JP2016172877A - Lubricating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricating composition.SOLUTION: The present invention relates to a lubricating composition containing a dispersant, a corrosion inhibitor and an antioxidant. The invention further provides a method for lubricating a mechanical device with the lubricating composition. In one embodiment, the present invention provides an ashless lubricating composition comprising (a) a dispersant, (b) an antioxidant, (c) a corrosion inhibitor, and (d) an oil of lubricating viscosity. In one embodiment, the present invention provides a method for lubricating a mechanical device (typically requiring a working fluid, a hydraulic fluid, a circulating oil or a turbine oil), the method comprising a step of supplying the mechanical device with an ashless lubricating composition comprising (a) a dispersant, (b) an antioxidant, (c) a corrosion inhibitor, and (d) an oil of lubricating viscosity.SELECTED DRAWING: None

Description

(Field of Invention)
The present invention relates to a lubricating composition containing a dispersant, a corrosion inhibitor and an antioxidant. The present invention further provides a method for lubricating a mechanical device that typically requires working fluid, hydraulic fluid, circulating oil or turbine oil using the lubricating composition.

(Background of the Invention)
Ash-containing and ashless lubricating compositions are utilized in a variety of mechanical devices such as stationary or mobile machines that require working fluids, hydraulic fluids, circulating oils or turbine oils. These lubricating compositions often operate in a high temperature and / or high pressure manner in this mechanical device. This high temperature and / or high pressure regime is believed to degrade additives in the lubricating composition that have poor thermal and / or oxidative stability. Typically, additives that tend to decompose are often ash-containing additives that contain metals. In addition, as the ash-containing additive decomposes, divalent metals (eg, zinc, calcium or magnesium) are released into the lubricating composition. These divalent metals can then react with other performance additives present in the lubricating composition (eg, alkenyl succinic anhydride and alkenyl succinimide) to produce sludge and other particulate matter. These can cause clogging of the filter.

  In an attempt to overcome the difficulties associated with lubricating mechanical devices with ash-containing lubricating compositions, ashless formulations are contemplated. However, formulating ashless lubricating compositions suitable for mechanical devices can be difficult and many compositions have limited oxidative stability, limited thermal stability, filter clogging, and acceptance. It is believed to have at least one of producing an impossible level of sludge.

  Patent Document 1 discloses a synthetic antioxidant comprising an amine salt of alkyl phosphate and ethylenediamine, an ammonium salt or metal salt of alkylaryl sulfonate. This antioxidant composition is useful for anti-wear hydraulic fluids that do not contain zinc.

  Patent Document 2 describes (I) 100 pbw base oil, (II) antiwear agent, (i) 0.05 pbw to 10 pbw phosphorothionate and 0.01 pbw to 1.0 pbw phosphorus compound amine. A salt and / or (ii) an antiwear agent comprising 0.05 pbw to 10 pbw of dithiophosphate, and (III) a rust inhibitor comprising a polyalkylene polyamine and a carboxylic acid having 4 to 30 carbon atoms Disclosed is a lubricating composition containing a rust inhibitor, including 0.01 pbw to 1.0 pbw amide, obtained by reacting with an acid. This lubricating composition is suitable for hydraulic systems.

  Patent Document 3 discloses a base oil (selected from mineral oil, vegetable oil and synthetic oil, β-dithiophosphorylated propionic acid), and at least one oil additive (antioxidant, metal passivator, rust inhibitor) A hydraulic fluid containing a dispersant, a detergent, a viscosity index modifier, a pour point depressant, an antifoam agent, a solid lubricant and a further antiwear agent.

Patent Document 4 describes: (a) at least one compound selected from the group consisting of a phosphate ester, a thiophosphate ester, and an amine salt thereof; (b) an ester of an acid of phosphorus and / or an amine salt thereof Disclosed is an industrial oil, such as hydraulic oil, containing at least one; and (c) at least one compound selected from the group consisting of alkenyl succinimide, alkenyl succinate, benzylamine, and derivatives thereof .

  US Pat. No. 6,089,697 is (1) an anti-wear package comprising: (a) a hydrocarbyl phosphate and its amine salt; and (b) a hydrocarbyl substituted dithiophosphoric acid and an α, β-unsaturated carbonyl containing compound. An anti-wear package comprising an alkylene coupling adduct; (2) an antioxidant package comprising (a) a hydrocarbyl diphenylamine; and (b) a sterically hindered phenol; (3) An industrial fluid containing a metal deactivator; and (4) an oil of lubricating viscosity is disclosed.

European Patent Application Publication No. 0 821 053 International Publication No. 00/11122 Pamphlet US Pat. No. 5,922,657 US Patent Application Publication No. 2002/0010103 International Publication No. 04/113479 Pamphlet

  Thus, suitable lubrication for mechanical devices that can reduce or minimize at least one of filter clogging, limited oxidative stability, limited thermal stability and unacceptable levels of sludge production. It is desirable to discover a composition. The present invention provides a lubricating composition and mechanical device that can reduce or minimize at least one of filter clogging, limited oxidative stability, limited thermal stability, and generation of unacceptable levels of sludge. Provide a way to lubricate.

(Summary of the Invention)
In one embodiment, the present invention provides an ashless lubricating composition, wherein the ashless lubricating composition comprises:
(A) a dispersant;
(B) an antioxidant;
(C) a corrosion inhibitor; and (d) an oil of lubricating viscosity.

In one embodiment, the present invention provides a method for lubricating a mechanical device (typically requiring a working fluid, hydraulic fluid, circulating oil or turbine oil), the method comprising: On the device
(A) a dispersant;
(B) an antioxidant;
(C) a corrosion inhibitor; and (d) supplying an ashless lubricating composition containing an oil of lubricating viscosity.

In one embodiment, the present invention provides an ashless lubricating composition, wherein the ashless lubricating composition comprises:
(A) about 0.01% to about 2% by weight of a dispersant;
(B) about 0.01 wt% to about 2 wt% antioxidant;
(C) about 0.0001% to about 0.1% by weight of a corrosion inhibitor; and (d) containing an oil of lubricating viscosity.

In one embodiment, the present invention provides a method for lubricating a mechanical device (typically requiring a working fluid, hydraulic fluid, circulating oil or turbine oil), the method comprising: On the device
(A) about 0.01% to about 2% by weight of a dispersant;
(B) about 0.01 wt% to about 2 wt% antioxidant;
(C) providing about 0.0001% to about 0.1% by weight of a corrosion inhibitor; and (d) providing an ashless lubricating composition containing an oil of lubricating viscosity.

  In one embodiment, the ashless lubricating composition disclosed above further comprises an antiwear agent. In one embodiment, the ashless lubricating composition disclosed above further comprises from about 0.05% to about 1.5% by weight of an antiwear agent.

In one embodiment, the present invention provides an ashless lubricating composition as disclosed above in the form of a concentrate.
In a preferred embodiment of the present invention, the following is provided.
(Item 1)
A method for lubricating a mechanical device comprising supplying an ashless lubricating composition to the mechanical device, the ashless lubricating composition comprising:
(A) a dispersant;
(B) an antioxidant;
(C) a corrosion inhibitor;
(D) an oil of lubricating viscosity; and (e) an antiwear agent, if necessary,
Containing a method.
(Item 2)
The method of item 1, wherein the mechanical device requires a fluid selected from the group consisting of working fluid, hydraulic fluid, circulating oil, turbine oil, and mixtures thereof.
(Item 3)
Item 2. The method of item 1, wherein the mechanical device is a hydraulic system or a turbine system.
(Item 4)
Item 2. The method according to Item 1, wherein the dispersant is a borated dispersant.
(Item 5)
The method of item 1, wherein the antioxidant comprises (i) a hindered phenol or (ii) an alkylated diphenylamine.
(Item 6)
The corrosion inhibitor is (i) 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole, (ii) at least one of 4-position, 5-position, 6-position or 7-position of the ring. The method according to item 1, comprising a benzotriazole containing a hydrocarbyl substituent in (iii) or (iii) a benzotriazole containing a hydrocarbyl substituent in at least one of the 1-position or 2-position of the ring.
(Item 7)
Item 2. The method according to Item 1, wherein the lubricating composition further comprises (i) a nonionic phosphorus compound; (ii) an amine salt of a phosphorus compound; or (iii) an ammonium salt of a phosphorus compound.
(Item 8)
The lubricating composition is
(A) about 0.01% to about 2% by weight of a dispersant;
(B) about 0.01 wt% to about 2 wt% antioxidant;
(C) about 0.0001% to about 0.1% by weight of a corrosion inhibitor;
(D) an oil of lubricating viscosity; and (e) about 0% to about 5% by weight of an antiwear agent;
The method according to Item 1, comprising:
(Item 9)
The method of claim 1, wherein the lubricating composition further comprises about 0.05 wt% to about 1.5 wt% antiwear agent.
(Item 10)
An ashless lubricating composition comprising:
(A) a dispersant;
(B) an antioxidant;
(C) a corrosion inhibitor;
(D) an oil of lubricating viscosity; and (e) an antiwear agent, if necessary,
An ashless lubricating composition comprising:
(Item 11)
(A) about 0.01% to about 2% by weight of a dispersant;
(B) about 0.01 wt% to about 2 wt% antioxidant;
(C) about 0.0001% to about 0.1% by weight of a corrosion inhibitor;
(D) an oil of lubricating viscosity; and (e) about 0% to about 5% by weight of an antiwear agent;
Item 11. The ashless lubricating composition according to Item 10, comprising
(Item 12)
12. The ashless lubricating composition of item 11, wherein the antiwear agent is present from about 0.05% to about 1.5% by weight of the ashless lubricating composition.

(Detailed description of the invention)
The present invention provides an ashless lubricating composition and a method for lubricating a mechanical device as disclosed above.

  As used herein, the term “ashless” means that the lubricating compositions and / or additives discussed below are substantially free of metals. Substantially free, the composition contains less than about 150 ppm, or less than about 100 ppm of ash-forming material (eg, a metal, typically a divalent metal such as zinc, calcium or magnesium), or It means containing about 10 ppm or less, or less than about 1 ppm. Typically, ash-forming substances are present only in trace amounts and are usually associated with contaminants.

(Dispersant)
Suitable dispersants include succinimide dispersants (eg, N-substituted long chain alkenyl succinimides), Mannich dispersants, ester-containing dispersants, condensation products of fatty hydrocarbyl monocarboxylic acylating agents with amines or ammonia, alkyls Examples include aminophenol dispersants, hydrocarbyl-amine dispersants, polyether dispersants, or polyetheramine dispersants. In different embodiments, the dispersant comprises a succinimide dispersant, a succinate dispersant, or a Mannich dispersant.

In different embodiments, the succinimide dispersant contains an average of at least about 8, or about 30, or about 35 to about 350 or about 200, or up to about 100 carbon atoms. In one embodiment, the long chain alkenyl group is at least 500.

（数平均分子量）により特徴付けられるポリアルケンから誘導される。一般に、このポリアルケンは、約５００または約７００（または約８００、もしくはさらに約９００）〜約５０００（または約２５００まで、もしくは約２０００まで、もしくは約１５００まで、もしくは約１２００まで）の

Derived from polyalkene characterized by (number average molecular weight). Generally, the polyalkene is about 500 or about 700 (or about 800, or even about 900) to about 5000 (or up to about 2500, or up to about 2000, or up to about 1500, or up to about 1200).

により特徴付けられる。１つの実施形態において、この長鎖アルケニル基としては、ポリオレフィンから誘導されるものが挙げられる。これらのポリオレフィンは、約２個〜約１０個の炭素原子を有するモノオレフィン（例えば、エチレン、プロピレン、１−ブテン、イソブチレン、および１−デセン）が挙げられるモノマーから誘導され得る。特に有用なモノオレフィンの供給源は、約３５重量％〜約７５重量％のブテン含有量および約３０重量％〜約６０重量％のイソブテン含有量を有する、Ｃ_４の精油所ストリームである。有用なポリオレフィンとしては、約４００〜約５０００、または約４００〜約２５００、または約４００、または約５００〜約１５００の数平均分子量を有するポリイソブチレンが挙げられる。ポリイソブチレンのビニリデン二重結合含有量としては、異なる実施形態において、約５％〜約６９％、または約５０％〜約６９％、または約５０％〜約９５％の範囲が挙げられる。

Is characterized by In one embodiment, the long chain alkenyl group includes those derived from polyolefins. These polyolefins can be derived from monomers including monoolefins having from about 2 to about 10 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, and 1-decene. Particularly useful sources of mono-olefins, having a butene content of about 35 wt% to about 75 wt% and isobutene content of about 30 wt% to about 60 wt%, a refinery stream of C _4. Useful polyolefins include polyisobutylene having a number average molecular weight of about 400 to about 5000, or about 400 to about 2500, or about 400, or about 500 to about 1500. The vinylidene double bond content of the polyisobutylene may range from about 5% to about 69%, or from about 50% to about 69%, or from about 50% to about 95% in different embodiments.

  In one embodiment, the succinimide dispersant comprises polyisobutylene succinimide, wherein the polyisobutylene has a number average molecular weight of about 400 to about 5000.

  Succinimide dispersants and methods for their preparation are fully described in US Pat. Nos. 4,234,435 and 3,172,892.

  Suitable amines include monoamines or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, or distilled bottoms (commercially available from Dow as HPAX®). Hydrocarbyl-substituted amines can be prepared by mixing a mixture of a chlorinated olefin or polyolefin (eg, chlorinated polyisobutylene) and an amine (eg, ethylenediamine) with a base (as described in US Pat. No. 5,407,453). For example, it can be formed by heating in the presence of sodium carbonate).

  These dispersants can also be post-treated by reaction with any of a variety of agents by conventional methods. Among these, boron-containing compounds, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitrile, epoxide, phosphorus compound And / or a metal compound. In one embodiment, the dispersant is a borated dispersant. Typically, the boronated dispersant is derived from a succinimide dispersant including polyisobutylene succinimide, wherein the polyisobutylene has a number average molecular weight of 400-5000.

Boronated succinimide dispersants can be prepared using a boronating agent. Boronating agents include various forms of boric acid (metaboric acid (HBO ₂ ), orthoboric acid (H ₃ BO ₃ ), and tetraboric acid (H ₂ B ₄ O ₇ )), boron oxide, trioxide Boron, as well as those of alkyl borate (eg, (RO) _x B (OH) _y , where x is from about 1 to about 3 and y is from about 0 to about 2; the sum of x and y is 3, and R is an alkyl group containing from about 1 to about 6 carbon atoms). In one embodiment, the boron compound is an alkali metal borate or a mixture of alkali metal borate and alkaline earth metal borate. These metal borates are generally hydrated particulate metal borates that are known in the art. In one embodiment, these metal borates are a mixture of alkali metal borates and alkaline earth metal borates. Metal borates are commercially available.

  In different embodiments, the dispersant is from about 0.001% to about 5%, or from about 0.005% to about 2.5%, from about 0.05% to about 1% of the lubricating composition. 0.5 wt%, or from about 0.08 wt% to about 0.8 wt%.

(Antioxidant)
Antioxidants of the present invention include sulfurized olefins, sulfides (eg tert-nonyl mercaptan reacted with propylene oxide (molar ratio 1: 1)), hindered phenols, or aminic compounds (eg phenyl alpha naphthylamine or Alkylated diphenylamine).

  Examples of suitable hindered phenols include 2,6-di-tert-butyl-4-methylphenol, 3- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionic acid butyl ester, 3- (3,5-Di-tert-butyl-4-hydroxy-phenyl) -propionic acid isooctyl ester or 3- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionic acid 2- Ethyl hexyl ester), 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6- Di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, 4-pentyl-2-6-di tert-butylphenol, 4-hexyl-2,6-di-tert-butylphenol, 4-heptyl-2,6-di-tert-butylphenol, 4- (2-ethylhexyl) -2,6-di-tert-butylphenol, 4-octyl-2,6-di-tert-butylphenol, 4-nonyl-2,6-di-tert-butylphenol, 4-decyl-2,6-di-tert-butylphenol, 4-undecyl-2,6- Di-tert-butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, 4-tridecyl-2,6-di-tert-butylphenol, 4-tetradecyl-2,6-di-tert-butylphenol, or these Of the mixture.

  Examples of suitable methylene bridged sterically hindered phenols include 4,4'-methylenebis (6-tert-butyl-o-cresol), 4,4'-methylenebis (2-tert-amyl-o-cresol) 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-methylene-bis (2,6-di-tertbutylphenol), or mixtures thereof.

  Examples of suitable aminic compounds include nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine, butyloctyldiphenylamine, octylstyryldiphenylamine or diethyldinonyldiphenylamine.

  In one embodiment, the antioxidant comprises (i) a hindered phenol or (ii) an alkylated diphenylamine. In one embodiment, the antioxidant comprises a mixture of hindered phenol and alkylated diphenylamine.

  In different embodiments, the antioxidant is from about 0.01% to about 3%, or from about 0.01% to about 2%, or from about 0.05% to about 1% by weight of the lubricating composition. % Exists in the range mentioned.

(Corrosion inhibitor)
Corrosion inhibitors can also be described as metal deactivators or yellow metal passivators.

  Examples of corrosion inhibitors include benzotriazole, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzoimidazole, 2-alkyldithiobenzothiazole, 2- (N, N-dialkyldithiocarbamoyl) benzothiazole, 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole, 2,5-bis (N, N-dialkyldithiocarbamoyl) -1,3,4-thiadiazole, 2-alkyldithio-5-mercapto Thiadiazole or a mixture thereof may be mentioned. In one embodiment, the corrosion inhibitor comprises benzotriazole. In one embodiment, the corrosion inhibitor comprises 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole.

  Benzotriazoles include those containing a hydrocarbyl substituent at at least one of the 1-position, 2-position, 4-position, 5-position, 6-position, or 7-position of the ring. These hydrocarbyl groups contain 1 to about 30, or 1 to about 15, or 1 to about 16 carbon atoms in different embodiments. In one embodiment, the corrosion inhibitor comprises tolyltriazole. In one embodiment, the hydrocarbyl benzotriazole substituted at the 4-position, 5-position, 6-position or 7-position is further reacted with aldehydes and amines.

Examples of suitable hydrocarbyl benzotriazoles further reacted with aldehydes and amines include N, N-bis (2-ethylhexyl) -ar-methyl-1H-benzotriazole-1-methanamine, N, N-bis (2-ethylhexyl) ) -4-Methyl-1H-benzotriazole-1-methanamine, N, N-bis (2-ethylhexyl) -4-methyl-1H-benzotriazole-1-methanamine, 2H-benzotriazole-2-methanamine, N- (4-Methoxyphenyl) -1H-benzotriazole-1-methanamine, N, N-didodecyl-1H-benzotriazole-1-methanamine, N- (1H-benzotriazol-1-ylmethyl) -N- (2-ethylhexyl) ) -1H-benzotriazole-1-methane , N-methyl-N-phenyl-1H-benzotriazole-1-methanamine, 4,5,6,7-tetrahydro-N, N-ditridecyl-1H-benzotriazole-1-methanamine, N, N-dioctadecyl -1H-benzotriazole-1-methanamine, 5-methyl-N, N-dioctyl-1H-benzotriazole-1-methanamine, N, N-dibutyl-1H-benzotriazole-1-methanamine, N- (4-methyl Phenyl) -1H-benzotriazole-1-methanamine, N, N-bis (2-ethylhexyl) -1H-benzotriazole-1-methanamine, N, N-dioctyl-2H-benzotriazole-2-methanamine, N-dodecyl -1H-benzotriazole-1-methanamine, N-phenyl- H-benzotriazole-1-methanamine, N, N-didodecyl-4,5,6,7-tetrahydro-1H-benzotriazole-1-methanamine, N, N-bis (2-ethylhexyl) -5-methyl-1H -Benzotriazole-1-methanamine, N-octadecyl-1H-benzotriazole-1-methanamine, N, N-didodecyl-2H-benzotriazole-2-methanamine, N, N-dioctyl-1H-benzotriazole-1-methanamine N- (2-ethylhexyl) -1H-benzotriazole-1-methanamine, 4,5,6,7-tetrahydro-N, N-ditetradecyl-1H-benzotriazole-1-methanamine, or mixtures thereof. . In one embodiment, the corrosion inhibitor is N, N-bis (2-ethylhexyl) -4-methyl-1H-benzotriazole-1-methanamine or N, N-bis (2-ethylhexyl) -ar-methyl- Contains 1H-benzotriazole-1-methanamine.

  In one embodiment, the corrosion inhibitor is (i) 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole, (ii) the 4-position, 5-position, 6-position or 7-position of the ring. Benzotriazole containing a hydrocarbyl substituent in at least one of them, or (iii) a benzotriazole containing a hydrocarbyl substituent in at least one of the 1- or 2-positions of the ring (typically benzotriazole is an aldehyde and Further reaction with amines).

  In one embodiment, the corrosion inhibitor comprises 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole. In different embodiments, the alkyl group of 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole has 1 to about 30, or about 2 to about 25, or 4 to about 20 Or from about 6 to about 16 carbon atoms. Examples of suitable 2,5-bis (alkyl-dithio) -1,3,4-thiadiazoles include 2,5-bis (tert-octyldithio) -1,3,4-thiadiazole, 2,5-bis (Tert-nonyldithio) -1,3,4-thiadiazole, 2,5-bis (tert-decyldithio) -1,3,4-thiadiazole, 2,5-bis (tert-undecyldithio) -1,3,4 Thiadiazole, 2,5-bis (tert-dodecyldithio) -1,3,4-thiadiazole, or a mixture thereof.

  Corrosion inhibitors may be used alone or in combination with two, three or more corrosion inhibitors. In one embodiment, the corrosion inhibitor comprises (i) 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole and (ii) the 4-position, 5-position, 6-position or 7-position of the ring. A benzotriazole containing a hydrocarbyl substituent in at least one of them, and (iii) a benzotriazole containing a hydrocarbyl substituent in at least one of the 1-position or 2-position (typically benzotriazole is an aldehyde and an amine) Further react).

  In different embodiments, the corrosion inhibitor is from about 0.0001% to about 5% by weight of the lubricating composition, or from about 0.0001% to about 0.5%, or from about 0.0001% to about 0.1% by weight, or from about 0.0005% to about 0.06% by weight is present.

(Oil of lubricating viscosity)
The lubricating composition contains an oil having a lubricating viscosity. Such oils include natural oils, synthetic oils, oils derived from hydrocracking, oils derived from hydrogenation, oils derived from hydrorefining, unrefined oils, refined oils and recycled oils. Examples include refined oils, as well as mixtures thereof.

  Unrefined oils are oils that are generally obtained directly from natural or synthetic sources with no (or little) further processing.

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

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

  Natural oils useful in making the lubricants of the present invention include animal oils, vegetable oils (eg, castor oil, lard oil), mineral lubricants (eg, liquid petroleum, and paraffinic, naphthenic or mixed paraffins) Naphthenic solvent-treated or acid-treated mineral lubricants), as well as oils derived from charcoal or shale, or mixtures thereof.

  Synthetic lubricating oils are useful and hydrocarbon oils (eg, polymerized olefins and interpolymerized olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers)); poly (1-hexene), poly (1-octene), poly ( 1-decene) and mixtures thereof; alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) benzene); polyphenyls (eg, biphenyl, terphenyl, alkylated polyphenyl); Examples include alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologs thereof, or mixtures thereof.

  Other synthetic lubricating oils include polyol esters (eg, Priolube® 3970), diesters, liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, and diethyl ester of decanephosphonic acid), or Polymer tetrahydrofuran is mentioned. Synthetic oils include those produced by the Fischer-Tropsch reaction and can typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils include those prepared by Fischer-Tropsch gas-liquid synthesis procedures and other gas-liquid oils.

  Oils of lubricating viscosity may also be defined as detailed in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows: Group I (sulfur content> 0.03% by weight, and / or <90% by weight saturateds, viscosity index 80-120); Group II (sulfur) Content ≦ 0.03% by weight, and ≧ 90% by weight saturated material, viscosity index 80-120); Group III (sulfur content ≦ 0.03% by weight, and ≧ 90% by weight saturated material, viscosity index ≧ 120) Group IV (all poly alpha olefins (PAO)); and Group V (all others not included in either Group I, Group II, Group III, or Group IV). Oils of lubricating viscosity include API Group I oil, API Group II oil, API Group III oil, API Group IV oil, API Group V oil or mixtures thereof. Often the oil of lubricating viscosity is an API Group I oil, an API Group II oil, an API Group III oil, an API Group IV oil or mixtures thereof. Alternatively, the oil of lubricating viscosity is often an API Group II oil, an API Group III oil or an API Group IV oil, or mixtures thereof.

  The amount of oil of lubricating viscosity present is typically the remaining amount after subtracting the total amount of polymer, antiwear agent, corrosion inhibitor and other performance additives from 100% by weight.

The lubricating composition may be in the form of a concentrate and / or a fully formulated lubricant. If the dispersant, antioxidant, and corrosion inhibitor are in the form of a concentrate (which can be combined with additional oils to form, in whole or in part, a finished lubricant), an oil of lubricating viscosity And / or the ratio of components (a), (b) and (c) to diluent oil (ie, dispersants, antioxidants and corrosion inhibitors) is from about 1:99 to about 99: 1 by weight, or by weight In the range of about 80:20 to about 10:90.

(Other performance additives)
The composition of the present invention further contains at least one other performance additive as required. These other performance additives include antiwear agents, viscosity index modifiers (ie, viscosity modifiers), antifoam agents, deemulsifiers, pour point depressants, antifoam agents, carboxylic acids or anhydrides, and These mixtures are mentioned.

  The combined total amount of other performance additive compounds present is 0% to about 10%, or about 0% to about 5%, or about 0.00% by weight of the composition, based on the absence of oil. 005 wt% to about 4 wt%, or about 0.05 wt% to about 2.5 wt%, or about 0.1 wt% to about 1.5 wt%. Although one or more of these other performance additives may be present, typically these other performance additives are present in different amounts relative to each other.

(Abrasion-resistant agent)
In one embodiment, the antiwear agent comprises a phosphorus acid, salt or ester, or a mixture thereof. In one embodiment, the antiwear agent is in the form of a mixture.

  Anti-wear agents include those derived from phosphoric acid, phosphoric acid, thiophosphoric acid, thiophosphoric acid, or mixtures thereof.

  In one embodiment, the antiwear agent comprises (i) a nonionic phosphorus compound; (ii) an amine salt of the phosphorus compound; or (iii) an ammonium salt of the phosphorus compound.

  In one embodiment, the antiwear agent comprises an ammonium or amine salt of a phosphorus-containing acid or ester.

  As amine salts of phosphorus acids or esters, phosphate esters and amine salts thereof; dialkyldithiophosphate esters and amine salts thereof; phosphite amine salts; and phosphorus-containing carboxylic acid esters, ethers and amide amine salts; and These mixtures are mentioned.

  The amine salt of the phosphorus acid or ester may be used alone or in combination.

  In one embodiment, the phosphorus acid or ester amine salt includes a partial amine salt, or a partial amine-metal salt compound, or a mixture thereof. In one embodiment, the phosphorus acid or ester amine salt further comprises a sulfur atom in the molecule.

  The amine salt can be prepared from amines, including primary amines, secondary amines, tertiary amines, and mixtures thereof. These amines include amines having at least one hydrocarbyl group, or in certain embodiments, two or three hydrocarbyl groups. In different embodiments, these hydrocarbyl groups contain from about 2 to about 30, or from about 8 to about 26, or from about 10 to about 20, or from about 13 to about 19 carbon atoms. .

  Primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, and dodecylamine, and n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexa Examples include fatty amines such as decylamine, n-octadecylamine and oleylamine. Other useful fatty amines include commercially available fatty amines (eg, “Armeen®” amines (products available from Akzo Chemicals, Chicago, Illinois, such as Armen C, Armeen O, Armen OL, Armeen T, Armeen HT, Armeen S, and Armeen SD, where the designation of the letter includes a fatty group (eg, coco group, oleyl group, tallow, or stearyl group).

  Examples of suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine and ethylamylamine. These secondary amines also include cyclic amines such as piperidine, piperazine and morpholine.

  The amine can also be a tertiary aliphatic primary amine. The aliphatic groups of these tertiary aliphatic primary amines, in different embodiments, have from about 4 to about 30, or from about 6 to about 26, or from about 8 to about 24 carbon atoms. including. Tertiary alkylamines include monoamines such as tert-butylamine, tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine, tert-dodecylamine, tert-tetradecylamine. , Tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine).

In one embodiment, the amine salt of a phosphorus acid or ester includes an amine having a primary alkyl group of about C ₁₁ to about C ₁₄ or a mixture thereof. In one embodiment, the amine salt of the phosphorus compound includes an amine having from about C ₁₄ to about C ₁₈ tertiary alkyl primary amines or mixtures thereof. In one embodiment, the amine salt of the phosphorus compound includes an amine having about C ₁₈ to about C ₂₂ tertiary alkyl primary amines or mixtures thereof.

Mixtures of amines can also be used in the present invention. In one embodiment, useful amine mixtures are “Primene® 81R” and “Primene® JMT”. Primene® 81R and Primene® JMT (both manufactured and sold by Rohm & Haas) are each a mixture of C ₁₁ -C ₁₄ tertiary alkyl primary amines, and it is a mixture of primary amine tertiary alkyl C ₁₈ -C _22.

In one embodiment the amine salt of a phosphorus acid or _ester, an alkyl phosphoric acid C 14 _{-C 18,} are manufactured and sold by Primene (R) 81R (Rohm & Haas, which is C _{11 to} C ₁₄ tertiary alkyl primary amines).

Examples of amine salts of phosphorus acids or esters include isopropyl, methyl-amyl (1,3-dimethylbutyl or mixtures thereof), 2-ethylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, butadecyl, hexadecyl, octadecyl Or phosphoric acid (or dithiophosphoric acid) substituted with eicosyl, ethylenediamine, morpholine,
Reaction products with 2-ethylhexylamine or Primene® 81R, and mixtures thereof. In one embodiment, the antiwear agent comprises an amine salt of a phosphorus acid or ester, or a mixture thereof. In one embodiment, the phosphorus acid or ester is a C ₁₄ -C ₁₈ alkyl phosphorus acid or ester and is an amine salt with Primene® 81R or 2-ethylhexylamine.

  In one embodiment, dithiophosphoric acid includes dithiophosphoric acid reacted with epoxide or glycol. This reaction product is further reacted with a phosphorus acid, anhydride, or lower ester. Epoxides include aliphatic epoxides or styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, styrene oxide, and the like. In one embodiment, the epoxide is propylene oxide. Glycols include aliphatic glycols, the aliphatic groups of which in different embodiments are about 2 to about 12, or about 2 to about 6, or about 2 to about 3 Has carbon atoms. Dithiophosphoric acid, glycols, epoxides, inorganic phosphorus reagents and methods of reacting them are described in US Pat. Nos. 3,197,405 and 3,544,465. The resulting acid can then form a salt with the amine. An example of a suitable dithiophosphoric acid is phosphorus pentoxide (about 64 grams) at about 58 ° C. for about 45 minutes over about 514 grams of hydroxypropyl O, O′-di (1,3-dimethylbutyl) phospho Prepared by adding to dithiothioate (prepared by reacting di (1,3-dimethylbutyl) -phosphorodithioic acid with about 1.3 moles of propylene oxide at about 25 ° C.). The mixture is heated at about 75 ° C. for about 2.5 hours, mixed with diatomaceous earth, and filtered at about 70 ° C. The filtrate contains about 11.8% by weight phosphorus, about 15.2% by weight sulfur and has an acid number of about 87 (bromophenol blue).

  In one embodiment, the antiwear agent comprises an ester of an acid of dithioline including an amide. A more detailed description of dithiophosphorus acid esters including amides can be found in US Pat. No. 4,938,884. A description of its molecular structure can be found in column 2, lines 4 to 28. Suitable examples to be prepared are disclosed in Examples 1-7 (US Pat. No. 4,938,884, column 8, line 45 to column 10, line 13). Typically, esters of dithiophosphoric acid containing amides are prepared by adding dithiophosphoric acid to acrylamide (eg, acrylamide, methacrylamide, methylene bisacrylamide, or methylene bismethacrylamide). In one embodiment, the ester of an acid of dithioline containing an amide includes methylene bisacrylamide, or methylene bismethacrylamide product, which is added to diacrylamide to form an adduct. Subsequently prepared by reacting the adduct with formaldehyde to produce a methylene-linked product.

  In one embodiment, the antiwear agent is an ester of a dithiophosphorus acid containing carboxylic acid (eg, 3- (bis-pentoxy-thiophosphorylsulfanyl) -propionic acid methyl ester, 3- (dibutoxy-thiophosphorylsulfanyl)). -Propionic acid methyl ester, or mixtures thereof).

  In one embodiment, the antiwear agent comprises a nonionic phosphorus compound. Typically, the phosphorus atom of the nonionic phosphorus compound may have an oxidation state of +3 or +5. Different embodiments include phosphites, phosphates, or mixtures thereof.

  In one embodiment, the antiwear agent comprises a nonionic phosphorus compound that is a hydrocarbyl phosphite. The hydrocarbyl substituted phosphites of the present invention include those of the formula:

により表されるものが挙げられ、この式において、各Ｒ’’’は、独立して、水素またはヒドロカルビル基であり、ただし、これらのＲ’’’基のうちの少なくとも１つは、ヒドロカルビルである。

In which each R ′ ″ is independently hydrogen or a hydrocarbyl group, provided that at least one of these R ′ ″ groups is hydrocarbyl. is there.

Each hydrocarbyl group of R ′ ″ contains at least about 2, or at least about 4 carbon atoms in different embodiments. Typically, the total number of carbon atoms present in both R ′ ″ groups is less than about 45, or less than about 35, or less than about 25. Examples of suitable ranges of the number of carbon atoms present in the R ^{′ ″} group include from about 2 to about 40, from about 3 to about 24, or from about 4 to about 20. Examples of suitable hydrocarbyl groups include propyl, butyl, t-butyl, pentyl, hexyl, dodecyl, butadecyl, hexadecyl, or octadecyl. In general, hydrocarbyl phosphites are oil soluble or at least oil dispersible. In one embodiment, the hydrocarbyl phosphite is a C _16-18 alkyl ester or di-C _16-18 alkyl esters of dibutyl hydrogen phosphite or hydrogen phosphite. A more detailed description of the nonionic phosphorus compounds is contained in US Pat. No. 6,103,673, column 9, line 48 to column 11, line 8.

  In one embodiment, the antiwear agent comprises a phosphate ester. Examples of suitable phosphate esters include triaryl phosphate esters (eg, tricresyl phosphate, triphenyl phosphate, tri-dimethylphenyl phosphate, tributylphenyl phosphate, or mixtures thereof).

  In one embodiment, the antiwear agent comprises a thiophosphate ester. Examples of suitable thiophosphates include triaryl thiophosphates such as tricresyl thiophosphate, triphenyl thiophosphate, tri-dimethylphenyl thiophosphate, tributylphenyl thiophosphate, or mixtures thereof.

  In different embodiments, the antiwear agent is from about 0% to about 5%, or from about 0.001% to about 2%, or from about 0.05% to about 1.5% by weight of the lubricating composition. % By weight, or from about 0.1% to about 1% by weight.

(Viscosity modifier)
Viscosity modifiers include styrene-butadiene hydrogenated copolymer, ethylene-propylene copolymer, polyisobutene, hydrogenated styrene-isoprene copolymer, hydrogenated isoprene polymer, polymethacrylate, polyacrylate, polyalkylstyrene, hydrogenated alkenyl aryl conjugated diene copolymer. , Polyolefins, and esters of maleic anhydride-styrene copolymers.

Other performance additives (for example, antifoaming agents including copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide) And demulsifiers including (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates or polyacrylamides; and Exxon Necton-37 ^™
(FN 1380) and Exxon Mineral Seal Oil (FN 3200); and functionalized polyolefins (eg, ethylene-propylene copolymers functionalized with reaction products of maleic anhydride and amines, amines) Also used in the compositions of the present invention are dispersant viscosity modifiers (often referred to as DVMs), such as polymethacrylates functionalized with styrene, or styrene-maleic anhydride copolymers reacted with amines). Can be done.

(Industrial applicability)
The method of the present invention is useful for lubricating mechanical devices that typically require working fluid, hydraulic fluid, circulating oil or turbine oil.

  In one embodiment, the mechanical device requires a fluid selected from the group consisting of working fluid, hydraulic fluid, circulating oil, turbine oil, and mixtures thereof.

  In different embodiments, the mechanical device is a hydraulic system, a turbine system, or a circulating oil system.

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

(Lubricating compositions EX1 to EX5)
A series of lubricating compositions containing the following additives are prepared: a borated dispersant, an amine salt of a phosphorus compound, a mixture of a phenolic antioxidant and an amine antioxidant, two or more corrosion inhibitors, And antifoam. The combined total-rate of all these additives (based on the absence of oil, ie, excluding the standard amount of diluent oil normally associated with each additive) is shown in Example 1 (EX1 ) About 1.47% by weight, Example 2 (EX2) about 1.48% by weight, Example 3 (EX3) about 1.76% by weight, Example 4 (EX4) about 1 40% by weight, and about 1.27% by weight for Example 5 (EX5).

  Examples EX1-EX5 are evaluated in the following tests: (i) oxidation stability of the turbine oil (using ASTM method D2272), (ii) kinematic viscosity at about 40 ° C. (ASTM method D445), And (iii) Thermal stability of hydraulic fluid after heat stressing of fluid (using “Cincinnati Machine Thermal Stability Test” Procedure A). The Cincinnati Machine Thermal Stability Test assesses the corrosion and thermal stability of steel and copper.

  The data obtained for test (i) and test (ii) are shown in Table 1. The data obtained for test (iii) is shown in Table 2.

得られたデータは、本発明の潤滑組成物が、液圧流体、タービン油または循環油に、認容可能なスラッジ性能、認容可能な熱安定性および認容可能な酸化安定性のうちの少なくとも１つを提供し得ることを示す。

The data obtained indicates that the lubricating composition of the present invention is suitable for hydraulic fluid, turbine oil or circulating oil at least one of acceptable sludge performance, acceptable thermal stability and acceptable oxidative stability. It can be provided.

  Although the present invention has been described with respect to various embodiments thereof, it should be understood that various modifications of these embodiments will be apparent to those skilled in the art upon reading this specification. Accordingly, it is to be understood that the invention disclosed herein is intended to cover such modifications as are within the scope of the appended claims.

Claims (10)

A method for lubricating a hydraulic mechanical device, the method comprising supplying the hydraulic mechanical device with a lubricating composition comprising less than 150 ppm of an ash forming material, wherein the lubricating composition Is
(A) a dispersant;
(B) an antioxidant;
(C) a corrosion inhibitor; and (d) an oil of lubricating viscosity selected from the group consisting of Group I oil, Group II oil, Group III oil, Group IV oil, or mixtures thereof ; and
(E) The following:
(I) an ammonium or amine salt of a phosphorus-containing acid or ester, and
(Ii) esters of dithiophosphoric acid containing amides
Containing 0.05% to 5% by weight of an antiwear mixture comprising: The method of claim 1 , wherein the hydraulic mechanical device requires a fluid selected from the group consisting of working fluid, hydraulic fluid , circulating oil, turbine oil, and mixtures thereof . The method of claim 1 , wherein the dispersant is a borated dispersant. The method of claim 1 , wherein the antioxidant comprises (i) a hindered phenol or (ii) an alkylated diphenylamine. The corrosion inhibitor is (i) 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole, (ii) at least one of 4-position, 5-position, 6-position or 7-position of the ring. The method of claim 1 , comprising a benzotriazole containing a hydrocarbyl substituent at (iii) or a benzotriazole containing a hydrocarbyl substituent at at least one of the 1- or 2-positions of the ring. The lubricating composition is
(A) 0.01% to 2% by weight of a dispersant;
(B) 0.01 wt% to 2 wt% antioxidant;
(C) 0.0001% to 0.1% by weight of a corrosion inhibitor; and (d) an oil of lubricating viscosity;
The method according to claim 1, comprising: The method of claim 6 , wherein the lubricating composition further comprises 0.001 wt% to 2 wt% antiwear agent.   The method of claim 1, wherein the lubricating composition further comprises 0.05 wt% to 1.5 wt% antiwear agent. A lubricating composition comprising less than 150 ppm ash-forming material for a hydraulic mechanical device comprising:
(A) a dispersant;
(B) an antioxidant;
(C) a corrosion inhibitor; and (d) an oil of lubricating viscosity selected from the group consisting of Group I oil, Group II oil, Group III oil, Group IV oil, or mixtures thereof ; and
(E) The following:
(I) an ammonium or amine salt of a phosphorus-containing acid or ester, and
(Ii) esters of dithiophosphoric acid containing amides
A lubricating composition comprising 0.05% to 5% by weight of an antiwear mixture comprising (A) 0.01% to 2% by weight of a dispersant;
(B) 0.01 wt% to 2 wt% antioxidant;
(C) 0.0001% to 0.1% by weight of a corrosion inhibitor; and (d) an oil of lubricating viscosity;
The lubricating composition according to claim 9 , comprising: