JP3495043B2 - Fuel composition for two-stroke engine - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a small amount of a lubricant composition comprising a large amount of fuel boiling in the gasoline range, an additive formulation containing a molybdenum / sulfur complex of a basic nitrogen compound and a lubricating oil. To a fuel composition for a two-cycle internal combustion engine.

Over the last few decades, spark additions, including rotary engines such as the Wankel engine 2
The use of cycle (2-stroke) internal combustion engines is steadily increasing. They are currently found in powered lawnmowers and other powered gardening equipment, powered chainsaws, pumps, generators, outboard motors for ships, snowmobiles, motorcycles and the like.

The increasing use of two-stroke engines, coupled with the increasingly stringent conditions under which they are driven, has created an increasing need for oils that adequately lubricate such engines. Among the problems associated with the lubrication of two-stroke engines are piston ring adhesion, rust, loss of lubrication of connecting rods and main bearings, and general formation of carbon and varnish deposits on engine internal surfaces. The formation of varnish is a particularly troublesome problem. It is believed that the buildup of varnish on the piston and cylinder walls eventually causes sticking of the ring, which impairs the sealing function of the piston ring. Such seal damage causes a reduction in cylinder squeeze, which leads to its deterioration especially in two-stroke engines. This is because the two-cycle engine depends on the suction force that draws new fuel into the exhausted cylinder. For example, ring deposits can result in degraded engine performance and extra fuel and / or lubricant consumption. Two-cycle engines also suffer from problems with spark plug fouling and engine blockage.

Various compounds have been proposed as additives for fuel-lubricating oil mixtures used in two-stroke internal combustion engines.
For example, Davis U.S. Pat. No. 4,708,809
For a two-cycle engine consisting of a high oil of lubricating viscosity and at least one minor alkylphenol having at least one hydrocarbon-based group having at least 10 aliphatic carbon atoms Lubricant compositions are disclosed. Preferably, such a lubricant composition comprises (i) an organic sulfur acid, a neutral or basic metal salt of a phenol or carboxylic acid, (ii) a hydrocarbyl substituted amine, (iii) at least 10 aliphatic carbon atoms. An additive for a detergent / dispersant selected from the following: an acylated nitrogen-containing compound having a substituent, (iv) a nitrogen-containing condensate of a phenol, an aldehyde and an amino compound, and (v) an ester of a substituted polycarboxylic acid. Contains.

U.S. Pat.No. 4,724,091 by Davis,
Lubricating oil consisting of a large amount of oil and a small amount of a mixture of at least one alkylphenol and at least one aminophenol, each phenol being at least one carbonized of at least about 10 aliphatic carbon atoms. A lubricant composition for a two-cycle engine having a hydrogen group is disclosed. The composition preferably further comprises a detergent / dispersant additive.

Davis et al., U.S. Pat.No. 4,740,321, describes oils of high lubricating viscosity and at least one sulfurized alkylphenol or metal thereof having at least one hydrocarbon-based group of at least 10 aliphatic carbon atoms. A two-cycle engine lubricant composition comprising a small amount of salt is disclosed. This lubricant composition is a cleaning agent
It is preferred to include a dispersant additive.

US Pat. No. 4,705,643 to Nemo describes a hydrolysis reaction product of a lubricating oil and an aliphatic branched carboxylic acid of 16 to 20 carbon atoms and a polyamine having at least 3 amine groups. A two-cycle engine lubricating oil composition is disclosed which comprises an ashless detergent additive. The ashless detergent additive is preferably the hydrolysis reaction product of isostearic acid and tetraethylenepentamine.

U.S. Pat. No. 4,994,196 to Kagaya et al. Discloses a two-cycle engine oil composition comprising a base oil and a calcium phenate detergent additive, the base oil comprising (a) an α-olefin and a dicarboxylic acid. It is a copolymer of an acid ester and (b) a mixture of pentaerythritol and a fatty acid ester.

No. 1 US patent by Silverstein
3,888,776 describes a large amount of polypropylene glycol and a small amount of a sulfurized oxymolybdenum organic phosphorodithioate, finely divided molybdenum disulfide, and a halogenated hydrocarbon detergent such as 1,1,1-trichloroethylene,
A two-cycle engine lubricant composed of orthodichlorobenzene, perchlorinated biphenyl, etc. is disclosed.

Molybdenum / sulfur complexes of basic nitrogen compounds have been previously reported in the art as useful antioxidant additives for lubricant compositions, such as crosshead diesel engine lubricants, automotive and vehicle crankcase lubrication. It has been found to be used as a lubricant, a lubricant for heavy machinery, and a grease for bearings.

For example, US Pat. No. 4,26 by King et al.
No. 3,152 discloses an antioxidant for lubricating oils made by combining an acidic molybdenum compound, a polar promoter, a basic nitrogen-containing compound, and a sulfur source to form a molybdenum-sulfur-containing complex. Has been done. Similar molybdenum-containing antioxidant additives are described in U.S. Pat. No. 4,285,82.
No. 2, No. 4,283,295, No. 4,272,387, No. 4,265,773,
No. 4,261,843, No. 4,259,195, and No. 4,259,194. However, none of those patents teaches or recognizes the use of such antioxidant additives or lubricating oils containing such additives in admixture with fuels for two cycle engines. Absent. Furthermore,
In each of those patents, such an antioxidant additive would be an effective deposit control agent or reduce piston deposition when used in a fuel / lubricant mixture in a two-cycle engine. Is not taught or recognized.

Further, the unique problems and techniques associated with lubricating a two-stroke engine as taught in the aforementioned U.S. Pat. No. 4,708,809 have made those skilled in the art recognize a two-stroke engine lubricant as a unique lubricant type. .

Accordingly, the present invention provides a two-cycle engine varnish build-up and ring by providing an effective additive for a fuel / lubricant combination that eliminates or reduces two-cycle engine varnish deposits and piston ring seal damage. With regard to minimizing sticking problems.

DISCLOSURE OF THE INVENTION The present invention is directed to (A) a large amount of base oil of lubricating viscosity, and (B) a small amount of additive formulation, and (1) a small amount of an additive formulation. ) (I) Succinimide, carboxylic acid amide, hydrocarbyl monoamine, hydrocarbyl polyamine,
Reacting a basic nitrogen compound selected from the group consisting of Mannich base, phosphoramide, thiophosphoramide, phosphonamide, dispersant viscosity index improver, or a mixture thereof with an acidic molybdenum compound in the presence of a polar promoter. Forming a molybdenum complex in which 0.01 to 2 atoms of molybdenum are present per atom of basic nitrogen, said promoter being still present in a ratio of 0.01 to 50 moles of polar promoter per mole of molybdenum, and (ii ) The molybdenum complex and the sulfur-containing compound are added in an amount of about 1.54 to 1 atom per molybdenum.
A molybdenum sulfide-containing composition produced by reacting in an amount sufficient to give 4.0 atoms of sulfur, thereby forming a sulfur-molybdenum-containing composition, (2) a carboxylic acid amide, and (3) succinimide, A fuel composition for a two-cycle engine is provided which comprises an additive composition comprising

Among other factors, the present invention provides that when an additive formulation containing a molybdenum / sulfur complex of a basic nitrogen compound + a carboxylic acid amide and a succinimide is combined with a fuel-lubricating oil mixture for a two-cycle engine, Suppresses deposits,
It is based on the unexpected finding that it is a surprisingly effective drug in reducing piston ring adhesion.

DETAILED DESCRIPTION OF THE INVENTION The fuel composition of the present invention comprises a fuel boiling in a large amount of gasoline, a small amount of a lubricant composition and a base oil of lubricating viscosity,
And a lubricant composition comprising (1) a molybdenum sulfide content composition, (2) a carboxylic acid amide, and (3) an additive formulation containing succinimide.

The molybdenum sulfide-containing composition used in the present invention is generally characterized as a molybdenum / sulfur complex of a basic nitrogen compound. Such molybdenum / sulfur complexes are known in the art and are described, for example, in King et al., US Pat. No. 4,263,152, which is incorporated herein by reference.

The exact molecular formula of the molybdenum composition used in the present invention is certainly unknown. However, they do not consist of molybdenum whose valence is satisfied by oxygen or sulfur atoms, complexed with one or more nitrogen atoms of the basic nitrogen-containing compounds used in the preparation of these compositions or with salts thereof. Are considered to be compounds.

The molybdenum compound used to make the molybdenum / sulfur complex used in the present invention is an acidic molybdenum compound. Acidity means that those molybdenum compounds are
Means reacting with basic nitrogen compounds as measured by ASTM test D-664 or D-2896 titration method.
Typically, these molybdenum compounds are hexavalent,
It is represented by the following compositions: molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other molybdates such as alkali metal molybdates and hydrogen salts, eg sodium hydrogen molybdate, MoOCl ₄ , MoO ₂ Br ₂ , Mo ₂ O ₃ Cl ₆ , 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.

The basic nitrogen compound used to make the molybdenum / sulfur complex must have a basic nitrogen content as measured by ASTM D-664 or D-2896. It is preferably oil soluble. Typical of such compositions are succinimides, carboxamides, hydrocarbyl monoamines, hydrocarbon polyamines,
Mannich bases, phosphoramides, thiophosphoramide, phosphonamides, dispersants viscosity index improvers, and mixtures thereof. These basic nitrogen-containing compounds are described below (taking into account the requirement that each must have at least one basic nitrogen). Any of the nitrogen-containing compositions may be post-treated, for example with boron, using procedures well known in the art, as long as the compositions continue to contain basic nitrogen. These post-treatments can be applied especially to succinimide and Mannich base compositions.

The mono and polysuccinimides that can be used to make the molybdenum / sulfur complexes described herein are described in many references and are well known in the art. Certain basic types of succinimide and related substances encompassed by the term “succinimide” are:
U.S. Pat.Nos. 3,219,666, 3,172,892, and 3,272,
No. 746, the descriptions of which are hereby incorporated by reference. The term "succinimide" is understood in the art to include amides, imides, and many of the amidine materials that can also be formed. However, the predominant product is succinimide, which term is generally accepted as meaning the reaction product of an alkenyl-substituted succinic acid or anhydride with a nitrogen-containing compound. Preferred succinimides for commercial availability are hydrocarbyl succinic anhydrides where the hydrocarbyl group has from about 24 to about 350 carbon atoms, and ethylene, especially characterized by ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. It is a succinimide produced from an amine. Particularly preferred are succinimides prepared from polyisobutenyl succinic anhydrides having 70 to 128 carbon atoms and tetraethylenepentamine or triethylenetetramine or mixtures thereof.

Also included in the term "succinimide" are cooligomers of hydrocarbyl succinic acid or its anhydride with a polysecondary amine having at least one tertiary amino nitrogen in addition to two or more secondary amino groups. included. Usually the composition has an average molecular weight of 1,500 to 50,000. A typical compound is one made by reacting polyisobutenyl succinic anhydride with ethylene dipiperazine.

Carboxamide compositions are also suitable starting materials for making the molybdenum / sulfur complexes used in the present invention. Typical of such compounds are described in US Pat.
No. 405,064 (the description of which is included here for reference). These compositions have at least 12 to about 350 aliphatic carbon atoms in the predominant aliphatic chain and, if desired, sufficient pendant aliphatic groups to render the molecule oil soluble. It is usually prepared by reacting a carboxylic acid having ## STR3 ## or an anhydride thereof or an ester thereof with an amine such as ethyleneamine or a hydrocarbyl polyamine to give a mono- or polycarboxylic acid amide. Preferred is formula (1) R ² COOH
A carboxylic acid of which R ² is C _12-20 alkyl, or a mixture of this acid with a polyisobutenylcarboxylic acid (where the polyisobutenyl group has 72 to 128 carbon atoms),
And (2) ethyleneamine, especially triethylenetetramine or tetraethylenepentamine or mixtures thereof,
It is an amide produced from.

Another class of compounds useful in the present invention are hydrocarbyl monoamines and hydrocarbyl polyamines, preferably of the type described in U.S. Pat.No. 3,574,576, which description is incorporated herein by reference. It is a thing. Hydrocarbyl groups, which are preferably alkyl or olefins having one or more sites of unsaturation, usually have 9 to 350, preferably 20 to 200 carbon atoms. Particularly preferred hydrocarbyl polyamines include, for example, polyisobutenyl chloride and ethylene amines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, 2-aminoethylpiperazine, 1,3-propylenediamine, 1,2-propylenediamine and the like. It is derived by reacting with an alkylene polyamine.

Another class of compounds useful for providing basic nitrogen are Mannich base compositions. These compositions are made from phenol or aldehydes such as C _9-200 alkylphenols, formaldehyde precursors such as formaldehyde or paraformaldehyde, and amine compounds. The amine may be a mono- or polyamine and typical compositions are prepared from alkylamines such as methylamine or ethyleneamines such as diethylenetriamine or tetraethylenepentamine. The phenolic material may be sulfurized, preferably dodecylphenol or C
_80-100 alkylphenol. Typical Mannich bases that can be used in the present invention are described in US Pat.
No. 309, U.S. Pat. Nos. 3,649,229, 3,368,972, and 3,539,663, which descriptions are hereby incorporated by reference. The last cited patent describes an alkylphenol having at least 50, preferably 50-200, carbon atoms and formaldehyde and an alkylene polyamine, HN (ANH) nH, where A is 2
A saturated divalent alkyl hydrocarbon having 6 to 6 carbon atoms, n is 1 to 10, and the condensation product of the alkylene polyamine may be further reacted with urea or thiourea)
Mannich bases prepared by reacting with are disclosed. When these Mannich bases are used as the starting material for the production of lubricating oil additives, they can often be significantly improved by treating the Mannich bases using the conventional technique of incorporating boron into the composition.

Another class of compositions useful in making the molybdenum / sulfur complexes used in the present invention is US Pat. No. 3,909,430.
And phosphonamides such as those disclosed in US Pat. No. 3,968,157, the descriptions of which are incorporated herein by reference. These compositions can be made by forming a phosphorus compound having at least one P—N bond. For example,
They can be prepared by reacting phosphorus oxychloride with a hydrocarbyl diol in the presence of a monoamine or by reacting phosphorus oxychloride with a difunctional secondary amine and a monofunctional amine. Thiophosphoramide is an unsaturated hydrocarbon compound having 2 to 450 or more carbon atoms, for example, polyethylene, polyisobutylene, polypropylene, ethylene, 1-hexene, 1,3-hexadiene, isobutylene, 4-methyl-1. -Pentene, etc., with phosphorus pentasulfide and a nitrogen-containing compound as defined above,
In particular, it can be produced by reacting with alkylamine, alkyldiamine, alkylpolyamine, or alkyleneamine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like.

Another class of nitrogen-containing compositions useful for making the molybdenum complexes used in the present invention includes so-called dispersant viscosity index improvers (VI improvers). These VI modifiers contain additional units derived from hydrocarbon polymers, especially ethylene and / or propylene, and optionally from one or more comonomers such as cycloaliphatic or aliphatic olefins or diolefins. It is generally prepared by functionalizing the polymers it has. Functionalization can be accomplished by a variety of methods that typically introduce reactive site (s) with at least one oxygen atom into the polymer.
The polymer is then contacted with a nitrogen-containing source to introduce nitrogen-containing functional groups into the polymer backbone. Commonly used nitrogen sources include basic nitrogen compounds, especially the nitrogen-containing compounds and compositions described herein. Preferred nitrogen sources are alkylene amines such as ethylene amines, alkyl amines, and Mannich bases.

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

Typical sulfur sources for producing the molybdenum complex used in the present invention include sulfur, hydrogen sulfide, sulfur monochloride, sulfur dichloride, phosphorus pentasulfide, R ₂ Sx (wherein R is hydrocarbyl,
Preferably C _1-40 alkyl, x is at least 2), inorganic sulfides, and polysulfides, such as (N
H ₄ ) ₂ Sx (where x is at least 1), thioacetamide, thiourea, a mercaptan of the formula RSH, where R is as defined above. Conventional sulfur-containing antioxidants such as wax sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic acids and esters, sulfurized ester olefins, and sulfurized alkylphenols and their metal salts are also useful as sulfurizing agents.

Sulfurized fatty acid esters are produced by reacting sulfur, sulfur monochloride and / or sulfur dichloride with unsaturated fatty acid esters at elevated temperatures. Typical esters include palmitoleic acid, oleic acid, ricinoleic acid, petroselinic acid, vaccenic acid, linoleic acid, linolenic acid, oleostearic acid, licanoic acid, paranarin (pa).
Ranaric) acid, Taririn acid, gadoleic acid, arachidonic acid, C ₁ -C-mentioned C ₈ -C ₂₄ unsaturated fatty acids such as cetoleic
Includes ₂₀ alkyl esters. Especially good results are tall oil, linseed oil, olive oil, castor oil, peanut oil,
It is obtained using mixed unsaturated fatty acid esters such as those obtained from animal and vegetable oils such as rapeseed oil, fish oil, sperm whale oil and the like.

Examples of fatty acid esters include lauryl torate (laur
yl tallate), methyl oleate, ethyl oleate,
Included are lauryl oleate, cetyl oleate, cetyl linoleate, lauryl ricinoleate, oleyl linoleate, oleyl stearate, and alkyl glycerides.

C ₁₀ -C ₂₅ fatty acids and C ₁ -C ₂₅ alkyl or fatty esters of alkenyl alcohol (where fatty acids and (or) the alcohol is unsaturated) and, such as sulfide mixture of C ₁₀ -C ₂₅ olefins crosslinking Sulfated ester olefins can also be used.

Sulfurized olefins, low molecular weight polyolefin derived C ₃ -C ₆ olefin or from sulfur are prepared by reaction with sulfur monochloride, and (or) two such sulfur-containing compounds sulfur chloride.

Aromatic sulfides and alkyl sulfides such as dibenzyl sulfide, dixylyl sulfide, dicetyl sulfide, diparaffin wax sulfides and polysulfides, cracked wax / olefin sulfides and the like are also useful. They are starting materials such as olefinically unsaturated compounds, sulfur, sulfur monochloride,
It can be produced by reacting with sulfur dichloride. Particularly preferred are the paraffin wax thiomers described in US Pat. No. 2,346,156.

Sulfurized alkylphenols and their metal salts include compositions such as sulfurized dodecylphenol and its calcium salts. Alkyl groups usually have 9 to 300 carbon atoms. Metal salts are Group I or Group II salts, especially sodium, calcium, magnesium or barium salts.

Preferred sulfur sources are sulfur, hydrogen sulfide, phosphorus pentasulfide, R ₂ Sx
(In the formula, R is hydrocarbyl, preferably C ₁ -C
₁₀ alkyl, x is at least 3), mercaptans (R is C ₁ -C ₁₀ alkyl), inorganic and polysulfides, thioacetamide, and thiourea. The most preferred sulfur sources are sulfur, hydrogen sulfide, phosphorus pentasulfide, and inorganic sulfides and polysulfides.

The polar promoter used in the production of the molybdenum complex used in the present invention promotes the interaction between the acidic molybdenum compound and the basic nitrogen compound. A wide variety of such promoters are well known to those skilled in the art. Typical accelerators are 1,3-propanediol, 1,4-
Butanediol, diethylene glycol, butyl cellosolve, propylene glycol, 1,4-butylene glycol, methyl carbitol, ethanolamine, diethanolamine, N-methyl-diethanolamine, dimethylformamide, N-methylacetamide, dimethylacetamide, methanol, ethylene glycol, Dimethyl sulfoxide, hexamethylphosphoramide, tetrahydrofuran and water. Water and ethylene glycol are preferred. Especially preferred is water.

Usually the polar promoter is added separately to the reaction mixture,
It may be present as a component of the non-anhydrous starting material, especially in the case of water, or as water of hydration in acidic molybdenum compounds such as (NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O. . Water may be added as ammonium hydroxide.

The method for producing the molybdenum / sulfur complex used in the present invention is to prepare a solution of acidic molybdenum precursor and polar solubility promoter with a basic nitrogen-containing compound with or without a diluent. . If desired, a diluent is used to provide the proper viscosity to facilitate stirring. Typical diluents are lubricating oils and liquid compounds containing only carbon and hydrogen. If desired, ammonium hydroxide may be added to the reaction mixture to provide a solution of ammonium molybdate. The reaction is carried out at a temperature from the melting point of the mixture to the reflux temperature. Usually at atmospheric pressure, but higher or lower pressures may be used if desired. The reaction mixture is treated with a sulfur source as defined above at a suitable pressure and temperature at which the sulfur source reacts with the acidic molybdenum compound and the basic nitrogen compound. In some cases, it may be desirable to remove water from the reaction mixture before the reaction with the sulfur source is complete.

The ratio of molybdenum compound to basic nitrogen compound in the reaction mixture is not critical, but as the amount of molybdenum to basic nitrogen increases, the product becomes more difficult. Since the molybdenum component is probably oligomerized, it is advantageous to add as much molybdenum as can be easily maintained in the composition. Usually 0.01 to 2.00 atoms of molybdenum per basic nitrogen atom are introduced into the reaction mixture. Preferably basic nitrogen 1
0.4 to 1.0, most preferably 0.4 to 0.7 molybdenum atoms per atom are added to the reaction mixture. The sulfur source is typically introduced into the reaction mixture in a ratio to provide 1.5 to 4.0 atoms of sulfur per atom of molybdenum. Preferably 2.0 to 4.0 atoms of sulfur are added per atom of molybdenum, most preferably 2.5 to 4.0 atoms of sulfur are added per atom of molybdenum.

The polar promoter, which is preferably water, is usually molybdenum-1.
It is present in a ratio of 0.1 to 50 moles of promoter per mole. Preferably 0.5 to 25 moles and most preferably 1.0 to 15 moles of promoter are present per mole of molybdenum.

As mentioned above, the additive formulation used in the present invention comprises (1) a molybdenum sulfide containing composition (2) a carboxylic acid amide, and (3) succinimide.

The carboxylic acid amide component of the additive formulation currently used can be any of the carboxylic acid amide compounds described herein as useful in the preparation of molybdenum / sulfur complexes. Preferred carboxamide components include those of the formula R ² COOH
A carboxylic acid, wherein R ² is C ₁₂ -C ₂₀ alkyl,
And amides derived from ethyleneamines such as triethylenetetramine or tetraethylenepentamine.

Similarly, the succinimide component of the additive formulation currently used can be any of the succinimide compounds described herein as useful in the preparation of molybdenum / sulfur complexes. Preferred succinimide components include those derived from polyisobutenyl succinic anhydride (wherein the polyisobutenyl group has about 50 to 250 carbon atoms) and ethylene amines such as triethylene tetramine or tetraethylene pentamine. Is included.

The additive formulation used in the present invention may further include an anti-agglomeration agent such as polyisobutene and / or a lubricant. Diluent oil may be included if desired.

Other additives such as viscosity index improvers, antioxidants, dispersants, coupling agents, pour point depressants, extreme pressure additives, color stabilizers, rust inhibitors, corrosion inhibitors, etc. May be present in.

The lubricant composition used in the present invention comprises a large amount of base oil of lubricating viscosity and a small amount of the above additive formulation.

The base oil used may be any of a wide variety of oils of lubricating viscosity. For example, the base oil is a refined paraffinic base oil, a refined naphthenic base oil, or a synthetic hydrocarbon or non-hydrocarbon oil of lubricating viscosity. The base oil may be a mixture of mineral oil and synthetic oil. Mineral lubricating oils are preferred for the purposes of the present invention. Because they are now more commonly used in two-stroke engines.

Currently used lubricant compositions containing the additive formulations described herein can be prepared simply by using conventional techniques to mix the appropriate amount of each component of the additive formulation with the lubricating oil. It can be prepared.

Generally, the amount of molybdenum-containing additive will range from about 0.05 to 15% by weight, preferably about 0.2 to 10% by weight, based on the total lubricant composition including base oil. The carboxylic acid amide component is in the range of about 0.05-20% by weight, preferably about 0.2-15% by weight. The succinimide component is about 0.5-15
%, Preferably in the range of about 0.2-10% by weight.

A two-cycle engine fuel composition of interest according to the present invention comprises a major amount of boiling gasoline fuel and a minor amount of the lubricant composition disclosed herein.

For purposes of the present invention, the lubricant composition is generally added directly to the fuel to form a mixture of lubricant and fuel, which is then introduced into the two-stroke engine cylinder. Generally, the resulting fuel composition is about 15-250 parts per part lubricant.
Parts of fuel, more typically about 1 part per part of lubricant
Contains 50-100 parts fuel. For some two-stroke engines, the lubricant may be injected directly with the fuel into the combustion chamber, or it may be injected into the fuel shortly before it enters the combustion chamber.

The fuel used in the fuel composition of the present invention is a hydrocarbon distillation fuel boiling in the gasoline range. In such gasoline fuels, anti-knock agents such as methylcyclopentadienyl manganese tricarbonyl, tetramethyl or tetraethyl lead, or other fuel additives such as dispersants or detergents such as various substituted amines, etc. It may be contained. It may also contain a lead scavenger such as an aryl halide, eg dicyclobenzene or an alkyl halide, eg ethylene dibromide. In addition, antioxidants, metal deactivators, pour point depressants, corrosion inhibitors, and demulsifiers may be present.

The following examples are provided to illustrate particular embodiments of the invention and are not intended to limit the scope of the invention in any way.

Example 1 In a 5000 ml flask, 114 g of molybdenum trioxide and 19
6g of water was added. Stirring was begun and polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride having a number average molecular weight of about 950 polyisobutenyl groups and tetraethylenepentamine was placed in oil at a concentration of 45%. 1200 g of solution and 1200 g of hydrocarbon thinner were added. The mixture was refluxed at 100 ° C. for 3 hours. The temperature was gradually raised to 170 ° C. over a period of about 1 hour while distilling the water. After the water was removed, the temperature was maintained for another hour. The temperature was reduced to 100-120 ° C, the mixture was passed and returned to the reaction vessel. 51 g of sulfur was added to the solution. The mixture was heated to 160 ° -180 ° C for 7 hours. Pressure gradually about
It decreased to 50 mmHg and removed the hydrocarbon thinner. This resulted in 1244 g of product containing 1.80% nitrogen, 5.63% molybdenum, and 3.57% sulfur.

Example 2 In a 5000 ml flask, 523 g of molybdenum trioxide and 11
1 g of water was added. Stirring was started and 1184 g of a 45% strength solution of the succinimide described in Example 1 in oil and 1184 g of hydrocarbon thinner were added. The mixture was refluxed at 100 ° C. for 3 hours. While distilling water, the temperature is kept for about 1 hour. 17
The temperature was gradually raised to 0 ° C. After the water was removed, the temperature was maintained for another hour. The temperature drops to 100 ° C-120 ° C,
The mixture was passed and returned to the reaction vessel. 47 g of sulfur was added to the solution. The mixture was heated to 160 ° -180 ° C for 7 hours. The pressure was gradually reduced to about 50 mmHg to remove the hydrocarbon thinner. This yielded 1220 g of product containing 1.94% nitrogen, 2.78% molybdenum, and 3.64% sulfur.

Example 3 In a 5000 ml flask, 49 g of molybdenum trioxide and 105
g water was added. Stirring was started and 1133 g of a 45% strength solution of succinimide as described in Example 1 in oil and 1133 g of hydrocarbon thinner were added. The mixture was refluxed at 100 ° C. for 3 hours. While distilling water, the temperature is kept for about 1 hour. 17
The temperature was gradually raised to 0 ° C. After the water was removed, the temperature was maintained for another hour. The temperature drops to 100 ° C-120 ° C,
The mixture was passed and returned to the reaction vessel. 22 g of sulfur was added to the solution. The mixture was heated to 160 ° -180 ° C for 7 hours. The pressure was gradually reduced to about 50 mmHg to remove the hydrocarbon thinner. This resulted in 1163 g of product containing 1.83% nitrogen, 2.79% molybdenum, and 1.97% sulfur.

Example 4 In a 5000 ml flask, 1200 g prepared from C ₁₈ carboxylic acid and tetraethylenepentamine and containing 6.4% nitrogen
Of polyamide, 1200 g of hydrocarbon thinner, 42 g of molybdenum trioxide and 90 g of water. The mixture was refluxed at 100 ° C. for 3 hours. While distilling water, the temperature is kept for about 1 hour. 17
The temperature was gradually raised to 0 ° C. After the water was removed, the temperature was maintained for another hour. The temperature drops to 100 ° C-120 ° C,
The mixture was passed and returned to the reaction vessel. 21 g of sulfur was added to the solution. The mixture was heated to 160 ° -180 ° C for 7 hours. The pressure was gradually reduced to about 50 mmHg to remove the hydrocarbon thinner. This resulted in a product containing 5.88% nitrogen, 2.29% molybdenum, and 1.63% sulfur.

Example 5 Compounding the molybdenum / sulfur complex of Examples 1, 2 and 4,
Carboxamide reaction product of isostearic acid and tetraethylenepentamine 10%, polyisobutenyl group about 95
2% polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride having a number average molecular weight of 0 and tetraethylene pentamine, 2% each of the molybdenum / sulfur complexes of Examples 1, 2 and 4, as a lubricant Polyisobutene having a number average molecular weight of about 950 5%, anti-agglomeration agent 0.5
%, Diluent oil 1%, and base oil about 79.5%. The base oil is 10% 150 bright stock, about 70% 350N and 650N neutral oil mixture, and about 20%.
% Petroleum distillate solvent.

Example 6 Two-Cycle Gasoline Engine Test This test was used to evaluate the cleaning and general performance of fuel compositions of the present invention in a two-cycle water-cooled outboard engine.
Piston varnish, ring deposits, and general engine deposits were evaluated.

The test engine used was the Outboard Marine Company Johnson Mo.
del) No.J70ELEIE outboard engine, which is 70 hp,
It was a water-cooled 3-cylinder 2-cycle engine.

The test method involved a two-hour break-in period in which the engine was run at 3,000 rpm for 1 hour and then at 4,000 rpm for 1 hour using a fuel: lubricant ratio of 50: 1. there were.

A 98 hour test was then conducted using a 55: 1 wide open throttle, 5 minute idling cycle using a 50: 1 fuel: lubricant ratio. The total test time including the rest time was 100 hours.

At the end of the test, the engine was disassembled and evaluated. Three
The average piston grade value and the average second ring attachment grade value for the cylinder were measured. In the grade system used, the higher the grade value, the better the cleaning performance, with 10.0 being the highest grade value. Except for piston rings, these grades are for cleanliness. The piston rings were evaluated for adhesion, with a grade value of 10.0 indicating completely adhered piston rings.

The second ring adhesion value is the National Marin Manufacturers Association (National Marin Manufacturers Association).
e Manufacturers Association (NMMA) grade value, macroscopic observation grade value, and adjustment grade value which is the average value of NMMA and macroscopic observation grade value.

The reference oil used in this test was NMMA reference oil TCW II, which is used as the industry standard in the two-cycle engine test to measure engine cleanliness. TCW II base oil is a standard mineral lubricating oil containing commercial ashless dispersant for gasoline two-stroke engines. The reference oil is
It is available from Citgo Petroleum Corp. of Tulsa, Oklahoma.

Engine test experiments were conducted with a lubricant composition containing the molybdenum / sulfur complex of Examples 1, 2 and 4, formulated as described in Example 5, at a fuel to lubricant ratio of 50: 1. . The results of the engine test are shown in Table 1.

The results shown in Table 1 show that the fuel composition of the present invention is extremely effective in reducing piston deposits and piston ring deposits in two-stroke engines, and generally contains fuels containing industry standard reference oils. Has exceeded the performance of.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C10L 1/30 C10L 1/30 Z C10M 159/12 C10M 159/12 159/18 159/18 163/00 163/00 // ( C10M 159/12 159/12 133: 16 133: 16 133: 56 133: 56 133: 06 133: 06 137: 16 137: 16 159: 16 159: 16 125: 10) 125: 10 (C10M 163/00 C10M 159: 12 159: 12 C10N 10:12 133: 56) 30:04 C10N 10:12 40:26 30:04 60:10 40:26 70:00 60:10 70:00 (58) Fields investigated (Int .Cl. ⁷ , DB name) C10L 1/14 C10L 1/22 C10L 1/24 C10L 1/26 C10L 1/30 C10M 159/12 C10M 159/18 C10M 163/00

Claims (36)

(57) [Claims] 1. A large amount of fuel boiling in the gasoline range, a small amount of a lubricant composition, (A) a large amount of base oil of lubricating viscosity, and (B) a small amount of an additive formulation, (1) ( i) succinimide, carboxylic acid amide, hydrocarbine monoamine, hydrocarbyl polyamine,
Reacting a basic nitrogen compound selected from the group consisting of Mannich base, phosphoramide, thiophosphoramide, phosphonamide, dispersant viscosity index improver, or a mixture thereof with an acidic molybdenum compound in the presence of a polar promoter. Forming a molybdenum complex in which 0.01 to 2 atoms of molybdenum are present per atom of basic nitrogen, said promoter being still present in a ratio of 0.01 to 50 moles of polar promoter per mole of molybdenum, and (ii ) Sulfurization prepared by 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, thereby forming a sulfur-molybdenum-containing composition. A lubricant composition comprising a molybdenum-containing composition, (2) a carboxylic acid amide, and (3) succinimide. For 2-cycle engine fuel composition comprising a composition. 2. The sulfur source for component (1) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R ₂ Sx (wherein R is hydrocarbyl and x is at least 2), an inorganic sulfide, 2. The fuel composition according to claim 1, which is also an inorganic polysulfide, thioacetamide, thiourea, a mercaptan of formula RSH, where R is hydrocarbyl, or a sulfur-containing antioxidant. 3. The sulfur source for component (1) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R ₂ Sx, where R is C _1-4 hydrocarbyl and x is at least 3. Inorganic sulfide or inorganic polysulfide, thioacetamide, thiourea, or RS
H (wherein R is C _1-40 alkyl) and the acidic molybdenum compound is molybdic acid, ammonium molybdate, or an alkali metal molybdate.
The fuel composition according to. 4. A sulfur source is sulfur, hydrogen sulfide, RSH (in the formula,
R is C _1-10 alkyl), phosphorus pentasulfide, or (NH ₄ ) ₂ S
xc (where xc is at least 1), the acidic molybdenum compound is molybdic acid, ammonium molybdate, and the basic nitrogen compound is succinimide, carboxylic acid amide, or Mannich base. The fuel composition according to. 5. The fuel composition according to claim 4, wherein the basic nitrogen compound is C _24-350 hydrocarbyl succinimide, a carboxylic acid amide, or a Mannich base prepared from a C _9-200 alkylphenol, formaldehyde, and an amine. object. 6. The fuel composition according to claim 5, wherein the basic nitrogen compound is polyisobutenyl succinimide produced from polyisobutenyl succinic anhydride and tetraethylene pentamine or triethylene tetramine. 7. A basic nitrogen compound having one or more kinds of formula R ²
A carboxylic acid of COOH (R ² is C _12-350 alkyl or C _12-350 alkenyl), or a derivative thereof which, upon reaction with an amine, yields a carboxylic acid amide, and a carboxylic acid amide prepared from hydrocarbyl polyamines, The fuel composition according to claim 5. 8. R ⁷ is C _12-20 alkyl or C _12-20 alkenyl and the hydrocarbyl polyamine is tetraethylene pentamine or triethylene tetramine.
The fuel composition according to. 9. The fuel composition according to claim 5, wherein the basic nitrogen compound is a Mannich base produced from dodecylphenol, formaldehyde, and methylamine. 10. The fuel composition according to claim 5, wherein the basic nitrogen compound is a Mannich base made from C _80-100 alkylphenol, formaldehyde and triethylenetetramine, tetraethylenepentamine, or a mixture thereof. . 11. The fuel composition according to claim 1, wherein the polar promoter is water. 12. The carboxylic acid amide of component (2) has the formula R ²
The fuel composition according to claim 1, which is derived from a carboxylic acid of COOH (wherein R ² is C _12-20 alkyl) and ethyleneamine. 13. The succinimide of component (3) is derived from ethylene oxide and polyisobutenyl succinic anhydride in which the polyisobutenyl group has about 50 to 250 carbon atoms. The composition as described. 14. A lubricant composition comprising about 0.05 to 15% by weight of a molybdenum-containing composition of component (1), about 0.05 to 20% by weight of a carboxylic acid amide of component (2), and about succinimide of component (3). The fuel composition according to claim 1, comprising 0.05 to 15% by weight. 15. The fuel composition according to claim 1, wherein the molybdenum complex is reacted with a sulfur-containing compound in an amount sufficient to provide about 2.0 to 4.0 atoms of sulfur per atom of molybdenum. 16. The fuel composition according to claim 15, wherein the molybdenum complex is reacted with a sulfur-containing compound in an amount sufficient to provide about 2.5 to 4.0 atoms of sulfur per atom of molybdenum. 17. The additive formulation further comprises a coagulation inhibitor.
The fuel composition according to claim 1. 18. The fuel composition according to claim 17, wherein the additive formulation further comprises a lubricant. 19. Fuel boiling in a large amount of gasoline,
(1) (i) with a small amount of lubricant composition, (A) a large amount of base oil of lubricating viscosity, and (B) a small amount of additive formulation effective to reduce engine deposits and piston ring deposits. ) Succinimide, carboxylic acid amide, hydrocarbyl monoamine, hydrocarbyl polyamine,
Reacting a basic nitrogen compound selected from the group consisting of Mannich base, phosphoramide, thiophosphoramide, phosphonamide, dispersant viscosity index improver, or a mixture thereof with an acidic molybdenum compound in the presence of a polar promoter. Forming a molybdenum complex in which 0.01 to 2 atoms of molybdenum are present per atom of basic nitrogen, said promoter being still present in a ratio of 0.01 to 50 moles of polar promoter per mole of molybdenum, and (ii ) Sulfurization prepared by 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, thereby forming a sulfur-molybdenum-containing composition. A lubricant composition comprising a molybdenum-containing composition, (2) a carboxylic acid amide, and (3) succinimide. It consists of operating the two-cycle engine with a fuel composition comprising a composition, engine deposits of a two-stroke engine and a method of reducing piston ring attachment. 20. The sulfur source for component (1) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R ₂ Sx (wherein R is hydrocarbyl and x is at least 2), an inorganic sulfide, Or inorganic polysulfide, thioacetamide, thiourea, formula RSH
A mercaptan of the formula where R is hydrocarbyl,
20. The method according to claim 19, which is a sulfur-containing antioxidant. 21. The sulfur source for component (1) is sulfur, hydrogen sulfide, phosphorus pentasulfide, R ₂ Sx, wherein R is C _1-4 hydrocarbyl and x is at least 3. Inorganic sulfide, or inorganic polysulfide, thioacetamide, thiourea, or
RSH (wherein R is C _1-40 alkyl) and the acidic molybdenum compound is molybdic acid, ammonium molybdate, or an alkali metal molybdate.
The method described in 20. 22. The sulfur source is sulfur, hydrogen sulfide, RSH (wherein R is C _1-10 alkyl), phosphorus pentasulfide, or (N
H ₄ ) ₂ Sxc, where xc is at least 1;
22. The method of claim 21, wherein the acidic molybdenum compound is molybdic acid, ammonium molybdate, and the basic nitrogen compound is succinimide, carboxylic acid amide, or Mannich base. 23. The basic nitrogen compound is C _24-350 hydrocarbyl succinimide, carboxylic acid amide, or C _9-200.
23. The method of claim 22, which is a Mannich base prepared from an alkylphenol, formaldehyde, and an amine. 24. The method of claim 23, wherein the basic nitrogen compound is polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride and tetraethylene pentamine or triethylene tetramine. 25. The basic nitrogen compound is one or more kinds of compounds represented by the formula:
A carboxylic acid of R ² COOH (where R ² is C _12-350 alkyl or C _12-350 alkenyl), or a derivative thereof which upon reaction with an amine yields a carboxylic acid amide, and a carboxylic acid amide prepared from a hydrocarbyl polyamine Yes, claim 23
The method described in. 26. The R ² is C _12-20 alkyl or C _12-20 alkenyl and the hydrocarbyl polyamine is tetraethylene pentamine or triethylene tetramine.
The method described in 25. 27. The method of claim 23, wherein the basic nitrogen compound is a Mannich base prepared from dodecylphenol, formaldehyde, and methylamine. 28. The method of claim 23, wherein the basic nitrogen compound is a Mannich base made from C _80-100 alkylphenol, formaldehyde and triethylenetetramine, tetraethylenepentamine, or a mixture thereof. 29. The method of claim 19, wherein the polar promoter is water. 30. The carboxylic acid amide of component (2) has the formula R ²
COOH (wherein, R ² is C _12-20 alkyl) and carboxylic acids, derived from ethylene amine The method of claim 19. 31. The method according to claim 19, wherein the succinimide of component (3) is derived from polyisobutenyl succinic anhydride having a polyisobutenyl group having about 50 to 250 carbon atoms and ethyleneamine. . 32. The lubricant composition comprises about 0.05 to 15% by weight of a molybdenum-containing composition of component (1), about 0.05 to 20% by weight of a carboxylic acid amide of component (2), and about succinimide of component (3). 20. The method of claim 19, comprising 0.05 to 15% by weight. 33. The method of claim 19, wherein the molybdenum complex is reacted with a sulfur-containing compound in an amount sufficient to provide about 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 a sulfur-containing compound in an amount sufficient to provide about 2.5 to 4.0 atoms of sulfur per atom of molybdenum. 35. The additive formulation further comprises an anti-agglomeration agent,
20. The method of claim 19. 36. The method of claim 35, wherein the additive formulation further comprises a lubricant.