GB2247457A - (Keto) diacid amides - Google Patents

Abstract

(Keto) diacid amides of poly(olefin)-N-substituted amines are used alone or in combination with certain carriers, such as poly(olefin) polymers or hydrogenated forms of the polymers as fuel additives to prevent or reduce engine deposits and have formula <IMAGE> in which R is a poly(olefin) chain having an average molecular weight of from about 500 to about 9,900; each R<1> is independently a hydrocarbyl or substituted hydrocarbonyl group containing up to 15 carbon atoms; m is 0 or 1; Y is an N-substituted amino group in which the substituent is a hydrocarbyl or substituted hydrocarbyl group containing up to 20 carbon atoms; and A may be hydroxy, halogen or hydrocarbyloxy of up to 10 carbon atoms.

Description

KETO-DIACID AMIDES The present invention relates to (keto)diacid amides, their use in preventing deposit formation in engines and to fuel compositions containing such amides.

It is known that during the initial operation of a new or clean internal combustion engine, octane requirement (OR), i.e. the fuel octane number required for knock-free operation, gradually increases with the build up of combustion chamber deposits until a stable level is reached which generally corresponds to a time when deposits remain relatively constant. The actual stable level can vary with engine design and even with individual engines of the same design.

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

Continued improvement in design of internal combustion engines, e.g., fuel injection and the like, brings changes to the atmosphere of the combustion chamber so there is a continuing need for new additives to control the problem of deposits and improve drivability which is usually related to deposits.

The present invention provides novel (keto) diacid amides of poly(olefin)-N-substituted-amines, useful in fuel compositions for preventing or reducing deposits in engines, of formula

in which R is a polyolefin polymer chain with an average molecular weight of from about 500 to about 9,000; each R1 is independently a hydrocarbyl or substituted hydrocarbyl group containing up to about 15 carbon atoms; m is zero or 1; Y is an N-substituted amino group in which the substituent is a hydrocarbyl or substituted hydrocarbyl group containing up to 20 carbon atoms, and A is hydroxy, halogen, preferably chloro or bromo, or hydrocarbyloxy in which the hydrocarbyl group contains up to 10 carbon atoms. A can be (cyclo)aliphatic or aromatic and is preferably alkyl of up to 6 carbon atoms. M is preferably 1.

The novel amides of the invention are a new class of detergent additives, useful for fuels, e.g., in the gasoline boiling range, for prevention or reducing deposits in engines while also readily breaking down cleanly producing very little residue and are miscible with carriers, such as polymeric olefins and the like or are intermediates to such additives. The novel amides of the invention are prepared by treating a secondary amine compound with a (keto)diacid precursor.

The amine moiety Y, of the amides of the invention is derived from an N-substituted monoamine or polyamine, having from 2 to 10 amine nitrogen atoms. The amine moiety can contain up to about 20 carbon atoms. The hydrocarbyl and substituted hydrocarbyl groups of the amine includes aliphatic, alicyclic, aromatic or heterocyclic groups. The substituted hydrocarbyl group includes those hydrocarbyl groups substituted by non-interfering atoms or substituents, including ring oxygen, keto, hydroxy, nitro, cyano, alkoxy, acyl and the like. The hydrocarbyl or substituted hydrocarbyl groups are preferably relatively free of aliphatic unsaturation.

Non-limiting illustrative embodiments of the inventions include those of formula I wherein:

R Y hydrogenated polyisoprene phenyl-N ethylene-propylene copolymer ethyl-N polybutadiene methyl-N polypropylene benzylethyl-N polybutylene isopropyl-N polyisobutylene 3-(N,N-dimethyl)aminopropyl-N polyisobutylene 3-(N,N-diethyl)aminopropyl-N polyisobutylene 2-(N,N-propyl)aminopropyl-N polyisobutylene - N N The preferred novel (keto)diacid amides of poly(olefin)-N-substituted-amines contain at least one olefinic polymer chain and include those of formula I wherein m is 1, each R1 is -Z-Z- and Y is > N-R2 of formula II

wherein R and A have the above meanings;R2 is a hydrocarbyl group or a hydrocarbylaminohydrocarbyl group, each containing up to 20 total carbon atoms in the hydrocarbyl group(s); and each Z is independently > C(Z')2 in which Z' independently is hydrogen, lower alkyl of up to 4 carbon atoms, preferably methyl, halogen, preferably chloro or fluoro, or aryl of 1 to 2 rings and up to 10 carbon atoms, preferably phenyl, or Z is such that two adjacent Z groups, taken together, form a ring system Z" of 1 to 2 rings, each of from 5 to 7 ring atoms, up to 2 of which ring atoms are selected from nitrogen atoms, oxygen atoms, sulfur atoms or mixtures thereof, with the remainder of the ring atoms being carbon atoms, there being up to 14 carbon atoms in each Z", two of which ring carbon atoms form a bridge between the two carbon atoms (spiro and carbonyl carbon atoms) connected by adjacent Z groups.The Z" rings can be substituted by inert substituents such as halogen, alkyl, alkoxy, alkylthio, aryloxy, tertiary amino, tertiary-aminoalkyl and the like as disclosed in U.S.

Patent 4,847,388.

Preferred compounds of formula II of the invention include those compounds wherein R is a poly(olefin) polymer having an average molecular weight of from about 550 to about 4,900; and R is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms or an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms; or R2 is a group of formula III

wherein R' is an alkylene group containing from 1 to 8 carbon atoms and each R" is independently a hydrogen atom or an alkyl group containing from 1 to 7 carbon atoms and x is O to 5.Preferably, when R2 is a group of formula III, R' is an alkylene group containing from 1 to 4 carbon atoms; each R" is independently an alkyl group containing from 1 to 4 carbon atoms and x is o to 1, especially R' is propylene, each R" is a methyl group and x is 0.

The poly(olefin)-secondary-amine intermediates (including polyamines) can be prepared by reacting olefinic polymers with amines employing conventional procedures as hereinafter described.

These oil soluble poly(olefin)-secondary amine intermediates have at least one polymer chain having a molecular weight in the range from about 500 to about 9,900 and preferably from about 550 to about 4,900, and particularly from 600 to 1,300, and which can be saturated or unsaturated and straight or branch chain and are attached to a nitrogen and/or a carbon atom of the amine.

Preferred poly(olefin)-N-substituted- secondary-amine intermediates are polyalkylene polyamines having the structural formula IV

wherein R"' is selected from polyolefin having a molecular weight from about 500 to about 9,900, each R' is an alkylene radical having from 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, each R" is hydrogen or lower alkyl containing 1 to 7 carbon atoms and x is 0 to 5. Preferred is a polyalRylene polyamine wherein R ''' is a branch-chain olefin polymer in the molecular weight range of 550 to 4,990, with a molecular weight range of 600-1300 being particularly preferred.

The olefinic polymers (R in formulas I and II and R " ' in in formula IV) which are reacted with amines to form the poly(olefin) -N-substituted-sacondary-amine intermediates of the present invention are known in the art, such as U.S. Patent 4,357,148 and include olefinic polymers derived from alkanes or alkenes with straight or branched chains, which may or may not have aromatic or cycloaliphatic substituents, for instance, groups derived from polymers or copolymers of olefins which may or may not have a double bond. Examples of non-substituted alkenyl and alkyl groups are polyethylene groups, polypropylene groups, polybutylene groups, polyethylene-polyalpha-methyl styrene groups and the corresponding groups without double bonds. Particularly preferred are polypropylene and polyisobutylene groups.

The R" group can be hydrogen but is preferably lower alkyl, i.e., containing up to 7 carbon atoms and more preferably is selected from methyl, ethyl, propyl, butyl and the like.

Suitable amine reactants are broadly referred to as (poly)amines to include both polyamines and monoamines as hereinafter more fully described. The (poly)amines used to react with the polyolefins to form the poly(olefin)-N-substituted-secondary-amine intermediates include aliphatic, alicyclic, aromatic and heterocyclic monoamines and polyamines. A variety of such amines is well documented in the art including U.S, Patent 4,191,537, incorporated by reference. The amines can contain other non-reactive substitutes.

Suitable substitutes for such amines include alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, and the like; alkenyls such as propenyl, isobutenyl, hexenyl, octenyl and the like; hydroxyalkyls, such as 2-hydroxyethyl, 3-hydroxypropyl, hydroxy-isopropyl, 4-hydroxybutyl, etc.; ketoalkyls, such as 2-ketopropyl, 6-ketooctyl, and the like; alkoxy and lower alkenoxyalkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 2 - (2-ethoxyethoxy) ethyl, and acyl groups such as propionyl, acetyl, and the like.

Preferred substituents are C1-C6 alkyls.

Heterocyclic amines can be saturated, unsaturated and substituted or unsubstituted. Suitable heterocyclic amines include piperazines, such as 2-methylpiperazine, N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-piperazinyl)ethane, and N,N'-bis(N-piperazinyl)piperazine, 2-methylimidazoline, 3-aminopiperidine, 2-aminopyridine, 2-(3-aminoethyl)-3-pyrroline, 3-aminopyrroidine, N-(3-aminopropyl)-morpholine, and the like. Among the heterocyclic compounds, the piperazines are preferred.

The amine reactants include mixtures of compounds, such as mono and polysubstituted polyamines or isomers.

The polyamines used to form the preferred poly(olefin) polyamine intermediate compounds of this invention include low molecular weight aliphatic polyamines such as ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, butylene diamine, trimethyl trimethylene diamine, tetramethylene diamine, diaminopentane or pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, diaminooctane, decamethylene diamine, and higher homologues up to 18 carbon atoms.

Compounds possessing triamine as well as tetramine and pentamine groups are applicable for use because these can be prepared from technical mixtures of polyethylene polyamines, which offer economic advantages.

The polyamine starting materials from which the polyamine groups can be derived can also be a cyclic polyamine, for instance, the cyclic polyamines formed when aliphatic polyamines with nitrogen atoms separated by ethylene groups are heated in the presence of hydrogen chloride.

Monoamines which can be used to prepare the poly(olefin)-secondary-amines include monoamines in which the hydrocarbyl groups contains from 1 to 14 carbon atoms. For example, each hydrocarbyl group is independently selected from an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms or an aryl, aralkyl, or alkaryl group containing from 6 to 10 total carbon atoms. Preferably, the hydrocarbyl groups are independently selected from an alkyl group containing from 1 to 4 carbon atoms, e.g., ethyl, propyl or the like.

An example of a suitable process for the preparation of the poly(olefin)amine compounds employed according to the invention is the reaction of a halogenated hydrocarbon having at least one halogen atom as a substituent and hydrocarbon chain as defined herein before with a (poly)amine. The reaction between halogenated hydrocarbon and (poly)amine is preferably effected at elevated temperature in the presence of a solvent; particularly a solvent having a boiling point of at least 1600C.

The reaction between polyhydrocarbon halide and a (poly)amine having more than one nitrogen atom available for this reaction is preferably effected in such a way that cross-linking is reduced to a minimum, for instance, by applying an excess of (poly)amine.

The (poly)amine reactants according to the invention can be prepared, for instance, by alkylation of low molecular weight aliphatic (poly)amines. For instance, a (poly)amine is reacted with an alkyl or alkenyl halide. The formation of the alkylated (poly)amine is accompanied by the formation of hydrogen halide, which is removed, for instance, as a salt of starting (poly)amine present in excess. With this reaction between alkyl or alkenyl halide and the strongly basic (poly)amines, dehalogenation of the alkyl or alkenyl halide may occur as a side reaction, so that hydrocarbons are formed as by-products, which need not be removed.

The amides of formula I and II of the invention are prepared by treating a secondary amine compound with a (keto)diacid precursor.

The secondary amine compound or acid addition salt thereof and (keto)diacid precursor react in molar ratio of 1:1 although in practice reactant ratios from about 10-20% excess amine or precursor is satisfactory. Reactant ratios of amine compound to precursor which are substantially stoichiometric are preferred. Reaction is conducted in a liquid phase solution in an inert reaction diluent such as an N-alkylamide, e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like. Reaction takes place under reaction conditions at an elevated temperature, typically from about 80"C to about 250"C, and at a reaction pressure sufficient to maintain the reaction mixture in a liquid phase, e.g., pressures up to about 20 atmospheres (2 x 106 Pa).Subsequent to reaction the amide product is recovered from the reaction product mixture by conventional methods such as solvent removal, precipitation and chromatographic separation and the like.

Small amounts of poly (olefin) -secondary-unreacted amine intermediate need not be removed from the product as the presence thereof does not interfere with the usefulness of the product of formula I or II.

Unreacted amine can aid in the effects of the poly(olefin)-N-substituted-amides of the invention by acting as a carrier, assisting in enhancing the preventing, removing or retarding of engine deposits or by providing their known fuel detergents properties. Other known materials for use in fuels can also serve one or more of these purposes, including the polymer additives described later.

Any dicarboxylic acid or ketodiacid or reactive derivatives thereof, which can form the amides defined by formulas I or II, can be used as the (keto)diacid precursor reactant. This includes the free (keto)diacid, the digesters of said acid, the corresponding dihalides or preferably the corresponding anhydride.

Suitable dicarboxylic acid precursors include dicarboxylic acids having at least three to about 24 carbon atoms and include, for example, lower aliphatic dicarboxylic acids, such as malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, suberic acid, sebacic acid as well as higher aliphatic dicarboxylic acids containing between about 11 and about 22 carbon atoms, such as undecanedioic and dodecanedioic acids as well as tri-, tetra-, penta-, hexa-, hepta-, octa-decanedioic acids and similar higher aliphatic dicarboxylic acids. Also useful are aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and similar aromatic dicarboxylic acids. Preferably, the dicarboxylic acid precursor is an aliphatic acid anhydride, especially succinic or glutaric anhydride.

The amides of the invention comprise amides of a single (keto)diacid precursor, or when mixtures comprise amides of more than one (keto)diacid precursor. Such mixtures are usually comprised of from about 1% to about 50% equivalent of amides from one or more dicarboxylic acid precursor based on the total amine groups in the amide, preferably from about 5% to about 30%, and the remainder of the amides form one or more ketodiacid precursors.

The (keto)diacid precursor is a ketodiacid or reactive derivative thereof or a spirodilactone. By reactive drivative of the ketodiacid is meant the corresponding diester of the acid or the dihalide of the acid, either of which derivative can be converted to the free acid group by conventional chemistry known to those of skill in the art, either before, during or subsequent to the reaction with the secondary amine compound.

Suitable spirodilactones useful as ketodiacid precursors in the present invention contain from about 7 to about 30 carbon atoms and include those of formula V

wherein n is a number from 1 to 10, preferably 2.

Suitable ketodiacids include those ketodiacids containing from about 5 to about 30 carbon atoms and containing one or more keto groups or their diesters or dihalides.

The preferred precursor is a 4-oxoheptanedioic acid compound or a 1,6-ioxospiroE4,4]nonane-2,7-ione. The 4-oxoheptanedioic acid compound spirodilactam precursors are represented by the formula VI

wherein Z has the previously stated meaning and A is hydroxy, lower alkoxy or halo, preferably middle halo.

When the Z moieties are linked together to form a ring system the ring system is aromatic, cycloaliphatic or heterocyclic and is hydrocarbyl containing only atoms of carbon and hydrogen besides any heteroatoms or substituted hydrocarbon containing additional atoms such as halogen,preferably middle halogen, in the form of inert carbon atom substituents.

In one embodiment employing the ketodiacid compound precursor, each Z moiety is > C(Z')2 and the ketodiacid compound is an 4-oxoheptanedioic acid compound. In one such embodiment, largely because of a particularly convenient method of producing the precursor, preferred 4-oxoheptanedioic acid compound has at least one hydrogen on the carbon atom adjacent to each carboxy function, that is, at least one Z' on each carbon atom adjacent to a carboxy function is hydrogen. Such 4-oxoheptanedioic acid compounds are represented by the formula VIIa

wherein Z' and A have the previously stated meanings.

Such 4-oxoheptane-dioic acid compounds include 4-oxoheptanedioic acid, dimethyl 4-oxoheptane-dioate, 2,6-dimethylheptanedioic acid, 2,3,5, 6-tetramethyl-4-oxoheptanedioyl chloride, di-n-propyl 2,6-di-n-butyl-4-heptanedioate, 7-carbomethoxy-3,3,S,5-tetramethyl-4-oxoheptanedioic acid and the like. The preferred ketodiacids of the above formula VIIa are those wherein each Z' is hydrogen or methyl, especially hydrogen, and each A is hydroxy or methoxy, especially hydroxy.

These ketodiacid compounds are known compounds or are produced by known methods, but the esters of formula VIIa, i.e., the compounds wherein A is alkoxy, are produced by reaction of formaldehyde with an alpha, beta -ethylenically unsaturated carboxylic acid ester such as methyl acrylate, ethyl methacrylate, methyl crotonate, methyl ethacrylate, propyl 2,3-dimethylbutanoate and the like. This reaction is conducted in the presence of a catalyst system which comprises a thiazolium salt and tertiary amine and produces the dialkyl 4-oxoheptanedioate derivative in good yield. This process is described in greater detail in U.S. Patent 4,800,231, incorporated herein by reference. Conversion of the esters thereby obtained to free acids or acid halides is by conventional methods as is general interconversion of the acids, ester or acid halides of formula VIIa.

In a second embodiment of the ketodiacid compound precursor, the 4-ketodiacid incorporates cyclic moieties between the keto group and the carboxy functions, i.e., two adjacent Z moieties form a fused cyclic ring structure Z". Such diacid compounds are represented by the formula VIIb

wherein A and Z" have the previously stated meanings.

Illustrative of these cyclic ketodiacid compounds are di (2-carboxycyclohexyl) ketone, di (2-carboiphenyl) ketone, di(2-carbopropoxycyclo-4-pentenyl) ketone, di (2-chlorocarbonlylphenyl) ketone, di(2-carboxypyridyl) ketone, 2-carboxyphenyl N-menthyl-3-carboxy-2-pyrryl ketone, di(3-carbethoxy-2-morpholyl)ketone, di(3-carbomethoxy-2-napthyl) ketone and the like. The preferred cyclic ketodiacid compounds of formula VIIb are those wherein each Z" is a ring system of from 5 to 6 carbon atoms, inclusive, and up to one nitrogen atom, particularly benzo.

Such ketodiacids are known compounds or are produced by known methods, such as the method of U.S.

Patent 1,999,181 or the method of Cava et al, J. Am.

Chem. Soc., 77, 6022 (1955).

In yet another embodiment of the ketodiacid compound precursor, the ketodiacid incorporates one fused cyclic moiety with the remainder of the Z moieties being > C(Z')2, i.e., the compounds are of the formula VIIc

wherein A, Z' and Z" have the previously stated meanings. Such ketodiacids of one cyclic moiety are illustrated by 3-(2-carboxy-benzoly)propionic acid, 3- (2-carbomethoxy-2-pyridyloyl) -2-ethyl-propionic acid, ethyl 3-(2-carboethoxybenzoyl)propionate, 3-(2carboxy-4-methylbenzoylbutyryl) chloride and the like.

The ketodiacids of the above formula VIIc are known compounds or are produced by known methods. For example, 2-carboxymethylbenzaldehyde reacts with methyl acrylate according to the general teachings of U.S. Patent 4,800,231, to produce methyl 3-(2-carbomethoxybenzoyl)-propionate.

In a a second embodiment of the invention, the ketodiacid precursor is a 1, 6-dioxaspiro [4. 4]nonane-2 , 7-dione compound wherein the spiro ring system is substituted with hydrogen, alkyl or halogen, or which incorporates fused cyclic substituents which include the 3- and 4-spiro ring positions and/or a the 8- and 9-spiro ring positions of the spiro ring system.

The precursor, in terms of the amides of formula I, is represented by the formula VIII

wherein Z has the previously stated meaning.

In the embodiment of these precursors of the above formula VIII wherein each Z is > C(Z')2, the spirodilactone is represented by the formula VIIIa

wherein Z' has the previously stated meaning.

Illustrative of such spiro-dilactones are 1, 6-dioxaspiro [4.4] nonane-2, 7-dione, 3,8-dimethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione, 3,4,8,9-tetra-methyl-1,6-dioxaspiro[4.4]-nonane-2,7- dione, 4,9-diphenyl-1,6-diaza-spiro[4.4]nonane-2,7-dione, 3,3,8,8-tetramethyl-1,6-dioxaspiro[4.4]-nonane-2,7- dione, 3,3,4,4,8,8,9,9-octamethyl-1,6-dioxaspiroC4.4]-nonane -2 ,7-dione, 3,4,8,9-tetrafluoro-1,6-dioxaspiro[4.4]nonane-2,7- dione and the like. The preferred spirodilactones of the above formula VIIIa are those wherein at least one Z' of each Z'-substituted carbon atom is hydrogen.

The compounds of formula VIIa are known compounds or are produced by known methods such as the process of Pariza et al, Synthetic Communications, Vol. 13(3), pp. 243-254 (1983), herein incorporated by reference.

In the embodiment of the precursors of the above formula VIII which incorporates a fused cyclic moiety as a part of the two rings of the spiro ring system, the spirodilactones are represented by the formula VIIIb

wherein Z" has the previously stated meaning. Typical compounds of this formula VIIIb are 3,4,8,9-dibenzo-1,6-dioxaspiro[4.4]nonane-2,7-dione, di(3,5-dimethoxybenzo)-8,9-benzo-1,6-dioxaspiro[4.4] nonane-2,7-dione, 3,4,8,9-di(cyclopentano)-1,6-dioxaspi- roE4.4]nonane-2,7-dione, 3,4,8,9-di(4-methylbenzo)-1,6-dioxaspiro[4.4]nonane- 2, 7-dione, 3,4,8,9-diCpyrido)-1,6-dioxaspiro[4.4]nonane -2,7-dione and the like.These compounds are known compounds or are produced by known methods, for example, the process of the above Cava et al article, Am. Chem Soc., 77 6022 (1955) or by the process of U.S. Patent 1,999,181.

In a third embodiment of the precursor, a cyclic moiety is fused to one spiro ring and the other spiro ring is free from fused ring substituents. Such spirodilactones are represented by the formula VIIIc

wherein Z' and Z" have the previously stated meanings.

Such spirodilactones are illustrated by 3-methyl-8,9-benzo-l,6-dioxaspiro-[4.4)nonane-2,7- dione, 3,4-benzo-1,6-dioxaspiro[4.4]nonane-2,7-dione and 3,3,4,4-tetramethyl-8,9-morphoyl-1,6-diazaspiro[4.4] nonane-2,7-dione and the like. The spirodilactones of the above formula VIIIc are produced by known methods, for example, the dehydration of the corresponding ketodiacid. By way of illustration, 3,4-benzo-1,6-dioxaspiroC4.4]nonane-2,7-dione, is produced by dehydration of 3-(2-carboxybenzoyl)propionic acid through application of heat.

In general, the preferred precursors are hydrocarbon except for the oxygen atoms of the lactone moieties, and particularly preferred are those spirodilactones which are free from fused ring substituents (formula VIIIa) or those which have a fused ring substituent on each of the spiro rings (formula VIIIb). An especially preferred precursor of the first class is 1,6-dioxaspiro[4.4]nonane-2,7-dione.

The acyclic 4-oxoheptanedioic acid compounds are known or are produced by the methods described above, but certain of the esters are also produced by the reaction of formaldehyde and unsaturated carboxylic acid esters by the process disclosed and claimed in U.S. Patent 4,800;231. Interconversion of the acids, esters or acid halides of formula VI is by conventional methods. The production of 4-oxoheptanedioic acid compounds of formula VII which contain cyclic moieties is by the process of Cava et al, J. Am. Chem. Soc.,77 6022 (1955). The spirodilactones of formula VIIIb are produced by the process of Pariza et al, Synthetic Communications, Vol. 13(3), pp. 243-254 (1983), Gourmelon et al., Bull. Soc. Chem., 4032 (1971), Sikes et al., Meeting Am. Chem. Soc. April 1988, p. 614, and U.S.Patent 1,999,181.

Suitable liquid hydrocarbon fuels of the gasoline boiling range are mixtures of hydrocarbons having a boiling range of from about 25lc (77of) to about 232 C (450"F), and comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferred are gasoline blends having a saturated hydrocarbon content ranging from about 40 to about 80 percent volume, an olefinic hydrocarbon content from about 0 to about 30 percent volume and an aromatic hydrocarbon content from ranging from about 10 to about 60 percent volume.The base fuel can be derived from straight run gasoline, polymer gasoline, natural gasoline, dimer and trimerized olefins, synthetically produced aromatic hydrocarbon mixtures, from thermally or catalytically reformed hydrocarbons, or from catalytically cracked or thermally cracked petroleum stocks, and mixtures of these. The hydrocarbon composition and octane level of the the base fuel are not critical. Any conventional motor fuel base can be employed in the practice of this invention.

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 and the like. The fuels can also contain antiknock compounds such as tetraethyl lead, a methyl cyclopentadienylmanganese tricarbonyl, ortho-azidophenol and the like.

An effective amount of the amides of the present invention can be introduced into the combustion zone of the engine in a variety of ways to prevent build-up of deposits, or the accomplish reduction or modification of deposits. Thus, the amides of the invention can be injected into the intake manifold intermittently or substantially continuously, as described, preferably in a hydrocarbon carrier having a final boiling point (by ASTM D86) lower than about 232"C (450"F). A preferred method is to add the agent to the fuel. For example, the agent can be added separately to the fuel or blended with other fuel additives. The effective amount of the amides of the invention used will of course depend on the particular compound(s) used, the engine and the fuel and carrier types. For example, the amides of the invention can be used in an amount of from about 20 to about 750 ppm weight based on the total weight of the fuel composition and preferably from about 40 to about 500 ppm weight based on the total weight of the fuel composition and preferably from about 40 to about 500 ppm by weight.

For use in the fuel compositions of the invention, mixtures of different amide compounds of the invention can be used. For example, the A or the R could be mixtures of different groups in formula I or II.

The amide compounds of the invention can also be used in combination with certain polymeric components which are polymers of monoolefins having up to 6 carbon atoms; poly(oxyalkylene) alcohols, glycols or polyols or mono- or diethers thereof; or polyolefin amines. Such materials are well known in the art.

For example, polymers of monoolefins are described in U.S. Patents 2,692,257, 2,692,258, 2,692,259, 2,918,508, and 2,970,179.

Such polymers include (1) polymers of C2 to C6 monoolefins, (2) copolymers of C2 to C6 monoolefins, (3) the corresponding hydrogenated polymer (1) or copolymer (2) or (4) mixtures of at least two of (1),(2) and (3), and polymeric component having an average molecular weight by osmometry in the range of from about 500 to about 3500, preferably about 500 to about 1500. Particularly preferred are those having said average molecular weight in the range from about 600 to abut 950. Mixtures of polymers wherein a substantial portion of the mixture has a molecular weight above 1500 are considerably less effective.

The polyolefins may be prepared from unsaturated hydrocarbons having from 2 to 6 carbon atoms including, e.g., ethylene, propylene, butylene, isobutylene, butadiene, amylene, isoprene, and hexene.

Preferred for their efficiency and commercial availability are polymers of propylene and butylene; particularly preferred are polymers of polyisobutylene. Also suitable and part of this invention are derivatives resulting after hydrogenation of the above polymers.

Poly(-C2 to C6-oxyalkylene) alcohols, glycols and polyols, monoethers or diethers thereof can be used alone or in mixtures as carriers, such as the "Pluronic" (trade mark) materials marketed by BASF Wyandotte Corp., and the "UCON LB"-series (trade mark) fluids marketed by Union Carbide Corp. Preferably, these carriers include poly(oxypropylene) alcohol, glycol or polyol of molecular weight of about 300 to about 4000, which may or may not be capped by an alkyl group, e.g., a (C1-20 hydrocarbyl)poly(oxypropylene) alcohol and polyethylene glycols of molecular weight of from about 300 to 4000.

The poly(olefin) amines of a C2 to C6 monoolefin, described hereinbefore for use as the starting materials used to make the compounds of formula I are also useful as the poly(olefin) amine fuel additives.

The invention further provides a concentrate for use in liquid (hydrocarbon) fuel in the gasoline boiling range comprising (a) from 25 to about 500 ppm by weight (preferred from about 50 to about 200 ppm) of the hereinabove described amides of the invention; (b) from about 10 to about 1000 ppm (preferably 50-400 ppm) by weight of at least one polymeric component which is (i) a polymer of a C2 to C6 monoolefin, (ii) a copolymer of a C2 to C6 monoolefin, (iii) the corresponding hydrogenated polymer or copolymer, (iv) a poly(oxy-C2 to C6-alkylene) alcohol, glycol or polyol or mono- or diethers thereof, (v) a poly(olefin)amine of a C2 to C6 monolefin or mixtures of at least two of (i), (ii), (iii), (iv) and (v); (c) from about 0 to abut 20 ppm by weight of a dehazer; and (d) balance a fuel-compatible diluent, boiling in the range from about 50"C (122"F to about 232"C (450 F). Very suitable fuel-compatible diluent include oxygen-containing hydrocarbons and non-oxygen-containing hydrocarbons. Suitable oxygen-containing hydrocarbon solvents include, e.g., methanol, ethanol, propanol, methyl tert-butyl ether and ethylene glycol monobutyl ether. The solvent can be an alkane such as heptane, but preferably is an aromatic hydrocarbon solvent such as toluene, xylene alone or in admixture with said oxygen-containing hydrocarbon solvents. Optionally, the concentrate can contain from about 0 to about 20 ppm by weight of a dehazer, particularly a polyester-type ethoxylated alkylphenol-formaldehyde resin, or other conventional dehazer.

The invention further provides a method for operating a spark ignition internal combustion engine (ICE) which comprises introducing with the combustion intake fuel charge to said engine a deposit preventing or reducing effective amount of a least one amide of formulas I or II in which the poly(olefin) chain has an average molecular weight of from about 500 to about 9,900 and the substituent on the nitrogen atom is a hydrocarbyl group or a hydrocarbylaminoiydrocarbyl group, each containing up to 20 total carbon atoms in the hydrocarbyl group(s).

The preferences expressed earlier with regard to (a) the amides of formulas I or II and/or (b) the polymeric component or other additives also apply to the concentrate, motor fuel composition and method of operating the ICE.

The invention will be further understood from the following illustrative examples. The identity of the products was confirmed by Nuclear Magnetic Resonance Spectral Analysis. In the examples, parts and percentages are parts and percentages by weight, unless otherwise indincated.

Example l-Preparation of a Compound of Formula I with R = Polyisobutylene of 900 Averaqe Molecular Weiqht; and A = N-CH2CH2CH2NtCH3? Three hundred sixty-eight and four-tenths grams of the polyisobutylene-NH-(CH2)3-N(CH3)2 (80.58 non-volatile, 19.5% xylenes, and containing 1.50% basic nitrogen ) was stirred with 34.5 grams of l,6-dioxaspiro[4.4)-nonane-2,7-dione at 100"C for 12 hours. The material was submitted for engine tests without further purification.

Example 2 Three hundred sixty-eight and four-tenths grams of the polyisobutylene-NH-(CH2)3-N(CH3)2 of Example, 1 was stirred with 23 g of succinic anhydride at 100 C for 12 hours. The resulting material was submitted for engine tests without further purification.

Example 3 Three hundred sixty-eight and four-tenths grams of the polyisobutylene-NH-(CH2)3-N(CH3)2 of Example 1 was stirred with 17.25g of the spirodilactone used in Example 1 and 11 g of succinic anhydride at 1000C for 12 hours. The resulting material was submitted for engine tests without further purification.

Example 4 Three hundred sixty-eight and four-tenths grams of the polyisobutylene-NH-(CH2)3-N(CH3)2 of Example I was stirred with 25.2 g of glutaric anhydride at 100"C for 12 hours. The resulting material was submitted for engine tests without further purification.

Example 5 A 2.3L Oldsmobile port fuel-injected engine with automatic transmission was mounted on a dynamometer stand and subjected to an operating cycle (engine speeds and dynamometer loads) and temperatures use to simulate actual level road load conditions. The engine was run on premium unleaded gasoline containing 200 ppm of the compound of Example 1 above. The average intake valve deposit weight was 105 mg as compared to 155 mg for the base gasoline alone.

Claims (25)

1. A compound comprising a (keto)diacid amide of poly-(olefin)-N-substituted-amine of formula I

in which R is a poly(olefin) chain having an average molecular weight of from about 500 to abut 9,900; each R1 is independently a hydrocarbyl or substituted hydrocarbyl group containing up to 15 carbon atoms; m is 0 or 1; Y is an N-substituted amino group in which the substituent is a hydrocarbyl or substituted hydrocarbyl group containing up to 20 carbon atoms; and A is hydroxy, halogen or hydrocarbyloxy of up to 10 carbon atoms.

2. A compound of formula I according to claim I of the formula II

wherein R and A are as defined in Claim 1; R2 is a hydrocarbyl or hydrocarbyl-aminohydrocarbyl group, each containing up to 20 total carbon atoms in the hydrocarbyl group(s); and each Z independently is > C(Z')2 in which each Z' independently is hydrogen, lower alkyl of up to 4 carbon atoms, or aryl of 1 or 2 rings and up to 10 carbon atoms, or Z is such that two adjacent Z groups, taken together, form a ring system Z" of 1 to 2 rings, each of from 5 to 7 ring atoms, up to 2 of which are ring atoms selected from nitrogen atoms, oxygen atoms, sulfur atoms or mixtures thereof, with the remainder of the ring atoms being carbon atoms, there being up to 14 carbon atoms in each Z", two of which ring carbon atoms form a bridge between the two carbon atoms connected by adjacent Z groups.

3. A compound according to claim 2 wherein R is a poly(olefin) having an average molecular weight of from about 550 to about 4,900.

4. A compound according to claim 3 wherein the poly(olefin) has an average molecular weight of from about 600 to about 1,300.

5. A compound according to claim 4 wherein the R is a polyisobutylene group.

6. A compound according to any one of claims 2 to 6 wherein R2 is an alkyl group containing from 1 to 10 carbon atoms, an alkenyl group containing from 2 to 7 carbon atoms, a cycloalkyl group containing from 3 to 7 ring carbon atoms and a total of 3 to 10 carbon atoms or an aryl, aralkyl or alkaryl group containing from 6 to 10 total carbon atoms.

7. A compound according to claim 2 wherein R2 is a group of Formula III

wherein R' is an alkylene radical containing from 1 to 8 carbon atoms, each R" is independently a hydrogen atom or an alkyl group containing from 1 to 7 carbon atoms and x is 0 to 5.

8. A compound according to claim 7 wherein each R' is independently an alkylene containing from 1 to 4 carbon atoms, each R" is independently an alkyl group containing from 1 to 4 carbon atoms and x is 0 to 2.

9. A compound according to claim 8 wherein R' is propylene, each R" is a methyl group and x is 0.

10. A compound according to claim 8 wherein A is hydroxy.

11. A compound according to any one of claims 2 to 10 wherein Z is a > (CZ')2 group.

12. A compound according to claim 11 wherein Z' is hydrogen or a methyl group.

13. A compound according to any one of claims 2 to 10 wherein adjacent Z groups taken together form a ring system Z".

14. A compound according to claim 13 wherein Z" is benzo.

15. A compound of formula I according to claim 1 substantially as herein before described in any one of Examples 1 to 4.

16. A composition comprising a mixture of two or more amide compounds of formula I as defined in any one of claims 1 to 15.

17. A motor fuel composition comprising a mixture of hydrocarbons in the gasoline boiling range containing a deposit preventing or reducing effective amount of a least one amide compound according to any one of claims 1 to 15.

18. A motor fuel composition according to claim 17 wherein (a) is at least one amide compound and the fuel further comprises (b) a polymeric component which is (i) a polymer of a C2 to C6 monoolefin, (ii) a copolymer of a C2 to C6 monoolefin, (iii) the corresponding hydrogenated polymer or copolymer, (iv) a poly(oxy -C2 to C6- alkylene) alcohol, gylcol or polyol or mono or diether thereof, (v) a poly(olefin) amine of a C2 to C6 monoolefin or mixtures thereof; (c) from about 0 to about 20 ppm by weight of a dehazer; and (d) balance a diluent, boiling in the range form about 50"C to about 232"C.

19. A motor fuel composition according to claim 18 wherein the polymeric component has an average molecular weight of from about 500 to about 1500.

20. A motor fuel composition according to claim 19 wherein the polymeric component has an average molecular weight of from about 600 to about 950.

21. A motor fuel composition according to claim 20 wherein the polymeric component is a polymer of a C3 or C4 monoolefin.

22. A motor fuel composition according to claim 21 wherein the polymeric component is present in a concentration of from about 10 to about 1000 ppm.

23. A concentrate suitable for use in liquid fuels in the gasoline boiling grange comprising (a) from about 25 to about 500 ppm by weight of at least one amide compound according to any one of claims 1 to 15; and (b) from about 10 to about 1000 ppm by weight of a polymeric component which is (i) a polymer of a C2 to C6 monoolefin, (ii) a copolymer of a C2 to C6 monoolefin, (iii) the corresponding hydrogenated polymer or copolymer, (iv) a poly(oxy-C2 to C6-alkylene alcohol, glycol or polyol or mono- or diether thereof, (v) a poly(olefin)amine of a C2 to C6 monoolefin, or mixture thereof; (c) from about 0 to about 20 ppm by weight of a dehazer; and (d) balance a diluent, boiling in the range form about 50"C to about 232"C.

24. A method for operating a spark ignition internal combustion engine which comprise introducing with the combustion intake fuel charge to said engine a deposit preventing or reducing effective amount of a least one amide compound according to any one of claims I to 15.

25. A method according to claim 24 wherein (a) is at least one amide compound and the fuel also contains (b) a polymeric component which is (i) a polymer of a C2 to C6 monoolefin, (ii) a copolymer of a C2 to C6 monoolefin, (iii) the corresponding hydrogenated polymer or copolymer, (iv) a poly)oxy-C2 to C6-alkylene) alcohol, glycol or polyol or mono- or diether thereof, (v) a poly(olefin) amine of a C2 to C6 monoolefin, or mixture thereof; (c)from about 0 to about 20 ppm by weight of a dehazer; and (d) balance a diluent, boiling in the range from about 50"C to about 232it.