CA2122825C

CA2122825C - Fuel composition for two-cycle engines

Info

Publication number: CA2122825C
Application number: CA002122825A
Authority: CA
Inventors: Glenn E. Callis; Edward T. Sabourin
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1992-09-11
Filing date: 1993-09-09
Publication date: 2003-12-30
Anticipated expiration: 2013-09-09
Also published as: EP0616635A4; US20020038525A1; AU670118B2; JPH07501360A; AU4852593A; WO1994006897A1; CA2122825A1; DE69322952D1; SG71668A1; JP3495043B2; EP0616635A1; DE69322952T2; EP0616635B1

Abstract

A fuel composition for two-cycle engines comprising a major amount of fuel boiling in the gasoline range and a minor amount of a lubricant composition comprising a base oil of lubricating viscosity and an additive formulation comprising (1) a molybdenum/sulfur complex of a basic nitrogen compound, (2) a carboxylic acid amide, and (3) a succinimide.

Description

,'O 94/06897 ~ ~ ~ ~ ~ PCT/US93/08471 FUEL COMPOSITION FOR TWO-CYCLE ENGINES
Oa 0 ~~
0:5 The present invention relates to a fuel composition for two-cycle internal combustion engines which comprises a 0'1 major amount of fuel boiling in the gasoline range and a 0~3 minor amount of a lubricant composition comprising a lubricating oil and an additive formulation containing a 1~~ molybdenum/sulfur complex of a basic nitrogen compound.
1.1 12 Over the past several decades the use of spark-ignited 13 two-cycle (two-stroke) internal combustion engines including 1~~ rotary engines such as those of the Wankel type has steadily 1.5 increased. They are presently found in power lawn mowers 16 and other power-operated garden equipment, power chain saws, 1'~ pumps, electrical generators, marine outboard engines, 1e snowmobiles, motorcycles, and the like.

20 The increasing use of two-cycle engines coupled with 21 increasing severity of the conditions in which they have 22 operated has led to an increasing demand for oils to 23 adequately lubricate such engines. Among the problems 24 associated with lubrication of two-cycle engines are piston 25 ring sticking, rusting, lubrication failure of connecting 26 rods and main bearings. and the general formation on the 2~ engine's interior surface of carbon and varnish deposits.
28 The formation of varnish is a particularly vexatious problem 29 since the build-up of varnish on piston and cylinder walls 30 is believed to ultimately result in ring sticking which 31 leads to failure of the sealing function of piston rings.
32 Such seal failure cau~;es loss of cylinder compression which 33 is particularly damaging in two-cycle engines because they 34 depend on suction to draw the new fuel charge into the WO 94/06897 PCT/US93/08.
j -z-01 exhausted cylinder. Thus, ring sticking can lead to 02 deterioration in engine performance, and unnecessary 03 consumption of fuel and/or lubricant. Spark plug fouling and engine port plugging problems also occur in two-cycle 05 engines.

A variety of compounds have been proposed as additives for 08 fuel-lubricating oil mixtures to be used in two-cycle O9 internal combustion engines. For example, U.S. Patent No. 4,708,809 to Davis discloses a lubricant composition for 11 two-cycle engines comprising a major amount of an oil of 12 lubricating viscosity and a minor amount of at least one 13 alkyl phenol having at least one hydrocarbon-based group of 14 at least 10 aliphatic carbon atoms. Preferably, such lubricant composition will also contain a detergent-16 dispersant additive selected from (i) a neutral or basic 1~ metal salt of an organic sulfur acid, phenol or carboxylic 18 acid, (ii) a hydrocarbyl-substituted amine, (iii) an 19 acylated, nitrogen-containing compound having a substituent of at least 10 aliphatic carbon atoms, (iv) a 21 nitrogen-containing condensate of a phenol, aldehyde and 22 amino compound, and (v) an ester of a substituted 23 polycarboxylic acid.

U.S. Patent No. 4,724,091 to Davis discloses a lubricant 26 composition for two-cycle engines comprising a major amount 2~ of an oil of lubricating viscosity and a minor amount of a 28 mixture of at least one alkyl phenol and at least one amino 29 phenol, each phenol having at least one hydrocarbon-based group of at least about 10 aliphatic carbon atoms.
31 Preferably, this composition will additionally contain a 32 detergent-dispersant additive.

VO 94/06897 ~ . ~ ~ ~ 2 ~ PCT/US93/08471 ~)1 U.S. Patent No. 4,740,321 to Davis et. al. discloses a ~)2 lubricant composition for two-cycle engines comprising a ~)3 major amount of an oil of lubricating viscosity and a minor ~)4 amount of at least one sulfurized alkyl phenol or metal salt thereof having at least one hydrocarbon-based group of at least 10 aliphatic carbon atoms» This lubricant composition will also preferably contain a detergent-dispersant additive.
t) 9 U.S. Patent No. 4,705,643 to Nemo discloses a lubricating 11 oil composition for two-cycle engines comprising a 12 lubricating oil and an ashless detergent additive which is 13 the hydrolyzed reaction product of an aliphatic branched chain carboxylic acid of 16 to 20 carbon atoms and a 15 polyamine of at least 3 amine groups. Preferably, the 16 ashless detergent additive is the hydrolyzed reaction 17 product of isostearic acid and tetraethylenepentamine.
:l8 U.S. Patent No. 4,994,196 to Kagaya et al. discloses a a0 two-cycle engine oil composition comprising a base oil and a a1 calcium phenate detergent additive, wherein the base oil is a2 a mixture of (a) a copolymer of an alpha-olefin with an a3 ester of a dicarboxylic acid and (b) an ester of pentaerythritol and a fatty acid.
26 U.S. Patent No. 3,888,776 to Silverstein discloses a two-cycle engine lubricant which comprises a major amount of as a polypropylene glycol and minor amounts of a sulfurized .Z9 oxymolybdenum organophosphorodithioate, a finely divided molybdenum disulfide and a halogenated hydrocarbon :31 detergent, such as 1,1,1-trichloroethylene, :32 orthodichlorobenzene, perchlorinated biphenyl, and the like.
:33 WO 94/06897 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08 01 Molybdenum/sulfur complexes of basic nitrogen compounds have 02 previously been described in the art as useful antioxidant 03 additives for lubricant compositions finding application, 04 for example, as crosshead diesel engine lubricants, 05 automobile and railroad crankcase lubricants, lubricants for 06 heavy machinery, greases for bearings, and the like.

O8 For example, U.S. Patent No. 4,263,152 to King et al.
O9 discloses an antioxidant additive for lubricating oils which is prepared by combining an acidic molybdenum compound, a 11 polar promoter, a basic nitrogen-containing compound and a 12 sulfur source to form a molybdenum and sulfur-containing 13 complex. Similar molybdenum-containing antioxidant 14 additives are disclosed in U.S. Patent Nos. 4,285,822;
4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195; and 16 4,259,194. However, none of these patents teaches or 1~ appreciates the use of such antioxidant additives, or is lubricating oils containing such additives, in admixture i9 with fuels in two-cycle engines. Furthermore, none of these patents teaches or appreciates that such antioxidant 21 additives would be effective deposit control agents or would 22 reduce piston sticking when utilized in fuel-lubricating oil 23 mixtures in two-cycle engines.

Moreover, as taught in the aforementioned U.S. Patent 26 No. 4,708,809, the unique problems and techniques associated 2~ with the lubrication of two-cycle engines has led to the 28 recognition by those skilled in the art of two-cycle engine 29 lubricants as a distinct lubricant type.
31 Accordingly, the present invention is directed to minimizing 32 the problems of varnish build-up and ring sticking in 33 two-cycle engines through the provision of effective 34 additives for fuel-lubricating oil combinations which CA~02122825 2002-10-16 2 eliminate or reduce two-cycle engine varnish deposits and 3 piston ring seal failure SUMMARY OF THE INVENTION

7 The present invention provides a fuel composition for 8 two-cycle engines comprises a major amount of fuel 9 boiling in the gasoline range and a minor amount of a lubricant which comprises:
11 (A) a major amount of a base oil of lubricating 12 viscosity; and 13 (B) a minor amount of an additive formulation 14 comprising:
(1) from 0.05 to 15% by weight of a sulfurized 16 molybdenum-containing composition prepared by (I) 17 reacting an acidic molybdenum compound and a basic 18 nitrogen compound selected from the group consisting 19 of a succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a hydrocarbyl polyamine, a 21 Mannish base, a phosphoramide, a thiophosphoramide, 22 a phosphonamide, or a mixture thereof, in the 23 presence of a polar promoter, to form a molybdenum 24 complex wherein from 0.01 to 2 atoms of molybdenum are present per basic nitrogen atom, and the 26 promoter is present in the ratio of 0.01 to 50 moles 27 of polar promoter per mole of molybdenum; and (ii) ~ CA~02122825 2002-10-16 2 reacting the molybdenum complex with a sulfur-3 containing compound in an amount sufficient to 4 provide about 1.5 to 4.0 atoms of sulfur per atom of molybdenum, to thereby form a sulfur- and 6 molybdenum-containing composition, (2) from 0.05 to 20 % by weight of a 8 carboxylic acid amide, and 9 (3) from 0.05 to 15 % by weight of a succinimide.
11 In accordance with another aspect of the invention, a 12 method for reducing engine deposits and piston ring 13 sticking in a two-cycle engine which comprises operating 14 the two-cycle engine with a fuel composition comprising a major amount of fuel boiling in the gasoline range and a 16 minor amount of a lubricant composition comprising:
17 (A) a major amount of a base oil of lubricating 18 viscosity, and 19 (B) a minor amount effective to reduce engine deposits and piston ring sticking of an additive 21 formulation comprising:
22 (1) from 0.05 to 15% by weight of a sulfurized 23 molybdenum-containing composition prepared by (i) 24 reacting an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting 26 of a succinimide, a carboxylic acid amide, a 1 6a 2 hydrocarbyl monoamine, a hydrocarbyl polyamine, a 3 Mannich base, a phosphoramide, a thiophosphoramide, 4 a phosphonamide, or a mixture thereof, in the presence of a polar promoter, to form a molybdenum 6 complex wherein from 0.01 to 2 atoms of molybdenum 7 are present per basic nitrogen atom, and the 8 promoter is present in the ratio of 0.01 to 50 moles 9 of polar promoter per mole of molybdenum; and (ii) reacting the molybdenum complex with a sulfur-11 containing compound in an amount sufficient to 12 provide 1.5 to 4.0 atoms of sulfur per atom of 13 molybdenum, to thereby form a sulfur- and 14 molybdenum-containing composition;
(2) from 0.05 to 20 % by weight of a 16 carboxylic acid amide; and 17 (3) from 0.05 to 15 % by weight of a 18 succinimide.

Among other factors, the present invention is based upon 21 the unexpected discovery that additive formulations 22 containing a molybdenum/sulfur complex of a basic 23 nitrogen compound, plus a carboxylic acid amide and a 24 succinimide are surprisingly effective agents for deposit control and reduction of piston ring sticking when 26 combined in fuel-lubricating oil mixtures in two-cycle 27 engines.

CA~02122825 2002-10-16 1 6b The fuel composition of the present invention will 6 comprise a major amount of fuel boiling in the gasoline 7 range and a minor amount of a lubricant composition 8 comprising a base oil of lubricating viscosity and an 9 additive formulation containing (1) a sulfurized molybdenum-containing composition, (2) a carboxylic acid 11 amide, and (3) a succinimide.

13 The sulfurized molybdenum-containing composition employed 14 in the present invention may be generally characterized as a molybdenum/sulfur complex of a basic nitrogen 16 compound. Such molybdenum/sulfur complexes are known in 17 the art and are described, for example, in U.S. Patent 18 No. 4,263,152 to King et al.

The precise molecular formula of the molybdenum 21 compositions employed in this invention is not known with 22 certainty; however, they are believed to be compounds in 23 which molybdenum, whose valences are satisfied with atoms 24 of /O 94/06897 ~ ~ ~ ~ ~ ~ ~ PCT/US93/08471 oxygen or sulfur, is either complexed by, or the salt of, «Z one or more nitrogen .atoms of the basic nitrogen containing compound used in the ;preparation of these compositions.
t14 The molybdenum compounds used to prepare the molybdenum/sulfur complexes employed in this invention are acidic molybdenum compounds. By acidic is meant that the molybdenum compounds will react with a basic nitrogen «9 compound as measured :by ASTM test D-664 or D-2896 titration procedure. Typically these molybdenum compounds are hexavalent and are represented by the following compositions: molybdic acid, ammonium molybdate, sodium molybdate, potassium ;molybdate and other alkaline metal ~~4 molybdates and other ;molybdenum salts such as hydrogen salts, e.g., hydrogen sodium molybdate, MoOCl4, Mo02Br2, Mo203C16, molybdenum trioxide or similar acidic molybdenum compounds. Preferred acidic molybdenum compounds are molybdic acid, ammonium molybdate, and alkali metal molybdates. Particularly preferred are molybdic acid and ammonium molybdate.
::1 ''2 The basic nitrogen compound used to prepare the molybdenum~'sulfur comvplexes must have a basic nitrogen ''4 content as measured by ASTM D-664 or D-2896. It is ''S preferably oil-soluble. Typical of such compositions are succinimides, carboxylic acid amides, hydrocarbyl monoamines, hydrocarbon polyamines, Mannich bases, ''8 phosphoramides, thiop:hosphoramides, phosphonamides, ''9 dispersant viscosity index improvers, and mixtures thereof.
:!0 These basic: nitrogen-containing compaunds are described :!1 below (keeping in mind the reservatian that each must have :!2 at least one basic nitrogen). Any of the :!3 nitrogen-cantaining compositions may be after-treated with, :! 4 1 e.g., boron, using procedures well known in the art so 2 long as the compositions continue to contain basic 3 nitrogen. These after-treatments are particularly 4 applicable to succinimides and Mannich base compositions.
6 The mono and polysuccinimides that can be used to prepare 7 the molybdenum/sulfur complexes described herein are 8 disclosed in numerous references and are well known in 9 the art. Certain fundamental types of succinimides and the related materials encompassed by the term of art 11 "succinimide" are taught in U.S. Patent Nos. 3,219,666;
12 3,172,892; and 3,272,746. The term "succinimide" is 13 understood in the art to include many of the amide, 14 imide, and amidine species which may also be formed. Th predominant product however is a succinimide and this 16 term has been generally accepted as meaning the product 17 of a reaction of an alkenyl substituted succinic acid or 18 anhydride with a nitrogen-containing compound. Preferred 19 succinimides, because of their commercial availability, are those succinimides prepared from a hydrocarbyl 21 succinic anhydride, wherein the hydrocarbyl group 22 contains from about 24 to about 350 carbon atoms, and an 23 ethylene amine, said ethylene amines being especially 24 characterized by ethylene diamine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine.
26 Particularly preferred are those succinimides prepared 27 from polyisobutenyl succinic anhydride of 70 to 128 28 carbon atoms and tetraethylene pentamine or triethylene 29 tetramine or mixtures thereof.
31 Also included within the term "succinimide" are the 32 cooligomers of a hydrocarbyl succinic acid or anhydride 33 and a poly secondary amine containing at least one 34 tertiary amino nitrogen in addition to two or more g_ 1 secondary amino groups. Ordinarily this composition has 2 between 1,500 and 50,000 average molecular weight. A
3 typical compound would be that prepared by reacting 4 polyisobutenyl succinic anhydride and ethylene dipiperazine.

7 Carboxylic acid amide compositions are also suitable 8 starting materials for preparing the molybdenum/sulfur 9 complexes employed in this invention. Typical of such compounds are those disclosed in U.S. Patent No.
11 3,405,064. These compositions are ordinarily prepared by 12 reacting a carboxylic acid or anhydride or ester thereof, 13 having at least 12 to about 350 aliphatic carbon atoms in 14 the principal aliphatic chain and, if desired, having sufficient pendant aliphatic groups to render the 16 molecule oil soluble with an amine or a hydrocarbyl 17 polyamine, such as an ethylene amine, to give a mono or 18 polycarboxylic acid amide. Preferred are those amides 19 prepared from (1) a carboxylic acid of the formula R2COOH, where Rz is Clz.zo alkyl or a mixture of this acid with a 21 polyisobutenyl carboxylic acid in which the 22 polyisobutenyl group contains from 72 to 128 carbon atoms 23 and (2) an ethylene amine, especially triethylene 24 tetramine or tetraethylene pentamine or mixtures thereof.
26 Another class of compounds which are useful in this 27 invention are hydrocarbyl monoamines and hydrocarbyl 28 polyamines, preferably of the type disclosed in U.S.
29 Patent No. 3,574,576. The hydrocarbyl group, which is preferably alkyl, or olefinic having one or two sites of 31 unsaturation, usually contains from 9 to 350, preferably 32 from 20 to 200 carbon atoms. Particularly preferred 33 hydrocarbyl polyamines are those which are derived, e.g., 34 by reacting polyisobutenyl chloride and a polyalkylene 1 polyamine, such as an ethylene amine, e.g., ethylene 2 diamine, diethylene triamine, tetraethylene pentamine, 2 3 -aminoethylpiperazine, 1,3-propylene diamine, 1,2-4 propylenediamine, and the like.
6 Another class of compounds useful for supplying basic 7 nitrogen are the Mannish base compositions. These 8 compositions are prepared from a phenol or alkylphenol, 9 an aldehyde, such as formaldehyde or formaldehyde precursor such as paraformaldehyde, and an amine 11 compound. The amine may be a mono or polyamine and 12 typical compositions are prepared from an alkylamine, 13 such as methylamine or an ethylene amine, such as, 14 diethylene triamine, or tetraethylene pentamine, and the like. The phenolic material may be sulfurized and 16 preferably is dodecylphenol or a C8o-loo alkylphenol.
17 Typical Mannish bases which can be used in this invention 18 are disclosed in U.S. Patent No. 4,157,309 and U.S.
19 Patent Nos. 3,649,229; 3,368,972; and 3,539,663. The last referenced patent discloses Mannish bases prepared by 21 reacting an alkylphenol having at least 50 carbon atoms, 22 preferably 50 to 200 carbon atoms with formaldehyde and 23 an alkylene polyamine HN(ANH)nH where A is a saturated 24 divalent alkyl hydrocarbon of 2 to 6 carbon atoms and n is 1-10 and where the condensation product of said 26 alkylene polyamine may be further reacted with urea or 27 thiourea. The utility of these Mannish bases as starting 28 materials for preparing lubricating oil additives can 29 often be significantly improved by treating the Mannish base using conventional techniques to introduce boron 31 into the composition.

33 Another class of composition useful for preparing the 34 molybdenum/sulfur complexes employed in this invention ~a -1 are the phosphoramides and phosphonamides such as those 2 disclosed in U.S. Patent Nos. 3,909,430 and 3,968,157.
3 These compositions may be prepared by forming a 4 phosphorus compound having at least one P-N bond. They can be prepared, for example, by reacting phosphorus 6 oxychloride with a hydrocarbyl diol in the presence of a 7 monoamine or by reacting phosphorus oxychloride with a 8 difunctional secondary amine and a mono-functional amine.
9 Thiophosphoramides can be prepared by reacting an unsaturated hydrocarbon compound containing from 2 to 450 11 or more carbon atoms, such as_polyethylene, 12 polyisobutylene, polypropylene, ethylene, 1-hexene, 1, 3-13 hexadiene, isobutylene, 4-methyl-1-pentene, and the like, 14 with phosphorus pentasulfide and a nitrogen-containing compound as defined above, particularly an alkylamine, 16 alkyldiamine, alkylpolyamine, or an alkyleneamine, such 17 as ethylene diamine, diethylenetriamine, 18 triethylenetetramine, tetraethylenepentainine, and the 19 like.
21 Another class of nitrogen-containing compositions useful 22 in preparing the molybdenum complexes employed in this 23 invention includes the so-called dispersant viscosity 24 index improvers (VI improvers). These VI improvers are commonly prepared by functionalizing a hydrocarbon 26 polymer, especially a polymer derived from ethylene 27 and/or propylene, optionally containing additional units 28 derived from one or more co-monomers such as alicyclic or 29 aliphatic olefins or diolefins. The functionalization may be carried out by a variety of processes which introduce 31 a reactive site or sites which usually has at least one 32 oxygen atom on the polymer. The polymer is then contacted 33 with a WO 94/06897 ~ ~ ~~ ~" g ~ ~ PCT/US93/08w.

01 nitrogen-containing source to introduce nitrogen-containing 02 functional groups on the polymer backbone. Commonly used 03 nitrogen sources include any basic nitrogen compound especially those nitrogen-containing compounds and OS compositions described herein. Preferred nitrogen sources 06 are alkylene amines, such as ethylene amines, alkyl amines, and Mannich bases.

O9 Preferred basic nitrogen compounds for use in this invention are succinimides, carboxylic acid amides, and Mannich bases.

12 Representative sulfur sources for preparing the molybdenum 13 complexes used in this invention are sulfur, hydrogen 14 sulfide, sulfur monochloride, sulfur dichloride, phosphorus pentasulfide, R2SX where R is hydrocarbyl, preferably C1~
16 alkyl, and x is at least 2, inorganic sulfides and 1~ polysulfides such as (NH4)2SX, where x is at least 1, 18 thioacetamide, thiourea, and mercaptans of the formula RSH
i9 where R is as defined above. Also useful as sulfurizing agents are traditional sulfur-containing antioxidants such 21 as wax sulfides and polysulfides, sulfurized olefins, 22 sulfurized carboxylic and esters and sulfurized 23 ester-olefins, and sulfurized alkylphenols and the metal 24 salts thereof.
26 The sulfurized fatty acid esters are prepared by reacting 2~ sulfur, sulfur monochloride, and/or sulfur dichloride with 28 an unsaturated fatty ester under elevated temperatures.
29 Typical esters include C1-C2~ alkyl esters of Cg-C24 unsaturated fatt acids such as y , palmitoleic, oleic, 31 ricinoleic petroselinic, vaccenic, linoleic, linolenic, 32 oleostearic licanic paranaric, tariric, gadoleic, 33 arachidonic, cetoleic, etc. Particularly good results have VO 94/06897 N~ PCT/US93/08471 0~1 been obtained with mi:Ked unsaturated fatty acid esters, such 0'2 as are obtained from animal fats and vegetable oils, such as 0'3 tall oil, linseed oil, olive oil, caster oil, peanut oil, 0'4 rape oil, fish oil, sperm oil, and so forth.
0~ 5 Exemplary fatty ester:~ include lauryl tallate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl 0'8 linoleate, lauryl ric:inoleate, oleyl linoleate, oleyl stearate, and alkyl g:Lycerides.
1. 0 1.1 Cross-sulfurized ester olefins, such as a sulfurized mixture 1.2 of C1~-C25 olefins with fatty acid esters of C1~-C25 fatty 1.3 acids and C:1-C25 alkyl or alkenyl alcahols, wherein the 14 fatty acid and/or the alcohol is unsaturated may also be 15 used.

1~ Sulfurized olefins are prepared by the reaction of the f8 olefin or a low-molecular-wei ht g polyolefin derived f9 therefrom with a sulfur-containing compound such as sulfur, 20 Sulfur monochloride, <ind/or sulfur dichloride.

22 p,lso useful. are the aromatic and alkyl sulfides, such as 23 dibenzyl sulfide, dixy:lyl sulfide, dicetyl sulfide, 24 diparaffin wax sulfide and polysulfide, cracked wax-olefin 25 Sulf ides and so forth .. The can be 26 y prepared by treating the starting material, e.g., olefinically unsaturated compounds, with sulfur, sulfur monochloride, and sulfur dichloride.
2$ Particularly preferred are the paraffin wax thiomers 29 described in U.S. PatEant No. 2,346,156.
31 Sulfurized alkyl phenols and the metal salts thereof include 32 compositions such as sulfurized dodecylphenol and the 33 calcium salts thereof.. The alkyl group ordinarily contains WO 94/06897 ~ ~ ~ ~ ~ ~ PCT/US93/0&~

01 from 9-300 carbon atoms. The metal salt may be preferably, 02 a Group I or Group II salt, especially sodium, calcium, 03 magnesium, or barium.

05 preferred sulfur sources are sulfur, hydrogen sulfide, 06 phosphorus pentasulfide, R2SX where R is hydrocarbyl, preferably C1-C1~ alkyl, and x is at least 3, mercaptans O8 wherein R is C1-C10 alkyl, inorganic sulfides and O9 polysulfides, thioacetamide, and thiourea. Most preferred sulfur sources are sulfur h dro en sulfide Y g , phosphorus 1l entasulfide and inor anic sulfides and P . g polysulfides.

13 The olar romoter used in the p p preparation of the molybdenum 14 complexes employed in this invention is one which facilitates the interaction between the acidic molybdenum 16 compound and the basic nitrogen compound. A wide variety of such promoters are well known to those skilled in the art.
1s T ical romoters are 1 3 yp p , -propanediol, 1,4-butane-diol, 19 dieth lene 1 col but 1 cellosolve Y g Y . Y , propylene glycol, 1,4-butyleneglycol, methyl carbitol, ethanolamine, 21 diethanolamine, N-methyl-diethanol-amine, dimethyl 22 formamide, N-methyl acetamide, dimethyl acetamide, methanol, 23 ethylene glycol, dimethyl sulfoxide, hexamethyl 24 phosphoramide, tetrahydrofuran and water. Preferred are water and eth lene 1 col. Particularl Y 9 Y y preferred is water.

2~ While ordinaril the y polar promoter is separately added to 28 the reaction mixture, it may also be present 29 . particularly in the case of water, as a component of non-anhydrous starting materials or as waters of hydration in the acidic 31 molybdenum compound, such as (NH4) 6Mo7024. 4 H20. Water may also be added as ammonium hydroxide.

~'O 94/06897 2 ~ ? ~ g ~ j PCT/US93/08471 01 A method for preparing the molybdenum/sulfur complexes used 02 in this invention is 1:.o prepare a solution of the acidic 03 molybdenum precursor and a polar promoter with a basic 04 nitrogen-containing compound with or without diluent. The 05 diluent is used, if necessary, to provide a suitable f6 viscosity for easy starring. Typical diluents are lubricating oil and liquid compaunds containing only carbon f$ and hydrogen. If desired, ammonium hydroxide may also be added to th.e reaction mixture to provide a solution of 1.0 ammonium molybdate. '.Chis reaction is carried out at a 1.1 temperature. from the melting point of the mixture to reflux 1.2 temperature.. It is ordinarily carried out at atmospheric 1.3 pressure although higher or lower pressures may be used if 1.4 desired. This reaction mixture is treated with a sulfur 1.5 source as defined above at a suitable pressure and 1.6 temperature. for the sulfur source to react with the acidic 1.7 molybdenum and basic nitrogen compounds. In some cases, 1.8 removal of water from the reaction mixture may be desirable 1.9 prior to completion of reaction with the sulfur source.
21 In the reaction mixture, the ratio of molybdenum compound to 22 basic nitrogen compound is not critical; however, as the 23 amount of molybdenum with respect to basic nitrogen 24 increases, the filtration of the product becomes more difficult. Since the molybdenum component probably 26 oligomerizes, it is advantageous to add as much molybdenum 2'1 as can easily be mainl:.ained in the composition. Usually, 28 the reaction mixture will have charged to it from 0.01 to 29 2.00 atoms of molybdenum per basic nitrogen atom.
3.0 Preferably from 0.4 to 1.0, and most preferably from 0.4 to 3.1 0.7, atoms of molybdenum per atom of basic nitrogen is added 3~2 to the reaction mixture.
3. 3 f. 4 WO 94/06897 PCT/US93/08~
~~2~,~~,5 01 The sulfur source is usually charged to the reaction mixture 02 in such a ratio to provide 1.5 to 4.0 atoms of sulfur per 03 atom of molybdenum. Preferably from 2.0 to 4.0 atoms of 04 sulfur per atom of molybdenum is added, and most preferably, 05 2.5 to 4.0 atoms of sulfur per atom of molybdenum.

The polar promoter, which is preferably water, is ordinarily O8 present in the ratio of 0.1 to 50 moles of promoter per mole O9 of molybdenum. Preferably from 0.5 to 25 and most l0 preferably 1.0 to 15 moles of the promoter is present per 11 mole of molybdenum.

13 As described above, the additive formulation employed in the 14 present invention contains (1) a sulfurized 15 molybdenum-containing composition, (2) a carboxylic acid 16 amide, and (3) a succinimide.

l8 The carboxylic amide component of the presently employed 19 additive formulation may be any of the carboxylic acid amide 20 compounds described herein as useful in the preparation of 21 the molybdenum/sulfur complex. Preferred carboxylic acid 22 amide components include those amides derived from a 23 carboxylic acid of the formula R2COOH, wherein R2 is C12-C20 24 alkyl, and an ethylene amine, such as triethylene tetramine 25 or tetraethylene pentamine.

2~ Similarly, the succinimide component of the presently 28 employed additive formulation may be any of the succinimide 29 compounds described herein as useful in the preparation of 30 the molybdenum/sulfur complex. Preferred succinimide 31 components include those derived from polyisobutenyl 32 succinic anhydride, wherein the polyisobutenyl group 33 contains from about 50 to 250 carbon atoms, and an ethylene i'0 94/06897 ~ ~ ~ ~ ~ ~ PCT/US93/08471 O1 amine, such as triethylene tetramine or tetraethylene 02 pentamine.

04 The additive formulation employed in the present invention 05 may additionally contain a flocculant inhibitor and/or a 06 lubricity agent, such as a polyisobutene. If necessary, a diluent oil may also be included.

O9 Other additives such as viscosity index improvers, antioxidants, dispersants, coupling agents, pour point 11 depressants, extreme pressure agents, color stabilizers, 12 rust inhibitors, anticorrosion agents, and the like, may 13 also be present in the additive formulation.

The lubricant composit:i.on employed in the present invention 16 comprises a major amount of a base oil of lubricating viscosity and a minor amount of the additive formulation 18 described above.

The base oil employed may be any of a wide variety of oils 21 of lubricating viscosity. Thus, the base oil can be a 22 refined paraffin type base oil, a refined naphthenic base 23 oil, or a synthetic hydrocarbon or non-hydrocarbon oil of 24 lubricating viscosity. The base oil can also be a mixture of mineral and synthetic oils. For purposes of the present 26 invention, the mineral. lubricating oils are preferred, since 2~ they are presently in more general use in two-cycle engines.

29 The presently employed lubricant composition containing the additive formulation described herein can be conveniently 31 prepared using conventional techniques by admixing the 32 appropriate amount of each component of the additive 33 formulation with a lubricating oil.

1~ -1 Generally, the amount of the molybdenum-containing additive 2 will vary from about 0.05 to 15% by weight and preferably from 3 about 0.2 to 10% by weight, based on the total lubricant 4 composition, including base oil. The carboxylic acid amide component will vary from about 0.05 to 20% by weight and 6 preferably from about 0.2 to 15% by weight. The succinimide 7 component will vary from about 0.2 to 15% by weight and 8 preferably from about 0.2 to 10% by weight.

The two-cycle engine fuel composition contemplated by the 11 present invention comprises a major amount of fuel boiling in 12 the gasoline range and minor amount of the lubricant 13 composition disclosed herein.

For purposes of the present invention, the lubricant 16 composition will generally be added directly to the fuel to 17 form a mixture of lubricant and fuel which is then introduced 18 into the two-cycle engine cylinder. Generally, the resulting 19 fuel composition will contain from about 15 to 250 parts fuel per 1 part lubricant, and more typically about 50 to 100 parts 21 fuel per 1 part lubricant. For some two-cycle engine 22 applications, the lubricant may be directly injected into the 23 combustion chamber along with the fuel or into the fuel just 24 prior to the time the fuel enters the combustion chamber.
26 The fuel employed in the present fuel composition is a 27 hydrocarbon distillate fuel boiling in the gasoline range. In 28 such gasoline fuels, other fuel additives may also be included 29 such as antiknock agents, e.g., methylcyclopentadienyl manganese tricarbonyl, tetramethyl or tetraethyl lead, or 31 other dispersants or detergents such as various substituted 32 amines, etc. Also included may be lead scavengers such as aryl 33 halides, e.g., dichlorobenzene or 'V0 94/06897 ~ ~ ~ ~ ~ ~ PCT/US93/08471 01 alkyl halides, e.g., ethylene dibromide. Additionally, 02 antioxidants, metal deaactivators, pour point depressants, 03 corrosion inhibitors and demulsifiers may be present.

05 The following examp les are presented to illustrate specific 06 embodiments of this invention and are not to be construed in any way as limiting the scope of the invention.

11 Example 1 13 To a 5000 ml flask was added 114 grams molybdenum trioxide 14 and 196 grams of water. Stirring was started and 1200 grams of a solution of a 45% concentrate in oil of the 16 polyisobutenyl succinimide prepared from polyisobutenyl 1~ succinic anhydride having a number average molecular weight 18 for the polyisobuteny:l group of about 950 and tetraethylene 19 pentamine, and 1200 grams of hydrocarbon thinner were added.
The mixture was refluxed at 100°C for 3 hours. The 21 temperature was gradually increased over approximately 22 1 hour to 170°C while distilling water. The temperature was 23 maintained an additional hour after the water was removed.
24 The temperature was lowered to 100°C-120°C and the mixture filtered and returned to the reaction vessel. To the 26 solution was added 51 grams of sulfur. The mixture was 2~ heated to 160°C-180°C for 7 hours. The pressure was slowly 28 reduced to about 50 mrn of mercury to remove the hydrocarbon 29 thinner. This produced 1244 grams of product containing 1.80% nitrogen, 5.63% molybdenum, and 3.57% sulfur.

3. 2 3. 3 f. 4 WO 94/06897 ~ ~ ~ ~ ~ ? ~ PCT/US93/08~

01 Example 2 03 To a 5000 ml flask was added 52 grams molybdenum trioxide 04 and 111 grams of water. Stirring was started and 1184 grams 05 of a solution of a 45% concentrate in oil of the succinimide 06 described in Example 1 and 1184 grams of hydrocarbon thinner were added. The mixture was refluxed at 100°C for 3 hours.
08 The temperature was gradually increased over approximately 09 1 hour to 170°C while distilling water. The temperature was maintained an additional hour after the water was removed.
11 The temperature was lowered to 100°C-120°C and the mixture 12 filtered and returned to the reaction vessel. To the 13 solution was added 47 grams of sulfur. The mixture was 14 heated to 160°C-180°C for 7 hours. The pressure was slowly reduced to about 50 mm of mercury to remove the hydrocarbon 16 thinner. This produced 1220 grams of product containing 1~ 1.94% nitrogen, 2.78% molybdenum, and 3.64% sulfur.

i9 Example 3 21 To a 5000 ml flask was added 49 grams molybdenum trioxide 22 and 105 grams of water. Stirring was started and 1133 grams 23 of a solution of a 45% concentrate in oil of the succinimide 2~ described in Example 1 and 1133 grams of hydrocarbon thinner were added. The mixture was refluxed at 100°C for 3 hours.
26 The temperature was gradually increased over approximately 2~ 1 hour to 170°C while distilling water. The temperature was 28 maintained an additional hour after the water was removed.
29 The temperature was lowered to 100°C-120°C and the mixture filtered and returned to the reaction vessel. To the 31 solution was added 22 grams of sulfur. The mixture was 32 heated to 160°C-180°C for 7 hours. The pressure was slowly 33 reduced to about 50 mm of mercury to remove the hydrocarbon ,CVO 94/06897 ~ ~ ~ ~ ~ ~ i~ PCT/US93/08471 ~~1 thinner. This produced 1163 grams of product containing 1.83% nitrogen, 2.79% molybdenum, and 1.97% sulfur.

~~ 4 Examu 1 a 4 OS
To a 5000 ml flask was added 1200 grams of a polyamide prepared from a C18 carboxylic acid and tetraethylene pentamine and containing 6.4% nitrogen, 1200 grams hydrocarbon thinner, 42 grams molybdenum trioxide, and :L0 90 grams water. The mixture was refluxed at 100°C for 11 3 hours. 'the temperature was gradually increased over :L2 approximately 1 hour to 170°C while distilling water. The :L3 temperature was maintained an additional hour after the :L4 water was .removed. The temperature was lowered to :LS 100°C-120°C and the mixture filtered and returned to the :L6 reaction vessel. To the solution was added 21 grams of sulfur. The mixture was heated to 160°C-180°C for 7 hours.
'L8 The pressure was slowly reduced to about 50 mm of mercury to 'L9 remove the hydrocarbon thinner. This produced a product :20 containing 5.88% nitrogen, 2.29% molybdenum, and 1.63%
:21 sulfur.
:Z 2 :23 Example 5 :24 :25 The molybdenum/sulfur complexes of Examples 1, 2 and 4 were :26 formulated to provide lubricant compositions containing 10%
of the carboxylic acid amide reaction product of isostearic '28 acid and tetraethylen.e pentamine, 2% of a polyisobutenyl '29 succinimide prepared from polyisobutenyl succinic anhydride :30 wherein the polyisobu.tenyl group has a number average :31 molecular weight of about 950 and tetraethylene pentamine, :32 2% of the molybdenum/sulfur complex of Examples 1, 2 and 4, 33 respectively, 5% of a. polyisobutene :having a number average WO 94/06897 ~ ~ ~ ~ ~ c~ ~ PCT/US93/08~.

01 molecular weight of about 950 as a lubricity agent, 0.5~ of 02 a flocculant inhibitor, 1~ of a diluent oil and about 79.5%
03 of a base oil. The base oil contains about lOg of a 04 150 bright stock, about 70% of a mixture of 350N and 650N
OS neutral oils, and about 20% of a petroleum distillate 06 solvent.

OS Example 6 O9 Two-Cycle Gasoline Enctine Test 11 This test was used to evaluate the detergency and general 12 performance of the fuel composition of this invention in a 13 two-cycle water-cooled outboard engine. Piston varnish, 14 ring sticking and general engine deposits were evaluated.
16 The test engine used was an Outboard Marine Company Johnson 1~ Model No. J70ELEIE outboard engine, which is a i8 70 horsepower, water-cooled, three-cylinder, two-cycle i9 engine.
21 The test procedure involved a two-hour break-in period, 22 wherein the engine was run at 3,000 rpm for 1 hour, then at 23 4,000 rpm for 1 hour, using a fuel: lubricant ratio of 50:1.
2~
The test was then conducted for 98 hours using a 50:1 fuel 26 to lubricant ratio on a 55 minute wide-open throttle, 2~ 5 minute idle cycle. The total test time, including 28 break-in, was 100 hours.

At the conclusion of the test, the engine was disassembled 31 and rated. The average piston rating and average 32 second-ring sticking rating for 3 cylinders was measured.
33 In the rating system employed, the higher the numerical 34 rating, the better the cleanliness performance, with 10.0 YO 94/06897 ~ ~ ~ ~ PCT/US93/08471 being the maximum rating. Except for. the piston rings, the ~~2ratings are for cleanliness. The piston rings are rated for ~~3the degree of sticking, with a rating of 10.0 indicating a completely free piston ring.

OS

The second-ring sticking values include National Marine a Manufacturers Association (NMMA) rating, a visual rating, ~~8and an adjusted rating, which is an avera ge of the NINA and n9 visual ratings.

:L

:L1The reference oil employed in this test as NN~IA reference w :L2oil TCW II" used as an industry standard in two-cycle engine :L3tests to measure engine cleanliness. The TCW II reference :L4oil is a standard mineral lubricating oil containing a :15commercial ashless dispersant for gasolin e two-cycle :L6engines. The reference oil is available from Citgo :L7Petroleum Corporation, Tulsa, Oklahoma.

:L 8 :L9 Engine test runs were performed with a 50:1 fuel to :20 lubricant ratio, using lubricant compositions containing the :21 molybdenum,~sulfur complexes of Examples 1, 2 and 4, 22 formulated as described in Example 5» The results of the :23 engine tests are shown in Table 1.
.24 :25 The results shown in Table 1 demonstrate that the fuel :26 composition of the present invention is highly effective in reducing piston deposits and piston ring sticking in 28 two-cycle engines, and generally exceeds the performance of :29 a fuel containing the industry standard reference oil.

:32 :33 WO 94/06897 PCT/US93/O~S _ 'J

Ol ENGINE TEST
RESOLTS

04 Average Rating for 3 Cylinders 05 Second-Ring Sticking 06 Piston 2-Ring Under-Additive Skirt Crown Land Crown NMMA Visual Adj.

07 T~ II

08 Reference Oil 7.1 2.8 3.7 2.8 6.8 5.7 6.3 Example l~a~7.4 3.4 4.4 2.5 7.1 6.1 6.6 l 7 4~a~

xamp . 3.1 4.8 3.9 7.8 6.8 7.3 11 e Example 2~a~7.8 3.4 4.4 3.3 8.5 6.5 7 12 .

~a~Formulated as in Example 5.

Claims

1. A fuel composition for two-cycle engines comprising a major amount of fuel boiling in the gasoline range and a minor amount of a lubricant comprising:
(A) a major amount of a base oil of lubricating viscosity; and (B) a minor amount of an additive formulation comprising:
(1) from 0.05 to 15% by weight of a sulfurized molybdenum-containing composition prepared by (I) reacting an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of a succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a hydrocarbyl polyamine, a Mannich base, a phosphoramide, a thiophosphoramide, a phosphonamide, or a mixture thereof, in the presence of a polar promoter, to form a molybdenum complex wherein from 0.01 to 2 atoms of molybdenum are present per basic nitrogen atom, and the promoter is present in the ratio of 0.01 to 50 moles of polar promoter per mole of molybdenum; and (ii) reacting the molybdenum complex with a sulfur-containing compound in an amount sufficient to provide about 1.5 to 4.0 atoms of sulfur per atom of molybdenum, to thereby form a sulfur- and molybdenum-containing composition, (2) from 0.05 to 20 % by weight of a carboxylic acid amide, and (3) from 0.05 to 15 % by weight of a succinimide.

2. The fuel composition of Claim 1, wherein the sulfur source for component (1) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R2Sx where R is hydrocarbyl, and x is at least 2, inorganic sulfides or inorganic polysulfides, thioa-cetamide, thiourea, mercaptans of the formula RSH where R is hydrocarbyl, or a sulfur-containing antioxidant,

3. The fuel composition of Claim 2, wherein the sulfur source for component (1) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R2S x where R is C1-4 hydrocarbyl, and x is at least 3, inorganic sulfides, or inorganic polysulfides, thioacetamide, thiourea or RSH where R is C1-40 alkyl, and the acidic molybdenum compound is molybdic acid, ammonium molybdate, or alkali metal molybdate.

4. The fuel composition of Claim 3, wherein said sulfur source is sulfur, hydrogen sulfide, RSH where R is C-1-40 alkyl, phosphorus pentasulfide, or (NH4)2S x, where x is at least 1, said acidic molybdenum compound is molybdic acid, or ammonium molybdate, and said basic nitrogen compound is a succinimide, carboxylic acid amide, or Mannich base.

5. The fuel composition of Claim 4, wherein said basic nitrogen compound is a C24-350 hydrocarbyl succinimide, carboxylic acid amide, or a Mannich base prepared from a C9-200 alkylphenol, formaldehyde, and an amine.

6. The fuel composition of Claim 5, wherein said basic nitrogen compound is a polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride and tetraethylene pentamine or triethylene tetramine.

7. The fuel composition of Claim 5, wherein said basic nitrogen compound is a carboxylic acid amide prepared from one or more carboxylic acids of the formula R2 COOH, or a derivative thereof which upon reaction with an amine yields a carboxylic acid amide, wherein R2 is C12-350 alkyl or C12-350 alkenyl and a hydrocarbyl polyamine.

8. The fuel composition of Claim 7, wherein R2 is C12-20 alkyl or C12-20 alkenyl and the hydrocarbyl polyamine is tetraethylene pentamine or triethylene tetramine.

9. The fuel composition of Claim 5, wherein said basic nitrogen compound is a Mannich base prepared from dodecylphenol, formaldehyde, and methylamine.

10. The fuel composition of Claim 5, wherein said basic nitrogen compound is a Mannich base prepared from C80-100 alkylphenol, formaldehyde and triethylene tetramine, tetraethylene pentamine, or mixtures thereof.

11. The fuel composition of Claim 1, wherein the polar promoter is water.

12. The fuel composition of Claim 1, wherein the carboxylic acid amide of component (2) is derived from a carboxylic acid of the formula R2COOH, wherein R2 is C12-20 alkyl, and an ethylene amine.

13. The fuel composition of Claim 1, wherein the succinimide of component (3) is derived from polyisobutenyl succinic anhydride, wherein the polyisobutenyl group contains from 50 to 250 carbon atoms, and an ethylene amine.

14. The fuel composition of Claim 1, wherein the lubricant composition contains 0.05 to 15% by weight of the molybdenum-containing composition of component (1), 0.05 to 20% by weight of the carboxylic acid amide of component (2), and 0.05 to 15% by weight of the succinimide of component (3).

15. The fuel composition of Claim 1, wherein the molybdenum complex is reacted with the sulfur-containing compound in an amount sufficient to provide 2.0 to 4.0 atoms of sulfur per atom of molybdenum.

16. The fuel composition of Claim 15, wherein the molybdenum complex is reacted with the sulfur-containing compound in an amount sufficient to provide 2.5 to 4.0 atoms of sulfur per atom of molybdenum.

17. The fuel composition of Claim 1, wherein the additive formulation further contains a flocculent inhibitor.

18. The fuel composition of Claim 17, wherein the additive formulation further contains a lubricity agent.

19. A method for reducing engine deposits and piston ring sticking in a two-cycle engine which comprises operating the two-cycle engine with a fuel composition comprising a major amount of fuel boiling in the gasoline range and a minor amount of a lubricant composition comprising:
(A) a major amount of a base oil of lubricating viscosity, and (B) a minor amount effective to reduce engine deposits and piston ring sticking of an additive formulation comprising:
(1) from 0.05 to 15% by weight of a sulfurized molybdenum-containing composition prepared by (i) reacting an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of a succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a hydrocarbyl polyamine, a Mannich base, a phosphoramide, a thiophosphoramide, a phosphonamide, or a mixture thereof, in the presence of a polar promoter, to form a molybdenum complex wherein from 0.01 to 2 atoms of molybdenum are present per basic nitrogen atom, and the promoter is present in the ratio of 0.01 to 50 moles of polar promoter per mole of molybdenum; and (ii) reacting the molybdenum complex with a sulfur-containing compound in an amount sufficient to provide 1.5 to 4.0 atoms of sulfur per atom of molybdenum, to thereby form a sulfur- and molybdenum-containing composition;
(2) from 0.05 to 20 % by weight of a carboxylic acid amide;
and (3) from 0.05 to 15 % by weight of a succinimide.

20. The method of Claim 19 wherein the sulfur source for component (1) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R2S x where R is hydrocarbyl, and x is at least 2, inorganic sulfidos or inorganic polysulfides, thioacetamide, thiourea, mercaptans of the formula RSH where S is hydrocarbyl, or a sulfur-containing antioxidant

21. The method of Claim 20 wherein the sulfur source for component (1) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R2S2 where R is C1-4 hydrocarbyl, and x is at least 3, inorganic sulfides, or inorganic polysulfides, thioacetamide, thiourea or RSH where R is C1-40 alkyl, and the acidic molybdenum compound is molybdic acid, ammonium molybdate, or alkali metal molybdate.

22. The method of Claim 21 wherein said sulfur source is sulfur, hydrogen sulfide, RSH where R is C1-10 alkyl, phosphorus pentasulfide, or (NH4)2S x, where x is at least 1, said acidic molybdenum compound is molybdic acid, or ammonium molybdate, and said basic nitrogen compound is a succinimide, carboxylic acid amide, or Mannich base,

23. The method of Claim 22 wherein said basic nitrogen compound is a C24-350 hydrocarbyl succinimide, carboxylic acid amide, or a Mannich base prepared from a C9-200 alkylphenol, formaldehyde, and an amine.

24. The method of claim 23 wherein said basic nitrogen compound is a polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride and tetraethylene pentamine or triethylene tetramine.

25. The method of Claim 23 wherein said basic nitrogen compound is a carboxylic acid amide prepared from one or more carboxylic acids of the formula R2COOH, or a derivative thereof which upon reaction with an amine yields a carboxylic acid amide, wherein R2 is C12-350 alkyl or C12-350 alkenyl and a hydrocarbyl polyamine.

26. The method of Claim 25 wherein R2 is C12-20 alkyl or c12-20 alkenyl and the hydrocarbyl polyamine is tetraethylene pentamine or triethylene tetramine.

27. The method of Claim 23 wherein said basic nitrogen compound is a Mannich base prepared from dodecylphenol, formaldehyde, and methylamine.

28. The method of Claim 23 wherein said basic nitrogen compound is a Mannich base prepared from C80-100 alkyl-phenol, formaldehyde and triethylene tetramine, tetraethylene pentamine, or mixtures thereof,

29. The method of Claim 19 wherein the polar promoter is water.

30. The method of Claim 19 wherein the carboxylic acid amide of component (2) is derived from a carboxylic acid of the formula R2COOH, wherein R2 is C12-20 alkyl, and an ethylene amine.

31. The method of Claim 19 wherein the succinimide of component (3) is derived from polyisobutenyl succinic anhydride, wherein the polyisobutenyl group contains from 50 to 250 carbon atoms, and an ethylene amine.

32. The method of Claim 19 wherein the lubricant composition contains 0.05 to 15% by weight of the molybdenum-containing composition of component (1), 0.05 to 20% by weight of the carboxylic acid amide of component (2), and 0.05 to 15% by weight of the succinimide of component (3).

33. The method of Claim 19 wherein the molybdenum complex is reacted with the sulfur-containing compound in an amount sufficient to provide 2.0 to 4.0 atoms of sulfur per atom of molybdenum.

34. The method of Claim 33 wherein the molybdenum complex is reacted with the sulfur-containing compound in an amount sufficient to provide 2.5 to 4.0 atoms of sulfur per atom of molybdenum.

35. The method of Claim 19 wherein the additive formulation further contains a flocculent inhibitor.

36. The method of Claim 35 wherein the additive formulation further contains a lubricity agent.