JP2001294884A - Lubricant composition for air-cooled two stroke cycle engine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cleaner capable of improving cleaning properties when used as a lubricating oil composition for an air-cooled two stroke cycle engine. SOLUTION: This cleaner is suitable for the lubricating oil composition used in the air-cooled two stroke cycle engine and has a Mannich cleaner and an ashless dispersant in (3:1) to (5:1) ratio of the Mannich cleaner to the ashless dispersant. At least one of the following compounds may be contained in the detergent: a molybdenum compound, a perbasic alkyloxybenzenesulfonate and an alkyl salicylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to detergents useful in lubricating oil compositions suitable for use in two-stroke cycle engines, and to lubricating oil compositions containing the detergents of the present invention. According to another aspect, the present invention relates to a method for improving the cleanliness of a two-stroke cycle engine by lubricating the engine with the lubricating oil composition of the present invention. According to yet another aspect, the present invention relates to a concentrate of a detergent. The detergent of the present invention exhibits excellent cleaning properties.

[0002]

BACKGROUND OF THE INVENTION Over the past several decades, the use of spark ignited two-stroke internal combustion engines has steadily increased. At present, two-stroke internal combustion engines are found in electric lawn mowers and other electrically operated garden tools, electric chainsaws, pumps, power generators, marine outboard engines, snowmobiles, motorcycles, and the like.

[0003] Due to the unique problems and techniques associated with lubricating two-stroke cycle engines, two-stroke cycle engine lubricants are regarded by those skilled in the art as a completely different type of lubricant. For example, U.S. Pat. Nos. 3,085,975, 3,004837 and 37.
Reference is made to each of the specifications of No. 53905.

[0004] US Pat. No. 4,025,316, issued May 24, 1977 (Stover), discloses high molecular weight alkylhydroxybenzyl N-substituted amines having a high degree of ring formation with C ₈ -C ₄₀ aliphatic. From the condensation reaction of the alkyl-substituted hydroxyaromatic, aldehyde and amine, the molar ratio of the aromatic to the amine is about 2: 1 and the aldehyde is present in an excess molar amount to the aromatic. It is disclosed. These novel amines can be used as detergents for liquid hydrocarbons, for example lubricating oils for gasoline engines having two-stroke cycles, and / or
Or it is useful as an antioxidant.

[0005] US Patent No. 4 issued May 9, 1978
No. 088586 (Willgas et al.) Discloses that tetrapropenylphenol, formaldehyde and diethylenetriamine can be used in a molar ratio of reactants of 1 mole of tetrapropenylphenol, 0.5 to 0.85 mole of formaldehyde, and at least 0.3 mole of formaldehyde. Novel Mannich bases prepared by condensation with moles of diethylenetriamine, and their calcium salts, are disclosed to be useful as dispersants for lubricating oils, and particularly suitable for use in marine cylinder lubricating oils. .

[0006] US Patent No. 4 issued April 29, 1980
US Pat. No. 200555 (Clayson et al.) Discloses aminophenols wherein the phenol comprises a substantially saturated hydrocarbon substituent having at least 10 aliphatic carbon atoms;
(I) neutral or basic metal salts of organic sulfonic acids, phenols or carboxylic acids; (II) hydrocarbon-substituted amines wherein the hydrocarbon substituent is substantially aliphatic and contains at least 12 carbon atoms; (III) a nitrogen-containing acylated compound having a substituent of at least 10 aliphatic carbon atoms;
And (IV) a combination with one or more detergent dispersants selected from the group consisting of nitrogen-containing condensates of phenols, aldehydes and amino compounds. Lubricants, including fuels and such combinations, are particularly useful for two-stroke (two-stroke) engines.

US Pat. No. 46, issued May 5, 1987
63063 (Davis) discloses a functional fluid for a two-stroke engine having a base oil and a combination of an alkylated phenol and a polyalkylene polyamine. The patent discloses that metal thiocarbamates are useful as extreme pressure agents.

[0008] US Patent No. 4, issued April 26, 1988
740321 (Davis, et al.) Discloses lubricating oils useful in two-stroke engines. These lubricating oils have the general formula: (R) _a- Ar- (OH) _b , where R is a substantially saturated hydrocarbon-based group having an average of at least 10 aliphatic carbon atoms. A and b are each independently an integer from 1 to 3 times the number of aromatic nuclei present in Ar, provided that the sum of a and b does not exceed the unsatisfactory valency of Ar; Ar is a sulfur-containing moiety whose cross-linking is a substituted group of lower alkyl, lower alkoxyl, methylol or lower hydrocarbon-based substituted methylol, halo and any combination of two or more of these optional substituents. Have ~ 3
At least one phenolic compound having a bonding polynuclear moiety) or a salt thereof.

[0009] International Patent Application No. WO 91/13950 published September 19, 1991 (excluding Seita) discloses a lubricating oil used in a two-stroke engine that sometimes causes clogging (gelling) of a fuel filter. ing. Gelation is particularly pronounced when compositions containing alkali metals or alkaline earth metals in lubricating oils or fuels are present. The present invention addresses this particular problem by injecting hydrocarbon-soluble or dispersible polycarboxylic acids into fuel and oil mixtures.

[0010] International Patent Application No. WO 92/21736 (Chamberlin) issued December 10, 1992
Discloses a two-stroke cycle engine lubricant composition comprising: at least one oil of lubricating viscosity at 40 ° C. that is equal to or greater than 100 cSt and has at least one oil of lubricating viscosity. Amount of (A) at least one phenol selected from the reaction product of (A-1) aminophenol and (A-2) nitrophenol with an amino compound, and (B) at least one ashless dispersant. A sufficient amount of the mixture to reduce or prevent piston scuffing. The composition may also contain up to about 10% by weight of (C) at least one polyalkene having a number average molecular weight of about 500 to about 2500. This reference also includes fuel-lubricant mixtures, as lubricant compositions for two-stroke engines are often mixed with fuel before or during combustion. The composition acts to suppress piston scuffing while also contributing to piston lubrication, sediment control, ring sticking protection, reduced exhaust port blockage and reduced visible smoke emissions.

US Pat. No. 5, issued Jan. 25, 1994
No. 281,346 (Adams, et al.) Discloses a two-stroke cycle engine lubricant comprising a major amount of at least one oil of lubricating viscosity and a minor amount of at least one metal carboxylate.

US Pat. No. 5, issued May 14, 1996
No. 516444 (Gains, et al.) Discloses a base oil,
Having a nitrogen-containing acylated compound having an oil-soluble olefin substituent, and at least one detergent dispersant;
A functional fluid for a two-stroke engine is disclosed. The patent discloses that molybdenum and molybdenum / sulfur containing compounds are more or less useful antiwear and lubricant agents in the invention.

US Pat. No. 5,688,751, issued Nov. 18, 1997 (Cleveland, et al.) Discloses an alkali metal salt of salicylic acid as a lubricant for two-stroke engines.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a detergent particularly useful for a lubricating oil composition used in an air-cooled two-stroke cycle engine.

[0015]

SUMMARY OF THE INVENTION In its broadest aspect, the present invention provides a detergent comprising a Mannich detergent and an ashless dispersant, wherein the ratio of the Mannich detergent to the ashless dispersant is from 3: 1 to 5: 1. About. In a further aspect, the detergent may also include at least one of the following compounds:
Molybdenum compounds, overbased alkyloxybenzene sulfonates, and alkyl salicylates.

In another aspect, the present invention relates to a lubricating oil composition comprising a major amount of at least one lubricating viscosity base oil and an effective minor amount of the detergent of the present invention. Optionally, the lubricating oil composition may further comprise at least a solvent and / or polyisobutylene.

The lubricating oil composition can be prepared by blending a major amount of a base oil of lubricating viscosity, an effective minor amount of a detergent, and optionally a minor amount of other additives, such as a solvent or polyisobutene. . To improve the cleanliness of an air-cooled two-stroke cycle engine by supplying the lubricating oil composition to the engine crankcase and operating the engine, or by supplying fuel to operate the engine, the lubricant composition Things can be used.

The present invention also provides an additive concentrate suitable for mixing with a base oil to provide a lubricating oil that may be used to lubricate an air-cooled two-stroke cycle engine. There is also. This additive concentrate has 5.0
It has １５15% by weight of organic diluent and 85-95% by weight of the inventive detergent.

Among other things, the present invention provides a low ash detergent exhibiting excellent cleanliness, including dispersibility and lubricity, in a lubricating oil composition for an air-cooled two-stroke cycle engine. Lubricating oil compositions containing the detergents of the present invention keep air-cooled two-stroke cycle engines clean by preventing ring sticking, piston deposits, plug fouling, and exhaust deposits. Other advantages include wear and corrosion protection.

[0020]

DETAILED DESCRIPTION OF THE INVENTION In its broadest aspect, the present invention encompasses detergents that exhibit excellent cleaning properties when used in lubricating oil compositions for air-cooled two-stroke cycle engines. The detergent comprises a Mannich detergent and an ashless dispersant, the ratio of the Mannich detergent to the ashless dispersant being 3: 1 to 5: 1. The detergent may further include at least one of the following compounds: molybdenum compounds, overbased alkyloxybenzene sulfonates, and alkyl salicylates. Before describing the present invention in further detail, the following terms are defined.

[Definition] As used herein, the following terms have the following meanings unless otherwise indicated. "Alkylphenol" means a phenol group having one or more alkyl substituents, at least one of the alkyl substituents having a sufficient number of carbon atoms to confer oil solubility to the phenol.

"Alkaline earth metal" means calcium, barium, magnesium, and strontium. "Alkaline earth alkyl salicylate" means an alkaline earth salt of alkyl salicylic acid. "Internal olefin" means an olefin in which the double bond is at the 4- and higher positions instead of the 1, 2, or 3 positions of the alkene.

It is understood in the art that "succinimide" also includes those formed by the reaction of succinic anhydride with an amine, such as a number of amides and imides. However, the main product is succinimide, which term is generally considered to mean the product of the reaction of an alkenyl or alkyl substituted succinic acid or anhydride with a polyamine. Alkenyl or alkyl succinimides have been disclosed in numerous documents and are well known in the art. For certain basic types of succinimides and related substances included in the terminology "succinimide", see US Pat. Nos. 2,929,708 and 3,018,291.
No. 3024237, No. 3100673, No. 32
No. 19666, No. 3172892 and No. 327274
No. 6, the disclosures of which are referred to. "Polysuccinimide" means a compound formed by reacting an unsaturated acidic reagent copolymer and an alkenyl or alkyl succinic acid derivative with an amine.

"Polyamine" means a polyamine containing from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms, including acyclic and cyclic polyamines, and wherein the substitution is based on the composition of the present invention. May be substituted with various substituents as long as it has no serious adverse effect on the characteristics of suppressing deposits and fuel compatibility. "Polyalkylenepolyamine" naturally contains at least two amino groups.

"Total base number" or "TBN" refers to sample 1
It means the amount of base equivalent to milligrams of KOH in grams. Thus, a high TBN number reflects the stronger alkalinity of the product and therefore the greater alkalinity possessed. The TBN of a sample can be determined by ASTM Test No. D664, or any other similar method. Unless otherwise stated, all percentages are weight percentages and all molecular weights are number average molecular weight.

[Detergent] The detergent of the present invention comprises a Mannich detergent and an ashless dispersant, and the ratio of the Mannich detergent to the ashless dispersant is 3: 1 to 5: 1. The detergent may further include at least one of the following compounds: molybdenum compounds, overbased alkyloxybenzene sulfonates, and alkyl salicylates.

[Mannich Detergent] The Mannich base of the present invention can be synthesized from phenol or a C _{9 to} C ₂₀₀ alkylphenol, an aldehyde such as formaldehyde or a formaldehyde precursor such as paraformaldehyde, and an amine compound. The amine may be a mono- or polyamine, and typical compositions are synthesized from alkylamines, such as methylamine, or ethyleneamines such as diethylenetriamine and tetraethylenepentamine. Phenol material may be sulfurized and preferably alkylphenol dodecylphenol or C ₈ -C _100. A representative Mannich base that can be used in the present invention is U.S. Pat.
No. 972, No. 3539663, No. 3649229,
Nos. 4,088,586, 4,157,308 and 4,157
No. 309, No. 4,178,759 and No. 4,219,430, and the contents of those disclosures can be referred to.

For example, US Pat. No. 4,088,586 discloses that tetrapropenylphenol, formaldehyde and diethylenetriamine are used in a reaction in a molar ratio of 1 to 1.
Moles of tetrapropenylphenol, vs. 0.5-0.8
Synthesis of Mannich bases by condensation with 5 moles of formaldehyde versus at least 0.3 moles of diethylenetriamine, and that the alkaline earth metal salts of Mannich bases of this invention are particularly useful as lubricating oil additives. It has been disclosed. Preferred alkaline earth metal salts are calcium and magnesium.

The alkaline earth metal salt of Mannich base is
Using conventional methods, for example, Mannich bases can be promoted using an alkaline earth metal hydroxide such as calcium hydroxide or magnesium methoxide, with an accelerator such as water, ethylene glycol, 1,3-propanediol, 1,4- It is synthesized by treating in the presence of butanediol, diethylene glycol, butyl cellosolve, propylene glycol, 1,3-butylene glycol, methyl carbitol, diethanolamine, N-methyldiethanolamine, dimethylformamide, N-methylacetamide, or dimethylacetamide. You. Preferred accelerators are water, ethylene glycol and dimethylacetamide. Most preferred is ethylene glycol. The reaction is performed at 100 ° C-175 ° C. After the reaction is completed, the product is stripped at high temperature, such as 175 ° -202 ° C., and reduced pressure, such as 20 mmHg, to remove unreacted low molecular weight polyamines such as ethylenediamine and diethylenetriamine and other volatile components.

The Mannich base and its alkaline earth metal salts according to the invention give high alkalinity values. Alkaline earth metal salts provide particularly high alkalinity values at lower ash contents than those present in acid neutralizers used in conventional dispersants and lubricating oil additives.

As the detergent, 5.0 to 3 Mannich detergents are used.
0% by weight, preferably 15 to 23% by weight, and most preferably 21 to 23% by weight.

[Ashless dispersant] The ashless dispersant according to the present invention is a polyalkylene succinimide. Polyalkylene succinimides are disclosed in a number of documents and are known in the art. For some basic types of succinimides and related substances included in the terminology "succinimide", see US Pat.
No. 72892 and No. 3272746, and the disclosures thereof can be referred to. "Succinimide" is understood in the art to also include a number of amides, imides, and possible amidines. However, the main product is succinimide, which term is generally considered to mean the product of the reaction of an alkenyl or alkyl substituted succinic acid or anhydride with a nitrogen-containing compound such as a polyalkylene polyamine. . Representative polyalkylene polyamines are
For example, ethylenediamine, diethylenetriamine, triethylenetetraamine, and tetraethylenepentamine.

The polyalkylene succinimide of the present invention can be prepared by a conventional method, for example, as described in US Pat.
No. 018250, No. 3018291, No. 302423
No. 7, No. 3100673, No. 3172892, No. 3
No. 219666, No. 3272746, No. 336167
No. 3, No. 3380222, No. 3912764, No. 4
No. 234435, No. 4612132, No. 474796
No. 5, No. 5112507, No. 524003, No. 5
No. 266186, No. 5286799, No. 531903
No. 5,533,321, No. 5,356,552 and No. 5,716,912, and can be synthesized by reference to any and all purposes disclosed for all purposes. Can be.

The polyalkylene succinimide additive is an ashless dispersant, comprising an average of 4 to 10 nitrogen atoms (preferably 5 to 7 nitrogen atoms) per mole of high molecular weight alkenyl or alkyl substituted succinic anhydride. ) Can be synthesized by reaction with a polyalkylene polyamine having The polyalkylene of the polyalkylene succinimide additive is derived from polyalkylenes having a molecular weight of at least 1000. Preferably, the polyalkylene succinimide has a molecular weight of 1000-2700, more preferably 1900-2700, and most preferably 200
It is a polybutene succinimide derived from 0 to 2400 polybutenes. A particularly preferred polyalkylene succinimide additive is derived from a polyalkylene having a molecular weight of 1300.

The polyalkylene succinic acid additive can be obtained by reacting a mixture of a polybutene succinic acid derivative, a copolymer of an unsaturated acidic reagent and an unsaturated acidic reagent of an olefin, and a polyamine under the reaction conditions described in US Pat. No. 5,716,912. Synthesized by reacting as taught.

The detergent may contain from 50 to 90%, preferably from 73 to 81%, and most preferably from 75 to 79% by weight of the ashless dispersant.

Various other ashless cleaning and dispersing agents can also be used in the present invention. The ashless detergent dispersant is preferably oil-soluble. Representative of such compositions include carboxylic amides, hydrocarbon monoamines, hydrocarbon polyamines, ashless Mannich bases, succinates,
There are phosphoric amides, phosphonic amides, dispersant type viscosity index improvers, and mixtures thereof. These basic nitrogen-containing compounds are described below. As long as the composition continues to contain basic nitrogen, any nitrogen-containing composition
Post-treatment can be carried out using means known in the art. Post-treatment is achieved by contacting the basic nitrogen-containing compound with the post-treatment compound (s) simultaneously or in any order. Suitable post-treatment compounds include urea, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, nitrile, epoxide, boron compound, organic phosphorus compound, inorganic phosphorus compound (for example, H ₃ PO ₃ , H ₃ PO _4, etc.), and mixtures thereof. These post-treatments are particularly applicable to succinimide and Mannich base compositions.

[Molybdenum Compound] Suitable molybdenum compounds usable in the present invention include, for example, molybdenum dithiophosphate (MoDTP) and molybdenum dithiocarbamate (MoDTC).
This MoDTP can include molybdenum dialkyl (or diaryl) dithiophosphates such as molybdenum diisopropyl dithiophosphate, molybdenum di- (2-ethylhexyl) dithiophosphate, and molybdenum di (nonylphenyl) dithiophosphate. MoDTC may include molybdenum dibutyldithiocarbamate, molybdenum dialkyldithiocarbamate such as molybdenum di- (2-ethylhexyl) dithiocarbamate, and molybdenum dilauryl dithiocarbamate. Other molybdenum compounds include molybdenum oxydisulfide and molybdenum 855 (trade name, sulfur-free and phosphorus-free molybdenum compound sold by RT Vanderbilt). A particularly preferred molybdenum compound is molybdenum oxydisulfide.

The amount of sulfur-containing molybdenum compounds (eg, molybdenum dithiophosphate, molybdenum dithiocarbamate, molybdenum oxydisulfide) should be kept low so that the lubricating oil composition has less than 0.2% sulfur. .

The detergent is prepared by adding a molybdenum compound to a detergent
It can contain 10% by weight, preferably 2.0-6.0% by weight, and most preferably 3.0-5.0% by weight.

[Overbased alkyloxybenzene sulfonate] The lubricating oil has a TBN of at least 200, preferably 250, and at least 40% by weight of the alkyl groups of the sulfonate are bonded at the 4-position or higher of the alkyl groups. Has a small amount of overbased alkyloxybenzene sulfonate. Oxy groups are hydroxy, methoxy,
It may be propoxy, butoxy, pentoxy, or hexoxy. Preferably it is hydroxy.

The alkyl groups of the overbased alkyloxybenzene sulfonates preferably have from 18 to 30 carbon atoms per alkyl group. More preferably,
Alkyl groups have from 20 to 24 carbon atoms per alkyl group.

The additive according to the present invention is obtained by alkylating oxybenzene with an olefin containing from 40% by weight to 80% by weight of an internal olefin, thereby producing an alkyloxybenzene, and sulfonating the alkyloxybenzene to form an alkyloxybenzene. It can be produced by forming benzene sulfonic acid and overbasing the alkyloxybenzene sulfonic acid to form an overbased alkyloxybenzene sulfonate. Olefins containing from 40% to 80% by weight of internal olefins are:
Alpha olefins can be produced by isomerization using iron pentacarbonyl catalyst.

The methods of alkylating alkyloxybenzene with an olefin to produce alkyloxybenzene and the method of sulfonating alkyloxybenzene to produce alkyloxybenzene sulfonic acid are both described in US Pat.
No. 64 is described in detail, and the disclosure thereof can be referred to for any purpose. Our alkylation and sulfonation methods differ only in the olefin used and the reaction time. Our batch alkylation reaction requires only about 6-8 hours. A preferred sulfonation method is a 1.1: 1 charge mole ratio of sulfur trioxide to alkylphenol, and 70 ° C.
This is a falling film method using a reaction temperature in the range of 100 ° C., whereupon neutralization is performed immediately.

The neutralized slurry of alkyloxybenzene sulfonic acid is added to a slurry of xylene, methanol and calcium hydroxide. The resulting slurry is then carbonated while a second slurry of alkyloxybenzene sulfonic acid and a second slurry of xylene, methanol and calcium hydroxide are added. After carbonation, the material is stripped to remove methanol and water. Next, lubricating oil is added to remove solids. The remainder of the solvent is then stripped off and additional lubricating oil is added to adjust the product to a final base number.

The detergent comprises 1.0 to 10% by weight of an overbased alkyloxybenzene sulfonate, preferably 2.
0-5.0% by weight, and most preferably 3.0-4.
0% by weight can be contained.

[Alkyl salicylate] The detergent of the present invention may further contain an alkyl salicylate.
Alkyl salicylates are known to provide improved performance (cleanability, water resistance, thermal stability, antioxidant properties) to lubricating oil compositions used for lubricating internal combustion engines. It falls into the category of agents. This class of detergents is known in the art and is described, for example, in U.S. Patent Nos. 2,197,832, 5,808,145, and 543.
Nos. 4293 and 5,415,792, all of which are incorporated by reference.

Both sulfurized and non-sulfurized alkaline earth alkyl salicylates are well known. Such alkyl salicylates are usually double aromatic ring alkyl salicylates, but single aromatic ring alkyl salicylates are also known. Preferably, the non-sulfurized alkaline earth alkyl salicylate is a calcium alkyl salicylate.

A) Preferred Method for Preparing Non-Sulfurized Alkaline Earth Alkyl Salicylates One of the preferred methods for preparing non-sulfurized alkaline earth alkyl salicylates involves much more alkyl phenol and alkali than those produced by other routes. It can be said that it is characterized by its unique composition using an earth single aromatic ring alkyl salicylate. The reaction product has the following composition:
(A) 40-60% by weight alkylphenol, (b)
10-40% by weight alkaline earth alkyl phenate,
And (c) 20 to 40% by weight of an alkaline earth single aromatic ring alkyl salicylate.

Unlike other processes for preparing alkaline earth alkyl salicylates, this reaction product is characterized in that it contains only a small amount of alkaline earth double aromatic ring alkyl salicylate. The molar ratio between the single aromatic ring alkyl salicylate and the double aromatic ring alkyl salicylate is at least 8: 1.

B) Neutralization Step In the first step, the alkylphenol is neutralized with an alkaline earth base in the presence of at least one C ₁ -C ₄ carboxylic acid. This reaction is carried out in the absence of an alkali base and in the absence of a dialcohol or monoalcohol.

The alkylphenol is a linear alkylphenol of up to 85% by weight (preferably at least 35%).
% By weight of a linear alkyl phenol)
It is contained as a mixture with a weight% of branched alkylphenol. Preferably, the straight chain alkyl group contains 12 to 40 carbon atoms, more preferably 18 to 30 carbon atoms.
Contains carbon atoms. At least 9 branched alkyl groups
Carbon atoms, preferably 9 to 24 carbon atoms, more preferably 10 to 15 carbon atoms.

The use of alkylphenols containing at least 35% by weight of long straight-chain alkylphenols (18-30 carbon atoms) is particularly preferred. Long linear alkyl chains promote the compatibility and solubility of the additives in the lubricating oil. However, the presence of relatively heavy linear alkyl groups in the alkylphenols makes the latter linear alkylphenols less reactive than the branched chain alkylphenols, and requires harsh reaction conditions to cause neutralization with alkaline earth bases. Must be used.

[0054] Branched alkyl phenols can be obtained by reacting phenol with a branched olefin, generally an olefin derived from propylene.
Branched alkylphenols consist of a mixture of monosubstituted isomers, with most of the substituents being in the para position, very slightly in the ortho position, and few in the meta position. That makes the branched-chain alkylphenol relatively responsive to alkaline earth bases, since the phenol function is actually devoid of steric hindrance.

On the other hand, linear alkylphenols can be obtained by reacting phenol with linear olefins, generally olefins derived from ethylene.
Linear alkyl phenols consist of a mixture of monosubstituted isomers, with a more uniform distribution of the ortho, meta and para linear alkyl substituents. This means that linear alkyl phenols are much more reactive to alkaline earth bases since the phenol function is only slightly accessible due to the presence of close overall weight alkyl substituents due to considerable steric hindrance. Hard to do.

Alkaline earth bases which can be used to carry out this step include oxides or hydroxides of calcium, magnesium, barium or strontium, especially calcium oxide, calcium hydroxide, oxide Magnesium, and mixtures thereof. In some embodiments, slaked lime (calcium hydroxide) is preferred.

Examples of the C ₁ -C ₄ carboxylic acid used in this step include formic acid, acetic acid, propionic acid and butyric acid, and they can be used alone or in a mixture. It is preferred to use a mixture of acids, most preferred is a formic / acetic acid mixture. The molar ratio of the formic / acetic acid mixture should be between 0.2: 1 and 100: 1, preferably between 0.5: 1 and 4: 1, and most preferably between 1: 1.
It is one. The carboxylic acid acts as a transfer agent that helps the alkaline earth base to transfer from the inorganic reagent to the organic reagent.

The neutralization operation is performed at a temperature of at least 200 ° C., preferably at least 215 ° C., and more preferably at least 240 ° C. The pressure is gradually reduced below atmospheric pressure to distill off the water of the reaction. Thus, the neutralization should be performed without a solvent that forms an azeotrope with water. Preferably, the pressure is reduced to 7000 Pa (70 mbar) or less.

The amounts of reagents used should correspond to the following molar ratios: (1) Alkaline earth base / alkylphenol 0.2: 1 to 0.7: 1, preferably 0.3 : 1 to 0.5: 1, and (2) carboxylic acid / alkylphenol is 0.01: 1 to 0.5: 1, preferably 0.03: 1 to 0.15: 1.

At the end of this neutralization step, the alkylphenate obtained is brought to a temperature of at least 215 ° C. and 500
It is preferred to maintain the absolute pressure between 0 and 10 ⁵ Pa (0.05-1.0 bar) for a period not exceeding 15 hours. More preferably, at the end of this neutralization step, the resulting alkyl phenate is 10,000-20,000 Pa
It is preferably maintained at an absolute pressure between (0.1-0.2 bar) for 2-6 hours.

If the operation is carried out at a sufficiently high temperature and the pressure in the reactor is gradually reduced below atmospheric pressure, the neutralization reaction requires a solvent which forms an azeotrope with the water formed in the reaction. Performed without the need for addition.

C) Carbonation Step The carbonation step is carried out by simply blowing carbon dioxide into the reaction medium resulting from the previous neutralization step, for at least two steps.
Continue until 0 mol% of the alkyl phenate becomes alkyl salicylate (measured as salicylic acid by potentiometry). It must be carried out under pressure in order to avoid decarboxylation of the alkyl salicylates formed.

Preferably, using carbon dioxide at 180 ° C.
At a temperature of up to 240 ° C and above atmospheric pressure, up to 15 × 10 ⁵ Pa
At least 22 mol% of the starting alkylphenol is converted to alkyl salicylate over a period of 1 to 8 hours at a pressure in the range (15 bar). In another embodiment, 4 × 10 ⁵ P at a temperature equal to or greater than 200 ° C. using carbon dioxide.
At a pressure of 4 bar, at least 25 mol% of the starting alkylphenol is converted to an alkyl salicylate.

D) Filtration step The purpose of the filtration step is to remove sediment and, in particular, crystalline calcium carbonate which can be formed in previous steps and which can clog filters installed in the lubricating oil circuit. is there.

As the detergent, the alkyl salicylate is used in an amount of 1.0 to 1.0.
-15% by weight, preferably 4.0-10% by weight, and most preferably 6.0-8.0% by weight.

[Solvent] The lubricating oil composition of the present invention may optionally contain
It may contain small amounts of suitable solvents. Solvents are used to adjust the viscosity of the finished oil. Suitable solvents include aromatic and dearomatic aliphatic 190 ° C. to 290 ° C.
Can be listed.

[Polyisobutylene] The lubricating oil composition of the present invention may optionally contain a polyisobutylene having a molecular weight of 350-2300, preferably about 950. The polyisobutylene can be present in an amount up to 35%, preferably up to 30%, more preferably 25% by weight based on the total weight of the lubricating oil composition. Polyisobutylene has the effect of enhancing the lubricity and anti-scuffing effect of a lubricant.

[Other Additives] The following additive components include:
It is an example of some components which can be preferably used in the present invention. The examples of these additives are for illustrating the present invention and do not limit the present invention.

1) Metal detergents Sulfurized or non-sulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, sulfurized or non-sulfurized metal salts of polyhydroxyalkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, Sulfurized or non-sulfurized alkyl or alkenyl naphthenates, metal salts of alkanolic acids, metal salts of alkyl or alkenyl polyacids, and chemical and physical mixtures thereof.

2) Antioxidants Antioxidants reduce the tendency of mineral oil to deteriorate in service, and the deterioration is caused by oxidation products such as sludge and varnish-like deposits generated on metal surfaces. It is also demonstrated by an increase in viscosity. Examples of the antioxidant that can be used in the present invention include phenol type (phenol type).
Antioxidants such as 4,4'-methylenebis (2,6-
Di-tert-butylphenol), 4,4′-bis (2,
6-di-tert-butylphenol), 4,4′-bis (2-methyl-6-tert-butylphenol), 2,
2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidene-bis (2, 6-di-tert-butylphenol), 2,2′-methylene-bis (4-methyl-6-nonylphenol), 2,2′-isobutylidene-bis (4,6-dimethylphenol), 2,2′-methylene -Bis (4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6 -Tert-butylphenol,
2,6-di-tert-I-dimethylamino-p-cresol, 2,6-di-tert-4- (N, N′-dimethylaminomethylphenol), 4,4′-thiobis (2-methyl- 6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) -sulfide, and bis (3 5-di-tert-
(Butyl-4-hydroxybenzyl) -sulfide. However, it is not limited to these.

The diphenylamine type antioxidants include:
Mention may be made of alkylated diphenylamine, phenyl-alpha-naphthylamine, and alkylated alpha-naphthylamine. Other types of antioxidants can include metal dithiocarbamates (eg, zinc dithiocarbamate), and methylene bis (dibutyldithiocarbamate). However, it is not limited to these.

3) Antiwear Agent As the name implies, this additive reduces wear of moving metal parts. Examples of such additives include phosphonates, phosphites, carbamates, esters, sulfur-containing compounds, and molybdenum complexes. However, it is not limited to these.

4) Rust inhibitor (rust inhibitor) a) Nonionic polyoxyethylene surfactant: polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether , Polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate. b) Other compounds: stearic acid and other fatty acids, dicarboxylic acids, metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acids, partial carboxylic acid esters of polyhydric alcohols, and phosphoric acid esters.

5) Demulsifiers: adducts of alkylphenol and ethylene oxide, polyoxyethylene alkyl ethers, and polyoxyethylene sorbitan esters. 6) Extreme pressure agent (EP agent): zinc dialkyldithiophosphate (primary alkyl type, secondary alkyl type and aryl type), sulfurized oil, diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, fluoroalkyl poly Siloxane, and lead naphthenate. 7) Friction modifiers: fatty alcohols, fatty acids, amines, borates, and other esters.

8) Multifunctional additives: oxymolybdenum sulfide dithiocarbamate, oxymolybdenum sulfide organic phosphorus dithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex compound, and sulfur-containing molybdenum complex compound. 9) Viscosity index improver: polymethacrylate type polymer,
Ethylene-propylene copolymer, styrene-isoprene copolymer, hydrated styrene-isoprene copolymer, polyisobutylene, and a dispersant type viscosity index improver. 10) Pour point depressant: polymethyl methacrylate. 11) Antifoam: alkyl methacrylate polymer and dimethyl silicone polymer.

[Base Oil of Lubricating Viscosity] The base oil of lubricating viscosity used in such a composition may be a mineral oil or a synthetic oil having a viscosity suitable for use in a crankcase of an internal combustion engine. Is also good. The base oil may be derived from synthetic or natural sources. Mineral oils that can be used as base oils in the present invention include, for example, paraffinic petroleum, naphthenic petroleum, and other petroleum commonly used in lubricating oil compositions. Synthetic oils can include, for example, both hydrocarbon synthetic oils and synthetic esters, and mixtures thereof having the desired viscosity.
Useful synthetic hydrocarbon oils can include liquid polymers of alpha olefins having the proper viscosity. Particularly useful are C ₆ -C such as 1-decene trimer.
It is a hydrogenated liquid oligomer of ₁₂ alpha olefins. Similarly, alkyl benzenes of appropriate viscosity, such as didodecyl benzene, can be used. Useful synthetic esters include esters of monocarboxylic acids and polycarboxylic acids with monohydroxyalkanols and polyols. Representative examples include didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilauryl sebacate, and the like. Complex esters synthesized from mixtures of mono- and dicarboxylic acids with mono- and dihydroxyalkanols can also be used. Blends of mineral and synthetic oils are also useful.

[Lubricating Oil Composition] The detergent of the present invention is useful for imparting higher detergency to an engine lubricating oil composition. Such lubricating oil compositions consist of a major amount of a base oil of lubricating viscosity and a minor and effective amount of a detergent.

In one embodiment, the lubricating oil composition comprises the following components: (a) a major amount of a base oil of at least one lubricating viscosity; And (c) optionally at least one of the following components: (1) a small amount of solvent, and (2) a small amount of polyisobutylene.

The lubricating oil may optionally contain a solvent and / or polyisobutylene, the solvent comprising 10-20
%, Preferably 15-20% by weight, and the polyisobutylene may be 0-35%, preferably 25-30% by weight.

The lubricating oil composition of the present invention is useful in a method for lubricating an air-cooled two-stroke cycle engine. In that method, a lubricant composition is supplied to a crankcase of an engine or fuel added to the engine to operate the engine.

In another embodiment, an engine lubricating oil composition is made by blending a mixture of the above components.
The lubricating oil composition produced by that method may have a slightly different composition than the initial mixture because the components may interact.

The components can be blended in any order and can be blended as a combination of components. For example, Mannich base and ashless dispersant,
Optionally comprising a molybdenum compound, an overbased alkyloxybenzene sulfonate and an alkyl salicylate,
It can also be blended together before blending with the remaining components of the mixture. Similarly, the solvent and polyisobutylene can be blended with the detergent prior to blending with the base oil.

[Additive Concentrate] Additive concentrates are also included in the claims of the present invention. The concentrate according to the invention consists of a compound or a mixture of compounds according to the invention, preferably
It contains at least one other additive as described above.
The concentrate contains sufficient organic diluent to facilitate handling during transport and storage.

The additive concentrate preferably comprises 5.0 to 15% by weight of organic diluent and 85 to 95% by weight of the detergent according to the invention. Suitable organic diluents that can be used include mineral or synthetic oils as described in the section [Base oil of lubricating viscosity].

Fuel Oils As is well known to those skilled in the art, two-stroke engine lubricating oils are often added directly to fuel to form a mixture of oil and fuel, which is then added to the engine cylinder. Inject into Such lubricant-fuel oil mixtures are also included in the claims of the present invention. Such lubricant-fuel blends generally contain oil 1
It contains about 15-250 parts of fuel per part, usually about 25-100 parts of fuel per part of oil.

Depending on the two-stroke engine, the lubricating oil can be injected directly into the combustion chamber together with the fuel, or added to the fuel immediately before it is separated into the combustion chamber.
The two-stroke lubricant of the present invention can also be used in this type of engine.

The fuel used for the two-stroke engine is
It is well known to those skilled in the art, and most of the time, most are standards such as hydrocarbonaceous petroleum distillate fuels (eg, automotive gasoline as defined by ASTM standard D-439-73). Liquid fuel. Such fuels may also include non-hydrocarbon materials such as alcohols, ethers, organic nitro compounds, and the like (eg, methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane). Liquid fuels derived from plant or mineral sources such as cereals, alfalfa, shale and coal are also within the scope of the claims of the present invention. Examples of such fuel mixtures include combinations of gasoline and ethanol, diesel fuel, diesel fuel and ether, gasoline and nitromethane, and the like. Particularly preferred is gasoline, ie AS
It is a hydrocarbon mixture having a TM boiling point of 60 ° C. at a 10% distillation point to about 250 ° C. at a 90% distillation point.

[0088]

The present invention will be further described with reference to the following examples. These examples illustrate particularly advantageous method embodiments. It should be noted that the examples are for describing the present invention, and the present invention is not limited thereby.

The detergent of the present invention was prepared according to CEC L-7.
The evaluation was performed according to the 9-T-97 test method, "3-hour cleanliness test method for evaluating two-stroke cycle gasoline engine lubricants". The method is under development by the 2T Engine Oil Subcommittee of the Japan Automobile Standards Association (JASO), and was developed at the 7th International Two-Stroke Oil Standards Meeting.
This was done using the draft method published on September 9, 1992.

The method is designed to be tested on a single cylinder engine, the Honda SK-50Mm air-cooled engine, to evaluate the performance of a two-stroke cycle gasoline lubricant related to engine cleanliness. The test is carried out using a mixture of unleaded gasoline and the lubricant to be evaluated at a fuel oil ratio of 100: 1. For the following critical regions, JP
Inspection according to the I-5S-34-91 evaluation manual,
evaluate. Piston ring sticking (top and second rings) Piston land deposits (top and second lands) Piston ring groove deposits (top and second grooves) Piston skirt deposits Piston undercrown deposits Piston crown Sediment ・ Cylinder head sediment

The total effective merit is calculated as the sum of the above evaluations. The higher the number, the better the performance.
In addition to those specified in the examples below, all formulations included polyisobutene, a mixture of heavy and light neutral base oils, and a solvent. The test results are shown in Table 1.

Example 1 Formulation I contained 1.12% by weight
Contained 4.75% by weight of an ashless dispersant.

Example 2 Formulation II contained 1.12% by weight
Containing 3.85% by weight of an ashless dispersant.

Example 3 Formulation III comprises 1.12% by weight of Mannich detergent, 3.85% by weight of ashless dispersant,
And 0.25% by weight of a molybdenum compound.

Example 4 Formulation IV contained 0.80% by weight
Of Mannich detergent, 3.85% by weight of ashless dispersant, and 0.38% by weight of alkyl salicylate.

Example 5 Formulation V was 0.80% by weight
A Mannich detergent, 3.85% by weight of an ashless dispersant,
It contained 0.25% by weight of a molybdenum compound and 0.38% by weight of an alkyl salicylate.

Example 6 Formulation VI was 0.80% by weight
Of Mannich detergent, 3.85% by weight of an ashless dispersant, and 0.16% by weight of an overbased alkyloxybenzene sulfonate.

Example 7 Formulation VII contains 0.80 wt% Mannich detergent, 3.85 wt% ashless dispersant,
It contained 0.16% by weight of an overbased alkyloxybenzene sulfonate and 0.19% by weight of an alkyl salicylate.

Example 8 Formulation VIII contains 0.80% by weight Mannich detergent, 3.85% by weight ashless dispersant,
It contained 0.25% by weight of a molybdenum compound, 0.16% by weight of an overbased alkyloxybenzenesulfonate, and 0.19% by weight of an alkyl salicylate.

[0100]

[Table 1]

[0101]

The detergent of the present invention exhibits excellent cleaning properties including dispersibility and lubricity when used in a lubricating oil composition for an air-cooled two-stroke cycle engine. Thus, the lubricating oil composition of the present invention containing this detergent keeps the air-cooled two-stroke cycle engine clean, preventing ring sticking, piston deposits, plug fouling, and exhaust deposits. The additive concentrates of the present invention also exhibit excellent cleaning properties when used in air-cooled two-stroke cycle engines and are useful. Further, the cleanliness of the air-cooled two-stroke cycle engine can be improved by supplying the lubricating oil composition to the engine crankcase or fuel and operating the engine.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C10M 133/18 C10M 133/18 133/56 133/56 137/10 137/10 A 143/06 143/06 159/16 159/16 159/24 159/24 // C10N 10:04 C10N 10:04 10:12 10:12 20:00 20:00 Z 30:04 30:04 40:26 40:26 (72) Inventor Michael A. Shroud 4318 Bordeaux Drive, Oakley, CA 94561, United States

Claims (15)

[Claims] 1. A detergent suitable for a lubricating oil composition used in an air-cooled two-stroke cycle engine, comprising: a) a Mannich detergent; b) an ashless dispersant; The ratio is 3:
1-5: 1] and c) at least one of the following compounds: 1) a molybdenum compound, 2) an overbased alkyloxybenzene sulfonate, and 3) an alkyl salicylate. 2. The detergent according to claim 1, wherein the Mannich detergent is a condensate of tetrapropenylphenol, formaldehyde, and diethylenetriamine. 3. The detergent according to claim 2, wherein the Mannich detergent is a calcium salt of the condensate. 4. The detergent according to claim 1, wherein the ashless dispersant is a polyalkylene succinimide derived from a reaction product of an alkenyl or alkyl-substituted succinic acid or an anhydride thereof and a polyalkylene polyamine. 5. The detergent according to claim 1, wherein the molybdenum compound is molybdenum oxydisulfide. 6. The overbased alkyloxybenzenesulfonate having a TBN of at least 200 and 40% by weight.
８０80% by weight of the alkyl group is attached at the 4-position or higher of the alkyl group and the oxy group is hydroxy,
The detergent according to claim 1, wherein the detergent is selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy. 7. The overbased alkyloxybenzenesulfonate having a TBN of at least 250 and 45% by weight
7. The detergent according to claim 6, wherein from about 70% by weight of the alkyl group is attached at the 4-position or higher of the alkyl group and the oxy group is hydroxy. 8. The detergent according to claim 1, wherein the alkyl salicylate is a non-sulfided alkaline earth alkyl salicylate. 9. The detergent according to claim 8, wherein the non-sulfided alkaline earth alkyl salicylate is a calcium alkyl salicylate. 10. A lubricating oil composition suitable for an air-cooled two-stroke cycle engine, comprising: a) a base oil of at least one lubricating viscosity, b) 1.0 to 10% by weight. A detergent according to 1 and c) optionally at least one of the following components: 1) a small amount of solvent, and 2) a small amount of polyisobutene. 11. A process for producing a lubricating oil composition suitable for an air-cooled two-stroke cycle engine, comprising blending together the following components: a) a major amount of at least one lubricating viscosity base. Oil, b) 1.0 to 10% by weight of the detergent according to claim 1, and c) optionally at least one of the following components: 1) a small amount of solvent, and 2) a small amount of polyisobutylene. 12. The lubricating oil composition according to claim 10, wherein the lubricating oil composition optionally comprises polyisobutylene. 13. A method for improving the cleanliness of an air-cooled two-stroke cycle engine, said method comprising supplying a lubricating oil composition according to claim 10 to a crankcase of said engine and operating said engine. . 14. A method for improving the cleanliness of an air-cooled two-stroke cycle engine, comprising operating the engine by supplying the lubricating oil composition of claim 10 to the fuel of the engine. 15. A detergent concentrate suitable for an air-cooled two-stroke cycle engine, comprising: a) 5.0 to 15% by weight of an organic diluent, and b) 85 to 95% by weight. A detergent as described.