CA2133796C

CA2133796C - Fuel compositions and additives therefor

Info

Publication number: CA2133796C
Application number: CA002133796A
Authority: CA
Inventors: Dennis J. Malfer; Lawrence J. Cunningham
Original assignee: Ethyl Corp
Current assignee: Afton Chemical Intangibles LLC
Priority date: 1993-10-06
Filing date: 1994-10-06
Publication date: 2005-08-23
Anticipated expiration: 2014-10-06
Also published as: CA2133796A1; DE69421784T2; DE69421784D1; EP0647700A1; AU678514B2; EP0647700B1; JP2744205B2; JPH07197052A; AU7445294A

Abstract

A highly effective fuel additive composition for control of intake valve deposits is described. It comprises (a) a gasoline-soluble Mannich reaction product of (i) 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 (b) 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 parts by weight of active Mannich base in (a) per part by weight of (b).

Description

~l~~r~~t~
Case EP-6800-A

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 publi-aation date of August 21 , 1993 describes a similar additive system. In particular, the gasoline is to contain (a) from 75 to 450 ppmw of ,a specified group of Mannich base deter-gents in combination with (b) from 75 to 175 ppmw of an oil-soluble'poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0.43.
THE INVENTION
It has now been discovered that oil-soluble poly(oxy-a~kyl,ene) 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, the viscosity properties of the poly(oxyalkylene) component appear to have a profound effect on the intake valve clean-liness performance of the overall.composition.
Accordingly, in one of'its embodiments; this invention provides, a fuel-soluble additive composition which com prises a) a'Mannich reaction'product of (i) a high molecular weight alkyl-substituted phenol, (ii) amine; and (iii) aldehyde: and ~b) ~a-po7.y(o~yalkylene} compound shaving '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.
preferably, he.composition-will contain one or more liquid hydrocarbons which, whether a single hydrocarbon or a mix-ture of different hydrocarbons, has a viscosity that is not substantially in excess of the viscosity of the paly(oxyal-kylene) compaund.

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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 (i} a high molecular weight alkyl-substituted phenol, (ii) amine, and (iii) aldehyde: and b} a poly(~xyalkylene) compound having in its undiluted state a viscosity of at least about ?0 centistokes (cSt} at 40°C and at least about 13 cSt at 100°C.
1~ Typically the :proportions of a} to b} in the composi-tions of this invmtion are such that there are from about 0.2 to about 5' parts by weight of a) peg part by weight of b),~preferably from about 0.5 to about 3 parts by weight of a) per part by'weight of b), and mare preferably from about 0.8 to about 2 parts by Freight of a} per part by weight of b}, 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 polyolefin used in making the alkylated phenol from which the Mannish detergent is produced. Thus the foregoing proportions of,a) to b),are based on the content of Mannish base detergent iri component a) excluding the weight of any, diluent or-solvent and any unreac~~d polyolefin which may be associated therewith in 'the form in rahich it is supplied.
Component b} wily: normally be supplied in undiluted form, and. iW such.case .its. weight can be used directly in calcu-lating tho ratio of a) to b}. But if the poly(oxyalkyIene) vocampound is,boing' blended with a} when the' poly(oityal,kylenej 30. compound is in admixture with a solvent or diluent, the weight of b} should be. based on the weight of the poly(oxy-alkylene) compound 'itself and should likewise exclude the weight of any such solvent or diluent associated therewith.
It will be understcaod that any such ancillary solvent or diluent, whether hydrocarbon or otherwise; must not adversely affect the intake valve deposit control porfor Case EP-6800-A

manes 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 o~ 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 visco-shies 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(oxyaTkylene) compound being used. Not only does th~.s 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 composi-Lion to a minimum.
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 composi-tion comprising (a) a major amount of hydrocarbonaceous fuel in the gasoline boiling range and-(b) a minor intake valve deposit controlling amount of .a) a Manniah reaction product of (i) 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.
,, ~ i , ; , As noted'above, the Mannish reaction product component of this invention typically contains a significant portion of hydrocarbonaceous ingredients which are inactive in the sense that they do not possess polarity or surface'activity and therefore do not serve as detergents. For example, sub-sequent to the manufacture of the Mannish reaction product;
hydrocarbon solvent is typically added to dilute the product to facilitate handling and blending. Thus, the ,Mannish '"1 Case EP-6800-A

product as received typically contains about 40 to about 55 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 o-, p-, and m-xylene, mesitylene, and higher boiling aromatics such as Aromatic 150 (commercially available from ~h~mtech).
The Mannich reaction products of this invention are ~,0 obtained by condensing an alkyl-substituted hydroxyaromatic compound whose alkyl-substituent has a number average mol~
cula~ weight'of from about 600 to about 14,000, preferably alkylphenol whose alkyl substituent is derived from 1-~mono olefin 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 pre-ferabZy about 800 to about 950; an amine having-at least one r>NH group, preferably an alkylene polyamine of the formula HzN - (A - NIi -)xH
where A is a divalent alkylene radical having 2 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 mixtures of linear, branched and cyclic species:
High molecular weight Mannieh reaction products useful as additives in the fuel additive compositions of this in ., ,v~ntion are preferably ;prepared according' to conventional methods employed for the preparation of Mannish condensation products, using the'abo~e-named reactants in the respective 'molar ratios of (i) high'molecular weight alkyl-substituted hydroxyaromatic compound, (ii') amine, and (iii) aldehyde of ap~aroximately l.0 0.1-10 i-10. Usually the reactants are charged in proportions such that there are an excess of the aldehyde and an excess o~ a polyamine relative to he hydroxyaromatic compound such as an alkylphenol which f"°:: Case EP-6800-A ~s c r ,. ..
~~.~3 l ~~i thereby becomes the limiting reactant: For example it is common to charge about l to 3 moles of polyamine and about 1:2 to 4 moles of aldehyde per mole of (i). A suitable condensation procedure involves adding at a temperature of from room temperature to about 95°C, the formaldehyde rea-gent (e. g:, Formalin) to a mixture of amine and alkyl-sub-stituted hydroxyaromatic compounds alone or in an easily remoued organic salvent, such as benzene, xylene, or toluene or in solvent-refined neutral oil and then heating'the re-action mixture at an elevated temperature (120°-175'°C) while preferably blowing with an inert stripping gas, such as ni-trogen, 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 his -invention are derived from high molecular weight Manni.ch condensation products, formed by reacting an alkyl- ~ .
phenol, 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 a-bout':3,000, and more preferably .from' about 750 to about 1,208.
Representative of the high molecular weight alkyl substituted hydroxyaromatic compounds are- polypropylphenol (formed by alkylating,phenol with;polypropylene); polybutyl phenol (formed by alkyLating phenol with polybutenes or poly isobut~rlefie) , mind other similar.long-chain al~kylpheriols.
polypropylphenol is the most; preferred reactant. Polyalkyl phenols may be obtained by the a~kylation, in the presence of an alkylating oatalyst such as BF3,: of phenol with high molecular weight polypropylene, polybutyl.ene and other poly-alkylene compounds o give alkyl substituents on the benzene ring of phenol'having.a number average'molecular weight '(Mn) 'of from about 600 to about 14,000.

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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 copoly-mer molecule contains at least 90% by weight, of ~ano-olefin units. Specific examples are copolymers of butanes (butene-1, butane-2, and isobutylene) with monomers copolymerizable therewith wherein the copolymer molecule contains at least 90% by weight of propylene and butane units, respectively.
The'monomers copolymerizable with propylene or butanes in-clude mon~mers containing a small proportion of unreactive polar groups such as chloro, bromo, keto, ether, aldehyde, which do appreciably lower the oil-solubility of the.poly-mar: The comonomers polymerized with propylene or such bu-tenes may be aliphatic and can also contain non-aliphatic groups, e:g:, styrene, methylstyrene, p-dimethylstyrene, divinyl benzene and the like: from the foregoing limitation placid on the monomer copolymerized with propylene or the butanes, it is clear that the resulting polymers and copoly-mers are substantially aliphatic hydrocarbon polymers:
Thus; the resu7aing alkylated phenols, contain substantially alkyl hydrocarbon substituents having a number average molecular weight (Mn) of from about 600 to about 14,000.
Tn addition to the foregoing high molecular weight hy-droxyaromatic 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, naphthol, to3ylnaphthal, among others. Preferred for the preparation of such preferred Mannich condensation products aye the polyaTkylphenol reactants, e.g., 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-Case EP°6800-A

propyl group having a number average molecular weight of about 900950.
The preferred configuration of the alkyl-substituted hydroxyaromatic compound is that of a para-substituted mono-alkylphenol. 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 suit-able for use in this invention:
1Q ' Representative amine reactants are alkylene polyamines, principally polyethylene polyamines. Other representative organic compounds containing at least one FiN< group, suitable for use in the~preparation of the Mannish reaction'products are well known and include he mono and 'di-amino alkaries and theix substituted analogs, e.g., ethylamine, dimethylamine, dimethylaminopropyl amine, and diethanol amine; aromatic di amines, e:g., phenylene diamine, diamino naphthalenes; het erocyclic amines, e.g., morgholine, pyrrole, pyrrolidine, imidazole; imidazolidine, and piperidine; melamine and their substituted analogs.
The'alkylene polyamine reactants which are useful with this.:invention include polyamines whicli~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 mole-,c~lfe, or a ~ mixture off." 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 hexaminehexaethyl-ene heptamine, heptaethylene octamine, octaethylene nona-mine, nonaethylene; decamine, and' mixtures of such amines.
Corresponding propylene: polyamines such as propylene di-amine, and dipropylene triamine; tripxopylen,e tetramine, tetrapropylene pentamine, pentapropylene hex~mine are also Case EP-6800-A
_ g -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 chemi-cal 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 mix-ture with which it is mixed:
Ordinarily the most highly preferred polyamine, dieth-ylene triamine, will comprise a commercially available mix-ture 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 o 'is diethylene triamine.
The alkylene polyamines, are usually obtained bg the reaatioz~ of ammonia and di:haloalkanes, such as dichloro-alkanes. Thus, the alkylene polyamines are obtained from-the reaction of 2 to lL moles., of ammonia with 1 to 10 moles of dichloroaTkanes having 2 to 6 carbon atoms and chlorine atoms on different'carbon atoms:
Representative aldehydes for use in the,preparat~ion-of i high molecular weight Mannich products include the aliphatic aldehydes uch as formaldehyde, acetaldehyde, propionalde-hyde, butyraldehyde, valeraldehyde, caproaldehyde, heptal-dehyde, stearaldehyde. Aromatic aldehydes which may be used include benzaldehyde and salicylaldehyde: illustrative het-erocyclic aldehydes for use -herein are furfural and thio-phene aldehyde; etc': AIso useful are formaldehyde-producing reagents such as paraformaldehyde, or aqueous formaldehyde CdSe EP-6800-A

solutions such as formalin. Most preferred is formaldehyde or formalin.
hnportant considerations insofar as the present inven tion is concerned, are to insure that the alkylphenol having an alkyl substituent with the desired number average molecu lar weight be reacted with the preferred polyethylene poly-amine and aldehyde comgounds and that the reactants be em-ployed in.proportiorrs such that the resultant Mannich reac-tion product contains the requisite proportions of the chem-'ically combined reactants, all as specified herein. When utilizing'this combination of features, he resultant compo itions of this invention not only possess exceptional effectiveness in control~.ing;or reducing the amount of in duction system,deposits formed during engine operation but which permit adequate demulsification performance.
A key feature. of this invention is that the Mannich reaction products are used in coiabination 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 gasoline-soluble poly(oxyalkylene) alcohol , glycols or polyols or mono or diethers thereof, with the proviso that such com-pounds have in theirvundi:luted state a viscosity of at least about 70 centistokes,(cSt) at 40°C and'at Least about 13 cSt at-104°C. Such compounds can be represented by the follow-i~a formula , i. , y ~, ~~
Rt- ( -R20-) n-.R3 ( I
wherein R~;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, RZ is an alkylene group having '2-10 carbon atoms (-preferably 2-5 carbon atoms}, R3: 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 (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 gaso-line-soluble liquid having a viscosity of at least about 70 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(oxyal-kylene) glycol compounds and monoether derivatives thereof that satisfy the above viscosity requirements and that are comprised of repeating units formed by reacting an alcohol 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 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. U.S. Patent Nos. 2,425,755; 2,425,845; 2,448,664; and 2,457,139 also describe such procedures.

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Preferred poly(oxyalkylene) compounds can be represent-ed by the formula R40 (RSC!) p R6 (II) wherein R4 is a hydrogen atom, or a hydrocarbyl group having up to l8 carbon atoms, and more preferably an alkyl group having up to 10-l2 carbon atoms; RS is an alkylene group of 2-5 carbon atoms which thus can be an ethylene group (i.a., dimethylene) group, but which preferably is a propylene (i:e., methyldimethylene) group, or a butylene (i:e., ethyl-dimethylene), group; R~'is a hydrogen atom, or a hydrocarbyl group having up to-18 carbon atoms; and more preferably an alkyl group havr~g up to 10-12 carbon atoms; 'and p is a integer that yields a product having the viscosity parame-ters given above.'Commercially available products are.often 15- composed of mixtures in which°the individual species'iof 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 differ-ent, can be arranged either randomly' ar 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 pro-pylene 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 ~ b~ty~.ene~ groins,, ~ or bath, proport~.oned ,to yie~,d a nliqu,id gasoline-soluble product having the requisite viscosity properties specified above. Monools derived by, propoxy-lation of alkanols (R4 in Formula (II) is alkyl;, RS is methyldimethylene groups, Rb is~a'hydrogen atom, and p 'is a~
defined above) are'most preferred'. Such compoua~ds can also be thought of as monoethers of poly(oxyalkylene) glycols-.

Other poly(oxyalkylene) glycols and ethers which may be employed can be represented by the formula RIO- ( -R80- ) q-Rq- ( -ORS o- ) ~-OR> > ( I I I ) wherein R~ and R» can be the same or different and each is independently a hydrogen atom or a hydrocarbyl group, pre-ferably an alkyl group of up to 18 carbon atoms, and more preferably of up to 10-12 carbon atoms; R$ and Rio can be the same or different and are alkylene groups of 2-5 carbon atoms each, which thus can be ethylene groups (i.e., dimeth-ylene groups), but which preferably comprise or consist of propylene (i.e., methyldimethylene) groups, and/or butylene (i.e., ethyldimethylene) groups; R9 is an divalent hydrocar-bylene 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 (i.e., dimethylene) group, a propylene (i.e., methyldimethylene) group, or a butylene (i.e., ethyldimethylene) group, and q and r are independent-ly integers that yield a product having the viscosity para-meters 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 all be the same or they can be different and if different, can be arranged either randomly or in blocks or sequences.
The poly(oxyalkylene) compounds used pursuant to this invention will contain a sufficient number of branched oxyalkylene units (e. g., methyldimethyleneoxy units and/or 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 20°C, *Trade-mark Case EP-6800-A

an open cup flash point of about 230°C, a viscosity of about 90 cSt (typically in the range of about 87 to about 98 cSt) preferably about 10 centistokes at 100°C. The volatility of the poly-a-olefin is also of significance and may be deter-mined by the Volatility Determination Method described below.
To determine the volatility of a substance the follow-ing Volatility Determination Method is used. The substance, e.g., a poly-a-olefin (110-135 grams) is placed in a three-neck, 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 (e. g., poly-a-olefin) is heated in an oil bath to 300°C for 1 hour while stirring the sub-stance in the flask at a rate of 150 rpm. During the heat-ing and stirring, the free space above the substance in the flask is swept with 7.5 L/hr of inert gas (e. g., nitrogen, argon, etc.). The volatility of the substance poly-a-olefin thus determined is expressed in terms of the weight percent of material lost based on the total initial weight of mate rial tested. Utilizing the foregoing procedure, it is particularly preferred to select poly-a-olefins for use in the additive formulations of this invention that have a volatility of less than about 50~, more preferably less than about 25%.
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 oxi-dation inhibitors can be utilized in the practice of this invention. These include phenolic antioxidants, amine anti-oxidants, sulfurized phenolic compounds, and organic phos-*Trade-mark /.-.~ Case EP-6800-A ~ r ~ r; s H
~~~~ ~~Jv trademark by Emery Chemicals. Another useful type of corrosion inhibitor for use in the practice of this invert-tion are the alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetra-;propenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, hexadecenylsucci:nic anhydride, and the life. Also useful are the half esters of alkenyl suc- -citzic 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:

R3 C C 0Rt R2 ~~
wherein each of R2,, R3, RS and R6' is, independently; a hydro gen atom or a hydrocarbyl group containing 1 to 30 carbon atoms, and wherein each of Rt and R4 is, independently, a 'hydrogen atom; a hydrocarbyl group containing 1 to 30 carbon atoms, pr an aryl group containing- from 1 0 30 carbon 'atoms.
,i . ~ , ,;
The groups R~. R2~ R3, R4, R5> and R6 when in the form of ' hydrocarbyl groups; can be, for example, alkyl; cycloalkyl or aromatic containing groups. Preferably R'; R2, R3, R4 and RS are hydrogen or the samQ or different straight-chain or branched-chain hydrocarbon radicals containing 1-20 carbon atoms. Most preferably, R', RZ, R3, R4, and R5 are hydrogen 'na'. .
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weight) of antioxidant; from 0 to 10 parts by weight (pre-ferably, from 0.1 to 3 parts by weight) of demulsifier; from 25 to 80 parts by weight (preferably 30 to 75 parts by weight) of aromatic hydrocarbon solvent (including any dilu-ant or solvent present in the Mannish .detergent as re-ceived); and from 0 to 5 parts by weight (preferably, from 0.025 to 1.0 parts by raeight) -of corrosion inhibitor per each one hundred parts by weight of fuel additive composi-tion.
7,0, The above additive compositions of this invention are preferably employed in hydrocarbon mixtures in he gasoline boiling range or hydrocarbon/oxygenate mixtures, or oxygen-ates, but are also suitable far use in middle distillate fuels, notably, diesel fuels and fuels for gas turbine en-gives. The nature of such fuels is so well known to those skirled in the art as +_o require no further comment. By oxygenates is meant alkanols and ethers such 'as methanol, ethanol, propanal,~nethyl-tart-butyl ether, ethyl=tart-butyl ether, tart-amyl-methyl; ether and the'like, or combinations 'thereof. It will of'course be understood that the base fuels may contain other commonly used ingredients such as '; , cold startling aids, dyes, metal deactivators, lubricity additives, octane improvers, cetane improvers, emission con-trol additives, antioxidants; metallic combustion imprbvers, and the-like: Cyclopentadienyl manganese tricarbonyl aom-pounds such as methylcyclopentadienyl manganese tricarbonyl are preferred because of their outstanding ability to reduoe ta~;lpipe emissions such as NOX and smog'forming precursors Case EP-6800-A

be blended into the fuel individually or in various sub-combinations. However, it is definitely preferable to blend all of the components concurrently using an additive con-centrate of this invention as this takes advantage of the mutual compatibility afforded by the combination of ingredi-eats when in the form of an additive-concentrate, and re-duces the possibility of blending errors.
In order to illustrate the 'advantages of this inven ion, the following examples are given. In these examples, 7,0 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 spec-ifid gravity is generally equivalent to about 3.8 to about 4.0 parts; per million (ppm) on a weight basis. In addition, 'the amount of the Mannich dispersant is given on an "as received basis~~. Since the Mannich dispersant contained approximately 40% by weight of; active Mannish Reaction Product (the balance being hydrocarbon diluent and unreacted polyolefin), the actualquantityof active Mannish detergent is approximately 4U% of the values reported in the examples.
' I i ~ ' ' ~ ~ i,~
Examtol a . 1 The'vital importance of the viscosity properties of component b) in providing the exhaust valve deposit'control perfarmance achievable by the practice of this invention was ~5 demonstrated bx a series of series of 'engine tests: For each: run, a 1991 Oldsmabile Cutlass equipped with a General Case EP-6800-A
Motors 2.3L QUAD 4 engine was operated on an chassis dyna-mometer far the equivalent of 5,000 miles and the amount of hydrocarbon diluent was 70:35:100. The additive concen-trates 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 (i.e., 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 viscosi-ty parameters of this invention were:
A - EMKAROX AF22 (ICI Chemicals & Polymers Ltd.), apparent-ly a poly(oxypropylene) monool with a molecular weight 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°C.
B - DFA36 (ICI Chemicals & Polymers Ltd.), a proprietary 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_°C by Method NFT60105;
and Flash Point, 228°C by Method C&P/CO/pm/578.
*Trade-mark Case EP-6800-A

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°C and 8 cst at 100°C. Properties specified by the manufacturer were Approximate Molecular Weight, 1000; Mw/Mn, 1.79: OH
Number (meq KOH/g), 86: and Viscosity, 120 cP at 25°C.
D - A commercially available polyoxypropylene glycol butyl ether'having a viscosity of 57 cSt at 40°C and 11 cSt ~0 at 100°C. Typical properties specified by the manufac turer were Average Molecular Weight, 1150; Average Freezing Point,, -40°C; Flash Point (PMCC), >400°F
(>204.r~°C); Refractive Index, 1°446 at 25°C; Specific Gravity, 0.9888 at 25°C; and Viscosity Index, 177:
E - A proprietary experimental poly(oxyalkylene) product obtained under a non~analysis agreement, but identified by the manufacturer to be::an alkylphenol propoxylate.'' Iic has a viscosity of 67 to 70 cSt at 40°C and 10 cSt at 100°C.
F - A proprietary experimental pol,y(axya2kylene)'product obtained under a non'-analysis agreement having a vis-cosity of 44 to 45 cSt at 40°C and 8.4 to 8.6 cSt at 1'p0 ° ~ ~ Other properties' given were Appearance; Clear by Method C&P Appendix 2-1; Water Content; 0.07% 'by M~thod C&P/~CO/pm/584Color (Hazen), 15 by Method G&P/CO/pm/579; Density, 0.9586 g/mL by Method C&PjCO/pm/561; Paur Point, -39°C by Method NFT60105;
and Flash Point,, 220°C by Method C&P/CO/pm/578:

''~ Case EP-6800-A

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 identi-Pied 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 inventi4n: Fuels A through F each contained component a) at a concentration of 70 pounds per th.ou~and barrels (equivalent to approximately 0.027 wt~), the respective,poly(oxyalkylene) compound at a concentration of 35 pounds per thousand -barrels (ec;uivalent ' to approxi-mately 0.013 wto), and the aromatic hydrocarbon solvent .
(which in effect became part of: the gasoline) at a concen-tration of 100 pounds per thousand barrels (equivalent to aPProximately 0.04 wt%).
I i .' a ' , i ,!, Case EP-6800-A

Table 1 Fuel 40C Viscosity, 100C Viscosity, Intake csb cgt Valve De-posits, mg A 96 2~ 36.3*

B 73 13.5 ?4.2 C 63 8 221.5 D 5? 11 143.4 E 67- l0 142.6 F 44-45 8:4-86 105:3 Control -- 128.0 * 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, p, E and F:

Example Another group of tests was conducted in a 191, General Motors 2:3L
QUAD
4 engine operated as described in Example 2. Once again the base fuel:was an unadditized regular un-leaded gasoline,iand the fuel detergent used was the reac-;; , :

, tion product of (i) a 900 number average mole~ulax weight polypropyl-substituted phenol, (ii) formalin, and (iii) di--ethylene triamine.
In this group of tests some of the test fuels.contained, in addition-to the combination of the de-tergent and a poly(oxyalkylehe) compound, a poly-a-olefin oligomer (a lO.cSt unhydrotreated poly-a-olefin of 1-decene, 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 tert-butyl phenols containing about 10 wt.% 2-tert-butyl phenol, about 75 wt.% 2,6-di-tert-butyl phenol, about 2 wt.% 2,4-di-tert-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 com-mercially 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 Average Molecular Weight, 1200; Average Pour Point, -40°C;
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 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 chamber deposits are a combination of the piston top depo-sits 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 inven-tion and illustrate the reduction in deposits that can be *Trade-mark Case EP-6800-A
_ 2g _ achieved by additive formulations containing Mannich deter-gentjdispersant and a poly(oxyalkylene) compound having the viscosity properties required pursuant to this invention.
Table 2 Run HiTEC~HiTEC~ Prod. Prod. PAO, Avg.

No: X997, 4733,, A, G, ptb dep., ptb ptb ptb ptb, mg ;

1 _- 905 2 $~ 4 40 g77 3- g0 __ 4p _ 962 4 80 4 40, _. T36 6 80 4 40 _ 846 ' Example In 1985, another Ford series of runs, a stationary 2.3~, cylinder, 4 single spark plug engine was run for hours l and under con-various loads utilizing Union'oil fue taini.ng the transient additives indicated ih Table 3.
The , dle .t,est; consiisted cy of minutes at 1,4f0 rpmiand under' a load l8 minutes of inches at of Hg intake manifold vacuum, 2,000 rgm and a load of inches 'of Hg intake manifold vacuum, 'and Hg intake 3'minutes at 2,500 rpm at inches manifold was vacuum: main-The engine coolant temperature tamed at controlled about and the combustion air was at grains a of temperature of and a humidity of Case EP-6800-A

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 dif-ferenae in pctane 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 APL-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 pur-poses and represent the baseline case of fuel without addi-tive. Runs 10, 11, 12, and 13 were run with a different lot of the same fuel;as runs ,14, 15-, 16, and 17. Results of the tests indicate a sign.ficant reduction in intake valve depo-sibs (IVDj with surprisingly little change in 0RI or combus-tion chamber deposits. The poly(o~cyalkylene) compound used pursuant to the: invention was the same as product A of Example 1. The fuelin Run 26 contained 4 ptb of sulfurized 2,6-di-tart-butylphenol as antioxidant and the fuel in run 17 had 4 ptb of nonyl phenol sulfide as antioxidant: No antioxidant, was added to ' the athe~ ~fttels . of ! ~his~ series . ~' Case EP-6800-A

Table 3 Run HiTEC~ Product PAO IVD CCD ORI
No. 4997 A (ptb) (mg) (mg) (ptb) (ptb) 1~ __ _o _- 721.0 1587 10 1~; __ 519.8 1668 8 12 _ ~_ 577 1855 8-10 13 90 g5 _ 28.3 2210 11 14 90 4~ - 43.1 1481 10 90 22:5 22:5 41.6 1655 11 10 ~.6 90 45 -- 37.8 1745 .11 1'7 ,90 45 28.0 1740 9 Example 4 This series of runs is similar to the runs of Example 2. Tn this series of runs, a 1985, 2:3L,- 4 cylinder Ford 15 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 can-trolled: The octane requirement increase is the difference inn octane requirement as measured ~~at 0 and 112''hours. ' the crankcase oil used in the test runs was an SAE loW-40 SG
APT-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 grad subse-quent to each test run; the intake valves; ports; manifolds, and throttle blade were weighed andjor rated. Table 4 Case EP-6800-A ~ ~, ~ ~ ~ ~1 illustrates 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-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.
Table 4 Run HiTEC~ Product PAO IVD CCD DRI
A' No. 499T (ptb). (ptb) (mg) (mgt (ptb) 18 90 45 19.8 1348 7 19 90 45 - 14.1 1469 8 90 22.5 22.5 22.5 1282 10 2a g0 ,~5 - 29.6 1273 8 15 22 90 45 -- 24.9 11g3 10 Example This to the runs series of of runs Example is similar 4. >In rk plug,4 cylinder this 2:3 series, a 1993, dua3.
spa L Fdrd 'opera~ting engine between was a 3-run for hours, 20 minute and 1-minute "power" a "idle"
cycle at 2800 ' , rpm . ~
I j , :
.. i , w , . .. .
L,. air .
s ~ was controlled ~ , .. at ~cycl~ a at 2,000 rpm:
The combustion temperature f 80,grains of 32C of and moisture a humidity o per pound were of dry run air. at Runs an 23-27 engine coolant 29 temperature were of 91C run and at Runs 28 and an engine C. the octane coolant require-emperature of 74 meat octane requirement increase' as is the difference in Case EP-6800-A ~ ~ ~ ~ ~ ~ D

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 subseguent to each test run, the intake valves, ports, mani-folds, and throttle blade were weighed and/or rated. New spark plugs, intake valves and valve guide seals were in-stalled every test run. New exhaust valves were installed every fourth test run. ' Table 5 illustrates the advantages of fu~l 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.

Run HiTEC~ Product A PAO IV~ CCD ORI

No. 4997 (p~b~ (ptb~ (mg} (mq) tptby 23 ._ 261.0 647 6 24 ~0 45 -- 41.6 961 5 , g0 22'~ 22.5 29.5 1283 5 26 90 45 - 31.2 1183 6 -2? 90 22.5 22.5 3T:3 2258 6 20 28 _- 338.0 719 8 29, 90 45 - 29.5 1283 5 Example 6 A group of road tests conducted in a 1991 Pontiac Grand Prix equipped with a General Motors 2.3L QUAD 4 engine de-25 monstrated the excellent intake valve cleanliness perfor mance achievable by, practice of this invention. Tn these Table 5 Case EP-6800-A ~ ~ ~ ~ ~

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 detergent additives in use in current gasolines. This 7: b . /" J
Case EP-6800-A

about 840 miles per day. Before each test was begun, the intake manifold and cylinder head were cleaned and inspect-ed, the fuel injectors were checked for proper flow and spray pattern. Following each cleaning and inspection, tha Run Mannich Product ProductIVD CCD
A

No. Detergent (pt~} X (mg) (mg) (ptb} (ptb) 1 80 40 4.7 1622 2 80 40 2p.2 1653 3 80 40 6:2 1498 4* --~ 125 28.4 1770 *
Average of two runs.

Example Similar performance excellent was exhibited in a pair of standard tests BMW conducted engine in the same vehicle using l, an the unleaded same regular base gasoline.
fue In ,, ~
one : ~.
run ,, the fuel fuel of was this a invention wherein the 'base ptb fuel of contained HiTEC~

additive as coin-ponent Product a} and'40 A of ptb Example of l as componen~c b}. The composition fuel in additive the comparative fuel was product X-at tYie ptb concentration level.
Table ?

'summarizes-the results.

5 engine was rebuilt with new intake valves and the crankcase oil was changed. The results of these tests are summarized in Tsble 6.
Table 6 Case EP-6800-A

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 he term "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 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 solubility than this.
However,;the term does not require hat the additive be soluble in all proportions in the;
gasoline:
fuel:
composition.

~
~
~~
I
!
a ~
~
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Claims

1. A fuel additive composition for control of intake valve deposits comprising a) a gasoline-soluble Mannich reaction product of (i) 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 b) 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;
wherein the proportions of a) to b) are such that there are from about 0.2 to about 5 parts by weight of active Mannich base in a) per part by weight of b).

2. The fuel additive composition of Claim 1 wherein the alkyl group has a number average molecular weight within the range of from about 800 to about 950.

3. The fuel additive composition of Claim 1 wherein the amine is a polyalkylene amine selected from diethylene triamine, triethylene tetramine and mixtures thereof.

4. The fuel additive composition of Claim 1 wherein the poly(oxyalkylene) compound is a monoether derivative of poly(oxyalkylene) glycol.

5. The fuel additive composition of Claim 1 wherein the proportions of a) to b) are such that there are from about 0.5 to about 3 parts by weight of active Mannich base in a) per part by weight of b).

6. The fuel additive composition of Claim 1 wherein the proportions of a) to b) are such that there are from about 0.8 to about 2 parts by weight of active Mannich base in a) per part by weight of b).

7. The fuel additive composition of Claim 1 wherein said poly(oxyalkylene) compound has an average molecular weight in the range of 1500 to 2500.

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 said poly(oxyalkylene) compound has a viscosity in the range of about 87 to about 98 cSt at 40°C and in the range of about 15 to about l9 cSt at 100°C, and an average molecular weight of about 1700.

9. The fuel additive composition of Claim 8 further comprising one or more hydrocarbons collectively having viscosities at 40°C and 100°C that are no higher than about 25% of the respective viscosities of said poly(oxyalkylene) compound at 40°C and 100°C.

10. The fuel additive composition of Claim 9 wherein said hydrocarbons comprise an aromatic hydrocarbon component that has a boiling point or a final boiling point no higher than about 240°C.

11. The fuel additive composition of Claim 10 wherein said hydrocarbons further comprise polyolefin polymer having a number average molecular weight of from about 800 to about 1200.

12. The fuel additive composition of Claim 11 wherein the proportions of a) to b) are such that there are from about 0.5 to about 3 parts by weight of active Mannish base in a) per part by weight of b).

13. The fuel additive composition of Claim 11 wherein the proportions of a) to b) are such that there are from about 0.8 to about 2 parts by weight of active Mannich base in a) per part by weight of b).

14. The fuel additive composition of Claim 11 further comprising, per 100 parts by weight of said composition, about 1 to about 5 parts by weight of gasoline-soluble antioxidant, about 0.1 to about 3 parts by weight of gaso-line-soluble demulsifier, and about 0.025 to 1.0 part by weight of gasoline-soluble corrosion inhibitor.

15. A composition which comprises a major amount of hydrocarbons of the gasoline boiling range and a minor engine deposit-inhibiting amount of a fuel additive composition according to any one of Claims 1-14.

16. A method for controlling intake valve deposits in a gasoline engine comprising fueling and operating said engine with a fuel composition which comprises a major amount of hydrocarbons of the gasoline boiling range and a minor engine deposit-inhibiting amount of a fuel additive composition according to any one of Claims 1-14.