WO1998016598A1

WO1998016598A1 - Fuel compositions

Info

Publication number: WO1998016598A1
Application number: PCT/EP1996/004430
Authority: WO
Inventors: Jiang Jen Lin; Sarah Louise Weaver
Original assignee: Infineum Holdings Bv
Priority date: 1996-10-11
Filing date: 1996-10-11
Publication date: 1998-04-23
Also published as: JP2001505595A; CA2268116A1; KR20000049097A; AU7290796A; EP0932655A1

Abstract

Multiple amide polyether alcohol compounds of formula (I), wherein R1 and R2 are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to 100 carbon atoms; R3 and R4 are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms; R5 is selected from the group consisting of alkylene of 2 to 20 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one methylene group replaced by at least one oxygen atom or at least one acylated nitrogen atom; x and y are each from 1 to 50 and the weight average molecular weight of the additive compound is greater than about 600 when used as gasoline additives, are found to decrease intake valve deposits.

Description

FUEL COMPOSITIONS Background of the Invention Field of the Invention

The present invention relates to the use of multiple amide polyether alcohol compounds as additives in fuel compositions and the use of these compounds to decrease intake valve deposits, control octane requirement increases and reduce octane requirment. The present invention further relates to multiple amide polyether alcohol compounds. Background

The accumulation of deposits on the intake valves of internal combustion engines presents a variety of problems . The accumulation of such deposits is characterized by overall poor driveability including hard starting, stalls, and stumbles during acceleration and rough engine idle.

Many additives are known which can be added to hydrocarbon fuels to prevent or reduce deposit formation, or remove or modify formed deposits, in the combustion chamber and on adjacent surfaces such as intake valves, ports, and spark plugs, which in turn causes a decrease in octane requirement.

Continued improvements in the design of internal combustion engines, e.g., fuel injection and carburetor engines, bring changes to the environment of such engines thereby creating a continuing need for new additives to control the problem of inlet system deposits and to improve driveability which can be related to deposits.

It would be an advantage to have fuel compositions which would reduce the formation of deposits and modify existing deposits that are related to octane requirement increase and poor driveability in modern engines which burn hydrocarbon fuels. Summary Of The Invention

The present invention is directed to the use of multiple amide polyether alcohol compounds as additives in fuel compositions comprising a major amount of a mixture of hydrocarbons in the gasoline boiling range and a minor amount of one or more multiple amide polyether alcohol compounds of Formula I :

O O

R₃- -N -Rs -N R₄ (D

(Ri—O)x—H (R₂—O)y—H

wherein R, and R₂ are each independently selected from the group consisting of hydrocarbyl of 2 to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbon atoms; R₃ and R₄ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms; R₅ is selected from the group consisting of alkylene of 2 to 20 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one methylene group replaced by at least one oxygen atom or at least one acylated nitrogen atom; and x and y are each from 1 to 50.

The invention is also directed to the use of multiple amide polyether alcohol compounds for decreasing intake valve deposits, controlling octane requirement increases and reducing octane requirement. The present invention is further directed to multiple amide polyether alcohol compounds. Description Of The Preferred Embodiments Compounds

The compounds of the present invention, broadly expressed as multiple amide alkoxylates, are a new class of additives useful for hydrocarbon fuels, e.g., fuels in the gasoline boiling range and for preventing deposits in engines, while also decomposing during combustion to environmentally acceptable products. The compounds are also proposed for controlling octane requirement increases and reducing octane requirement. The compounds produce very little residue and are miscible with carriers and other detergents. Non-limiting illustrative embodiments of the compounds useful as additives in the instant invention include those of Formula I :

O O

R₃- ^•N Rs -N 4 (D

(Ri — O)x— H (R₂ — 0)y — H

In Formula I, R, and R₂ are each independently selected from the group consisting of hydrocarbyl of 2 to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbon atoms; x is from 1 to 50; and y is from 1 to 50. When R, and/or R₂ are hydrocarbyl of a relatively high number of carbon atoms, i.e., greater than about 50 carbon atoms, each will be represented by polymeric hydrocarbyls derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefin.

As used herein, the term "hydrocarbyl" represents a radical formed by the removal of one or more hydrogen atoms from a carbon atom of a hydrocarbon (not necessarily the same carbon atom) . Useful hydrocarbyls are aliphatic, aromatic, acyclic or cyclic. Preferably, the hydrocarbyls are aryl, alkyl, alkenyl or cycloalkyl and are straight-chain or branched-chain. Representative hydrocarbyls include methyl, ethyl, butyl, pentyl, ethylpentyl, hexenyl, ethylhexyl, dimethylhexyl , octamethylene, octenylene, cyclooctylene, methylcyclσoctylene, dimethylcyclooctyl, isooctyl, dodecyl, hexadecenyl , octyl, eicosyl, hexacosyl, triacontyl and phenylethyl . The hydrocarbyls utilized may also be substituted. As used herein the term "substituted hydrocarbyl" refers to any "hydrocarbyls" which contain a functional group such as carbonyl, carboxyl, nitro, amino, hydroxy (e.g. hydroxyethyl ) , oxy, cyano, sulfonyl, and sulfoxyl. The majority of the atoms, other than hydrogen, in substituted hydrocarbyls are carbon, with the heteroatoms (i.e., oxygen, nitrogen, sulfur) representing only a minority, 33% or less, of the total non-hydrogen atoms present.

Preferably R, and Rs are each selected from hydrocarbyl of 2 to 50 carbon atoms and substituted hydrocarbyl of 2 to 50 carbon atoms. More preferably, R, and R₂ are each selected from hydrocarbyl of 2 to 20 carbon atoms and substituted hydrocarbyl of 2 to 20 carbon atoms. Particularily preferred compounds are those in which R, and Rj are each independently selected from hydrocarbyl selected from the group consisting of alkyl of 2 to 20 carbon atoms, more preferably alkyl of 2 to 4 carbon atoms, especially alkyl of 4 carbon atoms.

Particularly preferred compounds of Formula I are those in which R, and R^ are hydrocarbyl (geminal or vicinal) of the formula:

Rs —CH₂-C— (||) or —CH-CH— _(|||)

Rs R? s

wherein R^, R₇ and R₈ are each independently selected from hydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms and substituted hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms. Preferred R^, R- and R₈ groups are those independently selected from hydrogen, hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms. In addition, R^ and _?, or alternatively R^ and R₈, may be taken together to form a divalent linking hydrocarbyl group of 3 to 12 carbon atoms. When R^, R_? and/or R₈ are substituted hydrocarbyl, they are preferably oxy- substituted hydrocarbyl.

The most preferred compounds of Formula I are those in which R, and R₂ are each selected from hydrocarbyl and substituted hydrocarbyl as represented by Formula II above wherein each R₈ is hydrogen and each R^ is independently selected from hydrogen, alkyl of 1 to 18 carbon atoms and oxy-substituted hydrocarbyl of 1 to 18 carbon atoms, particularly those compounds wherein each R₈ is hydrogen and each R^ is independently hydrogen or alkyl of 1 to 2 carbon atoms, especially those compounds wherein each R₈ is hydrogen and each R_j is alkyl of 2 carbon atoms . When R₆ is oxy-substituted hydrocarbyl of 1 to 18 carbon atoms, R^ is preferably an alkoxy-substituted alkylene of 1 to 18 carbon atoms or an aryloxy-subεtituted alkylene of 1 to 18 carbon atoms. Particularly preferred alkoxy-substituted alkylene groups include ethylhexyleneoxymethylene , isopropoxymethylene, butoxymethylene and mixtures thereof. Particularly preferred aryl-substituted alkylene groups include nonylphenoxymethylene, phenoxymethylene and mixtures thereof.

In Formula I above, each x is from 1 to 50, preferably from 1 to 40, and even more preferably from 1 to 26. Those of ordinary skill in the art will recognize that when the compounds of Formula I are used in compositions, x will not have a fixed value but will instead be represented by a range of different values. As used in this specification, x is considered to be a (number) average of the various values of x that are found in a given composition, which number has been rounded to the nearest integer. The range of x is indicated in the various examples by the polydispersity (polydispersity = molecular weight based on the weight average divided by the molecular weight based on the number average) .

When x is greater than 1, the individual R,'s may be the same or different. For example, if x is 20, each R, can be alkyl of four carbon atoms. Alternatively, the R,'s can differ and for instance, independently be alkyl from two to four carbon atoms. When the R, ' s differ, they may be present in blocks, i.e., all x groups in which R, is alkyl of three carbon atoms will be adjacent, followed by all x groups in which R, is alkyl of two carbon atoms, followed by all x groups in which R, is alkyl of four carbon atoms. When the R, ' s differ, they may also be present in any random distribution. In Formula I above, each y is also from 1 to 50, preferably from 1 to 40, and even more preferably from 1 to 26. Those of ordinary skill in the art will recognize that when the compounds of Formula I are used in compositions, y will not have a fixed value but will instead be represented by a range of different values. As used in this specification, y is considered to be a (number) average of the various values of y that are found in a given composition, which number has been rounded to the nearest integer. The range of y is indicated in the various examples by the polydispersity (polydispersity = molecular weight based on the weight average divided by the molecular weight based on the number average) .

When y is greater than 1, the individual R₂'s may be the same or different. For example, if y is 20, each R₂ can be alkyl of four carbon atoms. Alternatively, the R₂'s can differ and for instance, independently be alkyl from two to four carbon atoms. When the R₂'s differ, they may be present in blocks, i.e., all y groups in which R_j is alkyl of three carbon atoms will be adjacent, followed by all y groups in which R₂ is alkyl of two carbon atoms, followed by all y groups in which R₂ is alkyl of four carbon atoms. When the R₂'s differ, they may also be present in any random distribution. In the more preferred embodiments, R, and R₂ will be the same and x and y will have the same value.

R₃ and R₄ of Formula I are each independently selected from the group consisting of hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms, substituted hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms.

When R₃ and/or R₄ are hydrocarbyl or substituted hydrocarbyl, each will preferably be independently selected from hydrocarbyl or substituted hydrocarbyl of 1 to 50 carbon atoms, more preferably of 1 to 20 carbon atoms and most preferably of 1 to 10 carbon atoms. When R₃ and/or R₄ are hydrocarbyl of a relatively high number of carbon atoms, i.e., greater than about 50 carbon atoms, each will be represented by polymeric hydrocarbyls derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefin.

Preferably, R₃ and R₄ are each independently selected from hydrocarbyl of 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms and more preferably 1 to 10 carbon atoms. Particularly preferred compounds are those in which when R₃ and R₄ are hydrocarbyl, they are selected from alkyl of 1 to 20 carbon atoms, preferably alkyl of 1 to 10 carbon atoms.

R₃ and/or R₄ can also be polyoxyalkylene alcohol of 2 to 200 carbon atoms. When R₃ and/or R₄ are polyoxyalkylene alcohol, they are preferably polyoxyalkylene alcohol of Formula IV:

wherein each R, is independently selected from the group consisting of hydrocarbyl, as defined hereinbefore, of 2 to 100 carbon atoms and substituted hydrocarbyl, as defined hereinbefore, of 2 to 100 carbon atoms and z is from 1 to 50. When R is hydrocarbyl of a relatively high number of carbon atoms, i.e., greater than about 50 carbon atoms, each will be represented by polymeric hydrocarbyls derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefin. Preferably, each R, is independently selected from hydrocarbyl of 2 to 50 carbon atoms and substituted hydrocarbyl of 2 to 50 carbon atoms. More preferably, each R, is independently selected from hydrocarbyl of 2 to 20 carbon atoms and substituted hydrocarbyl of 2 to 20 carbon atoms. Preferred compounds are those in which each R, is hydrocarbyl selected from the group consisting of alkyl of 2 to 20 carbon atoms, more preferably alkyl of 2 to 4 carbon atoms, especially alkyl of 4 carbon atoms .

Particularly preferred compounds of Formula I are those in which when R₃ and/or R₄ are polyoxyalkylene alcohol of Formula IV, the R, of the polyoxyalkylene alcohol is hydrocarbyl (geminal or vicinal) of formula:

-CH_?

(VI)

wherein R₁₀, R_u and R₁₂ are each independently selected from hydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms or substituted hydrocarbyl, as defined hereinbefore, of 1 to 98 carbon atoms. Preferred R₁₀, R_u and R₁₂ groups . are those independently selected from hydrogen, hydrocarbyl of 1 to 18 carbon atoms or substituted hydrocarbyl of 1 to 18 carbon atoms. In addition, R₁₀ and R_π, or alternatively R₁₀ and R_u, may be taken together to form a divalent linking hydrocarbyl group of 3 to 12 carbon atoms. When R_I0, R_π and/or R₁₂ are substituted hydrocarbyl, the are preferably oxy- substituted hydrocarbyl.

The most preferred compounds of Formula I are those in which the Ro of the polyoxyalkylene alcohol is hydrocarbyl or substituted hydrocarbyl as represented by Formula V above wherein each R_I2 is hydrogen and each R₁₀ is independently selected from hydrogen, alkyl of 1 to 18 carbon atoms and oxy- substituted hydrocarbyl of 1 to 18 carbon atoms, particularly those compounds where each R₁₂ is hydrogen and each R_I0 is independently selected from hydrogen or alkyl of 1 to 2 carbon atoms, especially those compounds where each R₁₂ is hydrogen and each R₁₀ is alkyl of two carbon atoms .

When R₁₀ is oxy-substituted hydrocarbyl of 1 to 18 carbon atoms, R_l0 is preferably an alkoxy-substituted alkylene of 1 to 18 carbon atoms or an aryloxy-substituted alkylene of 1 to 18 carbon atoms. Particularly preferred alkoxy-substituted alkylene groups include ethylhexyleneoxymethylene , isopropoxymethylene, butoxymethylene and mixtures thereof. Particularly preferred aryl-substituted alkylene groups include nonylphenoxymethylene, phenoxymethylene and mixtures thereof.

In Formula IV above, z is from 1 to 50, preferably from 1 to 40, and even more preferably from 1 to 26. Those of ordinary skill in the art will recognize that when the compounds of Formula I which contain the polyoxyalkylene alcohols of Formula IV are used in compositions, z will not have a fixed value but will instead be represented by a range of different values. As used in this specification, z is considered to be a (number) average of the various values of z that are found in a given composition, which number has been rounded to the nearest integer. The range of z is indicated in the various examples by the polydispersity (polydispersity = molecular weight based on the weight average divided by the molecular weight based on the number average ) .

When z is greater than 1, the individual Ro's may be the same or different. For example, if z is 20, each R, can be alkyl of four carbon atoms. Alternatively, the R_o's can differ and for instance, independently be alkyl from two to four carbon atoms. When the Ro's differ, they may be present in blocks, i.e., all z groups in which R, is alkyl of three carbon atoms will be adjacent, followed by all z groups in which Ro is alkyl of two carbon atoms, followed by all z groups in which R, is alkyl of four carbon atoms. When the Ro's differ, they may also be present in any random distribution.

R₃ and R₄ may differ or R₃ and R₄ can be the same. In the most preferred embodiments, R₃ and R₄ will be the same. In one preferred embodiment, R₃ and R₄ are selected from hydrocarbyl of 1 to 100 carbon atoms. When R₃ and R₄ are hydrocarbyl, preferably the sum of the values of x and y will not exceed 40, even more preferably, the sum of the values of x and y will not exceed 26. In the preferred embodiment when R₃ and R₄ are hydrocarbyl, x will preferably be from 1 to 13 and y will preferably be from 1 to 13. In an alternative preferred embodiment, R₃ and R₄ will be polyoxyalkylene alcohol of Formula

IV. When R₃ and R₄ are polyoxyalkylene alcohol of Formula IV, preferably the sum of the values of x, y and both z'ε (the z for R₃ and _R₄) will not exceed 40, even more preferably, the sum of the values of x, y and both z's will not exceed 26. In the preferred embodiment when R₃ and R₄ are polyoxyalkylene alcohol of Formula IV, x will preferably be from 1 to 13, y will preferably be from 1 to 13 and each z will preferably be from 1 to 13. R₅ is selected from the group consisting of alkylene of 2 to 20 carbon atoms and alkylene of 2 to 20 carbon atoms having at least methylene group replaced by at least one oxygen atom or at least one acylated nitrogen atom.

When Rj is alkylene of 2 to 20 carbon atoms, the alkylene may be in any form, including straight chained alkylenes or branched chained alkylenes. For instance, R₅ can be ethylene (-CH₂-CH₂-) , propylene (~CH₂-CH₂-CH₂-) or butylene (-CH₂-

CH₂-CH₂-CH₂- or -CH₂-CH-CH₂) . Preferably, when R₅ is alkylene, it

I CH₃ will be alkylene of 2 to 10 carbon atoms, even more preferably alkylene of 2 to 4 carbon atoms. s can also be alkylene of 2 to 20 carbon atoms in which at least one methylene group is replaced by at least one oxygen atom or at least one acylated nitrogen atom. When R₅ has at least one methylene group replaced by at least one oxygen atom, R₅ will preferably be oxyalkylene having from 2 to 10 carbon atoms and from 1 to 4 oxygen atoms. When ^ is oxyalkylene it will preferably be oxyalkylene of Formula VII:

—CH2CH2OCH2CH2OCH2CH2— (VII)

When R₅ is a nitrogen-containing alkylene of 2 to 20 carbon atoms, the nitrogen-containing alkylene will preferably be of Formula VIII:

—CH2CH2NCH2CH2— (VIII)

wherein R₁₃ is alkyl of 1 to 18 carbon atoms, preferably alkyl of 1 to 8 carbon atoms and most preferably alkyl of 1 carbon atom.

The present invention is also directed to compounds of Formula I wherein R,, R₂, R₃, R₄, x and y are as defined hereinbefore .

The compounds of Formula I have a weight average molecular weight of at least 600. Preferably, the weight average molecular weight is from about 800 to about 4000, even more preferably from about 800 to about 2000. Typical compounds represented by Formula I include those listed by structure, along with the initiator used to make each, in Table 1.

Example Initiator Product

o o 0 O

II II II II

H₃C— C-N -CHj— CH₂— N -C- CH₃ H₃C-C-N-CH₂— CH₂— N-C-CH₃

H H

H(0-CH-CH₂)_x (CH₂CH-0)_yH

CH₂ CH₂

I I CH₃ CH₃

CΛ wherein x is f rom 1 to 26 and y i s f rorπ 1 to

C CD 26 .

m m m H₃C- -C-N-CH₂— CH₂- θ-CH₂-CH 0 -CH₂-CH₂-N-C-CHj

3 H H

C

HjC— C-N-CH₂— CH₂— O-CH2-CH2-O-CH₂— CH₂-N-C-CH,

(CH2— CH-θ)χ-H (CH₂-CH -θ>γ- H

CH₂ CH, CH,

wherein x is from 1 to 26 and y is from 1 to 26.

GO

03 CO

m O C m m — { c r- rπ ro

= o ^c

The compounds of Formula I are illustratively prepared by alkoxylation, i.e., reacting an initiator selected from dia ideε, triamides, polya ides, amidoalcohols and polyamidoalcohols with one or more epoxides in the presence of a potassium compound.

In one embodiment, the compounds of Formula I are prepared utilizing initiators represented by the general formula:

o o

II II

Ri6— C-N—R₁₈-N-C-R₁₇ (IX)

R-I4 Rl!

wherein R₁₄ and R₁₅ are each independently selected from the group consisting of hydrogen and hydroxyalkyls of 2 to 100 carbon atoms, R₁₆ and R,₇ are selected from the group consisting of hydrogen, hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms, substituted hydrocarbyl, as defined hereinbefore, of 1 to 100 carbon atoms and hydroxyalkyls of 2 to 100 carbon atoms and R_I8 is selected from the group consisting of alkylene of 2 to 20 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one methylene group replaced with at least one oxygen or at least one acylated nitrogen atom (note that R₁₈ is defined the same as B^ above). Preferably R₁₄ and R₁₅ are each independently selected from the group consisting of hydrogen and hydroxyalkyls of 2 to 50 carbon atoms. Even more preferably, R₁₄ and R₁₅ are each independently selected from the group consisting of hydrogen and hydroxyalkyls of 2 to 20 carbon atoms. Preferably R_I6 and R_I7 are each independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 50 carbon atoms, substituted hydrocarbyl of 1 to 50 carbon atoms and hydroxyalkyls of 2 to 50 carbon atoms. Even more preferably, R,₆ and R₁₇ are each independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 20 carbon atoms, substituted hydrocarbyl of 1 to 20 carbon atoms and hydroxyalkyls of 2 to 20 carbon atoms .

Non-limiting examples of initiators which are employed include diamides such as N,N'-ethylenebisstearamide, N,N'- bisacetamide and Diacetamide of JEFFAMINE® EDR-148; triamides such as Diethylenetriamine amide or diethylene triacetamide; polyamides such as triethylenetetramine amide and tetraethylenepentamine amide; and diamidoalcohols such as JEFFAMINE® EDR-148 gamma butyrolactone adduct; with diamidoalcohols being the most preferred. Select initiators are also available commercially, including, but not limited to, N,N'-ethylenebisstearamide (Kemanide® W-45, obtained from Witco Chemical Corporation), N,N'-ethylenebisstearamide (Kemanide® W- 40, obtained from Witco Chemical Corporation), N,N'- ethylenebisstearamide (Kemanide® W-39, obtained from Witco Chemical Corporation) and N,N'-ethylenebisoleamide (Kemanide® W- 20, obtained from Witco Chemical Corporation). The initiators may also be prepared by any of the methods known and described in the art. For example, diamides can be formed by reacting a diamine with a carboxylic acid, ester or lactones (such as gamma-butyrolactone) .

The one or more epoxides employed in the reaction with the initiators to prepare the compounds of Formula I contain from 2 to 100 carbon atoms, preferably from 2 to 50 carbon atoms, more preferably from 2 to 20 carbon atoms, most preferably from 2 to 4 carbon atoms. The epoxides may be internal epoxides such as 2,3 epoxides of the formula:

wherein R^ R₇, R₁₀ and R_π are as defined hereinbefore or terminal epoxides such as 1,2 epoxides of the formula:

H₂ C-Rg (XII) _or H₂C C- R₁₂ (XIII)

R* R 10

wherein R₆, R_g, R₁₀ and R₁₂ are as defined hereinbefore. (Note that Formulas X and XII correspond to geminal and vicinal hydrocarbyls for R, and R₂ while Formulas XI and XIII correspond to geminal and vicinal hydrocarbyls for Ro) . In both of the above formulas, any one of R^ and R₇, R₁₀ and R_π, R₆ and R₈ or R₁₀ and R₁₂, may be taken together to form a cycloalkylene epoxide or a vinylidene epoxide by forming a divalent linking hydrocarbyl group of 3 to 12 carbon atoms.

When R^, R₇, R₈, R₁₀, R_π and/or R₁₂ are oxy-substituted hydrocarbyl, suitable compounds of Formulas X, XI, XII and XIII will include compounds such as nonylphenyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, butyl glycidyl ether, alkyl C₁₂-C₁₃ glycidyl ether, alkyl C₈-C₁₀ glycidyl ether, 2- ethylhexyl glycidyl ether and isopropyl glycidyl ether. In the preferred embodiment, the terminal epoxides represented by Formulas XII and XIII are utilized. Ideally these terminal epoxides are 1 , 2-epoxyalkanes . Suitable 1,2- epoxyalkanes include 1 , 2-epoxyethane, 1 , 2-epoxypropane, 1,2- epoxybutane, 1 , 2-epoxydecane, 1, 2-epoxydodecane, 1,2- epoxyhexadecane, 1 , 2-epoxyoctadecane and mixtures thereof.

In a typical preparation of Formula I compounds , the one or more epoxides and initiator are contacted at a ratio from about 7 : 1 to about 55:1 moles of epoxide per mole of initiator. Preferably, they are contacted at a molar ratio from about 10:1 to about 30:1, with the most preferred molar ratio being about 20:1.

The reaction is carried out in the presence of potassium compounds which act as alkoxylation catalysts. Such catalysts are conventional and include potassium methoxide, potassium ethoxide, potassium hydroxide, potassium hydride and potassium-t-butoxide. The preferred catalysts are potassium hydroxide and potassium-t-butoxide. The catalysts are used in a base stable solvent such as alcohol, ether or hydrocarbons. The catalysts are employed in a wide variety of concentrations . Generally, the potassium compounds will be used in an amount from about 0.02% to about 5.0% of the total weight of the mixture, preferably from about 0.1% to about 2.0% of the total weight of the mixture, and most preferably about 0.2% of the total weight of the mixture.

The reaction is conveniently carried out in a conventional autoclave reactor equipped with heating and cooling means. The process is practiced batchwise, continuously or semicontinuously . The manner in which the alkoxylation reaction is conducted is not critical to the invention. Illustratively, the initiator and potassium compound are mixed and heated under vacuum for a period of at least 30 minutes. The one or more epoxides are then added to the resulting mixture, the reactor sealed and pressurized with nitrogen, and the mixture stirred while the temperature is gradually increased.

The temperature for alkoxylation is from about 80°C to about 180°C, preferably from about 100°C to about 150°C, and even more preferably from about 120°C to about 140°C. The alkoxylation reaction time is generally from about 2 to about 20 hours, although longer or shorter times are employed.

Alkoxylation processes of the above type are known and are described, for example in U.S. Patent No. 4,973,414, U.S. Patent No. 4,883,826, U.S. Patent No. 5,123,932 and U.S. Patent No. 4,612,335, each incorporated herein by reference.

The product of Formula I is normally liquid and is recovered by conventional techniques such as filtration and distillation. The product is used in its crude state or is purified, if desired, by conventional techniques such as aqueous extraction, solid absorption and/or vacuum distillation to remove any remaining impurities .

Other methods for making the compounds of Formula I are known by those skilled in the art. For example, the compounds of Formula I are prepared by reacting a carboxylic ester as described hereinbefore with a diaminoalcohol or diamine. In addition, other catalyst chemistry, such as the use of acidic catalysts, can be employed to achieve the compounds of Formula I . Fuel Compositions The compounds of Formula I are useful as additives in fuel compositions which are burned or combusted in internal combustion engines. The fuel compositions of the present invention comprise a major amount of a mixture of hydrocarbons in the gasoline boiling range and a minor amount of one or more of the compounds of Formula I. As used herein, the term "minor amount" means less than about 10% by weight of the total fuel composition, preferably less than about 1% by weight of the total fuel composition and more preferably less than about 0.1% by weight of the total fuel composition. Suitable liquid hydrocarbon fuels of the gasoline boiling range are mixtures of hydrocarbons having a boiling range of from about 25°C to about 232°C, and comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferred are gasoline mixtures having a saturated hydrocarbon content ranging from about 40% to about 80% by volume, an olefinic hydrocarbon content from 0% to about 30% by volume and an aromatic hydrocarbon content from about 10% to about 60% by volume. The base fuel is derived from straight run gasoline, polymer gasoline, natural gasoline, dimer and trimerized olefins, synthetically produced aromatic hydrocarbon mixtures, or from catalytically cracked or thermally cracked petroleum stocks, and mixtures of these. The hydrocarbon composition and octane level of the base fuel are not critical. The octane level, (R+M)/2, will generally be above about 85.

Any conventional motor fuel base can be employed in the practice of the present invention. For example, hydrocarbons in the gasoline can be replaced by up to a substantial amount of conventional alcohols or ethers, conventionally known for use in fuels. The base fuels are desirably substantially free of water since water could impede a smooth combustion.

Normally, the hydrocarbon fuel mixtures to which the invention is applied are substantially lead-free, but may contain minor amounts of blending agents such as methanol, ethanol, ethyl tertiary butyl ether, methyl tertiary butyl ether, and the like, at from about 0.1% by volume to about 15% by volume of the base fuel, although larger amounts may be utilized. The fuels can also contain conventional additives including antioxidants such as phenolics, e.g., 2,6-di-tert- butylphenol or phenylenediamineε , e.g., N,N'-di-sec-butyl-p- phenylenediamine, dyes, metal deactivators , dehazers such as polyester-type ethoxylated alkylphenol-formaldehyde resins. Corrosion inhibitors, such as a polyhydric alcohol ester of a succinic acid derivative having on at least one of its alpha- carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group having from 20 to 500 carbon atoms, for example, pentaerythritol diester of polyisobutylene-substituted succinic acid, the polyisobutylene group having an average molecular weight of about 950, in an amount from about 1 ppm by weight to about 1000 ppm by weight, may also be present. The fuels can also contain antiknock compounds such as methyl cyclopentadienylmanganese tricarbonyl and orthoazidophenol as well as co-antiknock compounds such as benzoyl acetone.

An effective amount of one or more compounds of Formula I are introduced into the combustion zone of the engine in a variety of ways to prevent build-up of deposits, or to accomplish the reduction of intake valve deposits or the modification of existing deposits that are related to octane requirement. As mentioned, a preferred method is to add a minor amount of one or more compounds of Formula I to the fuel . For example, one or more compounds of Formula I are added directly to the fuel or are blended with one or more carriers and/or one or more additional detergents to form an additive concentrate which can be added at a later date to the fuel.

The amount of multiple amide polyether alcohol compounds used will depend on the particular variation of Formula I used, the engine, the fuel, and the presence or absence of carriers and additional detergents. Generally, each compound of Formula I is added in an amount up to about 1000 ppm by weight, especially from about 1 ppm by weight to about 600 ppm by weight based on the total weight of the fuel composition. Preferably, the amount will be from about 50 ppm by weight to about 400 ppm by weight, and even more preferably from about 75 ppm by weight to about 250 ppm by weight based on the total weight of the fuel composition.

The carrier, when utilized, will have a weight average molecular weight from about 500 to about 5000. Suitable carriers, when utilized, include hydrocarbon based materials such as polyisobutylenes (PIB's), polypropylenes (PP's) and polyalphaolefins (PAO'ε); polyether based materials such as polybutylene oxides (poly BO'ε), polypropylene oxides (poly PO's), polyhexadecene oxides (poly HO's) and mixtures thereof (i.e., both (poly BO) + (poly PO) and (poly-BO-PO) ) ; and mineral oils such as Exxon Naphthenic 900 sus and high viscosity index (HVI) oils. The carrier is preferably selected from PIB's, poly BO's, and poly PO's, with poly BO's being the most preferred.

The carrier concentration in the final fuel composition is up to about 1000 ppm by weight. When a carrier is present, the preferred concentration is from about 50 ppm by weight to about 400 ppm by weight, based on the total weight of the fuel composition. Once the carrier is blended with one or more compounds of Formula I, the blend is added directly to the fuel or packaged for future use.

The fuel compositions of the present invention may also contain one or more additional detergents . When additional detergents are utilized, the fuel compoεition will comprise a mixture of a major amount of hydrocarbons in the gasoline boiling range as described hereinbefore, a minor amount of one or more compounds of Formula I as described hereinbefore and a minor amount of an additional detergent such as polyalkylenyl amines, Mannich amines, polyalkenyl succinimides , poly(oxyalkylene) carbamateε, poly(alkenyl )-N-substituted carbamateε and mixtures thereof. As noted above, a carrier as described hereinbefore may also be included. As used herein, the term "minor amount" means less than about 10% by weight of the total fuel composition, preferably less than about 1% by weight of the total fuel composition and more preferably less than about 0.1% by weight of the total fuel composition. The polyalkylenyl amine detergents utilized comprise at least one monovalent hydrocarbon group having at least 50 carbon atoms and at least one monovalent hydrocarbon group having at most five carbon atoms bound directly to separate nitrogen atoms of a diamine. Preferred polyalkylenyl amines are polyisobutenyl amines. Polyisobutenyl amines are known in the art and representative examples are diεclosed in various U.S. Patents including U.S. Patent No. 3,753,670, U.S. Patent No. 3,756,793, U.S. Patent No. 3,574,576 and U.S. Patent No. 3,438,757, each incorporated herein by reference. Particularly preferred polyisobutenyl amines for use in the present fuel composition include N-polyisobutenyl-N' ,N'-dimethyl-l, 3- dia inopropane (PIB-DAP) and OGA-472 (a polyisobutenyl ethylene diamine available commercially from Oronite) .

The Mannich amine detergents utilized comprise a condensation product of a high molecular weight alkyl- substituted hydroxyaromatic compound, an amine which contains an amino group having at least one active hydrogen atom (preferably a polyamine), and an aldehyde. Such Mannich amines are known in the art and are disclosed in U.S. Patent No. 4,231,759, incorporated herein by reference. Preferably, the Mannich amine is an alkyl substituted Mannich amine.

The polyalkenyl εuccinimide detergents comprise the reaction product of a dibasic acid anhydride with either a polyoxyalkylene diamine, a hydrocarbyl polyamine or mixtures of both. Typically the succinimide is subεtituted with the polyalkenyl group but the polyalkenyl group may be found on the polyoxyalkylene diamine or the hydrocarbyl polyamine. Polyalkenyl succinimides are also known in the art and representative examples are disclosed in various U.S. Patents including U.S. Patent No. 4,810,261, U.S. Patent No. 4,852,993, U.S. Patent No. 4,968,321, U.S. Patent No.4, 985, 047 , U.S. Patent No. 5,061,291 and U.S. Patent No. 5,147,414, each incorporated herein by reference.

The poly(oxyalkylene) carbamate detergents comprise an amine moiety and a poly(oxyalkylene) moiety linked together through a carbamate linkage, i.e.,

—O-C(O)— — (XIV)

These poly(oxyalkylene) carbamates are known in the art and representative examples are disclosed in various U.S. Patents including, U.S. Patent No. 4,191,537, U.S. Patent No. 4,160,648, U.S. Patent No. 4,236,020, U.S. Patent No. 4,270,930, U.S. Patent No. 4,288,612 and U.S. Patent No. 4,881,945, each incorporated herein by reference. Particularly preferred poly(oxyalkylene) carbamateε for use in the present fuel composition include OGA-480 (a poly(oxyalkylene) carbamate which is available commercially from Oronite).

The poly( alkenyl )-N-subεtituted carbamate detergents utilized are of the formula:

(XV)

R-A-C-ORi

in which R iε a poly( alkenyl ) chain; R¹ is a hydrocarbyl or subεtituted hydrocarbyl group; and A iε an N-substituted amino group. Poly(alkenyl )-N-substituted carbamates are known in the art and are disclosed in U.S. Patent No. 4,936,868, incorporated herein by reference.

The one or more additional detergents are added directly to the hydrocarbons, blended with one or more carriers, blended with one or more compounds of Formula I, or blended with one or more compounds of Formula I and one or more carriers before being added to the hydrocarbons .

The concentration of the one or more additional detergents in the final fuel composition is generally up to about 1000 ppm by weight for each additional detergent. When one or more additional detergents are utilized, the preferred concentration for each additional detergent is from about 50 ppm by weight to about 400 ppm by weight, based on the total weight of the fuel composition, even more preferably from about 75 ppm by weight to about 250 ppm by weight, based on the total weight of the fuel composition. Engine Tests

Decreasing Intake Valve Deposits

The invention further provides a procesε for decreaεing intake valve deposits in engines utilizing the multiple amide polyether alcohols of the present invention. The process comprises supplying to and combusting or burning in an internal combustion engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of one or more compounds of Formula I as described hereinbefore.

By supplying to and combusting or burning the fuel composition in an internal combustion engine, deposits in the induction system, particularly deposits on the tulips of the intake valves, are reduced. The reduction is determined by running an engine with clean induction system components and pre-weighed intake valves on dynamometer test stands in such a way as to simulate road operation using a variety of cycles at varying speeds while carefully controlling specific operating parameterε . The tests are run for a specific period of time on the fuel composition to be tested. Upon completion of the test, the induction system depoεits are visually rated, the valves are reweighed and the weight of the valve depoεits is determined. Controlling Octane Requirement Increaseε

The invention further provides a process for controlling octane requirement increaseε in engines utilizing the multiple amide polyether alcohols of the present invention. The procesε compriεeε supplying to and combusting or burning in an internal combustion engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of one or more compounds of Formula I as described hereinbefore.

Octane requirement is the maximum octane number of a gasoline that presents trace knock in a given engine within the engine's normal operating range. An increase in octane requirement is generally experienced during mileage accumulation on a new engine. The increase is typically attributed to an increase in engine deposits. Octane requirement increase control iε a performance feature that iε usually expressed as a comparison of the octane requirement increase developed with a gasoline containing additives (test gasoline) relative to a version of the same gasoline without additives (base gasoline), i.e., the positive difference obtained by subtracting the results of gasoline containing additives from gasoline which does not contain additives. The test protocol for octane requirement increase control must establish the stable octane requirement of the base gasoline relative to a clean engine. Base gasoline is typically the teεt gasoline without additives or special treatment; however, it may be gasoline containing additives for a specific compariεon. Octane requirement increaεe control testing consists of operating an engine aεεembled with clean combuεtion chambers and induction εyεtem componentε on a test gasoline to octane stabilization, measuring the octane requirement at regular intervals. The octane requirement increase control is the difference between the stabilized octane requirement of the engine operated on test gasoline and that of the stabilized octane requirement of the engine on base gasoline. Reduction of Octane Requirement

The invention still further provides a process for reducing octane requirement in engines utilizing the multiple amide polyether alcohols of the present invention. The process comprises supplying to and combusting or burning in an internal combustion engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of one or more compounds of Formula I as described hereinbefore.

Octane requirement reduction is the reduction of the octane requirement of an engine by the action of a particular gasoline, usually measured as a decrease from a stabilized octane requirement condition. Octane requirement reduction is a performance feature that demonstrates a reduction from the established octane requirement of a base gasoline in a given engine. Octane requirement reduction testing consists of operating an engine, which has achieved εtable octane requirement using base gasoline, on a test gasoline for approximately 100 to 250 hours. Octane meaεurementε are made daily and octane requirement reduction iε a reduction of octane requirement from that of base gasoline . Several octane requirement reduction tests may be conducted in a series for fuel to fuel comparison, or test fuel to base fuel comparison, by reεtabilizing on base fuel between octane requirement reduction tests.

The contribution of specific depoεits is determined by removing deposits of interest and remeasuring octane requirement immediately after the engine is warmed to operating temperature.

The octane requirement contribution of the deposit is the difference in ratings before and after deposit removal.

The ranges and limitations provided in the instant specification and claims are thoεe which are believed to particularly point out and diεtinctly claim the instant invention. It is, however, understood that other ranges and limitations that perform substantially the same function in substantially the same way to obtain the same or substantially the same result are intended to be within the scope of the instant invention as defined by the instant specification and claims . The invention will be described by the following examples which are provided for illustrative purposes and are not to be construed as limiting the invention. Exampleε Compound Preparation

The multiple amide polyether alcohols used in the following examples were prepared by reacting an initiator with one or more epoxides in the presence of a potassium compound to produce compounds of Formula I having a weight average molecular weight from about 600 to about 4000. The weight average molecular weight (MW) was measured by gel permeation chromatography (GPC). Rotary evaporation under reduced pressure typically was conducted at a temperature from room temperature to 120°C. Example 1

Step 1-Preparation of Initiator

Gamma-butyrolactone (180 g, 2.1 moleε) waε added to a 4- necked, round bottomed flask, equipped with a mechanical stirrer, nitrogen inlet line, temperature controller, heating mantle and Dean-Stark trap. While stirring, JEFFAMINE® EDR-148 (a triethyleneglycol diamine manufactured by Texaco Chemical Company, 148 g, 1.0 mole) was added. The mixture was heated to 139°C-157°C for three hours. A low melting, white solid was obtained. C¹³ NMR analysis showed 90% amide formation and approximately 5% unreacted amine and 5% unreacted gamma-butyrolactone. The product was used without further purification. Step 2-Butoxylation of Initiator

The Initiator from Step 1 (80 g) was mixed with potasεium hydroxide (1.7 g in 1.78 water) and then εubjected to rotary evaporation under reduced preεεure at 80°C to remove water and form potaεεium salt. The mixture was then charged along with 1,2-epoxybutane (320 g, 4.4 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged of air with nitrogen and then presεurized to 50 pεi with nitrogen at room temperature. The mixture waε then heated to a temperature of 135°C-140°C for 6 hourε . During the reaction, the pressure ranged from 125 psi to 64 psi. The autoclave reactor was then cooled to room temperature and excess gas was vented. The final product, a light colored liquid which is soluble in gasoline, was achieved by removing unreacted light material from the crude product by first subjecting the product to rotary evaporation under reduced pressure followed by water extraction and then repeating rotary evaporation. GPC analysis showed MW=1190 and a polydispersity of 1.10. Example 2 The initiator of Step 1 of Example 1 (JEFFAMINE® 148-gamma butyrolactone adduct, 95 g) was mixed with potassium hydroxide (1.7 g in 1.7 g water) and then subjected to rotary evaporation under reduced pressure to remove water and form potassium salt. The mixture was then charged along with 1,2-epoxybutane (505 g, 7.01 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor waε sealed, purged of air with nitrogen and then preεεurized to 50 psi with nitrogen at room temperature. The mixture was then heated to a temperature of 137°C-140°C for 5 hours. The autoclave reactor was then cooled to room temperature and excess gas was vented. The crude product subjected to rotary evaporation under reduced pressure followed by water extraction and then rotary evaporation was repeated in order to remove unreacted light material from the crude product. GPC analysis of the final product showed MW=1340 and a polydisperεity of 1.14. Example 3 Step 1-Preparation of Initiator Ethylene diamine (108 g, 1.8 moles) and ethyl acetate (475 g, 5.4 moles) were charged into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling εyεtem. The autoclave reactor waε εealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature. The mixture was heated to 200°C for 6 hours. The autoclave reactor was then cooled to room temperature and excess gas was vented. The product was then subjected to rotary evaporation under reduced pressure to remove unreacted ethyl acetate. A light yellow solid (N,N'~ ethylene bis-acetamide) showing 100% yield and purity by NMR analysis was obtained. Step 2-Butoxylation of Initiator

The initiator of Step 1 (56 g, 0.25 mole), toluene (150 g) and potassium-t-butoxide (2.3 g) was subjected to rotary evaporation under reduced pressure at 80°C. The resulting mixture was then charged along with 1,2-epoxybutane (344 g, 4.8 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged of air with nitrogen and then presεurized to 50 pεi with nitrogen at room temperature. The mixture waε then heated to a temperature of 134°C-142°C for 10 hourε . The autoclave reactor was then cooled to room temperature, excess gas was vented and the crude product was recovered. The crude product was subjected to rotary evaporation under reduced pressure, water washed and then subjected to rotary evaporation again to achieve a brown liquid final product (310 g) . GPC analysis showed MW=837 and a polydispersity of 1.04. Example 4

The initiator of Step 1 of Example 3 (Ethylenediamine diacetamide, 67 g) , potasεium-t-butoxide (3.1 g) and toluene (50 g) were mixed and subjected to rotary evaporation under reduced pressure to remove water and form potassium salt. The mixture was then charged along with 1,2-epoxybutane (533 g, 7.4 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature. The mixture was then heated to 125°C-129°C for 7 hours. The autoclave reactor was then cooled to room temperature, excesε gaε waε vented and the crude product was recovered. The crude product was subjected to rotary evaporation under reduced pressure, water washed and then rotary evaporation was repeated to achieve a final product which was confirmed by NMR. GPC analysis showed MW=1070 and a polydispersity of 1.03. Example 5

Step 1-Preparation of Initiator

Diethylene triamine (103 g, 1.0 moles) and ethyl acetate (396 g, 4.5 moles) were charged into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical εtirrer and water cooling system. The autoclave reactor was sealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature. The mixture was heated to 198°C for 6 hours. The autoclave reactor waε allowed to cool to room temperature and excess gas was vented. The product was then subjected to rotary evaporation under reduced pressure to remove unreacted ethyl acetate. A dark brown semiεolid product (201 g) εhowing 95% yield and purity by NMR analysis was obtained. Step 2-Butoxylation of Initiator The initiator of Step 1 (diethylene triacetamide, 82 g, 0.35 mole), potasεium hydroxide (2.4 g in 2.0 g water) and toluene (10 g) were mixed and εubjected to rotary evaporation under reduced pressure to remove water and form potassium salt. The mixture was then charged along with 1,2-epoxybutane (514 g, 7.1 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged of air with nitrogen and then pressurized to 50 psi with nitrogen at room temperature. The mixture was then heated to a temperature of 114°C-120°C for 12 hours. The autoclave reactor was then cooled to room temperature, excess gas was vented and crude product was recovered. The crude product was subjected to rotary evaporation under reduced presεure, water waεhed and then rotary evaporation was repeated to achieve a yellow, transparent, liquid product. GPC analysis showed MW=1260 and a polydispersity of 1.05. Example 6

Step 1-Preparation of Initiator JEFFAMINE® EDR-148 (obtained from Texaco Chemical Company, 148 g, 1.0 mole) and ethyl acetate (264 g, 3.0 moles) were charged into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature. The mixture was heated to 200°C for six hours. The autoclave reactor was then allowed to cool to room temperature and excess gas was vented. The resulting product was εubjected to rotary evaporation under reduced preεsure to remove unreacted ethyl acetate. A solid crystalline diamide (222 g) showing 97% purity by NMR analysiε waε obtained. Step 2- Butoxylation of Initiator

A mixture of the Initiator of Step 1, (Diacetamide of JEFFAMINE® EDR-148, 73.5 g, 0.375 mole), potaεεium hydroxide (2.4 g in 2.0 g water) and toluene (10 g) waε subjected to rotary evaporation under reduced pressure to remove water and form potaεεium salt. The resulting mixture was charged along with 1,2-epoxybutane (527 g, 7.3 moles) into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged of air with nitrogen and pressurized with nitrogen to 50 psi at room temperature. The mixture was then heated to 122°C-135°C for seven hours. The autoclave reactor waε then cooled to room temperature, excess gas was vented and the crude product recovered. The crude product was subjected to rotary evaporation under reduced presεure, washed with water and then subjected to rotary evaporation again to achieve a light yellow liquid product (553 g) confirmed by NMR analysis. GPC analysis showed MW=1510 and a polydispersity of 1.04. Example 7

A mixture of N,N'-ethylenebiεsteramide (Kenamide® W-40 from Witco Chemical Corporation, 148 g, 0.25 mole, solid material with a melting point of 140°C), potasεium-t- butoxide (2.8 g) and 1,2-epoxybutane (352 g, 4.9 moles) was directly charged into a one liter autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor waε εealed, purged of air with nitrogen and presεurized with nitrogen to 52 psi at room temperature. The mixture was then heated to 122°C-130°C for 6.5 hourε . During the reaction, the pressure ranged from 129 psi to 70 psi. The autoclave reactor was cooled to room temperature, excess gas was vented and the crude product recovered. The crude product was subjected to rotary evaporation under reduced preεsure, water washed and then subjected to rotary evaporation again to give a light color liquid product which waε εoluble in gasoline. GPC analyεis showed MW=1490 and a polydispersity of 1.05. Test Results

In each of the following tests, the base fuel utilized comprised either premium unleaded gasoline (PU) (90+ octane, [R+M/2]) and/or regular unleaded gasoline (RU) (85-88 octane, [R+M/2]). Those skilled in the art will recognize that fuels containing heavy catalytically cracked stockε, such as most regular fuels, are typically more difficult to additize in order to control deposits and effectuate octane requirement reduction and octane requirement increase control. The multiple amide polyether alcohol compounds utilized were prepared as indicated by Example number and were used at the concentration indicated in ppm by weight. The tests employed are described below and the results of the various testε are εet forth in the tableε below.

Intake Valve Deposit Testε Engineε from vehicles were installed in dynamometer cells in such a way as to simulate road operation using a cycle of idle, low speed and high speed components while carefully controlling specific operating parameters. Fuels with and without the compounds of Formula I were tested in a variety of engines having port fuel injection including a 3.3 L Dodge to determine the effectiveness of the instant compounds in reducing intake valve deposits ("L" refers to liter). Carbureted 0.359 L Honda generator engines were also utilized to determine the effectiveness of the instant compounds in reducing intake valve deposits . Before each test, the engine was inspected, the induction system components were cleaned and new intake valves were weighed and installed. The oil was changed and new oil and fuel filters, gaskets and spark plugε were installed.

In all engines except the Honda, the tests were run in cycles consisting of idle, 35 mph and 65 mph for a period of 100 hours unless indicated otherwise. In the Honda engines, the tests were run in cycles consisting of a no load idle mode for one minute followed by a three minute mode with a load at 2200 rpm's for a period of 40 hourε unleεs indicated otherwise. At the end of each teεt, the intake valves were removed and weighed.

Intake valve deposit results from Honda generator engines and 3.3 L Dodge engines obtained using the multiple amide polyether alcohols of the present invention are included in the tables below. All testε of the compoundε of the preεent invention were carried out with additive concentrationε (the amount of Compound Example # used) of 200 parts per million (ppm) non-volatile matter (nv ) except where otherwise indicated. Base fuel results which have 0 ppm additive are also included for comparision purposes. The base fuel are indicated by the absence of a Compound Example # (indicated in the Compound Example # column by " —").

TABLE 2

Intake Valve Depoisits in Honda Generator Engines

Compound ConcentraAveraqe Example tion, ppm Deposit # Fuel Engine By Weight Wt . , mo

1 PU H3A 200 19.0

0 39.2 7 RU H3C 200 40.2 * 0 45.9

—Indicates the resultε achieved with baεe fuel in the absence of any additive compound (0 ppm additive compound).

*Indicates that this was an average of 4 runs in the same base fuel in other Honda generator engines.

TABLE 3 Intake Valve Deposits in Various Engines

Compound Concentra- Average

Example tion, ppm Deposit # Fuel Engine By Weight Wt . , mg

3 PU 3.3 L 200 118.2

Dodge * " 0 250.0

—Indicates the results achieved with base fuel in the absence of any additive compound (0 ppm additive compound).

*Indicates that this was an average of 3 runs of similar base fuels in the same engine.

Claims

WHAT IS CLAIMED IS:

1. A fuel composition comprising a mixture of a major amount of hydrocarbons in the gaεoline boiling range and a minor amount of an additive compound of the formula:

O O

R₃ C N R₅ N C R₄ (I)

(Rl—O)χ—H (R₂—O)y—H

wherein R, and R₂ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to 100 carbon atoms; R₃ and R₄ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms; R₅ is selected from the group consisting of alkylene of 2 to 20 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced by at least one oxygen atom or at least one nitrogen atom; x is from 1 to 50; y is from 1 to 50 and the weight average molecular weight is at least about 600.

2. The fuel composition of claim 1 wherein said additive compound is present in an amount from about 50 ppm by weight to about 400 ppm by weight of the fuel composition.

3. The fuel composition of claim 2 wherein the weight average molecular weight of the additive compound is from about 800 to about 4000.

4. The fuel composition of claim 3 wherein R, and R₂ are each hydrocarbyl of the formula:

wherein each R^ is independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms and each R₈ is independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms.

5. The fuel composition of claim 4 wherein Rg and R₈ are each independently selected from the group consisting of hydrogen and hydrocarbyl comprising alkyl of 1 to 2 carbon atoms .

6. The fuel composition of claim 5 wherein R₃ and R₄ are each independently selected from hydrocarbyl of 1 to 20 carbon atoms .

7. The fuel compoεition of claim 6 wherein R₃ and R₄ are each independently selected from hydrocarbyl comprising alkyl of 1 to 20 carbon atoms; R₅ is alkylene of 2 to 10 carbon atoms; x is from 1 to 26; and y iε from 1 to 26.

8. The fuel compoεition of claim 4 wherein R^ and R₈ are each independently εelected from the group conεisting of hydrogen and hydrocarbyl comprising alkyl of 1 to 2 carbon atoms; R₃ and R₄ are each hydrocarbyl of 1 carbon atom; R₅ is alkylene of 2 carbon atoms; x iε from 1 to 26 and y is from 1 to 26.

9. The fuel composition of claim 4 wherein R₃ and R₄ are each independently selected from polyoxyalkylene alcohol of 2 to 200 carbon atoms.

10. The fuel composition of claim 9 wherein R₃ and R₄ are each polyoxyalkylene of the formula:

wherein each R, is independently selected from the group consisting of hydrocarbyl of 2 to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbon atoms and z is from 1 to 50.

11. The fuel composition of claim 10 wherein each R_o is independently selected from hydrocarbyl of the formula:

wherein each R₁₀ iε independently εelected from the group consisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms and each R₁₂ is independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms.

12. The fuel compoεition of claim 11 wherein R₅ alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced by at least one oxygen atom.

13. The fuel composition of claim 12 wherein each R„, R₈, R₁₀ and R₁₂ are independently εelected from the group consisting of hydrogen and hydrocarbyl comprising alkyl of 1 to 2 carbon atoms; R₅ is alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced by at least one oxygen atom of the formula: —CH2CH2OCH2CH2OCH2CH2—

x is from 1 to 26; y is from 1 to 26; and each z is from 1 to 26.

14. A method for decreasing intake valve deposits in an internal combustion engine which comprises burning in said engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of an additive compound of the formula:

O O

R₃ C ^■N R₅ -N -R4 (D

(Ri—O)x—H (R₂—O)y—H

wherein R, and R₂ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to 100 carbon atoms; R₃ and R₄ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms; R₅ is selected from the group consisting of alkylene of 2 to 10 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced by at least one oxygen atom or at least one acylated nitrogen atom; x is from 1 to 50; y is from 1 to 50 and the weight average molecular weight iε at leaεt about 600.

15. The method of claim 14 wherein εaid additive compound is present in an amount from about 50 ppm by weight to about 400 ppm by weight of the fuel composition.

16. The method of claim 15 wherein weight average molecular weight of the additive compound is from about 800 to about 4000.

17. The method of claim 16 wherein R, and R₂ are each hydrocarbyl of the formula:

wherein each R^ is independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms and each R₈ is independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms and subεtituted hydrocarbyl of 1 to 18 carbon atomε .

18. The method of claim 17 wherein R₆ and R₈ are each independently selected from the group consisting of hydrogen and hydrocarbyl comprising alkyl of 1 to 2 carbon atoms.

19. The method of claim 18 wherein R₃ and R₄ are each independently selected from hydrocarbyl of 1 to 20 carbon atoms.

20. The method of claim 19 wherein R₃ and R₄ are each independently selected from hydrocarbyl comprising alkyl of 1 to 20 carbon atoms; R₅ is alkylene of 2 to 10 carbon atoms; x is from 1 to 26; and y is from 1 to 26.

21. The method of claim 17 wherein B^ and R₈ are each independently selected from the group conεisting of hydrogen and hydrocarbyl comprising alkyl of 1 to 2 carbon atoms; R₃ and R₄ are each hydrocarbyl of 1 carbon atom; R₅ is alkylene of 2 carbon atoms; x is from 1 to 26 and y is from 1 to 26.

22. The method of claim 17 wherein R₃ and R₄ are each independently selected from polyoxyalkylene alcohol of 2 to 200 carbon atoms .

23. The method of claim 22 wherein R₃ and R₄ are each polyoxyalkylene of the formula: wherein each R, is independently selected from the group consisting of hydrocarbyl of 2 to 100 carbon atoms and substituted hydrocarbyl of 2 to 100 carbon atoms and z is from 1 to 50.

24. The method of claim 23 wherein each R, is independently selected from hydrocarbyl of the formula:

wherein each R₁₀ is independently selected from the group consisting of hydrogen, hydrocarbyl of 1 to 18 carbon atoms and substituted hydrocarbyl of 1 to 18 carbon atoms and each R_u is independently selected from the group consiεting of hydrogen, hydrocarbyl of 1 to 18 carbon atomε and εubstituted hydrocarbyl of 1 to 18 carbon atoms.

25. The method of claim 24 wherein R₅ alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced by at least one oxygen atom.

26. The method of claim 25 wherein each R₆, R₈, R₁₀ and R_I2 are independently selected from the group consisting of hydrogen and hydrocarbyl comprising alkyl of 1 to 2 carbon atoms; R₅ is alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced by at least one oxygen atom of the formula:

—CH₂CH2θCH2CH₂OCH₂CH2—

x is from 1 to 26; y is from 1 to 26; and each z iε from 1 to 26.

27. A method for controlling the octane requirement increase in an internal combustion engine which comprises burning in said engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of an additive compound of the formula:

O O

R₃ C N R₅ N C R4 (I)

(Rl—O)x—H (R₂—O)y—H

wherein R_t and R₂ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to 100 carbon atoms; R₃ and R₄ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms; R₅ is selected from the group consisting of alkylene of 2 to 10 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one of the alkylene groups replaced with one oxygen atom or at least one nitrogen atom; x is from 1 to 50; y is from 1 to 50; and the weight average molecular weight is at least about 600.

28. A method for reducing octane requirement in an internal combustion engine which comprises burning in said engine a fuel composition comprising a major amount of hydrocarbons in the gasoline boiling range and a minor amount of an additive compound of the formula:

O

R₃- -N Rs -N -R4 (D

(Rl—O)x-H (R₂—O)y—H

wherein R, and R₂ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to 100 carbon atoms; R₃ and R₄ are each independently selected from the group conεiεting of hydrocarbyl of 1 to 100 carbon atomε, εubstituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms; R₅ is selected from the group consisting of alkylene of 2 to 10 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced with at least one oxygen atom or at least one acylated nitrogen atom; x is from 1 to 50; y is from 1 to 50; and the weight average molecular weight is at least about 600.

29. A compound of the formula:

O

R —C ^■N R₅ -N -R4 (D

(Rl—O)x—H (R₂—O)y—H

wherein R, and R_j are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms and substituted hydrocarbyl of 1 to 100 carbon atoms; R₃ and R₄ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon ato ε, substituted hydrocarbyl of 1 to 100 carbon atomε and polyoxyalkylene alcohol of 2 to 200 carbon atoms; R^ iε εelected from the group consisting of alkylene of 2 to 10 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced with at least one oxygen atom or at least one acylated nitrogen atom; x is from 1 to 50; and y is from 1 to 50.

30. fuel composition comprising a mixture of:

(a) a major amount of hydrocarbons in the gasoline boiling range;

(b) a minor amount of an additive compound having the general formula:

O O

R₃- ^■N Rs -N -R4 (D

(Rl—O)x—H (R₂—O)y—H

wherein R, and R₂ are each independently selected from the group consiεting of hydrocarbyl of 1 to 100 carbon atoms and subεtituted hydrocarbyl of 1 to 100 carbon atoms; R₃ and R₄ are each independently selected from the group consisting of hydrocarbyl of 1 to 100 carbon atoms, substituted hydrocarbyl of 1 to 100 carbon atoms and polyoxyalkylene alcohol of 2 to 200 carbon atoms; R_j iε εelected from the group consiεting of alkylene of 2 to 10 carbon atoms and alkylene of 2 to 20 carbon atoms having at least one of the methylene groups replaced with at least one oxygen atom or at least one acylated nitrogen atom; x is from 1 to 50; y is from 1 to 50; and the weight average molecular weight is at least about 600; and

(c) a minor amount of an additional detergent selected from the group consisting of polyalkylenyl amines, mannich amines, polyalkenyl succinamides , poly(oxyalkylene) carbamates, poly(alkenyl) -N-substituted carbamates and mixtures thereof.