JP2011214013A - Lubricating composition substantially free of zddp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition providing detergency and antiwear performance to an oil of lubricating viscosity often used in an engine oil and that is substantially free of a metal hydrocarbyl dithiophosphate.SOLUTION: There is provided a composition comprising: (a) a metal salixarate; (b) at least one additive selected from the group consisting of (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; (5) a dispersant viscosity modifier; and (6) an antiwear agent other than a metal hydrocarbyl dithiophosphate; and (c) an oil of lubricating viscosity. The composition contains ≤400 ppm of phosphorus derived from a metal hydrocarbyl dithiophosphate. In addition, a process for preparing the composition and its use are provided.

Description

(Field of Invention)
The present invention relates to lubricating oil compositions containing metal salixarates and other performance additives. The lubricating oil composition has wear and cleaning properties in the absence of the metal hydrocarbyl dithiophosphate.

(Background of the Invention)
Lubricants are well known to contain a number of additives that are used to protect the engine from wear, sludge build-up and filter clogging. Common additives for engine lubricants are zinc dialkyldithiophosphates (ZDDP) as antiwear additives and overbased calcium sulfonate detergents. ZDDP antiwear additives are believed to protect the engine by forming a protective film on the metal surface. Typical handling amounts of ZDDP range from 1% to 2% by weight based on the total weight of the lubricant. Detergents such as overbased calcium sulfonate help maintain engine parts free of soot and other deposits and provide a reserve of alkalinity. Typical handling amounts of cleaning agents are in the range of 0.05% to 10% by weight, based on the total weight of the lubricant.

Recently, phosphates and sulfonates derived from engine lubricants have been shown to contribute in part to particle release. Furthermore, sulfur and phosphorus tend to contaminate the NO _x catalysts used in catalytic converters, resulting in a decrease in the performance of these catalysts. Any decrease in catalytic converter performance tends to result in an increase in the amount of greenhouse gases such as nitrogen oxides and / or sulfur oxides. However, reducing the amount of ZDDP increases the amount of engine wear. Also, reducing the amount of cleaning agent reduces the cleanliness of the engine and results in increased soot deposits.

  U.S. Patent No. 6,057,028 (Cressey et al.) Discloses additives for lubricants containing linear compounds containing phenolic units and salicylic acid units in the form of oligomers or polymers. The linear compound can form a salt with calcium and, if necessary, a co-salt with boric acid. These additives have cleaning properties and / or wear resistance properties. Examples of lubricants include ashless dispersants and zinc dithiophosphate.

  U.S. Patent No. 6,099,096 (Morton) discloses a compound containing phenolic units and salicylic acid units in a lubricating composition. These compounds can form salts with calcium. An example of a lubricating composition includes phenolic units having dodecylalkyl groups. The compounds of this invention can be used as cleaning agents in gasoline or diesel fuel. These compounds also stabilize gasoline or diesel compositions against pyrolysis.

  Patent Document 3 (Taylor) discloses a fuel composition containing kerosene and a compound containing a phenol unit and a salicylic acid unit. These compounds can form salts with calcium. An example of a lubricating composition includes phenolic units having dodecylalkyl groups.

  Patent Document 4 (Taylor et al.) Discloses a cyclic compound containing a phenol unit and a salicylic acid unit. The salicylic acid unit can form a salt with a metal or ammonia cation.

  Patent Document 5 (Lacke et al.) Discloses metal detergents derived from aromatic carboxylic acids and metal detergents derived from phenol. These metal detergents exhibit oxidation resistance in lubricating oil compositions. Can be granted. In a preferred embodiment, the aromatic carboxylic acid is salicylic acid substituted with an alkyl group.

International Publication No. 03/18728 Pamphlet US Pat. No. 6,200,936 International Publication No. 99/25793 Pamphlet International Publication No. 01/56968 Pamphlet European Patent Application No. 1262538

  The compositions of the present invention have been found to provide cleaning and anti-wear performance to oils of lubricating viscosity often used in engine oils, and the compositions contain metal hydrocarbyl dithiophosphates. It does not contain substantially.

(Summary of the Invention)
The present invention includes the following:
(A) metal salixarate;
(B) at least one additive comprising: (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; (5) (6) an additive selected from the group consisting of antiwear agents other than metal hydrocarbyl dithiophosphates; and (c) a composition containing an oil of lubricating viscosity. The composition contains up to about 400 ppm phosphorus derived from the metal hydrocarbyl dithiophosphate.

The present invention further provides a process for preparing the composition, the process comprising:
(A) metal salixarate;
(B) at least one additive comprising: (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; (5) A dispersant viscosity modifier; and (6) an additive selected from the group consisting of antiwear agents other than metal hydrocarbyl dithiophosphates; and (c) mixing an oil of lubricating viscosity; The composition contains about 400 ppm or less phosphorus derived from the metal hydrocarbyl dithiophosphate.

の少なくとも１つの単位を含む、実質的に線状の化合物の１つまたは混合物によって表され、該化合物の各末端は、式（ＩＩＩ）または式（ＩＶ）：
（化２）

の末端基を有し、該基は、二価の架橋基によって連結されており、該架橋基は、各連結について同じであっても異なっていてもよく；
式（Ｉ）〜（ＩＶ）において、
ｆは、１、２または３であり、好ましくは、１または２であり；
Ｕは、−ＯＨ、−ＮＨ _２ 、−ＮＨＲ ^１ 、−Ｎ（Ｒ ^１ ） _２ またはその混合物であり、Ｒ ^１ は、１個〜５個の炭素原子を含むヒドロカルビル基であり；
Ｒ ^２ は、ヒドロキシル基またはヒドロカルビル基であり、そしてｊは、０、１、または２であり；
Ｒ ^３ は、水素またはヒドロカルビル基であり；
Ｒ ^４ は、ヒドロカルビル基または置換されたヒドロカルビル基であり；
ｇは、１、２または３であり、ただし、少なくとも１つのＲ ^４ 基は、８個以上の炭素原子を含み；そして
該分子は、平均して、少なくとも１つの単位（Ｉ）または単位（ＩＩＩ）、および少なくとも１つの単位（ＩＩ）または単位（ＩＶ）を含み、そして該組成物全体における、単位（Ｉ）および単位（ＩＩＩ）の総数対単位（ＩＩ）および単位（ＩＶ）の総数の比は、約０．１：１〜約２：１であるが、該組成物中の個々の分子は、該範囲外であり得る、項目１に記載の組成物。
（項目３）
前記金属サリキサレートの金属が、アルカリ金属またはアルカリ土類金属である、項目１に記載の組成物。
（項目４）
全硫黄含有量が、約０．５重量％未満であり、そして全リン含有量が、約０．０７重量％未満である、項目１に記載の組成物。
（項目５）
全硫酸塩灰分含有量が、約１．５重量％未満である、項目１に記載の組成物。
（項目６）
前記分散剤が、Ｎ置換長鎖アルケニルスクシンイミドである、項目１に記載の組成物。
（項目７）
前記酸化防止剤が、ジフェニルアミン、ヒンダードフェノール、またはこれらの混合物である、項目１に記載の組成物。
（項目８）
前記ジフェニルアミンが、式：
（化３）

によって表され、
各Ｒ ^６ およびＲ ^７ は、独立して、ヒドロカルビル基であり；そして
ｚは、０以上であり、ただし、少なくとも１つの環において、ｚは、０ではない、
項目７に記載の組成物。
（項目９）
前記ヒンダードフェノールが、式：
（化４）

によって表され、
Ｒ ^８ およびＲ ^９ は、独立して、１個〜２４個の炭素原子を含む、分枝鎖または直鎖のアルキル基であり；
Ｙは、架橋基であり；そして
Ｅは、水素、ヒドロカルビル基、第二の芳香族基に連結する架橋基、エステル含有基、またはこれらの混合物である、
項目７に記載の組成物。
（項目１０）
前記摩擦改質剤が、ポリオールと脂肪族カルボン酸とのモノエステルを含有する、項目１に記載の組成物。
（項目１１）
前記粘度改質剤が、オレフィンコポリマーを含有する、項目１に記載の組成物。
（項目１２）
前記オレフィンコポリマーが、エチレンモノマーと、少なくとも１種の他のコモノマーとを含み、該他のコモノマーが、式Ｈ _２ Ｃ＝ＣＨＲ ^１０ を有するα−オレフィンから誘導され、ここでＲ ^１０ は、ヒドロカルビル基である、項目１１に記載の組成物。
（項目１３）
前記分散剤粘度改質剤が、（ａ）不飽和ジカルボン酸水素無水物またはその誘導体およびアミンとグラフト重合した、オレフィンコポリマー；（ｂ）アミンで官能基化されたポリメタクリレート；（ｃ）（ｉ）スチレン、（ｉｉ）必要に応じてアミンで官能基化された、不飽和ジカルボン酸無水物またはその誘導体を含むエステル化コポリマー；ならびにこれらの混合物からなる群より選択される、項目１に記載の組成物。
（項目１４）
前記潤滑粘度の油が、ＡＰＩ Ｇｒｏｕｐ ＩＩ油、ＡＰＩ Ｇｒｏｕｐ ＩＩＩ油、ＡＰＩ Ｇｒｏｕｐ ＩＶ油、またはＡＰＩ Ｇｒｏｕｐ Ｖ油およびこれらの混合物からなる群より選択される、項目１に記載の組成物。
（項目１５）
前記金属サリキサレートが、油なしでの状態に基づいて、前記組成物の約０．０１重量％〜約２０重量％で存在し；前記成分（ｂ）の添加剤（１）〜（６）の各々は、油なしでの状態に基づいて、該組成物の約０重量％〜２５重量％で存在し、ただし、少なくとも１種の添加剤が、該組成物の０．１重量％以上で存在し；そして前記潤滑粘度の油が、該組成物の９９．８９重量％までで存在する、項目１に記載の組成物。
（項目１６）
組成物の調製のためのプロセスであって、該プロセスは、以下：
（ａ）金属サリキサレート；
（ｂ）少なくとも１種の添加剤であって、該添加剤は、（１）酸化防止剤；（２）摩擦改質剤；（３）分散剤；（４）粘度改質剤；（５）分散剤粘度改質剤；および（６）金属のヒドロカルビルジチオリン酸塩以外の耐磨耗剤からなる群より選択される、添加剤；ならびに
（ｃ）潤滑粘度の油、
を混合する工程を包含し、該組成物は、金属のヒドロカルビルジチオリン酸塩由来の、約４００ｐｐｍ以下のリンを含有する、プロセス。
（項目１７）
項目１６のプロセスによって調製された製品。
（項目１８）
内燃機関を潤滑するための方法であって、該内燃機関に、項目１に記載の組成物を含有する潤滑剤を供給する工程を包含する、方法。
（項目１９）
改善された機関清浄度、低下した磨耗、低下したＮＯ _ｘ 放出および低下した粒子放出からなる群より選択されるうちの１つ以上を与えるための、項目１の組成物の使用。 Use of the compositions of the present invention provide improved engine cleanliness, decreased wear, one or more of the reduced _the NO _x releasing and reduced particle emission.
For example, the present invention provides the following items.
(Item 1)
A composition comprising:
(A) metal salixarate;
(B) at least one additive comprising: (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; (5) A dispersant viscosity modifier; and (6) an additive selected from the group consisting of antiwear agents other than metal hydrocarbyl dithiophosphates; and
(C) an oil of lubricating viscosity,
And the composition contains about 400 ppm or less of phosphorus derived from a metal hydrocarbyl dithiophosphate.
(Item 2)
Said metal salixarate is of formula (I) or (II):
(Chemical formula 1)

Represented by one or a mixture of substantially linear compounds comprising at least one unit of formula (III) or formula (IV):
(Chemical formula 2)

Wherein the groups are linked by a divalent bridging group, which may be the same or different for each linkage;
In the formulas (I) to (IV),
f is 1, 2 or 3, preferably 1 or 2;
U is —OH, —NH ₂ , —NHR ¹ , —N (R ¹ ) ₂ or a mixture thereof, and R ¹ is a hydrocarbyl group containing 1 to 5 carbon atoms;
R ² is a hydroxyl group or a hydrocarbyl group, and j is 0, 1, or 2;
R ³ is hydrogen or a hydrocarbyl group;
R ⁴ is a hydrocarbyl group or a substituted hydrocarbyl group;
g is 1, 2 or 3, provided that at least one R ⁴ group contains 8 or more carbon atoms; and
The molecule comprises, on average, at least one unit (I) or unit (III) and at least one unit (II) or unit (IV), and unit (I) and unit in the entire composition The ratio of the total number of (III) to the total number of units (II) and units (IV) is about 0.1: 1 to about 2: 1, but individual molecules in the composition are outside of the range. A composition according to item 1, which may be.
(Item 3)
Item 2. The composition according to Item 1, wherein the metal of the metal salixarate is an alkali metal or an alkaline earth metal.
(Item 4)
The composition of claim 1, wherein the total sulfur content is less than about 0.5 wt% and the total phosphorus content is less than about 0.07 wt%.
(Item 5)
Item 2. The composition of item 1, wherein the total sulfate ash content is less than about 1.5 wt%.
(Item 6)
Item 2. The composition according to Item 1, wherein the dispersant is an N-substituted long chain alkenyl succinimide.
(Item 7)
Item 2. The composition according to Item 1, wherein the antioxidant is diphenylamine, hindered phenol, or a mixture thereof.
(Item 8)
The diphenylamine has the formula:
(Chemical formula 3)

Represented by
Each R ⁶ and R ⁷ is independently a hydrocarbyl group; and
z is greater than or equal to 0, but in at least one ring, z is not 0;
Item 8. The composition according to item 7.
(Item 9)
The hindered phenol has the formula:
(Chemical formula 4)

Represented by
R ⁸ and R ⁹ are independently branched or straight chain alkyl groups containing 1 to 24 carbon atoms;
Y is a bridging group; and
E is hydrogen, a hydrocarbyl group, a bridging group linked to a second aromatic group, an ester-containing group, or a mixture thereof.
Item 8. The composition according to item 7.
(Item 10)
Item 2. The composition according to Item 1, wherein the friction modifier contains a monoester of a polyol and an aliphatic carboxylic acid.
(Item 11)
Item 2. The composition according to Item 1, wherein the viscosity modifier comprises an olefin copolymer.
(Item 12)
The olefin copolymer comprises an ethylene monomer and at least one other comonomer, wherein the other comonomer is derived from an α-olefin having the formula H ₂ C═CHR ¹⁰ where R ¹⁰ is a hydrocarbyl group. The composition according to item 11, wherein
(Item 13)
The dispersant viscosity modifier is (a) an olefin copolymer graft polymerized with an unsaturated dicarboxylic acid anhydride or derivative and an amine; (b) an amine functionalized polymethacrylate; (c) (i Item 2. The item according to item 1, selected from the group consisting of:) styrene, (ii) an optionally functionalized with an amine, an esterified copolymer comprising an unsaturated dicarboxylic anhydride or a derivative thereof; and mixtures thereof Composition.
(Item 14)
Item 2. The composition according to Item 1, wherein the oil of lubricating viscosity is selected from the group consisting of API Group II oil, API Group III oil, API Group IV oil, or API Group V oil and mixtures thereof.
(Item 15)
Each of the metal salixalate is present in about 0.01% to about 20% by weight of the composition, based on the state without oil; each of the additives (1) to (6) of component (b) Is present in about 0% to 25% by weight of the composition, based on the absence of oil, provided that at least one additive is present in more than 0.1% by weight of the composition. And the oil of lubricating viscosity is present in up to 99.89% by weight of the composition.
(Item 16)
A process for the preparation of a composition comprising the following:
(A) metal salixarate;
(B) at least one additive comprising: (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; (5) A dispersant viscosity modifier; and (6) an additive selected from the group consisting of antiwear agents other than metal hydrocarbyl dithiophosphates; and
(C) an oil of lubricating viscosity,
Wherein the composition contains no more than about 400 ppm phosphorus derived from a metal hydrocarbyl dithiophosphate.
(Item 17)
A product prepared by the process of item 16.
(Item 18)
A method for lubricating an internal combustion engine comprising supplying a lubricant containing the composition according to item 1 to the internal combustion engine.
(Item 19)
Use of the improved engine cleanliness, decreased wear, to provide one or more of selected from the group consisting of reduced _the NO _x releasing and reduced particle emission, the composition of item 1.

(Detailed description of the invention)
The present invention provides a composition as described above. Often the composition has a total sulfur content of less than 0.5 wt%, preferably less than 0.3 wt%, more preferably less than 0.1 wt%, and most preferably about 0 wt%. Have Often, the primary source of sulfur in the compositions of the present invention comes from diluent oil. This diluent oil is typically used in the manufacturing process used to prepare many of the components (b) additives. Except for diluent oil, the compositions of the present invention often have 700 ppm or less, preferably 600 ppm or less, more preferably 300 ppm or less, even more preferably 100 ppm or less, and most preferably 50 ppm or less (eg, 30 ppm or less). 25 ppm or less, 20 ppm or less and 15 ppm or less). Where diluent oil-derived sulfur is included, the sulfur content of the composition is often increased to 800 ppm, preferably to 600 pp, and most preferably to 400 ppm (eg, about 200 ppm or about 300 ppm). .

  Often the composition is less than 0.1% by weight of the composition, preferably 0.085% or less, more preferably 0.07% or less, and even more preferably 0.055% or less. And most preferably having a total phosphorus content of 0.05% by weight or less (eg, 200 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less). In one embodiment, phosphorus is present at 1 ppm or 10 ppm to 50 ppm or 200 ppm.

  Often the composition is less than 1.5% by weight of the composition, preferably 1.1% or less, more preferably 1.0% or less, as recommended by ASTM D-874. Even more preferably, it has a total ash content of 0.8 wt% or less, and most preferably 0.5 wt% or less. In one embodiment, the total ash content is present at 0.1 wt% or 0.2 wt% to 0.6 wt% or 0.7 wt%.

(Salixate salt detergent)
The metal salixarate substrates of the present invention are often of formula (I) or (II):

の少なくとも１つの単位を含む、実質的に線状の化合物の１つまたは混合物によって、代表され、この化合物の各末端は、式（ＩＩＩ）または式（ＩＶ）：

Represented by one or a mixture of substantially linear compounds comprising at least one unit of the formula wherein each end of the compound is of formula (III) or formula (IV):

の末端基を有し、このような基は、二価の架橋基によって連結されており、これらの架橋基は、各連結について同じであっても異なっていてもよく；
式（Ｉ）〜（ＩＶ）において、
ｆは、１、２または３であり、好ましくは、１または２であり；
Ｕは、−ＯＨ、−ＮＨ_２、−ＮＨＲ^１、−Ｎ（Ｒ^１）_２またはその混合物であり、Ｒ^１は、１個〜５個の炭素原子を含むヒドロカルビル基であり；
Ｒ^２は、ヒドロキシル基またはヒドロカルビル基であり、そしてｊは、０、１、または２であり；
Ｒ^３は、水素またはヒドロカルビル基であり；
Ｒ^４は、ヒドロカルビル基または置換されたヒドロカルビル基であり；
ｇは、１、２または３であり、ただし、少なくとも１つのＲ^４基は、８個以上の炭素原子を含み；そして
この分子は、平均して、少なくとも１つの単位（Ｉ）または単位（ＩＩＩ）、および少なくとも１つの単位（ＩＩ）または単位（ＩＶ）を含み、そしてこの組成物全体における、単位（Ｉ）および（ＩＩＩ）の総数対単位（ＩＩ）および（ＩＶ）の総数の比は、約０．１：１〜約２：１であるが、この組成物中の個々の分子は、この範囲外であり得る。

And such groups are linked by a divalent bridging group, which may be the same or different for each linkage;
In the formulas (I) to (IV),
f is 1, 2 or 3, preferably 1 or 2;
U is —OH, —NH ₂ , —NHR ¹ , —N (R ¹ ) ₂ or a mixture thereof, and R ¹ is a hydrocarbyl group containing 1 to 5 carbon atoms;
R ² is a hydroxyl group or a hydrocarbyl group, and j is 0, 1, or 2;
R ³ is hydrogen or a hydrocarbyl group;
R ⁴ is a hydrocarbyl group or a substituted hydrocarbyl group;
g is 1, 2 or 3, provided that at least one R ⁴ group contains 8 or more carbon atoms; and on average, the molecule comprises at least one unit (I) or unit (III ), And at least one unit (II) or unit (IV), and the ratio of the total number of units (I) and (III) to the total number of units (II) and (IV) in the entire composition is From about 0.1: 1 to about 2: 1, the individual molecules in the composition can be outside this range.

The U group in formulas (i) and (iii) may be located in one or more positions ortho, meta, or para with respect to the —COOR ³ group. Preferably, the U group is located ortho to the —COOR ³ group. When the U group is an —OH group, the formulas (i) and (iii) can be converted to 2-hydroxybenzoic acid (often referred to as salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, or these Derived from the mixture. When U is a —NH ₂ group, the formulas (i) and (iii) are 2-aminobenzoic acid (often referred to as anthranilic acid), 3-aminobenzoic acid, 4-aminobenzoic acid, or these Derived from a mixture of

Divalent bridging groups, which may be the same or different in each case, include —CH ₂ — (methylene bridge) and —CH ₂ OCH ₂ — (ether bridge), each of which It may be derived from aldehydes such as formaldehyde or formaldehyde equivalents (eg paraform, formalin), etanal or propanal.

  The metal of the metal salixarate is often monovalent, divalent, or a mixture thereof. Preferably, the metal is selected from alkali metals or alkaline earth metals (eg, magnesium, calcium, potassium or sodium), with magnesium, calcium, potassium or mixtures thereof being most preferred.

  A significant portion of the salixarate molecule (before neutralization), on average, has the following formula:

によって表され得ると考えられる。この式において、各Ｒ^５は、同じであっても異なっていてもよく、そして水素またはアルキル基であるが、ただし、少なくとも１つのＲ^５は、アルキルである。好ましい実施形態において、Ｒ^５は、ポリイソブテン基（特に、分子量２００〜１，０００、または約５５０のもの）である。式（ＩＩＩ）の１つのサリチル酸末端基を含む、かなりの量の複核種または三核種もまた、存在し得る。このサリキサレート洗浄剤は、単独で使用されてもよく、他の洗浄剤と共に使用されてもよい。

It can be represented by In this formula, each R ⁵ may be the same or different and is hydrogen or an alkyl group, provided that at least one R ⁵ is alkyl. In preferred embodiments, R ⁵ is a polyisobutene group (particularly having a molecular weight of 200 to 1,000, or about 550). There may also be a significant amount of di- or tri-nuclide containing one salicylic acid end group of formula (III). This salixarate detergent may be used alone or in combination with other detergents.

  Salixalate derivatives and methods for their preparation are described in more detail in US Pat. No. 6,200,936 and PCT application publications WO 01/56968 and WO 03/818728. Salixate derivatives are believed to have a structure that is preferentially linear rather than a macrocyclic structure, although both structures are intended to be encompassed by the term “salixate”. Further, “linear” does not exclude branching structures or other structures in the substituent R group.

  The metal salixarate is often 0.01% to 20%, preferably 0.1% to 10%, more preferably 0.2% by weight of the composition, based on the absence of oil. Present at ˜8 wt%, and most preferably 0.5 wt% to 5 wt%.

(Component (b) Additive)
The present invention contains at least one additive, which is (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; (5 Selected from the group consisting of: a) a dispersant viscosity modifier; and (6) an anti-wear agent other than the hydrocarbyl dithiophosphate of the metal.

  The present invention contains at least one additive, which is (1) an antioxidant; (2) a friction modifier; (3) a dispersant; (4) a viscosity modifier; (5 Selected from the group consisting of: a) a dispersant viscosity modifier; and (6) an anti-wear agent other than the hydrocarbyl dithiophosphate of the metal. Often two or more and most preferably three or more additives (1) to (6) are present in the present invention.

  Often, the amount of each of the additives (1) to (6) is 0% to 25%, preferably 0.1% to 20% by weight of the composition, based on the absence of oil, More preferably from 0.3% to 15%, and most preferably from 1% to 10% by weight, provided that at least one additive is 0.1% by weight of the composition. It exists in the above.

(Antioxidant)
When present in the present invention, antioxidants often include diphenylamine antioxidants, hindered phenol antioxidants, or mixtures thereof.

  Other antioxidant additives (eg, molybdenum dithiocarbamate or sulfurized olefins) may also be added to the composition of the present invention, but preferably the composition is substantially free of molybdenum dithiocarbamate and sulfurized olefins. Absent. As used herein, the term “substantially free of molybdenum dithiocarbamate and sulfurized olefin” means that the composition is less than 100 ppm, preferably less than 20 ppm, and most preferably 1 ppm or less. Means containing present molybdenum dithiocarbamate or sulfurized olefin.

  When present, diphenylamines suitable for the present invention are often of the formula:

によって表される。ここで、Ｒ^６およびＲ^７は、独立して、ヒドロカルビル基であり；そしてｚは、０以上であるが、少なくとも１つの環において、ｚは、０ではない。しばしば、このヒドロカルビル基は、１個〜２４個、好ましくは、２個〜１８個、そして最も好ましくは、４個〜１２個の炭素原子を含む。

Represented by Where R ⁶ and R ⁷ are independently hydrocarbyl groups; and z is 0 or greater, but in at least one ring, z is not 0. Often the hydrocarbyl group contains 1 to 24, preferably 2 to 18, and most preferably 4 to 12 carbon atoms.

  Examples of suitable diphenylamine antioxidants include octyl diphenylamine, nonyl diphenylamine, bisoctyl diphenylamine, bisnonyl diphenylamine, or mixtures thereof.

  When present, diphenylamine is often 0.01% to 20%, preferably 0.05% to 10%, more preferably 0.00% by weight of the composition, based on the absence of oil. It is present at 1 wt% to 5 wt%, and most preferably 0.2 wt% to 3 wt%.

  When present, hindered phenols suitable for the present invention are often of the formula:

によって表され、ここで、Ｒ^８およびＲ^９は、独立して、１個〜２４個、好ましくは、４個〜１８個、そして最も好ましくは、４個〜１２個の炭素原子を含む、分枝鎖または直鎖のアルキル基であり；そしてＥは、水素、ヒドロカルビル基、第二の芳香族基に連結する架橋基、エステル含有基、またはこれらの混合物である。

Where R ⁸ and R ⁹ are independently 1 to 24, preferably 4 to 18, and most preferably 4 to 12 carbon atoms, A branched or straight chain alkyl group; and E is hydrogen, a hydrocarbyl group, a bridging group linked to a second aromatic group, an ester-containing group, or a mixture thereof.

R ⁸ and R ⁹ may be linear or branched; branched chains are preferred. Suitable examples of R ⁸ and R ⁹ include secondary butyl and tertiary butyl.

  In one embodiment, the hindered phenol of formula (VII) suitable for the present invention is of the formula:

によって表されるエステルまたは酸であり、ここで、Ｒ^８およびＲ^９は、上で定義されたとおりであり、そしてＲ^１０は、水素、ヒドロカルビル基またはこれらの混合物である。

Wherein R ⁸ and R ⁹ are as defined above, and R ¹⁰ is hydrogen, a hydrocarbyl group, or a mixture thereof.

When R ¹⁰ is a hydrocarbyl group, R ¹⁰ is preferably butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl, nonyl, decyl, Selected from the group consisting of undecyl, dodecyl, and mixtures thereof.

In one embodiment, the hindered phenol of formula (VII) suitable for the present invention comprises a bridging group. Examples of suitable bridging groups include 1 to 8, preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 2 carbon atoms. Examples include alkylene bridges or ether bridges. Examples of suitable bridging _{groups, -CH 2 -, - CH 2} CH 2 -, - CH 2 OCH 2 - and _{-CH 2 CH 2 OCH 2 CH 2} - and the like.

  When present, hindered phenols with crosslinking groups are often of the formula:

によって表され、ここで、Ｒ^１１およびＲ^１２は、上で定義されており、そしてＹは、架橋基である。メチレン架橋されたヒンダードフェノールの例としては、４，４’−メチレン−ビス−（６−ｔｅｒｔ−ブチル−ｏ−クレゾール）、４，４’−メチレン−ビス−（２−ｔｅｒｔ−アミル−ｏ−クレゾール）および４，４’−メチレン−ビス−（２，６−ジ−ｔｅｒｔ−ブチルフェノール）が挙げられる。

Where R ¹¹ and R ¹² are defined above and Y is a bridging group. Examples of methylene-bridged hindered phenols include 4,4'-methylene-bis- (6-tert-butyl-o-cresol), 4,4'-methylene-bis- (2-tert-amyl-o -Cresol) and 4,4'-methylene-bis- (2,6-di-tert-butylphenol).

  The hindered phenols of the present invention also have the formula

によって表される化合物を含み、ここで、Ｒ^８、ＥおよびＹは、上で定義されている。適切なメチレン架橋された式（ＶＩＩＩ）のヒンダードフェノールの例としては、２，２’−メチレン−ビス−（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、および２，２’−メチレン−ビス−（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレン−ビス−（４−プロピル−６−ｔｅｒｔ−ブチルフェノール）が挙げられる。

Wherein R ⁸ , E and Y are defined above. Examples of suitable methylene bridged hindered phenols of formula (VIII) include 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), and 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol) and 2,2′-methylene-bis- (4-propyl-6-tert-butylphenol).

  When present, the hindered phenol is often 0.01% to 25% by weight of the composition, preferably 0.1% to 20% by weight, more preferably, based on the absence of oil. It is present at from 0.5 wt% to 15 wt%, and most preferably from 1 wt% to 10 wt%.

(Dispersant)
When present, the present invention further comprises a dispersant, which is derived from an N-substituted long chain alkenyl succinimide or a mixture thereof. These dispersants may be used alone or in combination with other dispersants.

  N-substituted long chain alkenyl succinimides have various chemical structures and include monosuccinimide and / or disuccinimide. Often, the long chain alkenyl group has a number average molecular weight of 350 to 10,000, preferably 400 to 7000, more preferably 500 to 5000, and most preferably 500 to 4000. In one embodiment, the long chain alkenyl group is a polyisobutylene group, which has a number average molecular weight of 800-1600, and in another embodiment, a number average molecular weight of 1600-3000. Succinimides are often hydrocarbyl substituted acylating agents (eg, hydrocarbyl substituted succinic anhydride) and polyamines or amino alcohols, often polyalkylene polyamines or poly (ethylene amines) (eg, triethylenetetramine, tetraethylene). Prepared by condensation with pentamine, pentaethylenehexamine, or in one embodiment, polyamine distillation bottoms).

  N-substituted long chain alkenyl succinimide dispersant additives and their preparation are disclosed, for example, in US Pat. Nos. 3,361,673, 3,401,118, and 4,234,435. Yes.

  Another class of suitable dispersants includes Mannich bases, which include alkylphenols whose alkyl groups typically contain at least 30 carbon atoms, aldehydes (especially formaldehyde) and amines (especially polyalkylenes). Reaction product with polyamines) and is described in more detail in US Pat. No. 3,634,515.

  Another class of ashless dispersants are high molecular weight esters. These materials are described above, except that these materials may appear to be prepared by reaction of a hydrocarbyl acylating agent with a polyhydric aliphatic alcohol (eg, glycerol, pentaerythritol, or sorbitol). It is similar to succinimide. Such materials are described in more detail in US Pat. No. 3,381,022.

  Other dispersants include polymeric dispersant additives, which are generally hydrocarbon-based polymers that contain polar functional groups to impart dispersant properties to the polymer.

  The dispersant can also be worked up by reaction with any of a variety of reagents. Among these are urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, succinic anhydrides substituted with hydrocarbons, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in US Pat. No. 4,654,403.

  When present, the dispersant is often from 0.01% to 20%, preferably from 0.1% to 15%, more preferably from 0.1% to 15% by weight of the composition, based on the absence of oil. It is present at 2-10% by weight, and most preferably at 0.5-6% by weight.

(Friction modifier)
When present in the present invention, the friction modifier may be a monoester of a polyol and an aliphatic carboxylic acid (often an acid containing 12 to 24 carbon atoms). Often, the monoester of polyol and aliphatic carboxylic acid is in the form of a mixture with sunflower oil or the like, the oil being in the friction modifier 5% to 95% by weight of the mixture, preferably It may be present at 10% to 90%, more preferably 20% to 85%, and most preferably 20% to 80%.

  Polyols include diols, triols, and alcohols having a higher number of alcoholic OH groups. Polyhydric alcohols include ethylene glycol (including diethylene glycol, triethylene glycol and tetraethylene glycol); propylene glycol (including dipropylene glycol, tripropylene glycol and tetrapropylene glycol); glycerol; butanediol; hexanediol; Sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexanediol; erythritol; and pentaerythritol (including dipentaerythritol and tripentaerythritol). Preferred are diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol and dipentaerythritol.

  The aliphatic carboxylic acid that forms the ester is an acid containing 12 to 24 carbon atoms. Preference is given to acids containing straight-chain hydrocarbyl groups containing 12 to 24 carbon atoms (for example 14 to 20 or 16 to 18 carbon atoms). Such acids can also be used in combination with acids having more or fewer carbon atoms.

  In general, the acid is a monocarboxylic acid. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.

  The esters used in the present invention are in particular monoesters of such polyols with such carboxylic acids. A preferred ester is glycerol monooleate. Glycerol monooleate is a material such as glycerol, oleic acid, other long chain acids, glycerol dioleate, and glycerol trioleate in its commercial grade, as is the case with other such materials. It is a mixture containing Commercially available materials are believed to contain about 60 ± 5 wt% of the chemical species “glycerol monooleate” along with 35 ± 5% glycerol dioleate, and less than 5% glycerol trioleate and oleic acid. The amount of monoester described below is calculated based on the actual corrected amount of polyol monoester present in any such mixture.

  Other friction modifiers suitable for the present invention include fatty amines, fatty phosphites, fatty acid amides, fatty epoxides, alkoxylated fatty amines, fatty acid metal salts, sulfurized olefins, fatty imidazolines, carboxylic acids and poly Examples include condensation products with alkylene-polyamines and amine salts of alkylphosphoric acids. Preferably, the friction modifier does not contain sulfur and / or phosphorus.

  When present, the friction modifier is often 0.01 wt% to 20 wt%, preferably 0.05 wt% to 10 wt%, more preferably, based on the absence of oil. It is present at 0.1% to 5% by weight, and most preferably 0.2% to 3% by weight (eg 0.5% to 2% by weight).

(Viscosity modifier)
When present in the present invention, the viscosity modifier is often an olefin copolymer. The backbone of the olefin copolymer often comprises two to four, preferably two to three, and most preferably two different olefin monomers. These olefin monomers often contain 2 to 20, preferably 2 to 10, more preferably 2 to 6, and most preferably 2 to 4 carbon atoms.

  When present, the viscosity modifier is often 0.01% to 15%, preferably 0.05% to 10%, more preferably, based on the absence of oil. It is present at 0.1% to 5% by weight, and most preferably 0.2% to 3% by weight.

The olefin copolymer preferably comprises an ethylene monomer and at least one other comonomer derived from an α-olefin having the formula H ₂ C═CHR ¹⁰ where R ¹⁰ is a hydrocarbyl group, preferably Is an alkyl group containing 1 to 18, preferably 1 to 10, more preferably 1 to 6, and most preferably 1 to 3 carbon atoms. Examples of the hydrocarbyl group include a linear alkyl group, a branched alkyl group, or a mixture thereof.

  Examples of suitable comonomers include propylene, 1-butene, 1-hexene, 1-octene, 4-methylpentene-1, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, -Hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, or mixtures thereof. Preferably, the comonomer is 1-butene, propylene, or a mixture thereof. Examples of olefin copolymers include ethylene-propylene copolymers or ethylene-butene-1 copolymers.

  Other viscosity modifiers suitable for the present invention include hydrogenated styrene-butadiene rubber, hydrogenated styrene-isoprene polymer, hydrogenated radical isoprene polymer, polymethacrylate ester, polyacrylate ester, polyalkylstyrene. , Alkenyl aryl-conjugated diene copolymers, polyalkyl methacrylates, esters of maleic anhydride-styrene copolymers, or mixtures thereof.

  If desired, the olefin copolymers of the present invention can be further graft polymerized with an unsaturated dicarboxylic anhydride or derivative thereof and an amine to form a dispersant viscosity modifier (often referred to as DVM, these are dispersants). The properties are also shown, thus forming a name). DVM additives and their preparation are disclosed, for example, in US Pat. Nos. 6,107,258 and 6,107,257.

Examples of olefin copolymers DVM include those commercially available from DSM as PA1250 ^™ , PA1260 ^™ and PA1274 ^™ , and Hitec 5777 ^™ (commercially available from Ethyl Corporation).

  Often, the dispersant viscosity modifier is (a) an olefin copolymer graft polymerized with an unsaturated dicarboxylic acid anhydride or derivative and an amine; (b) an amine functionalized polymethacrylate; (c) ( selected from the group consisting of i) styrene, (ii) an esterified copolymer comprising an unsaturated dicarboxylic anhydride or derivative thereof, optionally functionalized with an amine; and mixtures thereof. Often, DVMs derived from polymethacrylates and / or styrene copolymers are prepared by reaction with amines as described in US Pat. Nos. 6,107,258 and 6,107,257. A DVM may be used alone or in combination with other DVMs.

  When present, the dispersant viscosity modifier is often 0.01% to 10%, 0.05% to 6%, more preferably 0% by weight of the composition, based on the absence of oil. 0.08 wt% to 4 wt%, and most preferably 0.1 wt% to 2 wt%.

(Abrasion-resistant agent)
The compositions of the present invention may further contain antiwear agents other than the metal hydrocarbyl dithiophosphate. Suitable antiwear agents include phosphate esters or salts thereof; phosphites; and phosphorus containing carboxylic esters, ethers, and amides, or mixtures thereof. Preferably, the composition of the present invention is substantially free of antiwear agents containing phosphorus and / or sulfur. In one embodiment of the invention, the composition does not include an antiwear agent.

  As used herein, the term “substantially free of antiwear agents containing sulfur and / or phosphorus” means that the composition is less than 50 ppm, preferably less than 10 ppm, and most preferably Means to contain an antiwear agent present at less than 1 pm. In one embodiment of the invention, no antiwear agent containing sulfur and / or phosphorus is present. In one embodiment of the present invention there is an antiwear agent containing 1 to 15 ppm of sulfur and / or phosphorus.

(Oil of lubricating viscosity)
The lubricating oil composition of the present invention can be added to oils of lubricating viscosity. These oils include natural and synthetic oils, oils derived from hydrocracking processes, oils derived from hydrogenation, oils derived from hydrofinishing, unrefined oils, refined oils and rerefined oils. Or mixtures thereof.

  Unrefined oils are oils obtained directly from natural or synthetic sources, generally without (or little) further purification processing.

  Rerefined oils are similar to unrefined oils except that they are further processed in one or more refining steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid extraction or base extraction, filtration, leaching and the like.

  Rerefined oils are also known as reclaimed oils or reprocessed oils and are obtained by processes similar to those used to obtain refined oils, and often of spent additives and oil breakdown products It is further processed by a technique intended for removal.

  Natural oils useful in making the lubricants of the present invention include animal oils, vegetable oils (eg, castor oil, lard oil), inorganic lubricants (eg, treated with liquid petroleum and solvents or treated with acids. In addition, paraffinic, naphthalene-based, or mixed paraffin-naphthalene-based inorganic lubricating oils), and oils derived from coal or shale, or mixtures thereof.

  Synthetic lubricating oils are useful and include polymerized olefins or fused olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers); poly (1-hexene), poly (1-octene), poly (1-decene). ), And mixtures thereof; alkyl-benzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene)); polyphenyls (eg, biphenyl, terphenyl, alkylated polyphenyls) ); Hydrocarbon oils such as alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogs and homologs, or mixtures thereof. Preferably, the synthetic lubricating oil does not contain alkylated diphenyl sulfide.

  Other synthetic lubricating oils include, but are not limited to, polyol esters, liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphate), and polymeric tetrahydrofuran. Not. Synthetic oils can be produced by Fischer-Tropsch reactions and can typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. Preferably, the synthetic lubricating oil does not contain an ester containing phosphorus.

Oils of lubricating viscosity can also be defined as detailed in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows: Group I (sulfur content> 0.03% by weight, and / or <90% by weight saturation, viscosity index 80-120); Group II (sulfur content ≦ 0.03% by weight, and ≧ 90% by weight saturation, viscosity index 80-120); Group III (sulfur content ≦ 0.03% by weight, and ≧ 90% by weight saturation, viscosity index ≧ 120); Group IV (all Poly alpha olefins (PAO)); and Group V (all others not included in Groups I, Groups II, Groups III, or Groups IV). Oils of lubricating viscosity are API Group I, API Group II, and API Group.
III, API Group IV, API Group V oils, and mixtures thereof, preferably from API Group II, API Group III, API Group IV, or API Group V oils, and mixtures thereof And most preferably selected from the group consisting of oils of API Group III, API Group IV, or API Group V, and mixtures thereof. When the oil of lubricating viscosity is an API Group II, API Group III, API Group IV, or API Group V oil, up to 20% by weight of the lubricating oil, preferably up to 10% by weight, more preferably Up to 5% by weight and most preferably up to 1.5% by weight of API Group I oil may be present.

Examples of suitable API Group III oils include Nexbase ^™ 3050, Nexbase ^™ 3043, Yubase ^™ 4, Yubase ^™ 6, and Shell ^™ XHVI 5.2.

  Oils of lubricating viscosity are often up to 99.98%, preferably up to 99.8%, more preferably up to 99.65%, and most preferably up to 99.3% by weight of the composition. Exists.

  When the present invention is in the form of a concentrate, which is combined, in whole or in part, with a further oil to form a finished lubricant, each of the aforementioned dispersants and other components The ratio of diluent oil is often 80:20 to 10:90 by weight.

(Metal hydrocarbyl dithiophosphate)
The present invention has the formula:

によってしばしば表される金属のヒドロカルビルジチオリン酸塩を、実質的に含まないか、または含まない。この式において、Ｒ^１１およびＲ^１２は、独立して、水素、ヒドロカルビル基、またはその混合物であるが、ただし、Ｒ^１１とＲ^１２とのうちの少なくとも１つは、ヒドロカルビル基であり、好ましくは、１個〜３０個、好ましくは、２個〜２０個、そして最も好ましくは、２個〜１５個の炭素原子を有する、アルキルまたはシクロアルキルである。

Is substantially free or free of hydrocarbyl dithiophosphates of metals often represented by In this formula, R ¹¹ and R ¹² are independently hydrogen, a hydrocarbyl group, or a mixture thereof, provided that at least one of R ¹¹ and R ¹² is a hydrocarbyl group, preferably Alkyl or cycloalkyl having 1 to 30, preferably 2 to 20, and most preferably 2 to 15 carbon atoms.

  The term “substantially free” means that the composition is 400 ppm or less phosphorus, preferably 300 ppm or less, more preferably 200 ppm or less, even more preferably, from a metal hydrocarbyl dithiophosphate. , 100 ppm or less, and most preferably 100 ppm or less (eg, 50 ppm, 20 ppm, or 1 ppm or less). In one embodiment of the invention, the composition contains 0.5 ppm or 10 ppm to 50 ppm phosphorus derived from a metal hydrocarbyl dithiophosphate. In one embodiment of the invention, the composition does not comprise a metal hydrocarbyl dithiophosphate.

  M 'is a metal and n is an integer equal to the available valence of M'. M 'is monovalent, divalent or trivalent, preferably divalent, and more preferably a divalent transition metal. In one embodiment, M 'is zinc. In one embodiment, M 'is calcium. In one embodiment, M 'is barium. Examples of metal hydrocarbyl dithiophosphates include zinc hydrocarbyl dithiophosphate (often referred to as ZDDP, ZDP or ZDTP).

(Other performance additives)
The composition of the present invention further contains other performance additives as required. Other performance additives include the group consisting of cleaning agents other than the component (a) of the present invention, corrosion inhibitors, scratch inhibitors, antifoaming agents, demulsifiers, pour point depressants, sealing swelling agents, and mixtures thereof. More selected.

  The total metering of other performance additives present is often 0% -20% by weight of the composition, preferably 0.01-15% by weight, more preferably based on the absence of oil. 0.05 wt% to 10 wt%, and most preferably 0.1 wt% to 5 wt%. Although one or more other performance additives may be present, the other performance additives are usually present in different amounts relative to each other.

  Detergents other than component (a) of the present invention are known and include alkali metal, alkaline earth metal and transition metal phenates, sulfonates, carboxylic acids, phosphoric acids, monothiophosphoric acids and / or dithiophosphoric acids, saligenin , Neutral or overbased salts, Newtonian or non-Newtonian salts, basic salts, or mixtures thereof with alkyl salicylates. Commonly used metals include sodium, potassium, calcium, magnesium, lithium, or mixtures thereof. The most commonly used metals include sodium, magnesium and calcium. Preferably, the composition of the present invention does not contain a detergent containing sulfur and / or phosphorus.

Other performance additives (corrosion inhibitors (octylamine octanoate, dodecenyl succinic acid or succinic anhydride and condensation products of fatty acids (eg oleic acid) with polyamines; metal deactivators (benzotriazole, 1,2 , 4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzimidazole derivatives); antifoams (copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate) ); Demulsifiers (including trialkyl phosphates, polyethylene glycols, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers); pour point depressants (maleic anhydride-esters of styrene, Li methacrylate, polyacrylates or polyacrylamides); and sealing a swelling agent ^{(Exxon Necton-37 TM (FN} 1380) and Exxon Mineral Seal Oil (FN 3200) and the like) and the like)) Kamata, the present invention In the composition.

(process)
The present invention further provides a process for the preparation of a composition as described above.

  Components (a)-(c) are often continuously mixed separately for the compositions of the present invention. Mixing conditions are often 15 ° C to 130 ° C, preferably 20 ° C to 120 ° C, and most preferably 25 ° C to 110 ° C; and 30 seconds to 48 hours, preferably 2 minutes to 24 hours, more preferably Is from 5 minutes to 16 hours, and most preferably from 10 minutes to 5 hours; and 86 kPa to 266 kPa (650 mmHg to 2000 mmHg), preferably 91 kPa to 200 kPa (690 mmHg to 1500 mmHg), and most preferably 95 kPa to The pressure is in the range of 133 kPa (715 mmHg to 1000 mmHg).

  This process includes mixing other optional performance additives as described above, if desired. This optional performance additive is often added continuously, separately or as a concentrate.

  The following examples provide an illustration of the present invention. These examples are not exclusive and are not intended to limit the scope of the invention.

(Preparation Example 1: Preparation of salixarate substrate (salixarene))
A sample of salixarene substrate was divided into a flange flask with a volume of about 2 liters, a flange and a clip, an overhead stirrer with feathers and a polytetrafluoroethylene (PTFE) stirrer, a Dean Stark trap and a double surface cooler, Using an electric mantle / thermocouple / Eurotherm ^™ temperature control system, the glassware from just above the mantle to just below the cooler is covered with glass wool and prepared. The flask is charged with 475 g polyisobutenyl phenol derived from high vinylidene polyisobutylene having a number average molecular weight of 550 (GLISSSOPAL® 550 commercially available from BASF), and 330 g mineral oil (SN 150); Then heat to 30 ° C. and add 3.4 g of a 50% aqueous solution of KOH through a pressure equalizing dropping funnel. The contents of the flask are heated to 75 ° C. and the temperature is held constant for 30 minutes while 81.6 g of a 37% aqueous solution of formaldehyde (formalin) is added. The reaction is charged with 51.6 g of salicylic acid and heated to 140 ° C. with controlled reflux. Remove water using a Dean Stark trap. The product is vacuum stripped at 140 ° C./13 kPa (equivalent to 100 mmHg) for 30 minutes. A more detailed description of this reaction process is given in Examples 1 and 5 on International Publication WO 03/018728, pages 22 and 23.

(Preparation Example 2: Calcium Salixarate)
A container is charged with 1200 g of salixarate obtained from Preparative Example 1, 25 g of ethylene glycol, 130 g of calcium hydroxide and 410 g of 2-ethylhexanol. The vessel and contents are heated to 95 degrees and stirred at reduced pressure (64 kPa, which is equivalent to 480 mmHg). The vessel and contents are then subjected to a vacuum of 6.7 kPa (equivalent to 50 mmHg) for 15 minutes and heated to 130 ° C. Then, another 120 g of ethylene glycol was dropped into this container over 10 minutes, and then 48 g of carbon dioxide was added through the dip tube with a slight negative pressure (1.0 g / min or less). Add until When the carbon dioxide addition is complete, the dip tube is removed and the temperature is raised to 200 ° C. under a reduced pressure of 6.7 kPa (equivalent to 50 mm Hg) to remove the solvent. The residue is vacuum filtered through a 12 mm diatomaceous earth pad in a semi-melt filter to give a viscous brown liquid.

(Preparation Example 3: Magnesium Salixarate)
A container is charged with 560.5 g of salixarene and 433 g of xylene obtained from Preparative Example 1. The vessel and contents are heated to 35 ° C. under a nitrogen atmosphere where 53 g of magnesium oxide is added. The vessel is then charged with 20.2 g of glacial acetic acid and then a mixture of methanol (42 g) and water (30 g) is added. The vessel and contents are heated to 61 ° C. and carbonated. The vessel and contents are maintained at 61 ° C. for an additional 2 hours and a further mixture of methanol (36 g) and water (26.2 g) is added. The vessel is heated to 150 ° C. and maintained for 1 hour. The product is vacuum stripped.

(Preparation Example 4: Potassium Salixarate)
A container is charged with 313 g of salixarate from Preparative Example 1 and heated to 80 ° C. under a nitrogen atmosphere where 12.1 g of potassium hydroxide in 7 g of water is added dropwise, followed by 85 g Add diluent oil. The vessel and contents are heated at 110 ° C. for 10 minutes, then heated at 120 ° C. for 90 minutes and heated at 140 ° C. for 3 hours. A dark brown product is formed.

(Reference Example 1)
(A) 42.5 g Nexbase ^™ 3050 oil, (b) 34.4 g Nexbase ^™ 3043 oil, (c) 0.4 g amine dispersant viscosity modifier based on the absence of oil, (D) 2.8 g polyisobutylene succinimide dispersant, (e) 5 g antioxidant (including diphenylamine and hindered phenol), (f) 0.7 g olefin copolymer viscosity modification based on oil free condition And (g) glycerol monooleate friction modifier. The composition contains 0 wt% calcium, 0 wt% phosphorus, 190 ppm sulfur and 0 wt% zinc. The composition has a KV100 of 13.11 mm ² / s (sSt) and a 0% wt ash sulfide content.

(Reference Example 2: Upper-seat European passenger car oil formulation)
Reference Example 2 is a successful European upper seat passenger car oil formulation containing zinc dithiosulfate. Elemental analysis of this oil formulation shows a calcium content of 3307 ppm, a phosphorus content of 889 ppm, a sulfur content of 2645 ppm, and a zinc content of 889 ppm. This oil formulation has a KV100 of 11.3 mm ² / s (cSt) and a ash sulfide content of 1.26% by weight.

Example 1
Example 1 has the same composition as Reference Example 1, except that 2.5 g (based on the absence of oil) of the product of Preparative Example 2 is also added. The phosphorus content is 0% by weight and the sulfur content is 190 ppm (all derived from diluent oil).

(Example 2)
Example 2 has the same composition as Reference Example 1 except that 2.5 g (based on the absence of oil) of the product of Preparation Example 3 is also added. The phosphorus content is 0% by weight and the sulfur content is 190 ppm (all derived from diluent oil).

(Example 3)
Example 3 has the same composition as Reference Example 1, except that 2.5 g (based on the absence of oil) of the product of Preparation Example 4 is also added. The phosphorus content is 0% by weight and the sulfur content is 190 ppm (all derived from diluent oil).

A number of lubricating oil compositions were formed using Reference Example 1, based on the absence of oil, by adding 2.5 g of Examples 1-3, thereby producing “Lubrication Including Example 1”. An oil composition "is formed. Example 2 is titled “Lubricating oil composition comprising Example 2”, “Lubricating oil composition comprising Example 3”. The lubricating oil composition comprising Reference Example 1 and the corresponding Examples 1-3 has a KV100 of 13.11 mm ² / s (ie cSt).

(Test 1: HFRR of Examples 1-3 and Reference Examples 1-2)
The lubricating oil composition comprising Examples 1-3 and Reference Examples 1-2 are evaluated for wear performance in a programmed temperature high frequency reciprocating rig (HFRR) available from PCS Instruments. The HFRR conditions for the evaluation are: 200 g load, 75 minutes duration, 1000 micrometer stroke, 20 Hz frequency, and 15 minutes at 40 ° C. followed by a rate of 2 ° C. per minute up to 160 ° C. Is the temperature profile of the temperature rise. Scratches due to abrasion (micrometers) and film formation (percentage of film thickness) are measured, with lower wear scratch values and higher film formation values indicating improved wear performance.

  The percentage of film thickness is based on the measurement of the potential difference between the HFRR upper and lower metal test plates. If the film thickness is 100%, there is a high potential for the full length of the 1000 micrometer stroke, suggesting no metal-to-metal contact. Conversely, for 0% film thickness, there is no potential, suggesting continuous metal-to-metal contact between the plates. For intermediate film thickness, there is an electrical potential and the upper and lower metal test plates have some metal-to-metal contact and other areas where there is no metal-to-metal contact To suggest. The results obtained for abrasion and film formation are provided in Table 1:

（試験２：実施例１および参照実施例１〜２のＣａｍｅｒｏｎ Ｐｌｉｎｔ）
Ｃａｍｅｒｏｎ Ｐｌｉｎｔ ＴＥ−７７^ＴＭは、往復磨耗試験機である。この試験において、鋼球の上部標本が、鋼の平坦な下部標本に押し付けられて往復される。Ｃａｍｅｒｏｎ Ｐｌｉｎｔに、１０ｍｌのサンプルを充填し、そして５０℃まで加熱し、そして１分間維持する。次いで、そのサンプルを、２分間にわたって１００Ｎの負荷に供し、同時に、往復を、１０Ｈｚで１５ｍｍの行程の長さにわたって開始する。次いで、そのサンプルを、１分間あたり３℃で２５０℃まで加熱する。この試験の終了時に、この球に対する磨耗による傷の平均直径（マイクロメートル）（Ｘ次元およびＹ次元で測定）を、較正された顕微鏡を使用して測定する。得られる結果は、以下である：

(Test 2: Cameron Print of Example 1 and Reference Examples 1-2)
The Cameron Print TE-77 ^™ is a reciprocating wear tester. In this test, an upper specimen of a steel ball is reciprocated against a flat lower specimen of steel. The Cameron Print is filled with 10 ml of sample and heated to 50 ° C. and maintained for 1 minute. The sample is then subjected to a 100 N load for 2 minutes while simultaneously starting a round trip over a length of 15 mm stroke at 10 Hz. The sample is then heated to 250 ° C. at 3 ° C. per minute. At the end of the test, the average diameter of the scratches due to wear on the sphere (micrometers) (measured in the X and Y dimensions) is measured using a calibrated microscope. The results obtained are as follows:

（試験３：ＡＳＴＭ Ｄ４１７２を使用する、４つの球での磨耗試験）
この試験において使用される、「実施例４の潤滑湯組成物」および「実施例５の潤滑油組成物」は、「実施例４」が、油がない状態に基づいて、２ｇの調製実施例２から得られた生成物を含み、そして約１９００ｐｐｍのカルシウムおよび約１４６のＴＢＮを有すること；ならびに「実施例５」が、油がない状態に基づいて、１．２ｇの調製実施例２から得られた生成物を含み、そして約１３００ｐｐｍのカルシウムおよび約１４６のＴＢＮを有することを除いて、「実施例１の潤滑油組成物」と同じである。参照実施例３は、アルキルサリチル酸カルシウム（ＩｎｆｉｎｅｕｍからＡＣ６０Ｃ^ＴＭ範囲の製品から市販されている）が、約１３００ｐｐｍのカルシウムおよび約１４６のＴＢＮを有するために充分な量で添加されていることを除いて、参照実施例１と同じ油の組成を有する。参照実施例４は、サリゲニンマグネシウム（Ｔｈｅ Ｌｕｂｒｉｚｏｌ Ｃｏｒｐｏｒａｔｉｏｎから市販されている）が、約１３００ｐｐｍのマグネシウムおよび約１４６のＴＢＮを有するために充分な量で添加されていることを除いて、参照実施例１と同じ油の組成を有する。

(Test 3: Abrasion test with four balls using ASTM D4172)
The “lubricating water composition of Example 4” and the “lubricating oil composition of Example 5” used in this test are “Example 4” based on the absence of oil. And containing about 1900 ppm calcium and about 146 TBN; and "Example 5" was obtained from 1.2 g of Preparation Example 2 based on the absence of oil. The same as “Lubricating oil composition of Example 1” except that it contains about 1300 ppm calcium and about 146 TBN. Reference Example 3 except that calcium alkyl salicylate (commercially available from products in the AC60C ^TM range from Infineum) is added in an amount sufficient to have about 1300 ppm calcium and about 146 TBN. Having the same oil composition as in Reference Example 1. Reference Example 4 is a reference example, except that saligenin magnesium (commercially available from The Lubrizol Corporation) is added in an amount sufficient to have about 1300 ppm magnesium and about 146 TBN. 1 has the same oil composition.

  The ASTM D4172 test is performed on a number of examples using the modified B condition shown on page 8 of ASTM D 4172-94 (reauthorized in 1999). The scratches due to wear are measured in micrometers. The results obtained are as follows:

試験１および試験２からのデータの全体の分析は、本発明の組成物が、参照実施例１と比較して、良好な耐磨耗結果およびフィルム形成結果を生じることを示す。この分析はまた、実施例１の潤滑油組成物が、ジチオリン酸亜鉛を含有する、首尾よいヨーロッパの上段座席の乗用車の油処方物に匹敵する、耐磨耗結果およびフィルム形成結果を有することを示す。

An overall analysis of the data from Test 1 and Test 2 shows that the composition of the present invention produces good wear and film formation results compared to Reference Example 1. This analysis also shows that the lubricating oil composition of Example 1 has wear resistance and film formation results comparable to a successful European upper seat passenger car oil formulation containing zinc dithiophosphate. Show.

  As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group”, as used herein, is used in its original meaning, which meaning is well known to those skilled in the art. Specifically, the term refers to a group consisting primarily of carbon and hydrogen atoms and bonded to the rest of the molecule through the carbon atom, and the molecule has preferential hydrocarbon character. It does not exclude the presence of other atoms or groups in a proportion insufficient to impair it. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group; typically, the hydrocarbyl group has no non-hydrocarbon substituent ,not exist. A more detailed definition of the term “hydrocarbyl substituent” or “hydrocarbyl group” is described in US Pat. No. 6,583,092.

  Each of the documents referenced above is incorporated herein by reference. Except in the examples or where otherwise explicitly indicated, all numerical quantities specifying the amount of material, reaction conditions, molecular weight, number of carbon atoms, etc. herein are expressed in the word “about”. Should be understood to be modified by Unless otherwise indicated, each of the chemistries or compositions described herein should be construed as commercially available grade materials, which are isomers, by-products, derivatives, and It may contain other materials normally understood to be present in commercial grades. However, the amount of each chemical component is present excluding any solvent or diluent oil that would normally be present in commercially available materials, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements. As used herein, the expression “consisting essentially of” permits the inclusion of substances that do not significantly affect the basic and novel characteristics of the composition under consideration.

  The compositions of the present invention are useful in internal combustion engines (eg, diesel fuel engines, gasoline fuel engines, natural gas fuel engines, or mixed gasoline / alcohol fuel engines).

One embodiment of the invention provides a method for lubricating an internal combustion engine that provides the internal combustion engine with a lubricant containing a composition as described herein. Process. Use of the compositions of the present invention, improved engine cleanliness, decreased wear, can confer one or more of selected from the group consisting of reduced _the NO _x releasing and reduced particle emission.

Claims (1)

Invention described in this specification.