weight in the range of about 450 to 5,000. The aromatic
amine, triethylene tetramine, and the like. The aldehyde reac esters of polyalkylphenoxyalkanols shown in Formula II
tant is generally analiphatic aldehyde, Such as formaldehyde, above and their preparations are described in detail in U.S.
paraformaldehyde, formalin, and acetaldehyde. A preferred 55 Pat. No. 5,618,320, the disclosure of which is incorporated
Mannich reaction product is obtained by condensing a poly herein by reference.
isobutylphenol with formaldehyde and diethylene triamine, Mixtures of nitro and amino aromatic esters of polyalky
wherein the polyisobutyl group has an average molecular lphenoxyalkanols and hydrocarbyl-substituted poly(oxy
weight of about 1,000. The Mannich reaction products are alkylene) amines are also preferably contemplated for use as
described, for example, in U.S. Pat. Nos. 4.231,759 and 60
reactants in the manufacture of the deposit control additives
5,697.988, the disclosures of which are incorporated herein of the present invention. These mixtures are described in
by reference. detail in U.S. Pat. No. 5,749,929, the disclosure of which is
A still further class of detergent additives suitable for use as incorporated herein by reference. Preferred hydrocarbyl-sub
reactants in the manufacture of the deposit control additives stituted poly(oxyalkylene) amines which may be employed
of the present invention are polyalkylphenoxyaminoalkanes. 65
Preferred polyalkylphenoxyaminoalkanes include those hav as detergent additives in the present invention include those
ing the formula: having the formula:
 US 8,465,560 B1
8
100) carbon number. Each of the above described unmodified
(III) deposit control additives contains a primary and/or secondary
amine functionality, which functionality can be modified by
R13 O-C-C
s s B reaction with suitable low carbon number aldehydes or
H H / ketones having the formulas: RCHO. R. CHO, R,
(C=O)Rs and R7 CH (C=O) Rs, where Re, R7, and Rs
wherein: R is a hydrocarbyl group having from about 1 to can be the same or different and are each independently a
about 30 carbon atoms; R and Rs are each independently straight or branched chain hydrocarbyl or aryl group that
hydrogen or lower alkyl having about 1 to about 6 carbon 10
contains from 1 to 18 carbon atoms, preferably from 1 to 8
atoms and each Ra and Rs is independently selected in each carbon atoms. Typically a solvent Such as isobutanol is
—O—CHR CHRs —unit; B is amino, N-alkyl amino employed in the reaction. When R. R., and Rs contain no
having about 1 to about 20 carbon atoms in the alkyl group, C. hydrogens, the reactions and reaction products of Such
N,N-dialkyl amino having about 1 to about 20 carbon atoms aldehydes and ketones with the above described conventional
in each alkyl group, or a polyamine moiety having about 2 to 15 deposit control additives containing primary amine function
about 12amine nitrogenatoms and about 2 to about 40 carbon ality are:
atoms; and m is an integer from about 5 to about 100. The
hydrocarbyl-substituted poly(oxyalkylene) amines of For RNH2+RCHO->RN=CHR+HO (Reaction 1)
mula III above and their preparations are described in detail in
U.S. Pat. No. 6,217,624, the disclosure of which is incorpo
rated herein by reference.
The hydrocarbyl-substituted poly(oxyalkylene) amines of where R is an N-alkyl or N-polyamine moiety shown in
Formula III are preferably utilized either by themselves or in Reactions 1 and 2 attached to a nitrogen atom in a primary
combination with other aforesaid unmodified deposit control amine functionality in any of the unmodified conventional
additives, particularly with the polyalkylphenoxyaminoal 25 deposit control additives described above-for example, in A
kanes of Formula I or the nitro and amino aromatic esters of of Formula I, in R or Rs in Formula II, or in B of Formula
polyalkylphenoxyalkanols shown in Formula II, as reactants III—and within R, the alkyl group contains from 1 to 20
in the manufacture of the detergent additives of the present carbon atoms and the polyamine group contains from 2 to 12
invention. More preferably, combinations of the hydrocarbyl nitrogen atoms and from 2 to 40 carbon atoms. When excess
substituted poly(oxyalkylene) amines of Formula III with the 30
RNH is employed, the product of Reaction 1 is (R.
nitro and amino aromatic esters of polyalkylphenoxyalkanols NH),CHR.
shown in Formula II are employed together as reactants in the
manufacture of the detergent additives of the present inven If the aldehyde or ketone does contain C-hydrogens, addi
tion. A particularly preferred hydrocarbyl-substituted poly tional condensation products can be formed by aldol-like or
(oxyalkylene) amine is dodecylphenoxy poly(oxybutylene) 35 Mannich-like reactions as in Reactions 3,3', 4 and 4'.
amine and a particularly preferred combination is the combi
nation of dodecylphenoxy poly(oxybutylene) amine and
4-polyisobutylphenoxyethyl para-aminobenzoate. (Reaction 3 -aldol-like)
Another class of conventional deposit control additives
Suitable for use as reactants in the manufacture of the deposit 40 RNH + RCHCHO -> R-CH-CH=NR
control additives of the present invention is the nitrogen R-CH-CH-NHR
containing carburetor/injector detergents. The carburetor/in
jector detergent additives are typically relatively low molecu
lar weight compounds having a number average molecular O
weight of about 100 to about 600 and possessing at least one 45
polar moiety and at least one non-polar moiety. The non-polar
moiety is typically a linear or branched-chain alkyl or alkenyl
group having about 6 to about 40 carbon atoms. The polar (Reaction 3 - Mannich like)
moiety is typically nitrogen-containing Typical nitrogen-con R-CH-CHO
taining polar moieties include amines (for example, as 50
described in U.S. Pat. No. 5,139,534 and PCT International RCH-H-NHR
Publication Number WO 90/10051), ether amines (for
example, as described in U.S. Pat. No. 3,849,083 and PCT
International Publication Number WO 90/10051), amides,
polyamides and amide-esters (for example, as described in 55
U.S. Pat. Nos. 2,622,018; 4,729,769; and 5,139,534; and (Reaction 4 - Mannich like)
RNH + RCH(C=O)Rs - -
European Patent Publication Number 149.486), imidazolines
(for example, as described in U.S. Pat. No. 4,518.782), amine R18
oxides (for example, as described in U.S. Pat. Nos. 4,810.263
and 4,836,829), hydroxyamines (for example, as described in 60
U.S. Pat. No. 4,409,000), and succinimides (for example, as R-CH-C-NHR
described in U.S. Pat. No. 4,292,046).
The compositions of the detergent or deposit control addi R18
tives of the present invention are the imine or tertiary amine
products of the reaction between the aforesaid unmodified 65
O
conventional deposit control additive compositions described
above and selected aldehydes or ketones of low (less than
 US 8,465,560 B1
10
(Reaction 4 - Mannich like) (Reaction 13)
R18
R-CH-CFO
RCH-C-NHR
R18
10
Generally an equimolar or slightly excess amount of car
bonyl compound is used to limit the formation of multiple (Reaction 14)
condensation products.
In addition a secondary amine functionality can react with 15
RCHO and R., (C=O)Rs according to:
R17 R18
2(R) (R2)NH--RCHO->(R)(R2)N-2CHR (Reaction 5)
The deposit control additive of the present invention is
2CR17R18 (Reaction 6) employed in the aforesaid liquid automotive fuel at a level in
the range of from about 50 preferably from about 100, to
where R, and R2 are independently each an N,N-dialkyl or about 4000, preferably to about 2000, more preferably to
N-polyamine shown in Reactions 5 and 6 attached to a nitro about 1000 parts per million by volume.
gen atom in the aforesaid secondary amine functionality, and 25 An additional material that may optionally be used with the
each alkyl group therein contains from 1 to 20 carbon atoms gasoline detergent additive composition of the present inven
and each polyamine group therein contains 2 to 12 nitrogen tion is a fluidizer or solvent, for example, an alkoxy mono- or
atoms and 2 to 40 carbonatoms, and R. R., and Rs have no poly(oxylene) alcohol and/oran aliphatic or aromatic organic
C-hydrogens. Solvent. The alkoxy mono- or poly (oxyalkylene) alcohol
However, if the aldehyde or ketone does contain C-hydro 30 which may be employed as a fluidizer or solvents in the
gens, a typical product will be the enamine: present invention has the following general formula:
Rio-O-(CH-CHR20 —O)-CH2-CHR2 —OH (IV)
NCH=CHR (Reaction 7) wherein Rio is an alkyl group of 1 to about 10 carbon atoms,
35 and Ro and R are independently hydrogen or methyl, andy
is an integer from 0 to 4. Rio is preferably an alkyl group of 2
NCR 7=CHRs (Reaction 8) to 6 carbon atoms, Ro and R are preferably hydrogen, and
As in the case of the primary amines, Mannich-like prod y is preferably an integer from 0 to 2. More preferably, R is
ucts can be formed from a secondary amine functionality, as an alkyl group of 4 carbonatoms (i.e., butyl), Ro and R2 are
follows:
40 hydrogen, and y is 0.
Suitable alkoxy mono- or poly(oxyalkylene) alcohols for
use in the present invention include, for example, 2-methoxy
(CHRCHO)CHR (Reaction 9) ethanol, 2-ethoxyethanol, 2-n-butoxyethanol, 1-methoxy-2-
propanol. 1-ethoxy-2-propanol. 1-n-butoxy-2-propanol,
45 diethylene glycol methyl ether, diethylene glycol butyl ether,
(CHR (C=O)Rs)CHR, (Reaction 10)
propylene ethylene glycol methyl ether, propylene ethylene
glycol butyl ether, dipropylene glycol methyl ether, dipropy
When the aldehyde or ketone is an O.B-unsaturated carbo lene glycol butyl ether, and the like, including mixtures
nyl compound. Such as mesityl oxide (4-methyl-3-penten-2- thereof. A preferred alkoxy mono-or poly (oxyalkylene) alco
one), the following reaction can occur by Michael-type addi 50 hol is 2-n-butoxyethanol. A commercial 2-n-butoxyethanol,
tion: or ethylene glycol mono-butyl ether, is available as EB Butyl
Cellusolve from Union Carbide, a subsidiary of Dow Chemi
cal Company.
An aliphatic or aromatic hydrocarbyl organic solvent or
2C=C-(C=NR)CH (Reaction 11) 55 fluidizer may also be employed in the present invention. Suit
able aromatic solvents include benzene, toluene, Xylene or
(R) (Rb)NH+mesityl oxide->(R)(R)NC(CH) higher boiling aromatics or aromatic thinners, such as a Co
2CH2(C=O)CH (Reaction 12) aromatic solvent. Suitable aliphatic solvents include dearo
matized solvents such as EXXsol D40 and D60, available from
The resulting carbonyl amine compounds could react further 60 ExxonMobil, other aliphatic solvents, such as D15-20
with the amine functionality, but an equimolar or slight excess Naphta, D115-145 Naphtha and D31-35 Naphtha, also avail
amount of carbonyl can be used to prevent this further reac able from ExxonMobil, and nonaromatic mineral spirits, and
tion. the like. A preferred solvent or fluidizer for use in the present
When the amine is a polyethylene polyamine, for example, invention is a Co aromatic solvent.
ethylene diamine, diethylene triamine, triethylene tetramine, 65 Preferably, the solvent employed will be a mixture of both
and the like, the following reactions produce compositions an alkoxy mono- or poly(oxyalkylene) alcohol and an ali
that have cyclic structures: phatic or aromatic organic solvent. In a particularly preferred
 US 8,465,560 B1
11 12
embodiment, the solvent will be a mixture of 2-n-butoxyetha A third reference fuel, designated "Gas base' was 100
nol and a C9 aromatic solvent. gallons of the all hydrocarbon conventional regular gasoline.
Further conventional components and assistants that may This fuel blend contained no isobutanol and no deposit con
also be employed are corrosion inhibitors, for example based trol additive.
on ammonium salts of organic carboxylic acids, which salts 5 Each of the above four fuels was evaluated for intake-valve
tend to form films, or on heterocyclic aromatics in the case of deposit keep-clean performance by running them for 40 hours
corrosion protection of nonferrous metals, antioxidants or on a General Motors 3.8 liter V-6 engine and dynamometer
stabilizers, for example based on amines, such as p-phe test bed. The engine ran a repeated cycle consisting of two
nylenediamine, dicyclohexylamine orderivatives thereofand modes: 2600 rpm at 56 ft-lbs torque for 190 seconds followed
on phenols, such as 2,4-di-tert-butylphenol or 3,5-di-tert 10 by 2900 rpm at 99 ft-lbs torque for 25 seconds. Speed/load
butyl-4-hydroxyphenylpropionic acid, dehazers, demulsifi changes were accomplished with approximately a 30 second
ers, antistatic agents, metallocenes Such as ferrocene or meth ramp up or ramp down as needed to maintain engine-dyna
ylcyclopentadienyl manganese tricarbonyl, lubricity mometer control.
additives (different from compound (I)), such as certain fatty Results of these experiments are shown in Table 1. The
acids, alkenylsuccinic esters, bis(hydroxyalkyl)fatty amines, 15 Gas-base fuel was formulated to give a relatively high deposit
hydroxyacetamides and castor oil, antiknock additives, anti level. So the high deposit level and low CRC rating shown in
icing additives, octane requirement additives, and also colo Table 1 was expected. When isobutanol was added to the
rants (markers). Sometimes amines are also added to adjust Gas-BuOHi3 fuel, there was no significant change in the
the pH of the fuel. deposit or rating. When a conventional deposit control addi
The present invention will be explained in more detail tive was added to the isobutanol-gasoline blend Gas
below by reference to the following examples. However, the BuOHi2, a marked reduction of deposit was observed. When
present invention should not be construed as being limited iso-BUPIBA#1, a deposit control additive of the present
thereto. invention was used, an IVD reduction and improved CRC
rating similar to that obtained when a conventional deposit
GENERAL METHODS FOR EXAMPLES 25 control additive was observed. These experiments show that a
deposit control additive of the present invention has at least
Where provided, intake valve deposit(s) (IVD) were mea similar efficacy as a conventional deposit control additive.
Sured by weighing the dirty valve and Subtracting the weight
of clean valve as measured before the testing began, consis TABLE 1
tent with ASTM D6201–97, “Standard Test Method for Dyna 30
mometer Evaluation of Unleaded Spark-Ignition Engine Fuel Deposit Control CRC IVD Average,
for Intake Valve Deposit Formation’. Coordinating Research Fuel Iso-butanol, 90 Additive rating mg/valve
Council (CRC) ratings, where given, were designated accord Gas-base None None 8.3 256.2
ing to the “CRC Manual No. 16 Carburetor and Induction Gas-BuOH #3 16.5 None 8.6 213.2
System Rating Manual for visually rating the condition of 35 Gas-BuOH #2 16.5 AP-NA4M 9.5 28.8
Gas-BuOH #1 16.5 iso-BuPIBA #1 9.5 25.7
intake valves (10-clean, 1=very heavy deposits).
EXAMPLE1 A similar preparation of the deposit control additive of the
present invention was made for use in fuel blends evaluated
A modified deposit control additive of the present inven 40 by a low-temperature valve-sticking test. A mixture of 2.00
tion, iso-BuPIBA #1, was prepared by refluxing 3.64 grams of grams of iso-butyraldehyde, 96.8 grams of AP-NA4M and 20
isobutyraldehyde with 176 grams of AP-NA4M and 20 grams grams of isobutanol as solvent was refluxed to make iso
of isobutanol as a solvent for 3 hours. AP-NA4M is a formu BuPIBA#2, a deposit control additive of the present inven
lated PIB amine type conventional deposit control additive tion. Infrared spectroscopy indicated conversion of about
manufactured by BASF Corporation including fluidizer, 45 58% of the aldehyde carbonyl and appearance of an imine
demulsifier and corrosion inhibitor and contains approxi absorption. All of the resulting iso-BuPIBA#2 was mixed
mately 0.26 milli-equivalents of nitrogen. The equivalents of with 45.92 gallons of a winter grade all hydrocarbon regular
isobutyraldehyde added were 1.1 times the equivalents of gasoline and 9.08 gallons of isobutanol to make the test fuel
nitrogen in the AP-NA4M. Infrared spectroscopy indicated designated Wgas-BuOH #4. This fuel blend would have con
conversion of about 79% of the aldehyde carbonyl and the 50 tained four times the LAC dose of the conventional deposit
appearance of an imine absorption. control additive if the conventional deposit control additive
All of the resulting iso-BuPIBA #1 was mixed with 83.5 had not been modified.
gallons of all hydrocarbon conventional regular gasoline and A reference fuel designated “W gas-BuOH #5” was pre
16.5 gallons of isobutanol. The resulting fuel blend would pared by mixing 45.92 gallons of winter grade all hydrocar
have contained four times the LAC dose of the conventional 55 bon regular gasoline and 9.08 gallons of iso-butanol and 60.5
deposit control additive if the conventional deposit control grams of AP-NA4M. This fuel blend contained four times the
additive had not been modified. This fuel blend is designated LAC dose of the conventional deposit control additive.
GaS-BuOHH1. A second reference fuel, designated “Wgas-BuOH #6”.
A reference fuel designated “Gas-BuOH #2 was prepared was prepared by mixing 45.92 gallons of winter grade all
by mixing 83.5 gallons of all hydrocarbon conventional regu 60 hydrocarbon regular gasoline and 9.08 gallons of iso-butanol
lar gasoline and 16.5 gallons of iso-butanol and 176 grams of and 60.5 grams of AP-NA4M. This fuel blend contained 2.5
AP-NA4M. This fuel blend contained four times the LAC times the LAC dose of the conventional deposit control addi
dose of the conventional deposit control additive. tive.
A second reference fuel, designated “Gas-BuOH #3, was A third reference fuel designated “Wgas-BuOH base' was
prepared by mixing 83.5 gallons of all hydrocarbon conven 65 prepared by mixing 45.92 gallons of winter grade all hydro
tional regular gasoline and 16.5 gallons of isobutanol. This carbon regular gasoline and 9.08 gallons of iso-butanol. This
fuel blend contained no deposit control additive. fuel blend contained no deposit control additive.
 US 8,465,560 B1
13 14
All four of the above fuels were tested at Southwest marked reduction of deposit is observed. When the PEA
Research Institute according to its standard Chevrolet Truck deposit control additive of the present invention of the present
Valve Sticking Test. Briefly, that test was performed by driv invention, iso-BUPEA#1, was used, an IVD reduction and
ing the truck having a 5.0 liter V-8 engine with the test fuel improved CRC rating similar to the conventional deposit
over four cycles consisting of 56 minutes at 55 mph and 3 control additive was observed. These experiments demon
minute at idle, with a 1 minute ramp up or ramp down strate that the PEA deposit control additive of the present
between idle and speed. After the driving cycles were com invention has similarly efficacy as the conventional deposit
pleted, the test vehicle was cold soaked for 16 hours at -20° control additive.
C. Following the cold soak, a cold engine compression test 10
was performed to determine if valve sticking had occurred. TABLE 3
This entire test sequence was repeated on two more days for Deposit IVD
a total of 3 sequences. If all valves stuck on all days a maxi Control CRC Average,
mum total of 24 valves could stick. Fuel Iso-butanol, 9%. Additive rating mg/valve
Low temperature valve sticking test results are shown in 15 Gas-base None None 8.3 256.2
Table 2. The iso-butanol fuel itself passed the test, but the Gas-BuOH #3 16.5 None 8.6 213.2
conventional deposit control additive did not pass at either Gas-BuOHis 16.5 HiTec (R) 6400 9.5 28.0
high (4X LAC) or lower (2.5X LAC) treat rates. The deposit Gas-BuOH #4 16.5 iso-BuPEA #1 9.3 30.2
control additive of the present invention did pass the test even
though it was used in an amount that was equivalent to a high A similar preparation of the PEA deposit control additive
treat rate equivalent to 4X of conventional deposit control of the present invention was made for use in fuel blends
additive.
evaluated by a low-temperature valve-sticking test. A mixture
TABLE 2 of 3.68 grams of iso-butyraldehyde, 118.1 grams HiTec(R)
6400 and 20 grams of isobutanol as solvent was refluxed to
25
Deposit Control Total make a PEA deposit control additive of the present invention
Iso-butanol, Additive, treat stuck Test designated iso-BuPEA#2. Infrared spectroscopy indicated
Fuel % rate (LAC) valves Result
conversion of about 93% of the aldehyde carbonyl and
Wgas-BuOHbase 16.5 None O Pass appearance of an imine absorption. All of the resulting iso
W gas-BuOH #6 16.5 AP-NA4M, 2.5X 2 Fail
W gas-BuOH #5 16.5 AP-NA4M, 4X 3 Fail 30
BuPEA#2 was mixed with 45.92 gallons of a wintergrade all
W gas-BuOH #4 16.5 iso-BuPIBA #2 O Pass hydrocarbon regular gasoline and 9.08 gallons of isobutanol
to make test fuel Wgas-BuOH #7. This fuel blend would have
contained six times the LAC dose of the conventional deposit
EXAMPLE 2 control additive if the conventional deposit control additive
35 had not been modified.
A sequence similar to Example 1 was employed with a A reference fuel, designated “Wgas-BuOH #8, was pre
polyether amine type of deposit control additive. A deposit pared by mixing 45.92 gallons of winter grade all hydrocar
control additive of the present invention, iso-BuPEA #1, was bon regular gasoline and 9.08 gallons of iso-butanol and
prepared by refluxing 6.00 grams of isobutyraldehyde with 250.8 grams of HiTec(R) 6400. This fuel blend contained eight
228 grams of HiTec R 6400 and 20 grams of isobutanol as 40 times the LAC dose of the conventional deposit control addi
solvent for 3 hours. HiTec 6400 is a formulated polyether tive.
amine (PEA) type of conventional deposit control additive A second reference fuel designated “Wgas-BuOH #9” was
manufactured by Afton Chemical Company and contains prepared by mixing 45.92 gallons of winter grade all hydro
approximately 0.25 milli-equivalents of nitrogen. The carbon regular gasoline and 9.08 gallons of iso-butanol and
equivalents of isobutyraldehyde added were 1.5 times the 45
125.4 grams of HiTec(R) 6400. This fuel blend contained four
equivalents of nitrogen in HiTec 6400. Infrared spectroscopy times the LAC dose of the conventional deposit control addi
indicated conversion of about 85% of the aldehyde carbonyl tive.
and appearance of an imine absorption. A third reference fuel designated “W gas-BuOH #10 was
All of the resulting iso-BuPEA #1 was mixed with 83.5 prepared by mixing 48.68 gallons of winter grade all hydro
gallons of conventional all hydrocarbon regular gasoline and 50
carbon regular gasoline and 6.32 gallons of iso-butanol and
16.5 gallons of isobutanol. This fuel blend would have con 188.1 grams of HiTec R 6400. This fuel blend contained six
tained four times the LAC dose of the conventional deposit times the LAC dose of the conventional deposit control addi
control additive if the the conventional deposit control addi tive but a lower isobutanol concentration.
tive had not been modified. This fuel blend is designated All four of the above fuels were tested at Southwest
GaS-BuOH H4'. 55
A reference fuel designated “Gas-BuOH #5” was prepared Research Institute according to its standard Chevrolet Truck
by mixing 83.5 gallons of conventional all hydrocarbon regu Valve Sticking Test as described in Example 1. Low tempera
lar gasoline and 16.5 gallons of iso-butanol and 228 grams of ture valve sticking test results are shown in Table 4. The fuels
HiTec(R) 6400. This fuel blend contained four times the LAC with the conventional deposit control additive did not pass the
dose of the conventional deposit control additive. 60 test at either high (8X LAC) or low (4X LAC) treat rates.
Each of the above two fuels was evaluated for intake-valve However, the fuel with the deposit control additive of the
deposit keep clean performance by running them for 40 hours present invention passed at the equivalent of 6X LAC. An
on a General Motors 3.8 liter V-6 engine and dynamometer additional test using fuel with conventional deposit control
test bed as described in Example 1. The results and compari additive but a lower iso-butanol concentration (11.5%)
son to other reference fuels described in Example 1 are shown 65 passed the test indicating significant test dependency on the
in Table 3. When the the conventional deposit control additive base fuel solvency characteristics for the deposit control addi
was added to the isobutanol-gasoline blend, Gas-BuOHi5, a tive.
 US 8,465,560 B1
16
TABLE 4 deposit control additives of this invention pass a low-tem
perature valve-sticking test at concentration levels at which
Deposit Control Total the aforesaid unmodified additives do not pass.
Iso-butanol, Additive, treat stuck Test From the above description, it is apparent that the objects of
Fuel % rate (LAC) valves Result
the present invention have been achieved. While only certain
W gas-BuOH #8 16.5 HiTec (R) 6400, 8X 2 Fail embodiments have been set forth, alternative embodiments
W gas-BuOH #9 16.5 HiTec (R) 6400, 4X 2 Fail and various modifications will be apparent from the above
W gas-BuOH #10 11.5 HiTec (R) 6400, 6X O Pass
W gas-BuOH #7 16.5 iso-BuPEA ii.2 O Pass description to those skilled in the art and are within the spirit
and scope of the present invention.
10 That which is claimed is:
EXAMPLE 3
1. A liquid automotive fuel comprising from about 70 to
about 95 volume percent of hydrocarbons boiling in the gaso
line range, from about 5 to about 30 volume percent of at least
Four deposit control additives of the present invention were one alcohol, and an imine or tertiary amine product of the
prepared using the amounts in Table 5 by refluxing for 3 15 reaction between
hours. The molar ratio of amine to carbonyl compound was (a) at least one aldehyde having the formula R CHO or
1:1 for all these additives. These four additives and/or R CH, CHO, wherein R is a straight or branched
AP-NA4M were combined with an all hydrocarbon regular chain hydrocarbyl or aryl group that contains from 1 to
gasoline base mixed with n-butanol in a 9:1 volume: Volume 18 carbon atoms, and
ratio to make fuels described in Table 6. (b) a primary or secondary amine functionality of the for
mula:
TABLE 5
Carbonyl AP-NA4M n-Butanol Modified
Carbonyl compound, weight, weight, DCA
compound weight, grams grams grams designation 25
4-methyl-3- O.70 27.5 20.8 ModPIBA #1
pente-2-one
4-methyl-3- 2.25 88.0 2O.O ModPIBA #2
pente-2-one
n-butyraldehyde 1.65 88.0 2O.O ModPIBA #3 30
Acetone 1.33 88.0 20.0 ModPIBA #4
wherein: R is nitro or —(CH2), NRoRo wherein Ro
and Rio are independently hydrogen or lower alkyl hav
The fuels in Table 6 were tested for IVD keep clean per ing 1 to 6 carbon atoms and n is 0 or 1; Rs is hydrogen,
formance by running them in a General Motors 3.8 liter V-6 hydroxy, nitro or —NR, R2, wherein R and R are
engine dynamometer test rig for 20 hours. The continuously 35 independently hydrogen or lower alkyl having 1 to 6
repeated speed-load cycle for these tests consisted of 2000 carbonatoms; R and R-7, are independently hydrogen or
rpm at manifold absolute pressure of 230 kPa (approximately lower alkyl having 1 to 6 carbon atoms; and Rs is a
9 ft-lb) for 240 seconds and 2800 rpm at manifold absolute polyalkyl group having an average molecular weight in
pressure of 540 kPa (approximately 60ft-lbs) for 480 seconds the range of about 450 to 5,000.
with an approximately 30 second ramp up or ramp down 40 2. The liquid automotive fuel of claim 1 wherein R of the
transition between conditions. aldehyde contains from 1 to 8 carbon atoms.
3. The liquid automotive fuel of claim 1 wherein R con
TABLE 6 tains from 1 to 12 atoms.
4. The liquid automotive fuel claim 1 wherein the liquid
DCA equivalent CRC Valve Average automotive fuel comprises about 2 to about 30 volume per
Fuel DCA treat rate, LAC Rating IVD, mg cent of the at least one alcohol.
Baseline 2.5X AP-NA4M 2.5X 8.9 47.3 5. The liquid automotive fuel of claim 1 wherein the at least
unmodified + AP-NA4M - 125X -- 9.0 49.O one alcohol comprises ethanol or a butanol or both.
modified #1 ModPIBA #1 1.2SX
Baseline 4.0X AP-NA4M 4.OX 9.2 31.3
6. The liquid automotive fuel of claim 5 wherein the at least
Modified H1 ModPIBA #2 4.OX 9.1 29.7 50 one alcohol comprises a butanol isomer.
Modified H2 ModPIBA #3 4.OX 8.8 46.8 7. The liquid automotive fuel of claim 6 wherein the at least
Modified i3 ModPIBA #4 4.OX 9.2 30.8 one alcohol comprises isobutanol.
8. The liquid automotive fuel of claim 1 comprising the
The results in Table 6 demonstrate that the deposit control imine or tertiary amine product of the reaction between the
additives of the present invention perform similarly to the 55 aldehyde and a primary amine functionality.
conventional deposit control additives 9. The liquid automotive fuel of claim 1 comprising from
Thus, the performance in internal combustion engines of about 50 to about 4000 parts per million by volume of the
the detergent or deposit control additives of the present inven imine or tertiary amine.
tion is not affected by carbonyl impurities that may be present 10. The liquid automotive fuel of claim 9 wherein the imine
in bio-derived fuels or blends and have improved capability. 60 or tertiary amine is at a level of from about 100 to about 2000
The additives of the present invention exhibit intake-valve parts per million by Volume.
keep-clean and clean-up performance that is comparable to 11. The liquid automotive fuel of claim 10 wherein the
the aforesaid conventional additives described above. More imine or tertiary amine is at a level of from about 100 to about
over, the low temperature valve-sticking performance of the 1000 parts per million by volume.
additives of the present invention is improved such that the k k k k k