KR20000049097A - Fuel compositions - Google Patents

Abstract

PURPOSE: Multiple amide polyether alcohol compounds as additives of fuel compositions are provided which decrease intake valve deposits when used as gasoline additives. CONSTITUTION: A multiple amide polyether alcohol compounds are represented by 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.

Description

Fuel compositions

Deposition on the intake valve of the internal combustion engine is also a problem. Accumulation of such deposits is generally characterized by poor driveability and coarse engine idle, including difficulty starting, stall, and malfunctioning during acceleration.

Can be added to the hydrocarbon fuel in the fuel chamber or on adjacent surfaces such as intake valves, ports and flame plugs, or to remove or modify deposits formed and to reduce octane requirements. Many additives are known.

In the design of internal combustion engines, such as fuel injector and carburetor engines, environmental changes in these engines are creating a continuing need for new additives to control problems with injection system deposits and to improve the driveability associated with deposits.

It is advantageous to have a fuel composition that reduces the formation of deposits in today's engines burning hydrocarbon fuels and reforms existing deposits associated with increased octane requirements and inferior driveability in modern engines burning hydrocarbon fuels.

Summary of the Invention

The present invention relates to the use of a multi amide polyether alcohol compound as an additive in a fuel composition comprising a major amount of gasoline boiling range hydrocarbon mixture and a small amount of at least one of the multi amide polyether alcohols of formula (I).

In Formula I,

R ₁ and R ₂ are each independently selected from the group consisting of hydrocarbyl having 2 to 100 carbon atoms and substituted hydrocarbyl having 2 to 100 carbon atoms,

R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms, substituted hydrocarbyl having 1 to 100 carbon atoms and polyoxyalkylene alcohol having 2 to 200 carbon atoms,

R ₅ is selected from the group consisting of alkylene having 2 to 20 carbon atoms and at least one group of methylene groups substituted with at least one oxygen atom or at least one acylated nitrogen atom;

x and y are each a number from 1 to 50.

The present invention also relates to the use of multiple amide polyether alcohol compounds to reduce intake valve deposits, control octane demand increase and reduce octane demand. The present invention also relates to multiple amide polyether alcohol compounds.

The present invention relates to the use of multiple amide polyether alcohol compounds as additives in fuel compositions, and to the use of such compounds to reduce intake valve deposits, control octane demand increases and reduce octane requirements. The present invention also relates to multiple amide polyether alcohol compounds.

In a broad sense, the compounds of the present invention, which can be represented by multi amide alkoxylates, are useful for hydrocarbon fuels, for example fuels in the gasoline boiling range and not only prevent deposit formation in the engine, but also environmentally during combustion. It relates to a new class of additives that degrade the product to an acceptable level. The compounds are proposed for the purpose of controlling the increase in octane requirements and reducing the octane requirements. The compound produces only a very small amount of residues and is miscible with carriers and other detergents. Exemplary embodiments of compounds useful as additives in the present invention include, but are not limited to, compounds of formula (I)

Formula I

In Formula I,

R ₁ and R ₂ are each independently selected from the group consisting of hydrocarbyl having 2 to 100 carbon atoms and substituted hydrocarbyl having 2 to 100 carbon atoms;

x and y are each a number from 1 to 50.

In the above formula (I), when R ₁ and / or R ₂ are hydrocarbyl having a relatively high carbon number, for example at least about 50 carbon atoms, they are each a polymer derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefin, respectively. It can be represented as a sex hydrocarbyl.

As used herein, the term “hydrocarbyl” is a radical formed by removing one or more hydrogen atoms from the carbon atoms of a hydrocarbon (not necessarily of the same atom). Useful hydrocarbyls are aliphatic, aromatic, acyclic or cyclic hydrocarbyls. Preferably, the hydrocarbyl is aryl, alkyl, alkenyl or cycloalkyl and is straight or branched chain. Representative hydrocarbyls are methyl, ethyl, butyl, pentyl, methylpentyl, hexenyl, ethylhexyl, dimethylhexyl, octamethylene, octenylene, cyclooctylene, methylcyclooctylene, dimethylcyclooctyl, isooctyl, dodecyl, hexa Decenyl, octyl, eicosyl, hexacosyl, triacontyl and phenylethyl. As noted, the hydrocarbyl used may be substituted. As used herein, the term "substituted hydrocarbyl" includes functional groups such as carbonyl, carboxyl, nitro, amino, hydroxy (e.g. hydroxyethyl), oxy, cyano, sulfonyl and sulfoxyl. Refers to any "hydrocarbyl". Most of the atoms, except hydrogen, in the substituted hydrocarbyl are carbon, and the heteroatoms (ie, oxygen, nitrogen, sulfur) account for only a small amount, ie up to 33% of the total non-hydrogen atoms present.

Preferably, R ₁ and R ₂ are each selected from hydrocarbyl having 2 to 50 carbon atoms and substituted hydrocarbyl having 2 to 50 carbon atoms. More preferably, R ₁ and R ₂ are each selected from hydrocarbyl having 2 to 20 carbon atoms and substituted hydrocarbyl having 2 to 20 carbon atoms. Particularly preferred compounds are those in which R ₁ and R ₂ are each independently selected from the group consisting of alkyl having 2 to 20 carbon atoms, more preferably alkyl having 2 to 4 carbon atoms, particularly preferably alkyl having 4 carbon atoms.

Particularly preferred compounds of formula I are those wherein R ₁ and R ₂ are hydrocarbyl (identical or neighboring sites) of formula II or formula III.

In Chemical Formulas II and III,

R ₆ , R ₇ and R ₈ are each independently selected from the group consisting of hydrogen, hydrocarbyl as defined above having 1 to 98 carbon atoms and substituted hydrocarbyl as defined above having 1 to 98 carbon atoms.

Preferred groups of R ₆ , R ₇ and R ₈ are independently selected from hydrogen, hydrocarbyl having 1 to 18 carbon atoms and substituted hydrocarbyl having 1 to 18 carbon atoms. In addition, R ₆ and R ₇ , or optionally R ₆ and R ₈ together form a divalent bonded hydrocarbyl group having 3 to 12 carbon atoms. When R ₆ , R ₇ and / or R ₈ are substituted hydrocarbyls they are preferably oxy-substituted hydrocarbyls.

Most preferred compounds of formula I are hydrocarbyl and substituted hydrocarbyl, wherein R ₁ and R ₂ may each be represented as formula II as defined above, wherein each R ₈ is hydrogen and each R ₆ is hydrogen, having from 1 to 18 carbon atoms Are independently selected from alkyl and oxy substituted hydrocarbyl having 1 to 18 carbon atoms, particularly preferably each R ₈ is hydrogen and each R ₆ is independently hydrogen or alkyl having 1 to 2 carbon atoms, more particularly preferred Preferably each R ₈ is hydrogen and each R ₆ is alkyl of 2 carbon atoms.

When R ₆ is an oxy-substituted hydrocarbyl having 1 to 18 carbon atoms, R ₆ is preferably alkoxy-substituted alkylene having 1 to 18 carbon atoms or aryloxy-substituted alkylene having 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 the general formula (I), x is 1 to 50, preferably 1 to 40, more preferably 1 to 26. One skilled in the art will recognize that when a compound of Formula I is used in this composition, x does not have a fixed value and has a range of different values. As used herein, x is considered as the mean value (number) of the various x values measured in a given composition, which is the ambient value of the most recent integer. The range of x is indicated in various examples by polydispersity (polydispersity = molecular weight based on weight average divided by molecular weight based on number average).

When x is greater than 1, each R ₁ ′ may be the same or different. For example, when x is 20, each R ₁ may be alkyl having 4 carbon atoms. Optionally, R ₁ ′ can be different, for example independently can be alkyl having 2 to 4 carbon atoms. When R ₁ ′ is different, it may be present in the form of a block, for example, all x groups in which R ₁ is alkyl having 3 carbon atoms are adjacent to each other, and then there are all x groups in which R ₁ is alkyl having 2 carbon atoms, Then there are all x groups in which R ₁ is alkyl having 4 carbon atoms. If R ₁ ′ is different they may also be present in any irregular distribution.

In the general formula (I), each y is 1 to 50, preferably 1 to 40, more preferably 1 to 26. Those skilled in the art will appreciate that when compounds of formula I are used in the composition, y does not have a fixed value and has a range of different values. As used herein, y is the average of the various values of y measured in a given composition (considered to be a number and this number is the ambient value of the most recent integer). The range of y is polydispersity (polydispersity = Molecular weight based on weight average value divided by molecular weight based on number average).

When y is greater than 1, each R ₂ ′ may be the same or different. For example, when y is 20, each R ₂ may be alkyl having 4 carbon atoms. In addition, R ₂ ′ may be different, for example, may independently be alkyl having 2 to 4 carbon atoms. If R ₂ ′ is different they may be present in block form, for example all y groups in which R ₂ is alkyl having 3 carbon atoms are adjacent, then all y groups in which R ₂ is alkyl having 2 carbon atoms are located, Subsequently, y groups in which R ₂ is alkyl having 4 carbon atoms are located. If R ₂ ′ is different they may also be present in an irregular distribution.

In a more preferred embodiment, R 1 and R 2 are the same and x and y have the same value.

R ₃ and R ₄ of formula I are each independently composed of hydrocarbyl as defined above having 1 to 100 carbon atoms, substituted hydrocarbyl as defined above having 1 to 100 carbon atoms and polyoxyalkylene alcohol having 2 to 200 carbon atoms Is selected from the group.

When R ₃ and / or R ₄ are hydrocarbyl or substituted hydrocarbyl, they each preferably have 1 to 50 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 to 10 carbon atoms or substitutions. Independently from hydrocarbyl. If R ₃ and / or R ₄ are hydrocarbyl having a relatively high carbon number, for example at least about 50 carbon atoms, these are polymeric hydrocarbyls derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefins, respectively. Can be represented.

Preferably, R ₃ and R ₄ are each independently selected from hydrocarbyl having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and most preferably 1 to 10 carbon atoms. Particularly preferred compounds are those in which R ₃ and R ₄ are hydrocarbyl wherein these groups are selected from alkyl having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms.

R ₃ and / or R ₄ may also be polyoxyalkylene alcohols having 2 to 200 carbon atoms. When R ₃ and / or R ₄ are polyoxyalkylene alcohols, these groups are preferably polyoxyalkylene alcohols of the general formula (IV).

-(R ₉ -O) _z -H

In Formula IV,

Each R ₉ is independently selected from the group consisting of hydrocarbyl having 2 to 100 carbon atoms and substituted hydrocarbyl having 2 to 100 carbon atoms;

z is a number from 1 to 50.

In the above formula (IV), when R ₉ is a hydrocarbyl having a relatively high carbon number, for example at least about 50 carbon atoms, they are each represented by polymeric hydrocarbyl derived from polyisobutylene, polybutene, polypropylene or poly-alphaolefin, respectively. Can be.

Preferably, R ₉ is independently selected from hydrocarbyl having 2 to 50 carbon atoms and substituted hydrocarbyl having 2 to 50 carbon atoms, respectively. More preferably, R ₉ is independently selected from hydrocarbyl having 2 to 20 carbon atoms and substituted hydrocarbyl having 2 to 20 carbon atoms, respectively. Particularly preferred compounds are those in which each R ₉ is independently selected from the group consisting of alkyl having 2 to 20 carbon atoms, more preferably alkyl having 2 to 4 carbon atoms, particularly preferably alkyl having 4 carbon atoms.

Particularly preferred compounds of formula (I) are those in which R ₉ of the polyoxyalkylene alcohol is a hydrocarbyl of the formula (V) or of the formula (VI) when R ₃ and / or R ₄ is a polyoxyalkylene alcohol of Compound.

In Formula V and Formula VI,

R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from hydrogen, hydrocarbyl as defined above having 1 to 98 carbon atoms or substituted hydrocarbyl as defined above having 1 to 98 carbon atoms.

Preferred R ₁₀ , R ₁₁ and R ₁₂ are groups independently selected from hydrogen, hydrocarbyl as defined above having 1 to 18 carbon atoms or substituted hydrocarbyl as defined above having 1 to 18 carbon atoms. In addition, R ₁₀ and R ₁₁ , or optionally R ₁₀ and R _11, may together form a divalent bonded hydrocarbyl group having 3 to 12 carbon atoms. When R ₁₀ , R ₁₁ and / or R ₁₂ are substituted hydrocarbyls they are preferably oxy substituted hydrocarbyls.

Most preferred compounds of formula (1) are those in which R ₉ of a polyoxyalkylene alcohol is of formula (5) wherein each R ₁₂ is hydrogen, and R ₁₀ is independently hydrogen, alkyl of 1 to 18 carbon atoms and of 1 to 18 carbon atoms. Hydrocarbyl or substituted hydrocarbyl, specifically selected from oxy-substituted hydrocarbyl, specifically each R ₁₂ is hydrogen and each R ₁₀ is independently selected from hydrogen or alkyl of 1 to 2 carbon atoms Compound, in particular, each R ₁₂ is hydrogen and each R ₁₀ is alkyl having 2 carbon atoms.

When R ₁₀ is an oxy-substituted hydrocarbyl having 1 to 18 carbon atoms, R ₁₀ is preferably alkoxy-substituted alkylene having 1 to 18 carbon atoms or aryloxy-substituted alkylene having 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, pexoxymethylene and mixtures thereof.

In Chemical Formula 4, z is 1 to 50, preferably 1 to 40, more preferably 1 to 26. Those skilled in the art will recognize that when a compound of Formula 1 containing a polyoxyalkylene alcohol of Formula 4 is used in the composition, z does not have a fixed value and will be represented by a range of different values. In the context of the present invention, z is considered to be the (number) average of the various values of z found in a given composition, which number is rounded to the nearest integer. The range of z is given by the polydispersity (polydispersity = weight average molecular weight divided by the number of pieces of bacteria) in various examples.

When z is greater than 1, each R ₉ may be the same or different. For example, if z is 20, each R ₉ may be alkyl having 4 carbon atoms. In contrast, R _{9 is} different and in some cases may independently be alkyl having 2 to 4 carbon atoms. If R ₉ is different, the block, i.e. all z groups in which R ₉ is alkyl having 3 carbon atoms are adjacent, and all z groups in which R ₉ is alkyl having 2 carbon atoms are next, then all z groups in which R ₉ is alkyl having 4 carbon atoms It is then located. In addition, when R ₉ is different, it may exist in any irregular distribution.

R ₃ and R ₄ may be different or the same. In the most preferred embodiment, R ₃ and R ₄ are the same.

In a preferred embodiment, R ₃ and R ₄ are selected from hydrocarbyl having 1 to 100 carbon atoms. When R ₃ and R ₄ are hydrocarbyl, the sum of the x and y values preferably does not exceed 40, more preferably does not exceed 26. In a preferred embodiment when R ₃ and R ₄ are hydrocarbyl, x is preferably 1 to 13 and y is preferably 1 to 13. In another preferred embodiment, R ₃ and R ₄ are polyoxyalkylene alcohols of formula (4). When R ₃ and R ₄ are polyoxyalkylene alcohols of formula 4, the sum of x, y and amounts z (z for R ₃ and R ₄ ) preferably does not exceed 40, more preferably 26 Do not exceed In a preferred embodiment when R ₃ and R ₄ are polyoxyalkylene alcohols of the general formula (4), x is preferably 1 to 13, y is preferably 1 to 13, and each z is preferably 1 to 13.

R ₅ is selected from the group consisting of alkylene having 2 to 20 carbon atoms, and alkylene having 2 to 20 carbon atoms having at least one or more methylene groups substituted with at least one oxygen atom or at least one acylated nitrogen atom.

When R ₅ is alkylene having 2 to 20 carbon atoms, the alkylene may be in any form, including straight chain alkylene or branched chain alkyl. For example, R ₅ is ethylene (-CH ₂ -CH _2- ), propylene (-CH ₂ -CH ₂ -CH _2- ) or butylene (-CH ₂ -CH ₂ -CH ₂ -CH ₂ -or May be). When R ₅ is alkylene, it is preferably alkylene having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms.

R ₅ may be an alkylene having 2 to 20 carbon atoms in which at least one methylene group is substituted with at least one oxygen atom or at least one acylated nitrogen atom. When R ₅ has at least one methylene group substituted with at least one oxygen atom, R ₅ is preferably oxyalkylene having 2 to 10 carbon atoms and 1 to 4 oxygen atoms. When R ₅ is oxyalkylene, it is preferably oxyalkylene of the following formula (VII).

-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2-

When R ₅ is a nitrogen-containing alkylene having 2 to 20 carbon atoms, the nitrogen-containing alkylene is preferably of the following general formula (VIII).

In the above formula, R ₁₃ is alkyl having 1 to 18 carbons, preferably alkyl having 1 to 8 carbons, and most preferably alkyl having 1 carbon.

The present invention also relates to compounds of formula 1 wherein R ₁ , R ₂ , R ₃ , R ₄ , z and y are as defined above.

The compound of formula 1 has a weight average molecular weight of at least 600 or more. To be windproof, the weight average molecular weight is about 800 to about 4,000, more preferably about 800 to about 2,000.

Representative compounds represented by Formula 1 include those listed in Table 1 as structural formulas together with the initiators used in the preparation.

Compounds of formula (I) are diagrammatically prepared by reacting an alkoxylation reaction in the presence of a potassium compound, ie an initiator selected from diamides, triamides, polyamides, amido alcohols and polyamido alcohols with epoxides.

In one embodiment, the compound of formula (I) is prepared using an initiator represented by formula (IX) below.

In Chemical Formula IX,

R ₁₄ and R ₁₅ are each independently selected from the group consisting of hydrogen, hydroalkyl having 2 to 100 carbon atoms,

R ₁₆ and R ₁₇ are selected from the group consisting of hydrogen, hydrocarbyl as defined above having 1 to 100 carbon atoms, substituted hydrocarbyl as defined above having 1 to 100 carbon atoms, and hydroxyalkyl having 2 to 100 carbon atoms,

R ₁₈ is selected from the group consisting of alkylene of 2 to 20 carbon atoms substituted with an alkylene having 2 to 20 carbon atoms, and a methylene group one or more oxygen atoms one or more of one or more or acylating the nitrogen atom to the definition of [R ₁₈ is Same as the definition of R ₅ above].

Preferably, R ₁₄ and R ₁₅ are each independently selected from the group consisting of hydrogen and hydroxyalkyl having 2 to 50 carbon atoms. More preferably, R ₁₄ and R ₁₅ are each independently selected from the group consisting of hydrogen and hydroxyalkyl having 2 to 20 carbon atoms. Preferably R ₁₆ and R ₁₇ are each independently selected from the group consisting of hydrogen, hydrocarbyl having 1 to 50 carbon atoms, substituted hydrocarbyl having 1 to 50 carbon atoms and hydroxyalkyl having 2 to 50 carbon atoms. More preferably R ₁₆ and R ₁₇ are each independently selected from the group consisting of hydrogen, hydrocarbyl having 1 to 20 carbon atoms, substituted hydrocarbyl having 1 to 20 carbon atoms and hydroxyalkyl having 2 to 20 carbon atoms.

Non-limiting examples of initiators used are diamides (e.g., N, N'-ethylenebisstearamide, N, N'-bisacetamide and diacetamide (JEFFAMINE ^R EDR-148)), triamides [ Examples: diethylenetriamine amide or diethylene triacetamide], polyamides such as triethylenetetramine amide and tetraethylenepentamine amide and diamido alcohols such as JEFFAMINE ^R EDR-148 gamma butyrolactone adduct ], Most preferably diamido alcohol. Initiators are also not limited to, N, N'-ethylenebisstearicamide (trade name: Kemanide ^R W-45, manufactured by Witco Chemical Corporation), N, N'-ethylenebisstearic acid (trade name: Kemanide ^R W-40) , Manufactured by Witco Chemical Corporation], N, N'-ethylenebisstearamide (trade name: Kemanide ^R W-39, manufactured by Witco Chemical Corporation), and N, N'-ethylenebisoleamide [trade name: Kemanide ^R W-20 , Manufacturer: Witco Chemical Corporation].

The at least one epoxide used in the reaction with the initiator for preparing the compound of formula (I) has 2 to 100 carbon atoms, preferably 2 to 50 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 2 to 4 carbon atoms. It contains. The epoxide may be an internal epoxide of formula X or formula XI, for example 2,3 epoxide:

In Formula X and Formula XI,

R ₆ , R ₇ , R ₁₀ and R ₁₁ are as defined above or mean terminal epoxides such as 1,2-epoxide of formula XII or formula XIII.

In formulas (XII) and (XIII), R ₆ , R ₈ , R ₁₀ and R ₁₂ are the same as defined above. [Formula X and Formula XII correspond to the same site or neighboring site hydrocarbyl for R ₁ and R ₂ whereas Formula XI and Formula XIII correspond to the same site or neighborhood hydrocarbyl for R _9. ]

In the above formula, R ₆ and R ₇ , R ₁₀ and R ₁₁ , R ₆ and R ₈ or R ₁₀ and R ₁₂ together form a cycloalkylene epoxide or vinyl by forming a bivalent bonded hydrocarbyl group having 3 to 12 carbon atoms Liden epoxides may be formed.

When R ₆ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , and R ₁₂ are oxy substituted hydroxycarbyls, suitable compounds of the formulas X, XI, XII and XIII are nonylphenyl glycidyl ether, phenyl glycidyl Ethers, cresyl glycidyl ethers, butyl glycidyl ethers, alkyl C ₁₂ -C ₁₃ glycidyl ethers, alkyl C ₈ -C ₁₀ glycidyl ethers, 2-ethylhexyl glycidyl ethers and isopropyl glycidyl And compounds such as dill ethers.

In a preferred embodiment, terminating epoxides represented by the formulas XII and XIII can be used. An ideal terminating epoxide is 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-epoxyhexa Decane, 1,2-epoxyoctadecane and mixtures thereof.

In a typical preparation of the compound of formula I, one or more epoxides and initiators are contacted in a ratio of about 7: 1 to about 55: 1 epoxy per mole of initiator. Preferably they are contacted in a molar ratio of about 10: 1 to about 30: 1, most preferably at about 20: 1.

The reaction is carried out in the presence of a potassium compound which acts as an alkoxylation catalyst. Such catalysts are conventional and include potassium methoxide, potassium ethoxide, potassium hydroxide, potassium hydride and potassium tert-butoxide. Preferred catalysts are potassium tetrahydrate and potassium tert-butoxide. The catalyst is used in base stable solvents such as alcohols, ethers or hydrocarbons. Catalysts are used in a wide variety of concentrations. Generally, the potassium compound will be used at about 0.02% to about 5.0%, preferably about 0.1% to about 2.0%, and most preferably about 0.2% of the total weight of the mixture.

The reaction is conveniently carried out in a conventional autoclave reactor with heating and cooling means. The process is carried out batchwise, continuously or intermittently.

The manner in which the alkoxylation reaction is carried out is not critical to the invention. For example, the initiator and the potassium compound are mixed for up to 30 minutes and heated under vacuum. One or more epoxides were then added to the resulting mixture, the reactor was sealed, pressurized with nitrogen, and the mixture was stirred as the temperature gradually increased.

The temperature for the alkoxylation is about 80 ° C to about 180 ° C, preferably about 100 ° C to about 150 ° C, and more preferably about 120 ° C to about 140 ° C. Alkoxylation reaction times are generally about 2 to about 20 hours, although longer or shorter times may be used.

Alkoxylation processes of this type are known and described, examples of which are US Pat. Nos. 4,973,414, US Pat. No. 4,883,826, US Pat. No. 5,123,932 and US Pat. No. 4,612,335, each of which is hereby incorporated by reference.

The product of formula (I) is normally liquid and recovered by conventional techniques such as filtration and distillation. The product is used as crude or is purified by conventional techniques such as aqueous extraction, solids uptake and / or vacuum distillation to remove any residual impurities if necessary.

Other methods of preparing the compounds of formula I are known to those skilled in the art. For example, compounds of formula (I) are prepared by reacting carboxylic esters with aminoalcohols or amines. In addition, other catalytic chemistries, such as the use of acidic catalysts, can be used to obtain compounds of formula (I).

Fuel composition

Compounds of formula (I) are useful as additives in fuel compositions that burn in internal combustion engines. The fuel composition of the present invention comprises a mixture of a large amount of hydrocarbons and a small amount of one or more compounds of formula I in the gasoline boiling range. As used herein, the term “small amount” means less than about 10 weight percent, preferably less than about 1 weight percent, and more preferably less than about 0.1 weight percent of the total fuel composition.

Suitable liquid hydrocarbon fuels in the gasoline boiling range are mixtures of hydrocarbons having a boiling range from about 25 ° C. to about 232 ° C., which includes mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferably, the gasoline mixture has a saturated hydrocarbon content of about 40% to about 80%, a olefinic hydrocarbon content of 0% to about 30%, and an aromatic hydrocarbon content of about 10% to about 60% by volume. Basic fuels are derived from straight run gasoline, polymeric gasoline, natural gasoline, dimers and trimerized olefins, synthetically prepared aromatic hydrocarbon mixtures, or from pulverized or thermally pulverized petroleum feedstocks and mixtures thereof. do. The hydrocarbon composition and octane levels of the base fuel are not critical. Octane levels, (R + M) / 2, are generally above about 85.

Any conventional automotive base fuel may be used in the practice of the present invention. For example, hydrocarbons in gasoline can be replaced by conventional alcohols or ethers up to the net mass known to be commonly used in fuels. It is desirable for the base fuel to be almost free of water because water interferes with the desired combustion.

Normally, hydrocarbon fuel mixtures to which the present invention is applied are substantially free of lead, but may contain more small amounts of blending agents (e.g., methanol, ethanol, ethyl tertiary butyl ether, methyl tertiary butyl ether, etc.). And from about 0.1% to about 15% by volume of the base fuel, although used in amounts. The fuel may also be used as an antioxidant such as phenolic (e.g., 2,6-di-tert-butylphenol) or phenylenediamine (e.g., N, N'-di-tert-butyl-para-phenylenediamine), Dye, metal deactivator, dehazer (polyester ethoxylated alkylphenol-formaldehyde resin). Corrosion inhibitors such as unsubstituted or substituted aliphatic hydrocarbon groups having 20 to 500 carbon atoms (e.g., pentaerythritol diester of polyisobutylene-substituted succinic acid) and an amount of about 1 ppm to about 1000 ppm by weight Polyhydric alcohol esters of succinic acid derivatives having one or more of the polyisobutylene groups having an average molecular weight of about 950. The fuel may also contain co-antinock compounds (eg benzoyl acetone) in addition to antiknock compounds (eg, methyl cyclopentadienylmanganese tricarbonyl and ortho-azidophenyl).

An effective amount of one or more compounds of formula (I) is introduced into the engine's combustion zone in a variety of ways to prevent precipitation of deposits associated with essential octane, to reduce inlet valve deposits, or to modify existing deposits. As mentioned, the preferred method is to add a small amount of one or more compounds of formula (I) to the fuel. For example, one or more compounds of formula (I) may be added directly to the fuel or blended with one or more carriers and / or one or more additional detergents to form additional concentrates that can later be added to the fuel.

The amount of monoamide-containing polyether alcohol used will depend upon the particular modifications of the formula (I) used, the engine, the fuel and the carrier and the presence of additional detergents. In general, each compound of formula I is added in an amount of about 100 ppm by weight, in particular about 1 ppm to about 600 ppm by weight, based on the total weight of the fuel composition. Preferably, they are added in an amount of about 50 ppm to about 400 ppm, more preferably about 75 ppm to about 250 ppm by weight, based on the total weight of the fuel composition.

The used carrier will have an average molecular weight of about 500 to about 5000. Suitable carriers include hydrocarbon base materials such as polyisobutylene (PIB), polypropylene (PP) and polyalphaolefin (PAO); Polyether based materials such as polybutylene oxite (poly BO), polypropylene oxide (poly PO), polyhexadecene oxite (poly HO) and mixtures thereof) (i.e. (poly BO) + (poly PO ) And (poly-BO-PO))); And mineral oils such as Exxon Naphthenic 900 sus and high conductivity index (HVI) oils. The carrier is preferably selected from PIB, poly BO and poly PO, with poly BO being most preferred.

The carrier concentration in the final fuel composition is about 1000 ppm by weight or less. When present, the preferred concentration is from about 50 ppm to about 400 ppm by weight based on the total weight of the fuel composition. If the carrier is blended with one or more compounds of formula (I), the blend is added directly to the fuel or packaged for subsequent use.

The fuel composition of the present invention may also contain one or more additional detergents. If an additional detergent is used, the fuel composition may contain a large amount of hydrocarbons in the gasoline boiling range as described above, one or more small amounts of the compounds of formula I as described above and a small amount of additional detergents such as polyalkylenyl amines, Mannich ) Amines, polyakenyl succinamides, poly (oxyalkylene) carbamates, poly (alkenyl) -N-substituted carbamates and mixtures thereof). As noted above, the aforementioned carriers may also be included. As used herein, the term “small amount” means less than about 10 weight percent, preferably less than about 1 weight percent, and more preferably less than about 0.1 weight percent of the total fuel composition.

The polyalkylenyl amine detergents used comprise at least one monovalent hydrocarbon group having at least 50 carbon atoms and at least one monovalent hydrocarbon group having up to 5 carbon atoms to separate the nitrogen atoms of the diamine. Preferred polyalkylenyl amines are polyisobutenyl amines. Polyisobutenyl amines are known in the art, and representative examples thereof are various US, including U.S. Patent 3,753,670, U.S. Patent 3,756,793, U.S. Patent 3,574,576, and U.S. Patent 3,438,757, each of which is hereby incorporated by reference. It is disclosed in a patent document. Particularly preferred polyisobutenyl amines for use in the present invention include N-polyisobutenyl-N ', N'-dimethyl-1,3-diaminopropane (PIB-DAP) and OGA-472 (Oronite). Commercially available polyisobutenyl ethylene diamine).

Manic amine detergents used include condensation products of high molecular weight alkyl-substituted hydroxyaromatic compounds, amines (preferably polyamines) containing amine groups having at least one active hydrogen atom and aldehydes. Such manic amines are known in the art and are disclosed in US Pat. No. 4,231,759, which is incorporated herein by reference. Preferably the manic amine is an alkyl substituted manic amine.

Polyalkenyl succinimide detergents include reaction products of dihydric acid anhydrides with both polyoxyalkylene diamines and hydrocarbyl polyamines or mixtures thereof. Typical succinimides are substituted with polyalkenyl groups, but polyalkenyl groups can be found on polyoxyalkylene diamines or hydrocarbyl polyamines. Polyalkenyl succinamides are also known in the art and representative examples thereof are described in US Pat. Nos. 4,810,261, US Pat. No. 4,852,993, US Pat. No. 4,968,321, US Pat. No. 4,985,047, US Various US patent documents are disclosed, including patents 5,061,291 and US Pat. No. 5,147,414.

Poly (oxyalkyrene) carbamate detergents include amine moieties and poly (oxyalkylene) moieties linked through carbamate linkages, ie compounds of the formula XIV.

--O-C (O) -N--

These poly (oxyalkylene) carbamates are known in the art and are incorporated herein by reference, for example, U.S. Patent 4,191,537, U.S. Patent 4,160,648, U.S. Patent 4,236,020, U.S. Patent 4,270,930, U.S. Patent Various US patents are disclosed, including US Pat. No. 4,288,612 and US Pat. No. 4,881,945. Particularly preferred poly (oxyalkylene) carbamates for use in the fuel compositions of the present invention include OGA-480 (poly (oxyalkylene) carbamates available from Oronite).

The poly (alkenyl) -N-substituted carbamate detergents used consist of Formula (IX):

In Chemical Formula XV,

R is a poly (alkenyl) chain;

R ¹ is a hydrocarbyl or substituted hydrocarbyl group;

A is an N-substituted amino group.

Poly (alkenyl) -N-substituted carbamates are known in the art and are disclosed in US Pat. No. 4,936,868, which is incorporated herein by reference.

One or more additional surfactants may be added directly to a hydrocarbon and then blended with one or more carriers and blended with one or more compounds of formula (I), or additional surfactants may be blended with one or more compounds of formula (I) and one or more carriers. Then add to the hydrocarbon.

The concentration of one or more additional surfactants in the final fuel composition is generally about 1000 ppm by weight for each additional surfactant. When one or more additional surfactants are used, the preferred concentration of each additional surfactant is from about 50 ppm to about 400 ppm by weight based on the total weight of the fuel composition, more preferably about about based on the total weight of the fuel composition 75 ppm to about 250 ppm by weight.

Engine test

Reduction of intake valve deposits

The invention also provides a method for reducing intake valve deposits in an engine using the monoamide-containing polyether alcohols of the invention. The method comprises the steps of supplying a fuel composition comprising a large amount of gasoline boiling range hydrocarbon and a small amount of one or more compounds of formula I as described herein above to an internal combustion engine and burning or burning the fuel composition in an internal combustion engine. Steps.

By supplying a fuel composition to the internal combustion engine and burning or burning the fuel composition in the internal combustion engine, deposits in the induction system, in particular on the tulip of the intake valve, are reduced. The engine is operated with clean induction system components by carefully adjusting road conditions using various circuits while carefully adjusting specific work parameters and varying speed, and pre-weighing the intake valve on the dynamometer test stand to reduce deposits. Determine. The test is carried out over a specific time for the fuel composition being tested. At the end of the test, the induction system deposits are visually evaluated and the valve is reweighed to determine the weight of the valve deposits.

Control of Octane Demand Growth

The present invention also provides a method of controlling the octane demand increase in engines using the monoamide-containing polyether alcohols of the present invention. The present invention is directed to supplying a fuel composition comprising a large amount of gasoline boiling range hydrocarbon and a small amount of one or more compounds of formula (I) as described above and combusting or burning the fuel composition in an internal combustion engine. Include.

Octane demand is the maximum octane number of gasoline that provides trace knock in a given engine within the engine's standard operating range. Octane demand generally increases as the number of miles driven by the new engine increases. The increase in octane demand is typically due to an increase in engine deposits. Control of octane demand increase is generally a comparison of the octane demand increase developed in the same gasoline (test gasoline) containing additives relative to gasoline without additives (reference gasoline), i.e. in the result of gasoline without additives. It is a performance characteristic expressed as a difference in quantity calculated by subtracting the result of gasoline included.

In the test mode of regulating octane demand growth, a stable octane requirement of the reference gasoline should be established for clean engines. Reference gasoline is typically test gasoline without additives or without specific treatment. However, the reference gasoline may be gasoline with additives for specific comparisons.

The octane demand increase control test consists of operating an engine combined with a clean combustion chamber and induction system components with test gasoline until the octane demand is stabilized and measuring the octane requirement at a single interval. The degree of octane demand increase control is the difference between the stabilized octane requirement of the engine operated with the test gasoline and the stabilized octane requirement of the engine operated with the reference gasoline.

Reduction of Octane Requirements

The present invention also provides a method for reducing the octane requirement in engines using the monoamide-containing polyether alcohols of the present invention. The present invention provides a fuel composition comprising a large amount of gasoline boiling range hydrocarbon and a small amount of one or more compounds of formula (I) as described herein above to an internal combustion engine and for burning or burning the fuel composition in an internal combustion engine. Steps.

The reduction in octane demand is the reduction in octane demand of the engine by the action of a particular gasoline, and is generally measured as it is reduced in stabilized octane requirements.

Reduction of octane demand is a performance characteristic that represents a reduction from the established octane demand of the reference gasoline in a given engine. The octane demand reduction test consisted of operating an engine for which a stable octane demand was established using the reference gasoline with the test gasoline for about 100 to 250 hours. Octane number is measured daily, and the decrease in octane demand is a decrease in octane demand from the reference gasoline. Several octane requirement reduction tests may be performed in series as a fuel to fuel comparison, or as a reference fuel to test fuel comparison by restabilizing the reference fuel between octane requirement reduction test pieces.

The effect of certain deposits is determined by removing the focal deposits immediately after the engine has warmed to operating temperature and immediately re-measuring octane requirements. The effect on the octane demand of deposits is the difference in the evaluation results before and after removal of the deposits.

It is intended that the scope and limitations indicated in the present specification and claims particularly refer to the invention and clearly claim the invention. However, other ranges and other limitations that perform substantially the same function in substantially the same manner to achieve the same or substantially the same result are intended to be within the scope of the invention as defined in the specification and claims. to be.

The invention will be illustrated by the following examples, which are provided to explain in detail, not to limit the invention.

Synthetic Preparation

The monoamide-containing polyether alcohols used in the examples below are prepared by reacting one or more initiators with one or more epoxides in the presence of a potassium compound to produce a compound of formula (I) having a weight average molecular weight of about 600 to about 4000 It was. Weight average molecular weight (MW) was determined by gel permeation chromatography (GPC). Rotary evaporation was typically performed at a temperature of about room temperature to about 120 ° C.

Example 1

Step 1-preparation of the initiator

γ-butyrolactone (180 g, 2.1 mol) was added to a four necked round flask equipped with a mechanical stirrer, nitrogen inlet line, temperature controller, heating mantle and Dean-Stark trap. At the time of stirring was added Jeffamine (JEFFAMINE®) EDR-148 (triethyleneglycol diamine, 148 g, 1.0 mol, manufactured by Texas Chemical Company). The mixture was heated to 139-157 ° C. for 3 hours. A low melting white solid was obtained. C ¹³ NMR analysis showed 90% amide formation and about 5% unreacted amine and 5% unreacted γ-butyrolactone. The product was used without further purification.

Step 2-Butoxylation of Initiator

The initiator (80 g) from step 1 was mixed with potassium hydroxide (1.7 g in 1.78 g of water) and rotary evaporated at 80 ° C. under reduced pressure to remove water and form potassium salts. The mixture was then fed into a 1 L autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system along with 1,2-epoxybutane (320 g, 4.4 mol). The autoclave reactor was sealed, purged with nitrogen and pressurized to 50 psi with nitrogen at room temperature. The mixture was then heated to 135-140 ° C. for 6 hours. During the reaction, the pressure ranged from 125 to 64 psi. The autoclave reactor was then cooled to room temperature and excess gas was vented. The product was rotary evaporated under reduced pressure followed by water extraction and rotary evaporation again to remove unreacted light colored material from the crude product, yielding the final product, a light colored liquid (soluble in gasoline). GPC analysis showed a molecular weight of 1190 and a polydispersity of 1.10.

Example 2

The initiator of Example 1 (zephamine 148-γ butyrolactone additive, 95 g) was mixed with potassium hydroxide (1.7 g in 1.7 g of water) and rotary evaporated under reduced pressure to remove water and form a potassium salt. . The mixture was then fed into a 1 L autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system along with 1,2-epoxybutane (505 g, 7.01 mol). The autoclave reactor was sealed, purged with nitrogen and pressurized to 50 psi with nitrogen at room temperature. The mixture was then heated to 137-140 ° C. for 5 hours. The autoclave reactor was then cooled to room temperature and excess gas was vented. The crude product was rotary evaporated under reduced pressure followed by water extraction and then repeated rotary evaporation to remove unreacted light colored material from the crude product. GPC analysis of the final product showed a molecular weight of 1340 and a polydispersity of 1.14.

Example 3

Step 1-preparation of the initiator

Ethylene diamine (108 g, 1.8 mol) and ethyl acetate (475 g, 5.4 mol) were introduced into a 1 L autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged with nitrogen and pressurized to 50 psi with nitrogen at room temperature. The mixture was then heated to 200 ° C. for 6 hours. The autoclave reactor was then cooled to room temperature and excess gas was vented. The product was rotary evaporated under reduced pressure to remove unreacted ethyl acetate. A light yellow solid (N, N'-ethylene bis-acetamide) was obtained, showing 100% yield and purity by NMR.

Step 2-Butoxylation of Initiator

One stage of initiator (56 g, 0.25 mol), toluene (150 g) and potassium t-butoxide (2.3 g) were rotary evaporated at 80 ° C. under reduced pressure. The resulting mixture was then introduced into a 1 L autoclave reactor with a heating device, temperature controller, mechanical stirrer and water cooling system, together with 1,2-epoxybutane (344 g, 4.8 mol). The autoclave reactor was sealed, purged with nitrogen and then pressurized to 50 psi with nitrogen at room temperature. The mixture was heated to 134-142 ° C. for 10 hours. The autoclave reactor was cooled to room temperature, excess gas was vented and the crude product was recovered. The crude product was rotary evaporated under reduced pressure, water washed and rotary evaporated again to give a brown liquid final product (310 g). GPC analysis showed a molecular weight of 837 and polydispersity of 1.04.

Example 4

The first stage initiator of Example 3 (ethylenediamine diacetamide, 67 g), potassium t-butoxide (3.1 g) and toluene (50 g) were mixed and rotary evaporated under reduced pressure to remove water and form a potassium salt. The mixture was then fed into a 1 L autoclave reactor with 1,2-epoxybutane (533 g, 7.4 mol) equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged with nitrogen, and then pressurized to 50 psi with nitrogen at room temperature. The mixture was heated to 125-129 ° C. for 7 hours. The autoclave reactor was cooled to room temperature, excess gas was vented and the crude product was recovered. The crude product was rotary evaporated under reduced pressure, water washed and rotary evaporated again to give the final product, which was confirmed by NMR. GPC analysis showed a molecular weight of 1070 and polydispersity of 1.03.

Example 5

Step 1-preparation of the initiator

Diethylene triamine (103 g, 1.0 mol) and ethyl acetate (396 g, 4.5 mol) were charged to a 1 L autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged with nitrogen, and then pressurized to 50 psi with nitrogen at room temperature. The mixture was heated to 198 ° C. for 6 hours. The autoclave reactor was cooled to room temperature and excess gas was vented. The product was rotary evaporated under reduced pressure to remove unreacted ethyl acetate. A dark brown semi-solid product (201 g) was obtained, showing 95% yield and purity by NMR.

Step 2-Butoxylation of Initiator

One stage of initiator (diethylene triacetamide, 82 g, 0.35 mol), potassium hydroxide (2.4 g in 2.0 g of water) and toluene (10 g) were mixed and rotary evaporated under reduced pressure to remove water and form potassium salts. . The mixture was then introduced into a 1 L autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system along with 1,2-epoxybutane (514 g, 7.1 mol). The autoclave reactor was sealed, purged with nitrogen, and then pressurized to 50 psi with nitrogen at room temperature. The mixture was heated to 114-120 ° C. for 12 hours. The autoclave reactor was cooled to room temperature, excess gas was vented and the crude product was recovered. The crude product was rotary evaporated under reduced pressure, water washed and rotary evaporated again to give a yellow clear liquid product. GPC analysis showed a molecular weight of 1260 and polydispersity of 1.05.

Example 6

Step 1-preparation of the initiator

Jeffamine EDR-147 (obtained from Texas Chemical Company, 148 g, 1.0 mol) and ethyl acetate (264 g, 3.0 mol) were charged to a 1 L autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. It was. The autoclave reactor was sealed, purged with nitrogen, and then pressurized to 50 psi with nitrogen at room temperature. The mixture was heated to 200 ° C for 6 h. The autoclave reactor was cooled to room temperature and excess gas was vented. The resulting product was rotary evaporated under reduced pressure to remove unreacted ethyl acetate. NMR analysis yielded a solid crystalline diamide (222 g) showing 97% purity.

Step 2-Butoxylation of Initiator

A mixture of one stage initiator (diacetamide of Jeffamine EDR-148, 73.5 g, 0.375 mol), potassium hydroxide (2.4 g in 2.0 g of water) and toluene (10 g) was evaporated under reduced pressure to remove water and potassium A salt was formed. The resulting mixture, along with 1,2-epoxybutane (527 g, 7.3 mol), was placed in a 1 L autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged with nitrogen, and then pressurized to 50 psi with nitrogen at room temperature. The mixture was heated to 122-135 ° C. for 7 hours. The autoclave reactor was then cooled to room temperature, excess gas was vented and the crude product was recovered. The crude product was rotary evaporated under reduced pressure, washed with water and rotary evaporated again to give a light yellow liquid product (553 g) which was confirmed by NMR analysis. GPC analysis showed a molecular weight of 1510 and polydispersity of 1.04.

Example 7

N, N'-ethylenebissteramide (Kenamid® W-40, 148 g, 0.25 mol, solid material having a melting point of 140 DEG C) from Potco Chemical Corporation, Potassium t -Butoxide (2.8 g) and 1,2-epoxybutane (352 g, 4.9 mol) were charged directly into a 1 L autoclave reactor equipped with a heating device, temperature controller, mechanical stirrer and water cooling system. The autoclave reactor was sealed, purged with nitrogen, and then pressurized to 52 psi with nitrogen at room temperature. The mixture was heated to 122-130 ° C. for 6.5 hours. The pressure during the reaction was 129-70 psi. The autoclave reactor was cooled to room temperature, excess gas was vented and the crude product was recovered. The crude product was rotary evaporated under reduced pressure, washed with water and again rotary evaporated to yield a light colored liquid product (soluble in gasoline). GPC analysis showed a molecular weight of 1490 and polydispersity of 1.05.

Test result

In each of the tests below, the basic fuel used was superlative unleaded gasoline (PU: 90+ octane, [R + M / 2]) and / or ordinary unleaded gasoline (RU: 85-88 octane, [R + M / 2] ). Those skilled in the art will appreciate that it is generally difficult to add fuel containing severely catalytically cracked feedstock, such as most common fuels, to control deposits and to control the required decreases in octane and the required increase in octane. The complex amide polyether alcohol compound used was prepared as shown in Example No. and used at the concentration indicated in ppm by weight. The test method used is described below and the results of the various tests are listed in the table below.

Intake valve deposit experiment

The engine from the vehicle was installed in a dynanometer cell to mimic road maneuvers using cycles of stationary, slow and high speed components, with careful adjustment of special operating parameters. Fuels containing and not containing a compound of Formula I were tested in various engines having a port fuel inlet including 3.3 liters of Dodge to determine the efficacy of the compound in reducing intake valve deposits. In addition, the efficacy of the compounds in reducing intake valve deposits was measured using a carbonized 0.359 L Honda generator engine.

Before each test, the engine was inspected to clean the induction system components and to weigh and install new intake valves. The oil was changed and new oil and fuel filters, gaskets and spark plugs installed.

For all engines except Honda, the test was conducted in cycles of 35 mph and 65 mph for 100 hours unless otherwise indicated. Unless otherwise indicated in the Honda engine, the tests were conducted in a cycle consisting of a stationary state with no rpm increase for 1 minute followed by a 3 minute mode raised to 2200 rpm for 40 hours. At the end of each test, the intake valve was removed and weighed.

Intake valve deposit results from a Honda generator engine and intake valve deposit results from a 3.3 liter Dodge engine obtained using the composite amide polyether alcohol of the present invention are shown in the table below. All tests of the compounds of the present invention were carried out using an additive concentration of 200 ppm of nonvolatile material (nvm) (amount used in each example), except where noted. The results of the base fuel with 0 ppm additive are also disclosed for comparison purposes. Base fuel is shown without using an example number (example number is indicated by "-").

Claims (30)

A fuel composition comprising a mixture of a large amount of hydrocarbon mixture in the gasoline boiling range and a small amount of an additive compound of formula (I): Formula I In Formula I, R ₁ and R ₂ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms and substituted hydrocarbyl having 1 to 100 carbon atoms, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms, substituted hydrocarbyl having 1 to 100 carbon atoms and polyoxyalkylene alcohol having 2 to 200 carbon atoms, R ₅ is selected from the group consisting of alkylene of 2 to 20 carbon atoms, and alkylene of 2 to 20 carbon atoms, in which one or more methylene groups are substituted with one or more oxygen atoms or one or more nitrogen atoms x is a number from 1 to 50, y is a number from 1 to 50 The weight average molecular weight is about 600 or more. The method of claim 1, And the additive wp compound is present in an amount of from about 50 to about 400 weight ppm based on the weight of the fuel composition. The method of claim 2, A fuel composition having a weight average molecular weight of the additive compound from about 800 to about 4000. The method of claim 3, A fuel composition wherein R ₁ and R ₂ are each hydrocarbyl of formula: Where R ₆ is independently selected from hydrogen, hydrocarbyl having 1 to 18 carbon atoms, and substituted hydrocarbyl having 1 to 18 carbon atoms, Each R ₈ is independently selected from hydrogen, hydrocarbyl having 1 to 18 carbon atoms, and substituted hydrocarbyl having 1 to 18 carbon atoms. The method of claim 4, wherein And R ₆ and R ₈ are each independently selected from the group consisting of hydrogen and hydrocarbyl comprising alkyl having 1 to 2 carbon atoms. The method of claim 5, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 20 carbon atoms. The method of claim 6, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl comprising alkyl having 1 to 20 carbon atoms, R ₅ is alkylene having 2 to 10 carbon atoms, x is from 1 to 26 a fuel composition wherein y is 1 to 26. The method of claim 4, wherein R ₆ and R ₈ are each independently selected from the group consisting of hydrogen, hydrocarbyl containing alkyl having 1 to 20 carbon atoms, R ₃ and R ₄ are each C 1 hydrocarbyl, R ₅ is alkylene having 2 carbon atoms, x is from 1 to 26 a fuel composition wherein y is 1 to 26. The method of claim 4, wherein And R ₃ and R ₄ are each independently selected from the group consisting of polyoxyalkylene alcohols having 2 to 200 carbon atoms. The method of claim 9, A fuel composition wherein R ₃ and R ₄ are each polyoxyalkylene of the formula: -(R ₉ -O) _z -H Where R ₉ is selected from the group consisting of hydrocarbyl having 2 to 100 carbon atoms, and substituted hydrocarbyl having 2 to 100 carbon atoms; z is a number from 1 to 50. The method of claim 10, A fuel composition wherein each R ₉ is selected from the group consisting of hydrocarbyl of the formula: Where R ₁₀ is each selected from the group consisting of hydrogen, hydrocarbyl having 1 to 18 carbon atoms, substituted hydrocarbyl having 1 to 18 carbon atoms, R ₁₂ is each selected from the group consisting of hydrogen, hydrocarbyl having 1 to 18 carbon atoms, and substituted hydrocarbyl having 1 to 18 carbon atoms. The method of claim 11, A fuel composition wherein R ₅ is alkylene having 2 to 20 carbon atoms in which one or more methylene groups are substituted with one or more oxygen atoms. The method of claim 12, R ₆ , R ₈ , R ₁₀ and R ₁₂ are selected from the group consisting of hydrogen and hydrocarbyl comprising alkyl having 1 to 2 carbon atoms, A fuel composition in which R ₅ is alkylene having the formula of 2 to 20 carbon atoms having at least one methylene group in which at least one methylene is replaced with at least one oxygen atom: Chemical formula -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2- x is 1 to 26, y is 1 to 26, Each z is from 1 to 26. A method for reducing intake valve deposits in an internal combustion engine comprising a fuel composition comprising a mixture of a large amount of hydrocarbon mixture in the gasoline boiling range and a small amount of an additive compound of formula (I): Formula I In Formula I, R ₁ and R ₂ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms and substituted hydrocarbyl having 1 to 100 carbon atoms, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms, substituted hydrocarbyl having 1 to 100 carbon atoms and polyoxyalkylene alcohol having 2 to 200 carbon atoms, R ₅ is selected from the group consisting of alkylene having 2 to 10 carbon atoms, and alkylene having 2 to 20 carbon atoms in which at least one methylene group is substituted with at least one oxygen atom or at least one acylated nitrogen atom, x is a number from 1 to 50, y is a number from 1 to 50 The weight average molecular weight is about 600 or more. The method of claim 1, Wherein the additive compound is present in an amount from about 50 ppm to about 400 ppm by weight of the fuel composition. The method of claim 15, The weight average molecular weight of the additive compound is about 800 to about 4000. The method of claim 16, A fuel composition wherein R ₁ and R ₂ are each hydrocarbyl of Formula II: Formula II Where Each R ₆ is independently selected from hydrogen, hydrocarbyl having 1 to 18 carbon atoms and substituted hydrocarbyl having 1 to 18 carbon atoms; Each R ₈ is independently selected from hydrogen, hydrocarbyl having 1 to 18 carbon atoms and substituted hydrocarbyl having 1 to 18 carbon atoms. The method of claim 17, R ₆ and R ₈ are each independently selected from the group consisting of hydrogen and hydrocarbyl comprising alkyl having 1 to 2 carbon atoms. The method of claim 18, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 20 carbon atoms. The method of claim 19, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl comprising alkyl having 1 to 20 carbon atoms, R ₅ is alkylene having 2 to 10 carbon atoms, x is from 1 to 26 y is 1 to 26. The method of claim 17, R ₆ and R ₈ are each independently selected from the group consisting of hydrogen, hydrocarbyl containing alkyl having 1 to 2 carbon atoms, R ₃ and R ₄ are each C 1 hydrocarbyl, R ₅ is alkylene having 2 carbon atoms, x is from 1 to 26 y is 1 to 26. The method of claim 17, R ₃ and R ₄ are each independently selected from the group consisting of polyoxyalkylene alcohols having 2 to 200 carbon atoms. The method of claim 22, R ₃ and R ₄ are each a polyoxyalkylene of the formula: -(R ₉ -O) _z -H Where R ₉ is selected from the group consisting of hydrocarbyl having 2 to 100 carbon atoms, and substituted hydrocarbyl having 2 to 100 carbon atoms; z is 1 to 50. The method of claim 23, R ₉ is, R ₁₀ are each independently hydrogen, a hydro-C 1 -C 18 hydrocarbyl, and having 1 to 18 carbon atoms selected from the group consisting of substituted hydrocarbyl, and R ₁₂ is hydrogen, C 1 -C 18, each independently of the hydrocarbyl And a substituted hydrocarbyl having 1 to 18 carbon atoms Independently from hydrocarbyl. The method of claim 24, R ₅ is at least one methylene group and alkylene having 2 to 20 carbon atoms substituted with at least one oxygen atom. The method of claim 25, R ₆ , R ₈ , R ₁₀ and R ₁₂ are each independently selected from the group consisting of hydrogen and a hydrocarbyl comprising alkyl having 1 to 2 carbon atoms, and R ₅ is substituted with one or more oxygen atoms, Methylene group of the formula -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -wherein x, y and z are each 1 to 26; A method of controlling the octane requirement of an internal combustion engine comprising a fuel composition comprising at the time of engine combustion a fuel composition comprising a mixture of a large amount of hydrocarbon mixture in the gasoline boiling range and a small amount of an additive compound of formula (I): Formula I In Formula I, R ₁ and R ₂ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms and substituted hydrocarbyl having 1 to 100 carbon atoms, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms, substituted hydrocarbyl having 1 to 100 carbon atoms and polyoxyalkylene alcohol having 2 to 200 carbon atoms, R ₅ is selected from the group consisting of alkylene having 2 to 10 carbon atoms, and alkylene having 2 to 20 carbon atoms in which at least one methylene group is substituted with at least one oxygen atom or at least one acylated nitrogen atom, x is a number from 1 to 50, y is a number from 1 to 50 The weight average molecular weight is about 600 or more. A method of reducing the octane requirement of an internal combustion engine comprising a fuel composition comprising a mixture of a large amount of hydrocarbon mixture in the gasoline boiling range and a small amount of an additive compound of formula (I) in combustion of the engine. Formula I In Formula I, R ₁ and R ₂ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms and substituted hydrocarbyl having 1 to 100 carbon atoms, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms, substituted hydrocarbyl having 1 to 100 carbon atoms and polyoxyalkylene alcohol having 2 to 200 carbon atoms, R ₅ is selected from the group consisting of alkylene having 2 to 10 carbon atoms, and alkylene having 2 to 20 carbon atoms in which at least one methylene group is substituted with at least one oxygen atom or at least one acylated nitrogen atom, x is a number from 1 to 50, y is a number from 1 to 50 The weight average molecular weight is about 600 or more. Compounds of formula (I). Formula I In Formula I, R ₁ and R ₂ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms and substituted hydrocarbyl having 1 to 100 carbon atoms, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms, substituted hydrocarbyl having 1 to 100 carbon atoms and polyoxyalkylene alcohol having 2 to 200 carbon atoms, R ₅ is selected from the group consisting of alkylene having 2 to 10 carbon atoms, and alkylene having 2 to 20 carbon atoms in which at least one methylene group is substituted with at least one oxygen atom or at least one acylated nitrogen atom, x is a number from 1 to 50 y is a number from 1 to 50. (a) a large amount of hydrocarbons in the gasoline boiling range, (b) small amounts of additive compounds of formula (I) and (c) polyalkylenyl amides, manni amides, polyalkenyl succinamides, poly (oxyalkylene) carbamates, poly (al A fuel composition comprising a small amount of a further detergent selected from the group consisting of kenyl) -N-substituted carbamates and mixtures thereof. Formula I In Formula I, R ₁ and R ₂ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms and substituted hydrocarbyl having 1 to 100 carbon atoms, R ₃ and R ₄ are each independently selected from the group consisting of hydrocarbyl having 1 to 100 carbon atoms, substituted hydrocarbyl having 1 to 100 carbon atoms and polyoxyalkylene alcohol having 2 to 200 carbon atoms, R ₅ is selected from the group consisting of alkylene having 2 to 10 carbon atoms, and alkylene having 2 to 20 carbon atoms in which at least one methylene group is substituted with at least one oxygen atom or at least one acylated nitrogen atom, x is a number from 1 to 50, y is a number from 1 to 50, The weight average molecular weight is about 600 or more.