KR101576783B1 - Lubricant compositions comprising boroxines to improve fluoropolymer seal compatibility - Google Patents

Abstract

A lubricant composition comprising a boroxyne compound is disclosed. Also disclosed are lubricant compositions and additive packages comprising prodrone compounds and sterically hindered amines. The precursor compound of the lubricant composition acts to improve the compatibility of the fluoropolymer chamber with the lubricant composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a lubricant composition containing a borosilicate composition for improving fluoropolymer yarn compatibility,

The present invention generally relates to a lubricant composition comprising a base oil, a boronic acid compound and a sterically hindered amine compound. The present invention also relates to an additive package for a lubricant composition.

It is known to add stabilizers to lubricant compositions based on mineral or synthetic oils to improve their performance characteristics, which is conventional. Some conventional amine compounds are effective stabilizers for lubricants. These conventional amine compounds can help neutralize the acid formed during the combustion process. However, these conventional amine compounds are generally not used in combustion engines due to their deleterious effects on fluoropolymer seals.

It is an object of the present invention to provide a new type of lubricant composition having improved fluoropolymer yarn compatibility.

The present invention provides a lubricant composition comprising a base oil, a boronic compound, and a sterically hindered amine compound. The prodrug compound has the formula (I)

(I)

Wherein each R ¹ is an alkyl group having independently from 1 to 7 carbon atoms.

The present invention provides a lubricant composition comprising a base oil, a boronic compound, and a sterically hindered amine compound. The prodrug compound has the formula (I)

(I)

Wherein each R ¹ is an alkyl group having independently from 1 to 7 carbon atoms.

The present invention also relates to a lubricant composition comprising a base oil, a boronic acid compound, and a hindered amine compound having the formula (II) or (III)

≪

(III)

Wherein each R ² is independently a hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at least two groups designated as R ² are alkyl groups; Each R < ³ > is independently a hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon atoms; Each R ⁴ is independently a hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at least two groups designated as R ⁴ are alkyl groups; Each R ⁵ is independently a hydrogen atom or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein each of the hydrocarbyl groups designated as R ² , R ³ , R ⁴ , and R ⁵ is independently an alcohol group, An alkyl group, an amide group, an ether group or an ester group.

The present invention is also directed to an additive package for lubricant compositions comprising a boronic acid compound and a sterically hindered amine compound.

The lubricant compositions comprising the boroxyne compounds exhibit improved compatibility with the fluoropolymer chamber as evidenced by CEC L-39-T96.

As described below, the boronic compounds may be included to improve the practical applicability of the lubricant composition in a lubricant composition or additive package for the lubricant composition. The boronic compounds can be combined with one or more hindered amine compounds in the lubricant composition. The present invention relates to a process for the preparation of a sterically hindered amine compound that interacts with a sterically hindered amine compound to prevent the tendency of the hindered amine compound to adversely interact with the fluoropolymer chamber when present in the lubricant composition with the hindered amine compound, It is believed that the fluoropolymer seal and the lubricant composition are in contact without affecting the effect.

The prodrug compound has the formula (I)

(I)

In formula (I), each R < ^{1 >} is independently an alkyl group having up to 7 carbon atoms. For example, each R ¹ may independently be an alkyl group having 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2 carbon atoms. Each R < ^{1 >} may independently be linear or branched. In one specific formulation, each R < ¹ > may be a methyl group. Exemplary R ¹ groups may independently comprise methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl and n-hexyl groups.

The ascorbic compounds can be exemplified by trimethoxyboroxine, tripropoxyboroxine, triisopropoxyboroxine, tributoxyboroxine, tripentoxyboroxine, trihexoxyboroxine, and triheptoxyboroxine. have. For example, trimethoxyboroxane may have the formula:

In certain embodiments, each R < ¹ > may represent a separate alkyl group. For example, the protonic compounds can be illustrated by the following formulas.

Here, the 1-methyl group is designated as R ¹ in formula I, one ethyl group is designated as R ¹ in Formula I, is one group profile specified by the R ¹ in formula I. Alternatively, the groups assigned to R ¹ in formula (I) may be the same and one group designated as R ¹ may be different.

The boronic compound may be included in an amount sufficient to provide the desired concentration of boron in the lubricant composition and / or additive package in the lubricant composition and / or additive package. For example, the precursor compound may be included in an amount sufficient to provide from 1 to 5000 ppm of boron in the lubricant composition, based on the total weight of the lubricant composition. Alternatively, the boronic compound may be present in the lubricant composition or additive package in an amount sufficient to provide 100 to 5000 ppm, 300 to 3000 ppm, 500 to 1500 ppm, or 700 to 1200 ppm of boron in the lubricant composition, based on the total weight of the lubricant composition . Alternatively, the borosilicate compound may be provided in an amount sufficient to provide 1 to 100 ppm, 1 to 40 ppm, 1 to 20 ppm, or 10 to 20 ppm boron in the lubricant composition based on the total weight of the lubricant composition.

Alternatively, the boronic acid compound may be present in the lubricant composition in an amount of from 0.1 to 10% by weight, from 0.1 to 5% by weight, from 0.1 to 1% by weight, from 0.3 to 0.7% by weight, from 0.5 to 3% by weight, May be present in an amount ranging from 0.5 to 1.5% by weight. In another embodiment, the proline-new compound is included in an amount of greater than 1 wt% to less than 5 wt% based on the total weight of the lubricant composition. Mixtures of different subcomponent compounds may also be used in combination in a lubricant composition or additive package.

When formulated as an additive package, the pro-new compound may be present in an amount ranging from 0.1 to 75% by weight, based on the total weight of the additive package. The subcomponent may also be present in the additive package in an amount ranging from 0.1 to 50% by weight, from 0.1 to 33% by weight, or from 0.1 to 25% by weight, based on the total weight of the additive package.

The boronic acid compounds can be prepared by a number of methods. As an example, the protonic compounds can be prepared by reacting 2 moles of orthoboric acid (H ₃ BO ₃ ) with 1 mole of tri-alkyl borate. The alkyl borate may have from 1 to 7 carbon atoms, depending on the number of carbon atoms preferred for the group designated as R < ¹ > in formula (I). The reaction may be carried out at a temperature ranging from 50 to 150 ° C to remove 1 mol H ₂ O.

Conventional use of conventional boron compounds involves the formation of reaction products between conventional amine compounds and conventional boron compounds. Conventional boron compounds may be exemplified by reactive borate esters and boric acid. In such applications, conventional boron compounds are consumed by chemical reactions so that the ultimately formed lubricant composition does not contain appreciable amounts of conventional boron compounds. Also, in such applications, conventional amine compounds react with conventional boron compounds to form salts. Salt formation is evidenced by electron impact during the reaction of conventional boron compounds with conventional amine compounds, which can be seen as chemical shifts in NMR spectroscopy. There is also a physical indication that the reaction takes place, such as the generation of heat and enrichment (bridging) of the solution.

In this application of conventional boron compounds, over 50% by weight of conventional boron compounds, based on the total weight of the conventional boron compounds prior to the reaction, typically react or hydrolyze with conventional amine compounds. In contrast, the lubricant compositions, additive packages, and methods of the present invention of the present invention can contain significant amounts of pro-new compounds in unreacted form. In addition, the lubricant composition of the present invention, the additive package of the present invention, and the method of the present invention do not include the formation of significant amounts of the proton-new compound salt. As such, the lubricant composition may not contain the salt formed through the reaction of the backbone compound, or the salt formed through the reaction of the backbone compound may be less than 10% by weight based on the total weight of the lubricant composition after any reaction , Less than 5 wt%, or less than 1 wt%.

In certain embodiments, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 80 wt%, based on the total weight of the precursor compounds used in the formation of the lubricant composition prior to any reaction in the lubricant composition At least 90% by weight of the borosiloxane remains unreacted in the lubricant composition. Alternatively, at least 95 wt.%, At least 96 wt.%, At least 97 wt.%, At least 98 wt.%, Or at least 99 wt.% Of the boroxine compound, based on the total weight of the precursor compound prior to any reaction in the lubricant composition, Remains unreacted in the lubricant composition.

The term "unreacted" refers to the fact that the specified amount of the borosilicate compound does not react with any component in the lubricant composition, such as a conventional amine compound or water. Thus, the unreacted amount of the proton new compound remains in its initial state when the lubricant composition is present in a lubricant composition prior to use in a end-use application, such as an internal combustion engine.

The phrase "pre-reacting in a lubricant composition" refers to the amount of the proton new compound in the lubricant composition. This substrate does not require that the borosiloxane compound reacts with the other components in the lubricant composition, i.e., 100% by weight of the borosiloxane based on the total weight of the borosiloxane prior to any reaction in the lubricant composition is present in the lubricant composition Remains unreacted.

In one embodiment, the percentage of the residual neodymium compound remaining unreacted is determined after all the components present in the lubricant composition have reached equilibrium with each other. The period of time required to reach equilibrium in the lubricant composition can vary widely. For example, the amount of time required to reach an equilibrium state may be from one minute to several days, or even an order range. In certain embodiments, the percentage of the retinoid compound that remains unreacted in the lubricant composition is 1 minute, 1 hour, 5 hours, 12 hours, 1 day, 2 days, 3 days, 1 week, 1 month, 6 months, or It is decided after one year. In general, the percentage of the backbone compound remaining unreacted in the lubricant composition is determined prior to final use.

In certain embodiments, the lubricant composition comprises less than 0.1% by weight, less than 0.01% by weight, less than 0.001% by weight, or less than 0.0001% by weight, based on the total weight of the lubricant composition, of the compound to be reacted with the borosilicate compound. In certain embodiments, the lubricant composition may comprise an acid, anhydride, triazole, and / or oxide in a total amount less than 0.1% by weight of the total weight of the lubricant composition. Alternatively, the lubricant composition may comprise an acid, anhydride, triazole, and / or oxide in a total amount of less than 0.01 wt%, less than 0.001 wt%, or less than 0.0001 wt% based on the total weight of the lubricant composition. Also alternatively, the lubricant composition may not contain an acid, anhydride, triazole, and / or oxide.

The term "acid " includes both typical acids and Lewis acids. For example, the acid may be a carboxylic acid such as lactic acid and hydracric acid; Alkylated succinic acid; Alkyl aromatic sulfonic acids; And fatty acids. Exemplary Lewis acids include alkyl aluminates; Alkyl titanates; Molybdenum mates, such as molybdenum thiocarbamate and molybdenum carbamate; And molybdenum sulfide.

"Anhydride" is exemplified by alkylated succinic anhydrides and acrylates. Triazole is benzotriazole and its derivatives; Tolloiazole and its derivatives; 2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole, 4,4'-methylene-bis-benzotriazole, 4,5,6,7-tetrahydro-benzotriazole, and its salts Lt; / RTI > Oxides include alkylene oxides such as ethylene oxide and propylene oxide; Metal oxides; Alkoxylated alcohols; Or alkoxylated esters.

The lubricant composition may comprise less than 100 ppm, less than 50 ppm, less than 10 ppm, or less than 5 ppm B (OH) ₃ ^- ion based on the total weight of the lubricant composition. Conventional prodrugs can be hydrolyzed before they are combined with conventional lubricant compositions, so that B (OH) ₃ ^- ions in excess of 100 ppm are present in conventional lubricant compositions. The inventors of the present invention have surprisingly found that, in this hydrolyzed state, the resultant common prodrug compounds do not provide a desired effect on practical availability. In other words, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% boroxyn The compound is present in an unhydrolyzed state in the lubricant composition. The amount of hydrolyzed subcombine compound is explained when determining the amount of the residual neodymium compound remaining unreacted.

In addition, the protonic compounds do not adversely affect the total base (TBN) of the lubricant composition. The TBN value of the lubricant composition can be determined according to ASTM D2896 and ASTM D4739 as described below.

As described above, the heterocyclic compounds may be combined with at least one hindered amine compound. It is to be understood that mixtures of different hindered amine compounds can also be combined with the boronic compounds. When included, the lubricant composition includes the hindered amine compound in an amount ranging from 0.1 to 25% by weight, 0.1 to 20% by weight, 0.1 to 15% by weight, or 0.1 to 10% by weight, based on the total weight of the lubricant composition do. Alternatively, the lubricant composition may comprise the hindered amine compound in an amount ranging from 0.5 to 5 wt%, 1 to 3 wt%, 1 to 2 wt% based on the total weight of the lubricant composition.

Substantially hindered amine compounds do not react with the borosiloxane compound to form salts. The absence of salt formation is evidenced by the lack of chemical shifts in the NMR spectrum of these compounds when the protonic and hindered amine compounds are combined in the lubricant composition and / or additive package. In other words, at least 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, or 99 wt% of hindered amines after the lubricant composition and / The compound remains unreacted.

The basicity of a sterically hindered amine compound can be determined by an acid titration method. The resulting neutralization value is expressed as TBN and can be measured using a variety of methods. ASTM D4739 is a potentiometric hydrochloric acid titration method. The ASTM D4739 method is preferred in engine testing and uses waste oil to measure TBN depletion / retention. When testing engine waste lubricants, certain weak bases should be recognized as being the result of use rather than being contained in the oil. This test method can be used to indicate the relative change taking place in the lubricant composition during use under oxidation or other use conditions, regardless of the color or other characteristics of the resulting lubricant composition.

The hindered amine compound may have a TBN value of at least 70 mg KOH / g when tested according to ASTM D4739. Alternatively, the hindered amine compound may have a solubility of at least 80 mg KOH / g, at least 90 mg KOH / g, at least 100 mg KOH / g, at least 110 mg KOH / g, at least 120 mg KOH / g when tested according to ASTM D4739 , At least 130 mg KOH / g, at least 140 mg KOH / g, at least 150 mg KOH / g or at least 160 mg KOH / g.

When the hindered amine compound is included in the additive package, the additive package comprises the hindered amine compound in an amount ranging from 0.1 to 50% by weight based on the total weight of the additive package. Alternatively, the additive package may comprise from 1 to 25 weight percent, from 0.1 to 15 weight percent, from 1 to 10 weight percent, from 0.1 to 8 weight percent, or from 1 to 5 weight percent, based on the total weight of the additive package, As shown in FIG. Combinations of various hindered amine compounds are also contemplated.

In some embodiments, the hindered amine compound comprises at least one nitrogen atom. In another embodiment, the hindered amine compound does not comprise a triazole, triazine, or similar compound in which there are more than three nitrogens present in the cyclic ring body.

In some embodiments, the hindered amine compound may consist of, or consist essentially of, hydrogen, carbon, nitrogen, and oxygen. Alternatively, the hindered amine compound may consist of, or consist essentially of, hydrogen, carbon, and nitrogen. In the context of sterically hindered amine compounds, the phrase "consisting essentially of" refers to a compound in which at least 95 mole% of the hindered amine compound is an atom (ie, hydrogen, carbon, nitrogen and oxygen; or hydrogen, carbon and nitrogen) Quot; For example, where the hindered amine compound consists essentially of hydrogen, carbon, nitrogen, and oxygen, at least 95 mole percent of the hindered amine compound is hydrogen, carbon, nitrogen, and oxygen. In certain embodiments, at least 96 mole%, at least 97 mole%, at least 98 mole%, at least 99 mole%, or at least 99.9 mole% of the hindered amine compound is hydrogen, carbon, nitrogen and oxygen, Nitrogen and hydrogen.

The hindered amine compound may be a covalent bond. The phrase "consisting of covalent bonds" is intended to exclude compounds bound to sterically hindered amine compounds through ionic associations with one or more ionic atoms or compounds. That is, in the configuration in which the hindered amine compound consists of a covalent bond, the hindered amine compound excludes salts of the hindered amine compound, such as a phosphate amine salt and an amine salt. Thus, in certain embodiments, the lubricant composition does not contain a salt of a sterically hindered amine compound. More specifically, the lubricant composition may not contain a phosphate amine salt, an amine salt and / or a sulfate amine salt.

In another embodiment, the hindered amine compound may have a weight average molecular weight in the range of 100 to 1200. Alternatively, the hindered amine compound may have a weight average molecular weight ranging from 200 to 800, or from 200 to 600. [ Also alternatively, the hindered amine may have a weight average molecular weight of less than 500.

As used herein, the term "hindered amine compound" means an organic molecule having less than two hydrogen atoms attached to at least one alpha-carbon in connection with a secondary or tertiary nitrogen atom. In another embodiment, the term "hindered amine compound" refers to an organic molecule that has no hydrogen atoms attached to at least one alpha-carbon associated with a secondary or tertiary nitrogen atom. In another embodiment, the term "hindered amine compound" refers to an organic molecule that has no hydrogen atoms attached to each of at least two alpha-carbon atoms in association with a secondary or tertiary nitrogen atom.

The hindered amine compound may have the formula (II) or (III)

≪

(III)

In formula (II), each R ² is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at least two of R ² are alkyl groups in one molecule; R ³ is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms. In Formula III, each R ⁴ is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at least two of R ⁴ are alkyl groups, and each R ⁵ is independently a hydrogen atom , Or a hydrocarbyl group having 1 to 17 carbon atoms.

Each of R ² , R ³ , R ⁴ and R ⁵ may independently be an alcohol group, an alkyl group, an amide group, an ether group or an ester group. Each R ² , R ³ , R ⁴ and R ⁵ independently has from 1 to 17, from 1 to 15, from 1 to 12, from 1 to 8, from 1 to 6, or from 1 to 4 carbon atoms . Each group designated as R ² , R ³ , R ⁴ and R ⁵ may be independently straight-chain or branched. For example, each of R ² , R ³ , R ⁴ and R ⁵ can be an alcohol group, an amino group, an alkyl group, an amide group, an ether group or an ester group having 1 to 17 carbon atoms, Alcohol, etc.) can be attached at various positions on the carbon chain.

In certain embodiments, at least one group designated as R ² , R ³ , R ^4, and R ⁵ is unsubstituted. Alternatively, at least 2, 3, 4, 5 or 6 groups designated as R ² , R ³ , R ⁴ and R ⁵ are unsubstituted. The term "unsubstituted" is intended to mean that it does not contain a designated gigapenta functional group such as hydroxyl, carboxyl, oxide, thio and thiol groups, and that the designated gigabits contain non-cyclic heteroatoms such as oxygen, sulfur and nitrogen heteroatoms It is intended that no. In other embodiments, all groups designated as R ² , R ³ , R ^4, and R ⁵ are unsubstituted. Alternatively, it is contemplated that 1, 2, 3, 4, 5, or 6 groups designated as R ² , R ³ , R ^4, and R ⁵ are substituted. The term "substituted" means that the designated group contains at least one pendant functional group, or that the designated group contains at least one non-cyclic heteroatom.

Exemplary R ² , R ³ , R ⁴ and R ⁵ groups are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert- butyl, n-hexyl, N-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl groups.

In formula (II), at least two, at least three, or all four groups designated as R < ² > are independently an alkyl group. Similarly, in Formula III, at least two groups designated as R < ⁴ > are alkyl groups. Alternatively, at least three, or all four groups designated by R < ⁴ > are alkyl groups.

The sterically hindered amine compounds of formula (II) can be illustrated by the following compounds:

2,2,6,6-tetramethyl-4-octylpiperidine:

2,2,6,6-Tetramethyl-4-decalpiperidine:

2,2,6,6-Tetramethyl-4-butylpiperidine:

2,2,6,6-tetramethyl-4-hexadecylpiperidine:

The hindered amine compound of formula (III) is non-cyclic. The term "non-cyclic" is intended to mean that the hindered amine compound of formula (III) has no cyclic structure and no aromatic structure. The hindered amine compounds of formula (III) can be illustrated by the following:

N-tert-Butyl-2-ethyl-N-methyl-hexan- 1 -amine:

tert-amyl-tert-butylamine:

N-tert-Butylheptan-2-amine:

Alternatively, the hindered amine compound may be further illustrated by the formula (IV)

(IV)

In formula IV, each R ² and R ³ is as described above, wherein at least three of R ² are independently alkyl groups. The hindered amine compounds of formula (IV) can be illustrated by the following compounds:

(1,2,2,6,6-pentamethyl-4-piperidyl) octanoate:

(1,2,2,6,6-pentamethyl-4-piperidyl) decanoate:

(1,2,2,6,6-pentamethyl-4-piperidyl) dodecanoate:

(2,2,6,6-tetramethyl-4-piperidyl) dodecanoate

The hindered amine compound may comprise a single ester group. Alternatively, however, the hindered amine compound may be free of ester groups. In certain embodiments, the hindered amine compound may comprise at least one, or only one, piperidine ring.

The boronic compound and the hindered amine compound may be provided in an amount such that 1 part boron is provided per 1 to 20 parts of nitrogen in the sterically hindered amine compound in the lubricant composition. Alternatively, the boronic acid compound and the hindered amine compound may be provided in an amount such that one boron 1 portion is provided for every 1 to 15, 1 to 10, or 1 to 5 parts of nitrogen in the sterically hindered amine compound in the lubricant composition .

In another embodiment, the lubricant composition may consist essentially of, or consist of, a base oil, a boronic compound and a sterically hindered amine compound. It is also contemplated that the lubricant composition may consist or essentially consist of a base oil, a borosiloxane compound and a sterically hindered amine compound, in addition to one or more additives that do not substantially affect the functionality or performance of the proinsulin compound. For example, a compound that substantially affects the overall performance of the lubricant composition may include compounds that have a negative effect on the TBN rise, lubricity, fluoropolymer compatibility, corrosion inhibition or acidity of the lubricant composition.

In another embodiment, the additive package may consist or consist essentially of a heterocyclic compound and a sterically hindered amine compound. It is also contemplated that the additive package may consist essentially of or consist of a backbone compound and a hindered amine compound, in addition to one or more additives that do not impair the functionality or performance of the backbone compound. When used for an additive package, the term "consisting essentially of " describes an additive package that does not have a compound that substantially affects the overall performance of the lubricant composition. For example, a compound that substantially affects the overall performance of an additive package may include compounds that have an adverse effect on TBN rise, lubricity, fluoropolymer compatibility, corrosion inhibition or acidity of the additive package.

In some aspects, the lubricant composition comprises a base oil. Base oils are classified according to the American Petroleum Institute (API) Base Oil Interchangeability Directive. In other words, the base oil can be further described as one or more of five types of base oils: Group I (sulfur content> 0.03% by weight, and / or <90% by weight, ; Group II (sulfur content 0.03 wt% or less, and 90 wt% or more, saturation, viscosity index 80-119); Group III (sulfur content 0.03 wt% or less, and 90 wt% or more, saturation, viscosity index 119 or more); Group IV (all polyalphaolefins (PAO)); And Group V (all others not included in Groups I, II, III or IV).

Base oil is API Group I base oil; API Group II Base Oil; API Group III base oil; API Group IV Base Oil; API Group V Base Oil; And combinations thereof. In one particular formulation, the base oil comprises API Group II base oil.

The base oil may have a viscosity ranging from 1 to 20 cSt when tested according to ASTM D445 at 100 占 폚. Alternatively, the viscosity of the base oil may range from 3 to 17, or from 5 to 14 cSt when tested according to ASTM D445 at 100 占 폚.

Base oils can be further defined as crankcase lubricating oils for spark-ignition and compression-ignition internal combustion engines, including automotive and truck engines, two-cycle engines, aircraft piston engines, marine engines and railroad diesel engines. Alternatively, the base oil may be further defined as an oil used in gas engines, diesel engines, stationary power engines and turbines. The base oil may be further defined as a large or small engine oil.

In another embodiment, the base oil may be further defined as a synthetic oil comprising one or more alkylene oxide polymers and copolymers and derivatives thereof. The terminal hydroxyl groups of the alkylene oxide polymers can be modified by esterification, etherification or similar reactions. These synthetic oils may be prepared by polymerization of ethylene oxide or propylene oxide, followed by further reaction to form a polyoxyalkylene polymer capable of forming a synthetic oil. For example, alkyl and aryl ethers of these polyoxyalkylene polymers can be used. Methyl polyisopropylene glycol ethers having an average molecular weight of, for example, 1000; Diphenyl ethers of polyethylene glycol having a molecular weight of 500-1000; Or of a polypropylene glycol having a molecular weight of 1000-1500 with diethyl ether and / or a mono- and polycarboxylic acid esters, such as acetic acid esters, mixed C ₃ -C ₈ fatty acid esters, and tetraethylene glycol in the C ₁₃ oxo acid Diesters can also be used as base oil.

In one embodiment, one or more of the ingredients described herein are blended into an additive package and subsequently blended into a base oil to prepare a lubricant composition. The additive package may be formulated to provide the desired concentration in the lubricant composition when the concentrate is combined with a predetermined amount of base oil. It should be appreciated that most references to lubricant compositions throughout this disclosure also apply to the description of additive packages. For example, it should be appreciated that the additive package, although different amounts, may include or exclude the same components as the lubricant composition.

The base oil may be present in an amount of from 50 to 99.9% by weight, from 60 to 99.9% by weight, from 70 to 99.9% by weight, from 80 to 99.9% by weight, from 90 to 99.9% by weight, from 75 to 95% by weight, 90 wt%, or 85-95 wt%, based on the total weight of the lubricant composition. Alternatively, the base oil may be present in an amount of 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95% % Or 99% by weight of the lubricant composition. In various embodiments, the amount of base oil in the fully formulated lubricant composition (including any diluent or carrier oil present) is from 50 to 99% by weight, from 60 to 90% by weight, from 80 to 99.5% by weight based on the total weight of the lubricant composition, , 85 to 96 wt%, or 90 to 95 wt%. In various embodiments, the amount of base oil in the additive package (including any diluent or carrier oil present), if included, is in the range of 0.1 to 50 wt%, 1 to 25 wt%, or 1 To 15% by weight.

In one or more embodiments, the lubricant composition may be classified as a low SAPS lubricant having a sulfated ash content of 3 wt%, 2 wt%, 1 wt%, or 0.5 wt% or less, based on the total weight of the lubricant composition . The term "SAPS" refers to ash, phosphorus and sulfur.

The lubricant composition may have a TBN value of at least 1 mg KOH / g of lubricant composition g. Alternatively, the lubricant composition has a TBN value in the range of 1 to 15, 5 to 15, or 9 to 12 mg KOH / lubricant composition g when tested according to ASTM D2896.

The lubricant composition or additive package may further comprise a dispersing agent, in addition to the boronic acid compound and / or the sterically hindered amine compound. The dispersant may be a polyalkenamine. Polyalkenamines include polyalkene moieties. The polyalkene moiety is the polymerization product of the same or different linear or branched C _2-6 olefin monomers. Examples of suitable olefin monomers are ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methylbutene, 1-hexene, 2-methylpentene, 3-methylpentene and 4-methylpentene. The polyalkene moiety has a weight average molecular weight ranging from 200 to 10000, 500 to 10000, or 800 to 5000.

In one embodiment, the polyalkenamines are derived from polyisobutene. Particularly suitable polyisobutene is known as "highly reactive" polyisobutene which is characterized by a high content of terminal double bonds. The terminal double bond is an alpha-olefinic double bond of the type shown in Formula V:

(V)

The bond shown in formula V is known as a vinylidene double bond. Suitable highly reactive polyisobutenes are, for example, polyisobutene having a fraction of vinylidene double bonds of greater than 70 mole%, 80 mole%, greater than 85 mole%. Particularly preferred is polyisobutene having a homogeneous polymer backbone. The homogeneous polymer backbone has in particular at least 85% by weight, 90% by weight or 95% by weight of isobutene units. Such highly reactive polyisobutene preferably has a number-average molecular weight in the above-mentioned range. In addition, the highly reactive polyisobutene may have a polydispersity in the range of 1.05 to 7, or 1.1 to 2.5. The highly reactive polyisobutene may have a polydispersity of less than 1.9, or less than 1.5. The polydispersity refers to the quotient of the weight-average molecular weight Mw divided by the number-average molecular weight Mn.

The amine dispersant may comprise moieties derived from succinic anhydride and may have hydroxyl and / or amino and / or amido and / or imido groups. For example, dispersants may be prepared from polyisobutenylsuccinic anhydrides obtainable by reacting conventional or highly reactive polyisobutene having a weight average molecular weight in the range of 500 to 5000 with a maleic anhydride via a thermal pathway or via chlorinated polyisobutene Lt; / RTI &gt; In one specific embodiment, derivatives having aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be used.

To prepare polyalkenamines, the polyalkene component can be aminated in a known manner. The illustrated process proceeds via hydroformylation in the presence of a suitable nitrogen compound and the preparation of the oxo intermediate by subsequent reductive amination.

The dispersant may be a poly (oxyalkyl) radical or a polyalkylene polyamine radical of formula (VI).

&Lt; Formula (VI)

R ⁶ -NH- (C ₁ -C ₆ -alkylene-NH) _m -C ₁ -C ₆ -alkylene

Wherein m is an integer ranging from 1 to 5 and R ⁶ is a hydrogen atom or a hydrocarbyl group having from 1 to 6 carbon atoms and C ₁ -C ₆ alkylene is the corresponding bridged analog of an alkyl radical . The dispersing agent may also be a polyalkyleneimine radical consisting of from 1 to 10 C ₁ -C ₄ alkyleneimine groups; Or optionally joined together with the nitrogen atom to which they are attached, an optionally substituted 5- to 7-membered ring optionally substituted by one to three C ₁ -C ₄ alkyl radicals and optionally bearing one additional ring heteroatom, Membered heterocyclic ring.

Examples of suitable alkenyl radicals include mono- or polyunsaturated, preferably mono- or di-unsaturated analogs of alkyl radicals having 2 to 18 carbon atoms, wherein the double bond may be in any position within the hydrocarbon chain have.

Examples of C ₄ -C ₁₈ cycloalkyl radicals include cyclobutyl, cyclopentyl and cyclohexyl, and also analogues thereof substituted by one to three C ₁ -C ₄ alkyl radicals. C ₁ -C ₄ alkyl radicals are selected, for example, from methyl, ethyl, iso- or n-propyl, n-, iso-, sec- or tert-butyl.

Examples of arylalkyl radicals include aryl or heteroaryl radicals derived from monocyclic or bicyclic, fused or unfused, 4- to 7-membered, especially 6-membered, aromatic or heteroaromatic groups such as phenyl, pyridyl, naphthyl and biphenyl Gt; C ₁ -C ₁₈ &lt; / RTI &gt; alkyl groups.

When additional dispersants other than those described above are used, these dispersants may have various types. Suitable examples of dispersants include polybutenyl succinic amide or -imide, polybutenylphosphonic acid derivatives and basic magnesium, calcium and barium sulfonates and phenolates, succinate esters and alkylphenol amines (Mannich bases) And combinations thereof.

When used, the dispersing agent can be used in various amounts. The dispersing agent is typically present in the lubricant composition in an amount ranging from 0.01 to 15% by weight, from 0.1 to 12% by weight, from 0.5 to 10% by weight, or from 1 to 8% by weight, based on the total weight of the lubricant composition. Alternatively, the dispersing agent may be present in an amount of less than 15 wt%, less than 12 wt%, less than 10 wt%, less than 5 wt%, or less than 1 wt%, based on the total weight of the lubricant composition, respectively.

In the additive package, the total weight of the dispersant and the borosilicate compound is less than 50 wt%, less than 45 wt%, less than 40 wt%, less than 35 wt%, or less than 30 wt%, based on the total weight of the additive package, &Lt; / RTI &gt; Surprisingly, it has been found that if the combined concentration of the dispersant and the borosilicate compound is too high in the additive package, the reaction between the dispersant and the borosilicate compound will occur, resulting in thickening of the fluoropolymer yarn and the formation of precipitates, lost.

The lubricant composition or additive package may further comprise a dihydrocarbyl dithiophosphate salt. The dihydrocarbyl dithiophosphate salt may be represented by the following formula: [R ⁷ O (R ⁸ O) PS (S)] ₂ M wherein R ⁷ and R ⁸ are each 1 to 20 carbon atoms And M is a metal atom or an ammonium group. For example, R ⁷ and R ⁸ are each independently a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _3-20 cycloalkyl group, a C _1-20 aralkyl group, or a C _3-20 aryl group . R ⁷ and R ⁸ may be substituted or unsubstituted. The metal atom may be selected from the group comprising aluminum, lead, tin, manganese, cobalt, nickel or zinc. The ammonium group may be derived from ammonia or a primary, secondary or tertiary amine. The ammonium group may have the formula R ⁹ R ¹⁰ R ¹¹ R ¹² N ⁺ wherein R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom or a hydrocarbyl group having from 1 to 150 carbon atoms Lt; / RTI &gt; In certain embodiments, R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently can be a hydrocarbyl group having from 4 to 30 carbon atoms. In one specific embodiment, the dihydrocarbyl dithiophosphate salt is zinc dialkyl dithiophosphate.

The dihydrocarbyl dithiophosphate salt is present in an amount of from 0.1 to 20% by weight, from 0.5 to 15% by weight, from 1 to 10% by weight, from 0.1 to 5% by weight, from 0.1 to 1% by weight, 0.1 to 0.5% by weight, or 0.1 to 1.5% by weight based on the total weight of the lubricant composition. Alternatively, the dihydrocarbyl dithiophosphate salts may each contain less than 20 wt%, less than 10 wt%, less than 5 wt%, less than 1 wt%, less than 0.5 wt%, or less than 1 wt%, based on the total weight of the lubricant composition May be present in an amount of less than 0.1% by weight. The additive package also comprises a dihydrocarbyl dithiophosphate salt in an amount of from 0.1 to 20% by weight, from 0.5 to 15% by weight, from 1 to 10% by weight, from 0.1 to 5% by weight, from 0.1 to 5% by weight, By weight to 1% by weight, 0.1 to 0.5% by weight, or 0.1 to 1.5% by weight.

The lubricant composition or additive package may further comprise one or more additives to improve various chemical and / or physical properties of the lubricant composition. These additives may be added to the prodrug compound, or may be added to the combination of the prodrug compound and the hindered amine compound. Specific examples of the one or more additives include antiwear additives, antioxidants, metal deactivators (or passivating agents), rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents and anti-friction additives. Each of the additives may be used alone or in combination. One or more additives may be used in varying amounts when used. The lubricant composition may be formulated with the addition of various auxiliary ingredients to achieve a particular performance purpose for use in a particular application. For example, the lubricant composition may be a rust and oxidizing lubricant agent, a hydraulic lubrication agent, a turbine lubricating oil, and an internal combustion engine lubricant. Thus, it is contemplated that the base oil may be formulated to achieve the objectives discussed below.

When used, the wear-resistant additive can have various types. Abrasion-proof additives include sulfur- and / or phosphorus- and / or halogen-containing compounds such as sulfurized olefins and vegetable oils, alkylated triphenyl phosphates, tritolyl phosphate, tricresyl phosphate, chlorinated paraffin, And trisulfide, amine salts of mono- and dialkyl phosphates, amine salts of methylphosphonic acid, diethanolaminomethyltolyl triazole, bis (2-ethylhexyl) aminomethyl tolyltriazole, 2,5-dimercapto (Diisopropoxyphosphinothioyl) thio] propionate, triphenylthiophosphate (triphenylphosphorothioate), tris (alkylphenyl) thiophosphate, ) Phosphorothioates and mixtures thereof, diphenyl monononyl phenyl phosphorothioate, isobutyl phenyl diphenyl phosphorothioate, dodecyl amine salts of 3-hydroxy-1,3-thiaphosphate 3-oxide , Trithiophosphoric acid 5 , 5,5-tris [isooctyl 2-acetate], derivatives of 2-mercaptobenzothiazole such as 1- [N, N-bis (2-ethylhexyl) aminomethyl] -2-mercapto- 1,3-benzothiazole, ethoxycarbonyl-5-octyldithiocarbamate, and / or combinations thereof.

When used, in addition to or in exchange for the dihydrocarbyl dithiophosphate salts described above, abrasion resistant additives can be used in varying amounts. The abrasion resistant additives may be present in the lubricant composition in an amount of from 0.1 to 20% by weight, from 0.5 to 15% by weight, from 1 to 10% by weight, from 0.1 to 1% by weight, from 0.1 to 0.5% by weight, % &Lt; / RTI &gt; by weight of the lubricant composition. Alternatively, the abrasion-proof additive may be present in an amount of less than 20 wt%, less than 10 wt%, less than 5 wt%, less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt%, based on the total weight of the lubricant composition, It can be present in an amount.

When used, antioxidants may have various types. Suitable antioxidants include alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6- Butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, But are not limited to, 2- (? -Methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6- 4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4- Methylphenol, 6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and combinations thereof.

Further examples of suitable antioxidants are alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4- Dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol, and combinations thereof. Hydroquinone and alkylated hydroquinone such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5- Di-tert-butylhydroquinone, 3,5-di-tert-butyl-4- Hydroxy-phenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and combinations thereof, Can be used.

Further, hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol) 4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis Di-sec-amylphenol), 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide, and combinations thereof may also be used.

Also, alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert- Methylene-bis (4-methyl-6-cyclohexylphenol), 2'-methylenebis [ Methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6- , 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- -Methylenebis [2,6-di-tert-butylphenol], 4,4'-methylenebis (6 (a, (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert- -Hydroxy-2-methyl-phenyl) -3-n-dodecyl mercaptobutane (3'-tert-butyl-4'-hydroxyphenyl) butyrate], ethylene glycol bis [3,3-bis Diene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert- butyl- (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra- It is contemplated that the combination may be used as an antioxidant in a lubricant composition.

O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl- 3,5-dimethylbenzylmercaptoacetate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, Combinations can also be used.

Hydroxybenzylated malonates such as dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, di-octadecyl- butyl-4-hydroxybenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis- (3,5-di- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] Combinations are also suitable for use as antioxidants.

Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis Butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert- ) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5- tert-butyl-3-hydroxy-2,6-dimethylbenzyl 2,4,6-tris (3,5-di-tert- butyl-4-hydroxyphenylethyl) (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5- 5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate, and combinations thereof, may also be used.

Further examples of antioxidants are aromatic hydroxybenzyl compounds, such as 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris -Butyl-4-hydroxybenzyl) phenol, and combinations thereof. Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert- butyl-4-hydroxybenzylphosphonate Di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy 3-methylbenzylphosphonate, 3,5-di calcium salt of the monoethyl ester of -tert-butyl-4-hydroxybenzylphosphonic acid, and combinations thereof, may also be used. In addition, acylaminophenols such as 4-hydroxylairanylid, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate .

The reaction of [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6- Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-dicyclohexylcarbodiimide, Bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- Cyclo [2.2.2] octane, and combinations thereof, can also be used. for example, mono- or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanyl Diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (Hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and combinations thereof, can be used.

Further examples of suitable antioxidants are those containing nitrogen, such as amides of? - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis , N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine. Other suitable examples of antioxidants include amine-based antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di- Bis (1-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylpentyl) ) -phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl- N'-phenyl-p-phenylenediamine, N- (1, 3-dimethyl-butyl) Phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl Di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- Phenyl-2-naphthylamine, octylated diphenylamines such as p, p'-di-tert-octyldiphenylamine, 4-n-butylamino 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butylphenol, -Butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl- Bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ' Phenyl-1-naphthylamine, a mixture of mono- and di-alkylated tert-butyl / tert-octyldiphenylamine, mono- and dialkylated isopropyl / Isohexyldiphenylamine, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, and combinations thereof.

Still further examples of suitable antioxidants are aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamic acid or dithiophosphoric acid, 2,2,12,12-tetramethyl- , 9-dihydroxy-3,7,1 trithiatridecane and 2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane, and And combinations thereof. In addition, sulfurized fatty acid esters, sulfurized fats and sulfurized olefins, and combinations thereof, may be used.

When used, antioxidants may be used in various amounts. The antioxidant may be present in the lubricant composition in an amount ranging from 0.01 to 5 wt%, 0.1 to 3 wt%, or 0.5 to 2 wt%, based on the total weight of the lubricant composition. Alternatively, the antioxidant may be present in an amount of less than 5 wt%, less than 3 wt%, or less than 2 wt%, based on the total weight of the lubricant composition.

When used, the metal deactivator may have various types. Suitable metal deactivators include, but are not limited to, benzotriazoles and derivatives thereof such as 4- or 5-alkylbenzotriazoles (e.g., toluliazole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole Sol and 5,5'-methylene bisbenzotriazole; Such as 1- [bis (2-ethylhexyl) aminomethyl) toluliazole and 1- [bis (2-ethylhexyl) aminomethyl) benzotriazole ; And alkoxyalkylbenzotriazoles such as 1- (nonyloxymethyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1- (1-cyclohexyloxybutyl) .

Further examples of suitable metal deactivators are 1,2,4-triazole and derivatives thereof, and Mannich bases of 1,2,4-triazole such as 1- [bis (2-ethylhexyl) aminomethyl- , 2,4-triazole; Alkoxyalkyl-1,2,4-triazoles such as 1- (1-butoxyethyl) -1,2,4-triazole; And acylated 3-amino-1,2,4-triazole, imidazole derivatives such as 4,4'-methylenebis (2-undecyl-5-methylimidazole) and bis [ ) Imidazol-2-yl] carbinol octyl ether, and combinations thereof. Further examples of suitable metal deactivators are sulfur-containing heterocyclic compounds such as 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and its derivatives; And 3,5-bis [di (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one, and combinations thereof. Still further examples of metal deactivators include amino compounds such as salicylidene propylenediamine, salicylaminoguanidine and salts thereof, and combinations thereof.

When used, the metal deactivator can be used in various amounts. The metal deactivator may be present in the lubricant composition in an amount ranging from 0.01 to 0.1% by weight, from 0.05 to 0.01% by weight, or from 0.07 to 0.1% by weight, based on the total weight of the lubricant composition. Alternatively, the metal deactivator may be present in an amount of less than 1.0 wt%, less than 0.7 wt%, or less than 0.5 wt%, based on the total weight of the lubricant composition.

When used, the rust inhibitor and / or friction modifier may have various types. Suitable examples of rust inhibitors and / or friction modifiers include organic acids, their esters, metal salts such as alkyl- and alkenylsuccinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, alkyl- and alkenyl Succinic acid, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids such as dodecyloxyacetic acid, partial amides of dodecyloxy (ethoxy) acetic acid, and also N-oleoyl sarcosine, sorbitan monoole Octadecanoate, lead naphthenate, alkenyl succinic anhydride, such as dodecenylsuccinic anhydride, 2-carboxymethyl-1-dodecyl-3-methylglycerol, and combinations thereof. Further examples are heterocyclic compounds such as substituted imidazolines and oxazolines, and 2-heptadecenyl-1- (2-hydroxyethyl) imidazolines, phosphorus-containing compounds such as phosphoric acid Amine salts of partial esters or phosphonic acid partial esters, molybdenum-containing compounds such as molybdenum dithiocarbamate, and other sulfur and phosphorus containing derivatives, sulfur-containing compounds such as barium dinonylnaphthalenesulfonate , Esters of aliphatic 2-sulfocarboxylic acid and salts thereof, glycerol derivatives such as glycerol monooleate, 1- (alkylphenoxy) -3 - (2-hydroxyethyl) glycerol, 1- (alkylphenoxy) -3- (2,3-dihydroxypropyl) glycerol and 2-carboxyalkyl-1,3-dialkyl glycerol, do.

When used, the rust inhibitor and / or friction modifier may be used in various amounts. The rust inhibitor and / or friction modifier may be present in the lubricant composition in an amount ranging from 0.01 to 0.1 wt%, 0.05 to 0.01 wt%, or 0.07 to 0.1 wt%, based on the total weight of the lubricant composition. Alternatively, the rust inhibitor and / or friction modifier may be present in an amount of less than 1 wt%, less than 0.7 wt%, or less than 0.5 wt%, based on the total weight of the lubricant composition.

When used, viscosity index improvers can have various types. Suitable examples of viscosity index improvers include polyacrylates, polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinylpyrrolidone, polybutene, olefin copolymers, styrene / acrylate copolymers and polyethers, And combinations thereof.

When used, viscosity index improvers may be used in various amounts. The viscosity index improver may be present in the lubricant composition in an amount ranging from 0.01 to 20 wt%, 1 to 15 wt%, or 1 to 10 wt%, based on the total weight of the lubricant composition. Alternatively, the viscosity index improver may be present in an amount of less than 10 wt%, less than 8 wt%, or less than 5 wt%, based on the total weight of the lubricant composition.

If used, the pour point depressant can have various types. Suitable examples of pour point depressants include polymethacrylates and alkylated naphthalene derivatives, and combinations thereof.

When used, the pour point depressant can be used in various amounts. The pour point depressant may be present in the lubricant composition in an amount ranging from 0.01 to 0.1 wt%, 0.05 to 0.01 wt%, or 0.07 to 0.1 wt%, based on the total weight of the lubricant composition, respectively. Alternatively, the pour point depressant may be present in an amount of less than 1.0 wt.%, Less than 0.7 wt.%, Or less than 0.5 wt.%, Based on the total weight of the lubricant composition.

If used, the detergent can have various types. Suitable examples of detergents include overbased or neutral metal sulfonates, phenates and salicylates, and combinations thereof.

If used, the detergent may be used in various amounts. The detergent may be present in the lubricant composition in an amount ranging from 0.01 to 5 weight percent, 0.1 to 4 weight percent, 0.5 to 3 weight percent, or 1 to 3 weight percent, based on the total weight of the lubricant composition. Alternatively, the detergent may be present in an amount of less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, or less than 1 wt%, based on the total weight of the lubricant composition.

Less than 4% by weight, less than 3% by weight, less than 2% by weight, based on the total weight of the lubricant composition, based on the total weight of the lubricant composition. In various embodiments, the lubricant composition is substantially free of water, , Less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt% water. Alternatively, the lubricant composition may contain no water at all.

Preferred lubricant compositions provided for use in accordance with the present invention and used in accordance with the present invention include those that have passed the CEC L-39-T96 compatibility test. The CEC L-39-T96 test involves holding a test specimen of a fluoropolymer at 150 占 폚 in a lubricant composition. Then, the test piece is taken out, dried, and the characteristics of the test piece are evaluated and compared with the non-heated test piece in the lubricant composition. The percent change in these properties is evaluated to quantify the compatibility of the fluoropolymer room with the lubricant composition. The incorporation of the prodrug compound into the lubricant composition reduces the tendency of the lubricant composition to deteriorate the yarn compared to the lubricant composition that does not contain the prodrug.

The pass / fail criteria include the maximum fluctuation of certain properties after 7 days immersion in fresh oil without pre-aging. The maximum variation for each characteristic depends on the type of elastomer used, the type of engine used, and whether the aftertreatment apparatus is used.

The properties measured before and after immersion were the hardness DIDC (points); The tensile strength (%); Elongation at break (%); Volume change (%). The pass / fail criteria for large diesel engines are shown in Table 1 below:

Table 1: Fluoropolymer Yarn Compatibility for CEC L-39-T96

In these tests, the exposed test specimen shows a change in hardness from -1% to + 5%; -50% to + 10% tensile strength (as compared to non-test specimens); A change in fracture elongation of -60% to + 10% (when compared to untested specimens); And a volume variation of -1% to + 5% (as compared to the non-test specimen), the conventional lubricant composition passes the test.

When the lubricant composition is tested on a large diesel engine in accordance with CEC L-39-T96, the hardness variation can be from -1 to 5%, from -0.5 to 5%, from -0.1 to 5%, from 0.5 to 5%, or from 1 to 5 % Range; The tensile strength change may range from -50 to 10%, -45 to 10%, -40 to 10%, or -35 to 10%; The fracture elongation change may range from -60 to 10%, -55 to 10%, -50 to 10%, or -45 to 10%; The volume variation may be in the range of -1 to 5%, -0.75 to 5%, -0.5 to 5%, -0.1 to 5%, or 0 to 5%.

When the borazine neodymium composition is used in the disclosed lubricant composition, the resultant lubricant composition, when tested for a large diesel engine according to CEC L-39-T96, has less than 10% fluoropolymer seams in the lubricant composition, less than 15% To exhibit a tensile strength change of less than 10%, less than 20%, less than 25%, less than 30%, less than 35%, less than 40%, less than 45%, less than 50%, less than 55%, or less than 60% And has compatibility. Similarly, when prodrug compounds are used in the disclosed lubricant compositions, the resulting lubricant compositions have a fluoropolymer content of less than 20%, less than 25%, 30% Less than 35%, less than 40%, less than 45%, less than 50%, less than 55%, or less than 60% tensile strength fracture elongation.

Some of the compounds described above may interact in the lubricant composition, so that the components of the final form of the lubricant composition may be different from those initially added or combined together. Some products formed thereby, such as the product formed when using the lubricant composition of the present invention for its intended use, are not readily described or explained. Nevertheless, all such modifications, reaction products, and products formed when using the lubricant compositions of the present invention for their intended use, are specifically contemplated and are hereby incorporated herein by reference. Various embodiments of the present invention include at least one of the products formed from the use of the reformate, the reaction product, and the lubricant composition as described above.

A method of lubricating the system is provided. The method includes contacting the system with the lubricant composition described above. The system may further include an internal combustion engine. Alternatively, the system may further include any combustion engine or application that utilizes a lubricant composition. The system comprises at least one fluoropolymer chamber.

The fluoropolymer yarn may comprise a fluoroelastomer. Fluoroelastomers can be classified, for example, under the names ASTM D1418 and ISO 1629 of FKM. The fluoroelastomers are copolymers of hexafluoropropylene (HFP) and vinylidene fluoride (VDF of VF2), terpolymers of tetrafluoroethylene (TFE), vinylidene fluoride and hexafluoropropylene, perfluoro Methyl vinyl ether (PMVE), copolymers of TFE and propylene, and copolymers of TFE, PMVE and ethylene. The fluorine content varies from 66 to 70% by weight, for example, based on the total weight of the fluoropolymer chamber. FKM is a fluoro-rubber of the polymethylene type with substituent fluoro and perfluoroalkyl or perfluoroalkoxy groups on the polymer chain.

In addition, a method of forming a lubricant composition is provided. The process comprises combining a base oil and a heterocyclic compound, and optionally a sterically hindered amine compound. The boronic compounds can be incorporated into the base oil in any convenient manner. Thus, the proton compound can be added directly to the base oil by dispersing or dissolving it in the base oil at the desired level of concentration. Alternatively, the base oil may be added directly to the new compound while stirring, until the protonic compound is provided at the desired level of concentration. Such blending can occur at ambient or sub-ambient temperatures, such as 30, 25, 20, 15, 10, or 5 ° C.

Example

In the following examples, illustrative lubricant compositions were formulated by blending the components together, but not necessarily, until homogeneity was achieved. A fully formulated lubricating oil composition was prepared containing dispersants, detergents, amine antioxidants, phenolic antioxidants, antifoaming agents, base oils, antiwear additives, pour point depressants and viscosity modifiers. This lubricant composition, representing a commercial crankcase lubricant, was designated as "reference lubricant" and used as a baseline to compare the effect of different components on yarn compatibility.

The reference lubricant was combined with a variety of different boron-containing compounds and a variety of different nitrogen-containing compounds to demonstrate the effect of boron-containing compounds on emissivity and the effect of nitrogen-containing compounds. Examples # 1, # 2, # 3, and # 4 of the present invention each include one of the inventive precursor compounds and one of the amine compounds of the present invention. Comparative Examples # 1-5 do not include the inventive voxine compounds. Comparative Examples # 6-8 do not include the amine compound of the present invention. Comparative Examples # 9- # 12 do not include the amine compound of the present invention or the inventive inventive heterocyclic compound.

The boron-containing compound added to the reference lubricant in Examples # 1 and # 2 of the present invention is trimethoxyboroxine. The boron-containing compound added to the reference lubricant in Example # 3 of the present invention is triethoxyboroxine. The boron-containing compound added to the reference lubricant in Example # 4 of the present invention is tri-n-butoxyboroxine.

As described above, Comparative Examples # 1-5 do not include the inventive voxine compounds. Instead, the compositions of both Comparative Example # 1 and Comparative Example # 2 do not contain any boron-containing compounds. Comparative Example # 1 contains the amine compound of the present invention, while Comparative Example # 2 does not include the amine compound of the present invention. The boron-containing compound added to the reference lubricant in Comparative Example # 3 is tris- (2-ethylhexyl) boroxine. The boron-containing compound added to the reference lubricant in Comparative Example # 4 is tributyl borate. The boron-containing compound added to the reference lubricant in Comparative Example # 5 is tri-isopropyl borate.

Comparative Examples # 6-9 include the inventive precursor compounds but do not include the amine compounds of the present invention. The comparative compounds added to the reference lubricant in Comparative Examples # 6 and 7 are trimethoxyboroxine. The comparative compound added to the reference lubricant in Comparative Example # 8 is triethoxyboroxine. The comparative compound added to the reference lubricant in Comparative Example # 9 is tri-n-butoxyboroxine.

Comparative Examples # 10-12 do not include the inventive inventive heterocyclic compound or the amine compound of the present invention. The boron-containing compound in Comparative Example # 10 is tris- (2-ethylhexyl) boroxine. The boron-containing compound in Comparative Example # 11 is tributyl borate. The boron-containing compound in Comparative Example # 12 is tri-isopropylborate.

The amine compound included in Examples # 1-4 of the present invention and Comparative Examples # 1 and 3-5 is (2,2,6,6-tetramethyl-4-piperidyl) dodecanoate.

The amounts of each of the reference lubricant and any additional components for each of the present and comparative examples are shown in Tables 2, 3 and 4 below.

Table 2: Formulation of Examples # 1- # 4 of the present invention

Table 3: Composition of Comparative Example # 1-5 (C1-C5)

Table 4: Composition of Comparative Example # 6-11 (C6-C12)

Industrial-Standard CEC L-39-T96 In-situ tests were used to evaluate the practical applicability of the present invention and comparative examples. The CEC-L-39-T96 yarn compatibility test is performed by providing a seal or gasket in the lubricant composition, heating the yarn-containing lubricant composition at an elevated temperature, and maintaining the elevated temperature for a period of time. The yarn is then removed, dried, the mechanical properties of the yarn are evaluated, and compared to the unheated yarn specimen in the lubricant composition. The percent change in these properties is analyzed to assess the compatibility of the yarn and lubricant compositions. Each formulation was tested twice (Run # 1 and Run # 2) under the same conditions. The results of the practical compatibility test are shown in Tables 5-10 below.

Table 5: Results of practical test (Run 1) - Examples # 1- # 4 of the present invention

Table 6: Practical compatibility test results (Run 2) - Examples # 1- # 4 of the present invention

Table 7: Results of practical test (Run 1) - Comparative Examples # 1- # 6 (C1-C6)

Table 8: Practical Compatibility Test Results (Run 2) - Comparative Examples # 1- # 6 (C1-C6)

Table 9: Practical compatibility test results (Run 1) - Comparative Examples # 7- # 12 (C7-C12)

Table 10: Results of practical test (Run 2) - Comparative Example # 7 - # 12 (C7-C12)

Comparative Example # 1 illustrates the effect of an amine compound on the toughness of the lubricant composition. Comparing the tensile strength and fracture elongation of the comparative example # 1 containing the amine compound of the present invention and the comparative example # 2 not containing the amine compound of the present invention, the present inventors found that the amine compound Of the additive has a negative effect on the practical applicability of the reference lubricant. The negative effect is quantified by the fact that tensile strength and fracture elongation are much worse for Comparative Example # 1 compared to Comparative Example # 2.

Examples # 1, # 2, # 3, and # 4 of the present invention each include the same amine compound of the present invention as in Comparative Example # 1, together with one species of the inventive heterocyclic compound. As shown in the results shown in Table 4-7, the practical applicability of Examples # 1-4 of the present invention was significantly improved compared to the practical use of Comparative Example # 1 in terms of both tensile strength and fracture elongation. This significant improvement in practical compatibility is evidenced by the fact that the tensile strength and fracture elongation are much worse for Comparative Example # 1 compared to Examples # 1-4 of the present invention.

Table 5-8 also demonstrates that the practical usefulness of Examples # 1 and # 2 of the present invention is improved in comparison with practical use of Comparative Example # 3-5 in terms of tensile strength and fracture elongation. The tensile strength of Example # 1 of the present invention is -39 and -32%; The tensile strength of Example # 2 of the present invention is -2 and -5%; While the tensile strengths of Comparative Examples # 3, 4 and 5 were -47 and -44%, respectively; -39 and -41; And -44 and -42%, respectively. Similarly, the fracture elongation for Example # 1 of the present invention is -54 and -51%; The breaking elongation for Example # 2 of the present invention is 8 and -5%; While the fracture elongations of Comparative Examples # 3, 4 and 5 were -72 and -68%, respectively; -64 and -61%; And -66% and -67%, respectively. This test shows that the lubricant compositions of Examples # 1 and # 2 of the present invention are far more compatible with yarns than the lubricant compositions of Comparative Examples # 3-5 in terms of tensile strength and fracture elongation. This comparison also shows that the combination of trimethoxyboroxine and the amine compound of the present invention in the lubricant composition is much more improved than the boron-containing compound used in the lubricant compositions comprising other boron-containing compounds, such as Comparative Examples # 3-5 Provides evidence that it provides a practical viability.

Finally, a comparison of Comparative Example # 2 and Comparative Examples # 6-12 shows that a lubricant composition comprising a boron-containing compound but not an amine compound of the present invention has a negative effect on the practical utility of the lubricant composition in a significant way Of the population. Thus, surprisingly, the inventors of the present invention have recognized that the combination of the amine compound of the present invention and the inventive voroxine compound has a synergistic effect on physical compatibility when present in the reference lubricant.

It is to be understood that the appended claims are not intended to be limited to the specific and specific compounds, compositions or methods set forth in the Detailed Description of the Invention, which may vary between certain embodiments falling within the scope of the appended claims. For any Makushi group that is hereby relied upon to describe a particular feature or aspect of the various embodiments, it is contemplated that different and / or special and / or unexpected results may be obtained for each Makushi group independent of all other Makushi members But may be obtained from each member of the group. Each member of the Makushi group may be individually and / or in combination, and provides sufficient support for specific embodiments within the scope of the appended claims.

It is also to be understood that any ranges and subranges dependent on describing various embodiments of the invention are to be regarded as independently and collectively falling within the scope of the appended claims, and that full and / It is understood that all ranges of inclusions are described and contemplated, even if these values are not expressly stated herein. It will be understood by those of ordinary skill in the art that the enumerated ranges and sub-ranges fully describe and enable various embodiments of the invention, and such ranges and sub- As will be appreciated by those skilled in the art. As only one example, a "range of 0.1 to 0.9" may be further described as a lower 1/3, ie 0.1 to 0.3, a median 1/3, ie 0.4 to 0.6, and a top one third, ie 0.7 to 0.9 Which are included individually and collectively within the scope of the appended claims, which may be individually and / or collectively dependent and provide sufficient support for specific embodiments within the scope of the appended claims .

In addition, it should be understood that such terms encompass subranges and / or upper or lower limits in relation to terms that define or modify ranges, such as "at least" . As another example, a range of "at least 10" inherently includes at least a subrange of from 10 to 35, at least a subrange of from 10 to 25, a subrange of from 25 to 35, etc., and each subrange may be individually and / May be collectively relied upon and provide sufficient support for specific embodiments within the scope of the appended claims. Finally, individual values within the disclosed ranges may be relied upon and provide sufficient support for specific embodiments within the scope of the appended claims. For example, "range of 1 to 9" includes various individual integers, such as 3, as well as individual values including a decimal point (or fraction), such as 4.1, which may be dependent, Lt; RTI ID = 0.0 &gt; embodiment. &Lt; / RTI &gt;

It is to be understood that the invention has been described in an illustrative manner, and that the terms used are intended to be essentially descriptive terms rather than restrictive terms. Many modifications and variations of the present invention are possible in light of the above teachings, and the invention may be practiced otherwise than as specifically described.

Objects of all combinations of independent and dependent terms (both single and multiple) are expressly contemplated herein. Examples include, but are not limited to:

Claim 3 can cite any one of claims 1 and 2;

Claim 4 can refer to any one of claims 1 to 3;

Claim 5 can refer to any one of claims 1 to 4;

Claim 6 can refer to any one of claims 1 to 5;

Claim 7 can refer to any one of claims 1 to 6;

Claim 9 can refer to any one of claims 1 to 8;

Claim 10 can refer to any one of claims 1 to 9;

Claim 11 can refer to any one of claims 1 to 10;

Claim 12 can refer to any one of claims 1 to 11.

Claims (15)

Base oil;
A bicyclic compound having the formula (I)
(I)

(Wherein each R ¹ is independently an alkyl giim having 1 to 7 carbon atoms); And
A hindered amine compound comprising an amount of from 0.5 to 5% by weight, based on the total weight of the lubricant composition
&Lt; / RTI > The method of claim 1, wherein the alkyl group of the lubricant composition, each R ¹ is independently having 1 to 5 carbon atoms. 2. The lubricant composition of claim 1 wherein each R &lt; ^{1 &gt;} is a methyl group. The lubricant composition of claim 1, wherein the proline-new compound is included in an amount ranging from 0.1 to 5% by weight based on the total weight of the lubricant composition. The lubricant composition of claim 1, wherein at least 50% of the proxine compound, based on the total weight of the proxine compound used to form the lubricant composition prior to any reaction in the lubricant composition, &Lt; / RTI &gt; The fluoropolymer of claim 1, wherein the fluoropolymer chamber immersed in the lubricant composition has a fluoropolymer compatibility such that it exhibits a tensile strength change of less than 45% when tested according to CEC L-39-T96; Or the fluoropolymer yarn soaked in the lubricant composition exhibits a fracture elongation change of less than 60% when tested according to CEC L-39-T96. The lubricant composition of claim 1, wherein, in testing according to ASTM D4739, the hindered amine compound has a total base weight of at least 70 mg KOH / g. 8. The lubricant composition according to any one of claims 1 to 7, wherein the hindered amine compound comprises at least one piperidine ring and at least one ester group. The lubricant composition of claim 1, wherein the hindered amine is (2,2,6,6-tetramethyl-4-piperidyl) dodecanoate. The composition of claim 1, wherein the base oil has a viscosity in the range of 1 to 20 cSt when tested at 100 占 폚 in accordance with ASTM D445 and comprises API Group I Oil, API Group II Oil, API Group III Oil, API Group IV Oil , API Group V oil, and combinations thereof. The lubricant composition of claim 1, further comprising a dispersant. The lubricant composition of claim 1, further comprising a dihydrocarbyl dithiophosphate salt. Base oil;
A bicyclic compound having the formula (I)
(I)

(Wherein each R ¹ is independently an alkyl giim having 1 to 7 carbon atoms); And
A hindered amine compound having the formula (II) or (III)
&Lt;

(III)

Wherein each R ² is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at least two groups designated as R ² are alkyl groups;
Each R &lt; ³ &gt; is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms;
Each R ⁴ is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at least two groups designated as R ⁴ are alkyl groups;
Each R &lt; ⁵ &gt; is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms,
The hydrocarbyl groups designated as R ² , R ³ , R ⁴ and R ⁵ are each independently an alcohol group, an alkyl group, an amide group, an ether group or an ester group.
&Lt; / RTI &gt; 14. The lubricant composition of claim 13, wherein the hindered amine compound has the formula (IV)
(IV)

Wherein each R ² and R ³ is as described above, wherein at least three of R ² are independently alkyl groups. A bicyclic compound having the formula (I)
(I)

(Wherein each R ¹ is independently an alkyl giim having 1 to 7 carbon atoms); And
A hindered amine compound having the formula (II) or (III)
&Lt;

(III)

Wherein each R ² is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at least two groups designated as R ² are alkyl groups;
Each R &lt; ³ &gt; is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms;
Each R ⁴ is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms, wherein at least two groups designated as R ⁴ are alkyl groups;
Each R &lt; ⁵ &gt; is independently a hydrogen atom, or a hydrocarbyl group having from 1 to 17 carbon atoms,
The hydrocarbyl groups designated as R ² , R ³ , R ⁴ and R ⁵ are each independently an alcohol group, an alkyl group, an amide group, an ether group or an ester group.
&Lt; / RTI &gt; additive package for a lubricant composition.