AU670118B2 - Fuel composition for two-cycle engines - Google Patents

Description

N

CLORRECTED]I under INID NumbLr (710 "Applicant", replace the VERSION* Iexisting text by 'CHEVRON RESEARCH AND TECH- NOLOGY COMPANY, a division of CHEVRON Pff U.S.A. INC. (US/US); P.O. Box 7141, San Francisco, CA 94120-7 141 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 5 _T Publ.,,;n.icaio Nuimber: WO 94/06897 CIOM 159/18, 133/16, 149/001 Al (43) International Publication Date: 31 March 1994 (31.03.94) (21) International Application Number: PCT/US93/08471 (22) International Filing Date: 9 September 1993 (09.09.93) Priority data: 07/943,844 11 September 1992 (11.09.92) us (71) Applic-.at -CIfF-'RO 111'sER I ,.F (81) Designa'ed States: AU, CA, IP, European patent (AT, BE, CH, [DE, DK, ES, FR, GB, OR, TE, IT, LU, MC, NL, PT, S EN Published With international search report.

It a. k a di4iie of- -5a12071 Kc~~ (72) Inventors: CALLIS, Glenn. E. ;1089 Walnut Avenue, Walnut Creek, CA 94598 SABOURIN, Edward, T.

I I Avichi Knoll, Novato, CA 94947 (US).

(74) Agents: CAROLI, Claude, J. et al.; Chevron Corporation, Law Department, Post Office Box 7141, San Francisco, CA 94120-7 141 (US).

(54)Title: FUEL COMPOSITION FOR TWO-CYCLE ENGiNES (57) 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 ant additive formulation comprising a molybdenum/sulfur complex of a basic nitrogen compound, a carboxylic acid amide, and a succinimide.

trred to III PWT Oat liq.S-±toi TIENS. SLetioll 11)

I

WO 94/06897 PCT/US93/08471 -1- 01 FUEL COMPOSITION FOR TWO-CYCLE ENGINES 02 03 BACKGROUND OF THE INVENTION 04 The present invention relates to a fuel composition for 06 two-cycle internal combustion engines which comprises a 07 major amount of fuel boiling in the gasoline range and a 08 minor amount of a lubricant composition comprising a 09 lubricating oil and an additive formulation containing a molybdenum/sulfur complex of a basic nitrogen compound.

11 12 Over the past several decades the use of spark-ignited 13 two-cycle (two-stroke) internal combustion engines including 14 rotary engines such as those of the Wankel type has steadily increased. They are presently found in power lawn mowers 16 and other power-operated garden equipment, power chain saws, 17 pumps, electrical generators, marine outboard engines, 18 snowmobiles, motorcycles, and the like.

19 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 i ring sticking, rusting, lubrication failure of connecting 26 rods and main bearings and the general formation on the 27 engine's interior surface of carbon and varnish deposits. i 28 The formation of varnish is a particularly vexatious problem 29 since the build-up of varnish on piston and cylinder walls is believed to ultimately result in ring sticking which 31 leads to failure of the sealing function of piston rings.

32 Such seal failure causes 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/US93/08471 -2- 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 04 and engine port plugging problems also occur in two-cycle engine3.

06 07 A variety of compounds have been proposed as additives for 08 fuel-lubricating oil mixtures to be used in two-cycle 09 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 a neutral or basic 17 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 an ester of a substituted 23 polycarboxylic acid.

24 U.S. Patent No. 4,724,091 to Davis discloses a lubricant 26 composition for two-cycle engines comprising a major amount 27 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.

33 34 (i' d i j~G I WO 94/06897 PCT/US93/08471 -3- 01 U.S. Patent No. 4,740,321 to Davis et al. discloses a 02 lubricant composition for two-cycle engines comprising a 03 major amount of an oil of lubricating viscosity and a minor 04 amount of at least one sulfurized alkyl phenol or metal salt thereof having at least one hydrocarbon-based group of at 06 least 10 aliphatic carbon atoms. This lubricant composition 07 will also preferably contain a detergent-dispersant 08 additive.

09 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 14 chain carboxylic acid of 16 to 20 carbon atoms and a polyamine of at least 3 amine groups. Preferably, the 16 ashless detergent additive is the hydrolyzed reaction 17 product of isostearic acid and tetraethylenepentamine.

18 19 U.S. Patent No. 4,994,196 to Kagaya et al. discloses a two-cycle engine oil composition comprising a base oil and a 21 calcium phenate detergent additive, wherein the base oil is 22 a mixture of a copolymer of an alpha-olefin with an 23 ester of a dicarboxylic acid and an ester of 24 pentaerythritol and a fatty acid.

26 U.S. Patent No. 3,888,776 to Silverstein discloses a 27 two-cycle engine lubricant which comprises a major amount of 28 a polypropylene glycol and minor amounts of a sulfurized 29 oxymolybdenum organophosphorodithioate, a finely divided molybdenum disulfide and a halogenated hydrocarbon 31 detergent, such as 1,1,l-trichloroethylene, 32 orthodichlorobenzene, perchlorinated biphenyl, and the like.

33 34 WO 94/06897 PCT/US93/08471 -4- 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, automobile and railroad crankcase lubricants, lubricants for 06 heavy machinery, greases for bearings, and the like.

07 08 For example, U.S. Patent No. 4,263,152 to King et al.

09 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 17 appreciates the use of such antioxidant additives, or s18 lubricating oils containing such additives, in admixture 19 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.

24 Moreover, as taught in the aforementioned. U.S. Patent 26 No. 4,708,809, the unique problems and techniques associated 27 with the lubrication of two-cycle engines has led to the 28 recognition by those skilled in the art of two-cycle engine A 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 11L 2 r WO 94/06897 PCT/US93/08471 01 eliminate or reduce two-cycle engine varnish deposits and 02 piston ring seal failure.

03 04 SUMMARY OF THE INVENTION 06 The present invention provides a fuel composition for 07 two-cycle engines comprising a major amount of fuel boiling 08 in the gasoline range and a minor amount of a lubricant 09 composition comprising: 11 a major amount of a base oil of lubricating viscosity, 12 and 13 14 a minor amount of an additive formulation comprising: 16 a sulfurized molybdenum-containing composition 17 prepared by reacting an acidic molybdenum 18 compound and a basic nitrogen compound selected 19 from the group consisting of a succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a 21 hydrocarbyl polyamine, a Mannich base, a 22 phosphoramide, a thiophosphoramide, a 23 phosphonamide, a dispersant viscosity index 24 improver, or a mixture thereof, in the presence of a polar promoter, to form a molybdenum complex 26 wherein from 0.01 to 2 atoms of molybdenum are 27 present per basic nitrogen atom, and the promoter 28 is present in the ratio of 0.01 to 50 moles of 29 polar promoter per mole of molybdenum; and (ii) reacting the molybdenum complex with a 31 sulfur-containing compound in an amount sufficient 32 to provide about 1.5 to 4.0 atoms of sulfur per 33 atom of molybdenum, to thereby form a sulfur- and 34 molybdenum-containing composition, P:\OPERADD48525-93.095-2/5/96 6 a carboxylic acid amide, and a succinimide.

The present invention also provides a method of reducing engine deposits and piston ring sticking in a two-cycle engine which comprises operating the two-cycle engine with a fuel composition as described in the immediately preceding paragraph.

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

DETAILED DESCRIPTION OF THE INVENTION The fuel composition of the present invention will comprise 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 containing a sulfurized 20 molybdenum-containing composition, a carboxylic acid amide, and a succinimide.

The sulfurized molybdenum-containing composition employed in the present invention may be generally characterized as a molybdenum/sulfur complex of a basic nitrogen compound. Such molybdenum/sulfur complexes are known in the art and are described, t 25 for example, in U.S. Patent No. 4,263,152 to King et al, the disclosure of which is hereby incorporated by reference.

The precise molecular formula of the molybdenum compositions employed in this invention is not known with certainty; however, they are believed to be compounds in which molybdenum, whose valences are satisfied with atoms of 0i WO 94/06897 PCT/US93/08471 -7- 01 oxygen or sulfur, is either complexed by, or the salt of, 02 one or more nitrogen atoms of the basic nitrogen containing 03 compound used in the preparation of these compositions.

04 The molybdenum compounds used to prepare the 06 molybdenum/sulfur complexes employed in this invention are 07 acidic molybdenum compounds. By acidic is meant that the 08 molybdenum compounds will react with a basic nitrogen 09 compound as measured by ASTM test D-664 or D-2896 titration procedure. Typically these molybdenum compounds are 11 hexavalent and are represented by the following 12 compositions: molybdic acid, ammonium molybdate, sodium 13 molybdate, potassium molybdate and other alkaline metal 14 molybdates and other molybdenum salts such as hydrogen salts, hydrogen sodium molybdate, MoOC14, MoO 2 Br 2 16 Mo20 3 C1 6 molybdenum trioxide or similar acidic molybdenum 17 compounds. Preferred acidic molybdenum compounds are 18 molybdic acid, ammonium molybdate, and alkali metal 19 molybdates. Particularly preferred are molybdic acid and ammonium molybdate.

21 V 22 The basic nitrogen compound used to prepare the 23 molybdenum/sulfur complexes must have a basic nitrogen 24 content as measured by ASTM D-664 or D-2896. It is preferably oil-soluble. Typical of such compositions are 26 succinimides, carboxylic acid amides, hydrocarbyl 27 monoamines, hydrocarbon polyamines, Mannich bases, 28 phosphoramides, thiophosphoramides, phosphonamides, 29 dipcprsant viscosity index improvers, and mixtures thereof.

These basic nitrogen-containing compounds are described 31 below (keeping in mind the reservation that each must have 32 at least one basic nitrogen). Any of the 33 nitrogen-containing compositions may be after-treated with, 34 i rr.~L WO 94/06 .97 PCT/US93/08471 -8- 01 boron, using procedures well known in the art so long 02 as the compositions continue to contain basic nitrogen.

03 These after-treatments are particularly applicable to 04 succinimides and Mannich base compositions.

06 The mono and polysuccinimides that can be used to prepare 07 the molybdenum/sulfur complexes described herein are 08 disclosed in numerous references and are well known in the 09 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 disclosures of which are 13 hereby incorporated by reference. The term "succinimide" is 14 understood in the art to include many of the amide, imide, and amidine species which may also be formed. The 16 predominant product however is a succinimide and this term 17 has been generally accepted as meaning the product of a 18 reaction of an alkenyl substituted succinic acid or 19 anhydride with a nitrogen-containing compound. Preferred succinimides, because of their commercial availability, are 21 those succinimides prepared from a hydrocarbyl succinic 22 anhydride, wherein the hydrocarbyl group contains from about 23 24 to about 350 carbon atoms, and an ethylene amine, said 24 ethylene amines being especially characterized by ethylene diamine, diethylene triamine, triethylene tetramine, and 26 tetraethylene pentamine. Particularly preferred are those 27 succinimides prepared from polyisobutenyl succinic anhydride 28 of 70 to 128 carbon atoms and tetraethylene pentamine or 29 triethylene tetramine or mixtures thereof.

31 Also included within the term "succinimide" are the 32 cooligomers of a hydrocarbyl succinic acid or anhydride and 33 a poly secondary amine containing at least one tertiary 34 amino nitrogen in addition to two or more secondary amino x i: ,l WO 94/06897 PCT/US93/08471 -9- 01 groups. Ordinarily this composition has between 1,500 and 02 50,000 average molecular weight. A typical compound would 03 be that prepared by reacting polyisobutenyl succinic 04 anhydride and ethylene dipiperazine.

06 Carboxylic acid amide compositions are also suitable 07 starting materials for preparing the molybdenum/sulfur 08 complexes employed in this invention. Typical of such 09 compounds are those disclosed in U.S. Patent No. 3,405,064, the disclosure of which is hereby incorporated by reference.

11 These compositions are ordinarily prepared by reacting a 12 carboxylic acid or anhydride or ester thereof, having at 13 least 12 to about 350 aliphatic carbon atoms in the 14 principal aliphatic chain and, if desired, having sufficient pendant aliphatic groups to render the molecule oil soluble 16 with an amine or a hydrocarbyl polyamine, such as an 17 ethylene amine, to give a mono or polycarboxylic acid amide.

18 Preferred are those amides prepared from a carboxylic 19 acid of the formula R 2 COOH, where R 2 is C 1 2 20 alkyl or a mixture of this acid with a polyisobutenyl carboxylic acid 21 in which the polyisobutenyl group contains from 72 to 22 128 carbon atoms and an ethylene amine, especially 23 triethylene tetramine or tetraethylene pentamine or mixtures 24 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. Patent 29 No. 3,574,576, the disclosure of which is hereby incorporated by reference. The hydrocarbyl group, which is 31 preferably alkyl, or olefinic having one or two sites of 32 unsaturation, usually contains from 9 to 350, preferably 33 from 20 to 200 carbon atoms. Particularly preferred 34 WO 94/06897 PCT/US93/08471 01 hydrocarbyl polyamines are those which are derived, by 02 reacting polyisobutenyl chloride and a polyalkylene 03 polyamine, such as an ethylene amine, ethylene 04 diamine, diethylene triamine, tetraethylene pentamine, 2-aminoethylpiperazine, 1,3-propylene diamine, 06 1,2-propylenediamine, and the like.

07 08 Another class of compounds useful for supplying basic 09 nitrogen are the Mannich base compositions. The compositions are prepared from a phenol or C9-20 11 alkylphenol, an aldehyde, such as formaldehyde or 12 formaldehyde precursor such as paraformaldehyde, and an 13 amine compound. The amine may be a mono or polyamine and 14 typical compositions are prepared from an alkylamine, such as methylamine or an ethylene amine, such as, diethylene 16 triamine, or tetraethylene pentamine, and the like. The 17 phenolic material may be sulfurized and preferably is 18 dodecylphenol or a Cg0.10 alkylphenl. Typical Mannich 19 bases which can be used in this invention are disclosed in U.S. Patent No. 4,157,309 and U.S. Patent Nos. 3,649,229; 21 3,368,972; and 3,539,663, the disclosures of which are 22 hereby incorporated by reference. The last referenced 23 patent discloses Mannich bases prepared by reacting an 24 alkylphenol having at least 30 carbon atoms, preferably to 200 carbon atoms with formaldehyde and an alkylene 26 polyamine HN(ANH)nH where A is a saturated divalent alkyl 27 hydrocarbon of 2 to 6 carbon atoms and n is 1-10 and where 28 Sthe condensation product of said alkylene polyamine may be 29 29 further reacted with urea or thiourea. The utility of these 3 Mannich bases as starting materials for preparing 31 lubricating oil additives can often be significantly 3 improved by treating the Mannich base using conventional Stechniques to introduce boron into the composition.

34 .1 WO 94/06897 PCT/US93/08471 -11- 01 Another class of composition useful for preparing the 02 molybdenum/sulfur complexes employed in this invention are 03 the phosphoramides and phosphonamides such as those 04 disclosed in U.S. Patent Nos. 3,909,430 and 3,968,157, the disclosures of which are hereby incorporated by reference.

06 These compositions may be prepared by forming a phosphor a 07 compound having at least one P-N bond. They can be 08 prepared, for example, by reacting phosphorus oxychlor.

09 with a hydrocarbyl diol in the presence of a monoamine o.

reacting phosphorus oxychloride with a difunctional 11 secondary amine and a mono-functional amine.

12 Thiophosphoramides can be prepared by reacting an 13 unsaturated hydrocarbon compound containing from 2 to 450 or 14 more carbon atoms, such as polyethylene, polyisobutylene, polypropylene, ethylene, 1-hexene, 1,3-hexadiene, 16 isobutylene, 4-methyl-l-pentene, and the like, with 17 phosphorus pentasulfide and a nitrogen-containing compound 18 as defined above, particularly an alkylamine, alkyldiamine, 19 alkylpolyamine, or an alkyleneamine, such as ethylene diamine, diethylenetriamine, triethylenetetramine, 21 tetraethylenepentamine, and the like.

22 23 Another class of nitrogen-containing compositions useful in 24 preparing the molybdenum complexes employed in this invention includes the so-called dispersant viscosity index 26 improvers (VI improvers). These VI improvers are commonly 27 prepared by functionalizing a hydrocarbon polymer, 28 especially a polymer derived from ethylene and/or propylene, 29 optionally containing additional units derived from one or more co-monomers such as alicyclic or aliphatic olefins or 31 diolefins. The functionalization may be carried out by a 32 variety of processes which introduce a reactive site or 33 sites which usually has at least one oxygen atom on the 34 polymer. The polymer is then contacted with a hB -L I WO 94/06897 PCT/US93/08471 -12- 31 nitrogen-containing source to introduce nitrogen-containing 02 functional groups on the polymer backbone. Commonly used 03 nitrogen sources include any basic nitrogen compound 04 especially those nitrogen-containing compounds and compositions described herein. Preferred nitrogen sources 06 are alkylene amines, such as ethylene amines, alkyl amines, 07 and Mannich bases.

08 09 Preferred basic nitrogen compounds for use in this invention are succinimides, carboxylic acid amides, and Mannich bases.

11 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, R 2

S

x where R is hydrocarbyl, preferably C 1 16 alkyl, and x is at least 2, inorganic sulfides and 17 polysulfides such as (NH 4 2 Sx, where x is at least 1, 18 thioacetamide, thiourea, and mercaptans of the formula RSH 19 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 27 sulfur, sulfur monochloride, and/or sulfur dichloride with 28 an unsaturated fatty ester under elevated temperatures.

S29 Typical esters include Ci-C 20 alkyl esters of C-C24 unsaturated fatty acids, such as palmitoleic, oleic, 31 ricinoleic, petroselinic, vaccenic, linoleic, linolenic, 32 oleostearic, licanic, paranaric, tariric, gadoleic, 33 arachidonic, cetoleic, etc. Particularly good results have 34 I WO 94/06897 PCT/US93/08471 -13- 01 been obtained with mixed unsaturated fatty acid esters, such 02 as are obtained from animal fats and vegetable oils, such as 03 tall oil, linseed oil, olive oil, caster oil, peanut oil, 04 rape oil, fish oil, sperm oil, and so forth.

06 Exemplary fatty esters include lauryl tallate, methyl 07 oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl 08 linoleate, lauryl ricinoleate, oleyl linoleate, oleyl 09 stearate, and alkyl glycerides.

11 Cross-sulfurized ester olefins, such as a sulfurized mixture 12 of CI 1

-C

25 olefins with fatty acid esters of C 10

-C

25 fatty 13 acids and CI-C 25 alkyl or alkenyl alcohols, wherein the 14 fatty acid and/or the alcohol is unsaturated may also be used.

16 17 Sulfurized olefins are prepared by the reaction of the C3-C 6 1 olefin or a low-molecular-weight polyolefin derived 19 therefrom with a sulfur-containing compound such as sulfur, 2 sulfur monochloride, and/or sulfur dichloride.

21 22 Also useful are the aromatic and alkyl sulfides, such as 23 dibenzyl sulfide, dixylyl sulfide, dicetyl sulfide, 24 diparaffin wax sulfide and polysulfide, cracked wax-olefin i 2 sulfides and so forth. They can be prepared by treating the 26 starting material, olefinically unsaturated compounds, 27 with sulfur, sulfur monochloride, and sulfur dichloride.

28S 28 Particularly preferred are the paraffin wax thiomers 29 described in U.S. Patent 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 34 i X Y' I i -sl WO 94/06897 PCT/US93/08471 -14- 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.

04 Preferred sulfur sources are sulfur, hydrogen sulfide, 06 phosphorus pentasulfide, R 2 Sx where R is hydrocarbyl, 07 preferably CI-CIO alkyl, and x is at least 3, mercaptans 08 wherein R is Cl-Cl 0 alkyl, inorganic sulfides and 09 polysulfides, thioacetamide, and thiourea. Most preferred 1 sulfur sources are sulfur, hydrogen sulfide, phosphorus 11 pentasulfide, and inorganic sulfides and polysulfides.

12 1 The polar promoter used in the preparation of the molybdenum 1 complexes employed in this invention is one which 1 facilitates the interaction between the acidic molybdenum compound and the basic nitrogen compound. A wide variety of 17 such promoters are well known to those skilled in the art.

STypical promoters are 1,3-propanediol, 1,4-butane-diol, 19 1 diethylene glycol, butyl cellosolve, propylene glycol, 1,4-butyleneglycol, methyl carbitol, ethanolamine, 21 diethanolamine, N-methyl-diethanol-amine, dimethyl 22 22 formamide, N-methyl acetamide, dimethyl acetamide, methanol, 23 2 ethylene glycol, dimethyl sulfoxide, hexamethyl 24 phosphoramide, tetrahydrofuran and water. Preferred are 2 water and ethylene glycol. Particularly preferred is water.

26 2 While ordinarily the polar promoter is separately added to 28 the reaction mixture, it may also be present, particularly 29 Sin the case of water, as a component of non-anhydrous 3 starting materials or as waters of hydration in the acidic 31 molybdenum compound, such as (NH 4 6 Mo70 24 .4 H 2 0. Water may 32 also be added as ammonium hydroxide.

33 34 I 1* WO 94/06897 PCT/US93/08471 01 A method for preparing the molybdenum/sulfur complexes used 02 in this invention is to 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 diluent is used, if necessary, to provide a suitable 06 viscosity for easy stirring. Typical diluents are 07 lubricating oil and liquid compounds containing only carbon 08 and hydrogen. If desired, ammonium hydroxide may also be 09 added to the reaction mixture to provide a solution of ammonium molybdate. This reaction is carried out at a 11 temperature from the melting point of the mixture to reflux 12 temperature. It is ordinarily carried out at atmospheric 13 pressure although higher or lower pressures may be used if 14 desired. This reaction mixture is treated with a sulfur source as defined above at a suitable pressure and 16 temperature for the sulfur source to react with the acidic 17 molybdenum and basic nitrogen compounds. In some cases, 18 removal of water from the reaction mixture may be desirable 19 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 27 as can easily be maintained 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.

Preferably from 0.4 to 1.0, and most preferably from 0.4 to 31 0.7, atoms of molybdenum per atom of basic nitrogen is added 32 to the reaction mixture.

33 34 o IB~ WO 94/06897 PCT/US93/08471 -16- 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, 2.5 to 4.0 atoms of sulfur per atom of molybdenum.

06 07 The polar promoter, which is preferably water, is ordinarily 08 present in the ratio of 0.1 to 50 moles of promoter per mole 09 of molybdenum. Preferably from 0.5 to 25 and most preferably 1.0 to 15 moles of the promoter is present per 11 mole of molybdenum.

12 13 As described above, the additive formulation employed in the 14 present invention contains a sulfurized molybdenum-containing composition, a carboxylic acid 16 amide, and a succinimide.

17 18 The carboxylic amide component of the presently employed 19 additive formulation may be any of the carboxylic acid amide 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 R 2 COOH, wherein R 2 is C 12

-C

20 24 alkyl, and an ethylene amine, such as triethylene tetramine or tetraethylene pentamine.

26 27 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 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 34 WO 94/06897 PCT/US93/08471 -17- 01 amine, such as triethylene tetramine or tetraethylene 02 pentamine.

03 04 The additie formulation employed in the present invention may additionally contain a flocculant inhibitor and/or a 06 lubricity agent, such as a polyisobutene. If necessary, a 07 diluent oil may also be included.

08 09 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.

14 The lubricant composition employed in the present invention 16 comprises a major amount of a base oil of lubricating 17 viscosity and a minor amount of the additive formulation 18 described above.

19 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 27 they are presently in more general use in two-cycle engines.

28 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.

34 (p, yl ZL WO 94/06897 PCT/US93/08471 -18- 01 Generally, the amount of the molybdenum-containing additive 02 will vary from about 0.05 to 15% by weight and preferably 03 from about 0.2 to 10% by weight, bazed on the total 04 lubricant composition, including base oil. The carboxylic acid amide component will vary from about 0.05 to 20% by 06 weight and preferably from about 0.2 to 15% by weight. The 07 succinimide component will vary from about 0.5 to 15% by 08 weight and preferably from about 0.2 to 10% by weight.

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

14 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 18 introduced into the two-cycle engine cylinder. Generally, 19 the resulting fuel composition will contain from about 15 to 250 parts fuel per 1 part lubricant, and more typically 21 about 50 to 100 parts fuel per 1 part lubricant. For some 22 two-cycle engine applications, the lubricant may be directly 23 injected into the combustion chamber along with the fuel or 24 into the fuel just prior to the time the fuel enters the combustion chamber.

26 27 The fuel employed in the present fuel composition is a 28 hydrocarbon distillate fuel boiling in the gasoline range.

29 In such gasoline fuels, other fuel additives may also be included such as antiknock agents, e.g., 31 methylcyclopentadienyl manganese tricarbonyl, tetramethyl or 32 tetraethyl lead, or other dispersants or detergents such as 33 various substituted amines, etc. Also included may be lead 34 scavengers such as aryl halides, dichlorobenzene or f -r: WO 94/06897 PCT/US93/08471 -19- 01 alkyl halides, ethylene dibromide. Additionally, 02 antioxidants, metal deactivators, pour point depressants, 03 corrosion inhibitors and demulsifiers may be present.

04 The following examples are presented to illustrate specific 06 embodiments of this invention and are not to be construed in 07 any way as limiting the scope of the invention.

08 09 EXAMPLES 11 Example 1 12 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 17 succinic anhydride having a number average molecular weight 18 for the polyisobutenyl group of about 950 and tetraethylene 19 pentamine, and 1200 grams of hydrocarbon thinner were added.

The mixture was refluxed at 100 0 C for 3 hours. The 21 temperature was gradually increased over approximately 22 1 hour to 170 0 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 0 C and the mixture filtered and returned to the reaction vessel. To the 26 solution was added 51 grams of sulfur. The mixture was 27 heated to 160 0 C-180 0 C for 7 hours. The pressure was slowly 28 reduced to about 50 mm of mercury to remove the hydrocarbon 29 thinner. This produced 1244 grams of product containing 30 1.80% nitrogen, 5.63% molybdenum, and 3.57% sulfur.

31 32 33 34

I

g. 4 il:~ WO 94/06897 P~T/US93/ 08471 01 Example 2 02 03 To a 5000 ml flask was added 52 grams molybdenum trioxide 04 and 1Ill grams of water. Stirring was started and 1184 grams of a solution of a 45% concentrate in oil of the succinimide 06 described in Example 1 and 1184 grams of hydrocarbon thinner 07 were added. The mixture was ref luxed at 100 0 C for 3 hours.

0S The temperature was gradually increased over approximately 09 1 hour to 170 0 C while distilling water. The temperature was maintained an additional hour after the water was removed.

11 The temperature was lowered to 100 0 C-120 0 C and the mixture 1.2 filtered and returned to the reaction vessel. To the 13 solution was added 47 grams of sulfur. The mixture was 14 heated to 160OC-180 0 C for 7 hours. The pressure was slowly is reduced to about 50 mm, of mercury to remove the hydrocarbon 16 thinner. This produced 1220 grams of product containing 17 1.4 irgn .~%molybdenum, and 3.64% sulfur.

19 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 24 described in Example 1 and 1133 grams of hydrocarbon thinner were added. The mixture was ref luxed at 100 0 C for 3 hours.

26 The temperature was gradually increased over approximately 27 1 hour to 170 0 C while distilling water. The temperature was 28 maintained an additional hour after the water was removed.

29 The temperature was lowered to 100OC-1200C and the mixture filtered and returned to the reaction vessel. To the 32. solution was added 22 grams of sulfur. The mixture was 32 heated to 160OC-180 0 C for 7 hours. The pressure was slowly *33 reduced to about 50 mm of mercury to remove the hydrocarbon 34 ~r 4 4 I WO 94/06897 PCT/US93/08471 -21.- 01 thinner. This produced 1163 grams of product containing 02 1.83% nitrogen, 2.79% molybdenum, and 1.97% sulfur.

03 04 Example 4 06 To a 5000 ml flask was added 1200 grams of a polyamide 07 prepared from a Cl 8 carboxylic acid and tetraethylene 08 pentamine and containing 6.4% nitrogen, 1200 grams 09 hydrocarbon thinner, 42 grams molybdenum trioxide, and 90 grams water. The mixture was refluxed at 100 0 C for 11 3 hours. The temperature was gradually increased over 12 approximately 1 hour to 170 0 C while distilling water. The 13 temperature was maintained an additional hour after the 14 water was removed. The temperature was lowered to 100oC-120°C and the mixture filtered and returned to the 16 reaction vessel. To the solution was added 21 grams of 17 sulfur. The mixture was heated to 160OC-180°C for 7 hours.

18 The pressure was slowly reduced to about 50 mm of mercury to 19 remove the hydrocarbon thinner. This produced a product containing 5.88% nitrogen, 2.29% molybdenum, and 1.63% 21 sulfur.

22 23 Example 24 The molybdenum/sulfur complexes of Examples 1, 2 and 4 were 26 formulated to provide lubricant compositions containing 10% L 27 of the carboxylic acid amide reaction product of isostearic 28 acid and tetraethylene pentamine, 2% of a polyisobutenyl S29 succinimide prepared from polyisobutenyl succinic anhydride wherein the polyisobutenyl 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 34

I,

WO 94/06897 PCT/US93/08471 -22- 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 10% of a 04 150 bright stock, about 70% of a mixture of 350N and 650N neutral oils, and about 20% of a petroleum distillate 06 solvent.

07 08 Example 6 09 Two-Cycle Gasoline Engine 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 17 Model No. J70ELEIE outboard engine, which is a 18 70 horsepower, water-cooled, three-cylinder, two-cycle 19 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.

24 The test was then conducted for 98 hours using a 50:1 fuel 26 to lubricant ratio on a 55 minute wide-open throttle, 27 5 minute idle cycle. The total test time, including 28 break-in, was 100 hours.

29 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 WO 94/06897 PCT/US93/08471 -23- 01 being the maximum rating. Except for the piston rings, the 02 ratings are for cleanliness. The piston rings are rated for 03 the degree of sticking, with a rating of 10.0 indicating a 04 completely free piston ring.

06 The second-ring sticking values include a National Marine 07 Manufacturers Association (NMMA) rating, a visual rating, 08 and an adjusted rating, which is an average of the NMMA and 09 visual ratings.

11 The reference oil employed in this test was NMMA reference 12 oil TCW II, used as an industry standard in two-cycle engine 13 tests to measure engine cleanliness. The TCW II reference 14 oil is a standard mineral lubricating oil containing a commercial ashless dispersant for gasoline two-cycle 16 engines. The reference oil is available from Citgo 17 Petroleum Corporation, Tulsa, Oklahoma.

18 19 Engine test runs were performed with a 50:1 fuel to 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 The results shown in Table 1 demonstrate that the fuel 26 composition of the present invention is highly effective in 27 reducing piston deposits and piston ring sticking in 28 two-cycle engines, and generally exceeds the performance of A ^29 a fuel containing the industry standard reference oil.

31 32 33 34 k

V

F

WO 94/06897 PCr/US93/0847 I -24- TABLE I TIWO-CYCLE ENGINE TEST RES.ILTS Averau Rating :or. 3 iA I Piston 2-Ring Under- Scn-igSikn Additive Skirt Crown Land Crown NHHA Visual Adj.

TCW II Reference Oil 7.1 2.8 3.7 2.8 6.8 5.7 _3 Example l(a) 74 3.4 4.4 2.5 7.1 6.1 6.6 Example 4 77 3.1 4.8 3.9 7.8 68 7 L6.7.

Example 2 7.8 3.4 4.4 13.3 B S 6.5 Fomulated as in Example Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integ,rs.

Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the invention includes all such variations and modifications which fall within its spirit and scope. The invention also includes all the steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations of any two or more of said steps or features.

S

4 F. U 4* a.

*4 4 4 4 a a a a, .4 a at..

o *S *4 a C *4&a

C

Claims (9)

1. 2. The fuel composition of Claim 1, wherein the sulfur 06 source for component is sulfur, hydrogen sulfide, 07 phosphorus pentasulfide, R 2 S x where R is hydrocarbyl 08 and x is at least 2, inorganic sulfides or inorganic 09 polysulfides, thioacetamide, thiourea, mercaptans of the formula RSH where R is hydrocarbyl, or a 11 sulfur-containing antioxidant. 12 13 3. The fuel composition of Claim 2, wherein the sulfur 14 source for component is sulfur, hydrogen sulfide, phosphorus pentasulfide, R 2 Sx where R is C14 16 hydrocarbyl and x is at least 3, inorganic sulfides, 17 or inorganic polysulfides, thioacetamide, thiourea or 18 RSH where R is C 1 40 alkyl, and the acidic molybdenum 19 compound is molybdic acid, ammonium molybdate, or alkali metal molybdate. 21 22 2 4. The fuel composition of Claim 3, wherein said sulfur 23 source is sulfur, hydrogen sulfide, RSH where R is CI. 10 24 alkyl, phosphorus pentasulfide, or (NH 4 2 Sx., where x' is at least 1, said acidic molybdenum compound is 26 molybdic acid, or ammonium molybdate, and said basic 27 nitrogen compound is a succinimide, carboxylic acid 28 amide, or Mannich base. 29 The fuel composition of Claim 4, wherein said basic 31 32 nitrogen compound is a C 24350 hydrocarbyl succinimide, carboxylic acid amide, or a Mannich base prepared from 33 a C 9 .200 alkylphenol, formaldehyde, and an amine. 34 I4, WO 94/06897 PCT/US93/08471 -27- 01 6. The fuel composition of Claim 5, wherein said basic 02 nitrogen compound is a polyisobutenyl succinimide 03 prepared from polyisobutenyl succinic anhydride and 04 tetraethylene pentamine or triethylene tetramine. 06 7. The fuel composition of Claim 5, wherein said basic 07 nitrogen compound is a carboxylic acid amide prepared 08 from one or more carboxylic acids of the formula 09 R 2 COOH, or a derivative thereof which upon reaction with an amine yields a carboxylic acid amide, wherein 11 R 2 is C 12350 alkyl or C 12 350 alkenyl and a hydrocarbyl 12 polyamine. 13 14 8. The fuel composition of Claim 7, wherein R 2 is C 1220 alkyl or C 12 20 alkenyl and the hydrocarbyl polyamine is 16 tetraethylene pentamine or triethylene tetramine. 17 18
2. 9. The fuel composition of Claim 5, wherein said basic 19 nitrogen compound is a Mannich base prepared from dodecylphenol, formaldehyde, and methylamirle. 21 22 The fuel composition of Claim 5, wherein said basic 23 nitrogen compound is a Mannich base prepared from 24 C 80 100 alkylphenol, formaldehyde and triethylene tetramine, tetraethylene pentamine, or mixtures 26 thereof. 27 28 9 11. The fuel composition of Claimsl, wherein the polar 29 A promoter is water. 31 es one. 4o i
3. 12. The fuel composition.of Claimil, wherein the carboxylic acid amide of component is derived from a 1 33 P:\OPER\ADD\48525-93.09-9/5/96 28 carboxylic acid of the formula R 2 COOH, wherein R 2 is C 1 2 -20 alkyl, and an ethylene amine.
4. 13. The fuel composition of any one of claims 1 to 12, wherein the succinimide of component is derived from polyisobutenyl succinic anhydride, wherein the polyisobutenyl group contains from about 50 to 250 carbon atoms, and an ethylene amine.
5. 14. The fuel composition of any one of claims 1 to 13, wherein the lubricant composition contains about 0.05 to 15% by weight of the molybdenum-containing composition of component about 0.05 to 20% by weight of the carboxylic acid amide of component and about 0.05 to 15% by weight of the succinimide of component
6. 15. The fuel composition of any one of claims 1 to 14, wherein the molybdenum complex is ieacted with the sulfur-containing compound in an amount sufficient to provide about 2.0 to 4.0 atoms of sulfur per atom of molybdenum. S16. The fuel composition of claim 15, wherein the molybdenum complex is reacted •t 20 with the sulfur-containing compound in an amount sufficient to provide about to 4.0 atoms of sulfur per atom of molybdenum.
7. 17. The fuel composition of any one of claims 1 to 16, wherein the additive .formulation further contains a flocculant inhibitor.
8. 18. The fuel composition of any one of claims 1 to 17, wherein the additive formulation further contains a lubricity agent.
9. 19. A fuel composition for two-cycle engines substantially as hereinbefore described with reference to the Examples. I *V 1 I t 1 b 3 j f. P:\OPER\ADD\48525-93.095 15/5/96 29 A method of reducing engine deposits and piston ring sticking in a two-cycle engine which comprises operating the two-cycle engine with a fuel composition according to any one of the preceding claims. DATED this 15th day of May, 1996 Chevron Chemical Company By DAVIES COLLISON CAVE Patent Attorneys for the applicant(s) H i tt 4a t r It i *4 a tI| at 4 a *I a t t i a t C r ai«t C. 4 I 4 4 1 t (44 4 3 t t e t Ui iI1i 1 :i rr INTERNATIONAL SEARCH REPORT A .r International application No. PCT/US93/08471 A. CLASSIFICATION OF SUBJECT MATTER :C10M 159/18, 133/16, 149/00 US CL :252/42.7, 46.4, 51.5A According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) U.S. 252/42.7, 46.4, 51.5A, 44/367, 330,331 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y US, A, 4,263,152 (King et al) 21 April 1981, see col. 2, 1-36 lines 10 et seq. and col. 7, lines 5-47. Y US, A, 3,405,064 (Miller) 08 October 1968, see col. 1, lines 1-36 19-40 and lines 55 et seq. Y US, A, 3,219,666 (Norman et al) 23 November 1965, see 1-36 entire document. A US, A, 4,266,945 (Karn) 12 May 1981, see entire 1-36 document. A US, A, 4,164,473 (Coupland et al) 14 August 1979, see 1-36 entire document. D Further documents are listed in the continuation of Box C. O See patent family annex. Special categories of cited documents: later documentpublished after the intertional filing date or priority date and not in conflict with the application but cited to undertand the documentdefining the general state of the art which is not considered principle or theory underlying the invention to be part of particular relevance S earlier docmet pbhed on or er the i n d document of particular relevance; the claimed invention cannot be E erlier document publhed on or after the internaonal fil de coidered novel or cano be coidered to involve an inventive t document which may throw doubts on priority claim(s) or which ia when the document i taken alone cited to establish the publication date of another citation or other special reason (as specified) Y" document of particular relevance; the claimed invention cannot be considered to involve an inventive step when the document i "0 document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combination meam being obvioua to a person akilld in the art document published prior to the international filing date but later than document member of the same paent family the priority date claimed Date of the actual completion of the international search Date of mailing of the international search report 19 NOVEMBER 1993 0 5 JAN 1994 Name and mailing address of the ISA/US Authorized office Commissioner of Patents and Trademarks Box PCr ELLEN MCAVOY Washington, D.C. 20231 Facsimile No. NOT APPLICABLE Telephone No. (703) 308-2510 Form PCT/ISA/210 (second sheet)(July 1992)* I LL