JP5897030B2 - Lubricant composition containing a viscosity index improver - Google Patents

Description

  The present invention relates to a lubricant composition comprising a viscosity index (VI) improver. More particularly, the present invention relates to a lubricant composition comprising a VI improver in the form of a polymer comprising structural units derived from ethylene, propylene and butylene.

  Petroleum products typically have large variations in viscosity due to temperature changes. However, in the case of a lubricating oil composition used for automobiles and the like, it is preferable that the temperature dependence of the viscosity is small. Olefin copolymers have been added to lubricating oil compositions as VI improvers to reduce the temperature dependence of viscosity.

  Ethylene-propylene copolymers have been used for many years as VI improvers in multigrade engine oil formulations. In most cases, these VI improvers contain at least about 40% ethylene by weight. While such copolymers are effective VI improvers, they have the disadvantage of promoting piston deposits and thickening of the oil when the oil is subjected to high temperature operation. The present invention provides a solution to this problem.

  The present invention relates to a lubricant composition comprising a VI improver comprising a polymer having structural units derived from ethylene, propylene and butylene. These lubricant compositions, when used as engine oils, exhibit reduced piston deposit levels and reduced levels of increased viscosity when the engine is operated under high temperature conditions compared to conventional lubricant compositions. . The present invention relates to a structural unit derived from an oil of lubricating viscosity and from about 5 mol% to about 20 mol% ethylene, from about 50 mol% or from 60 mol% to about 90 mol% propylene, and from about 5% to about 30 mol % Of a polymer comprising structural units derived from% butylene. In certain embodiments, the lubricant composition further comprises a dispersant and a detergent comprising an overbased sulfonate, the sulfonate having a total base number in the range of about 250 to about 600.

  Ranges and ratio limits disclosed in the specification and claims may be combined arbitrarily. Unless stated otherwise, when describing “one (a, an)” and / or “the”, it may include one or more than one, and some are described in the singular It will be understood that cases may also include more than one.

When referring to a group attached to the rest of the molecule, the terms “hydrocarbyl” and “hydrocarbon” in the context of the present invention refer to groups that are pure hydrocarbon groups or have predominantly hydrocarbon character. Say. These groups include the following:
(1) Pure hydrocarbon group; that is, aliphatic group, alicyclic group, aromatic group, aliphatic substituted aromatic group, alicyclic substituted aromatic group, aromatic substituted aliphatic group, aromatic substituted fat In addition to groups such as cyclic groups, a ring group is completed through another part of the molecule (ie, any two substituents indicated together can form an alicyclic group). Examples include methyl, octyl, cyclohexyl, phenyl and the like.

  (2) a substituted hydrocarbon group; that is, a group containing a non-hydrocarbon substituent that does not change the main hydrocarbon properties of the group. Examples include hydroxy, nitro, cyano, alkoxy, acyl and the like.

  (3) Hetero group; that is, a group mainly having hydrocarbon characteristics and originally containing a non-carbon atom in a chain or ring consisting of carbon atoms. Examples are nitrogen, oxygen and sulfur.

  For every 10 carbon atoms in the hydrocarbyl or hydrocarbon group, there are usually no more than about 3 substituents or heteroatoms, and in one embodiment no more than 1 substituent or heteroatom.

  Here, the term “lower” as used for hydrocarbyl, alkyl, alkenyl, alkoxy, etc. is intended to describe a group containing a total of up to 7 carbon atoms.

  The term “oil-soluble” refers to a material that is soluble in mineral oil in the range of at least about 0.5 grams per liter at 25 ° C.

  The term “TBN” refers to the total base number. This is the amount of acid (perchloric acid or hydrochloric acid) required to neutralize all or part of the basicity of the material, expressed in milligrams of KOH per gram of sample. TBN is generally reported without correction for the amount of oil or other diluent that may be present in the material and is used as such in this document unless otherwise stated.

  The term “TAN” refers to the total acid number. This is the amount of base (NaOH or KOH) required to neutralize all or part of the acidity of the material, expressed in milligrams of KOH per gram of sample.

Lubricant composition The lubricating composition may comprise one or more base oils, and the base oil may be present in a major amount. The base oil may be present in an amount greater than about 60%, or greater than about 70%, or greater than about 75% by weight of the lubricant composition.

  The lubricant composition has a viscosity of up to about 26.1 cSt at 100 ° C., or about 5.6 to about 26.1 cSt at 100 ° C., or about 6 to about 16.3 cSt at 100 ° C., or 100 ° C. And may have a viscosity of about 6 to about 13 cSt.

  The lubricant composition is 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W-20, It may have a SAE viscosity grade of 10W-30, 10W-40, 10W-50, 15W-20, 15W-30, 15W-40, 15W-50 or 15W-60.

Oil of lubricating viscosity Oil of lubricating viscosity is sometimes referred to as a base oil. The base oil can be selected from any of the Group I to V base oils described in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (Base Oil Interchangeability Guidelines). The five base oil groups are as follows:
Base oil category Sulfur (%) Saturation (%) Viscosity index group I> 0.03 and / or <90 80-120
Group II ≦ 0.03 and ≧ 90 80-120
Group III ≦ 0.03 and ≧ 90 ≧ 120
Group IV All poly alpha olefins (PAO)
Group V Other than Group I, II, III, or IV Base oil contains less than about 300 ppm sulfur and / or a saturate content of at least about 90% as measured by the test procedure described in ASTM D2007 But you can. The base oil may have a viscosity index of at least about 95, or at least about 115. The base oil has a viscosity index of at least about 120 and may include one or more polyalphaolefins. In certain embodiments, the base oil may have a viscosity index of up to about 130. In certain embodiments, the oil of lubricating viscosity may comprise a Group II oil. In certain embodiments, if the oil (s) of lubricating viscosity in the lubricant composition as a whole have Group II oil or Group III oil quality, multiple groups of oils of various groups may be used. The entire base oil may be prepared by blending.

  Groups I, II and III are base stocks of mineral oil. The base oil may include natural or synthetic lubricating oils and mixtures thereof. Mixtures of mineral and synthetic oils may be used, particularly polyalphaolefin oils and ester oils.

  Natural oils include animal and vegetable oils (eg, castor oil, lard oil and other vegetable acid esters), as well as mineral lubricating oils such as liquid petroleum and paraffinic, naphthenic or paraffin-naphthenic mixed solvents or acids. Mention may be made of treated mineral lubricants. Hydrotreated or hydrocracked oil may be included in the range of useful oils.

Base oils derived from coal or shale may also be useful. Synthetic lubricants include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and copolymerized olefins and mixtures thereof, alkylbenzenes, polyphenyls (eg, biphenyls, terphenyls and alkylated polyphenyls), alkylated diphenyl ethers and alkylated Diphenyl sulfide and derivatives thereof, analogs and homologues thereof may be included. Alkylene oxide polymers and copolymers, and their derivatives, and those having terminal hydroxyl groups modified, for example, by esterification or etherification, constitute another class of known synthetic lubricating oils that can be used. May be. Another suitable class also may synthetic lubricating oils used, there is an ester derived from an ester of a dicarboxylic acid, and about C ₅ ~ about C ₁₂ monocarboxylic acids and polyols or polyol ethers.

  Other suitable synthetic lubricating oils include liquid esters of phosphorus containing acids, polymeric tetrahydrofurans, silicone oils such as poly-alkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils May be included.

  Hydrotreated naphthenic oils may be used. Synthetic oils such as those produced by the Fischer-Tropsch reaction may be used, and the synthetic oil may typically be a hydroisomerized Fischer-Tropsch hydrocarbon or wax. Such base oils can be prepared by other gas-liquid methods besides the Fischer-Tropsch gas-liquid synthesis method.

  Natural or synthetic unrefined oils, refined oils and reclaimed oils of the type disclosed hereinabove (and mixtures of any two or more thereof) may be used. Unrefined oils are oils obtained directly from natural or synthetic raw materials without further purification. Refined oils are similar to unrefined oils except that they have been treated in one or more purification steps to improve one or more properties. Recycled oil can be obtained by applying a process similar to that used to obtain refined oil to refined oil that has already been used. Recycled oil is often further processed by techniques directed to removal of spent additives and oil breakdown products.

  The amount of fully formulated lubricant oil is typically 100 percent equal to the remaining amount minus the amount occupied by the remaining additives. Typically this may be about 60 to about 99 weight percent, or about 70 to about 97 weight percent, or about 80 to about 95 weight percent, or about 85 to about 93 weight percent. The lubricant composition may be provided as a concentrate, in which case the amount of oil typically decreases and the concentration of other components increases accordingly. The amount of oil in such cases can be from about 30 to about 70 weight percent, or from about 40 to about 60 weight percent.

The VI improver lubricant composition comprises an amount of polymer that improves the viscosity index, including structural units derived from ethylene, propylene, and butylene. The polymer can be prepared by polymerization of a mixture of monomers including ethylene, propylene and butylene. These polymers are sometimes referred to as copolymers or terpolymers.

  The polymer has a structural unit derived from about 5 mol% to about 20 mol%, or from about 5 mol% to about 10 mol% ethylene; from about 60 mol% to about 90 mol%, or from about 60 mol% to about 75 mol% propylene. Units; and about 5 mol% to about 30 mol%, or about 15 mol% to about 30 mol% of structural units derived from butylene. Butylene may include any isomers such as n-butylene, iso-butylene or mixtures thereof or mixtures thereof. Butylene may contain butene-1. Commercially available raw materials for butylene may include butene-2 and butadiene in addition to butene-1. Butylene may include a mixture of butene-1 and isobutylene in which the weight ratio of butene-1 to isobutylene is about 1: 0.1 or less. Butylene includes butene-1 and may or may not be substantially free of isobutylene.

  The polymer has a range of about 10,000 to about 500,000; or a range of about 30,000 to about 400,000, or a range of about 50,000 to about 350,000, or about 150,000 to about 250. May have a number average molecular weight in the range of 1,000 (measured by gel permeation chromatography (GPC) using polystyrene as a calibration standard). The molecular weight distribution of the polymer, Mw / Mn (measured by GPC using polystyrene as a calibration standard, Mw is the weight average molecular weight, Mn is the number average molecular weight) is about 4 or less, or about 3 or less, or about 2. It may be 5 or less, or in the range of about 2 to about 4, or in the range of about 2 to about 3, or in the range of about 2 to about 2.5.

  This polymer is produced by a known catalyst capable of stereoregular polymerization of an olefin into an isotactic structure or a syndiotactic structure (for example, a catalyst whose main component is a solid titanium component and an organometallic compound, or a metallocene compound). Polymerization of propylene, ethylene and butylene (eg, butene-1) in the presence of a metallocene catalyst used as a catalyst component) may be included. In particular, in order to obtain a lubricant composition having excellent fuel efficiency at a high temperature, a production method using a metallocene catalyst capable of performing stereotactic polymerization with an isotactic structure may be used. Examples of such metallocene catalysts include those described in WO 2004/106430, WO 2005/019283, WO 2006/025540, and WO 2004/087775. Metallocene compounds include diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenyl-methylene (3-tert-butyl-5- Methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) -zirconium dichloride, dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl)-(fluorenyl1) zirconium dichloride And the like.

  The polymer is present in the lubricant composition in a range from about 0.001% to about 2%, or from about 0.003% to about 1.5%, or from about 0.005 to about 1% by weight. It may be present in a range, or a concentration in the range of about 0.01% to about 0.75%. The polymer may be present at a concentration in the range of about 0.5 wt% to about 1 wt%, or in the range of about 0.6 to about 0.8 wt%. In other embodiments, the polymer may be present from about 0.3 to about 5 weight percent or from about 0.5 to about 2 weight percent.

  The polymer may be provided as a concentrate. The concentrate includes a diluent oil and from about 0.5 wt% to about 30 wt% polymer, or from about 1 wt% to about 15 wt% polymer, or from about 5 wt% to about 15 wt% polymer. But you can.

The following examples illustrate the preparation of ethylene-propylene-butylene polymers that can be used as viscosity index improvers in lubricant compositions.
[Example 1]
Purified and dehydrated n-hexane is continuously introduced at a flow rate of 27.1 L / hr into one feed port of a 310 L pressurized pressurized polymerization reactor equipped with a stirring blade and thoroughly purged with nitrogen. Methylaluminoxane (TMAO-341: Tosoh Finechem Corporation) at a concentration of 37.5 mmol / L; diphenylmethylene (3-tert-butyl-5-ethylcyclopentadiene) at a concentration of 0.15 mmol / L A hexane solution containing triethylbutylaluminum (TiBA: Tosoh Finechem Co., Ltd.) at a concentration of 15.0 mmol / L, and a hexane solution containing 2,9-di-tert-butylfluorenyl) zirconium dichloride; Introduce continuously at the flow rate of the hour. At the same time, another feed port of the continuous polymerization reactor is fed with ethylene at a flow rate of 0.8 kg / h, propylene at a flow rate of 11.1 kg / h, butene-1 at a flow rate of 6.5 kg / h, and 4.5 NL / h. Hydrogen is added continuously at a flow rate of hours (NL = liters at normal conditions, ie liters at 1 atm and 0 ° C.). The continuous solution polymerization is performed under the conditions of a polymerization temperature of 60 ° C., a total pressure of 1.0 MPa-G (G = gauge pressure), and a stirring rotational speed of 190 rpm. The coolant is circulated through a jacket equipped outside the polymerization reactor. Further, the gas phase is forcibly circulated using a separately installed gas blower, and the gas phase is cooled by a heat exchanger, thereby removing the polymerization heat. The polymerization product produced is a hexane solution containing ethylene / propylene / butene-1 polymer. This solution is withdrawn through the outlet equipped at the bottom of the polymerization reactor at a rate of 7.5 kg / hr for the ethylene / propylene / butene-1 copolymer to maintain the average solution volume in the polymerization reactor at 100 L. The resulting polymerization solution is poured into methanol to precipitate the ethylene / propylene / butene-1 polymer. The ethylene / propylene / butene-1 polymer is dried under reduced pressure at 130 ° C. for 24 hours. The polymer comprises 8.7 mol% structural units derived from ethylene, 68 mol% structural units derived from propylene, and 23.3 mol% structural units derived from butene-1. The polymer has a density of 865 kg / m ³ , a melting point of 47 ° C., a Mw of 220,000 and a Mw / Mn of 2.2 as measured by GPC using polystyrene as a calibration standard.

The overbased metal-containing detergent lubricant composition may comprise one or more overbased metal-containing detergents. Other overbased materials, also called overbased or superbasic salts, have a metal content that is stoichiometrically neutralized between the metal and the specific acidic organic compound that reacts with the metal. It is a single-phase, uniform Newton system characterized by the presence of excess. The overbased material comprises an acidic material (typically an inorganic acid or a lower carboxylic acid such as carbon dioxide), an acidic organic compound and at least one inert organic solvent (mineral oil) suitable for the acidic organic material. , Naphtha, toluene, xylene, etc.), a reaction mixture containing a stoichiometric excess of a metal base and a promoter such as calcium chloride, acetic acid, phenol or alcohol. . The acidic organic material may have a sufficient number of carbon atoms to provide a certain degree of solubility in the oil. The amount of excess metal is generally represented by the metal ratio. The term “metal ratio” is the ratio of the total equivalent of metal to the equivalent of acidic organic compound. The metal ratio of the neutral metal salt is 1. A salt having 3.5 times the metal present in the normal salt is an excess of 3.5 equivalents of metal, i.e. the ratio is 4.5. The term “metal ratio” refers to “Chemistry and Technology of Lubricants”, 2nd edition, R.A. M.M. Mortier and S.M. T. T. et al. It is also described in the standard instruction book titled Orszulik, copyright, 1997.

  The metal of the overbased metal-containing detergent may be zinc, sodium, calcium, barium, magnesium or a mixture of two or more thereof. The metal may be sodium, calcium or magnesium or a mixture thereof, and in one embodiment the metal may be a mixture of sodium and calcium.

  The overbased metal-containing detergent may be selected from non-sulfur-containing phenates, sulfur-containing phenates, sulfonates, salixalate, salicylates and mixtures thereof, or borated equivalents thereof. In one embodiment, the lubricant composition may be free or substantially free of phenolic detergent (s). “Substantially free” in this context is that less than 10 weight percent, or less than 5 weight percent, or less than 1 weight percent, or less than 0.1 weight percent of the detergent (s) is phenolic. Means good. The overbased detergent may be borated with a borated agent such as boric acid.

  Overbased metal-containing detergents also include phenate and / or sulfonate components, such as US Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and Including "hybrid" detergents formed with mixed surfactant systems including phenate-salicylate, sulfonate-phenate, sulfonate-salicylate, sulfonate-phenate-salicylate as described in US 6,281,179 Good. For example, when using a sulfonate-phenate hybrid detergent, the hybrid detergent is considered equivalent to each amount of separate phenate detergent and sulfonate detergent, each introducing corresponding amounts of phenate soap and sulfonate soap. Would be considered equivalent to

  The overbased metal-containing detergent may comprise a zinc, sodium, calcium or magnesium salt of phenate, sulfur-containing phenate, sulfonate, salixarate or salicylate. Overbased salixate, phenate and salicylate may have a total base number (ASTM D3896) in the range of about 180 to about 450 TBN. The overbased sulfonate may have a total base number in the range of about 250 to about 600, or in the range of about 300 to about 500. Overbased detergents are known in the art. Sulfonate detergents are mostly linear alkylbenzene or alkyltoluene sulfonate detergents having a metal ratio of at least about 8 as described in paragraphs [0026] to [0037] of US 2005/065045. An agent may be used. The linear alkyl group may be bonded to benzene at any position along the linear alkyl chain, for example, at the 2-position, 3-position or 4-position, or may be bonded to toluene. Linear alkyl benzene sulfonate detergents can be useful for improving fuel economy.

  The overbased metal-containing detergent may be a calcium overbased detergent or a magnesium overbased detergent. The lubricant composition may comprise overbased calcium sulfonate, overbased calcium phenate or mixtures thereof. The overbased detergent comprises a calcium sulfonate having a metal ratio of at least about 3.5, such as in the range of about 3.5 to about 40, or in the range of about 5 to about 25, or in the range of about 7 to about 20. But you can.

  The lubricant composition may be a low overbased detergent (having a metal ratio of less than about 3.5, such as in the range of about 0 to about 3.5, or in the range of about 0.5 to about 3.0, or about 1 To about 2.5, or about 1.5 to about 2), or a neutral detergent.

  The overbased metal-containing detergent may be present in the lubricant composition at a concentration ranging from about 0.05% to about 5% by weight of the lubricant composition. The overbased detergent is from about 0.1%, about 0.3% or about 0.5%, up to about 3.2%, or up to about 1.7% by weight of the lubricant composition. Or in concentrations ranging up to about 0.9% by weight. Similarly, the overbased detergent may be present in an amount suitable to provide the lubricant composition with a TBN (total base number) in the range of about 1 to about 10. The overbased detergent may be present in an amount that provides the lubricant composition with a TBN ranging from about 1.5 to about 3, or up to about 5, or up to about 7. In other embodiments, the overbased detergent may provide the lubricant composition with at least 3 TBN, such as 3-7 or 4-6 TBN.

  Metal-containing detergents provide not only TBN but also ash to the lubricant composition. Sulfated ash (ASTM D874) is another parameter frequently used to characterize overbased detergent and lubricant compositions. The lubricant composition may be from about 0.3 to about 1.2 wt%, or from about 0.3 to about 1.0 wt%, or from about 0.5 to about 1.0 wt%, or about 0.6 wt% It may have a sulfate ash level greater than%. In other embodiments (eg, for marine diesel engine cylinder lubricants), the ash level may be about 1 to about 15 wt%, or about 2 to about 12 wt%, or about 4 to about 10 wt% . The overbased detergent may comprise about 50% to about 100% sulfated ash, or at least about 70% ash, or at least about 80% ash, or 100% ash. Overbased detergents may provide about 95% or less sulfated ash, or about 98% or less sulfated ash.

  The lubricant composition may be a marine diesel engine cylinder lubricant (MDCL). This type of lubricant may be characterized by high TBN levels primarily provided by metal-containing overbased detergents. In some embodiments, the lubricant composition has a TBN of at least about 10, or at least about 20, such as 10-100, 20-100, 30-100, 40-80, 30-75, or 40-70. It may be. Most of the basicity of MDCL compositions can be obtained with detergent components, but typically a relatively small amount of TBN (eg, less than about 5%) is obtained with other species such as nitrogen-containing dispersants. May be.

Other performance additive lubricant compositions may include other performance additives. Performance additives include one or more metal activity reducing agents, viscosity adjusting aids, auxiliary cleaners, friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, Antioxidants, foam suppressors, demulsifiers, pour point depressants, seal swell agents, and mixtures of two or more thereof may be included.

  Antioxidants may include sulfurized olefins, diarylamines, alkylated diarylamines, hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamate), hydroxyl thioethers, or mixtures thereof. The antioxidant is from about 0 wt% to about 15 wt%, or from about 0.1 wt% to about 10 wt%, or from about 0.5 wt% to about 5 wt%, or from about 0.5 wt% to about 3 wt% of the lubricant composition. May be present at concentrations in the range.

  The diarylamine or alkylated diarylamine may be phenyl alpha-naphthylamine (PANA), alkylated diphenylamine, or alkylated phenylnaphthylamine, or mixtures thereof. The alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof. In one embodiment, the diphenylamine may comprise nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In one embodiment, the diphenylamine may comprise nonyl diphenylamine or dinonyl diphenylamine. Alkylated diarylamines may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decylphenylnaphthylamine.

  The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindrance group. The phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and / or a bridging group attached to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, There are 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. The hindered phenol antioxidant may be an ester such as an ester available from Ciba under the trade name Irganox ™ L-135. Such materials can be represented by the general formula:

Wherein R ³ is a hydrocarbyl group such as, for example, an alkyl group containing 1 to about 18, or 2 to about 12, or 2 to about 8, or 2 to about 6 carbon atoms, t -Alkyl may be t-butyl. A detailed description of hindered phenol antioxidants containing esters that may be used can be found in US Pat. No. 6,559,105.

  Examples of molybdenum dithiocarbamates that may be used as antioxidants include Vanrube 822 ™, and Polyvan ™ A from RT Vanderbilt Co., Ltd., and Commercial materials sold under the trade names such as Adeka Sakura-Lube ™ S-100, S-165, S-525 and S-600 from Asahi Denka Kogyo K.K. There are mixtures of these.

  The lubricant composition may further contain one or more viscosity adjusting aids. Viscosity control aids include hydrogenated styrene butadiene rubber, ethylene-propylene copolymer, polymethacrylate, polyacrylate, hydrogenated styrene-isoprene polymer, hydrogenated diene polymer, poly (alkylstyrene), polyolefin, maleic anhydride-olefin copolymer. Esters (such as those described in WO 2010/014655), esters of maleic anhydride-styrene copolymers, or mixtures or two or more thereof may be included.

  Dispersant viscosity modifiers are functionalized polyolefins, such as ethylene-propylene copolymers functionalized with acylating agents such as maleic anhydride and amines; amine functionalized polymethacrylates; or esterification reacted with amines. Styrene-maleic anhydride copolymers may be included. More detailed descriptions of dispersant viscosity modifiers can be found in WO 2006/015130 or US Pat. No. 4,863,623; 6,107,257; 6,107,258; No. 6,117,825. Dispersant viscosity modifiers are described in US Pat. No. 4,863,623 (see column 2, line 15 to column 3, line 52) or WO 2006/015130 (paragraph [0008] on page 2 and (See the preparation examples described in paragraphs [0065] to [0073]). The dispersant viscosity modifier is present in a concentration ranging up to about 15 wt% or up to about 10 wt%, or from about 0.05 wt% to about 5 wt%, or from about 0.2 wt% to about 2 wt% of the lubricant composition. Also good.

  The lubricant composition may further contain one or more dispersants. The dispersant may be a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin succinate, an amide, or an ester-amide, or a mixture thereof. The dispersant may be present as a single dispersant or as a mixture of two or more (eg, three) different dispersants, at least one of which may be a succinimide dispersant. .

  Succinimide dispersants can be obtained from one or more aliphatic polyamines. The aliphatic polyamine may be an aliphatic polyamine such as ethylene polyamine (ie, poly (ethylene amine)), propylene polyamine, butylene polyamine, or a mixture of two or more thereof. The aliphatic polyamine may be an ethylene polyamine. The aliphatic polyamine may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene-pentamine, pentaethylenehexamine, polyamine residue, or a mixture of two or more thereof.

  Succinimide dispersants may be obtained from aromatic amines, aromatic polyamines or mixtures thereof. The aromatic amine may have a hydrocarbylene group such as 4-aminodiphenylamine and / or one or more aromatic moieties joined by heteroatoms. The aromatic amine may be a nitro-substituted aromatic amine. As examples of nitro-substituted aromatic amines, mention may be made of 2-nitroaniline, 3-nitroaniline and 4-nitroaniline. 3-Nitroaniline is particularly useful. Other aromatic amines may be present with the nitroaniline. Condensation products with nitroaniline and optionally with Disperse Orange 3 (ie 4- (4-nitrophenylazo) aniline) are disclosed in US 2006/0025316.

  The dispersant may comprise an amine functionalized polymer, for example, a succinimide dispersant. The amine has at least 2, or at least 3, or at least 4 aromatic groups, such as about 4 to about 10, or about 4 to about 8, or about 4 to about 6 aromatic groups, and at least one It may be an amine having a primary or secondary amino group or at least one secondary amino group. The amine may contain both a primary amino group and at least one secondary amino group. The amine may comprise at least two of at least about 4 aromatic groups and any combination of secondary or tertiary amino groups.

  An example of an amine having two aromatic groups is N-phenyl-p-phenylenediamine. An example of an amine having at least 3 or 4 aromatic groups can be represented by the following formula (1).

Wherein each variable group are as follows independently: R ¹ is also hydrogen, or may be a C ₁ ~ ₅ alkyl group (typically hydrogen); R ² is also hydrogen or C ₁ ~ _5, An alkyl group (may be typically hydrogen); U may be an aliphatic group, an alicyclic group, or an aromatic group (if U is aliphatic, the number of aliphatic groups is 1 to about 5; Or a linear alkylene group containing 1 to about 2 carbon atoms, or a branched alkylene group); w may be 1 to about 10, or 1 to about 4, or 1 to 2 (typically 1). When U is an aliphatic group, U may be an alkylene group containing 1 to about 5 carbon atoms. Alternatively, the amine can also be represented by formula (1a).

In the formula, each of the variable groups U, R ¹ and R ² is the same as above, and w is 0 to about 9, or 0 to about 3, or 0 to about 1 (typically 0).

  The dispersant may be an ester, amide, or ester-amide of polyolefin succinic acid. For example, the polyolefin succinate may be a polyisobutylene succinate of pentaerythritol or a mixture thereof. Polyolefin succinate-amide reacted polyisobutylene succinic acid with alcohol (such as pentaerythritol) and amine (polyamine, typically diethylenetriamine, polyamine resid, tetraethylenepentamine (TEPA) and the like) It may be a thing.

  The dispersant may be an N-substituted long chain alkenyl succinimide. An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide, a polyisobutene-substituted succinimide dispersant. Typically, the polyisobutylene from which the polyisobutylene succinic anhydride is derived has a number average molecular weight of about 350 to about 5000, or about 550 to about 3000 or about 750 to about 2500. Regarding the succinimide dispersant and its preparation, for example, U.S. Pat. Nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281, and 3, 351, 552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405 US Pat. No. 3,542,680, US Pat. No. 3,576,743, US Pat. No. 3,632,511, US Pat. No. 4,234,435, US Pat. No. 26,433, and US Pat. No. 6,165,235, No. 7,238,650 and European Patent Application No. 0 355 895 A.

  The dispersant may be further reacted with any of a variety of agents and post-treated by conventional methods. Among them, boron compounds (boric acid etc.), urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid such as terephthalic acid, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitrile, epoxide And phosphorus compounds. The post-treatment dispersant may be borated. The post-treatment dispersant may be obtained from the reaction of the dispersant with dimercaptothiadiazole. The post-treatment dispersant may be obtained from the reaction of the dispersant with phosphoric acid or phosphorous acid.

  The dispersant is about 0.01 wt% to about 20 wt%, or about 0.1 wt% to about 15 wt%, or about 0.1 wt% to about 10 wt%, or about 1 wt% to about 6 wt% of the lubricating composition, Or it may be present in the lubricant composition at a concentration ranging from about 1 to about 3 wt%.

  If the dispersant contains a basic nitrogen atom, such basicity may be measured by the TBN of the dispersant. In one embodiment, the TBN of a useful succinimide dispersant may be from about 10 to about 30 on an oil-free (corrected) basis, which is about 5 when measured with a dispersant sample containing 50% oil. It is thought that it corresponds to about ~ 15.

  In one embodiment, the amount that improves the viscosity index of the polymer (ie, the amount of VI polymer) is about 0.5 to about 2 weight percent and the amount of dispersant is about 0.01 to about 20 weight percent. And the amount of overbased sulfonate is from about 0.05 to about 5 weight percent.

  Friction modifiers include amine long chain fatty acid derivatives, long chain fatty acid esters, or long chain aliphatic epoxide derivatives; fatty acid imidazolines; amine salts of alkyl phosphates; fatty acid alkyl tartrates; fatty acid alkyl tartrimides; It may be selected from ramides; fatty acid glycolates; and fatty acid glycol amides. As used herein, the term “fatty acid alkyl or fatty acid” with respect to friction modifiers means a carbon chain having from about 10 to about 22 carbon atoms, typically a straight chain carbon chain. Alternatively, a monobranched alkyl group may be used in place of the fatty acid alkyl group. Typical monobranched alkyl groups may include β-branching groups such as 2-ethylhexyl, 2-propylheptyl and the like. The friction modifier is 0 wt% to about 6 wt%, or about 0.01 wt% to about 4 wt%, or about 0.05 wt% to about 2 wt%, or about 0.1 wt% to about 2 wt% of the lubricant composition. It may be present in the lubricant composition in a range of concentrations.

  Examples of friction modifiers that may be used include long chain fatty acid derivatives, fatty acid esters or aliphatic epoxides of amines; fatty acid imidazolines, such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkyl phosphoric acids; Fatty acid alkyl tartrate; fatty acid alkyl tartrimide; fatty acid alkyl tartramide; aliphatic phosphonate; aliphatic phosphite; borated phospholipid, borated aliphatic epoxide; glycerol ester; borated glycerol ester; Alkoxylated aliphatic amines; borated alkoxylated aliphatic amines; hydroxyalkyl and polyhydroxyalkyl aliphatic amines such as tertiary hydroxyalkyl aliphatic amines; hydroxyalkylamides; fats Metal salts of alkyl salicylates; aliphatic oxazolines; aliphatic ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or aliphatic carboxylic acids and guanidine, aminoguanidine, urea or thiourea And the reaction products thereof and their salts.

  Friction modifiers also include materials such as sulfurized aliphatic compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, and monoesters of polyols with aliphatic carboxylic acids derived from or derivable from sunflower oil or soybean oil. Is also included.

  The friction modifier may be a long chain fatty acid ester. The long chain fatty acid ester may be a monoester, diester, (tri) glyceride, or a mixture of two or more thereof.

  The lubricant composition may optionally further comprise at least one antiwear agent. Examples of suitable antiwear agents include tartrate (tartrate), tartrimide, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyl dithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite) ), Phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-linked thiocarbamates, and bis (S-alkyldithiocarbamyl) disulfides. The antiwear agent may in one embodiment comprise a tartrate or tartrimide as disclosed in WO 2006/0444411 or Canadian Patent 1 183 125. The tartrate or tartrimide may contain alkyl group (s) in which the total number of carbon atoms of the alkyl group is at least about 8.

  Another class of additives may include oil-soluble titanium compounds as disclosed in US Pat. No. 7,727,943 and US Patent Application Publication No. 2006/0014651. These can serve as antiwear agents, friction modifiers, antioxidants, deposit control additives and the like. These additives may be multifunctional additives. For example, one of these additives can impart both abrasion resistance and antioxidant properties. The oil-soluble titanium compound may be a titanium (IV) alkoxide. Titanium alkoxides can be formed from monohydric alcohols, polyols or mixtures thereof. The monovalent alkoxide may contain 2 to about 16 carbon atoms, or 3 to about 10 carbon atoms. The titanium alkoxide may be titanium (IV) isopropoxide. The titanium alkoxide may be titanium (IV) 2-ethylhexoxide. The titanium compound may comprise an alkoxide of an adjacent 1,2-diol or polyol. The 1,2-adjacent diol may comprise a fatty acid mono-ester of glycerol, such as an oleate.

  The oil-soluble titanium compound may be a titanium carboxylate. The titanium carboxylate can be derived from a titanium alkoxide and a carboxylic acid selected from the group consisting of non-linear monocarboxylic acids and carboxylic acids having more than about 22 and up to about 25 carbon atoms. Examples of titanium / carboxylic acid products include caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, Mention may be made of titanium reaction products with acids selected from the group comprising benzoic acid, neodecanoic acid and the like. Methods for producing such titanium / carboxylic acid products are described, for example, in US Pat. No. 5,260,466.

Local pressure (EP) agents that are soluble in oil include sulfur-containing and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS ₂ derivatives of dispersants (typically succinimide dispersants), chlorinated hydrocarbon EP agents and A derivative of a phosphorus EP agent may be included. Examples of such EP agents include chlorinated waxes; sulfurized olefins (such as sulfurized isobutylene), hydrocarbyl substituted 2,5-dimercapto-1,3,4-thiadiazole or oligomers thereof, organic sulfides and polysulfides such as dibenzyl disulfide, bis- (Chlorobenzyl) disulfide, dibutyltetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels Alder adducts; reaction of phosphorous sulfides such as phosphorus sulfide with turpentine or methyl oleate Products; Phosphorous esters such as dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phosphite Nyl; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacids; amines of alkyl and dialkyl phosphates Salts, or derivatives such as, for example, amine salts of reaction products of dialkyldithiophosphoric acid and propylene oxide, and then further reacted with P ₂ O ₅ ; and mixtures thereof (US Pat. No. 3,197,405). In the issue).

  Antifoam agents that may be used in the lubricant composition include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers such as fluorinated polysiloxanes, trialkyl phosphates, polyethylene Glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers may be included.

  Pour point depressants that may be used in the lubricant composition may include poly alpha olefins, esters of maleic anhydride-styrene copolymers, poly (meth) acrylates, polyacrylates or polyacrylamides.

  Demulsifiers that may be used may include trialkyl phosphates and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures of two or more thereof.

  Metal activity reducing agents include benzotriazole derivatives (typically tolyltriazole), 1,2,4-triazole derivatives, benzimidazole derivatives, 2-alkyldithiobenzimidazole derivatives or 2-alkyldithio-benzothiazoles. May be included. Metal activity reducing agents are also called corrosion inhibitors.

  Seal swelling agents that may be used may include sulfolene derivatives such as Exxon Necton-37 ™ (FN 1380) and Exxon Mineral Seal Oil ™ (FN 3200).

  The lubricant composition can be used to lubricate the device by supplying a lubricant as described herein to the mechanical device. The apparatus may be an internal combustion engine such as a gasoline or diesel engine for automobiles, a diesel engine for heavy vehicles, a marine diesel engine, or a stationary gas engine. Such an engine can be sump lubricated, and the lubricant can be supplied to the sump, from which the lubricant can lubricate the working part of the engine. Alternatively, the lubricant may be supplied from another source instead of the sump section.

  The internal combustion engine may be a diesel fuel engine (typically a heavy vehicle diesel engine), a gasoline fuel engine, a natural gas fuel engine, a gasoline / alcohol mixed fuel engine, or a hydrogen fuel internal combustion engine. The internal combustion engine may be a diesel fuel engine or a gasoline fuel engine. The internal combustion engine may be a diesel engine for large vehicles.

  The internal combustion engine may be a two-cycle engine or a four-cycle engine. Suitable internal combustion engines may include marine diesel engines (which may include cylinders lubricated with the lubricant), aviation piston engines, low load diesel engines, and automobile and truck engines. Marine diesel engines are typically used for marine diesel engine cylinder lubricants (typically for 2-cycle engines), system oils (typically for 2-cycle engines), or crankcase lubricants (typically for 2-cycle engines). 4 cycle engine can be lubricated.

  One class of internal combustion engines are direct injection combustion engines that inject fuel directly into a cylinder. Specific examples of direct injection include a wall guide and a spray guide direct injection engine. The lubricant composition may be used for lubricating a gasoline direct injection engine.

  The lubricant composition can be suitably used as a lubricant for any engine regardless of the content of sulfur, phosphorus or sulfated ash. The sulfur content of the lubricant composition when used as an engine oil may be about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less. . The sulfur content may range from about 0.001 wt% to about 0.5 wt%, or from about 0.01 wt% to about 0.3 wt%. The phosphorus content is about 0.2 wt% or less, or about 0.12 wt% or less, or about 0.1 wt% or less, or about 0.085 wt% or less, or about 0.08 wt% or less, or about 0.06 wt% Or about 0.055 wt% or less, or about 0.05 wt% or less. The phosphorus content may be about 0.04 wt% to about 0.12 wt%. The phosphorus content may be from about 100 ppm to about 1000 ppm, or from about 200 ppm to about 600 ppm. The total sulfated ash content may be about 0.3 wt% to 1.2 wt%, or about 0.5 wt% to about 1.1 wt% of the lubricant composition. The sulfated ash content may be about 0.5 wt% to 1.1 wt% of the lubricant composition. The lubricant composition may be characterized by a chlorine content of up to about 100 ppm, or up to about 50 ppm, or up to about 10 ppm.

  The lubricant composition comprises: (i) a sulfur content of about 0.5 wt% or less of the lubricant composition, (ii) a phosphorus content of about 0.12 wt% or less, and (iii) about 0 It may be an engine oil that may be characterized as having at least one of a sulfated ash content of .5 wt% to about 1.1 wt%.

  The lubricant composition may be a cylinder lubricant for marine diesel engines that may be used for lubrication of marine diesel cylinders. The cylinder for marine diesel engines may be a cylinder of a two-cycle marine diesel engine. Marine diesel engine cylinder lubricants are typically used and consumed in a single supply without being held in a sump. These lubricants require high detergent levels that give the lubricant a high level of basicity, as measured by TBN, and typically have a TBN level of about 20 or higher, such as about 30 or higher, or about 40 or higher, or It may be about 50 or more, or about 70 or more, and typically up to about 80, or up to about 100, or up to about 300.

  The lubricant composition may be used in an operating method of an internal combustion engine in which the merit score of piston deposit is increased and the increase in viscosity is suppressed.

  In one embodiment, the disclosed technique provides a method for reducing the level of piston deposits in an internal combustion engine, comprising lubricating the engine with a lubricant composition as described herein. . In one embodiment, the disclosed technology includes structural units derived from about 5 mol% to about 20 mol% ethylene, about 50 mol% to about 90 mol% propylene in the lubricant composition, and about 5 % To about 30 mol% of a polymer comprising structural units derived from butylene, wherein the lubricating oil composition comprises an oil of lubricating viscosity, a dispersant, and a sulfonate of about 250- And a detergent comprising an overbased sulfonate having a total base number in the range of about 600, providing use for reducing the level of engine piston deposits lubricated by the lubricant composition. .

[Example 2]
The fully formulated engine oil is blended with a polymer made in accordance with the disclosure of Example 1 (hereinafter Polymer 1) and a commercially available olefin copolymer (hereinafter Comparative OCP or Comp OCP). Test for “advantages”. The ASTM Sequence IIIG test shows a significant improvement in deposit performance when using Polymer 1 compared to Comp OCP. Polymer 1 and Comp OCP have the properties shown in Table 1 below.

  The polymer of Table 1 is used to produce the engine oil (EO) formulation shown in Table 2. EO No. To formulate 1, polymer 1 is used. Comp OCP is used to formulate Comp EO. In Table 2, the mixed oil is added to a part of the additive, and the weight percentage of the mixed oil to the additive is shown. Further, in Table 2, all numerical values are parts by weight (all percentages are percentages by weight) except where otherwise noted.

  The ASTM Sequence IIIG test is performed using the engine oil formulation shown in Table 2. The test results are shown in Table 3.

  From these test results, EO No. Using 1 shows a significant increase in piston deposit rating and a significant suppression of engine oil thickening as compared to Comp EO.

  While the invention has been described in terms of various embodiments, it will be understood that various modifications of the invention will become apparent to those skilled in the art after reading this specification. Accordingly, it will be understood that the invention includes all such modifications that may be included within the scope of the appended claims.

  The amount of each chemical component listed is excluding any solvent or diluent oil that would normally be present in commercially available materials (ie on an active chemical basis) unless otherwise stated, for example, unless stated otherwise. ) On the other hand, unless otherwise stated, each chemical or composition referred to herein is commercially available that may include isomers, by-products, derivatives, and other such materials normally understood to be present in commercial grades. It should be interpreted as a grade material.

  It is known that some of the materials described above can interact in the final formulation, so that the components of the final formulation can be different from the material originally added. For example, metal ions (eg, in detergents) migrate to other acidic or anionic sites of other molecules. The products so formed may not be easily described, including products formed using the compositions of the present invention for that purpose. However, such modifications and reaction products are included within the scope of the present invention. The present invention includes a composition prepared by mixing the components described above.

  Each of the documents referred to above is incorporated herein by reference, including any prior applications that are the subject of priority claims, whether specifically stated or not. Reference to any document is not an admission that such document is considered prior art or constitutes general knowledge of those of ordinary skill in any jurisdiction. All quantities in this description that specify the amount of materials, reaction conditions, molecular weight, number of carbon atoms and the like, unless otherwise stated or explicitly stated otherwise, are "about" ) "Should be understood as being modified. It will be understood that the upper and lower amount, range and ratio limits set forth herein may be combined independently. Similarly, the range and amount of each element of the invention may be used with the range or amount of any other element. As used herein, the expression “consisting essentially of” can include substances that do not significantly affect the basic and novel characteristics of the composition under consideration.

Claims (13)

60 wt% or more of oil of lubricating viscosity;
Structural units derived from the 5 mol% ~ 10 mol% of ethylene, structural units derived from propylene of 60mol% ~75mol%, and saw including a structural unit derived from butylene in the 15 mol% 30 mol%, a number average molecular weight of 150,000 An amount that improves the viscosity index of 0.001 to 2 % by weight of a polymer in the range of ~ 250,000 and Mw / Mn in the range of 2 to 2.5 ;
A detergent comprising 0.01 to 20% by weight of a succinimide dispersant; and an overbased sulfonate selected from the group consisting of calcium sulfonate, magnesium sulfonate and sodium sulfonate, wherein the sulfonate is a total base in the range of 250 to 600 0.05 to 5% by weight of a detergent having a valence
A lubricant composition comprising:   The composition according to claim 1, wherein the amount of the polymer that improves the viscosity index is 0.5 to 2 wt%.   The composition of claim 1 or 2, wherein the dispersant comprises a polyisobutene-substituted succinimide.   4. A composition according to any preceding claim, wherein the overbased sulfonate is present in an amount suitable to provide the lubricant composition with a TBN (total base number) in the range of 1-10.   The said composition further contains at least 1 sort (s) chosen from the group which consists of an antiwear agent, antioxidant, a friction modifier, a pour point depressant, and an antifoamer in any one of Claims 1-4. Composition.   The composition is one or more metal activity reducing agents, additional viscosity adjusting aids, auxiliary detergents, corrosion inhibitors, dispersant viscosity adjusting agents, extreme pressure agents, demulsifiers, seal swelling agents, or these The composition according to any of claims 1 to 5, further comprising a mixture of two or more.   The composition according to any of claims 1 to 6, wherein the oil of lubricating viscosity comprises a Group II oil.   The composition according to claim 1, wherein the oil having a lubricating viscosity has a kinematic viscosity at 100 ° C. of less than 5 cSt and a viscosity index of less than 130. The composition has a sulfur content of 1 wt% or less, a phosphorus content of 0.2 wt% or less, and a sulfated ash content in the range of 0.3 to 1.2 wt%. The composition in any one of 1-8 .   A method for producing the lubricating oil composition according to claim 1,
  In the presence of a catalyst capable of stereoregular polymerization of olefin into an isotactic structure or a syndiotactic structure, propylene, ethylene and butylene are polymerized to form a structural unit derived from 5 mol% to 10 mol% ethylene, 60 mol% to 75 mol % Of structural units derived from propylene and structural units derived from 15 mol% to 30 mol% of butylene, the number average molecular weight is in the range of 150,000 to 250,000, and Mw / Mn is 2 to 2.5. A process for producing a lubricating oil composition comprising the step of obtaining a polymer in the range of   The method for producing a lubricating oil composition according to claim 10, wherein the catalyst is a metallocene catalyst capable of performing stereoregular polymerization of an isotactic structure. A method for lubricating an internal combustion engine comprising supplying the lubricant composition according to any one of claims 1 to 9 to the internal combustion engine. Method using a lubricant composition according to any one of claims 1 to 9 comprising lubricating an internal combustion engine, reduce the level of piston deposits of an internal combustion engine.