JP2020502338A - Ether based lubricant compositions, methods and uses - Google Patents

Abstract

The present invention provides a lubricant composition for an internal combustion engine, comprising a base oil of lubricating viscosity, wherein the base oil comprises an ether base oil of formula (A). Wherein: Ra and Rb are aliphatic hydrocarbyl groups, which may be the same or different, and at least one of Ra and Rb is a branched alkyl, alkoxy-substituted alkyl or cycloalkyl-substituted alkyl The lubricant composition further comprises at least one amine antioxidant and / or at least one phenolic antioxidant, wherein the lubricant composition comprises an amine antioxidant and a phenolic antioxidant. The total amount is no more than 4.0% by weight of the lubricant composition. In some embodiments, the ether base oil has the formula (1). Where: R1R2, R3, R4, R5, and R6 are as defined herein. The lubricant composition may be used to lubricate the surface of an internal combustion engine and to improve fuel economy performance and / or piston cleanliness performance of an engine and / or vehicle such as an automobile associated with the internal combustion engine. it can. [Selection diagram] Fig. 1

Description

  The present invention relates to lubricant compositions containing base oils including certain ether bases suitable for use in lubricant compositions intended for use in internal combustion engines. Also provided are lubricant compositions and ether-based manufacturing methods and uses.

  Lubricating compositions generally include one or more additives to provide properties including, for example, reduced friction and wear, improved viscosity index, improved dispersibility, detergency, and resistance to oxidation and corrosion. Contains a base oil of lubricating viscosity along with the agent The lubricating base oil may include one or more lubricating base oils.

  Lubricant basestocks used in automotive engine lubricants are generally obtained from petrochemical sources, for example, they can be isolated as high boiling fractions isolated during the refining of crude oil or from petrochemical sources. As a product of a chemical reaction of the feedstock from the feedstock. Lubricant basestocks can also be made from Fischer-Tropsch wax.

Lubricating oil basestocks are classified into groups I, II, and II according to API Standard 1509, `` Engine Oil Licensing and Certification System '', 17th Edition, Appendix E (October 2015, Errata March), as shown in Table 1. They can be classified as III, IV, and V basestocks.

  Group I basestocks are typically manufactured by known processes including, for example, solvent extraction and solvent dewaxing, or solvent extraction and catalytic dewaxing. Group II and Group III basestocks are typically produced by known processes including, for example, catalytic hydrogenation and / or catalytic hydrocracking, and catalytic hydroisomerization. Group IV basestocks include, for example, hydrogenated oligomers of alpha olefins.

  A combination of properties is desirable in a substrate for application to a lubricant composition containing the same. In some cases, for example, in passenger car engine oils, a base may be desirable because imparting a low viscosity profile to the lubricant composition leads to improved fuel economy. In particular, it is desirable for the basestock to have low kinematic viscosity as well as good low temperature viscosity properties, such as a low pour point or viscosity as measured using a mini-rotary viscometer (MRV). However, a general trend is that improving the viscosity profile of the base oil (ie, reducing the viscosity parameter) is accompanied by an undesirable increase in volatility.

  Further, it is desirable that the lubricant composition exhibit good oxidative stability, especially when used in internal combustion engines where oxidative degradation is exacerbated as a result of the high temperatures encountered in engines. Good oxidative stability can extend the useful life of the lubricant composition, e.g., by reducing oxidative thickening that could otherwise quickly lead to fuel economy loss, and It can be prolonged by reducing deposits and sludge formation that could otherwise lead to engine failure. Typically, the oxidative stability of a lubricant composition is improved by the addition of an antioxidant. Antioxidant levels, which are representative of high performance engine oils, can exceed 5% by weight of the lubricant composition. Thus, a significant proportion of the composition may be comprised of antioxidants, and thus represent a significant cost component of the lubricant composition. Common antioxidants used in lubricant compositions for use in internal combustion engines include phenolic and amine antioxidants. However, the presence of phenolic antioxidants is known to have deleterious environmental effects, while the presence of amine antioxidants can contribute to turbocharger deposits, piston varnishes and copper corrosion. It has been found by the inventors and can cause problems with elastomer compatibility. Negative interactions between the lubricant composition and the oil seal found in engines can sometimes result in lubricant loss due to oil seal failure.

  Accordingly, there is a need for a lubricant composition that has low volatility for a given viscosity profile, but is also suitable for use in internal combustion engines. Also, as typically associated with high performance engine oils, there is a need for a lubricant composition that exhibits good oxidative stability without requiring high antioxidant treat rates.

ここで:
R_aおよびR_bは、脂肪族ヒドロカルビル基であり、同一であっても異なっていてもよく、R_aおよびR_bの少なくとも1つは、分枝鎖アルキル、アルコキシ置換アルキルまたはシクロアルキル置換アルキルである。 Thus, in a first aspect, there is provided a lubricant composition for an internal combustion engine comprising a base oil of lubricating viscosity, wherein the base oil comprises an ether base oil of formula (A).

here:
R _a and R _b are aliphatic hydrocarbyl groups, which may be the same or different, and at least one of R _a and R _b is a branched alkyl, alkoxy-substituted alkyl or cycloalkyl-substituted alkyl. is there.

  The lubricant composition further comprises at least one amine antioxidant and / or at least one phenolic antioxidant, and the total amount of the amine antioxidant and the phenolic antioxidant in the lubricant composition Is 4.0% by weight or less of the lubricant composition.

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₃、R₄およびR₅はHまたはアルキルであり、
R₆はアルキルまたは

ここで:
R₇およびR₈は、H、アルキル、またはそれらが結合している炭素原子と一緒になってシクロアルキルである。
R₉はHまたはアルキルであり、
Xはアルキレンであるか、または存在せず、
pは0、1、2または3であり、
mおよびnは0、1、2または3であり、mはR₄およびR₅がHである場合0である。 In a particularly preferred embodiment, the ether base of the lubricant composition is selected from compounds of formula (A), ie a subset of compounds of formula (1).

here:
R ₁ and R ₂ are alkyl or, together with the carbon atom to which they are attached, cycloalkyl;
R ₃ , R ₄ and R ₅ are H or alkyl;
R ₆ is alkyl or

here:
R ₇ and R ₈ together with H, alkyl, or the carbon atom to which they are attached, are cycloalkyl.
R ₉ is H or alkyl;
X is alkylene or absent;
p is 0, 1, 2 or 3;
m and n are 0, 1, 2 or 3, and m is 0 when R ₄ and R ₅ are H.

  Also provided is a method of making a lubricant composition.

  Also provided is a method for lubricating a surface using a lubricant composition, as well as the use of the lubricant composition for lubricating a surface.

  Also provided are methods and uses for improving the oxidative stability of a lubricant composition, as well as improving fuel economy performance and / or piston cleanliness performance of an engine and / or vehicle, such as an automobile, associated with an internal combustion engine.

Detailed description

ここで:
R_aおよびR_bは、脂肪族ヒドロカルビル基であり、同一であっても異なっていてもよく、R_aおよびR_bの少なくとも1つは、分枝鎖アルキル、アルコキシ置換アルキルまたはシクロアルキル置換アルキルである。 A lubricant composition for an internal combustion engine is provided, comprising a base oil of lubricating viscosity, wherein the base oil comprises an ether base oil of formula (A).

here:
R _a and R _b are aliphatic hydrocarbyl groups, which may be the same or different, and at least one of R _a and R _b is a branched alkyl, alkoxy-substituted alkyl or cycloalkyl-substituted alkyl. is there.

  The lubricant composition further comprises at least one amine antioxidant and / or at least one phenolic antioxidant, and the total amount of the amine antioxidant and the phenolic antioxidant in the lubricant composition Is 4.0% by weight or less of the lubricant composition.

  For the purposes of the present invention, the following terms as used herein, unless otherwise indicated, shall be understood to have the following meanings:

  The term `` aliphatic hydrocarbyl '' as used herein refers to the group comprising hydrogen and carbon atoms, wherein one or more carbon atoms may be optionally substituted with -O-, This group may be saturated or unsaturated, preferably saturated, and examples of hydrocarbyl groups containing 1 to 40 carbon atoms include 2 to 28 carbon atoms, e.g., 3 to 26 carbon atoms. And hydrocarbyl groups containing 4 to 24 carbon atoms. Where one or more of the carbon atoms are replaced with -O-, it is preferred that 2% to 35% of the carbon atoms be replaced with -O-, or 5% to 25%. In another example, an aliphatic hydrocarbyl group has 1-3 carbon atoms substituted with -O-, for example, 2 carbon atoms substituted with -O-. In other examples, none of the carbon atoms are replaced with -O-.

  Examples of aliphatic hydrocarbyl groups include acyclic groups, non-aromatic cyclic groups, and groups that include both acyclic and non-aromatic cyclic moieties. Aliphatic hydrocarbyl groups may be straight or branched. Aliphatic hydrocarbyl groups include monovalent and polyvalent groups as specified. Examples of monovalent hydrocarbyl groups include alkyl, alkenyl, alkynyl and carbocyclyl (eg, cycloalkyl or cycloalkenyl).

  The term “alkyl,” as used herein, refers to a monovalent straight or branched chain alkyl moiety containing 1 to 40 carbon atoms. Examples of alkyl groups include 1 to 30 carbon atoms, such as 2, 3 or 4 carbon atoms to 24, 25 or 26 carbon atoms, such as 1 to 20 carbon atoms, 1 to 14 carbon atoms. Alkyl groups containing carbon atoms, 2 to 26 carbon atoms and 3 to 24 carbon atoms are included. Specific examples include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 22, Alkyl groups containing 23, 24, 25, 26, 27, 28, 29 and 30 carbon atoms are included. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tertbutyl, pentyl, hexyl, and the like. Unless otherwise indicated, the term "alkyl" does not include any substituents.

  The term `` cycloalkyl, '' as used herein, refers to a monovalent saturated, containing 3 to 40 carbon atoms, including at least one ring, wherein the ring has at least 3 ring carbon atoms. Refers to an aliphatic hydrocarbyl moiety. The cycloalkyl groups described herein may optionally have an alkyl group attached thereto. Examples of cycloalkyl groups include cycloalkyl groups containing 3 to 16 carbon atoms, for example, 3 to 10 carbon atoms. Particular examples include cycloalkyl groups containing 3, 4, 5, or 6 ring carbon atoms. Examples of cycloalkyl groups include groups that are monocyclic, polycyclic (eg, bicyclic) or bridged ring systems. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

  The term `` alkenyl, '' as used herein, contains from 2 to 40 carbon atoms and, unless otherwise specified, contains at least one carbon-carbon double bond in either the E or Z configuration. Refers to a monovalent linear or branched alkyl group. Examples of alkenyl groups include alkenyl groups containing from 2 to 28 carbon atoms, such as from 3 to 26 carbon atoms, such as from 4 to 24 carbon atoms. Particular examples include alkenyl groups containing 2, 3, 4, 5 or 6 carbon atoms. Examples of alkenyl groups include ethenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, and the like. included.

  The term "alkylene" refers to a divalent straight or branched chain saturated hydrocarbyl group consisting of hydrogen and carbon atoms and containing from 1 to 30 carbon atoms. Examples of alkylene groups include alkylene groups containing 1 to 20 carbon atoms, such as 1 to 12 carbon atoms, such as 1 to 10 carbon atoms. Particular examples include alkylene groups containing 1, 2, 3, 4, 5 or 6 carbon atoms.

  The term “alkoxy,” as used herein, refers to —O-alkyl, where alkyl is as defined herein. In some examples, the alkoxy group has 1 to 40 carbon atoms, such as 1 to 28 carbon atoms, or 1 to 26 carbon atoms, or 1 to 24 carbon atoms, such as 1 to 10 carbon atoms. Containing carbon atoms. Particular examples include alkoxy groups containing 1, 2, 3, 4, 5 or 6 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.

  The terms `` alkoxy-substituted alkyl '' and `` cycloalkyl-substituted alkyl '' are straight or branched, wherein one of the alkyl chain hydrogens is replaced with an alkoxy or cycloalkyl group, respectively, as described herein. Refers to a branched alkyl group.

In some embodiments, R _a and R _b in Formula (A) are independently selected from alkyl, alkoxy-substituted alkyl, and cycloalkyl-substituted alkyl, provided that R _a and R _b are both , _Ra and _Rb are branched alkyl. In a preferred embodiment, when _Ra and _Rb are both alkyl, _Ra and _Rb are both branched alkyl.

In some embodiments, R _a and R _b of formula (A) are C _1-30 alkyl, such as C _2-20 alkyl, C _5-30 cycloalkyl substituted alkyl, such as C _5-25 cycloalkyl substituted alkyl. Or C _2-30 alkoxy-substituted alkyl, such as C _2-20 alkoxy-substituted alkyl.

In some embodiments, R _a of Formula (A) contains more carbon atoms than R _b .

In some embodiments, R _a of formula (A), 12 to 30 carbon atoms, preferably comprising 12 to 26 carbon atoms, and / or R _b is from 2 to 20 carbon atoms , Preferably containing 2 to 12 carbon atoms.

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₃、R₄およびR₅はHまたはアルキルであり、
R₆はアルキルまたは

ここで:
R₇およびR₈は、H、アルキル、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₉はHまたはアルキルであり、
Xはアルキレンであるか、または存在せず、
pは0、1、2または3であり、
mおよびnは0、1、2または3であり、mはR₄およびR₅がHである場合0である。 In a particularly preferred embodiment, the ether base of the lubricant composition is a compound of formula (1).

here:
R ₁ and R ₂ are alkyl or, together with the carbon atom to which they are attached, cycloalkyl;
R ₃ , R ₄ and R ₅ are H or alkyl;
R ₆ is alkyl or

here:
R ₇ and R ₈ are H, alkyl, or cycloalkyl together with the carbon atom to which they are attached,
R ₉ is H or alkyl;
X is alkylene or absent;
p is 0, 1, 2 or 3;
m and n are 0, 1, 2 or 3, and m is 0 when R ₄ and R ₅ are H.

In some embodiments, R ₁ and R ₂ are C _1-15 alkyl, or C _5-30 cycloalkyl, such as C _2-12 alkyl, along with the carbon atom to which they are attached. Or C _5-25 cycloalkyl, together with the carbon atom to which they are attached.

In some embodiments, R ₃ , R ₄ and R ₅ are H or C _1-15 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₅ is H.

In some embodiments, R ₆ is C _1-20 alkyl or C _1-16 alkyl or such.

In some embodiments, R ₇ and R ₈ are H, C _1-20 alkyl, or C _5-30 cycloalkyl, such as H, C _2-12 alkyl, or C _5-25 cycloalkyl, with the carbon atom to which it is attached. Preferably, R ₇ and R ₈ are C _1-20 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₉ is H or C _1-20 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₉ is H.

In some embodiments, X is C _1-20 alkylene, eg, C _3-15 alkylene.

  In some embodiments, p is 0, 1 or 2, for example 0 or 1.

  In some embodiments, m and n are 0, 1 or 2, for example 0 or 1.

R ₁ and R ₂ are described as cycloalkyl, together with the carbon atom to which they are attached. When R ₁ and R ₂ are both alkyl groups, it will be understood that they may be the same or different from each other. Similar considerations apply to other substituents that are defined as part of the group of substituents. Thus, considerations apply, for example, to the values taken by R ₃ , R ₄ and R ₅ , R ₇ and R ₈ , and m and n. For example, if R ₃ , R ₄ and R ₅ are stated to be H or alkyl, each of R ₃ , R ₄ and R ₅ can be H, and each of R ₃ , R ₄ and R ₅ is alkyl Or a subset of R ₃ , R 4 and R 5 can be H and another subset of R ₃ , R 4 and R 5 can be alkyl. When R ₃ , R ₄ and R ₅ , or a subset thereof, are alkyl, each of R ₃ , R ₄ and R ₅ may be the same alkyl group, or they may be different alkyl groups. Good. In contrast, when R ₁ (or any other notation) is used at several positions in the formula, R ₁ is used to indicate the presence of the same group at each of these positions. You.

  In each of the embodiments disclosed herein, the ether compound of the lubricant composition can include a total number of about 20 to about 50 carbon atoms. For example, the total number of carbons in the ether compound can be about 25 to about 45, for example, about 28 to about 40 or about 28 to about 36.

As indicated above, the alkyl and alkylene groups referred to herein, namely, R _a , R _b , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R9 and X may be a linear alkyl group or an alkylene group, but may be branched. In some embodiments, each alkyl group and each alkylene group comprises a single branch point or is a straight chain alkyl or alkylene group. For example, if _Ra and _Rb are both alkyl groups, at least one of these alkyl groups is branched, preferably both. In some embodiments, for example, for R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and X groups, the alkyl and alkylene groups are straight chain alkyl. Or an alkylene group. It is understood that, in addition to the alkyl branch (if present), the alkyl and alkylene groups, unless otherwise indicated, are unsubstituted and, therefore, may not contain atoms other than carbon or hydrogen. Will.

  Compounds of formula (A) and / or formula (1) may have a kinematic viscosity at 40 ° C. of less than about 25 cSt, such as less than about 20 cSt, or less than about 17 cSt. The compound can have a kinematic viscosity at 100 ° C. of less than about 7 cSt, for example, less than about 5 cSt, or less than about 4 cSt. The compound may have a viscosity index greater than about 100, such as greater than about 110, or greater than about 120. Kinematic viscosity at 40 ° C. and kinematic viscosity at 100 ° C. can be measured according to ASTM D7279. The viscosity index can be measured according to ASTM D2270.

  The compound may have a Noack volatility of less than about 26% by weight, for example, less than about 20%, less than about 16%, or less than about 12% by weight. Noack volatility can be measured according to CEC-L-40-A-93.

The compound may have a viscosity at 150 ° C. and a shear rate of less than 1.7 cP, for example less than 1.5 cP, of 10 ⁶ s ⁻¹ . This high temperature high shear viscosity can be measured according to CEC-L-36-A-90.

  The ether compounds described herein are preferably used for internal combustion engines, such as those associated with automobiles, in order for the lubricant composition to achieve a certain level of oxidative stability performance. In addition, the antioxidant may be used to reduce the total amount of antioxidant additives required in the lubricant composition, wherein the antioxidant comprises at least one aminic antioxidant and / or at least one phenolic antioxidant. Contains oxidizing agents. In a preferred embodiment, the lubricant composition to be improved by the use of an ether compound as described herein comprises an amine and / or phenolic antioxidant, and the amine and phenolic in the lubricant composition. The total amount of antioxidant is 4.0% by weight or less, 3.0% by weight or less, 2.5% by weight or less, or 2.0% by weight or less of the lubricant composition. In a preferred embodiment, the lubricant composition to be improved by the use of an ether compound as described herein comprises an amine and / or phenolic antioxidant, and the amine and phenolic in the lubricant composition. The total amount of antioxidant is at least 0.25%, at least 0.5%, or at least 1.0% by weight of the lubricant composition.

  Accordingly, a method of reducing the total amount of antioxidant additives required in a lubricant composition in order for the lubricant composition to achieve a particular level of oxidation stability performance, wherein the antioxidant comprises at least Also provided is a method comprising one amine antioxidant and / or at least one phenolic antioxidant and comprising providing or supplying at least one of the ether compounds described herein to a lubricant composition. Is done. In a preferred embodiment, the lubricant composition is for an internal combustion engine such as that associated with a motor vehicle. In a preferred embodiment, the lubricant composition for improving with the ether compounds described herein comprises an amine and / or phenolic antioxidant, and the amine and phenolic antioxidant in the lubricant composition. The total amount of the agent is 4.0% by weight or less, 3.0% by weight or less, 2.5% by weight or less, or 2.0% by weight or less of the lubricant composition. In a preferred embodiment, the lubricant composition for improving with the ether compounds described herein comprises an amine and / or phenolic antioxidant, and the amine and phenolic in the lubricant composition. The total amount of antioxidant is at least 0.25%, at least 0.5%, or at least 1.0% by weight of the lubricant composition.

  The lubricant compositions described herein can be used to improve fuel economy performance and / or piston cleaning performance of engines and / or vehicles such as automobiles associated with internal combustion engines. Accordingly, the fuel economy and / or piston cleanliness performance of an engine and / or vehicle, such as an automobile, associated with an internal combustion engine, including providing the engine and / or vehicle with a lubricant composition as described herein. An improved method is provided.

  The ether compounds described herein can have a pour point of less than −10 ° C., for example, less than about −25 ° C., or less than about −35 ° C. The pour point can be measured according to ASTM D5950.

  The ether compound can have a cold crankcase simulator viscosity at −35 ° C. of less than about 1800 cP, such as less than about 1500 cP, or less than about 1200 cP as measured according to ASTM D5293.

  The ether compound may have a differential oxidation onset temperature, for example, greater than about 165 ° C, such as greater than about 175 ° C, or greater than about 185 ° C, as measured according to ASTM E2009 (Method B).

  In certain embodiments, the ether compound of formula (A) or formula (1) has a kinematic viscosity at 100 ° C. of about 3 to about 4 cSt, and less than about 20% by weight, such as less than about 16% by weight, or about 12% by weight. It may have a Noack volatility of less than about 10% by weight, or a kinematic viscosity at 100 ° C. of about 2 to about 3 cSt, and a Noack volatility of less than about 40% by weight, such as less than about 30% by weight.

  The ether compounds of formula (A) or (1) are particularly suitable for blending into a lubricant composition. In particular, the compounds are compatible with conventional basestocks, including hydrocarbon basestocks, as well as conventional lubricant additives. In addition, the compound may be present in the lubricant composition in relatively large amounts (e.g., about 10% higher, e.g., about 20% higher or about 30% higher by weight) while still meeting the elastomer compatibility requirements of the lubricant composition. Can be used with

  Compounds of formula (A) and formula (1) can be prepared from a wide variety of commercial feeds.

  In some embodiments, the compound is prepared from a biological source. For example, the compound may contain greater than about 50%, such as greater than about 70%, or greater than about 80% by weight biobased carbon. The biobased carbon content of a compound can be measured according to ASTM D6866.

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₃およびR₅はHまたはアルキルであり、
R₄はアルキルであり、
R₆はアルキルまたは

ここで:
R₇およびR₈は、H、アルキル、またはそれらが結合している炭素原子と一緒になってシクロアルキルである。
R₉はHまたはアルキルである。
X は、アルキレンであるか、または存在せず;そして
pは、0、1、2または3であり;そして
nは、0、1、2または3である。 Guerbet-Derived Basestock In a preferred embodiment, the compound of formula (1) is derived from a β-alkylated alcohol. In these embodiments, the compound can have Formula (2).

here:
R ₁ and R ₂ are alkyl or, together with the carbon atom to which they are attached, cycloalkyl;
R ₃ and R ₅ are H or alkyl;
R ₄ is alkyl;
R ₆ is alkyl or

here:
R ₇ and R ₈ together with H, alkyl, or the carbon atom to which they are attached, are cycloalkyl.
R ₉ is H or alkyl.
X is alkylene or absent; and
p is 0, 1, 2 or 3; and
n is 0, 1, 2 or 3.

In some embodiments, R ₁ and R ₂ are C _1-15 alkyl, or C _5-30 cycloalkyl, such as C _2-12 alkyl, along with the carbon atom to which they are attached. Or C _5-25 cycloalkyl, together with the carbon atom to which they are attached. Preferably, R ₁ and R ₂ are C _1-15 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₃ and R ₅ are H or C _1-15 alkyl (eg, H or C _2-12 alkyl). Preferably, R ₃ and R ₅ are H.
In some embodiments, R ₄ is C _1-15 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₆ is C _1-15 alkyl or C _1-12 alkyl or such.

In some embodiments, R ₇ and R ₈ are H, C _1-20 alkyl, or C _5-30 cycloalkyl, such as H, C _2-12 alkyl, or C _5-25 cycloalkyl, with the carbon atom to which it is attached. Preferably, R ₇ and R ₈ are C _1-20 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₉ is H or C _1-20 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₉ is H.

In some embodiments, X is C _1-20 alkylene, eg, C _3-15 alkylene.

  In some embodiments, p is 0, 1 or 2, for example 0 or 1.

  In some embodiments, n is 0, 1 or 2, for example 0 or 1.

ここで:
R₁はアルキルであり、
R₃およびR₅はHまたはアルキルであり、
R₄はアルキルであり、
R₆はアルキルまたは

ここで:
R₇およびR₈は、H、アルキル、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₉はHまたはアルキルであり、
X は、アルキレンであるか、または存在せず;そして
pは、0、1、2または3であり;そして
nは、0、1、2または3である。 If the compound is derived from a β-alkylated alcohol, it is preferably at least partially derived from Guerbet alcohol. Compounds derived at least in part from Guerbet alcohols can have formula (3).

here:
R ₁ is alkyl;
R ₃ and R ₅ are H or alkyl;
R ₄ is alkyl;
R ₆ is alkyl or

here:
R ₇ and R ₈ are H, alkyl, or cycloalkyl together with the carbon atom to which they are attached,
R ₉ is H or alkyl;
X is alkylene or absent; and
p is 0, 1, 2 or 3; and
n is 0, 1, 2 or 3.

In some embodiments, R ₁ is C _1-12 alkyl, such as C _2-10 alkyl.

In some embodiments, R ₃ is H or C _1-12 alkyl, eg, H or C _2-10 alkyl. Preferably, R ₃ is H.

いくつかの実施態様において、R₆は、C_1-15アルキルまたはC_1-12アルキルまたはそのようなものである。好ましくは、R₆はC_1-15アルキル、例えばC_1-12アルキルである。 In some embodiments, R ₄ is C _1-15 alkyl, such as C _2-12 alkyl.
In some embodiments, R ₅ is H or C _1-15 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₅ is H.

In some embodiments, R ₆ is C _1-15 alkyl or C _1-12 alkyl or such. Preferably, R ₆ is C _1-15 alkyl, for example C _1-12 alkyl.

In some embodiments, R ₇ and R ₈ are H, C _1-20 alkyl, or C _5-30 cycloalkyl, such as H, C _2-12 alkyl, or C _5-25 cycloalkyl, with the carbon atom to which it is attached. Preferably, R ₇ and R ₈ are C _1-20 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₉ is H or C _1-20 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₉ is H.

In some embodiments, X is C _1-20 alkylene, eg, C _3-15 alkylene.

  In some embodiments, p is 0, 1 or 2, for example 0 or 1.

  In some embodiments, n is 0, 1 or 2, for example 0 or 1.

ここで:
R₁およびR₄はアルキルであり、
R₃およびR₅はHまたはアルキルである。 One part of the compound of formula (3) is Guerbet alcohols (i.e., the portion containing R ₁ and R ₃₎ have a structure which can be derived from other parts, Guerbet alcohols (i.e., R ₄ need not be derived from the portion) containing R ₅ and R _6. However, in a preferred embodiment, the compound can be derived from a combination of two Guerbet alcohols. The compound thus prepared can have the formula (4)

here:
R ₁ and R ₄ are alkyl;
R ₃ and R ₅ are H or alkyl.

In some embodiments, R ₁ and R ₄ are C _1-12 alkyl, such as C _2-10 alkyl.

In some embodiments, R ₃ and R ₅ are H or C _1-12 alkyl (eg, H or C _2-10 alkyl). Preferably, R ₃ and R ₅ are H.

In certain embodiments:
R ₁ is C _4-12 alkyl, such as C _6-10 alkyl;
R ₃ is H,
R ₄ is C _1-10 alkyl, such as C _2-8 alkyl;
R ₅ is H.

Two different Guerbet alcohols can be combined to form a compound of formula (4), where R ₁ and R ₄ can be different. Alternatively, R ₃ and R ₅ may be different. In some embodiments, R ₁ and R ₄ are different and R ₃ and R ₅ are different.

ここで:
R₁はアルキルであり、
R₃はHまたはアルキルである。 However, in some embodiments, the compounds may be derived from reactions in which the same guerbe alcohol is combined. The compound thus prepared can have the formula (5)

here:
R ₁ is alkyl;
R ₃ is H or alkyl.

In some embodiments, R ₁ is C _1-10 alkyl, such as C _2-9 alkyl.

In some embodiments, R ₃ is H or C _1-9 alkyl, eg, H or C _2-8 alkyl. Preferably, R ₃ is H.

In certain embodiments:
R ₁ is C _3-10 alkyl, such as C _4-8 alkyl;
R ₃ is H.

  Compounds derived from Guerbet alcohol include compounds GE1-GE3, GE5, GE7-GE9, SE1, SE2 and TE1, as shown in Table 2.

ここで、R₁およびR₃は、前に定義した通りであり、
および/または:

ここで、R₄およびR₅は、前に定義した通りである。 Guerbet alcohols can be prepared, for example, by dimerizing a primary alcohol in a Guerbet reaction to form a β-alkylated alcohol product.

Where R ₁ and R ₃ are as defined above,
And / or:

Here, R ₄ and R ₅ are as defined above.

  The Guerbet reaction is well known to those skilled in the art. The reaction is typically performed at an elevated temperature in the presence of a catalyst.

ここで:
Yは脱離基であり、
R₁、R₃、R₄、R₅、R₆およびnは、式(3)の化合物について先に定義したとおりである。
2つのGuerbetアルコールが化合物を形成するために組み合わされる場合、Guerbetアルコールの1つは、脱離基Yを含むように最初に修飾されてもよく、次いで、化合物が調製される。

次に、

または:

次に、

ここで:
Yは脱離基であり、
R₁、R₃、R₄およびR₅は、式(4)の化合物について先に定義した通りである。 Compounds can be prepared from Guerbet alcohol, for example, according to the following reaction.

here:
Y is a leaving group,
R ₁ , R ₃ , R ₄ , R ₅ , R ₆ and n are as defined above for the compound of formula (3).
When two Guerbet alcohols are combined to form a compound, one of the Guerbet alcohols may be first modified to include a leaving group Y, and the compound is then prepared.

next,

Or:

next,

here:
Y is a leaving group,
R ₁ , R ₃ , R ₄ and R ₅ are as defined above for the compound of formula (4).

次に、

ここで:
Yは脱離基であり、
R₁およびR₃は、式(5)の化合物について先に定義したとおりである。 If the same Guerbet alcohols are combined to form a compound, they may be combined, for example, according to the following reaction.

next,

here:
Y is a leaving group,
R ₁ and R ₃ are as defined above for the compound of formula (5).

  Methods and reaction conditions for modifying Guerbet alcohols so that they contain the leaving group Y are known to those skilled in the art. For example, a mesylate group can be introduced by reacting Guerbet alcohol with mesyl chloride in the presence of triethylamine. Bromide groups can be introduced by reacting Guerbet alcohol with N-bromosuccinimide and triphenylphosphine.

  Methods and reaction conditions for performing the etherification reaction are known to those skilled in the art. A base (e.g., potassium hydroxide or potassium tert-butoxide), a catalyst (e.g., Starks' catalyst: N-methyl-N, N, N-trioctyloctane-1-ammonium chloride) or both are reacted with the compound to form the compound. That is, it can be used in an etherification reaction.

  In the compound formation reactions described above, Y may be any suitable leaving group such as a halogen (eg, bromine, chlorine or iodine) or a sulfonate ester (eg, mesylate or tosylate).

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素と一緒になって、シクロアルキルである。
R₃、R₄およびR₅はHまたはアルキルである。

R₆はアルキルまたは。
ここで:
R₇およびR₈は、H、アルキル、またはそれらが結合している炭素原子と一緒になってシクロアルキルである。
R₉はHまたはアルキルである。 Secondary and Tertiary Ether Based In some preferred embodiments, the compound of formula (1) is a secondary or tertiary ether compound. In these embodiments, the compound can have Formula (6).

here:
R ₁ and R ₂ are alkyl or, together with the carbon to which they are attached, are cycloalkyl.
R ₃ , R ₄ and R ₅ are H or alkyl.

R ₆ is alkyl or.
here:
R ₇ and R ₈ together with H, alkyl, or the carbon atom to which they are attached, are cycloalkyl.
R ₉ is H or alkyl.

X is alkylene or absent; and
p is 0, 1, 2 or 3; and
n is 0, 1, 2 or 3.

In some embodiments, R ₁ and R ₂ are C _1-15 alkyl, or C _5-30 cycloalkyl, such as C _2-12 alkyl, along with the carbon atom to which they are attached. Or C _5-25 cycloalkyl, together with the carbon atom to which they are attached. Preferably, R ₁ and R ₂ are C _1-15 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₃ , R ₄ and R ₅ are H or C _1-15 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₅ is H.

In some embodiments, R ₆ is C _1-20 alkyl or C _1-16 alkyl or such.

In some embodiments, R ₇ and R ₈ are H, C _1-20 alkyl, or C _5-30 cycloalkyl, such as H, C _2-12 alkyl, or C _5-25 cycloalkyl, with the carbon atom to which it is attached. Preferably, R ₇ and R ₈ are C _1-20 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₉ is H or C _1-20 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₉ is H.

In some embodiments, X is C _1-20 alkylene, eg, C _3-15 alkylene.

  In some embodiments, p is 0, 1 or 2, for example 0 or 1.

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素と一緒になって、シクロアルキルであり、
R₃、R₄およびR₅はHまたはアルキルであり、R₆はアルキルである。 In some embodiments, n is 0, 1 or 2, for example 0 or 1.
Secondary and tertiary ether compounds can have formula (7).

here:
R ₁ and R ₂ are alkyl or, together with the carbon to which they are attached, cycloalkyl;
R ₃ , R ₄ and R ₅ are H or alkyl, and R ₆ is alkyl.

In some embodiments, R ₁ and R ₂ are C _1-15 alkyl, or are together with the carbon to which the C _5-30 cycloalkyl is attached, such as C _2-12 alkyl, Or together with the carbon to which the C _5-25 cycloalkyl is attached.

In some embodiments, R ₃ , R ₄ and R ₅ are H or C _1-15 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₅ is H.

In some embodiments, R ₆ is C _1-20 alkyl, such as C _1-16 alkyl.

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素と一緒になって、シクロアルキルである。
R₄およびR₅はHまたはアルキルであり、R₆はアルキルである。 The compound may be a secondary ether compound of formula (8).

here:
R ₁ and R ₂ are alkyl or, together with the carbon to which they are attached, are cycloalkyl.
R ₄ and R ₅ are H or alkyl, and R ₆ is alkyl.

In some embodiments, R ₁ and R ₂ are C _1-15 alkyl, such as C _2-12 alkyl.

In other embodiments, the secondary ether can be obtained from a cyclic compound. In this case, R ₁ and R ₂ together with the carbon to which they are attached form a cycloalkyl group such as C _5-30 cycloalkyl or C _5-25 cycloalkyl. A cycloalkyl group may include a cyclopentyl, cyclohexyl, or cycloheptyl group, wherein the cycloheptyl group is bound to one or more alkyl groups, such as C _1-12 alkyl or C _1-8 alkyl. You may.

In some embodiments, R ₄ and R ₅ are H or C _1-15 alkyl (eg, H or C _2-12 alkyl). Preferably, R ₅ is H.

In some embodiments, R ₆ is C _1-20 alkyl, such as C _1-16 alkyl.

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素と一緒になって、シクロアルキルであり、
R₃はアルキルであり、
R₄およびR₅はHまたはアルキルであり、
R₆はアルキルである。 In certain embodiments: R ₁ and R ₂ are C _3-12 alkyl, such as C _5-10 alkyl.
R ₄ and R ₅ are H and R ₆ is C _4-20 alkyl, eg, C _6-15 alkyl.
In another specific embodiment:
R ₁ and R ₂ are C _3-12 alkyl, such as C _5-10 alkyl.
R ₄ is C _3-12 alkyl, such as C _5-10 alkyl.
R ₅ is H and R ₆ is C _3-12 alkyl, such as C _5-10 alkyl.
The compound may be a tertiary ether compound of formula (9).

here:
R ₁ and R ₂ are alkyl or, together with the carbon to which they are attached, cycloalkyl;
R ₃ is alkyl;
R ₄ and R ₅ are H or alkyl;
R ₆ is alkyl.

In some embodiments, R ₁ and R ₂ are C _1-15 alkyl, or are together with the carbon to which the C _5-30 cycloalkyl is attached, such as C _2-12 alkyl, Or together with the carbon to which the C _5-25 cycloalkyl is attached. Preferably, R ₁ and R ₂ are C _1-15 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₃ is C _1-12 alkyl, such as C _1-10 alkyl.

In some embodiments, R ₄ and R ₅ are H or C _1-15 alkyl (eg, H or C _2-12 alkyl).

In some embodiments, R ₆ is C _1-20 alkyl, such as C _1-16 alkyl.

In certain embodiments:
R ₁ and R ₂ are C _2-12 alkyl, such as C _4-10 alkyl;
R ₃ is C _1-10 alkyl, such as C _1-8 alkyl;
R ₄ and R ₅ are H;
R ₆ is C _4-20 alkyl, for example, C _6-15 alkyl.
In another specific embodiment:
R ₁ , R ₂ and R ₃ are C _2-12 alkyl, such as C _4-10 alkyl;
R ₃ is C _1-10 alkyl, such as C _1-8 alkyl;
R ₄ is C _3-12 alkyl, such as C _5-10 alkyl;
R ₅ is H,
R ₆ is C _3-12 alkyl, such as C _5-10 alkyl.

  Examples of secondary and tertiary ether compounds include, as shown in Table 2, SE1, SE2 and TE1.

または:

ここで:
Yは脱離基であり、R₁、R₂、R₃、R₄、R₅、R₆およびnは、式(6)の化合物について先に定義したとおりである。 Secondary and tertiary ether compounds can be prepared according to the following reaction.

Or:

here:
Y is a leaving group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and n are as defined above for the compound of formula (6).

または:

ここで:
Yは脱離基であり、
R₁、R₂、R₃、R₄、R₅およびR₆は、式(7)の化合物について先に定義したとおりである。
当業者は、これらのエーテル化反応を実施するための方法および反応条件を知っているであろう。例えば、反応は、硫酸マグネシウム、硫酸およびジクロロメタンの存在下で実施することができる。
エーテル化反応に使用するための第二および第三アルコール出発物質は、一般に市販されているか、または市販のケトンから入手することができる。
これらの基は、脱離基Yをアルコール出発物質に導入することによって調製することができる。脱離基をアルコールに導入するための方法および反応条件は、当業者に公知である。

Similarly:

Or:

here:
Y is a leaving group,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are as defined above for the compound of formula (7).
One skilled in the art would know methods and reaction conditions for performing these etherification reactions. For example, the reaction can be performed in the presence of magnesium sulfate, sulfuric acid and dichloromethane.
Secondary and tertiary alcohol starting materials for use in the etherification reaction are generally commercially available or can be obtained from commercially available ketones.
These groups can be prepared by introducing a leaving group Y into the alcohol starting material. Methods and reaction conditions for introducing a leaving group into an alcohol are known to those skilled in the art.

  In the above second and third ether compound forming reactions, Y may be any suitable leaving group such as a halogen (e.g., bromine, chlorine or iodine) or a sulfonate ester (e.g., mesylate or tosylate). .

ここで:
R₁およびR₄はアルキルであり、
R₃およびR₅はHまたはアルキルであり、
R₆はアルキルまたは

ここで:
R₇およびR₈は、H、アルキル、またはそれらが結合している炭素原子と一緒になってシクロアルキルである。
R₉はHまたはアルキルである。
X はアルキレンであるか、または存在せず、
pは0、1、2または3である。 Secondary or Tertiary Ethers Derived from Guerbet Alcohol In some embodiments, the compounds include an ether derived from secondary or tertiary alcohols on one side and Guerbet alcohol on the other side. May be. In these embodiments, the compound can have Formula (10).

here:
R ₁ and R ₄ are alkyl;
R ₃ and R ₅ are H or alkyl;
R ₆ is alkyl or

here:
R ₇ and R ₈ together with H, alkyl, or the carbon atom to which they are attached, are cycloalkyl.
R ₉ is H or alkyl.
X is alkylene or absent;
p is 0, 1, 2 or 3.

In some embodiments, R ₁ is C _1-12 alkyl, such as C _2-10 alkyl.

In some embodiments, R ₃ is H or C _1-12 alkyl, eg, H or C _2-10 alkyl. Preferably, R ₃ is H.

In some embodiments, R ₄ is C _1-15 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₅ is H or C _1-15 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₅ is H.

In some embodiments, R ₆ is C _1-15 alkyl or C _1-12 alkyl or such.

In some embodiments, R ₇ and R ₈ are H, C _1-20 alkyl, or C _5-30 cycloalkyl, such as H, C _2-12 alkyl, or C _5-25 cycloalkyl, with the carbon atom to which it is attached. Preferably, R ₇ and R ₈ are C _1-20 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₉ is H or C _1-20 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₉ is H.

In some embodiments, X is C _1-20 alkylene, eg, C _3-15 alkylene.

  In some embodiments, p is 0, 1 or 2, for example 0 or 1.

  Examples of secondary and tertiary ether compounds derived from Guerbet-alcohols include compounds SE1, SE2 and TE1 shown in Table 2.

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₃、R₄およびR₅はHまたはアルキルであり、
R₇およびR₈は、H、アルキル、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₉はHまたはアルキルであり、
X はアルキレンであるか、または存在せず、
pは0、1、2または3であり、
mおよびnは0、1、2または3である。 Diether basestocks Generally, it is preferred that the compound of formula (1) is a monoether. However, in some embodiments, the compound is a diether compound. Such a compound can have the formula (11).

here:
R ₁ and R ₂ are alkyl or, together with the carbon atom to which they are attached, cycloalkyl;
R ₃ , R ₄ and R ₅ are H or alkyl;
R ₇ and R ₈ are H, alkyl, or cycloalkyl together with the carbon atom to which they are attached,
R ₉ is H or alkyl;
X is alkylene or absent;
p is 0, 1, 2 or 3;
m and n are 0, 1, 2 or 3.

In some embodiments, R ₁ and R ₂ are C _1-15 alkyl, or are together with the carbon to which the C _5-30 cycloalkyl is attached, such as C _2-12 alkyl, Or together with the carbon to which the C _5-25 cycloalkyl is attached. Preferably, R ₁ and R ₂ are C _1-15 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₃ , R ₄ and R ₅ are H or C _1-15 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₃ and R ₅ are H.

In some embodiments, R ₇ and R ₈ are H, C _1-20 alkyl, or C _5-30 cycloalkyl, such as H, C _2-12 alkyl, or C _5-25 cycloalkyl, with the carbon atom to which it is attached. Preferably, R ₇ and R ₈ are C _1-20 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₉ is H or C _1-20 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₉ is H.

In some embodiments, X is C _1-20 alkylene, eg, C _3-15 alkylene.

  In some embodiments, p is 0, 1 or 2, for example 0 or 1.

  In some embodiments, m and n are 0, 1 or 2, for example 0 or 1.

ここで:
R₁およびR₂は、アルキルであるか、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₃、R₄およびR₅はHまたはアルキルであり、
R₇およびR₈は、H、アルキル、またはそれらが結合している炭素原子と一緒になってシクロアルキルであり、
R₉はHまたはアルキルであり、
X はアルキレンであるか、または存在せず、
pは0、1、2または3であり、
nは0、1、2または3である。 In some embodiments, the diether compound may contain two ether groups, at least one of which is derived from a β-alkylated alcohol. In such embodiments, the compound may have formula (12).

here:
R ₁ and R ₂ are alkyl or, together with the carbon atom to which they are attached, cycloalkyl;
R ₃ , R ₄ and R ₅ are H or alkyl;
R ₇ and R ₈ are H, alkyl, or cycloalkyl together with the carbon atom to which they are attached,
R ₉ is H or alkyl;
X is alkylene or absent;
p is 0, 1, 2 or 3;
n is 0, 1, 2 or 3.

In some embodiments, R ₁ and R ₂ are C _1-15 alkyl, or C _5-30 cycloalkyl, such as C _2-12 alkyl, along with the carbon atom to which they are attached. Or C _5-25 cycloalkyl, together with the carbon atom to which they are attached. Preferably, R ₁ and R ₂ are C _1-15 alkyl, such as C _2-12 alkyl.

In some embodiments, R ₃ , R ₄ and R ₅ are H or C _1-15 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₃ and R ₅ are H, preferably, R ₄ is C _1-15 alkyl, for example C _2-12 alkyl.

In some embodiments, R ₇ and R ₈ are H, C _1-20 alkyl, or C _5-30 cycloalkyl, such as H, C _2-12 alkyl, or C _5-25 cycloalkyl, with the carbon atom to which it is attached. Preferably, R ₇ and R ₈ are C _1-20 alkyl, such as C _2-12 alkyl.
In some embodiments, R ₉ is H or C _1-20 alkyl, eg, H or C _2-12 alkyl. Preferably, R ₉ is H.
In some embodiments, X is C _1-20 alkylene, eg, C _3-15 alkylene.
In some embodiments, p is 0, 1 or 2, for example 0 or 1.
In some embodiments, n is 0, 1 or 2, for example 0 or 1.
Examples of the Guerbet-derived base stock GE1GE9, the secondary ether base stocks SE1 and SE2, and the tertiary ether base stock TE1 of formula (1), which may preferably be used in connection with the present application, are shown in Table 2.

Base oil and lubricant composition The ether compound of formula (A) or a subset thereof of formula (1) is used as part of the base oil according to the invention.

  The base may contain a sufficient amount of the compound of formula (A), or a subset of the compounds of formula (1), to confer the beneficial properties of the compound to the base.

  In some embodiments, the base oil comprises greater than about 5%, for example, greater than about 25%, or greater than about 40%, by weight of the ether compound of Formula (A), or a subset thereof, of Formula (1). The base oil may contain up to about 100%, for example up to about 90%, of a compound of formula (A), or a subset thereof of formula (1). The compound of formula (A) in the base oil, or a subset thereof of formula (1), may be composed of a single compound or combination of compounds of formula (A) or a subset thereof of formula (1).

  The remainder of the base can be made up of a base that is not a compound of formula (A) and formula (1). Bases other than Formula (A) and Formula (1) suitable for use in the base include non-aqueous bases, such as Group I, Group II, Group III, Group IV and Group V bases. The remainder of the bases may include a single base or a combination of bases other than those of formulas (A) and (1).

  The base oil is used as part of the lubricant composition according to the present invention.

  The lubricant composition can contain a sufficient amount of base oil to impart to the lubricating composition the beneficial properties of the compound of formula (A) or a subset of the compounds of formula (1).

  In some embodiments, the lubricant composition comprises more than about 50% by weight, for example more than about 65% by weight, or more than about 80% by weight of the base oil. The base may be composed of a single base, or a combination of bases comprising a compound of formula (A), or a subset thereof of formula (1).

  The lubricant composition comprises at least one amine antioxidant and / or at least one phenolic antioxidant, and the total amount of the amine antioxidant and the phenolic antioxidant is 4% by weight or less. In a preferred embodiment, the lubricant composition reduces the total amount of amine and phenolic antioxidants in the lubricant composition by no more than 3.0%, 2.5%, or 2.0% by weight of the lubricant composition. Have. In a preferred embodiment, the lubricant composition has a total amount of amine and phenolic antioxidants in the lubricant composition of at least 0.25%, at least 0.5%, or at least 1.0% by weight of the lubricant composition. Have.

  The total amount of amine and phenolic antioxidants may be present in the lubricant composition of the present invention as long as it does not exceed 4% by weight of the lubricant composition. Thus, any sub-range of antioxidant concentrations falling within the above ranges can be used in accordance with the present invention. For example, according to the present invention, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.1, 1.2, 1.3, 1.4, 1.5 weight percent lower limit and 4.0, 3.9, 3.8, 3.7, 3.6, Utilize all sub-ranges formed from combinations with upper limits of 3.5, 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1 or 2.0 weight percent Can be.

  A particular advantage of the present invention relates to the oxidative stability conferred on the lubricant composition by the presence of the ether compound of formula (A) or a subset thereof of formula (1). This requires the same total concentration of amine and / or phenolic antioxidants as would normally be required in an equivalent lubricant composition formulated without the ether compound of Formula (A) or Formula (1). Without achieving the desired oxidative stability in the composition. The overall aminic and / or phenolic antioxidant levels representing high performance engine oils can exceed 5% by weight of the lubricant composition. The present invention compares to conventional lubricant compositions that do not contain any ether compound of formula (A) or formula (1), contain the same amine and / or phenolic antioxidants, but contain higher concentrations. The use of much lower concentrations of total amine and / or phenolic antioxidant combinations both before and during use, for example in internal combustion engines, to achieve the same or better oxidative stability Enable. This is particularly beneficial from a cost standpoint and from a lubricant composition life, fuel economy and piston cleanliness point of view. The reduction of amine-based antioxidants in lubricant compositions for internal combustion engines is particularly beneficial in reducing turbocharger deposits and reducing copper corrosion and increasing elastomer compatibility. On the other hand, the reduction of the phenolic antioxidant leads to improvement of the environmental toxicity of the lubricant composition.

  It is common to add one or more antiwear additives to a lubricant composition, examples of which include zinc dihydrocarbyl dithiophosphate (ZDDP). Furthermore, it has been found that some of the beneficial effects of the present invention are not affected by the presence of ZDDP, as observed in contrast to non-ether lubricant compositions. Surprisingly, some of the beneficial effects of the present invention are enhanced even by the presence of ZDDP in the lubricant composition. For example, the presence of ZDDP has been observed to exacerbate oxidative thickening in CEC-L-109 tests on non-ether compositions containing amine and / or phenolic antioxidants. In contrast, the presence of ZDDP in combination with the amine and phenolic antioxidants in the ether-based compositions of the present invention provided surprisingly high oxidative stability and resistance to oxidative thickening in the CEC-L-109 test. Shows a synergistic effect between the ether stock in the lubricant composition and the ZDDP and antioxidant components. Thus, a further advantage of the present invention is that a larger amount of ZDDP can be used with the ether composition of the present invention without significantly affecting the oxidative stability of the composition, resulting in the complete resistance of ZDDP. The advantage of abrasion can be realized.

  Furthermore, some of the beneficial effects of the present invention are observed to be due to the presence of significant amounts of boron or magnesium in the lubricant composition, for example, in the case of non-ether based lubricant compositions. It was also found that the formation of borated dispersants or magnesium detergents was unaffected. The presence of the borated dispersant and / or other boron-containing additives or magnesium is a substantial increase in the percentage change in kinematic viscosity at 100 ° C. for non-ether lubricant compositions in the CEC-L-109 test. Is generated. In contrast, the presence of boron and / or magnesium in the ether-based compositions of the present invention is well tolerated without a significant increase in oxidative thickening. This is particularly beneficial because increased boron in the lubricant composition leads to increased elastomer compatibility and reduced corrosion of lubricated surfaces, while magnesium reduces the incidence of slow pre-ignition.

  In some embodiments, the lubricant composition of the present invention can include both an amine-based antioxidant and a phenolic antioxidant.

  In some embodiments, the lubricant compositions of the present invention can include an amine-based antioxidant or a phenolic antioxidant, but not both.

  The aminic and / or phenolic antioxidants present in the compositions of the present invention are not particularly limited as long as they are suitable for use in a lubricant composition intended for use in an internal combustion engine, such as an internal combustion engine of a motor vehicle. Not done.

  In some embodiments, the phenolic antioxidants are derived from alkylated monophenols, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, acylaminophenols, and sulfurized alkylphenols, and their alkali and alkaline earth metal salts. Selected. In a preferred embodiment, the phenolic antioxidant is 2-t-butyl-4-heptylphenol, 2-t-butyl-4-octylphenol, 2,6-di-t-butyl-4-heptylphenol, 2,6 Selected from -di-t-butyl-4-dodecylphenol, 2-methyl-6-t-butyl-4-dodecylphenol. 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-bis (4-octyl-6-t-butylphenol), 2,2'-bis (4-dodecyl-6-t -Butylphenol), 4,4'-bis (2,6-di-t-butylphenol) derivatives thereof.

  In some embodiments, the amine antioxidant is selected from alkylated and unalkylated aromatic amines, alkylated diphenylamines, N-alkylated phenylenediamines, phenyl-α-naphthylamine, and alkylated phenyl-α-naphthylamine. Selected. In a preferred embodiment, the amino acid-forming inhibitor is p, p-dioctylphenylamine, t-octylphenyl-α-naphthylamine, p-octylphenyl-α-naphthylamine, monooctyldiphenylamine, N, N-di (2-naphthyl). ) -P-phenylenediamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkylphenyl-1-naphthylamine and alkylphenyl-2-naphthylamine and derivatives thereof.

The lubricant composition may also include other antioxidants that are not amine or phenolic. For example, the lubricant composition of the present invention comprises hydroxylated thiodiphenyl ether, thiopropionate, metal dithiocarbamate, 1,3,4-dimercaptothiadiazole and derivatives, oil-soluble copper compounds (e.g., copper dihydrocarbyl thiophosphate salt or thiophosphate, copper salts of synthetic or natural carboxylic acid, for example, C ₁₈ fatty acids from C _8, unsaturated acid or branched carboxylic acids, for example, basic derived from alkenyl succinic acids or anhydrides, neutral or acid Cu (I) and / or Cu (II) salts), alkaline earth metal salts of alkylphenol thioesters, preferably C ₁₂ alkyl side chains from C ₅ to barium t- octyl or sulfurized hydrocarbons, oil soluble sulfurized phenates And an antioxidant selected from phosphatized hydrocarbons. Sulfurized hydrocarbons, phosphorus esters, low sulfur peroxide decomposers, etc.

  As will be appreciated, it is preferred that the non-aminic and non-phenolic antioxidants, if present, be used in minimal amounts. In some embodiments, the total amount of non-aminic and non-phenolic antioxidants in the lubricant composition is no more than 1.0%, no more than 0.75%, or no more than 0.5% by weight of the lubricant composition. In some embodiments, the antioxidant present in the lubricant composition comprises or consists essentially of an amine and / or phenolic antioxidant.

  The lubricant composition may also include other lubricant additives in addition to the antioxidant. The additional lubricant additive is typically present in the lubricant composition in an amount from about 2% to about 40%, for example, from about 3% to about 30% by weight.

  Suitable additional lubricant additives include detergents (including metallic and non-metallic detergents), friction modifiers, viscosity modifiers, dispersants (including metallic and non-metallic dispersants), viscosity index modifiers, pour points Conditioners, pour point depressants, antiwear additives, rust inhibitors, corrosion inhibitors, antioxidants (also called antioxidants), defoamers (sometimes also called antifoams), seal swelling agents (seal Extreme pressure additives (including metal, non-metal, phosphorus-containing, non-phosphorus-containing, sulfur-containing and non-sulfur-containing extreme pressure additives), surfactants, demulsifiers, anti-seizing agents, waxes Modifiers, lubricants, anti-staining agents, chromophores, metal quenchers, and mixtures of two or more thereof are included.

  In some embodiments, the lubricant composition includes a detergent. Examples of detergents include ashless detergents (ie, non-metal containing detergents) and metal containing detergents. Suitable non-metallic detergents are described, for example, in US Patent No. 7,622,431. Metal-containing detergents comprise at least one metal salt of at least one organic acid called a soap or a surfactant. Suitable organic acids include, for example, sulfonic acids, phenols (preferably sulfurized, including, for example, phenols having more than one hydroxyl group), phenols having fused aromatic rings, modified phenols, such as alkylene-bridged phenols And Mannich base condensed phenols and saligenin-type phenols formed, for example, by reaction of a phenol with an aldehyde under basic conditions), and sulfurized derivatives, and, for example, aromatic carboxylic acids (e.g., hydrocarbyl-substituted salicylic acids and derivatives thereof, e.g., hydrocarbyl-substituted) Carboxylic acids including salicylic acid and its sulfurized derivatives).

  Advantageously, a magnesium detergent can also be used in the lubricant composition of the present invention without adversely affecting oxidative stability. In some embodiments, the amount of magnesium included in the lubricant composition is from 0.025% to 0.5%, preferably from 0.05% to 0.4%, more preferably from 0.08% to 0.35%, and even more. Preferably it is 0.1% to 0.25% by weight. This level of elemental magnesium can be derived from the use of magnesium detergents and / or other magnesium-containing additives or others.

  In some embodiments, the lubricant composition includes a friction modifier. Suitable friction modifiers include, for example, ash-forming and ashless additives. Examples of suitable friction modifiers include, for example, fatty acid esters, amides, amines, and fatty acid derivatives, including ethoxylated amines. Examples of suitable ester friction modifiers include esters of glycerol, such as mono-, di- and tri-oleates, mono-palmitates and mono-myristates. A particularly suitable fatty acid ester friction modifier is glycerol monooleate. Examples of suitable friction modifiers also include molybdenum compounds, such as organic molybdenum compounds, molybdenum dialkyldithiocarbamates, molybdenum dialkylthiophosphates, molybdenum disulfide, trimolybdenum cluster dialkyldithiocarbamates, non-sulfur molybdenum compounds, and the like. Suitable molybdenum-containing compounds are described, for example, in EP 1533362 Al, for example in paragraphs [0101] to [0117].

  In some embodiments, the lubricant composition includes a dispersant. Examples of suitable ashless dispersants include oil-soluble salts, esters, aminoesters, amides, imides and oxazolines of long-chain hydrocarbon-substituted mono- and polycarboxylic acids or their anhydrides; thiocarboxylate derivatives of long-chain hydrocarbons Long chain aliphatic hydrocarbons containing a polyamine moiety directly attached thereto; Mannich condensation products formed by condensing long chain substituted phenols with formaldehyde and polyalkylene polyamines; Koch reaction products and the like. Particularly preferred dispersants for use in the present invention are long-chain aliphatic hydrocarbons with directly attached polyamine moieties, such as polyisobutylene succinyl anhydride-polyamine (PIBSA-PAM).

  Advantageously, borated dispersants can also be used in the lubricant compositions of the present invention without adversely affecting oxidative stability. In some embodiments, the lubricant composition can contain boron in an amount of 0.005% to 0.05%, preferably 0.0075% to 0.035% by weight. This level of elemental boron can be derived from the use of borated dispersants and / or boron containing antiwear additives.

  In some embodiments, the lubricant composition includes a dispersant viscosity modifier. Examples of suitable dispersant viscosity modifiers and methods for making them are described in WO 99/21902, WO 2003/099890 and WO 2006/099250.

  In some embodiments, the lubricant composition includes a viscosity index improver. Examples of suitable viscosity modifiers include high molecular weight hydrocarbon polymers (e.g., polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins); polyesters (e.g., polymethacrylate); hydrogenated poly (styrene-co- Butadiene or isoprene) polymers and modified (eg, star polymers); and esterified poly (styrene-co-maleic anhydride) polymers. Oil soluble viscosity modifying polymers generally exhibit a number average molecular weight of at least about 15,000 to about 1,000,000, such as about 20,000 to about 600,000, as measured by gel permeation chromatography or light scattering.

In some embodiments, the lubricant composition includes a pour point depressant. Examples of suitable pour point depressants include dialkyl fumarate / vinyl acetate copolymers from C ₈ to C _18, methyl methacrylate, polyacrylates, polyaryl amide, polymethyl methacrylate, polyalkyl methyl methacrylate, vinyl fumarate, styrene Esters, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, terpolymers of dialkyl fumarate, vinyl esters of fatty acids and allyl vinyl ethers, wax naphthalenes and the like.

  In some embodiments, the lubricant composition includes at least one antiwear additive. Examples of suitable antiwear additives include non-phosphorus containing additives, such as sulfurized olefins. Examples of suitable antiwear additives also include phosphorus-containing antiwear additives. Examples of suitable ashless phosphorus-containing antiwear additives include trilauryl phosphite and triphenyl phosphorothionate, and those disclosed in paragraph [0036] of US Patent Application Publication No. 2005/0198894. No. Examples of suitable ash-forming phosphorus-containing antiwear additives include dihydrocarbyl dithiophosphate metal salts. Examples of suitable metals for dihydrocarbyl dithiophosphate metal salts include alkali and alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper and zinc. A particularly preferred dihydrocarbyl dithiophosphate metal salt is zinc dihydrocarbyl dithiophosphate (ZDDP).

  In some embodiments, the amount of phosphorus contained in the lubricant composition is less than 0.5%, preferably 0.001 to 0.3%, more preferably 0.025 to less than 0.5% by weight based on the total weight of the lubricant composition. It is 0.2% by weight, even more preferably 0.04 to 0.12% by weight.

  ZDDP is particularly well tolerated with respect to the oxidative stability of the lubricant composition of the present invention and appears to impart a synergistic effect when used in combination with an ether base stock and antioxidant, so The use of ZDDP in the composition is particularly beneficial to the overall properties of the lubricant composition, especially in terms of wear resistance. Thus, in some embodiments, the amount of the dihydrocarbyl dithiophosphate metal salt, preferably in the form of zinc dihydrocarbyl dithiophosphate (ZDDP), in the lubricant composition is from 0.01% to 10.0% by weight, preferably 0.1% by weight. % To 5% by weight, more preferably 0.2% to 2.5% by weight, even more preferably 0.3% to 1.0% by weight.

  In some embodiments, the lubricant composition includes a rust inhibitor. Examples of suitable rust inhibitors include nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, polyoxyalkylene polyols, anionic alkyl sulfonic acids, zinc dithiophosphate, metal phenolates, basic metal sulfonates, Contains fatty acids and amines.

  In some embodiments, the lubricant composition includes a corrosion inhibitor. Examples of suitable corrosion inhibitors include phosphosulfylated hydrocarbons and products obtained by reacting phosphosulfylated hydrocarbons with alkaline earth metal oxides or hydroxides, nonionic polyoxyalkylene polyols And its esters, polyoxyalkylene phenols, thiadiazoles, triazoles and anionic alkyl sulfonic acids. Examples of suitable epoxidized ester corrosion inhibitors are described in US Patent Application Publication No. 2006/0090393.

In some embodiments, the lubricant composition includes an antifoam.
Examples of suitable defoamers include silicones, organic polymers, siloxanes (including polysiloxanes and (poly) dimethylsiloxanes), phenylmethylsiloxanes, acrylates, and the like.

  In some embodiments, the lubricant composition includes a seal swell. Examples of suitable seal swell agents include long chain organic acids, organic phosphates, aromatic esters, aromatic hydrocarbons, esters (eg, butylbenzyl phthalate) and polybutenyl succinic anhydride.

The lubricant composition may include the amounts of the lubricant additives shown in Table 3.

  The lubricant composition can have a kinematic viscosity at 40 ° C. of less than about 60 cSt, such as less than about 55 cSt, or less than about 50 cSt. The lubricant composition can have a kinematic viscosity at 100 ° C. of less than about 12 cSt, for example, less than about 10 cSt, or less than about 9.5 cSt. The lubricant composition may have a viscosity index greater than about 100, such as greater than about 110, or greater than about 120. The kinematic viscosity at 40 ° C. and the kinematic viscosity at 100 ° C. can be measured according to ASTM D445. The viscosity index can be calculated according to ASTM D2270.

  The lubricant composition may have a Noack volatility of less than about 25% by weight, for example, less than about 15% by weight, or less than about 10% by weight. Noack volatility can be measured according to CEC-L-40-A-93.

The lubricant composition may have a viscosity at 150 ° C. and a shear rate of less than or equal to 3 cP, for example, less than or equal to 2.8 cP and 10 ⁶ s ⁻¹ . This high temperature high shear viscosity can be measured according to CEC-L-36-A-90.

  The lubricant composition can have at least one of the following:

  The oxidation stability performance of the CEC-L-088-02 test is indicated by an absolute viscosity increase of less than 45 cSt at 40 ° C, for example, less than 35 cSt, or less than 25 cSt, and the fuel economy performance of the CEC-L-054-96 test Is at least 2.5%, e.g. at least 3%, the piston cleaning performance of the CEC-L-088-02 test is at least 8.5, e.g. 9, and the oxidative stability performance of the CEC-L-109-14 test is 200 at 100C. %, Preferably less than 150%, less than 150% at 216 hours, and / or less than 200%, preferably less than 150%, 168 hours.

  The lubricant composition can have a cold crankcase simulator performance of less than about 3000 at -30 ° C, such as less than about 2800, or less than about 2750, measured according to ASTM D5293.

  Preferred lubricant compositions meet the requirements described in SAE J300.

  The lubricant composition can be used for a method of lubricating a surface.

  Suitable surfaces include power transmission systems such as drivelines and gearboxes, such as vehicles, including passenger cars and heavy vehicles, and internal combustion engines, such as those in crankcases of internal combustion engines. Suitable surfaces also include those in turbine bearings, for example, hydro turbine bearings.

  Suitable internal combustion engines include, for example, engines used in automotive applications, engines used in marine applications, and engines used in terrestrial power plants. The lubricant composition is particularly suitable for use in automotive internal combustion engines.

  The lubricant composition can be used to improve fuel economy and / or piston cleanliness performance of a vehicle, such as an internal combustion engine and / or an automobile associated with the internal combustion engine. Accordingly, the fuel economy and / or piston cleanliness performance of a vehicle, such as an internal combustion engine and / or an automobile associated with the internal combustion engine, comprising providing or supplying at least one of the lubricant composition to the engine and / or the vehicle. Are provided.

  The present invention will now be described with reference to the accompanying drawings and examples, which are not intended to be limiting in nature.

CEC-L-109 test of blend compositions containing Guerbet derived base (GE3) and / or Group III base (Yubase 4) with varying amounts of amine and / or phenol oxidizers and other lubricant additives 5 is a graph of the percentage increase in kinematic viscosity at 100 ° C. over time corresponding to the results of FIG.

Example 1 Ether-Based Properties Guerbet-derived base GE3 of formula (1) was prepared and its structure is shown in Table 4.

  The following properties of the base were tested:

  The kinematic viscosity at 100 ° C. (KV100) and the kinematic viscosity at 40 ° C. (KV40) were tested according to ASTM D7279.

  The viscosity index (VI) was calculated according to ASTM D2270.

  Pour points were measured according to ASTM D7346.

  Differential scanning calorimetry (DSC) oxidation onset temperatures were tested using a method based on ASTM E2009 (Method B). According to this method, a standard was heated from 50 ° C. to 300 ° C. at a rate of 50 ° C./min under a pressure of 500 psi in an aluminum SFI pan. The temperature at which an exotherm was observed was recorded.

  Noack volatility was measured using a method based on IP 393 and was considered to be similar to CEC-L-40-A-93. According to this method, a known Noack volatile reference oil was heated from 40 ° C to 550 ° C to determine the temperature at which each Noack volatile weight loss of the reference oil was reached. The same treatment was performed as for the base oil. Based on the results obtained from the reference oil, the knock weight of the reference oil could be determined.

The results of the study are summarized in Table 5, along with the results obtained from a conventional base stock (Yubase 4, Group III base stock).

  It can be seen that the Guerbet-derived base ether has lower volatility, lower pour point, and lower kinematic viscosity than the conventional base.

Example 2: Properties of a lubricant composition containing an ether base.
Guerbet-derived ether-based GE3 is replaced by conventional base additives (Additive A, a commercially available additive that provides a dispersant level representing 7-10% by weight, based on the total weight of the lubricant composition, of a high performance engine oil. Package; Additive B, cold flow improver; Additive C, antioxidant; and Additive D, viscosity index improver) and conventional base (Yubase 4, Group III base; and Yubase 6, Group III base) Blend to form a lubricant blend. A baseline blend was also prepared. Ubase 4 was chosen as the main component of the baseline blend because it exhibits a KV100 similar to GE3, a Guerbet-derived ether basestock. The baseline blend was considered a stringent baseline for comparison as it is a 5W-30 formulation that meets specific specifications (ACEA A5 / B5, API-SN / GF-4). Details of the composition are shown in Table 6 by weight%.

  No problems with miscibility were encountered during the preparation of the blended composition.

  The blended compositions were tested to determine if the beneficial properties of the basestock were reflected in a fully formulated lubricant composition. The following properties were tested:

  Kinematic viscosity at 100 ° C. (KV100) and kinematic viscosity at 40 ° C. (KV40) were tested according to ASTM D445 (part of SAE J300).

  The viscosity index (VI) was calculated according to ASTM D2270.

  Cold cranking simulator (CCS) analysis was performed at −30 ° C. according to ASTM D5293 (part of SAE J300).

  High temperature high shear (HTHS) analysis was performed according to CEC-L-36-A-90.

  Total base number (TBN) was determined according to ASTM D2896.

  Noack volatility was tested according to CEC-L-40-A-93.

  Sulphated ash content was measured according to IP 163.

The results of the test are summarized in Table 7.

  It can be seen that the properties of the Guerbet derived basestock are also exhibited in the blended composition. In particular, beneficial viscosity, volatility and cold flow properties are observed. The base stock from Guerbet also showed similar HTHS measurements, TBN and sulfated ash as the baseline blend.

Example 3: CEC-L-85-99 test Guerbet derived base (GE3), group III base (Yubase 4) or IV with varying amounts of amine oxidant (diphenylamine) and / or phenol oxidant (substituted phenol) The blend composition containing the family base (PAO 4) was subjected to the CEC-L-85-99 test, which measures the differential oxidation onset temperature and differential oxidation induction time of the tested blend. The results obtained from the CEC-L-85-99 test are shown in Table 8 (the composition data is shown in wt%).

  The results in Table 8 show the oxidation onset temperature and oxidation in the ether blend when either the phenolic antioxidant (blend K) or the amine antioxidant (blend L) was present (as compared to blend J). This shows that both induction times increase. Furthermore, when both amine and phenolic antioxidants are added (blend M), a substantial increase in the oxidation onset temperature and oxidation induction time is observed. In particular, when non-ether blends are compared (blends B to D and F to H), both amine and phenolic antioxidants are present alone (blends B, C, F and Oxidation onset temperature, compared to G), indicating that there is a synergistic effect associated with the ether basestock and the amine and phenolic antioxidants, which are not observed with the non-ether basestock. This can be easily seen when comparing test blends containing both aminic and phenolic antioxidants present (blends D, H and M), where they migrate to ether-based (blend M). Then, the oxidation induction time is increased by more than 25% compared to the group III and group IV systems (blends D and H).

Example 4: CEC-L-85-99 test-A fully formulated lubricant composition.
Guerbet-derived base (GE3) and Group III base (Yubase 4) are combined with various amounts of amine and / or phenol oxidizers, as well as (non-boronated) dispersants, detergents, viscosity index modifiers (VIM) and Fully formulated lubricant composition, including other lubricant additives, including secondary ZDDP, for CEC-L-85-99 testing. The results obtained from the CEC-L-85-99 test are shown in Table 9 (the composition data is shown in% by weight).

The results in Table 9 show that when the levels of phenolic antioxidants and amine antioxidants are increased in ether-based compositions, both the oxidation onset temperature and oxidation induction time increase, indicating an increase in oxidative stability Prove that. Furthermore, the substantial increase in oxidation onset temperature and oxidation induction time is due to the fact that when both the aminic antioxidant and the phenolic antioxidant are added at a level of 0.5% by weight each (compositions 12 and 16), the aminic antioxidant It is observed when one of the agent or phenolic antioxidant is present at a lower concentration of 0.1% by weight (compositions 10, 11, 14 and 15).

  In particular, in addition to the amine or phenolic antioxidants, the presence of ZDDP also surprisingly implies a substantial increase in oxidative stability, as indicated by a corresponding increase in oxidation onset temperature and oxidation induction time. Is applied (compositions 13-16 compared to compositions 9-12). Further, this effect is particularly remarkable when the amine-based and phenolic antioxidants are present in the ether-based composition (composition 16) at an equal amount of 0.5% by weight. However, this significant effect was not observed in the corresponding non-ether system (Composition 8), indicating that there is a synergistic effect associated with the combination of an amine system and a phenolic antioxidant and an ether system together with ZDDP. Is shown. Thus, the presence of ZDDP, while providing a further improvement in oxidative stability in the compositions of the present invention, also contributes to the improved antiwear performance of the lubricant composition.

Example 5: CEC-L-109 test.
With varying amounts of amine and / or phenol oxidizers, and other lubricant additives including (non-boronated) dispersants, borated dispersants, detergents, viscosity modifiers (VM) and secondary ZDDPs; A fully formulated lubricant composition including a Guerbet-derived substrate (GE3) and a Group III substrate (Yubase 4) was subjected to the CEC-L-109 test. The CEC-L-109 test is a high temperature oxidation test designed to determine the oxidative stability of engine lubricants through the measurement of the percentage increase in kinematic viscosity at 100 ° C (`` KV 100% change ''). The lower the percentage change, the higher the oxidative stability. The results obtained from the CEC-L-109 test are shown in Table 10 (composition data is shown by weight%).

  The results of the CEC-L-109 test show the benefit of increasing the total antioxidant concentration in the form of an average increase in kinematic viscosity at 100 ° C from duplicate runs (compare the results of composition b with the results of composition a). ) And the negative effect of the presence of ZDP on the oxidative stability of the non-ether lubricant composition in this test (compare the results for compositions a and b with the results for compositions c and d).

  However, it is clear from the results for composition f that the oxidative stability of the ether-based composition measured by the CEC-L-109 test was not significantly affected by the presence of ZDDP, which indicates that This is clearly not the case for the corresponding non-ether-based composition e with the same level of ZDDP and antioxidant (40.7% change in composition f vs. 227% change in composition e). These results indicate a synergistic effect between the ether basestock and the ZDDP and antioxidant components in the lubricant composition. Thus, this means that higher amounts of ZDDP can be used with the ether compositions of the present invention without significantly affecting the oxidative stability of the composition, thereby realizing the full abrasion resistance benefits of ZDDP. It can be done.

  For lubricant compositions g and h, the presence of 6% by weight of the borated dispersant provides about 0.021% by weight of boron (on an elemental basis) to the lubricant composition. The presence of the borated dispersant and associated boron results in a substantial increase in the percentage change in kinematic viscosity at 100 ° C. for the non-ether-based composition g (too viscous to measure). In contrast, the presence of the borated dispersant in the ether-based composition h is well tolerated with only a moderate average percentage increase in kinematic viscosity at 100 ° C. (84.4%). These results demonstrate that the oxidative stability of the ether compositions of the present invention is substantially maintained despite increasing boron content. This is particularly beneficial because increasing boron in the lubricant composition results in increased elastomer compatibility and reduced corrosion.

  For lubricant compositions i and j, the presence of 0.86% by weight of the magnesium-containing detergent provides about 0.072% by weight of magnesium (on an elemental basis) to the lubricant composition. The presence of the magnesium-containing detergent results in a substantial increase in the percentage change in kinematic viscosity at 100 ° C. for the non-ether-based composition i (too viscous to measure). In contrast, the presence of a magnesium-containing detergent in the ether-based composition j is well tolerated with only a moderate average percentage increase in kinematic viscosity at 100 ° C. (76.1%). These results demonstrate that the oxidative stability of the ether compositions of the present invention is substantially maintained despite increasing magnesium content. This is particularly beneficial because increasing the magnesium-containing detergent in the lubricant composition reduces the sulfated ash level for the same total base number (acid neutralizing ability) compared to the calcium-containing detergent.

  The effect of the presence of ZDDP and / or a borated dispersant in the compositions of the present invention (compositions f and h) compared to the conventional non-ether based compositions described above (compositions e and g) is also illustrated in FIG. Shown in 1.

  The results of the above examples demonstrate the benefits of ether base oils with amine and / or phenolic antioxidants to improve oxidative stability, as well as additional benefits resulting from synergy with ZDDP. These results show that the aminic and / or phenolic antioxidants can be used in lower amounts in the lubricant compositions comprising the ether basestocks according to the present invention and compared to conventional non-ether based lubricant compositions. Demonstrate that similar or better oxidative stability can be achieved. The reduction of amine-based antioxidants in lubricant compositions for internal combustion engines is particularly beneficial in reducing turbocharger deposits and reducing copper corrosion and increasing elastomer compatibility. On the other hand, the reduction of the phenolic antioxidant leads to improvement of the environmental toxicity of the lubricant composition.

  The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each of these dimensions is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

All documents cited herein, including any cross-references or related patents or applications, are herein incorporated by reference in their entirety, unless expressly excluded or otherwise limited. Incorporated as a reference. The citation of any document is prior art with respect to any invention disclosed or claimed herein, or by itself or in any combination with any other reference or reference. , Is not an admission that such inventions are taught, suggested or disclosed.
Further, the meaning or definition assigned to a term in this document shall be governed, provided that any meaning or definition of that term in this document conflicts with any meaning or definition of the same term in the document incorporated by reference. .

  While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended that all such changes and modifications that come within the scope and spirit of the invention be covered by the appended claims.

Claims (33)

A lubricant composition for an internal combustion engine, comprising a base oil of lubricating viscosity, wherein the base oil comprises an ether base oil of the formula (A),

(here:
R _a and R _b are aliphatic hydrocarbyl groups, which may be the same or different, and at least one of R _a and R _b is a branched alkyl, alkoxy-substituted alkyl or cycloalkyl-substituted alkyl. Yes, the lubricant composition further comprises at least one amine antioxidant and / or at least one phenolic antioxidant, wherein the amine antioxidant and the phenolic antioxidant in the lubricant composition The total amount of the lubricant composition is 4.0% by weight or less of the lubricant composition) The lubricant composition according to claim 1, wherein _Ra and _Rb are independently selected from alkyl, alkoxy-substituted alkyl, or cycloalkyl-substituted alkyl, provided that both _Ra and _Rb are R at least one of the alkyl _a and R _b, preferably represents both; and preferably, R _a and R _b are, C _2-26 C _1-30 alkyl, such as alkyl or C3~24 alkyl, C2-20 A lubricant composition independently selected from C2-30 alkoxy-substituted alkyl, such as alkoxy-substituted alkyl, or C5-30 cycloalkyl-substituted alkyl, such as C5-25 cycloalkyl-substituted alkyl. R _a lubricant composition according to claim 1 or 2 containing a number of carbon atoms than R _b. Wherein R _{a comprises 12} to 30 carbon atoms, preferably 12 to 26 carbon atoms, and / or R _b comprises 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. Item 4. The lubricant composition according to any one of Items 1 to 3. The lubricant composition according to claim 1, wherein the ether base is of the formula (1):

here:
R ₁ and R ₂ are alkyl or, together with the carbon atom to which they are attached, cycloalkyl;
R ₃ , R ₄ and R ₅ are H or alkyl;
R ₆ is alkyl or

here:
R ₇ and R ₈ are H, alkyl, or cycloalkyl together with the carbon atom to which they are attached,
R ₉ is H or alkyl; X is alkylene or absent;
p is 0, 1, 2 or 3; m and
n is 0, 1, 2 or 3;
m is 0 when R ₄ and R ₅ are H; R ₁ and R ₂ are C _1-15 alkyl, or C _5-30 cycloalkyl together with the carbon atoms to which they are attached, for example, C ₅ together with the carbon atom to C _2-12 alkyl, or which they are attached _-25 is cycloalkyl; and / or R _3, R ₄ and R ₅ are H or C _1-15 alkyl, for example H or C2~12 alkyl, preferably according to claim 5 R5 is H Lubricant composition.   7. The lubricant composition according to claim 5, wherein m and n are 0, 1 or 2, for example 0 or 1. The lubricant composition according to any one of claims 5 to 7, wherein the ether base material has the formula (4).

(here:
R ₁ and R ₄ are alkyl;
R ₃ and R ₅ are H or alkyl;
R ₁ is C _4-12 alkyl, such as C _6-10 alkyl;
R ₃ is H,
R ₄ is C _1-10 alkyl, such as C _2-8 alkyl, and R ₅ is H) The lubricant composition according to any one of claims 5 to 7, wherein the ether base has the formula (7).

(here:
R ₁ and R ₂ are alkyl or, together with the carbon to which they are attached, cycloalkyl;
R ₃ , R ₄ and R ₅ are H or alkyl, and R ₆ is alkyl)   The lubricant composition according to any one of claims 1 to 9, wherein the ether base contains a total of 20 to 50, such as 25 to 45, such as 28 to 40, or 28 to 36 carbon atoms. .   The ether-based material is prepared from a bio-derived material, preferably the ether-based material contains more than 50% by weight, such as more than 70% by weight, or more than 80% by weight of bio-based carbon. Lubricant composition.   The lubricant composition base oil comprises more than 10% by weight of the ether base oil, such as more than 25% by weight, or more than 40% by weight, and / or the lubricant composition comprises more than 50% by weight of the base oil, such as 65% by weight The lubricant composition according to any of claims 1 to 11, comprising more than 80% by weight or more than 80% by weight.   The base oil of the lubricant composition further comprises a base oil selected from Group I, Group II, Group III, Group IV and Group V base oils and mixtures thereof, preferably wherein the base oil is a Group III base oil 13. The lubricant composition according to claim 12, further comprising: The lubricant composition has at least one of the following,
A kinematic viscosity at 40 ° C. of less than 60 cSt, for example less than 55 cSt, or less than 50 cSt,
A kinematic viscosity at 100 ° C. of less than 12 cSt, for example less than 10 cSt, or less than 9.5 cSt,
A viscosity index greater than 100, such as greater than 110, or greater than 120;
The viscosity at 150 ° C and the shear rate at 106 of -1 is 3 cP or less, such as 2.8 cP or less; and the Noack volatility is less than 25%, such as 20% or less, 15% or less, or less than 10% by mass. 14. The lubricant composition according to any one of 1 to 13. The lubricant composition has at least one of the following,
Oxidation stability performance in the CEC-L-088-02 test is indicated by an increase in absolute viscosity at 40 ° C of not more than 45 cSt, for example not more than 35 cSt or not more than 25 cSt,
The oxidation stability performance in the CEC-L-109-14 test shows that the increase in kinematic viscosity at 100 ° C is less than 200% at 168 hours, preferably less than 150%, at 216 hours, and / or less than 200% , Preferably by less than 150%,
The fuel economy performance of the CEC-L-054-96 test is at least 2.5%, for example at least 3%,
A lubricant composition according to any of the preceding claims, wherein the piston cleanliness performance of the CEC-L-088-02 test is shown to be at least 8.5, for example 9.   The total amount of the amine and phenolic antioxidants in the lubricant composition is 3.0% by weight or less, 2.5% by weight or less, or 2.0% by weight or less of the lubricant composition, any one of claims 1 to 15. 3. The lubricant composition according to item 1.   The total amount of amine and phenolic antioxidants in the lubricant composition is at least 0.25%, at least 0.5%, or at least 1.0% by weight of the lubricant composition. 3. The lubricant composition according to item 1.   The total amount of non-aminic and non-phenolic antioxidants in the lubricant composition is 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less of the lubricant composition according to any one of claims 1 to 17. The lubricant composition according to any one of the preceding claims.   The lubricating composition according to any one of claims 1 to 18, wherein the lubricant composition contains an amine antioxidant or a phenolic antioxidant, but does not contain both an amine antioxidant and a phenolic antioxidant. Composition.   The at least one phenolic antioxidant is selected from alkylated monophenols, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, acylaminophenols, and sulfurized alkylphenols, and their alkali and alkaline earth metal salts. A lubricant composition according to any one of claims 1 to 19.   The at least one phenolic antioxidant is 2-t-butyl-4-octylphenol, 2-t-butyl-4-dodecylphenol, 2,6-di-t-butyl-4-heptylphenol, 2,6 -Di-t-butyl-4-dodecylphenol, selected from 2-methyl-6-t-butyl-4-dodecylphenol, 4,4′-methylenebis (2,6-di-t-butylphenol), 2, 2'-bis (4-octyl-6-t-butylphenol), 2,2'-bis (4-dodecyl-6-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol) ), 4,4 '-(2,6-di-t-butylphenol) and its derivatives   The claim wherein the at least one amine antioxidant is selected from alkylated and unalkylated aromatic amines, alkylated diphenylamines, N-alkylated phenylenediamines, phenyl-α-naphthylamine, and alkylated phenyl-α-naphthylamines Item 22. The lubricant composition according to any one of Items 1 to 21.   The at least one amino antioxidant is p, p-dioctylphenylamine, t-octylphenyl-α-naphthylamine, p-octylphenyl-α-naphthylamine, monooctylphenyl-α-naphthylamine, N, N-di ( (2-naphthyl) -p-phenylenediamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkylphenyl-1-naphthylamine, alkylphenyl-2-naphthylamine, and derivatives thereof selected from claims 1 to 22. The lubricant composition according to any one of the above.   The amount of phosphorus contained in the lubricant composition, based on the total weight of the lubricant composition, is less than 0.5% by weight, preferably 0.001-0.3% by weight, more preferably 0.025-0.2% by weight, even more preferably The lubricant composition according to any one of claims 1 to 23, wherein is 0.04 to 0.12% by weight.   The lubricant composition according to any one of claims 1 to 24, wherein the amount of boron contained in the lubricant composition is 0.005% by weight to 0.05% by weight, preferably 0.0075% by weight to 0.035% by weight.   The amount of magnesium contained in the lubricant composition is from 0.025% to 0.5% by weight, preferably 0.05% to 0.4% by weight, more preferably 0.08% to 0.35% by weight, most preferably 0.1% to 0.25% by weight. The lubricant composition according to any one of claims 1 to 25, which is a percentage by weight.   Wherein the lubricant composition comprises one or more dihydrocarbyl dithiophosphate metal salts, preferably in the form of zinc dihydrocarbyl dithiophosphate (ZDDP), 0.01% to 10.0% by weight, preferably 0.1% to 5% by weight, Lubricant composition according to any of the preceding claims, comprising more preferably from 0.2% to 2.5% by weight, even more preferably from 0.3% to 1.0% by weight.   A method for producing a lubricant composition, the method comprising providing a base oil according to any one of claims 1 to 13, and the amine and phenolic antioxidant in the lubricant composition. Blending the base oil with at least one amine antioxidant and / or at least one phenolic antioxidant such that the total amount is no more than 4.0% by weight of the lubricant composition; A method of making a lubricant composition, comprising also blending one or more additional lubricant additives to prepare the lubricant composition.   A method for lubricating a surface, comprising supplying the lubricant composition according to any one of claims 1 to 27 to the surface, wherein the lubricant composition is supplied to a surface of an internal combustion engine. How to use   28. Use of a lubricant composition according to any of the preceding claims for lubricating a surface, such as when the lubricant composition is used for lubricating a surface of an internal combustion engine.   12.A method according to any of claims 1 to 11, wherein the lubricant composition reduces the total amount of antioxidant additives required in the lubricant composition to achieve a certain level of oxidative stability performance. The use according to claim 1, wherein the lubricant composition comprises at least one aminic antioxidant and / or at least one phenolic antioxidant.   28.Providing the lubricant composition according to any one of claims 1 to 27 to an engine and / or a vehicle, including fuel efficiency and / or piston cleaning performance of an engine and / or vehicle such as an automobile associated with an internal combustion engine. How to improve.   28. Use of a lubricant composition according to any of the preceding claims for improving fuel economy performance and / or piston cleanliness performance of an engine and / or vehicle such as an automobile associated with an internal combustion engine.

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