JP5429728B2 - Lubricating oil composition - Google Patents

Description

  The present invention relates to a lubricating oil composition. In particular, the present invention relates to diesel engine lubricating oil compositions, more specifically trunk piston diesel engine lubricating oil compositions (ie, trunk piston engine oil (“TPEO”)) and crossheads (also referred to as two stroke or low speed). It relates to system oil for diesel engines.

Trunk piston diesel engines are used in marine, power and railway applications and have a rated speed of 300-1000 rpm. In trunk piston diesel engines, one lubricating oil composition is used for crankcase and cylinder lubrication. All the main moving parts of the engine, namely the main and big end bearings, camshaft and valve gear are lubricated by the pump circulation system. The cylinder liner is partially lubricated with oil from the circulation system that finds a way to the cylinder wall through the hole in the piston skirt via the splash lubrication and connecting rod and gadion pin. Crosshead diesel engines, on the other hand, are lubricated using two separate lubricants, engine cylinders are lubricated using marine diesel cylinder lubricants (ie, “MDCL”), and engine crankcases are separated by a system oil. It is lubricated using a lubricant.
Trunk piston diesel engines use a centrifuge system to remove contaminants such as soot or water from the lubricating oil composition. Similar centrifuge systems are used to process the system oil of some crosshead marine diesel engines. Centrifuge systems rely on the use of a sealing medium heavier than the lubricating oil composition. The sealing medium is generally water. As the lubricating oil composition passes through the centrifuge system, it comes into contact with water. Accordingly, the lubricating oil composition needs to be able to shed water and be stable in the presence of water. If the lubricating oil composition is unable to separate water, the water will accumulate in the lubricating oil composition, forming an emulsion, resulting in precipitates that accumulate in the centrifuge system, and the centrifuge system will operate properly Do not.

An object of the present invention is to provide a lubricating oil composition capable of separating a medium used in a centrifuge system.
Ship trunk piston engines operate with residual fuel containing a high concentration of asphaltenes. These engines have an essential engine sump that introduces asphaltenes into engine lubricants. Asphaltenes are high molecular weight compounds having multiple condensed aromatic rings and are generally insoluble in lubricating oils. They therefore accumulate on the engine surface producing harmful deposits. Trunk piston engines work better when asphaltenes can be dissolved.
Another object of the present invention is to provide a lubricating oil composition that exhibits improved asphaltene dispersibility.

In accordance with the present invention, there is provided a lubricating oil composition having a total base number of at least 15 mg KOH / g as determined by ASTM D2896, the composition comprising:
An oil having a lubricating viscosity of at least 40% by weight;
At least one overbased metal detergent;
It contains at least one compound of the following formula (I) and / or formula (II).

（式中、各Arは、独立して、アルキル、アルコキシ、アルコキシアルキル、アリールオキシ、アリールオキシアルキル、ヒドロキシ、ヒドロキシアルキル、ハロ及びこれらの組み合わせからなる群より選ばれる０〜３の置換基を有する芳香族部分を表し；
各Ｌは、独立して、炭素-炭素１重結合又は連結基を含む連結部分であり；
各Ｙは、独立して、-ＯＲ¹"又は式Ｈ(Ｏ(ＣＲ¹ ₂)_n)_yＸ-の部分であり（式中、Ｘは(ＣＲ¹'₂)_z、Ｏ及びＳからなる群より選ばれ；Ｒ¹及びＲ¹'は、それぞれ独立して、Ｈ、Ｃ₁〜Ｃ₆アルキル及びアリールから選ばれ；Ｒ¹"はＣ₁〜Ｃ₁₀₀アルキル及びアリールから選ばれ；ｚは１〜10であり；ｎは、Ｘが(ＣＲ¹'₂)_zである場合には０〜10であり、ＸがＯ又はＳである場合には２〜10であり；ｙは１〜30であり）；
各ａは、少なくとも１つのAr部分が少なくとも１つの基Ｙを有することを条件として、独立して、０〜３であり；
ｍは１〜100である。）

Wherein each Ar independently has 0 to 3 substituents selected from the group consisting of alkyl, alkoxy, alkoxyalkyl, aryloxy, aryloxyalkyl, hydroxy, hydroxyalkyl, halo and combinations thereof. Represents an aromatic moiety;
Each L is independently a linking moiety comprising a carbon-carbon single bond or linking group;
Each Y is independently -OR ¹ "or a part of the formula H (O (CR ¹ ₂ ) _n ) _y X- (where X consists of (CR ¹ ' ₂ ) _z , O and S R ¹ and R ¹ ′ are each independently selected from H, C ₁ -C ₆ alkyl and aryl; R ¹ ″ is selected from C ₁ -C ₁₀₀ alkyl and aryl; z is N is 0-10 when X is (CR ¹ ' ₂ ) _z , 2-10 when X is O or S; y is 1-30 And);
Each a is independently 0-3, provided that at least one Ar moiety has at least one group Y;
m is 1-100. )

（式中、各Ar'は、独立して、アルキル、アルコキシ、アルコキシアルキル、ヒドロキシ、ヒドロキシアルキル、アシルオキシ、アシルオキシアルキル、アシルオキシアルコキシ、アリールオキシ、アリールオキシアルキル、アリールオキシアルコキシ、ハロ及びこれらの組み合わせからなる群より選ばれる０〜３の置換基を有する芳香族部分を表し；
各Ｌ'は、独立して、炭素-炭素１重結合又は連結基を含む連結部分であり；
各Ｙ'は、独立して、式ＺＯ-又は式Ｚ(Ｏ(ＣＲ² ₂)_n')_y'Ｘ'-の部分であり（式中、Ｘ'は(ＣＲ²'₂)_z、Ｏ及びＳからなる群より選ばれ；Ｒ²及びＲ²'は、それぞれ独立して、Ｈ、Ｃ₁〜Ｃ₆アルキル及びアリールから選ばれ；ｚ'は１〜10であり；ｎ'は、Ｘ'が(ＣＲ²'₂)_z'である場合には０〜10であり、Ｘ'がＯ又はＳである場合には２〜10であり；ｙ'は１〜30であり；ＺはＨ、アシル基、ポリアシル基、ラクトンエステル基、酸エステル基、アルキル基又はアリール基であり）；
各ａ'は、少なくとも１つのAr'部分が少なくとも１つの基Ｙ'を有し、そのＺがＨでないことを条件として、独立して、０〜３であり；
ｍは１〜100である。）

Wherein each Ar ′ is independently from alkyl, alkoxy, alkoxyalkyl, hydroxy, hydroxyalkyl, acyloxy, acyloxyalkyl, acyloxyalkoxy, aryloxy, aryloxyalkyl, aryloxyalkoxy, halo and combinations thereof Represents an aromatic moiety having 0 to 3 substituents selected from the group consisting of:
Each L ′ is independently a linking moiety comprising a carbon-carbon single bond or linking group;
Each Y ′ is independently a moiety of formula ZO— or formula Z (O (CR ² ₂ ) _{n ′} ) _{y ′} X′—, where X ′ is (CR ² ′ ₂ ) _z , O R ² and R ² ′ are each independently selected from H, C ₁ -C ₆ alkyl and aryl; z ′ is 1-10; n ′ is X 0 'when' is (CR ² ' ₂ ) _z' , 2-10 when X 'is O or S; y' is 1-30; Z is H An acyl group, a polyacyl group, a lactone ester group, an acid ester group, an alkyl group or an aryl group);
Each a ′ is independently 0-3, provided that at least one Ar ′ moiety has at least one group Y ′ and the Z is not H;
m is 1-100. )

In accordance with the present invention, there is also provided a method of operating a trunk piston diesel engine having a centrifuge system including a sealing medium, the method comprising lubricating the engine with the lubricating oil composition. The sealing medium is preferably water.
According to the present invention, there is also provided a method of operating a crosshead diesel engine having a centrifuge system including a sealing medium, the method comprising lubricating the engine crankcase with the lubricating oil composition. The sealing medium is preferably water.
Also provided according to the present invention is the use of the above lubricating oil composition for lubricating trunk piston diesel engines and for reducing deposits.
Also provided according to the present invention is the use of the above lubricating oil composition for lubricating a crankcase of a crosshead diesel engine and for reducing deposits.
Also provided according to the present invention is the use of the above lubricating oil composition to improve asphaltene dispersibility in trunk piston diesel engines.

（式中、各Arは、独立して、アルキル、アルコキシ、アルコキシアルキル、アリールオキシ、アリールオキシアルキル、ヒドロキシ、ヒドロキシアルキル、ハロ及びこれらの組み合わせからなる群より選ばれる０〜３の置換基を有する芳香族部分を表し；各Ｌは、独立して、炭素-炭素１重結合又は連結基を含む連結部分であり；各Ｙは、独立して、-ＯＲ¹"又は式Ｈ(Ｏ(ＣＲ¹ ₂)_n)_yＸ-の部分であり（式中、Ｘは(ＣＲ¹'₂)_z、Ｏ及びＳからなる群より選ばれ；Ｒ¹及びＲ¹'は、それぞれ独立して、Ｈ、Ｃ₁〜Ｃ₆アルキル及びアリールから選ばれ；Ｒ¹"はＣ₁〜Ｃ₁₀₀アルキル及びアリールから選ばれ；ｚは１〜10であり；ｎは、Ｘが(ＣＲ¹'₂)_zである場合には０〜10であり、ＸがＯ又はＳである場合には２〜10であり；ｙは１〜30であり）；各ａは、少なくとも１つのAr部分が少なくとも１つの基Ｙを有することを条件として、独立して、０〜３であり；ｍは１〜100である。） Compounds of formula (I) and (II) are disclosed in co-pending U.S. Patent Application No. 11 / 061,800 filed on Feb. 18, 2005 (U.S. Patent No. 2006/0189492 published on Aug. 24, 2006). The subject matter of which is incorporated herein by reference. A compound of formula (I) represented by the formula:

Wherein each Ar independently has 0 to 3 substituents selected from the group consisting of alkyl, alkoxy, alkoxyalkyl, aryloxy, aryloxyalkyl, hydroxy, hydroxyalkyl, halo and combinations thereof. Each L is independently a linking moiety containing a carbon-carbon single bond or linking group; each Y is independently -OR ¹ "or the formula H (O (CR ¹ ₂ ) _n ) _y X-, wherein X is selected from the group consisting of (CR ¹ ' ₂ ) _z , O and S; R ¹ and R ¹ ' are each independently H, Selected from C ₁ -C ₆ alkyl and aryl; R ¹ ″ is selected from C ₁ -C ₁₀₀ alkyl and aryl; z is 1-10; n is X is (CR ¹ ′ ₂ ) _z 0-10 in the case, 2-10 if X is O or S; y is 1-30) Each a is the condition that at least one Ar moiety at least one group Y, are independently 0 to 3; m is 1 to 100).

  The aromatic moiety Ar of formula (I) may be a monocyclic carbocyclic moiety (phenyl) or a polynuclear carbocyclic moiety. The polynuclear carbocyclic moiety may include two or more fused rings, each ring having 4 to 10 carbon atoms (eg, naphthalene), or a linked monocyclic aromatic moiety such as biphenyl. Or it may contain a fused fused ring (eg binaphthyl). Examples of suitable polynuclear carbocyclic aromatic moieties include naphthalene, anthracene, phenanthrene, cyclopentenophenanthrene, benzanthracene, dibenzanthracene, chrysene, pyrene, benzpyrene and coronene, and their dimers, trimers And more multimers. Ar can also represent a monocyclic or polynuclear heterocyclic moiety. Heterocyclic moieties Ar include those containing one or more rings each containing 4 to 10 atoms containing one or more heteroatoms selected from N, O and S. Examples of suitable monocyclic heteroaromatic moieties include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine and purine. Suitable polynuclear heterocyclic moieties Ar include, for example, quinoline, isoquinoline, carbazole, dipyridyl, cinnoline, phthalazine, quinazoline, quinoxaline and phenanthroline. Each aromatic moiety (Ar) may be independently selected so that all Ar moieties are the same or different. Polycyclic carbocyclic aromatic moieties are preferred. Most preferred are compounds of formula I, wherein each Ar is naphthalene. Each aromatic moiety Ar may independently be unsubstituted or substituted with 1 to 3 substituents selected from alkyl, alkoxy, alkoxyalkyl, hydroxyl, hydroxyalkyl, halo and combinations thereof. . Preferably, each Ar is unsubstituted except for the group Y and the terminal group.

Each linking group (L) may be the same or different, and may be a carbon-carbon single bond between carbon atoms of adjacent portions Ar, or may be a linking group. Suitable linking groups include alkylene bonds, ether bonds, diacyl bonds, ether-acyl bonds, amino bonds, amide bonds, carbamide bonds, urethane bonds and sulfur bonds. Preferred linking groups include alkylene bonds, such as —CH ₃ CHC (CH ₃ ) ₂ — or —C (CH ₃ ) ₂ —; diacyl bonds, such as —COCO— or —CO (CH ₂ ) ₄ CO—; and sulfur bonds. For example, -S ₁ -or -S _x- . A more preferred linking group is an alkylene bond, most preferably —CH ₂ —.
Preferably, Ar in formula (I) represents naphthalene, more preferably Ar is derived from 2- (2-naphthyloxy) -ethanol. Preferably, each Ar is derived from 2- (2-naphthyloxy) -ethanol and m is 2-25. Preferably, Y in formula (I) is a group H (O (CR ₂ ) ₂ ) _y O—, where y is 1-6. More preferably, Ar is naphthalene, Y is HOCH ₂ CH ₂ O—, and L is —CH ₂ —.

Methods for producing compounds of formula (I) will be apparent to those skilled in the art. A hydroxyl aromatic compound, such as naphthol, can be reacted with an alkylene carbonate (eg, ethylene carbonate) to provide a compound of formula AR- (Y) _a . Preferably, the hydroxyl aromatic compound and alkylene carbonate are reacted at a temperature of about 25 to about 300 ° C., preferably at a temperature of about 50 to about 200 ° C., in the presence of a base catalyst such as aqueous sodium hydroxide. During the reaction, water may be removed from the reaction mixture by azeotropic distillation or other conventional means. If separation of the resulting intermediate product is desired, upon completion of the reaction (indicated by CO ₂ release cessation), the reaction product may be collected and cooled to solidify. Alternatively, hydroxyl aromatic compounds such as naphthol can be reacted with epoxides such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide to incorporate one or more oxy-alkylene groups.

To form the compound of formula (I), the resulting intermediate compound Ar— (Y) _a can be further converted to a polyhalogenated (preferably dihalogenated) hydrocarbon (eg, 1-4-dichlorobutane, 2,2 -Dichloropropane etc.) or a di- or poly-olefin (eg butadiene, isoprene, divinylbenzene, 1,4-hexadiene, 1,5-hexadiene etc.) to react with an alkylene (I) You may obtain the compound of. Reaction of the Ar— (Y) _a moiety with a ketone or aldehyde (eg, formaldehyde, acetone, benzophenone, acetophenone, etc.) provides an alkylene-linked compound. Acyl-linked compounds are formed by reacting an Ar- (Y) _a moiety with a diacid or acid anhydride (eg, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, succinic anhydride, etc.). Also good. Sulfide bonds, polysulfide bonds, sulfinyl bonds and sulfonyl bonds include an Ar- (Y) _a moiety and a suitable bifunctional sulfiding agent (eg, sulfur monochloride, sulfur dichloride, thionyl chloride (SOCl ₂ ), sulfuryl chloride ( SO ₂ Cl ₂ ) etc.). To provide a compound of formula (I) having an alkylene ether linkage, the Ar- (Y) _a moiety can be reacted with divinyl ether. Compounds of formula (I), wherein L is a direct carbon-carbon bond, are described, for example, in the document J. Polymer Science: Polymer Chem. Ed., 21, 457 (1983) by P. Kovacic et al. It may also be formed by oxidative coupling polymerization using a mixture of aluminum chloride and copper (I) chloride. Alternatively, such compounds can be prepared as described in, for example, MG Stevens, KMSellers, S. Subramoney and HC Foley “Catalytic Benzene Coupling on Caesium / Nanoporous Carbon Catalysts” Chemical Communications, pages 2679-2680 (1988). -(Y) You may form by reaction of _a part and an alkali metal.

In order to form a preferred compound of formula (I) having an alkylene linking group, more preferably a methylene linking group, the remaining base in the Ar- (Y) _a reaction mixture is acid, preferably an excess of acid (e.g. Neutralized with sulfonic acid) and reacted with an aldehyde, preferably formaldehyde, preferably in the presence of residual acid, to provide an alkylene bridged, preferably methylene bridged compound of formula (I). The degree of polymerization of the compound of formula (I) is from 2 to about 101 (corresponding to the value of m being from 1 to about 100), preferably from about 2 to about 50, most preferably from about 2 to about 25. .

（式中、各Ar'は、独立して、アルキル、アルコキシ、アルコキシアルキル、ヒドロキシ、ヒドロキシアルキル、アシルオキシ、アシルオキシアルキル、アシルオキシアルコキシ、アリールオキシ、アリールオキシアルキル、アリールオキシアルコキシ、ハロ及びこれらの組み合わせからなる群より選ばれる０〜３の置換基を有する芳香族部分を表し；各Ｌ'は、独立して、炭素-炭素１重結合又は連結基を含む連結部分であり；各Ｙ'は、独立して、式ＺＯ-又は式Ｚ(Ｏ(ＣＲ² ₂)_n')_y'Ｘ'-の部分であり（式中、Ｘ'は(ＣＲ²'₂)_z、Ｏ及びＳからなる群より選ばれ；Ｒ²及びＲ²'は、それぞれ独立して、Ｈ、Ｃ₁〜Ｃ₆アルキル及びアリールから選ばれ；ｚ'は１〜10であり；ｎ'は、Ｘ'が(ＣＲ²'₂)_z'である場合には０〜10であり、Ｘ'がＯ又はＳである場合には２〜10であり；ｙ'は１〜30であり；ＺはＨ、アシル基、ポリアシル基、ラクトンエステル基、酸エステル基、アルキル基又はアリール基であり）；各ａ'は、少なくとも１つのAr'部分が少なくとも１つの基Ｙ'を有し、そのＺがＨでないことを条件として、独立して、０〜３であり；ｍは１〜100である。）
式（II）の好ましい化合物としては、少なくとも１つのAr'部分が少なくとも１つの基Ｚ(Ｏ(ＣＲ² ₂)_n')_y'Ｘ'-（式中、ＺはＨではない）を有する化合物が挙げられる。 A compound of formula (II) can be formed by reacting a compound of formula (I) with at least one of an acylating agent, an alkylating agent and an arylating agent and is represented by the following formula:

Wherein each Ar ′ is independently from alkyl, alkoxy, alkoxyalkyl, hydroxy, hydroxyalkyl, acyloxy, acyloxyalkyl, acyloxyalkoxy, aryloxy, aryloxyalkyl, aryloxyalkoxy, halo and combinations thereof Represents an aromatic moiety having 0 to 3 substituents selected from the group consisting of; each L ′ is independently a linking moiety containing a carbon-carbon single bond or linking group; and each Y ′ is independently And a moiety of formula ZO- or formula Z (O (CR ² ₂ ) _{n '} ) _y' X'- (where X 'is from the group consisting of (CR ² ' ₂ ) _z , O and S R ² and R ² ′ are each independently selected from H, C ₁ -C ₆ alkyl and aryl; z ′ is 1-10; n ′ is X ′ (CR ² ′ ₂ ) When _{z '} is 0-10, X' is O or S In some cases 2 to 10; y ′ is 1 to 30; Z is H, acyl group, polyacyl group, lactone ester group, acid ester group, alkyl group or aryl group); each a ′ is , Independently at least one Ar ′ moiety has at least one group Y ′, and Z is not H, independently 0-3; m is 1-100.)
Preferred compounds of formula (II) are compounds in which at least one Ar ′ moiety has at least one group Z (O (CR ² ₂ ) _{n ′} ) _{y ′} X′—, where Z is not H Is mentioned.

  Suitable acylating agents include hydrocarbyl carbonic acid, hydrocarbyl carbonic acid halides, hydrocarbyl sulfonic acid and hydrocarbyl sulfonic acid halides, hydrocarbyl phosphoric acid and hydrocarbyl phosphoric acid halides, hydrocarbyl isocyanate and hydrocarbyl succinic acid acylating agents. Preferred acylating agents include hydrocarbyl isocyanates having 8 or more carbon atoms, such as dodecyl isocyanate and hexadodecyl isocyanate, and hydrocarbyl acylating agents having 8 or more carbon atoms, more preferably polybutenyl or polyisobutenyl succinic anhydride (PIBSA). Polybutenyl succinic acylating agent. Preferably, the hydrocarbyl succinic acylating agent has a number average molecular weight (average Mn) of about 100 to 5000, preferably about 200 to about 3000, more preferably about 450 to about 2500. Preferred hydrocarbyl isocyanate acylating agents have a number average molecular weight (average Mn) of from about 100 to 5000, preferably from about 200 to about 3000, more preferably from about 200 to about 2000.

The acylating agent can be prepared by conventional methods known to those skilled in the art, for example, chlorine-assisted methods, thermal methods, and radical grafting methods. The acylating agent may be monofunctional or polyfunctional. Preferably, the acylating agent has a functionality of less than 1.3. Here, the functionality (F) is determined according to the following formula.
F = (SAP × average Mn) / ((112,200 × AI) − (SAP × MW))
Where SAP is the saponification value (ie, milligrams of KOH consumed during complete neutralization of acid groups in 1 g of acyl group-containing reaction product (determined according to ASTM D94)), average Mn is the number average molecular weight of the starting polyalkene, AI is the proportion of active components of the acyl group-containing reaction product (the rest are unreacted polyalkene, saturateds, acylating agent and diluent), MW Is the molecular weight of the acyl group (eg 98 for succinic anhydride).
Acylating agents are used in the manufacture of dispersants, and a more detailed description of the method of forming the acylating agent will be given later in the description of suitable dispersants.
Suitable alkylating agents include alkane alcohols having 8 to 30 carbon atoms, preferably alkane alcohols having 8 to 18 carbon atoms. Suitable arylating agents include alkane substituted aryl mono- or polyhydroxides having 8 to 30 carbon atoms, preferably 8 to 18 carbon atoms.

  The molar amount of the compound of formula (I) and the acylating agent, alkylating agent and / or arylating agent is such that all or only a part of the Y group, for example 25% or more, 50% or more or 75% or more, 'Can be adjusted to be converted to a base. When the compound of formula (I) has a hydroxy and / or alkylhydroxy substituent, when the compound reacts with an acylating group, all or part of the hydroxy and / or alkylhydroxy substituent is converted to an acyloxy or acyloxyalkyl group. Expected to be converted. When a compound of formula (I) has a hydroxy and / or alkylhydroxy substituent, when the compound reacts with an arylating group, all or part of said hydroxy and / or alkylhydroxy substituent is aryloxy or aryloxyalkyl It is expected to be converted to the base. Accordingly, compounds of formula (II) substituted with an acyloxy, acyloxyalkyl, aryloxy and / or aryloxyalkyl group are considered within the scope of the present invention. Z is an acylating group resulting from neutralization with a base (which may occur due to interaction with a metal detergent, for example in either additive package or formulated lubricant) Salt forms of the compound of formula (II) are also considered to be included within the scope of the present invention.

（式中、１又は２以上のＹ'は基Ｚ(Ｏ(ＣＲ² ₂)_n')_y'Ｘ'-（式中、Ｚは下記式（IV）のラクトンエステル、下記式（Ｖ）の酸エステル又はこれらの組合せから誘導され；

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁵、Ｒ⁷及びＲ⁸は、Ｈ、最大200個の炭素原子を含むアルキル及びポリアルキル及びポリアルケニルから独立して選択される。）
及びＺは下記式（VI）のビスアシルである。

（式中、Ｒ⁹及びＲ¹⁰はＨ、最大300個の炭素原子を含むアルキル及びポリアルキル及びポリアルケニルから独立して選択される。））であり；ｍは０〜100であり；ｐ及びｓはそれぞれ独立して約０〜約25であるが、ｐ≦ｍ'；ｓ≦ｍ'；及びｐ＋ｓ≧１である。） One preferred type of compound of formula (II) is a compound of formula (III) below.

(In the formula, one or more Y 'is a group Z (O (CR ² ₂ ) _n' ) _{y '} X'- (wherein Z is a lactone ester of the following formula (IV), Derived from acid esters or combinations thereof;

Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁵ , R ⁷ and R ⁸ are independently selected from H, alkyl containing up to 200 carbon atoms and polyalkyl and polyalkenyl. .)
And Z is a bisacyl of the following formula (VI).

Wherein R ⁹ and R ¹⁰ are independently selected from H, alkyl and polyalkyl and polyalkenyl containing up to 300 carbon atoms); m is from 0 to 100; p and Each s is independently about 0 to about 25, but p ≦ m ′; s ≦ m ′; and p + s ≧ 1. )

Preferred compounds of formula (III) are those in which about 2% to about 98% of the Y ′ units are Z (O (CR ² ₂ ) ₂ ) _{y ′} O— (wherein Z is an acyl group and y ′ is 1 And about 98% to 2% of the Y ′ units are —OR ² , such as Ar is naphthalene; about 2% to about 98% of the Y ′ units are ZOCH _2. Compounds of formula (III) wherein CH ₂ O—, about 98% to 2% of Y ′ units are —OCH ₃ ; and L ′ is CH ₂ . Particularly preferably, Ar ′ is naphthalene; about 40% to about 60% of Y ′ units are ZOCH ₂ CH ₂ O—, and about 60% to 40% of Y ′ units are —OCH ₃ ; m Compounds of formula (III) wherein 'is from about 2 to about 25; p is from 1 to about 10; and s is from about 1 to about 10. Preferably, the group Z of formula (III) is derived from a polyalkyl or polyalkenyl succinic acylating agent (derived from a polyalkene having an average Mn of about 100 to about 5000) or a hydrocarbyl isocyanate.

The compound of formula (II) comprises an acylating agent and a liquid acid catalyst such as sulfonic acid, such as dodecylbenzenesulfonic acid, paratoluenesulfonic acid or polyphosphoric acid, or Amberlyst-15, Amberlyst By reacting at a temperature of about 0 ° C. to about 300 ° C., preferably about 50 ° C. to about 250 ° C. in the presence of a solid acid catalyst such as -36, zeolite, inorganic acid clay or tungsten polyphosphoric acid. Can be derived from Under the above conditions, preferred polybutenyl succinic acylating agents can form diesters, acid esters or lactone esters with compounds of formula (I).
The compound of formula (II) is a compound of formula (I) with an alkylating or arylating agent, preferably a liquid acid catalyst such as triphenylphosphine and diethyl azodicarboxylate (DEAD), sulfonic acid, such as dodecylbenzene. In the presence of a solid acid catalyst such as sulfonic acid, paratoluenesulfonic acid or polyphosphoric acid, or Amberlyst-15, Amberlyst-36, zeolite, inorganic acid clay or tungsten polyphosphoric acid, preferably from about 0 ° C to about 300 ° C, preferably It can be derived from a compound of formula (I) by reacting at about 50 ° C to about 250 ° C.
Preferably, the lubricating oil composition comprises about 0.005% to 15%, preferably about 0.1% to about 5%, more preferably about 0.5% by weight of the compound of formula (I) and / or (II). % To about 2% by weight, preferably about 0.005% to 15% by weight, for example about 0.1% to about 5% by weight, more preferably about 0.5% to about 2% by weight, of the compound of formula (II).

Oils of lubricating viscosity useful in the context of the present invention may be selected from natural lubricating oils, synthetic lubricating oils, and mixtures thereof. The lubricating oil may have a viscosity ranging from light distillate mineral oil to heavy lubricating oil such as gasoline engine oil, inorganic lubricating oil and heavy duty diesel oil. In general, the viscosity of the oil is from about 2 centistokes to about 40 centistokes, particularly from about 4 centistokes to about 20 centistokes when measured at 100 ° C.
Natural oils include animal oils and vegetable oils (eg, castor oil, lard oil); liquid petroleum and paraffinic, naphthenic and mixed paraffin-naphthenic type hydrorefining, solvent-treated or acid-treated mineral oils, and the like. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include polymerized and copolymerized olefins (eg, polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly (1-hexene), poly (1-octene), poly (1-decene)), etc. Hydrocarbon oils and halo-substituted hydrocarbon oils; alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene); polyphenols (eg, biphenyl, terphenyl, alkylated polyphenols); and alkyls Diphenyl ether and alkylated diphenyl sulfide and derivatives, analogs and homologues thereof. Also useful are synthetic oils obtained by a gas-to-liquid process from Fischer-Tropsch synthetic hydrocarbons, commonly referred to as gas to liquid or “GTL” base oils.

Alkylene oxide polymers and interpolymers and their derivatives, wherein the terminal hydroxyl groups are modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. Examples of these include polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of polyoxyalkylene polymers (for example, methyl-polyisopropylene glycol ether with a molecular weight of 1000 or molecular weight of 1000-1500. Diphenyl ethers of polyethylene glycol); and their mono- and polycarboxylic acid esters, such as acetate esters, mixed C ₃ -C ₈ fatty acid esters and C ₁₃ oxo acid diesters of tetraethylene glycol.
Other suitable types of synthetic lubricating oils include dicarboxylic acids (eg, phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid. Includes esters of acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid) with various alcohols (eg butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol) It is. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, phthalic acid Examples include didecyl, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by the reaction of 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid. .
Esters useful as synthetic oils include those synthesized from C ₅ -C ₁₂ monocarboxylic acids and polyols, and polyols such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. Examples include ether.

Silicone base oils such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-silicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetra Isopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-2-ethylhexyl) silicate, tetra- (p-tert-butyl-phenyl) silicate, hexa- (4-methyl-2-ethylhexyl) di Mention may be made of siloxanes, poly (methyl) siloxanes and poly (methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and tetrahydrofuran polymers.
The oil of lubricating viscosity may comprise a base oil blend of Group I, Group II or Group III, base stock or these base stocks. Preferably, the oil of lubricating viscosity is a Group II or Group III base stock or a mixture thereof, or a mixture of a Group I base stock and one or more of Group II and Group III. Preferably, the majority of the oil of lubricating viscosity is a Group II, Group III, Group IV or Group V base stock, or a mixture thereof. The base stock or base stock mixture preferably has a saturate content of at least 65%, more preferably at least 75%, such as at least 85%. Most preferably, the base stock or base stock mixture has a saturated component content greater than 90%. Preferably, the sulfur content of such oils or oil mixtures is less than 1% by weight, preferably less than 0.6% by weight, more preferably less than 0.4% by weight.

Preferably, the volatility of such an oil or oil mixture is 30% or less, preferably 25% or less, more preferably 20% or less, most preferably 16% or less, as measured by the Noack volatility test (ASTM D5880). It is. Preferably, the viscosity index (VI) of such an oil or oil mixture is at least 85, preferably at least 100, most preferably about 105-140.
The definitions of base stock and base oil in the present invention are found in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System”, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. It is the same. The publication classifies base oils as follows.
a) Group I base oils contain less than 90% saturated components and / or more than 0.03% sulfur and have a viscosity index of 80 to less than 120 using the test methods specified in Table 1 below.
b) Group II base oils, using the test methods specified in Table 1 below, contain 90% or more of saturated components and 0.03% or less of sulfur and have a viscosity index of 80 or more and less than 120.
c) Group III base oils, using the test methods specified in Table 1 below, contain 90% or more saturated components and 0.03% or less sulfur and have a viscosity index of 120 or more.
d) Group IV base oil is polyalphaolefin (PAO).
e) Group V base oils are all other base stocks not included in Group I, II, III or IV.

The lubricating oil composition includes at least one overbased metal detergent. Detergents are additives that reduce the formation of engine deposits, such as high temperature varnish and lacquer deposits, have acid neutralization capability, and hold the finally separated solids in suspension Can do. It is based on a metal “soap” and is a metal salt of an acidic organic compound, often referred to as a surfactant.
The cleaning agent includes a polar head with a long hydrophobic tail. Overbased cleaning comprising a detergent that is neutralized as an outer layer of a metal base (eg, carbonate) micelle by reacting an excess metal compound (eg, oxide or hydroxide) with an acid gas (eg, carbon dioxide) By obtaining the agent, a large amount of metal base is included.
The detergent is preferably an alkali metal or alkaline earth metal additive, for example a surfactant selected from phenol, sulfonic acid, carboxylic acid, salicylic acid and naphthenic acid, overbased oil-soluble or oil-dispersible calcium, magnesium, sodium Or a barium salt, overbasing is provided by an oil-insoluble salt of a metal, such as carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, and is stabilized by an oil-soluble salt of a surfactant. The metal of the oil-soluble surfactant salt may be the same as or different from the metal of the oil-insoluble salt. Preferably, the metal is calcium, whether it is an oil-soluble surfactant metal or an oil-insoluble salt metal.

The detergent TBN may be low (ie, less than 50 mg KOH / g), intermediate (ie, 50-150 mg KOH / g), or high (ie, as determined by ASTM D2896). , Over 150 mg KOH / g). Preferably the TBN is medium or high (ie greater than 50 TBN). More preferably, the TBN is at least 60, more preferably at least 100, more preferably at least 150, as determined by ASTM D2896, up to 500, for example up to 350 mg KOH / g.
Surfactants for overbased detergent surfactant systems preferably contain one or more hydrocarbyl groups, for example as substituents on the aromatic ring. As used herein, the term “hydrocarbyl” refers to a feature in which the group consists primarily of hydrogen and carbon atoms and is bonded to the rest of the molecule by a carbon atom, but the group is substantially hydrocarbon. It means that the presence of an insufficient proportion of other atoms or groups to lose is not excluded. The hydrocarbyl group of the surfactant used according to the invention is advantageously an aliphatic group, preferably an alkyl or alkylene group, in particular an alkyl group (which may be linear or branched). The total number of carbon atoms in the surfactant must be at least sufficient to provide the desired oil solubility.
The phenol used in the preparation of the cleaning agent may be unsulfurized or preferably sulfurized. Furthermore, as used herein, the term “phenol” includes those containing more than one hydroxyl group (eg, alkylcatechol) or fused aromatic rings (eg, alkylnaphthol), modified by chemical reaction. Such as alkylene bridged and Mannich base condensation and saligenin types (produced by reaction of phenol and aldehyde under basic conditions).

（式中、Ｒはヒドロカルビル基を表し、ｙは１〜４を表す。）
ｙが１よりも大きい場合、そのヒドロカルビル基は、同一または異なるものであってもよい。
前記フェノールは、しばしば硫化形で使用される。硫化ヒドロカルビルフェノールは、典型的には下記式によって示されてもよい。

（式中、ｘは、一般に１〜４である。）
場合によっては、２個よりも多いフェノール分子をＳ_xブリッジによって結合してもよい。 Preferred phenols may be derived from the following formula:

(In the formula, R represents a hydrocarbyl group, and y represents 1 to 4.)
When y is greater than 1, the hydrocarbyl groups may be the same or different.
The phenol is often used in sulfurized form. The sulfurized hydrocarbyl phenol may typically be represented by the following formula:

(Wherein x is generally 1 to 4)
In some cases, more than two phenol molecules may be linked by S _x bridges.

In each of the above formulas, the hydrocarbyl group represented by R is advantageously an alkyl group, which is advantageously 5 to 100, preferably 5 to 40, especially 9 to 12 carbon atoms. The average number of carbon atoms in the entire R group is at least 9 to ensure proper solubility in oil. A preferred alkyl group is a nonyl (tripropylene) group.
In the following description, the hydrocarbyl-substituted phenol is referred to as alkylphenol for convenience.
The sulfurizing agent used to prepare the sulfurized phenol or phenate may be any compound or element that introduces a-(S) _x -bridge group between alkylphenol monomer groups, where x is generally 1-4. . Thus, the reaction may be carried out with elemental sulfur or a halide thereof, such as sulfur dichloride or more preferably sulfur monochloride. When elemental sulfur is used, the sulfurization reaction can be carried out by heating the alkylphenol compound at 50-250 ° C, preferably at least 100 ° C. The use of elemental sulfur typically provides a mixture of-(S) _x -bridge groups as described above. When sulfur halides are used, the sulfurization reaction can be carried out by treating the alkylphenol at -10 to 120 ° C, preferably at least 60 ° C. The reaction can be carried out in the presence of a suitable diluent. The diluent advantageously comprises a substantially inert organic diluent such as mineral oil or alkane. In any case, the reaction is carried out for a time sufficient to effect a substantial reaction. In general, it is preferred to use 0.1 to 5 moles of alkylphenolic material per equivalent of sulfurizing agent.
When elemental sulfur is used as the sulfiding agent, it may be desirable to use a basic catalyst such as sodium hydroxide or an organic amine, preferably a heterocyclic amine (eg morpholine).
Details of the sulfiding process are well known to those skilled in the art.

Regardless of the method of manufacture, the sulfurized alkylphenols useful in the preparation of the overbased detergent generally comprise a diluent and unreacted alkylphenol, generally 2 to 20% by weight, preferably based on the weight of the sulfurized alkylphenol. It contains 4 to 14% by weight, most preferably 6 to 12% by weight of sulfur.
As mentioned above, the term “phenol” as used herein includes, for example, phenols modified by chemical reaction with aldehydes and Mannich base condensed phenols.
Examples of aldehydes that may be modified with phenol include formaldehyde, propionaldehyde, and butyraldehyde. A preferred aldehyde is formaldehyde. Suitable aldehyde-modified phenols for use are described, for example, in US Pat. No. 5,259,967.
Mannich base condensed phenol is prepared by reaction of phenol, aldehyde and amine. Examples of suitable Mannich base condensed phenols are described in GB-A-2121432.
In general, the phenol may contain substituents other than those described above as long as such substituents do not significantly reduce the surfactant properties of the phenol. Examples of such substituents are methoxy groups and halogen atoms.

The salicylic acids used in accordance with the present invention may be sulfurized or sulfurized, may be chemically modified and / or may have further substituents as described above for example for phenol. Similar methods as described above can be used in the sulfidation of hydrocarbyl-substituted salicylic acids and are well known to those skilled in the art. Salicylic acid is typically prepared by carboxylation by the Kolbe-Schmitt method of phenoxide, which is generally obtained in a mixture with uncarboxylated phenol (usually in a diluent).
A preferred substituent in the oil-soluble salicylic acid from which the overbased detergent of the present invention can be derived is the substituent represented by R in the above description of phenol. In alkyl-substituted salicylic acid, the alkyl group advantageously contains 5 to 100, preferably 9 to 30, especially 14 to 20 carbon atoms.
The sulfonic acids used according to the present invention are typically hydrocarbyl substituted, especially alkyl-substituted aromatic hydrocarbons, eg by sulfonation of hydrocarbons obtained by fractionation of petroleum by distillation and / or extraction or by alkylation of aromatic hydrocarbons. Can be obtained. Examples include hydrocarbons obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene or chloronaphthalene. Alkylation of aromatic hydrocarbons is carried out in the presence of a catalyst in the range of 3-100 such as haloparaffins, olefins obtainable by paraffin dehydrogenation, and polyolefins such as polymers of ethylene, propylene and / or butene. It can be carried out with alkylating agents having more than one carbon atom. These alkylaryl sulfonic acids usually contain from 7 to 100 or more carbon atoms. These sulfonic acids preferably contain 16 to 80 or 12 to 40 carbon atoms per alkyl-substituted aromatic component, depending on the raw material to be obtained.

When preparing these sulfonates by neutralizing these alkylaryl sulfonic acids, hydrocarbon solvents and / or diluent oils, and accelerators and viscosity modifiers may also be included in the reaction mixture.
Another type of sulfonic acid that may be used in accordance with the present invention includes alkylphenol sulfonic acids. Such sulfonic acids can be sulfurized. These sulfonic acids, whether sulfurized or non-sulfided, have surfactant properties comparable to those of sulfonic acid rather than surfactant properties comparable to those of phenol. I believe.
Sulfonic acids suitable for use in accordance with the present invention also include alkyl sulfonic acids such as alkenyl sulfonic acids. In such compounds, the alkyl group suitably contains 9 to 100, preferably 12 to 80, in particular 16 to 60 carbon atoms.
Carboxylic acids that may be used in accordance with the present invention include mono- and dicarboxylic acids. Preferred monocarboxylic acids are monocarboxylic acids containing 1 to 30, especially 8 to 24 carbon atoms. (When this specification indicates the number of carbon atoms in the carboxylic acid, the carbon atom of the carboxyl group is included in the number.) Examples of monocarboxylic acids are isooctanoic acid, stearic acid, oleic acid, palmitic acid and behenic acid. It is. Isooctanoic acid may optionally be used in the form of a C ₈ acid isomer mixture commercially available from Exxon Chemicals under the trade name “Cekanoic”. Other suitable acids are acids having tertiary substitution at the α-carbon atom and dicarboxylic acids having more than 2 carbon atoms apart from the carboxyl group. Furthermore, dicarboxylic acids having more than 35, for example 36-100 carbon atoms, are also suitable. Unsaturated carboxylic acids can be sulfided. Although salicylic acid contains a carboxyl group, for the purposes of the present invention, it is considered a separate group of surfactants and not a carboxylic acid surfactant. (Salicylic acid contains a hydroxyl group but is not considered a phenol surfactant).

Examples of other surfactants that can be used in accordance with the present invention include the following compounds and their derivatives: naphthenic acids, especially naphthenic acids, dialkylphosphonic acids, dialkylthios containing one or more alkyl groups. Phosphonic acid and dialkyldithiophosphonic acid, high molecular weight (preferably ethoxylated) alcohol, dithiocarbamic acid, thiophosphine, and dispersant. These types of surfactants are well known to those skilled in the art. Hydrocarbyl-substituted carboxyalkylene-linked phenol type surfactants, or dihydrocarbyl esters of alkylene dicarboxylic acids in which the alkylene group is substituted with a hydroxy group and a further carboxylic acid group, or at least one hydrocarbyl-substituted phenol and aromatic component Also suitable for use in the present invention are alkylene-linked polyaromatic molecules containing one carboxyphenol. Such surfactants are described in EP 708171.
Another example of a detergent useful in the present invention is an alkaline earth sulfide modified with a carboxylic acid such as stearic acid, as described, for example, in EP 271262 (LZ-Adibis). The metal hydrocarbyl phenates and phenolates as described in EP 750659 (Chevron).

Also, at least two surfactant groups, such as overbased metal compounds including phenol, sulfonic acid, carboxylic acid, salicylic acid and naphthenic acid, preferably overbased calcium detergents, are suitable for use in the present invention. And may be obtained by production of a hybrid material to which two or more different surfactant groups are added during the overbasing process.
Examples of hybrid materials include surfactant phenol and sulfonic acid overbased calcium salts, surfactant phenol and carboxylic acid overbased calcium salts, surfactant phenol, sulfonic acid and salicylic acid overbased calcium salts, And overbased calcium salts of surfactants phenol and salicylic acid.
If there are at least two overbased metal compounds, they may be used in any suitable weight ratio, preferably the weight ratio of the other metal overbased compound to one overbased metal compound is 5:95. 95: 5, for example 90:10 to 10:90, more preferably 20:80 to 80:20, in particular 70:30 to 30:70, advantageously 60:40 to 40:60.
The hybrid detergent preferably comprises at least 5% by weight salicylate, more preferably at least 10% by weight salicylate. The hybrid detergent preferably contains 5% by weight or more of phenate. The amount of salicylate and phenate in the hybrid detergent can be determined using techniques well known to those skilled in the art, such as chromatography, spectroscopy and / or titration. The hybrid detergent may also contain other surfactants such as sulfonates, sulfurized phenates, thiophosphates, naphthenates or oil soluble carboxylates. The hybrid detergent may contain 5% by weight or more sulfonate. Surfactants are added during the overbasing process.
Specific examples of hybrid materials are described in, for example, WO 97/46643 pamphlet, 97/46644 pamphlet, 97/46645 pamphlet, 97/46646 pamphlet and 97/46647 pamphlet. It is what.

“Surfactant overbased calcium salt” means an overbased detergent in which the metal cation of the oil-insoluble metal salt is essentially a calcium cation. Small amounts of other cations may be present in the oil-insoluble metal salt, but are typically at least 80 mol%, more typically at least 90 mol%, such as at least 95 in the oil-insoluble metal salt. The mol% cation is calcium ion. Cations other than calcium are derived, for example, by the use in the manufacture of overbased detergents of surfactant salts where the cation is a metal other than calcium. Also preferably, the surfactant metal salt is calcium.
Preferably, the TBN of the hybrid detergent is at least 300 mg KOH / g, for example at least 330 mg KOH / g, more preferably at least 350 mg KOH / g, more preferably at least 400 mg KOH / g as determined by ASTM D2896. And most preferably in the range of 400 to 600 mg KOH / g, for example up to 500 mg KOH / g.
Preferably, the amount of surfactant in the lubricating oil composition is 0.5% by weight or more, preferably in the range of 5-50% by weight, more preferably 8-50% by weight, based on the total amount of the lubricating oil composition. It is a range.
The cleaning agent may be boronated or non-borated, and it is typically believed that a boron-donating compound, such as a metal borate, forms part of the overbasing. The cleaning agent may include both non-boronated cleaning agents and borated cleaning agents.
The detergent preferably has a sulfated ash content of at least 0.85%, more preferably at least 1.0%, and even more preferably at least 1.2% (as determined by ASTM D874).
The lubricating oil composition may include at least one dispersant. Dispersants are additives for lubricating oil compositions whose primary function is to improve engine cleanliness.
A noteworthy type of dispersant is “ashless”, which refers to non-metallic organic materials that do not substantially form ash upon combustion, as opposed to metal-containing ash-forming materials. Ashless dispersants include long chain hydrocarbons with a polar head, the polarity being derived from inclusion of, for example, O, P or N atoms. Hydrocarbons are lipophilic groups that provide oil solubility, for example having 40 to 500 carbon atoms. Thus, the ashless dispersant comprises an oil-soluble polymeric hydrocarbon backbone having functional groups that can bind to the particles to be dispersed.
Examples of ashless dispersants are succinimides such as polyisobutene succinic anhydride, and polyamine condensation products with or without borate.
When present, the dispersant is preferably present in an amount of 0.5-5% by weight, based on the total amount of the lubricating oil composition.

The lubricating oil composition may also include at least one antiwear additive. The antiwear additive may be metallic or non-metallic, preferably the former.
The metal salt of dihydrocarbyl dithiophosphate is an example of an antiwear additive. The metal of the metal salt of dihydrocarbyl dithiophosphate may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. Zinc salts are preferred, preferably in the range of 0.1 to 1.5% by weight, preferably 0.5 to 1.3% by weight, based on the total weight of the lubricating oil composition. They are usually known by first forming dihydrocarbyl dithiophosphate (DDPA) by reacting one or more alcohols or phenols with P ₂ S ₅ and then neutralizing the formed DDPA with a zinc compound. It may be prepared according to the technique of For example, dithiophosphoric acid may be produced by reacting a mixture of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared that contain both hydrocarbyl groups that are all secondary and hydrocarbyl groups that are all primary. Basic or neutral zinc compounds may be used to form the zinc salt, but oxides, hydroxides and carbonates are most commonly used. Commercial additives often contain excess zinc due to the use of excess basic zinc compounds in the neutralization reaction.
A preferred zinc dihydrocarbyl dithiophosphate is an oil-soluble salt of dihydrocarbyl dithiophosphate and may be represented by the following formula:
[(RO) (R ¹ O) P (S) S] ₂ Zn
Wherein R and R ¹ are hydrocarbyl groups containing the same or different 1-18, preferably 2-12 carbon atoms, alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic. Groups such as groups are included.)
Particularly preferred as R and R ¹ are alkyl groups of 2 to 8 carbon atoms. Thus, the group is, for example, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, It may be 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. To be oil soluble, the total number of carbon atoms in dithiophosphoric acid (ie, in R and R ¹ ) will generally be 5 or 6 or more. Thus, the zinc dihydrocarbyl dithiophosphate can comprise a zinc dialkyldithiophosphate.
When present, the antiwear additive is preferably present in an amount of 0.10 to 3.0% by weight, based on the total amount of the lubricating oil composition.

The lubricating oil composition may also include at least one antioxidant. The antioxidant may be amine-based or phenol-based. Examples of amines include secondary aromatic amines such as diarylamines, such as diphenylamine, where each phenyl group is alkyl substituted with an alkyl group having 4 to 9 carbon atoms. Examples of antioxidants include hindered phenols such as monophenol and bisphenol.
Preferably, the antioxidant, if present, is provided in the composition in an amount up to 3% by weight, based on the total amount of the lubricating oil composition.
If desired, other additives such as pour point depressants, antifoaming agents, metal rust inhibitors, pour point depressants and / or demulsifiers may be provided.
As used herein, the term “oil-soluble” or “oil-dispersible” means that a compound or additive is soluble, dissolvable, miscible or suspendable in oil in all proportions. It does not necessarily have to be shown. However, it means to dissolve or stably disperse in the oil to an extent sufficient to give the intended effect, for example in the environment in which the oil is used. Furthermore, additional additions of other additives may also allow for the addition of certain additives at high concentrations if desired.
The lubricating oil composition of the present invention includes defined individual components (ie, individual components) that may or may not be chemically identical before and after mixing.
While not essential, it is desirable to prepare one or more additive packages or concentrates that contain additives that can be added simultaneously to an oil of lubricating viscosity to form a lubricating oil composition. Dissolution of the additive package in the lubricating oil can be facilitated by mixing with a solvent and with mild heating (not essential). The additive package typically includes an appropriate amount of additive to provide the desired concentration and / or the final formulation when the additive package is combined with a predetermined amount of lubricant base. It will be formulated to perform the intended function.
Thus, the additive, along with other desired additives, mixed with a small amount of base oil or other miscible solvent, for example 2.5-90% by weight, preferably 5-75%, based on the additive package. Additive packages may be formed containing active ingredients that are suitable proportions of additive, by weight, most preferably 8-60% by weight, with the remainder being base oil.
The final formulation may typically contain about 5-40% by weight additive package with the remainder being base oil.
The present invention will be described in the following examples, but the present invention is not limited thereto.

(Example)
Synthesis example 1
Preparation Step 1-2-2 (Naphtyloxy) ethanol for Compound of Formula (II) Preparation of 2-naphthol (2-naphthol (2 liters) into a 2 liter resin kettle equipped with a mechanical stirrer, condenser / Dean-Stark trap and nitrogen inlet 600 g, 4.16 mol), ethylene carbonate (372 g, 4.22 mol) and xylene (200 g) were added and the mixture was heated to 90 ° C. under nitrogen. Aqueous sodium hydroxide (50% by weight, 3.0 g) was added and water was removed by azeotropic distillation at 165 ° C. The reaction mixture was held at 165 ° C. for 2 hours. As the reaction progressed, CO ₂ was released, and when the release of CO ₂ ended, it was determined that the reaction was almost complete. The product was collected and solidified upon cooling to room temperature. The completion of the reaction was confirmed by FT-IR and HPLC. The structure of the 2- (2-naphthyloxy) ethanol product was confirmed by 1H and ¹³ C-NMR.

Step 2-2-2 (Naphthyloxy) ethanol oligomerization 2-2 (Naphtyloxy) obtained in Step 1 into a 2 liter resin kettle equipped with a mechanical stirrer, condenser / Dean-Stark trap and nitrogen inlet ) Ethanol, toluene (200 g) and SA 117 (60.0 g) were charged and the mixture was heated to 70 ° C. under nitrogen. Paraformaldehyde was added over 15 minutes at 70-80 ° C., heated to 90 ° C. and the reaction mixture was held at that temperature for 30 minutes to 1 hour. The temperature was gradually increased from 110 ° C. to 120 ° C. over 2-3 hours and water (75-83 ml) was removed by azeotropic distillation. The polymer was collected and solidified upon cooling to room temperature. The average Mn was determined by GPC using a polystyrene standard corrected with the elution volume of 2-2 (naphthyloxy) ethanol as an internal standard. THF was used as the eluent. The structure was confirmed by ¹ H and ¹³ C NMR (average Mn of 1000 Daltons). FDMS and MALDI-TOF are methylene-linked 2-2 (naphthyloxy) ethanol oligomers of formula (I) where the product contains 2-24 2-2 (naphthyloxy) ethanol units (m is 1-23) It is shown that it contains a mixture of

Step 3-Reaction of Methylene Bond 2-2 (Naphtyloxy) Ethanol Oligomer with Acylating Agent (PIBSA) 5 liters equipped with mechanical stirrer, condenser / Dean-Stark trap, nitrogen inlet and additional funnel The resin kettle was charged with poly (2- (2 naphthyloxy) ethanol) -co-formaldehyde) obtained in step 2 and toluene (200 g) and the mixture was heated to 120 ° C. under nitrogen. Polyisobutenyl succinic anhydride (PIBSA average Mn450, 2500 g) is added portionwise (approximately 250 g at 30 minute intervals), held at 120 ° C. for 2 hours, then 140 ° C. under nitrogen purge for an additional 2 hours Heat to remove all solvent to constant weight. Base oil (AMEXOM 100N, 1100 g) was added and the product was collected at room temperature. The desired structure was confirmed by GPC and FT-IR.
A reaction scheme representing the above synthesis is shown below.

Performance example 1
The following examples use a centrifugal water separation test that evaluates the ability of an oil to separate water from a prepared test mixture of oil and water. The test uses an Alfa Laval MAB103B 2.0 centrifuge coupled to a Watson Marlow plastic pump. The centrifuge is sealed with 800 ml of water. The measurement consists of the amount of precipitate formed in the centrifuge during the test. A pre-measured amount of water and test oil are mixed together and then passed through a centrifuge at a rate of 2 liters / minute. The test is performed for one and a half hours and the mixture is passed through the centrifuge about 10 times. The centrifuge is weighed before and after the test. Poor trunk piston diesel engine lubricants increase the amount of sediment in the centrifuge system.

  Since Comparative Example 1 does not contain a dispersant, it shows good water separation. Comparative Example 2 includes a PIBSA-PAM dispersant and shows that an emulsion is formed between the water and the lubricating oil composition, producing a greater amount of precipitate. Example 3 of the present invention shows that the use of the compound of formula (II) has a smaller emulsifying effect and is comparable to not using a dispersant. Therefore, Example 3 produces a smaller amount of precipitate than Comparative Example 2. Thus, the compound of formula (II) is preferred over the use of PIBSA-PAM.

Claims (11)

A lubricating oil composition having a total base number of at least 15 mg KOH / g as determined by ASTM D2896,
At least 40% by weight of an oil having a viscosity of 2 centistokes to 4 centistokes when measured at 100 ° C .;
At least one overbased metal detergent;
A lubricating oil composition comprising at least one compound of the following formula (II):

Wherein each Ar ′ is naphthalene ;
Each L ′ is an alkylene group ;
Each Y ′ is ZOCH ₂ CH ₂ O— (wherein Z is an acyl group);
Each a 'is at least one Ar' on condition that the portion to have at least one group Y ', independently, 0-3;
m ′ is 2 to 25 . ) The lubricating oil composition of claim 1, wherein L ′ is CH ₂ .   The lubricating oil composition of claim 1, wherein Z is derived from a polyalkyl or polyalkenyl succinic acylating agent having an average Mn of 100 to 5000.   The lubricating oil composition of claim 1, wherein Z is derived from a hydrocarbyl isocyanate. A method for operating a trunk piston diesel engine, comprising the step of lubricating the engine with a lubricating oil composition according to any one of claims 1 to 4 . A method of reducing deposits in a trunk piston diesel engine, comprising the step of lubricating the engine with a lubricating oil composition according to any one of claims 1 to 4 and operating the engine. 5. A method for improving asphaltene dispersibility in a trunk piston diesel engine, comprising the step of lubricating the engine with a lubricating oil composition according to any one of claims 1-4 . A method for operating a crosshead diesel engine, comprising the step of lubricating a crankcase of the engine with a lubricating oil composition according to any one of claims 1-4 . A method of reducing deposits in a crosshead diesel engine, comprising the step of lubricating the engine with a lubricating oil composition according to any one of claims 1 to 4 and operating the engine. The method of claim 5 , wherein the engine has a centrifuge system that includes a sealing medium. The method of claim 10 , wherein the sealing medium is water.