AU678514B2 - Fuel compositions and additives therefor - Google Patents

Description

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S): Ethyl Corporation ADDRESS FOR SERVICE: b

C,.

C

C. C DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street, Melbourne, 3000.

INVENTION TITLE: Fuel compositions and additives therefor The following statement is a full description of this invention, including the best method of performing it known to me/us:la- TECHNICAL FIELD This invention relates to fuel additive compositions that can be used for control of intake valve deposits without significantly affecting octane requirement increase in the engine.

BACKGROUND

Over the years considerable work has been devoted to additives for controlling (preventing or reducing) deposit formation in the fuel induction systems of spark-ignition internal combustion engines. In particular, additives that can effectively control intake valve deposits represent the focal point of considerable research activities in the field and despite these efforts, further improvements are desired.

15 Among relatively recent efforts along these lines is U.S.

:5,242,469 and published Canadian patent application 2,089,833.

The additive systems described in U.S. 5,242,469 comprise an ester and at least one dispersant component chosen from certain monosuccinimides, bis(succinimides), polyolefin polyamines, and benzylamine derivatives. The benzylamine derivatives appear to be Mannich-type detergents*. These additive combinations may further contain a polyoxyalkylene glycol or derivative thereof having a molecular weight of 500-5000, preferably 1000-3000.

According to the patent the hydroxybenzyl amine derivatives are made by alkylating a hydroxybenzyl amine which in turn presumably would be formed by a Mannich reaction among phenol, formaldehyde and polyamine. The resultant product should be similar, if not identical, to a product made in the more usual sequence of alkylating the phenol and then conducting the Mannich reaction with the resultant alkylated phenol, formaldehyde and a polyamine.

i ~1 ir sa~ps~ll8 Case EP-6800-A 2 Also, a specified type of lubricating oil fraction may be included in the additive mixture. The polyoxyalkylene glycol derivatives referred to in the text of the patent include the ethers, esters and ether aminoacid esters of the polyoxyalkylene glycol.

Canadian patent application 2,089,833 bearing a publication date of August 21, 1993 describes a similar additive system. In particular, the gasoline is to contain from to 450 ppmw of a specified group of Mannich base detergents in combination with from 75 to 175 ppmw of an oilsoluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of to (b) in the mixture is at least 0.43.

THE INVENTION It has now been discovered that oil-soluble poly(oxyalkylene) alcohols, glycols or polyols or mono or di ethers thereof do not yield equivalent results on intake valve :cleanliness when used in conjunction with a Mannich base detergent, and that for reasons not presently understood, 20 the viscosity properties of the poly(oxyalkylene) component appear to have a profound effect on the intake valve cleanliness performance of the overall composition.

Accordingly, in one of its embodiments, this invention provides, a fuel-soluble additive composition which com- 25 prises a) a Mannich reaction product of a high molecular weight alkyl-substituted phenol, (ii) amine, and (iii) aldehyde; and b) a poly(oxyalkylene) compound having in its undiluted 30 state a viscosity of at least about 70 ce istokes (cSt) at 40*C and at least about 13 cSt at 100*C.

Preferably, the composition will contain one or more liquid hydrocarbons which, whether a single hydrocarbon or a mixture of different hydrocarbons, has a viscosity that is not substantially in excess of the viscosity of the poly(oxyalkylene) compound.

I~ I I- c~a Case EP-6800-A 3 In another of its embodiments, this invention provides a fuel composition which comprises gasoline containing a minor intake valve deposit controlling amount of a) a Mannich reaction product of a high molecular weight alkyl-substituted phenol, (ii) amine, and (iii) aldehyde; and b) a poly(oxyalkylene) compound having in its undiluted state a viscosity of at least about 70 centistokes (cSt) at 40°C and at least about 13 cSt at 100°C.

Typically the proportions of a) to b) in the compositions of this invention are such that there are from about 0.2 to about 5 parts by weight of a) per part by weight of preferably from about 0.5 to about 3 parts by weight of a) per part by weight of and more preferably from about 0.8 to about 2 parts by weight of a) per part by weight of with the weight of a) being on an "active ingredient basis". By this is meant that component a) will usually be supplied in admixture on a weight basis with a minor amount of a hydrocarbon diluent and a minor amount of unreacted 20 polyolefin used in making the alkylated phenol from which the Mannich detergent is produced. Thus the foregoing proportions of a) to b) are based on the content of Mannich base detergent in component a) excluding the weight of any diluent or solvent and any unreacted polyolefin which may be 25 associated therewith in the form in which it is supplied.

Component b) will normally be supplied in undiluted form, and in such case its weight can be used directly in calculating the ratio of a) to But if the poly(oxyalkylene) compound is being blended with a) when the poly(oxyalkylene) 30 compound is in admixture with a solvent or diluent, the weight of b) should be based on the weight of the poly(oxyalkylene) compound itself and should likewise exclude the weight of any such solvent or diluent associated therewith.

It will be understood that any such ancillary solvent or diluent, whether hydrocarbon or otherwise, must not adversely affect the intake valve deposit control perfor- Case EP-6800-A 4 mance of the above additive composition in any material way.

Thus as long as they do not exert such adverse effect, ethers, esters or other inert solvents or diluents may be present in the additive composition. Preferably, however, the only ancillary diluents or solvents in the additive composition are hydrocarbons which collectively have viscosities at 40*C and 100"C that are not substantially in excess of the viscosity of the poly(oxyalkylene) compound.

For example, these collective hydrocarbon viscosities are preferably not more than approximately 25 percent higher than the corresponding 40"C and 100*C viscosities of the poly(oxyalkylene) compound being used. Not only does this ensure that the intake valve deposit control effectiveness of the composition will not be adversely affected in any material way, but it keeps the cost of the additive composiion to a minimum. Preferably the said hydrocarbons comprise an aromatic hydrocarbon component that has a boiling point or a final boiling point no higher than about 240 0

C.

S: In another embodiment, this invention provides a method for reducing intake valve deposits in gasoline engines. The method comprises fueling said engines with a fuel composition comprising a major amount of hydrocarbonaceous fuel 25 in the gasoline boiling range and a minor intake valve deposit controlling amount of a) a Mannich reaction product of a high molecular weight alkyl-substituted phenol, (ii) amine, and (iii) aldehyde; and b) a poly(oxyalkylene) compound having in its undiluted 30 state a viscosity of at least about 70 centistokes (cSt) at 40°C and at least about'13 cSt at 100°C.

As noted above, the Mannich reaction product component of this invention typically contains a significant portion of hydrocarbonaceous ingredients which are inactive in the P 1I.--C M -4Asense that they do not possess polarity or surface activity and therefore do not serve as detergents. For example, subsequent to the manufacture of the Mannich reaction product, hydrocarbon solvent is typically added to dilute the product to facilitate handling and blending. Thus, the Mannich e e 6 *S

SO

*S O o Case EP-6800-A 5 product as received typically contains about 40 to about wt.% of the active Mannich base ingredient, the balance being solvent or diluent, and unreacted materials from the synthesis steps, such as polyolefin polymer. A generally used dilution solvent is a mixture of aromatic hydrocarbons such as and m-xvlene, mesitylene, and higher boiling aromatics such as Aromatic 150 (commercially available from Chemtech).

The Mannich reaction products of this invention are obtained by condensing an alkyl-substituted hydroxyaromatic compound wnose alkyl-substituent has a number average molecular weight of from about 600 to about 14,000, preferably alkylphenol whose alkyl substituent is derived from 1-monoolefin polymer having a number average molecular weight of from about 600 to about 3000, preferably about 750 to about 1200, more preferably about 800 to about 1200, and most preferably about 800 to about 950; an amine having at least one >NH group, preferably an alkylene polyamine of the formula

H

2 N (A NH S 20 where A is a divalent alkylene radical having 1 to 10 carbon atoms and x is an integer from 1 to 10; and an aldehyde, preferably formaldehyde or a formaldehyde precursor, in the presence of a solvent.

Commercial grades of alkylene polyamines often contain 25 mixtures of linear, branched and cyclic species.

High molecular weight Mannich reaction products useful as additives in the fuel additive compositions of this invention are preferably prepared according to conventional methods employed for the preparation of Mannich condensation products, using the above-named reactants in the respective molar ratios of high molecular weight alkyl-substituted hydroxyaromatic compound, (ii) amine, and (iii) aldehyde of approximately 1.0 0.1-10 1-10. Usually the reactants are charged in proportions such that there are an excess of the aldehyde and an excess of a polyamine relative to the hydroxyaromatic compound such as an alkylphenol which I 1. II ~L ~slB~be~g~~ Case EP-6800-A 6 thereby becomes the limiting reactant. For example it is common to charge about 1 to 3 moles of polyamine and about 1.2 to 4 moles of aldehyde per mole of A suitable condensation procedure involves adding at a temperature of from room temperature to about 95°C, the formaldehyde reagent Formalin) to a mixture of amine and alkyl-substituted hydroxyaromatic compounds alone or in an easily removed organic solvent, such as benzene, xylene, or toluene or in solvent-refined neutral oil and then heating the reaction mixture at an elevated temperature (120°-175°C) while preferably blowing with an inert stripping gas, such as nitrogen, carbon dioxide, etc., until dehydration is complete.

The reaction product so obtained is finished by filtration and dilution with solvent as desired.

Preferred Mannich reaction product additives employed in this invention are derived from high molecular weight Mannich condensation products, formed by reacting an alkylphenol, an ethylene polyamine, and a formaldehyde affording reactants in the respective molar ratio of 1.0 0.5-2.0 1.0-3.0, wherein the alkyl group of the alkylphenol has a number average molecular weight (Mn) of from about 600 to about 3,000, and more preferably from about 750 to about 1,200.

Representative of the high molecular weight alkylsubstituted hydroxyaromatic compounds are polypropylphenol (formed by alkylating phenol with polypropylene), polybutylphenol (formed by alkylating phenol with polybutenes or polyisobutylene), and other similar long-chain alkylphenols.

Polypropylphenol is the most preferred reactant. Polyalkylphenols may be obtained by the alkylation, in the presence of an alkylating catalyst such as BF,, of phenol with high molecular weight polypropylene, polybutylene and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having a number average molecular weight (Mn) of from about 600 to about 14,000.

1 s~ l- _CI__L I I I_ I Case EP-6800-A 7 The alkyl substituents on the hydroxyaromatic compounds may be derived from high molecular weight polypropylenes, polybutenes, and other polymers of mono-olefins, principally 1-mono-olefins. Also useful are copolymers of mono-olefins with monomers copolymerizable therewith wherein the copolymer molecule contains at least 90% by weight, of mono-olefin units. Specific examples are copolymers of butenes (butene- 1, butene-2, and isobutylene) with monomers copolymerizable therewith wherein the copolymer molecule contains at least 90% by weight of propylene and butene units, respectively.

The monomers copolymerizable with propylene or butenes include monomers containing a small proportion of unreactive polar groups such as chloro, bromo, keto, ether, aldehyde, which do appreciably lower the oil-solubility of the .polymer. The comonomers polymerized with propylene or such butenes may be aliphatic and can also contain non-aliphatic groups, styrene, methylstyrene, p-dimethylstyrene, divinyl benzene and the like. From the foregoing limitation placed on the monomer copolymerized with propylene or the S 20 butenes, it is clear that the resulting polymers and copolymers are substantially aliphatic hydrocarbon polymers.

Thus, the resulting alkylated phenols contain substantially alkyl hydrocarbon substituents having a number average molecular weight (Mn) of from about 600 to about 14,000.

*0o 25 In addition to the foregoing high molecular weight hydroxyaromatic compounds, other phenolic compounds which may be used include, high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, cresol, catechol, xylenol, hydroxydi-phenyl, benzylphenol, phenethylphenol, 30 naphthol, tolylnaphthol, among others. Preferred for the preparation of such preferred Mannich condensation products are the polyalkylphenol reactants, polypropylphenol and polybutylphenol whose alkyl group has a number average molecular weight of 600-3000, the more preferred alkyl groups having a number average molecular weight of 740-1200, while the most preferred type of alkyl groups is a poly- ~a~a~i~ill~l-~s~e~p~l Case EP-6800-A 8 propyl group having a number average molecular weight of about 900-950.

The preferred configuration of the alkyl-substituted hydroxyaromatic compound is that of a para-subs':'tuted monoalkylphenol. However, any alkylphenol readily reactive in the Mannich condensation reaction may be employed. Thus, Mannich products made from alkylphenols having only one ring alkyl substituent, or two ring alkyl substituents are suitable for use in this invention.

Representative amine reactants are alky±j .ie polyamines, principally polyethylene polyamines. Other representative organic compounds containing at least one HN< group suitable for use in the preparation of the Mannich reaction products are well known and include the mono and di-amino alkanes and their substituted analogs, ethylamine, dimethylamine, dimethylaminopropyl amine, and diethanol amine; aromatic diamines, phenylene diamine, diamino naphthalenes; heterocyclic amines, morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their 20 substituted analogs.

The alkylene polyamine reactants which are useful with this invention include polyamines which are linear, branched or cyclic; or a mixture of linear, branched and/or cyclic polyamines wherein each alkylene group contains from about 1 to about 10 carbon atoms. A preferred polyamine is a polyamine containing from 2 to 10 nitrogen atoms per molecule or a mixture of polyamines containing an average of from about 2 to about 10 nitrogen atoms per molecule such as ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, octaethylene nonamine, nonaethylene decamine, and mixtures of such amines.

Corresponding propylene polyamines such as propylene diamine, and dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine, pentapropylene hexamine are also ~pl~p~ I Case EP-6800-A 9 suitable reactants. A particularly preferred polyamine is a polyamine or mixture of polyamines having from about 3 to 7 nitrogen atoms with diethylene triamine or a combination or mixture of ethylene polyamines whose physical and chemical properties approximate that of diethylene triamine being the most preferred. In selecting an appropriate polyamine, consideration should be given to the compatibility of the resulting detergent/dispersant with the gasoline fuel mixture with which it is mixed.

Ordinarily the most highly preferred polyamine, diethylene triamine, will comprise a commercially available mixture having the general overall physical and/or chemical composition approximating that of pure diethylene triamine but which can contain minor amounts of branched-chain and cyclic species as well as some other linear polyethylene polyamines such as triethylene tetramine and tetraethylene pentamine. For best results, such mixtures should contain at least 50% and preferably at least 70% by weight of the linear polyethylene polyamines of which at least 50 mole 20 is diethylene triamine.

The alkylene polyamines are usually obtained by the oo reaction of ammonia and dihaloalkanes, such as dichloroalkanes. Thus, the alkylene polyamines are obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles 25 of dichloroalkanes having 2 to 6 carbon atoms and chlorine atoms on different carbon atoms.

Representative aldehydes for use in the preparation of high molecular weight Mannich products include the aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, stearaldehyde. Aronatic aldehydes which may be used include benzaldehyde and salicylaldehyde. Illustrative heterocyclic aldehydes for use herein are furfural and thiophene aldehyde, etc. Also useful are formaldehyde-producing reagents such as paraformaldehyde, or aqueous formaldehyde i, la~ ra bls s P I~pl li s~R~ l~ I Case EP-6800-A 10 solutions such as formalin. Most preferred is formaldehyde or formalin.

Important considerations insofar as the present invention is concerned, are to insure that the alkylphenol having an alkyl substituent with the desired number average molecular weight be reacted with the preferred polyethylene polyamine and aldehyde compounds and that the reactants be employed in proportions such that the resultant Mannich reaction product contains the requisite proportions of the chemically combined reactants, all as specified herein. Wh."n utilizing this combination of features, the resultant compositions of this invention not only possess exceptional effectiveness in controlling or reducing the amount of induction system deposits formed during engine operation but which permit adequate demulsification performeace.

A key feature of this invention is that the Mannich reaction products are used in combination with one or more poly(oxyalkylene) compounds having the requisite viscosity parameters referred to hereinabove.

The poly(oxyalkylene) compounds suitable for use in the practice of this invention comprise one or more gasolinesoluble poly(oxyalkylene) alcohols, glycols or polyols or mono or diethers thereof, with the proviso that such com- 25 pounds have in their undiluted state a viscosity of at least about 70 centistokes (cSt) at 40*C and at least about 13 cSt at 100°C. Such compounds can be represented by the following formula R, -R3 (I) 30 wherein R 1 is a hydrogen atom, or hydroxy, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, cycloalkoxy, or amino group having in the range of 1-200 carbon atoms, R 2 is an alkylene group having 2-10 carbon atoms (preferably 2-5 carbon atoms), R 3 is a hydrogen atom or alkyl, cycloalkyl, aryl, alkaryl, aralkyl, or hydrocarbylamino group having 1-200 carbon atoms, and n is an integer in the range from 1 to 500

I

Case EP-6800-A 11 (and preferably in the range of from 3 to 120) representing the number of repeating alkyleneoxy groups, all with the proviso that the product in its undiluted state is a gasoline-soluble liquid having a viscosity of at least about centistokes (cSt) at 40*C and at least about 13 cSt at 100°C.

Generally speaking, the poly(oxyalkylene) compounds used in the practice of this invention will have viscosities of no more than about 400 cSt at 40*C and no more than about 50 cSt at 100*C. Preferably, the viscosities of the poly- (oxyalkylene) compounds used will not exceed about 300 cSt at 40°C and about 40 cSt at 100°C. The most preferred poly- (oxyalkylene) compounds will have viscosities of no more than about 200 cSt at 40°C, and no more than about 30 cSt at 100"C.

Preferred poly(oxyalkylene) compounds are poly(oxyalkylene) glycol compounds and monoether derivatives thereof that satisfy the above viscosity requirements and that are .comprised of repeating units formed by reacting an alcohol 20 or polyalcohol with an alkylene oxide, such as propylene oxide and/or butylene oxide with or without use of ethylene oxide, and especially products in which at least 80 mole of the oxyalkylene groups in the molecule are derived from 1,2-propylene oxide. Details concerning preparation of such 25 poly(oxyalkylene) compounds are referred to, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 18, pages 633-645 (Copyright 1982 by John Wiley Sons), and in references cited therein, the foregoing excerpt of the Kirk-Othmer encyclopedia and the references cited therein being incorporated herein in toto by "reference. U.S. Patent Nos. 2,425,755; 2,425,845; 2,448,664; and 2,457,139 also describe such procedures, and are also incorporated herein by reference as if fully set forth herein.

sl -uc rr VIH~XC--~P-I- I- Case EP-6800-A 12 Preferred poly(oxyalkylene) compounds can be represented by the formula (RS0) p-R 6 (II) wherein R 4 is a hydrogen atom, or a hydrocarbyl group having up to 18 carbon atoms, and more preferably an alkyl group having up to 10-12 carbon atoms; R is an alkylene group of carbon atoms which thus can be an ethylene group dimethylene) group, but which preferably is a propylene methyldimethylene) group, or a butylene ethyldimethylene) group; R 6 is a hydrogen atom, or a hydrocarbyl group having up to 18 carbon atoms, and more preferably an alkyl group having up to 10-12 carbon atoms; and p is .a integer that yields a product having the viscosity parameters given above. Commercially available products are often composed of mixtures in which the individual species of the mixture have different numerical values for p, and thus in the case of such mixtures the value of p for the overall product represents an average value. The alkylene groups R, can all be the same or they can be different and if different, can be arranged either randomly or in prearranged blocks or sequences. Particularly preferred are the poly- (oxyalkylene) alcohols and glycols in which from 70 to 100% and especially 80 to 100% of the alkylene groups are propylene groups (methyldimethylene groups) derived from use 1,2-propylene oxide in the alkoxylation reaction usually employed in the production of such products. In these particularly preferred poly(oxyalkylene) alcohols, glycols :and diethers, if less than 100% of the alkylene groups are propylene groups, the remainder are either ethylene or 30 butylene groups, or both, proportioned to yield a liquid gasoline-soluble product having the requisite viscosity properties specified above. Monools derived by propoxylation of alkanols (R 4 in Formula (II) is alkyl, R 5 is methyldimethylene groups, R 6 is a hydrogen atom, and p is as defined above) are most preferred. Such compounds can also be thought of as monoethers of poly(oxyalkylene) glycols.

I- g i Ba IIPIIIPI 'LIUIII IIIIII--r~31rrrr~- Case EP-6800-A -13- Other poly(oxyalkylene) glycols and ethers which may be employed can be represented by the formula

R

7 0- (-R 8 q-R- (-OR 10 r-OR11 (III) wherein R 7 and R11 can be the same or different and each is independently a hydrogen atom or a hydrocarbyl group, preferably an alkyl group of up to 18 carbon atoms, and more preferably of up to 10-12 carbon atoms; Rg and R 10 can be the same or different and are alkylene groups of 2-5 carbon atoms each, which thus can be ethylene groups dimethylene groups), but which preferably comprise or consist of propylene methyldimethylene) groups, and/or butylene ethyldimethylene) groups; R, is an divalent hydrocarbylene group derived from the initiator, and thus can be a group such as a phenylene group or an alkylene group which is preferably an ethylene dimethylene) group, a propylene methyldimethylene) group, or a butylene ethyldimethylene) group, and q and r are independently integers that yield a product having the viscosity parameters given above. Commercially available products are often composed of mixtures in which the individual species of the mixture have different numerical values for q and different numerical values for r, and thus in the case of such mixtures the values of q and r for the overall product represent average values. As noted, the alkylene groups can 25 all be the same or they can be different and if different, can be arranged either randomly or in blocks or sequences.

o: The poly(oxyalkylene) compounds used pursuant to this invention will contain a sufficient number of branched oxyalkylene units methyldimethyleneoxy units and/or 30 ethyldimethyleneoxy units) to render the poly(oxyalkylene) compound gasoline soluble.

The most preferred poly(oxyalkylene) glycol derivative compound useful in the compositions and methods of this invention is known commercially as EMKAROX AF22 available from ICI Chemicals Polymers Ltd. This compound has a pour point of about -42*C, a density of about 0.980 g/ml at a i epps 41 ~C n~u~--P-31 II~ Case EP-6800-A 14 an open cup flash point of about 230*C, a viscosity of about cSt (typically in the range of about 87 to about 98 cSt) at 40°C and about 17 cSt (typically in the range of about to about 19 cSt) at 100°C, an average molecular weight of about 1700, a viscosity index of about 200, and a volatility as determined by the Volatility Determination Method described hereinafter of less than about 50%. The number average molecular weight of the poly(oxyalkylene) compounds of this invention is preferably in the range of from about 200 to about 5000, more preferably from about 500 to about 3000, and most preferably from about 1500 to about 2500.

An optional hydrocarbon component of the fuel compositions of this invention is poly-a-olefin. The poly-a-olefins (PAO) useful in compositions and methods of this invention can be fully hydrogenated (hydrotreated), partially hydrogenated, or unhydrogenated poly-a-olefins. These materials are poly-a-olefin oligomers, primarily trimers, tetramers and pentamers of alpha-olefin monomers containing from 6 to 12, generally 8 to 12 and most preferably about 20 carbon atoms. Their synthesis is outlined in Hydrocarbon Processing, Feb. 1982, page 75 et seq. and essentially comprises catalytic oligomerization of short chain linear .alpha olefins (suitably obtained by catalytic treatment of ethylene). The nature of an individual PAO depends in part on the carbon chain length of the original alpha-olefin, and also on the structure of the oligomer. The exact molecular structure may vary to some extent according to the precise conditions of the oligomerization, which is reflected in changes in the physical properties of the final PAO. Since 30 the suitability of a particular PAO is determined primarily by its physical properties, and in particular its viscosity, the various products are generally differentiated and defined by their viscosity characteristics. Preferred for use in the compositions of the present invention are poly-a-olefins having a viscosity (measured at 100°C) in the range of from 2 to 20 centistokes. More preferably, the poly-a-olefin has a viscosity of at least 8 centistokes, and most R ~p~ Il L- 9 Case EP-6800-A 15 preferably about 10 centistokes at 100°C. The volatility of the poly-a-olefin is also of significance and may be determined by the Volatility Determination Method described below.

To determine the volatility of a substance the following Volatility Determination Method is used. The substance, a poly-a-olefin (110-135 grams) is placed in a threeneck, 250 mL round-bottomed flask having a threaded port for a thermometer. Such a flask is available from Ace Glass (Catalog No. 6954-72 with 20/40 fittings). Through the center nozzle of the flask is inserted a stirrer rod having a Teflon blade, 19 mm wide x 60 mm long (Ace Glass catalog No.. 8085-07). The substance poly-a-olefin) is heated in an oil bath to 300 0 C for 1 hour while stirring the substance in the flask at a rate of 150 rpm. During the heating and stirring, the free space above the substance in the flask is swept with 7.5 L/hr of inert gas nitrogen, argon, etc.). The volatility of the substance poly-a-olefin thus determined is expressed in terms of the weight percent 20 of material lost based on the total initial weight of material tested. Utilizing the foregoing procedure, it is particularly preferred to select poly-a-olefins for use in the additive formulations of this ,nvention that have a volatility of less than about 50%, more preferably less than about While not required for the purposes of this invention, it is preferred that the fuel compositions of this invention include other conventional additives such as antioxidants, demulsifiers, corrosion inhibitors, aromatic solvents, etc.

Accordingly, components for use in the formulations of this invention will now be described.

Antioxidant. Various compounds known for use as oxidation inhibitors can be utilized in the practice of this invention. These include phenolic antioxidants, amine antioxidants, sulfurized phenolic compounds, and organic phos-

-~I

I~Y~F~aff~ -r Case EP-6800-A 16 phites, among others. For best results, the antioxidant should be composed predominantly or entirely of either (1) a hindered phenol antioxidant such as 2-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4,4 -methylenebis(2 6-di-tertbutylphenol), and mixed methylene bridged polyalkyl phenols, or an aromatic amine antioxidant such as the cycloalkyldi-lower alkyl amines, and phenylenediamines, or a combination of one or more such phenolic antioxidants with one or more such amine antioxidants. Particularly preferred for use in the practice of this invention are tertiary butyl phenols, such as 2,6-di-tert-butylphenol, 2,4,6-tri-tertbutylphenol, o-tert-butylphenol, and mixtures thereof.

Demulsifier. A wide variety of demulsifiers are available for use in the practice of this invention, including, for example, poly(oxyalkylene) glycols, oxyalkylated phenolic resins, and like materials. Particularly preferred are mixtures of poly(oxyalkylene) glycols and oxyalkylated alkylphenolic resins, such as are available 20 commercially from Petrolite Corporation under the TOLAD trademark. One such proprietary product, identified as TOLAD 9308, is understood to be a mixture of these components dissolved in a solvent composed of heavy aromatic naphtha and isopropanol. This product has been found efficacious for use in the compositions of this invention.

:.However, other known demulsifiers can be used such as TOLAD S:286.

Corrosion Inhibitor. Here again, a variety of materials are available for use as corrosion inhibitors in the practice of this invention. Thus, use can be made of dimer and trimer acids, such as are produced from tall oil fatty acids, oleic acid, linoleic acid, or the like. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humko Chemical Division of Witco Chemical Corporation and under the EMPOL

I

BDl~ls~ Case EP-6800-A 17 trademark by Emery Chemicals. Another useful type of corrosion inhibitor for use in the practice of this invention are the alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, hexadecenylsuccinic anhydride, and the like. Also useful are the half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. Also useful are the aminosuccinic acids or derivatives thereof represented by the formula:

R

5 0 RI __ici__ R C OR R R R 0 wherein each of R 2

R

3

R

5 and R 6 is, independently, a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon 15 atoms, and wherein each of R 1 and R 4 is, independently, a hydrogen atom, a hydrocarbyl group containing 1 to 30 carbon atoms, or an acyl group containing from 1 to 30 carbon o* atoms.

The groups R 2

R

3

R

4

R

5 and R 6 when in the form of 20 hydrocarbyl groups, can be, for example, alkyl, cycloalkyl or aromatic containing groups. Preferably R 1

R

2

R

3

R

4 and

R

5 are hydrogen or the same or different straight-chain or branched-chain hydrocarbon radicals containing 1-20 carbon atoms. Most preferably, R 1

R

2

R

3

R

4 and R 5 are hydrogen i ~s la c _3C Case EP-6800-A 18 atoms. R 6 when in the form of a hydrocarbyl group is preferably a straight-chain or branched-chain saturated hydrocarbon radical.

Most preferred is a tetralkenyl succinic acid of the above formula wherein R 1

R

2

R

3

R

4 and R 5 are hydrogen and

R

6 is a tetrapropenyl group.

Aromatic Hydrocarbon Solvent A wide variety of aromatic hydrocarbon solvents can be used with this invention such as benzene, and alkyl substituted benzene or mixtures thereof, Particularly useful are mixtures of and m- xylenes and mesitylene and higher boiling aromatics such as Aromatic 150 which is available from Chemtech. However, other mixtures of aromatic hydrocarbon solvents may also be *o used.

S 15 The relative proportions of the various ingredients used in the additive concentrates and fuels of this invention can be varied within reasonable limits. However, for best results, the additive concentrate should contain, on an active ingredient basis, from about 20 to about 35 parts by 20 weight (preferably from about 25 to about 30 parts by weight) of Mannich reaction product; up to about 50 parts by weight (preferably from about 20 to about 40 parts by weight) of poly(oxyalkylene) component; up to about 40 parts by weight (preferably from about 0 to about 30 parts by weight) of hydrotreated or unhydrotreated poly-a-olefin; 0 to 5 parts by weight (preferably, from 1 to 3 parts by -I Il

I

Case EP-6800-A 19 weight) of antioxidant; from 0 to 10 parts by weight (preferably, from 0.1 to 3 parts by weight) of demulsifier; from to 80 parts by weight (preferably 30 to 75 parts by weight) of aromatic hydrocarbon solvent (including any diluent or solvent present in the Mannich detergent as received); and from 0 to 5 parts by weight (preferably, from 0.025 to 1.0 parts by weight) of corrosion inhibitor per each one hundred parts by weight of fuel additive composition.

The above additive compositions of this invention are preferably employed in hydrocarbon mixtures in the gasoline boiling range or hydrocarbon/oxygenate mixtures, or oxygenates, but are also suitable for use in middle distillate fuels, notably, diesel fuels and fuels for gas turbine en- .i 15 gines. The nature of such fuels is so well known to those skilled in the art as to require no further comment. By oxygenates is meant alkanols and ethers such as methanol, ethanol, propanol, methyl-tert-butyl ether, ethyl-tert-butyl ether, tert-amyl-methyl ether and the like, or combinations 20 thereof. It will of course be understood that the base fuels may contain other commonly used ingredients such as 4* cold starting aids, dyes, metal deactivators, lubricity additives, octane improvers, cetane improvers, emission con- 04 trol additives, antioxidants, metallic combustion improvers, and the like. Cyclopentadienyl manganese tricarbonyl compounds such as methylcyclopentadienyl manganese tricarbonyl are preferred because of their outstanding ability to reduce tailpipe emissions such as NOX and smog forming precursors rc 111 _1 Case EP-6800-A 20 and to significantly improve the octane quality of gasolines, both of the conventional varity and of the newer "reformulated" types.

When formulating the fuel compositions of this invention, the additives are employed in amounts sufficient to reduce or inhibit deposit formation on intake valves. Deposits on fuel injectors may also be reduced or at least controlled. Generally speaking, the finished additized fuel will contain, by weight and on an active ingredient basis, no more than (and usually less than) about 5000 parts of the combination of components a) and b) per million parts of gasoline, and preferably, up to (and more preferably less than) about 3000 parts of the combination of components a) and b) per million parts of gasoline. On an active ingredi- 15 ent basis, the total amount of components a) and proportioned as above, in the finished fuels of this invention, is preferably no more than about 2000 ppm (by weight), and most preferably in the range of about 200 to about 1000 ppm (by weight). An additive comprising a Mannich reaction product, a poly(oxyalkylene) compound, and at least one liquid hydrocarbon such as one or more low boiling aromatic hydrocar- *0 bons, a poly-a-olefin oligomer and/or a mineral oil of suitable viscosity will be employed in unleaded gasoline in minor amounts such that the gasoline portion of the fuel (including oxygenates such as ethers or alcohol blending agents) is the major component, usually amounting to over by weight. The other components which are preferably used in conjunction with the fuel additive composition can I- Caco BP-680O-A 21 be blended into the fuel individually or in various subcombinations. However, it is definitely preferable to blend all of the components concurrently using an additive concentrate of this invention as this takes advantage of the mutual compatibility afforded by the combination of ingredients when in the form of an additive concentrate, and reduces the possibility of blending errors.

In order to illustrate the advantages of this invention, the following examples are given. In these examples, the concentrations of additives are typically referred to, in terms of pounds per thousand barrels (ptb). One pound per thousand barrels of additive in a gasoline of typical specific gravity is generally equivalent to about 3.8 to about parts per million (ppm) on a weight basis. In addition, 15 the amount of the Mannich dispersant is given on an "as received basis". Since the Mannich dispersant contained *99e approximately 40% by weight of active Mannich Reaction Product (the balance being hydrocarbon diluent and unreacted polyolefin), the actual quantity of active Mannich detergent 20 is approximately 40% of the values reported in the examples.

Example 1 The vital importance of the viscosity properties of component b) in providing the exhaust valve deposit control performance achievable by the practice of this invention was demonstrated by a series of series of engine tests. For each run, a 1991 Oldsmobile Cutlass equipped with a General I Y I L_ Case EP-6800-A 22 Motors 2.3L QUAD 4 engine was operated on an chassis dynamometer for the equivalent of 5,000 miles and the amount of engine deposits was determined. The engine was operated on a driving cycle representative of 10% city, 20% suburban and 70% highway driving. Average speed was equivalent to about miles per hour with the engine accumulating about 900 miles per day. Before each test was begun, the intake manifold and cylinder head were cleaned and inspected, the fuel injectors were checked for proper flow and spray pattern.

Following each cleaning and inspection, the engine was rebuilt with new intake valves and the crankcase oil was changed. The base fuel was a clear unadditized) regular unleaded gasoline. The crankcase oil used in the test runs was an SAE 5W-30 SG API-quality oil.

15 In this series of engine tests various poly(oxyalkyle ene) compounds of differing viscosities were mixed in the same proportions with separate portions of the same Mannich base detergent, viz., a reaction product of a 900 number average molecular weight polypropyl-substituted phenol, (ii) SP:: 20 formalin, and (iii) diethylene triamine (a Mannich base detergent commercially available from Ethyl Petroleum Additives, Inc. as HiTECO 4997 additive.) Each additive mixture 6 also contained Super High Flash Naphtha, a liquid hydrocarbon product having a flash point of about 40°C (about 100°F) and consisting of essentially 100% of aromatic hydrocarbons.

These three additives were formulated into additive concentrates in which the weight ratio of component a) (using the weight on an as received basis): component b) aromatic O 1ON ~Fi~srr~aRIPlaar~a~Piraaauaa r Cao BP-60O0-A 23 hydrocarbon diluent was 70:35:100. The additive concentrates were then blended into separate quantities of the same base fuel and the resultant fuel compositions were then evaluated in the above engine test. A control run was also carried out in which the clear unadditized) base fuel was used in the test.

Six different poly(oxyalkylene) products from different commercial manufacturers were used in these tests. Two met the viscosity requirements of this invention, the other four did not.

The two poly(oxyalkylene) products meeting the viscosity parameters of this invention were: A EMKAROX AF22 (ICI Chemicals Polymers Ltd.), apparently a poly(oxypropylene) monool with a molecular weight 15 of about 1700 with a viscosity typically in the range of about 87 to about 98 cSt at 40"C and about typically in the range of about 15 cSt at 100*C. The sample used had a viscosity of 96 cSt at 40"C and 17 cSt at 100 0

C.

B DFA36 (ICI Chemicals Polymers Ltd.), a proprietary 20 experimental poly(oxyalkylene) product obtained under a non-analysis agreement, for which the manufacturer specified a viscosity of 73 cSt at 40"C and 13.5 cSt at 100°C. Other properties given were Appearance, Clear by Method C&P Appendix 2-1; Water Content, 0.055% by Method C&P/CO/pm/584; Color (Hazen), 10 by Method C&P/CO/pm/579; Density, 0.9725 g/mL by Method C&P/CO/pm/561; Pour Point, -34 0 C by Method NFT60105; and Flash Point, 228*C by Method C&P/CO/pm/578.

r"g~ Case EP-6800-A 24 The four poly(oxyalkylene) products not meeting the viscosity parameters of this invention were: C An experimental proprietary poly(oxyalkylene) monool having a viscosity of 63 cSt at 40 0 C and 8 cSt at 100 0 C. Properties specified by the manufacturer were Approximate Molecular Weight, 1000; Mw/Mn, 1.79; OH Number (meq KOH/g), 66; and Viscosity, 120 cP at D A commercially available polyoxypropylene glycol butyl ether having a viscosity of 57 cSt at 40°C and 11 cSt at 100 0 C. Typical properties specified by the manufacturer were Average Molecular Weight, 1150; Average Freezing Point, -40"C; Flash Point (PMCC), >400°F (>204.4 0 Refractive Index, 1.446 at 25*C; Specific Gravity, 0.9888 at 25 0 C; and Viscosity Index, 177.

E A proprietary experimental poly(oxyalkylene) product obtainel under a non-analysis agreement, but identified the manufacturer to be an alkylphenol propoxylate.

It has a viscosity of 67 to 70 cSt at 40*C and 10 cSt at 100"C.

F- A proprietary experimental poly(oxyalkylene) product obtained under a non-analysis agreement having a viscosity of 44 to 45 cSt at 40 0 C and 8.4 to 8.6 cSt at 100°C. Other properties given were Appearance, Clear

C

by Method C&P Appendix 2-1; Water Content, 0.07% by 25 Method C&P/CO/pm/584; Color (Haz 15 by Method C&P/CO/pm/579; Density, 0.9586 g/mL by Method C&P/CO/pm/561; Pour Point, -39 0 C by Method NFT60105; and Flash Point, 220°C by Method C&P/CO/pm/578.

~rrr~--eua U~IC~ LI_ Case EP-6800-A 25 The intake valve deposit performance of this series of tests is summarized in Table 1. The fuels designated A through F contained the poly(oxyalkylene) compounds identified above as A through F, respectively. Thus fuels A and B were fuels of this invention whereas Fuels C, D, E and E were fuels not of this invention. Fuels A through F each contained component a) at a concentration of 70 pounds per thousand barrels (equivalent to approximately 0.027 wt%), the respective poly(oxyalkylene) compound at a concentration of 35 pounds per thousand barrels (equivalent to approximately 0.013 and the aromatic hydrocarbon solvent (which in effect became part of the gasoline) at a concentration of 100 pounds per thousand barrels (equivalent to approximately 0.04 wt%).

OS

*o «fl a s o O Case EP-6800-A 26 Table 1 Fuel 40°C Viscosity, 100°C Viscosity, Intake cSt cSt Valve Deposits, mg A 96 17 36.3* B 73 13.5 74.2 C 63 8 221.5 D 57 11 143.4 E 67-70 10 142.6 F 44-45 8.4-8.6 105.3 Control 128.0 -7 *0 ro* *0 0C Co

C.

C

C. C Average of two runs.

In addition, the total combustion chamber deposits formed when using fuels A and B was almost 3% less than the total combustion chamber deposits formed in the runs using fuels C, D, E and F.

Example 2 Another group of tests was conducted in a 1991, General Motors 2.3L QUAD 4 engine operated as described in Example 1. Once again the base fuel was an unadditized regular unleaded gasoline, and the fuel detergent used was the reaction product of a 900 number average molecular weight polypropyl-substituted phenol, (ii) formalin, and (iii) diethylene triamine. In this group of tests some of the test fuels contained, in addition to the combination of the detergent and a poly(oxyalkylene) compound, a poly-a-olefin oligomer (a 10 cSt unhydrotreated poly-a-)lefin of 1-decene, h~ ~sU~Pp~ s Case EP-6800-A 27 hereinafter referred to as PAO) or an antioxidant (HiTEC" 4733 additive (commercially available from Ethyl Petroleum Additives, Inc.). HiTEC" 4733 additive is a mixture of tertbutyl phenols containing about 10 wt.% 2-tert'butyl phenol, about 75 wt.% 2,6-di-tert-butyl phenol, about 2 wt.% 2,4-ditert-butyl phenol, and about 13 wt.% 2,4,6-tri-tert-butyl phenol.

The poly(oxyalkylene) compounds used both satisfied the requirements of this invention, one of them being the poly- (oxyalkylene) product identified as A in Example 1. The other product, G, is P1200 (Dow Chemical Company), a commercially available polyoxypropylene glycol having a typical viscosity of about 90 cSt at 40'C and about 13.5 cSt at 100°C. Typical properties as given by the manufacturer were S.i 15 Average Molecular Weight, 1200; Average Pour Point, .Flash Point (PMCC), 345°F (174*C); Refractive Index, 1.448 at 25°C; Specific Gravity, 1.007 at 25°C; and Viscosity Index, 161.

Table 2 gives the compositions of additives in the fuel o for each run (where ptb is pounds per thousand barrels) as well as the average of the intake valve (IVD) and combustion chamber deposits (CCD) for each cylinder. The combustion 0chamber deposits are a combination of the piston top deposits and the cylinder head deposits. Runs 1 and 2 give base line results for the unadditized fuel, and fuel containing Mannich detergent and PAO only. Runs 3-8 are of the invention and illustrate the reduction in deposits that can be aa~- pe i 8%--988RP -I Case EP-6800-A 28 achieved by additive formulations containing Mannich detergent/dispersant and a poly(oxyalkylene) compound having the viscosity properties required pursuant to this invention.

Table 2 Run HiTEC® HiTEC' Prod. Prod. PAO, Avg.

No. 4997, 4733, A, G, ptb dep., ptb ptb ptb ptb mg 1 905 2 80 4 40 877 3 80 40 962 4 80 4 40 736 80 20 20 864 6 80 4 40 846 7 80 20 20 805 8 80 40 746 15 Example 3 In another series of runs, a stationary 1985, Ford 2.3L, 4 cylinder, single spark plug engine was run for 200 hours under various loads utilizing Union Oil fuel and containing the additives indicated in Table 3. The transient 20 test cycle consisted of 2 minutes at 1,400 rpm and under a load of 18 inch.u of Hg intake manifold vacuum, 5 minutes at 2,000 rpm and a load of 12 inches of Hg intake manifold vacuum, and 3 minutes at 2,500 rpm at 10 inches Hg intake manifold vacuum. The engine coolant temperature was maintained at about 74*C and the combustion air was controlled at a temperature of 32*C and a humidity of 80 grains of oe 0900 a. 09 0000 00.0 0 00 09 0 ,e0 0 ~II I i Al I Case EP-6800-A 29 moisture per pound of dry air. The test is primarily an intake valve deposit test, but measurements of combustion chamber deposits and octane requirement increase can be made. In Table 3 octane requirement increase is the difference in octane requirement of the engine as measured at 0 and 200 hours. The crankcase oil used in the test runs was an SAE 5W-30 SG API-quality oil. New intake valves and valve stem seals were installed after each test run, and new exhaust valves were installed every fourth test run. Prior to and subsequent to each test run, the intake valves, ports, manifolds, and throttle blade were weighed and/or rated. Runs 10, 11, and 12, are given for comparative purposes and represent the baseline case of fuel without additive. Runs 10, 11, 12, and 13 were run with a different lot 15 of the same fuel as runs 14, 15, 16, and 17. Results of the tests indicate a significant reduction in intake valve deposits (IVD) with surprisingly little change in ORI or combustion chamber deposits. The poly(oxyalkylen) compound used pursuant to the invention was the same as product A of 20 Example 1. The fuel in Run 16 contained 4 ptb of sulfurized 2,6-di-tert-butylphenol as antioxidant and the fuel in run 17 had 4 ptb of nonyl phenol sulfide as antioxidant. No antioxidant was added to the other fuels of this series.

I

Case EP-6800-A 30 Table 3 *Oe* 0* Run HiTEC Product A PAO IVD CCD ORI No. 4997 (ptb) (ptb) (mg) (mg) (ptb) 721.0 1587 11 519.8 1668 8 12 577 1855 8-10 13 90 45 28.3 2210 11 14 90 45 43.1 1481 90 22.5 22.5 41.6 1655 11 16 90 45 37.8 1745 11 17 90 45 28.0 1740 9 Example 4 This series of runs is similar to the runs of Example 2. In this series of runs, a 1985, 2.3L, 4 cylinder Ford engine containing a single spark plug was run for 112 hours, operating between a 3-minute "power" cycle (37 HP) at 2,800 rpm and a 1-minute "idle" cycle (0-4 HP) at 2,000 rpm. The engine coolant temperature was maintained at about 74°C and the combustion air was not temperature and humidity controlled. The octane requirement increase is the difference in octane requirement as measured at 0 and 112 hours. The crankcase oil used in the test runs was an SAE 10W-40 SG API-quality oil. New intake valves and valve stem seals were installed alter each test run, and new exhaust valves were installed every fourth test run. Prior to and subsequent to each test run, the intake valves, ports, manifolds, and throttle blade were weighed and/or rated. Table 4 -sP P~PIP II I k LCI_~~ Case EP-6800-A 31illustrates the advantages of fuel additives of this invention. The poly(oxyalkylene) compound used pursuant to the invention was the same as product A of Example 1. The fuel in Run 16 contained 4 ptb of sulfurized 2,6-di-tertbutylphenol as antioxidant and the fuel in run 17 had 4 ptb of nonyl phenol sulfide as antioxidant. No antioxidant was added to the other fuels of this series.

Table 4 e 4 .444 o 0.4 4* S *4* 15 Run HiTEC® Product A PAO IVD CCD ORI No. 4997 (ptb) (ptb) (mg) (mg) (ptb) 18 90 45 19.8 1348 7 19 90 45 14.1 1469 8 20 90 22.5 22.5 22.5 1282 21 90 45 29.6 1273 8 22 90 45 24.9 1193 Example This series of runs is similar to the runs of Example 4. In this series, a 1993, dual spark plug, 4 cylinder 2.3 L Ford engine was run for 100 hours, operating between a 3minute "power" cycle at 2,800 rpm and a 1-minute "idle" cycle at 2,000 rpm. The combustion air was controlled at a temperature of 32*C and a humidity of 80 grains of moisture per pound of dry air. Runs 23-27 were run at an engine coolant temperature of 91°C and Runs 28 and 29 were run at an engine coolant temperature of 74°C. The octane requirement increase is the difference in octane requirement as Ir I Illi~r Case EP-6800-A 32 measured at 0 and 100 hours. The crankcase oil used in the test runs was an SAE 5W-30 SG API-quality oil. Prior to and subsequent to each test run, the intake valves, ports, manifolds, and throttle blade were weighed and/or rated. New spark plugs, intake valves and valve guide seals were installed every test run. New exhaust valves were installed every fourth test run. Table 5 illustrates the advantages of fuel additives of this invention. The fuels in Runs 26 and 27 contained 4 ptb of sulfurized 2,6-di-tert-butylphenol as antioxidant. No antioxidant was added to the other fuels of'this series.

Table o 20 *g 20 Run HiTEC® Product A PAO IVD CCD ORI No. 4997 (ptb) (ptb) (mg) (mg) (ptb) 23 261.0 647 6 24 90 45 41.6 961 25 90 22.5 22.5 29.5 1283 26 90 45 31.2 1183 6 27 90 22.5 22.5 37.3 1258 6 28 338.0 719 8 29 90 45 29.5 1283 Example 6 A group of road tests conducted in a 1991 Pontiac Grand Prix equipped with a General Motors 2.3L QUAD 4 engine demonstrated the excellent intake valve cleanliness performance achievable by practice of this invention. In these I Ir I- i-~Ll~r II Case EP-6800-A 33 tests comparisons were made of the performance of unleaded regular gasoline fuels of this invention versus the same base fuel containing a commercially available proprietary detergent composition regarded as one of the most effective ~?etergent additives in use in current gasolines. This comparative fuel additive composition is herein referred to as Product X. The fuels of this invention (Runs 1-3) are based on use of Product A of Example 1 as the poly(o.yalkylene) component. In Runs 1 and 3 the same Mannich base detergent as in Example 1 was used whereas in Run 2 the Mannich base detergent was Amoco 596 additive, another Mannich base quite similar to that of Example 1. In Run 3 the fuel also contained a phenolic antioxidant (HiTEC® 4733 additive) at a concentration of 5 pounds per thousand barrels. The 15 additive concentrates for Runs 1-4 were diluted with an aromatic hydrocarbon diluent having a flash point of about 0 C. In Runs 1-3 this diluent was proportioned such that the finished fuels contained 56 ptb of the aromatic hydrocarbon diluent, which in effect became part of the base 20 gasoline. The amount of hydrocarbon diluent added to Product X for the fuels of Run 4 was such that the finished fuels contained 125 ptb of added aromatic hydrocarbon diluent, which again became part of the base gasoline.

In each test the vehicle was operated on for 5,000 miles and the amount of engine deposits was determined. The driving cycle used was representative of 10% city, 20% suburban and 70% highway driving. Average speed was equivalent to about 45 miles per hour with the vehicle accumulating t u L _s L~ F Case EP-6800-A 34 about 840 miles per day. Before each test was begun, the intake manifold and cylinder head were cleaned and inspected, the fuel injectors were checked for proper flow and spray pattern. Following each cleaning and inspection, the engine was rebuilt with new intake valves and the crankcase oil was changed. The results of these tests are summarized in Table 6.

Table 6 a.

0

S

S

0 S *0t Run Mannich Product A Product IVD CCD No. Detergent (ptb) X (mg) (mg) (ptb) (ptb) 1 80 40 4.7 1622 2 80 40 20.2 1653 3 80 40 6.2 1498 4* 125 28.4 1770 15 Average of two runs.

Example 7 Similar excellent performance was exhibited in a pair of standard BMW engine tests conducted in the same vehicle using the same base fuel, an unleaded regular gasoline. In one run the fuel was a fuel of this invention wherein the base fuel contained 80 ptb of HiTEC® 4997 additive as component a) and 40 ptb of Product A of Example 1 as component The fuel additive composition in the comparative fuel was Product X at the 125 ptb concentration level. Table 7 summarizes the results.

L Case EP-6800-A 35 Table 7 Composition tested IVD, mg CCD, mg Fuel of this Invention 1.8 1423.5 Fuel not of this Invention 230.5 1389.2 As used herein the cerm "fuel soluble" means that the additive under discussion has sufficient solubility in the particular gasoline fuel composition in which it is being used to dissolve at 20°C to the extent of at least the minimum concentration required to achieve control of intake valve deposits in an internal combustion engine operated.on the resulting fuel. Preferably, and in almost all cases, the additive should (and will) have a substantially greater gasoline solub.'lity than this. However, the term does not require that the additive be soluble in all proportions in S: 15 the gasoline fuel composition.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

rr- I- ls

Claims (3)

1. 8. The fuel additive composition of Claim 1 wherein said number average molecular weight is in the range of about 800 to about 1200, said amine is a polyamine, said aldehyde is formaldehyde or a formaldehyde precursor, and 5 said poly(oxyalkylene) compound has a viscosity in the range *S* 6 of about 87 to about 98 cSt at 40"C and in the range of 7 about 15 to about 19 cSt at 100*C, and an average molecular 8 weight of about 1700. 1 9. The fuel additive composition of Claim 8 further 2 comprising one or more hydrocarbons collectively having 3 viscosities at 40°C and 100°C that are no higher than about 4 25% of the respective viscosities of said poly(oxyalkylene) compound at 40°C and 100°C. p i ~s CI-~-I~-PT WP I I-- JLIPr;lLll~aU~Q*II~IIYIIU~HIF~~--- Case EP-6800-A 38 1 10. The additive composition of Claim 9 wherein 2 said hydrocarbons comprise an aromatic hydrocarbon component 3 that has a boiling point or a final boiling point no higher 4 than about 240*C. 1 11. The fuel additive composition of Claim 10 wherein 2 said hydrocarbons further comprise polyolefin polymer having 3 a number average molecular weight of froa about 800 to about 4 1200. 1 12. The fuel additive composition of Claim 11 wherein 2 the proportions of a) to b) are such that there are from S3 about 0.5 to about 3 parts by weight of active Mannich base 4 in a) per part by weight of b). Sc. 1 13. The fuel additive composition of Claim 11 wherein 2 the proportions of a) to b) are such that there are from 3 about 0.8 to about 2 parts by weight of active Mannich base 4 in a) per part by weight of b). 1 14. The fuel additive composition of Claim 11 further 2 comprising, per 100 parts by weight of said composition, 3 about 1 to about 5 parts by weight of gasoline-soluble 4 antioxidant, about 0.1 to about 3 parts by weight of gaso- line-soluble demulsifier, and about 0.025 to 1.0 part by 6 weight of gasoline-soluble corrosion inhibitor. 1 15. A composition which comprises a major amount of 2 hydrocarbons of the gasoline boiling range and a minor f i ;--~alrY g- Ill~rr r Case EP-6800-A 39 3 engine deposit-inhibiting amount of a fuel additive composi- 4 tion n accordance with any of Claims 1-14 inclusive.
2. 16. A method for controlling intake valve deposits in 2 a gasoline engine comprising fueling and operating said 3 engine with a fuel composition which comprises a major 4 amount of hydrocarbons of the gasoline boiling range and a minor engine deposit-inhibiting amount of a fuel additive 6 composition in accordance with any of Claims 1-14 inclusive.
3. 17. Fuel additive compositions or methods involving them substantially as hereinbefore described with reference to the Examples. S. Th otpo fatur, psition and mpo disclosed herein or referred to or inat in the specification and/or al~rl of this application, a individuall -colectively, and any and all combinations DATED this FIFTH day of OCTOBER 1994 Ethyl Corporation by DAVIES COLLISON CAVE Patent Attorneys for the applicant(s) L I1IU IIII~. FUEL COMPOSITIONS Abstract of the Disclosure A highly effective fuel additive composition for control of intake valve deposits is described. It comprises a gasoline-soluble Mannich reaction product of a high molecular weight alkyl-substituted phenol wherein the alkyl group has a number average molecular weight of from about 600 to about 3000, (ii) amine, and (iii) aldehyde; and a gasoline-soluble poly(oxyalkylene) compound having a viscosity in its undiluted state of at least about 70 cSt at 40"C and at least about 13 cSt at 100*C. These components are proportioned such that there are from about 0.2 to about 5 parts by weight of active Mannich base in per part by weight of 0* 0'" *oo I -a s ~~la I