KR20050096180A - Additives for lubricating oils and fuel oils, lubricating oil compositions, and fuel oil compositions - Google Patents

Abstract

Additives for lubricating oils and fuel oils, which contain as the main component disulfide compounds represented by the general formula (I) or (IV): R1OOC-A1-Sx-A2-COOR2 (I) (wherein R1 and R2 are each independently C1- 30 hydrocarbyl which may contain oxygen, sulfur or nitrogen; A 1 and A2 are each independently CR3R4 wherein R3 and R4 are each independently hydrogen or C1-20 hydrocarbyl; and x is 2), and R1OOC-A3- Sx-A4-COOR2 (IV) (wherein R1 and R 2 are as defined above; A3 and A4 are each independently CR5R6-CR7R8 wherein R5 to R8 are each independently hydrogen or C1- 20 hydrocarbyl; and x is 2). The additives exhibit excellent functions as extreme -pressure additive or anti-wear additive and little corrode nonferrous metals, thus being useful as sulfur-containing extreme- pressure additives suitable for lubricating oils and fuel oils.

Description

Lubricant and fuel oil additives, lubricating oil compositions and fuel oil compositions {ADDITIVES FOR LUBRICATING OILS AND FUEL OILS, LUBRICATING OIL COMPOSITIONS, AND FUEL OIL COMPOSITIONS}

The present invention relates to lubricant and fuel oil additives, and to lubricating oil compositions and fuel oil compositions. More specifically, the present invention relates to lubricant and fuel oil additives mainly comprising a disulfide compound of a specific structure having excellent functions as a friction modifier, especially an extreme pressure additive or an antiwear agent, and a lubricant oil composition and fuel oil each containing the above additives. It relates to a composition.

Conventionally, lubricating oil is used in internal combustion engines, drive systems such as automatic transmissions, shock absorbers, power steering, and the like to smoothly operate the lubricating oil. It is well known that friction and abrasion eventually lead to seizure. Therefore, the lubricating oil which mix | blended the extreme pressure additive, the antiwear agent, etc. is used. However, the conventional extreme pressure additives were not necessarily sufficiently satisfactory, such as not exhibiting sufficient anti-sticking effect due to interaction with other additives, corrosion of metals, or poor wear resistance.

In addition, as a metal processing oil used for metal processing, such as cutting, grinding processing, or caustic processing, it is prepared by mixing oily agents, such as alcohols, fatty acid esters, fatty acids, and extreme pressure additives, with mineral oil or synthetic hydrocarbon oil, and trying to improve workability. It is becoming.

However, a new process oil which can further improve workability is desired for such a metal process oil from a viewpoint of productivity improvement or energy saving. At the same time, chlorine-based extreme pressure additives, which have been widely used as extreme pressure additives in the past, tend to refrain from using them because they may cause deterioration of the working environment, such as causing rashes on the human body or rusting to a target metal.

In accordance with the above requirements, as the metal working oil, there are commercially available emulsions in which base oil containing sulfide olefins containing sulfur and an overbased sulfonate are added.

The commercially available metalworking oil has good weldability and has the capability of preventing abnormal wear (for example, rupture) of the tool and tearing of the processed surface. However, in a process in which friction with a relatively low load is repeated, corrosion wear of the tool by the active sulfur proceeds, and the period until the replacement or regrinding of the tool is shortened, which often hampered the production efficiency. Conversely, in metal processing where abnormal abrasion is not a problem from the start, it may lead to a decrease in production efficiency.

Next, the hydraulic fluid is a power transmission fluid used for the operation of power transmission, force control, shock absorbing, etc. in a hydraulic system such as a hydraulic device or a device, and also performs lubrication function of the sliding part.

In such hydraulic fluids, in particular, it is an essential performance that it is essential to be excellent in anti-sticking resistance and abrasion resistance. Therefore, the above-described performance is provided by incorporating an extreme pressure additive or an antiwear agent into base oil such as mineral oil or synthetic oil. However, the conventional extreme pressure additive was not necessarily satisfactory enough, even if the load preventing effect was sufficient, such as insufficient wear resistance or corrosion corrosion.

In addition, gear oils, in particular automotive gear oils, are urgently required to improve abrasion resistance and oxidation stability due to severe load conditions or severe driving conditions such as long-distance transportation due to the development of a high-speed road network, or an extension of oil change intervals. Has been.

Until now, although main components of extreme pressure additives such as sulfurized oils, sulfided olefins, phosphoric acid and thiophosphate compounds, and zinc dithiophosphate or antiwear additives have been mainly formulated with lubricating oil base oils, further, wear resistance, oxidation stability, It is required to reduce the wear factor ratio (low speed / high speed).

On the other hand, with respect to fuel oil, it is known that the lubrication performance is lacking as it is highly hydrogenated, and it was pointed out that the fuel pump using the high refine | purified fuel causes abrasion. However, recent high performance turbine fuels require high lubrication performance, and require high performance fuel oil additives that are adsorbed on the metal surface of fuel system equipment to form extreme pressure membranes, thereby improving lubricity and reducing wear.

Conventionally, sulfur type extreme pressure additive is used well as an extreme pressure additive of lubricating oil. These sulfur-based extreme pressure additives have sulfur atoms in their molecules and dissolve or disperse uniformly in base oil to exert extreme pressure effects. For example, sulfurized oils, sulfided fatty acids, sulfided esters, polysulfides, sulfided olefins, thiocarbamates, sulfided Terpenes, dialkylthiodipropionates, etc. are known. However, these sulfur-based extreme pressure additives were not necessarily satisfactory, including problems such as corrosion of the metal, interaction with other additives, insufficient adhesion effect or insufficient wear resistance.

Recently, as the sulfur-based extreme pressure additive, a compound represented by the following formula (VII) has been disclosed (for example, Japanese Patent Laid-Open No. 2001-288490):

Where

R ⁹ and R ¹⁰ are each a hydrocarbon group having 1 to 20 carbon atoms,

A ⁵ and A ⁶ are each a hydrocarbon group having 0 to 20 carbon atoms,

x is an integer of 1-6.

However, according to Japanese Patent Laid-Open No. 2001-288490, since the compound of formula (VII) is prepared by reacting a chlorinated ester such as monochloroacetic acid ester with sodium polysulfide, a polysulfide of monosulfide, disulfide and trisulfide or higher It is unavoidable to be a mixture of sulfides. In the divalent hydrocarbon represented by A ⁵ and A ⁶ , only the carbon number is described, and the structure thereof is not explained at all, and it is not entirely clear what kind of structure is preferable.

Disclosure of the Invention

The present invention has excellent load carrying capacity and abrasion resistance compared to conventional sulfur-based additives under such circumstances, and has a low corrosion resistance to nonferrous metals, a sulfur-based extreme pressure additive used for lubricating oils and fuel oils, and a lubricating oil composition comprising the additives. And a fuel oil composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventor discovered that the objective can be achieved by the lubricating oil and fuel oil additive which have a disulfide compound which has a specific structure as a main component. The present invention has been completed according to this finding.

That is, the present invention

 1. Additives for lubricating oils based on the disulfide compound represented by the following formula (I):

R ¹ OOC-A ¹ -S _x -A ² -COOR ²

Where

R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ¹ and A ² are each independently a group represented by CR ³ R ⁴ ,

R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms,

x represents 2.

2. Additives for lubricating oils based on disulfide compounds obtained by oxidatively coupling the mercaptoalkanecarboxylic acid esters represented by the following formulas (II) and / or (III):

R ¹ OOC-A ¹ -SH

Where

R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ¹ is a group represented by CR ³ R ⁴ ,

R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.

R ² OOC-A ² -SH

Where

R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ² is a group represented by CR ³ R ⁴ ,

R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.

3. Additives for lubricating oils based on the disulfide compound represented by the following general formula (IV):

R ¹ OOC-A ³ -S _x -A ⁴ -COOR ²

Where

R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ³ and A ⁴ are each independently a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ ,

R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms,

x represents 2.

4. Additives for lubricating oils based on disulfide compounds obtained by oxidatively coupling the mercaptoalkanecarboxylic acid esters represented by the following formulas (V) and / or (VI):

R ¹ OOC-A ³ -SH

Where

R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ³ is a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ ,

R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.

R ² OOC-A ⁴ -SH

Where

R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ⁴ is a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ ,

R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.

5. The additive for lubricating oil according to the above 1, wherein the content of the polysulfide compound having x of 3 or more in the general formula (I) is 30% by mass or less based on the total amount of the disulfide compound;

6. The additive for lubricating oil according to item 3, wherein the content of the polysulfide compound having x of 3 or more in the general formula (IV) is 30% by mass or less based on the total amount of the disulfide compound;

7. Additives for fuel oil mainly comprising a disulfide compound represented by the following formula (I):

Formula I

R ¹ OOC-A ¹ -S _x -A ² -COOR ²

Where

R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ¹ and A ² are each independently a group represented by CR ³ R ⁴ ,

R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms,

x represents 2.

8. Additives for fuel oil mainly comprising disulfide compounds obtained by oxidatively coupling the mercaptoalkanecarboxylic acid esters represented by the following general formula (II) and / or (III):

Formula II

R ¹ OOC-A ¹ -SH

Where

R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ¹ is a group represented by CR ³ R ⁴ ,

R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.

Formula III

R ² OOC-A ² -SH

Where

R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ² is a group represented by CR ³ R ⁴ ,

R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.

9. Additives for fuel oil mainly comprising a disulfide compound represented by the following formula (IV):

Formula IV

R ¹ OOC-A ³ -S _x -A ⁴ -COOR ²

Where

R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ³ and A ⁴ are each independently a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ ,

R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms,

x represents 2.

10. Additives for fuel oil mainly comprising disulfide compounds obtained by oxidatively coupling the mercaptoalkanecarboxylic acid ester represented by the following general formula (V) and / or the following general formula (VI):

Formula V

R ¹ OOC-A ³ -SH

Where

R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ³ is a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ ,

R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.

Formula VI

R ² OOC-A ⁴ -SH

Where

R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom,

A ⁴ is a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ ,

R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.

11. The fuel oil additive according to the item 7, wherein the content of the polysulfide compound having x of 3 or more in the general formula (I) is 30% by mass or less based on the total amount of the disulfide compound;

12. The fuel oil additive according to the above 9, wherein the content of the polysulfide compound having x of 3 or more in the general formula (IV) is 30% by mass or less based on the total amount of the disulfide compound;

13. A lubricating oil composition comprising (A) a lubricating oil base oil and (B) the lubricating oil additive according to any one of 1 to 6 above;

14. The lubricating oil composition according to item 13, wherein the content of (B) component is 0.01 to 50% by mass;

15. A fuel oil composition comprising (X) fuel oil and (Y) the additive for fuel oil according to any one of 7 to 12 above;

16. The fuel oil composition according to the above 15, wherein the content of the component (Y) is 0.01 to 1000 mass ppm.

To provide.

The compound represented by the formula (I) used in the lubricant and fuel oil additive of the present invention is a disulfide compound having the structure of formula (I):

Formula I

R ¹ OOC-A ¹ -S _x -A ² -COOR ²

In formula (I), R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 2 to 18 carbon atoms, especially 3 to 18 hydrocarbyl groups Is preferred. The hydrocarbyl group may be any of linear, branched and cyclic, and may also contain an oxygen atom, a sulfur atom or a nitrogen atom. Although these R <^1> and R <^2> may be mutually same or different, it is preferable that they are the same for manufacturing reasons.

Next, A ¹ and A ² are each independently a group represented by CR ³ R ⁴ , and R ³ and R ⁴ are each independently hydrogen or a monovalent hydrocarbyl group having 1 to 20 carbon atoms. The hydrocarbyl group preferably has 1 to 12 carbon atoms and further preferably 1 to 8 carbon atoms. Specific examples of A ¹ and A ² include a methylene group, an ethylidene group, a propylidene group, and the like, and a methylene group is particularly preferable. In addition, although A <^1> and A <^2> may be mutually same or different, it is preferable that they are the same for manufacturing reasons. And x is 2.

In the additive for lubricating oil and fuel oil of the present invention, the content of polysulfide in which x is 3 or more in the general formula (I) is preferably 30% by mass or less based on the total amount of the compound represented by the general formula (I). Do. If this content is 30 mass% or less, corrosiveness with respect to a nonferrous metal can fully be suppressed. Content of the polysulfide compound whose x is 3 or more becomes like this. More preferably, it is 10 mass% or less, Especially preferably, it is 5 mass% or less.

Therefore, in the production of the disulfide compound represented by the formula (I), it is important to adopt a method in which the byproduct amount of the polysulfide compound having x of 3 or more is within the above range. In this invention, it is preferable to manufacture according to the method shown below, for example.

That is, oxidative coupling is performed using a mercaptoalkane carboxylic acid ester represented by the formula (II) and / or the formula (III) as a raw material.

Formula II

R ¹ OOC-A ¹ -SH

Formula III

R ² OOC-A ² -SH

Wherein R ¹ and R ² , A ¹ and A ² are the same as above.

According to this production method, by-products of the polysulfide compound of trisulfide or more do not substantially occur.

Specifically, R ¹ OOC-A ¹ -S ₂ -A ² -COOR ² , R ¹ OOC-A ¹ -S ₂ -A ¹ -COOR ¹ , R ² OOC-A ² -S ₂ -A ² -COOR ² Is manufactured.

Examples of the oxidizing agent include oxygen, hydrogen peroxide, halogen (iodine and bromine), hypohalogenic acid (salt), sulfoxide (dimethyl sulfoxide, diisopropyl sulfoxide), and manganese oxide (W). Among these oxidizing agents, oxygen, hydrogen peroxide, and dimethyl sulfoxide are preferable because they are inexpensive and the disulfide is easily produced.

Specific examples of the disulfide compound represented by the formula (I) include bis (methoxycarbonylmethyl) disulfide, bis (ethoxycarbonylmethyl) disulfide, bis (n-propoxycarbonylmethyl) disulfide, bis (Isopropoxycarbonylmethyl) disulfide, bis (cyclopropoxycarbonylmethyl) disulfide, 1,1-bis (1-methoxycarbonylethyl) disulfide, 1,1-bis (1-methoxy Carbonyl-n-propyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-butyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-hexyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-octyl) disulfide, 2,2-bis (2-methoxycarbonyl-n-propyl) disulfide, α, α-bis (α-methoxy Carbonyl benzyl) disulfide, and the like.

In addition, the compound represented by the general formula (IV) used in the lubricant and fuel oil additives of the present invention is a disulfide compound having the following general formula (IV).

Formula IV

R ¹ OOC-A ³ -S _x -A ⁴ -COOR ²

In the above Formula IV, R ¹ and R ² are the same as R ¹ and R ² in the general formula I. Although these R <^1> and R <^2> may be mutually same or different, it is preferable that they are the same for manufacturing reasons.

Next, A ³ and A ⁴ are each independently a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ , and R ⁵ to R ⁸ are each independently hydrogen or a monovalent hydrocarbyl group having 1 to 20 carbon atoms. The hydrocarbyl group preferably has 1 to 12 carbon atoms, and preferably 1 to 8 carbon atoms thereon. In addition, although A <^3> and A <^4> may be mutually same or different, it is preferable that they are the same for manufacturing reasons. In addition, x is two.

In the additive for lubricating oil and fuel oil of the present invention, it is preferable that the content of the polysulfide whose x is 3 or more in the general formula (IV) is 30% by mass or less based on the total amount of the compound represented by the general formula (IV). If this content is 30 mass% or less, corrosiveness with respect to a nonferrous metal can fully be suppressed. Content of the polysulfide compound whose x is 3 or more becomes like this. More preferably, it is 10 mass% or less, Especially preferably, it is 5 mass% or less.

Therefore, in the production of the disulfide compound represented by the above formula (IV), it is important to adopt a method in which the byproduct amount of the polysulfide compound having x of 3 or more is within the above range. In this invention, it is preferable to manufacture according to the method shown below, for example.

That is, oxidative coupling is performed using a mercaptoalkane carboxylic acid ester represented by the following general formula (V) and / or general formula (VI) as a raw material.

Formula V

R ¹ OOC-A ³ -SH

Formula VI

R ² OOC-A ⁴ -SH

Where

R ¹ and R ² , A ³ and A ⁴ are as described above.

According to this production method, by-products of the polysulfide compound of trisulfide or more do not substantially occur.

Specifically, R ¹ OOC-A ³ -S ₂ -A ⁴ -COOR ² , R ¹ OOC-A ³ -S ₂ -A ³ -COOR ¹ , R ² OOC-A ⁴ -S ₂ -A ⁴ -COOR ² is prepared.

As the oxidizing agent used when the α-mercaptocarboxylic acid ester is oxidized to produce the corresponding disulfide, an oxidizing agent used to prepare disulfide from mercaptan can be used. Examples of the oxidizing agent include oxygen, hydrogen peroxide, halogen (iodine and bromine), hypohalogenic acid (salt), sulfoxide (dimethyl sulfoxide, diisopropyl sulfoxide), and manganese oxide (IV). Among these oxidizing agents, oxygen, hydrogen peroxide, and dimethyl sulfoxide are preferable because they are inexpensive and easy to produce disulfide.

Specific examples of the disulfide compound represented by Formula IV include 1,1-bis (2-methoxycarbonylethyl) disulfide, 1,1-bis (2-ethoxycarbonylethyl) disulfide, 1,1- Bis (2-n-propoxycarbonylethyl) disulfide, 1,1-bis (2-isopropoxycarbonylethyl) disulfide, 1,1-bis (2-cyclopropoxycarbonylethyl) disulfide , 1,1-bis (2-methoxycarbonyl-n-propyl) disulfide, 1,1-bis (2-methoxycarbonyl-n-butyl) disulfide, 1,1-bis (2-meth Methoxycarbonyl-n-hexyl) disulfide, 1,1-bis (2-methoxycarbonyl-n-propyl) disulfide, 2,2-bis (3-methoxycarbonyl-n-pentyl) disulfide And 1,1-bis (2-methoxycarbonyl-1-phenylethyl) disulfide and the like.

These disulfide compounds have excellent load carrying capacity and wear resistance as sulfur-based extreme pressure additives and are used as additives for lubricating oils and fuel oils.

In the additive for lubricating oil and fuel oil of the present invention, one or more of the disulfide compound represented by the formula (I) and / or the disulfide compound represented by the formula (IV) may be included.

Next, this lubricating oil composition contains the additive for lubricating oil containing (A) lubricating oil base oil and (B) the disulfide compound mentioned above. On the other hand, the lubricating oil composition according to the present invention includes a metal used for metal processing such as an internal combustion engine, an automobile transmission oil used for an automatic transmission, a shock absorber, a power steering device, a gear, etc. It is used as a working oil which is a power transmission fluid used for the operation of power transmission, a force control, a damping, etc. in hydraulic systems, such as a process oil, a hydraulic machine, an apparatus, etc., etc. are mentioned.

In the lubricating oil composition of the present invention, the lubricating oil base oil used as the component (A) is not particularly limited, and is appropriately selected from mineral oil and synthetic oil according to the purpose of use of the composition, conditions of use, and the like. Here, the mineral oil may be, for example, an extruded oil obtained by purifying paraffinic crude oil, an intermediate mechanical crude oil or a naphthenic crude oil under atmospheric pressure distillation or by distillation under reduced pressure of residual kerosene of atmospheric pressure distillation, or refined oil obtained by purifying them according to a conventional method, specifically, a solvent refined oil. And hydrogenated refined oil, dewaxed oil, clay treated oil and the like.

As the synthetic oil, for example, low molecular weight polybutene, low molecular weight polypropylene, α-olefin oligomers having 8 to 14 carbon atoms and their hydrides, and polyol esters (fatty acid esters of trimethylolpropane, fatty acids of pentaerythritol) Ester compounds such as esters), dibasic acid esters, aromatic polycarboxylic acid esters, and phosphoric acid esters; alkyl aromatic compounds such as alkylbenzenes and alkylnaphthalenes; polyglycol oils such as polyalkylene glycols and silicone oils; Can be mentioned.

1 type may be used for these base oils, and 2 or more types may be combined suitably.

Although content of the additive for lubricating oil of (B) component in the lubricating oil composition of this invention is suitably selected according to the purpose of use of a said composition, use conditions, etc., it is generally the range of 0.01-50 mass%. In the case of automotive lubricants and hydraulic oils, the range is usually in the range of 0.01 to 30% by mass, preferably in the range of 0.01 to 10% by mass. In the case of metal working oil, additives may be used alone, but usually in the range of 0.1 to 60% by mass, preferably It is selected in the range of 0.1-50 mass%.

In the lubricating oil composition of the present invention, depending on the purpose of use, various additives such as other friction modifiers (oil agent, other extreme pressure additives), antiwear agent, ashless dispersant, metal cleaner, viscosity index improver, pour point depressant, rust preventive agent, metal corrosion inhibitor, A defoaming agent, surfactant, antioxidant, etc. can be contained suitably.

Examples of other friction modifiers and antiwear agents include sulfur-based compounds such as sulfide olefins, dialkyl polysulfides, diarylalkyl polysulfides and diaryl polysulfides, phosphate esters, thiophosphate esters, phosphorous acid esters, alkylhydrogen phosphates, and phosphate esteramines. Phosphorus compounds such as salts, phosphorous esteramine salts, chlorinated oils such as chlorinated fats and oils, chlorinated paraffins, chlorinated fatty acid esters and chlorinated fatty acids, ester compounds such as alkyl or alkenylmaleic acid esters, alkyl or alkenyl succinic acid esters, alkyl or Organic acid compounds such as alkenyl maleic acid, alkyl or alkenyl succinic acid, naphthenate, dithiophosphate zinc (ZnDTP), dithiocarbamate zinc (ZnDTC), molybdenum dithiophosphate (MoDTP), molybdenum die Organometallic compounds such as thiocarbamate (MoDTC); and the like.

Examples of the ashless dispersant include succinic acid imides, boron-containing succinic acid imides, benzylamines, boron-containing benzylamines, succinic acid esters, amides of monovalent or divalent carboxylic acids represented by fatty acids or succinic acid, and the like. As the metal-based cleaning agent, for example, neutral metal sulfonate, neutral metal phenate, neutral metal salicylate, neutral metal phosphonate, basic sulfonate, basic phenate, basic salicylate, basic phosphonate, and overbased sulfo Nates, overbased phenates, overbased salicylates, overbased phosphonates, and the like.

Examples of the viscosity index improver include polymethacrylates, dispersed polymethacrylates, olefin copolymers (e.g., ethylene-propylene copolymers, etc.), dispersed olefin copolymers, and styrene copolymers (e.g., styrene copolymers). Lene-diene hydrogenated copolymer, etc.), and the like, for example, polymethacrylate, etc. may be selected as the pour point depressant.

As the rust inhibitor, for example, alkenyl succinic acid, partial esters thereof, and the like are used. As the metal corrosion inhibitor, for example, benzotriazole type, benzimidazole type, benzothiazole type, thiadiazole type, and the like are used. Methyl polysiloxane, polyacrylate, etc. are used, As a surfactant, polyoxyethylene alkyl phenyl ether etc. are used, for example.

Examples of the antioxidant include amine-based antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated naphthylamine, 2,6-di-t-butyl-p-cresol, and 4,4'-. Phenolic antioxidants such as methylenebis (2,6-di-t-butylphenol) and the like.

The lubricating oil composition of the present invention is, for example, an internal combustion engine, a metal working oil used for metal processing, such as automotive lubricants used in drive system devices such as automatic transmissions, shock absorbers, power steering devices, gears, and the like, cutting processing, reduction processing, and plastic working. It is used as hydraulic fluid which is a power transmission fluid used for the operation of power transmission, a force control, a damping, etc. in hydraulic systems, such as a hydraulic apparatus and an apparatus.

On the other hand, the fuel oil composition of this invention contains the additive for fuel oils containing (X) fuel oil and (Y) disulfide compound mentioned above.

In the fuel oil composition of the present invention, as the fuel oil which is the component (X), highly hydrogenated and refined fuel oil, such as a high performance turbine fuel oil, is preferably used.

Content of the fuel oil additive of (Y) component in the fuel oil composition of this invention is 0.01-100 mass ppm normally, Preferably it is the range of 0.01-100 mass ppm.

In the fuel oil composition of this invention, various additives can be mix | blended suitably as needed. Examples of such additives include antioxidants such as phenylenediamine, diphenylamine, alkylphenol, and aminophenol, cleaning agents such as polyetheramide and polyalkylamine, and Schiff-type compounds and thiamides. Metal inerts such as type compounds, surface ignition inhibitors such as organophosphorus compounds, freezing inhibitors such as polyhydric alcohols and ethers, coagulants such as alkali metal salts or alkaline earth metal salts of organic acids, sulfate esters of higher alcohols, anionic surfactants, Antistatic agents such as cationic surfactants and amphoteric surfactants, rust inhibitors such as esters of alkenyl succinic acid, identification agents such as kinizarine and coumarin, exploitative agents such as natural essential oils and synthetic fragrances, and colorants such as azo dyes Fuel oil additives.

Example

Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all as an example of these.

In addition, the friction coefficient, abrasion mark diameter, and corrosion property of the lubricating oil composition were calculated | required according to the method shown below.

(1) friction coefficient and wear mark diameter

A soda type dune test was performed under the following conditions.

At 80 rpm and oil temperature of 80 ° C., 1,080 while maintaining the load at each hydraulic load [0.5, 0.7, 0.9, 1.1, 1.3, 1.5 kgf / cm ² (× 0.09807 MPa) for 180 seconds while gradually raising the load, 1,080 The test was carried out for a second, the friction coefficient in each load was calculated | required, and the friction mark width was measured after completion | finish of a test.

(2) corrosive

According to JIS K-2513 "Petroleum Copper Plate Corrosion Test Method", test the corrosiveness by the test temperature of 100 ° C, test time 3 hours, and the test tube method, and observe the discoloration state of the copper plate in accordance with the "copper plate corrosion standard" Corrosionability was evaluated by symbols 1a to 4c. On the other hand, the smaller the number of subdivisions, the smaller the corrosiveness, and the higher the corrosiveness in alphabetical order.

Preparation Example 1 Preparation of Bis (ethoxycarbonylmethyl) disulfide

The mercaptoacetate acetate was oxidized to dimethyl sulfoxide according to the method shown below to prepare bis (ethoxycarbonylmethyl) disulfide. Among these compounds, the presence of polysulfides above trisulfide was not recognized.

20.9 g of methyl mercaptoacetate and 30.8 g of dimethyl sulfoxide were placed in a 100 ml recovery flask, and the mixture was heated for 8 hours in a 120 ° C oil bath. After cooling, the mixture was dissolved in 100 ml of toluene, washed with water ten times, and unreacted dimethyl sulfoxide was removed. Toluene was filtered off under reduced pressure to obtain 16.0 g of bis (ethoxycarbonylmethyl) disulfide.

Preparation Example 2 Preparation of Bis (n-Butoxycarbonylmethyl) Disulfide

Except having used mercaptoacetic acid n-butyl, it oxidized like Example 1 and produced bis (n-butoxycarbonylmethyl) disulfide. Among these compounds, the presence of polysulfides above trisulfide could not be recognized.

Preparation Example 3 Preparation of Bis (n-octoxycarbonylmethyl) disulfide

Except having used mercaptoacetic acid n-octyl, it oxidized like Example 1 and produced bis (n-octoxycarbonylmethyl) disulfide. Among these compounds, the presence of polysulfides more than trisulfide could not be recognized.

Preparation Example 4 Preparation of Bis (2-Ethyl Hexoxycarbonylmethyl) Disulfide

Except having used mercaptoacetic acid 2-ethylhexyl, it oxidized like Example 1 and produced bis (2-ethyl hexafluorocarbonylmethyl) disulfide. Among these compounds, the presence of polysulfides more than trisulfide could not be recognized.

Preparation Example 5 Preparation of Bis (Isooctoxycarbonylmethyl) Disulfide

Except having used mercapto isocyanate acetate, it oxidized like Example 1 and produced bis (isooctoxy carbonylmethyl) disulfide. Among these compounds, the presence of polysulfides above trisulfide could not be recognized.

Preparation Example 6 Preparation of Bis (n-Steaoxycarbonylmethyl) disulfide

Mercaptoacetic acid stearyl was oxidized in the same manner as in Production Example 1 to prepare bis (steaoxycarbonylmethyl) disulfide. Among these compounds, the presence of polysulfides above trisulfide could not be recognized.

Preparation Example 7 Preparation of 1,1-bis (1-ethoxycarbonylethyl) disulfide

 A 1,1-bis (1-ethoxycarbonylethyl) disulfide was prepared in the same manner as in Production Example 1 except that ethyl α-mercaptopropionate was used. Among these compounds, the presence of polysulfides above trisulfide could not be recognized.

Comparative Production Example 1. Preparation of Bis (n-Butoxycarbonylmethyl) Polysulfide

Bis (n-butoxycarbonylmethyl) polysulfide was prepared by preparing sodium polysulfide from sodium sulfide and sulfur and then reacting with chloroacetic acid n-butyl. At this time, the average value of sulfur (x) of the sodium polysulfide (Na ₂ Sx) in order to compare with a disulfide of the present invention such that the 2 was adjusted to a molar ratio of sodium sulfide and sulfur. In addition, sodium polysulfide was used in excess of 5% so that chloroacetic acid n-butyl remained. Specifically, it reacted according to the method shown below, and bis (n-butoxycarbonylmethyl) polysulfide was manufactured. That is, 26.4 g of sodium sulfide hydrate, 3.52 g of sulfur, and 150 ml of 95% ethanol were added to a 500 ml four-necked flask equipped with a stirrer and a heating reflux, and heated and stirred for 5 hours in an 80 ° C oil bath. After cooling to room temperature, 30.12 g of chloroacetic acid n-butyl was added little by little, and it stirred at room temperature for 2 hours. The reaction solution was transferred to a separatory funnel, dissolved in 500 ml of toluene, and washed with water ten times. Toluene was filtered off under reduced pressure to obtain 2.6.5 g of bis (n-butoxycarbonylmethyl) polysulfide.

This compound was analyzed by high performance liquid chromatography [column: ODS, solvent: acetonitrile, detector: refractive index (RI) detector], and the result was monosulfide: 21%, disulfide: 40%, and trisulfide: 20 %, Tetrasulfide body: 12%, pentasulfide body: 4%. Each value represents mass%.

Comparative Production Example 2. Preparation of Bis (2-ethylhexyloxycarbonylmethyl) sulfide

To a 500 ml glass branched flask equipped with a Dean Stark dehydrator, 45.1 g of 2,2'-thiodiglycolic acid, 101.6 g of 2-ethylhexanol, and 2.0 g of p-toluenesulfonic acid monohydrate were added. Heated for 5 hours and then refluxed. After cooling, the reaction solution was transferred to a separatory funnel, washed twice with aqueous sodium hydrogen carbonate solution, and then washed with water five times. Toluene was filtered off under reduced pressure, and 120.0 g of bis (2-ethylhexyloxycarbonylmethyl) sulfide was obtained.

Example 1

1 mass of bis (ethoxycarbonylmethyl) disulfide obtained in Production Example 1 in 500 neutral fractions of mineral oil P 500 N (100 ° C kinematic viscosity 10.9 mm ² / s,% CA 0.1 or less) based on the total amount of the composition It added so that it may be%, the lubricating oil composition was prepared, and performance was evaluated. The results are shown in Table 1.

Examples 2-7

As shown in Table 1, the additives obtained in Production Examples 2 to 7 were added to the mineral oil P 500 N of 500 neutral oil so as to be 1% by mass based on the total amount of the composition, to prepare a lubricating oil composition and to evaluate the performance. The results are shown in Table 1.

Comparative Example 1

It carried out like Example 1 except having used bis (2-ethylhexyloxycarbonylmethyl) sulfide obtained by the comparative manufacture example 1 in Example 1. The results are shown in Table 1.

Comparative Example 2

It carried out like Example 1 except having used bis (n-butoxycarbonylmethylene) polysulfide obtained by the comparative manufacture example 2 in Example 1. The results are shown in Table 1.

Comparative Example 3

It evaluated like Example 1, without adding an additive to the mineral oil P500N of 500 neutral fraction. The results are shown in Table 1.

Preparation Example 8 Preparation of 1,1-bis (2-ethoxycarbonylethyl) disulfide

Ethyl α-mercaptopropionate was oxidized to dimethyl sulfoxide according to the method shown below to prepare 1,1-bis (2-ethoxycarbonylethyl) disulfide. Among these compounds, the presence of polysulfides above trisulfide could not be recognized.

20.9 g of ethyl (alpha)-mercaptopropionate and 30.8 g of dimethyl sulfoxides were put into the 100 ml collection flask, and it heated in the 20 degreeC oil bath for 8 hours. After cooling, the resultant was dissolved in 100 ml of toluene, washed with water ten times, and unreacted dimethyl sulfoxide was removed. Toluene was filtered off under reduced pressure to obtain 16.0 g of 1,1-bis (2-ethoxycarbonylethyl) disulfide.

Preparation Example 9 Preparation of 1,1-bis (2,2-ethylhexoxycarbonylethyl) disulfide

Mercaptoacetic acid 2-ethylhexyl was oxidized in the same manner as in Production Example 1 to prepare 1,1-bis (2-2-ethylhexoxycarbonylethyl) disulfide. The presence of polysulfides above trisulfide in this compound was not recognized.

Example 8

1,1-bis (2-ethoxycarbonylethyl) disulfide obtained in Production Example 8 was prepared with 500 neutral fractions of mineral oil P 500 N (100 ° C kinematic viscosity 10.9 mm ² / s,% CA 0.1 or less). Based on whole quantity, it added so that it may become 1 mass%, the lubricating oil composition was prepared, and performance was evaluated. The results are shown in Table 1.

Example 9

In Example 8, it carried out similarly to Example 8 except having used the 1, 1-bis (2-2-ethylhexyl carbonylethyl) disulfide obtained by the manufacture example 9. The results are shown in Table 2.

As is clear from the above examples and comparative examples, it can be seen that the lubricating oil composition using the additive of the present invention has a small wear mark diameter, and has a very high load resistance and wear resistance. In comparison with Comparative Example 1, when the additive for lubricating oil having a high content of a polysulfide compound having x of 3 or more in the general formula (I) and the general formula (IV) is used, the lubricating oil of the present invention is exhibited. It can be seen that the composition is low in corrosion resistance to nonferrous metals and is very good.

According to the present invention, a sulfur-based extreme pressure additive used for lubricating oils and fuel oils, and a lubricating oil composition comprising the above additives, having a higher load resistance and wear resistance than those of conventional sulfur-based extreme pressure additives, having low corrosion resistance to nonferrous metals, and A fuel oil composition can be provided.

Claims (16)

An additive for lubricating oil whose main component is a disulfide compound represented by the following formula (I): Formula I R ¹ OOC-A ¹ -S _x -A ² -COOR ² Where R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ¹ and A ² are each independently a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, x represents 2. Additives for lubricating oils based on disulfide compounds obtained by oxidatively coupling the mercaptoalkanecarboxylic acid esters represented by the following formulas (II) and / or (III): Formula II R ¹ OOC-A ¹ -SH Where R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ¹ is a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. Formula III R ² OOC-A ² -SH Where R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ² is a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. Additives for lubricating oils based on the disulfide compound represented by the following formula (IV): Formula IV R ¹ OOC-A ³ -S _x -A ⁴ -COOR ² Where R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ³ and A ⁴ are each independently a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ , R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, x represents 2. An additive for lubricating oil whose main component is a disulfide compound obtained by oxidatively coupling a mercaptoalkanecarboxylic acid ester represented by the following formula (V) and / or (VI): Formula V R ¹ OOC-A ³ -SH Where R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ³ is a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ , R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. Formula VI R ² OOC-A ⁴ -SH Where R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ⁴ is a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ , R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. The method of claim 1, Content of the polysulfide compound whose x is 3 or more in the said Formula (I) is 30 mass% or less based on the total amount with the said disulfide compound, The additive for lubricating oils characterized by the above-mentioned. The method of claim 3, wherein Content of the polysulfide compound whose x is 3 or more in the said general formula (IV) is 30 mass% or less based on the total amount with the said disulfide compound, The additive for lubricating oils characterized by the above-mentioned. An additive for fuel oil mainly containing a disulfide compound represented by the following formula (I): Formula I R ¹ OOC-A ¹ -S _x -A ² -COOR ² Where R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ¹ and A ² are each independently a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, x represents 2. An additive for fuel oil mainly comprising a disulfide compound obtained by oxidatively coupling the mercaptoalkanecarboxylic acid ester represented by the following formula (II) and / or (III): Formula II R ¹ OOC-A ¹ -SH Where R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ¹ is a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. Formula III R ² OOC-A ² -SH Where R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ² is a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. A fuel oil additive mainly containing a disulfide compound represented by the following formula (IV): Formula IV R ¹ OOC-A ³ -S _x -A ⁴ -COOR ² Where R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ³ and A ⁴ are each independently a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ , R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, x represents 2. An additive for fuel oil mainly comprising a disulfide compound obtained by oxidatively coupling the mercaptoalkanecarboxylic acid ester represented by the following general formula (V) and / or the following general formula (VI): Formula V R ¹ OOC-A ³ -SH Where R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ³ is a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ , R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. Formula VI R ² OOC-A ⁴ -SH Where R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may include an oxygen atom, a sulfur atom or a nitrogen atom, A ⁴ is a group represented by CR ⁵ R ⁶ -CR ⁷ R ⁸ , R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. The method of claim 7, wherein Content of the polysulfide compound whose x is 3 or more in the said Formula (I) is 30 mass% or less based on the total amount with the said disulfide compound, The additive for fuel oils characterized by the above-mentioned. The method of claim 9, In the formula (IV), the content of the polysulfide compound having x of 3 or more is 30% by mass or less based on the total amount with the disulfide compound. A lubricating oil composition comprising (A) a lubricating oil base oil and (B) the lubricating oil additive according to any one of claims 1 to 6. The method of claim 13, The lubricating oil composition whose content of (B) component is 0.01-50 mass%. A fuel oil composition comprising (X) fuel oil and (Y) the additive for fuel oil according to any one of claims 7 to 12. The method of claim 15, The fuel oil composition whose content of (Y) component is 0.01-1000 mass ppm.