KR101815338B1 - Lubricant composition containing viscosity index improver - Google Patents

Abstract

The disclosed invention relates to a lubricating composition containing a viscosity index improver in the form of a polymer containing structural units derived from ethylene, propylene and butylene.

Description

TECHNICAL FIELD [0001] The present invention relates to a lubricating composition containing a viscosity index improver,

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

Petroleum products generally exhibit large changes in viscosity due to temperature changes. However, it is preferable that the lubricating oil composition used for automobiles and the like should have a small temperature dependence of viscosity. To reduce the temperature dependence of viscosity, an olefin copolymer was added to the lubricating oil composition as a VI improver.

Ethylene-propylene copolymers have been used as VI improvers in multi-grade engine oil formulations for many years. In most cases, this VI improver contains at least about 40% by weight of ethylene. These copolymers are effective VI improvers, but they have the disadvantage of contributing to piston deposits and oil enrichment when the oil is subjected to high temperature operation. The present invention provides a solution to this problem.

The present invention relates to a lubricating composition comprising a VI improver containing a polymer having structural units derived from ethylene, propylene and butylene. This lubricating composition, when used as an engine oil, exhibits reduced levels of piston deposits and reduced levels of viscosity increase over conventional lubricating compositions when the engine is operated under high temperature conditions. The present invention relates to an oil of lubricating viscosity; And from about 5 mol% to about 20 mol% structural units derived from ethylene, from about 50 mol% or from about 60 mol% to about 90 mol% structural units derived from propylene, and from about 5 mol% to about 30 mol% structural units derived from butylene. ≪ RTI ID = 0.0 > lubricating < / RTI > In certain embodiments, the lubricating composition further comprises a dispersant and a detergent containing an overbased sulfonate having a total base in the range of from about 250 to about 600.

All ranges and limitations set forth in this specification and claims may be combined in any manner. Unless otherwise indicated, singular expressions may include one or more than one, and references to singular items may include multiple items.

The terms "hydrocarbyl" and "hydrocarbon" when referring to groups attached to the remainder of the molecule refer to groups that are pure hydrocarbons or predominantly hydrocarbon features within the context of the present invention. These include:

(1) cyclic groups in which the ring is completed through different moieties of the molecule, such as pure hydrocarbon groups: aliphatic, alicyclic, aromatic, aliphatic and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, (I.e., any two of the presented substituents may together form an alicyclic group). Examples include methyl, octyl, cyclohexyl, phenyl, and the like.

(2) Substituted hydrocarbon groups: i.e., non-hydrocarbon substituent containing groups that do not alter the major hydrocarbon character of the group. Examples include hydroxy, nitro, cyano, alkoxy, acyl, and the like.

(3) Heterocyclic group: a group containing mainly carbon atoms and atoms other than carbon in the chain or ring which may consist only of carbon atoms. Examples include nitrogen, oxygen and sulfur.

Generally, no more than about 3 substituents or hetero groups per ten carbon atoms of the hydrocarbyl group or hydrocarbon group, and in one embodiment no more than one substituent or hetero group will be present.

The term "lower ", as used herein with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy and the like, is intended to indicate a group containing up to a total of 7 carbon atoms.

The term " oil solubility " means a material that is soluble in mineral oil at 25 ° C at least about 0.5 g / l.

The term "TBN" refers to the total base. This is the amount of acid (perchloric acid or hydrochloric acid) required to neutralize all or part of the basicity of the substance, expressed as KOH mg / g of sample. TBN is normally recorded without correction for the amount of oil or other diluent that may be present in the material and is used in this manner in this document unless otherwise specified.

The term "TAN" means the total acid value. This is the amount of base (NaOH or KOH) required to neutralize all or part of the acid of the substance, expressed as KOH mg / g of sample.

Lubricating composition

The lubricating composition may comprise one or more base oils which may be present in major amounts. The base oil may be present in an amount greater than about 60 weight percent, greater than about 70 weight percent, or greater than about 75 weight percent of the lubricating composition.

The lubricating composition may have a viscosity of less than about 26.1 cSt at 100 캜, from about 5.6 to about 26.1 cSt at 100 캜, or from about 6 to about 16.3 cSt at 100 캜, or from about 6 to about 13 cSt at 100 캜.

The lubricating composition has a SAE viscosity grade of 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W-20, 5W-30, 5W-40, 5W-50, 5W- , 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 may be called base oil. Base oils may be selected from any base oils belonging to Groups I to V as specified in the American Petroleum Institute (API) Base Oil Compatibility Guidelines. The five base groups are:

The base oil may contain less than about 300 ppm sulfur and / or greater than about 90% volatile content as determined according to the test procedures described in ASTM D2007. The base oil may have a viscosity index of at least about 95 or at least about 115. The base oil may have a viscosity index of at least about 120 and may contain one or more polyalphaolefins. According to certain embodiments, the base oil may have a viscosity index of about 130 or less. According to certain embodiments, the oil of lubricating viscosity may contain Group II oil. According to a particular embodiment, the oils or oils of lubricating viscosity in the lubricating composition may all be of the quality of a Group II oil, or alternatively a Group III oil, but various oils of various groups may also be combined to produce an entire base oil.

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

Natural oils can be derived from animal oils and vegetable oils (such as castor oil, lard oil and other vegetable acid esters) as well as mineral lubricating oils such as solvent-treated or acid-treated paraffinic, naphthenic or mixed paraffinic- Mineral lubricating oils such as mineral lubricating oils and liquid petroleum oils. Hydrotreated oils or hydrocracked oils can be included in the range of useful oils.

Base oils derived from coal or shale may be useful. Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized olefins and mixtures of olefins and mixtures thereof, alkylbenzenes, polyphenyls (e.g., biphenyl, terphenyl and alkylated polyphenyls), alkylated diphenyl ethers And alkylated diphenyl sulfide and derivatives, analogs and analogs thereof. Alkylene oxide polymers and interpolymers and their derivatives, and those in which the terminal hydroxy groups are modified, for example by esterification or etherification, can constitute another part of known synthetic lubricating oils that can be used. Other suitable synthetic lubricating oils that may be used include esters of dicarboxylic acids and esters prepared from about C ₅ to about C ₁₂ monocarboxylic acids and polyols or polyol ethers.

Other suitable synthetic lubricating oils can include liquid esters of phosphorus-containing acids, polymeric tetrahydrofuran, silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils have.

Hydrotreated naphthenic oil may be used. The synthetic oil may be, for example, those produced by the Fischer-Tropsch reaction, and may be generally hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. This base oil can be prepared by Fischer-Tropsch synthesis as well as other vapor-liquid processes.

Natural or synthetic crude, tablet and finishing oils of the kind described above (as well as mixtures of any two or more of these) may be used. The crude oil is obtained directly from natural or synthetic sources without further purification treatment. Is similar to crude oil except that it is further processed into one or more purification steps to improve one or more properties. The freshening oil can be obtained by applying a process similar to that used to obtain this refined oil to the currently used refining oil. Fiscal deficiencies are often further treated as a description of the removal of spent additives and oil degradation products.

The amount of oil in the fully formulated lubricant will generally be the remainder to make 100% after calculating the remaining additive. Generally, it may be from about 60 to about 99 weight percent, from about 70 to about 97 weight percent, from about 80 to about 95 weight percent, or from about 85 to about 93 weight percent. The lubricating composition can be delivered as a concentrate, in which case the amount of oil generally decreases and the concentration of the other components increases relatively. In this case, the amount of oil may be from about 30 to about 70 weight percent or from about 40 to about 60 weight percent.

VI Enhancer

The lubricating composition contains a viscosity index enhancement amount of a polymer containing structural units derived from ethylene, propylene and butylene. This polymer can be prepared by polymerizing a monomer mixture containing ethylene, propylene and butylene. This polymer may be referred to as a copolymer or a terpolymer.

The polymer may comprise from about 5 mol% to about 20 mol%, alternatively from about 5 mol% to about 10 mol%, of structural units derived from ethylene; From about 60 mol% to about 90 mol% or from about 60 mol% to about 75 mol% of structural units derived from propylene; And from about 5 mol% to about 30 mol% or from about 15 mol% to about 30 mol% of structural units derived from butylene. Butylene may contain any isomer or mixture thereof such as n-butylene, isobutylene or mixtures thereof. Butylene may contain butene-1. Commercial sources of butylene may contain butene-1 as well as butene-2 and butadiene. Butylene may contain a mixture of butene-1 and isobutylene, wherein the weight ratio of butene-1 to isobutylene is about 1: 0.1 or less. Butylene may contain butene-1 and be free or essentially free of isobutylene.

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

A method for producing a polymer is a known catalyst capable of stereochemically polymerizing an olefin in an isotactic arrangement or a syndiotactic arrangement (for example, a catalyst in which the main component is a titanium component in the solid form and an organometallic compound, or a metallocene compound is a catalyst Ethylene and butylene (e.g., butene-1) in the presence of a metallocene catalyst used as a catalyst. Specifically, a production process using a metallocene catalyst capable of performing stereoregular polymerization with an isotactic arrangement can be used to obtain a lubricating composition having excellent fuel efficiency at high temperatures. Examples of such metallocene catalysts include those described in International Publication WO 2004/106430, International Publication WO 2005/019283, International Publication WO 2006/025540 and International Publication WO 2004/087775. The metallocene compound is preferably selected from the group consisting of diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert- butylfluorenyl) zirconium dichloride, diphenylmethylene (3- (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylmethylene (3-tert- butyl-5-methylcyclopentadienyl) - (fluorenyl 1) zirconium dichloride and the like.

The polymer may be present in the lubricating composition at a concentration ranging from about 0.001% to about 2%, or from about 0.003% to about 1.5%, or from about 0.005% to about 1%, or from about 0.01% to about 0.75% have. The polymer may be present in a concentration ranging from about 0.5% to about 1% or from about 0.6 to about 0.8% by weight. In other embodiments, 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 may contain a dilute 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.

The following examples illustrate the preparation of an ethylene-propylene-butylene polymer that can be used as a viscosity index improver in lubricating compositions.

Example  One

The purified and dehydrated n-hexane was added in succession at a flow rate of 27.1 L / hr to one of the feed openings of a 310 L volumetric pressurized continuous polymerization reactor equipped with a stirring blade and sufficiently purged with nitrogen. Methyl aluminoxane (TMAO-341: TOSO FINECHEM CORPORATION) 37.5 mmol / L; 0.15 mmol / L diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride; And a hexane solution containing 15.0 mmol / L of triisobutyl aluminum (TiBA: TOSO FINECHEM CORPORATION) were continuously added at a flow rate of 0.1 L / hr. At the same time, as the other feed openings of the continuous polymerization reactor, 0.8 kg / hr of ethylene, 11.1 kg / hr of propylene, 6.5 kg / hr of butene-1 and 4.5 NL / hr of hydrogen (NL = And liter at 0 캜). The continuous solution polymerization was carried out under the conditions of a polymerization temperature of 60 ° C, a total pressure of 1.0 MPa-G (G = gauge pressure) and a stirring rotation frequency of 190 rpm. The coolant was circulated through a jacket mounted on the outside of the polymerization reactor. The vapor phase was forcedly circulated using a separate gas blower, and the vapor phase was cooled with a heat exchanger to remove polymerization heat. The produced polymerization product was a hexane solution containing an ethylene / propylene / butene-1 polymer. This solution was recovered through a vent at the bottom of the polymerization reactor at a rate of 7.5 kg / hr based on the ethylene / propylene / butene-1 copolymer so that the average amount of solution in the polymerization reactor was maintained at 100 L. The final polymer solution was poured into methanol to precipitate an ethylene / propylene / butene-1 polymer. This ethylene / propylene / butene-1 polymer was dried at 130 DEG C for 24 hours under reduced pressure. The polymer contained 8.7 mol% of a structural unit derived from ethylene, 68 mol% of a propylene-derived structural unit and 23.3 mol% of a butene-1-derived structural unit. The polymer had a density of 865 kg / m 3, a melting point of 47 캜, a Mw of 220,000, and a Mw / Mn of 2.2 as measured by GPC using polystyrene as a calibration standard material.

Overbased  Metal-containing detergents

The lubricating composition may contain one or more overbased metal containing detergents. An overbased material, also referred to as an overbased salt or a superabsorbed salt, is characterized by a metal content in excess of the amount that can be present in neutralization, depending on the stoichiometry of the metal and the particular acidic organic compound reacted with the metal Single phase can be homogeneous Newtonian. The overbased material may be an acidic organic compound, a reaction medium containing at least one inert organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for the acidic organic material, a stoichiometric excess of the metal base, , A mixture containing a cocatalyst such as phenol or alcohol, and an acidic substance (generally an inorganic acid or a lower carboxylic acid such as carbon dioxide). The acidic organic material may have a sufficient number of carbon atoms to provide solubility in the oil. The excess of metal is generally expressed in terms of metal ratio. The term "metal ratio" is the ratio of the total equivalents of metals to equivalents of acidic organic compounds. The neutral metal salt has a metal ratio of 1. Salts having 3.5 times more metal than the metal present in the general salt have 3.5 equivalents of metal excess, or the ratio is 4.5. Also, the term "metal ratio" is also described in Chemistry and Technology of Lubricants, Second Edition, Edited by R. M. Mortier and S. T. 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; According to one embodiment, the metal may be a mixture of sodium and calcium.

The overbased metal-containing detergent may be selected from a sulfur-free phenate, a sulfur fenate, a sulfonate, a salicylate, a salicylate and mixtures thereof, or a borated equivalent thereof. According to one embodiment, the lubricating composition may be free or substantially free of phenolic cleaners or detergents. By "substantially free" is meant in this context less than 10%, less than 5%, or less than 1% or less than 0.1% by weight of the detergents or detergents may be phenolic. The overbased detergent may be borated by a borating agent such as boric acid.

The overbased metal-containing detergent is also described in U.S. Patent 6,429,178; 6,429,179; 6,153,565; And mixed surfactant systems such as phenate-salicylate, sulfonate-phenate, sulfonate-salicylate, sulfonate-phenate-sulfonate-sulfonate-containing phenate and / or sulfonate components such as those described in US Pat. No. 6,281,179, "Hybrid" detergents made with salicylate. For example, if a hybrid sulfonate-phenate detergent is used, the hybrid detergent may be thought of as an equivalent amount of a separate phenate detergent and sulfonate detergent, respectively, providing a corresponding amount of phenate soap and sulfonate soap, respectively have.

The overbased metal-containing detergent may comprise a zinc salt, sodium salt, calcium salt or magnesium salt of phenate, sulfone phenate, sulfonate, salicylate or salicylate. The overbased salicylate, phenate, and salicylate may have a total base (ASTM D3896) in the range of about 180 to about 450 TBN. The overbased sulfonate can have a total base ranging from about 250 to about 600, or from about 300 to about 500. Perchlorated detergents are known in the art. The sulfonate detergent may be a predominantly linear alkylbenzene or alkyltoluene sulfonate cleaner having a metal ratio of at least about 8 as described in paragraphs [0026] to [0037] of U.S. Patent Publication No. 2005/065045. A linear alkyl group may be attached to the benzene or toluene at any position along the linear alkyl chain, e.g., at position 2, 3 or 4. Linear alkylbenzene sulfonate detergents can be useful in improving fuel economy.

The overbased metal-containing detergent may be a calcium or magnesium-earth detergent. The lubricating composition may contain an overbased calcium sulphonate, an overbased vaporized calcium phenate or a mixture thereof. The overbased detergent may contain a calcium sulfonate having a metal ratio of at least about 3.5, such as from about 3.5 to about 40, from about 5 to about 25, or from about 7 to about 20.

The lubricating composition may further comprise at least one overbased detergent (metal ratio not greater than about 3.5, such as from about 0 to about 3.5, or from about 0.5 to about 3.0, from about 1 to about 2.5, or from about 1.5 to about 2) ≪ / RTI >

The overbased metal-containing detergent may be present in the lubricating composition at a concentration ranging from about 0.05% to about 5% by weight of the lubricating composition. The overbased detergent may be present in a concentration ranging from about 0.1 wt.%, About 0.3 wt.%, Or from about 0.5 wt.% To about 3.2 wt.%, Up to about 1.7 wt.% Or up to about 0.9 wt.% Of the lubricating composition. Likewise, the overbased detergent may be present in an amount sufficient to provide TBN (total base) in the lubricating composition in the range of from about 1 to about 10. The overbased detergent may be present in the lubricating composition in an amount to provide a TBN in the range of about 1.5 to about 3, up to about 5, or up to about 7. According to other aspects, the overbased detergent can provide a lubricating composition with a TBN of at least 3, such as 3 to 7 or 4 to 6 TBN.

Metal-containing detergents can provide ash in addition to TBN to the lubricating composition. Sulfated ash (ASTM D874) is another parameter often used to characterize overbased detergents and lubricating compositions. The lubricating composition may have a sulfated ash level of from about 0.3 to about 1.2 weight percent, from about 0.3 to about 1.0 weight percent, or from about 0.5 to about 1.0 weight percent, or greater than about 0.6 percent. According to other embodiments (e.g., for marine diesel cylinder lubricants), the ash level may be from about 1 to about 15%, from about 2 to about 12%, or from about 4 to about 10%. The overbased detergent may comprise from about 50% to about 100% of the sulfated ash, at least about 70% of the ash, at least about 80% of the ash, or 100% of the ash. The overbased detergent may provide up to about 95% or up to about 98% of the sulfated ash.

The lubricating composition may be a marine diesel cylinder lubricant (MDCL). This type of lubricant may be characterized by a high TBN level that is predominantly delivered by metal-containing, perchlorinated detergents. According to some embodiments, the lubricating composition may have a TBN of about 10 or greater, about 20 or greater, such as 10-100, 20-100, 30-100, 40-80, 30-75, or 40-70. A relatively small amount (e.g., less than about 5%) of the TBN can generally be contributed by other species, such as a nitrogen-containing dispersant, although the bases of the MDCL composition can be mostly contributed by the detergent component.

Other performance additives

The lubricating composition may contain other performance additives. These additives may include one or more of a metal deactivator, an auxiliary viscosity modifier, an auxiliary detergent, a friction modifier, an antiwear agent, a corrosion inhibitor, a dispersant, a dispersant viscosity modifier, an extreme pressure agent, an antioxidant, an antifoaming agent, a pour point depressant, And mixtures of two or more thereof.

The antioxidant may include a vulcanized olefin, a diarylamine, an alkylated diarylamine, a hindered phenol, a molybdenum compound (e.g., molybdenum dithiocarbamate), a hydroxy thioether, or a mixture thereof. The antioxidant may be present in a concentration ranging from about 0 wt% to about 15 wt%, from about 0.1 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt%, or from about 0.5 wt% to about 3 wt% of the lubricating composition.

The diarylamine or alkylated diarylamine can be phenyl alpha-naphthylamine (PANA), alkylated diphenylamine or alkylated phenylnaphthylamine or mixtures thereof. The alkylated diphenylamine can be a di-nonylated diphenylamine, nonyldiphenylamine, octyldiphenylamine, dioctylated diphenylamine, didecylated diphenylamine, decyl diphenylamine, and mixtures thereof. According to one embodiment, the diphenylamine may comprise nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine or mixtures thereof. According to one embodiment, the diphenylamine may comprise nonyl diphenylamine or dinonyl diphenylamine. The alkylated diarylamines may include octyl, dioctyl, nonyl, dinonyl, decyl or didecylphenyl naphthylamines.

The hindered phenol antioxidant may contain secondary butyl and / or tertiary butyl groups as steric hinders. The phenolic group may be further substituted by a bridging group which bonds to a hydrocarbyl group (generally linear or branched alkyl) and / or to a secondary aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 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 under the trade name Irganox (TM) L-135 from Shiba. Such materials can be represented by the formula:

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

Examples of molybdenum dithiocarbamates that can be used as antioxidants include R.T. Commercially available under the trade names Vanlube 822 ™ and Molyvan ™ A and Asahi Denka Kogyo KK under the trade names Adeka Sakura-Lube ™ S-100, S-165, S-525 and S-600 from Vanderbilt Co., And mixtures thereof.

The lubricating composition may further comprise one or more auxiliary viscosity modifiers. Examples are hydrogenated styrene-butadiene rubbers, ethylene-propylene copolymers, polymethacrylates, polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, poly (alkylstyrenes), polyolefins, maleic anhydride- Esters of copolymers (such as those described in International Application WO 2010/014655), esters of maleic anhydride-styrene copolymers, or mixtures of two or more thereof.

Dispersing agent viscosity modifiers include ethylene-propylene copolymers functionalized with functionalized polyolefins such as maleic anhydride and an acylating agent such as an amine; Polymethacrylates functionalized by amines; Or an esterified styrene-maleic anhydride copolymer reacted with an amine. A more detailed description of dispersant viscosity modifiers can be found in International Publication WO 2006/015130 or U.S. Patent Nos. 4,863,623; 6,107,257; 6,107,258; And 6,117,825. Dispersant viscosity modifiers are described in U.S. Patent No. 4,863,623 (col. 2, line 15 to col. 3, line 52) or International Publication WO 2006/015130 (col. 2, paragraphs [0010] and paragraphs [0065] ). ≪ / RTI > The dispersant viscosity modifier may be present at a concentration of less than about 15 wt%, less than about 10 wt%, or about 0.05 wt% to about 5 wt%, or from about 0.2 wt% to about 2 wt%, of the lubricating composition.

The lubricating composition may further comprise one or more dispersing agents. The dispersing agent may be a succinimide dispersant, a Mannich dispersant, a succinic amide dispersant, a polyolefin succinic acid ester, an amide or an ester-amide, or a mixture thereof. The dispersing agent may be present as a single dispersing agent, or may be present in a mixture of two or more (e.g., three) different dispersing agents, at least one of which may be a succinimide dispersant.

The succinimide dispersant may be derived from one or more aliphatic polyamines. The aliphatic polyamines can be aliphatic polyamines such as ethylene polyamines (i.e., poly (ethylene amines)), propylene polyamines, butylene polyamines, or mixtures of two or more thereof. The aliphatic polyamine may be ethylene polyamine. The aliphatic polyamine may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine distillation residue or a mixture of two or more thereof.

The succinimide dispersant can be derived from aromatic amines, aromatic polyamines or mixtures thereof. An aromatic amine may have at least one aromatic moiety bonded by a hydrocarbylene group and / or a hetero atom, for example, 4-aminodiphenylamine. The aromatic amine may be a nitro-substituted aromatic amine. Examples of nitro-substituted aromatic amines may include 2-nitroaniline, 3-nitroaniline and 4-nitroaniline. 3-Nitroaniline may be particularly useful. Other aromatic amines may be present with the nitroaniline. Nitroaniline and, optionally, further condensation products of Disperse Orange 3 (i.e., 4- (4-nitrophenylazo) anilene) are disclosed in U.S. Patent Publication No. 2006/0025316.

The dispersing agent may comprise a polymer functionalized by an amine, such as a succinimide dispersing agent. Amines include amines having two or more, three or more, or four or more aromatic groups, such as about 4 to about 10 aromatic groups, about 4 to about 8, or about 4 to about 6 amines, and at least one primary Or a secondary amino group, or alternatively 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 any combination of at least about four aromatic groups and at least two secondary amino groups 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 three or four aromatic groups may be represented by formula (1): < EMI ID =

(1)

Independently, each variable is as follows: R ¹ can be hydrogen or a C _{1 -5} alkyl group (usually hydrogen); R ² can be hydrogen or a C _{1 -5} alkyl group (usually hydrogen); U may be an aliphatic, cycloaliphatic or aromatic group (where U is aliphatic, the aliphatic group may be a linear or branched alkylene group containing from 1 to about 5 carbon atoms or from 1 to about 2 carbon atoms); w can be from 1 to about 10, 1 to about 4 or 1 to 2 (typically 1). When U is an aliphatic group, U may be an alkylene group containing from 1 to about 5 carbon atoms. Alternatively, the amine can also be represented by the formula (1a)

(1a)

Wherein each variable U, R ¹ and R ² is as defined above and w is 0 to about 9, 0 to about 3 or 0 to about 1 (generally 0).

The dispersing agent may be a polyolefin succinic acid ester, an amide or an ester-amide. For example, the polyolefin succinic acid ester may be a polyisobutylene succinic ester of pentaerythritol, or a mixture thereof. The polyolefin succinic acid ester-amide can be obtained by reacting a polyisobutylene (hereinafter referred to as " polyisobutylene ") resin obtained by reacting with an alcohol (e.g., pentaerythritol) and an amine (e.g., polyamine, generally diethylene triamine, polyamine distillation residue, tetraethylene pentamine It may be new.

The dispersing agent may be an N-substituted long chain alkenyl succinimide. An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide, i.e. a polyisobutene substituted succinimide dispersant. Generally, the polyisobutylene in which the polyisobutylene succinic anhydride is derived has a number average molecular weight ranging from about 350 to about 5000, from about 550 to about 3000, or from about 750 to about 2500. The succinimide dispersant and its preparation method are disclosed in, for example, US Patent Nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433 and 6,165,235,7,238,650, 355 < / RTI > 895A.

Dispersants can also be post-treated in a conventional manner by reaction with any of a variety of agents. These include, but are not limited to, boron compounds such as boric acid, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid such as terephthalic acid, hydrocarbonsubstituted succinic anhydride, Phosphorus compounds. The post-treated dispersant may be borated. The post-treated dispersant can be obtained from the reaction of the dimercaptothiadiazole with the dispersant. The post-treated dispersant can be obtained from the reaction of phosphoric acid or phosphorous acid with a dispersant.

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

If the dispersant contains a basic nitrogen atom, this base can be measured by the TBN of the dispersant. According to one embodiment, the TBN of a useful succinimide dispersant can be from about 10 to about 30 on an oil-free (calibrated) basis, corresponding to from about 5 to about 15, as measured in a dispersant sample containing 50% oil will be.

According to one embodiment, the amount of the viscosity index enhancement of the polymer (i.e., the amount of VI polymer) is from about 0.5 to about 2 wt%, the amount of dispersant is from about 0.01 to about 20 wt%, and the amount of overbased sulfonate is from about 0.05 To about 5% by weight.

Friction modifiers include long chain fatty acid derivatives of amines, long chain fatty esters or derivatives of long chain fatty epoxides; Fatty imidazoline; Amine salts of alkylphosphoric acids; Fatty alkyl tartrates; Fatty alkyltartramides; Fatty alkyltartramides; Fatty glycolate; And fatty glycol amides. As used herein, the term "fatty alkyl or fats" associated with friction modifiers refers to carbon chains, generally straight chain carbon, having from about 10 to about 22 carbon atoms. Alternatively, a mono-branched alkyl group may be used in place of the fatty alkyl group. Typical mono-branched alkyl groups may include beta-branched groups such as 2-ethylhexyl, 2-propylheptyl, and the like. The friction modifier may be present in the lubricating composition at a concentration ranging from 0 wt% to about 6 wt%, from about 0.01 wt% to about 4 wt%, from about 0.05 wt% to about 2 wt%, or from about 0.1 wt% to about 2 wt% of the lubricating composition.

Examples of friction modifiers that can be used include long chain fatty acid derivatives of amines, fatty esters or fatty epoxides; Fatty imidazolines, such as condensation products of carboxylic acids and polyalkylene-polyamines; Amine salts of alkylphosphoric acids; Fatty alkyl tartrates; Fatty alkyltartramides; Fatty alkyltartramides; Fatty phosphonates; Fatty phosphite; Borated phospholipids; Borated fatty epoxide; Glycerol esters; Borated glycerol esters; Fatty amines; Alkoxylated fatty amines; Borated alkoxylated fatty amines; Hydroxyalkyl and polyhydroxyalkyl fatty amines such as tertiary hydroxyalkyl fatty amines; Hydroxyalkyl amides; Metal salts of fatty acids; Metal salts of alkyl salicylates; Fatty oxazoline; Fatty ethoxylated alcohols; A condensation product of a carboxylic acid and a polyalkylene polyamine; Or a reaction product of a fatty carboxylic acid with guanidine, aminoguanidine, urea or thiourea and salts thereof.

The friction modifier may also include materials such as vulcanized fatty compounds and monoesters of aliphatic carboxylic acids and polyols, which may or may not be derived from olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, and sunflower oils or soybean oil have.

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 lubricating composition may optionally further comprise at least one antiwear agent. Examples of suitable antiwear agents include, but are not limited to, tartrate, tartrate, oil soluble amine salts of phosphorus compounds, vulcanized olefins, metal dihydrocarbyl dithiophosphates (e.g., zinc dialkyldithiophosphates), phosphites Phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-coupled thiocarbamates, and bis (S-alkyldithiocarbamates) ) ≪ / RTI > disulfide. An anti-wear agent may comprise tartrate or tartrate as disclosed in International Publication WO 2006/044411 or Canadian patent CA 1 183 125, according to one embodiment. The tartrate or tartrate may contain an alkyl group (s), wherein the sum of the carbon atoms present in the alkyl group is at least about 8.

Other additives may include oil soluble titanium compounds as disclosed in U.S. Patent No. 7,727,943 and U.S. Patent Publication No. 2006/0014651. It can act as an antiwear agent, a friction modifier, an antioxidant, a sediment control additive, and the like. These additives may be polyfunctional additives. For example, one of these additives can provide both abrasion resistance and oxidation resistance. The oil soluble titanium compound may be titanium (IV) alkoxide. The titanium alkoxide can be prepared from monohydric alcohols, polyols or mixtures thereof. The monovalent alkoxide may contain from 2 to about 16 carbon atoms, or from 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 contain an adjacent 1,2-diol or an alkoxide of a polyol. The 1,2-proximate diol may contain fatty acid monoesters of glycerol, such as oleic acid esters.

The oil soluble titanium compound may be a titanium carboxylate. The titanium carboxylate may be derived from a carboxylic acid and a titanium alkoxide selected from the group consisting of a carboxylic acid having from about 22 carbon atoms to about 25 carbon atoms and a non-linear monocarboxylic acid. Examples of the titanium / carboxylic acid product 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, Benzoic acid, neodecanoic acid, and the like. Methods for producing such titanium / carboxylic acid products are described, for example, in U.S. Patent No. 5,260,466.

Extreme pressure (EP) agents that are soluble in oils include sulfur- and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS ₂ derivatives (generally succinimide dispersants) of dispersants, derivatives of chlorinated hydrocarbon EP agents, . ≪ / RTI > Examples of such EP agents include chlorinated waxes; Dimercapto-1,3,4-thiadiazole or oligomers thereof, organic sulfides and polysulfides such as dibenzyldisulfide, bis- (1, 2, 3, Vulcanized alkylphenols, vulcanized dipentenes, vulcanized terpenes and vulcanized Diels-Alder adducts, phosphorus sulfided hydrocarbons such as terpentine or methyl oleate and phosphorus sulfide (e.g., chlorobenzyl) disulfide, dibutyl tetrasulfide, vulcanized methyl esters of oleic acid, The reaction product of In esters such as hydrocarbons and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; Diphenylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphite; Metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol dic acid; Amine salts of alkylphosphoric acid and dialkyldithiophosphoric acid amine salts of dialkyldithiophosphoric acid, such as amine salts of dialkyldithiophosphoric acid reacted with P ₂ O ₅ after reaction with propylene oxide; And mixtures thereof (as described in US 3,197,405).

Defoamers that may be used in the lubricating composition may include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and, optionally, vinyl acetate; The anti-emulsifying agent may include fluorinated polysiloxane, trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymer.

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

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

Examples of the metal deactivator include derivatives of benzotriazole (generally, tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithio-benzothiazole . ≪ / RTI > In addition, metal deactivators may be described as corrosion inhibitors.

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

Industrial availability

The lubricating composition may be used to lubricate the machine by supplying the lubricant described herein to the machine. The machinery may be an internal combustion engine, such as a gasoline-fired or diesel-fired automobile engine, a medium diesel engine, a marine diesel engine, or a regulated gas engine. These organs can be sump lubricated and the lubricant is provided as a sump, from which the moving parts of the engine can be lubricated. Alternatively, the lubricant may be supplied from a separate source rather than being part of the sump.

The internal combustion engine may be a diesel fueled engine (generally a medium diesel engine), a gasoline engine, a natural gas engine, a mixed gasoline / alcohol fuel engine, or a hydrogen fueled 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 medium diesel engine.

The internal combustion engine may be a two-stroke or four-stroke engine. Suitable internal combustion engines may include a marine diesel engine (which may include cylinders lubricated with such lubricants), an aircraft piston engine, a diesel engine under degradation, and an engine and truck engine. Marine diesel engines can be lubricated with marine diesel cylinder lubricants (typically in two-stroke engines), system oil (typically in two-stroke engines) or crankcase lubricants (typically in four-stroke engines).

One of the internal combustion engines is a direct injection type combustion engine in which fuel is directly injected into the cylinder. Specific examples of the direct injection type include a wall-direct injection type engine and a spray induction type direct injection type engine. The lubricating composition can be used to lubricate a gasoline direct injection engine.

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

(I) the sulfur content is less than about 0.5 wt%, (ii) the phosphorus content is less than about 0.12 wt%, and (iii) the sulfated ash content is from about 0.5 wt% to about 1.1 wt% Or more than one.

The lubricating composition can be a marine diesel cylinder lubricant that can be used to lubricate marine diesel cylinders. Ship diesel cylinders may be present in a two-stroke marine diesel engine. Ship diesel cylinder lubricants are generally used for one pass and are consumed rather than stored in the sump. Such lubricants require a high level of detergent that imparts a high level of base to the lubricant as measured by TBN and are generally at least about 20, such as at least about 30, at least about 40, at least about 50, or at least about 70, About 80 or less, about 100 or less, or about 300 or less TBN levels.

The lubricating composition can be used in a method of operation of an internal combustion engine in which the piston sediment performance rating is increased and the viscosity increase is reduced.

According to one aspect, the disclosed technique provides a method for reducing the piston deposit level of an internal combustion engine, including lubrication of the engine with a lubricating composition as described herein. According to one aspect, the disclosed technology provides a lubricating oil, dispersant; And a detergent containing an overbased sulfonate wherein the total base of the sulfonate is in the range of from about 250 to about 600. The method of reducing the level of piston sediment in an engine lubricated by the lubricating composition From about 5 mol% to about 20 mol% structural units derived from ethylene, from about 50 mol% to about 90 mol% structural units derived from propylene, and from about 5 mol% to about 30 mol% structural units derived from butylene, ≪ / RTI >

Example  2

The fully compounded engine oil was tested for its "non-viscosity" advantage by combining it with a polymer prepared according to the disclosure set forth in Example 1 (hereinafter Polymer 1) and a commercial olefin copolymer (hereinafter, comparative OCP or Comp OCP) . According to the ASTM Sequence IIIG test, there is a significant improvement in sediment performance when polymer 1 is used compared to Comp OCP. Polymer 1 and Comp OCP have the properties shown in Table 1.

Polymer composition Polymer 1 Comp OCP Ethylene (mol%) 8.7 57 Propylene (mol%) 68.0 43 Butylene (mol%) 23.3 0 Mw 220,000 290,000 Shear stability index 35 45

The polymers of Table 1 are used to make the engine oil (EO) formulations shown in Table 2. Polymer 1 is used in the production of EO No. 1. [ Comp OCP is used in the manufacture of Comp EO. According to Table 2, a portion of the additive is provided with the blend oil and the wt% of the blend oil is presented for it. In addition, all numerical values in Table 2 are parts by weight unless otherwise indicated (all percentages are percentages by weight).

 Organic oil (EO) formulation Explanation EO No.1 Comp EO Group II base oil 100 100 Polyisobutene (PIB) substituted succinimide dispersants; PIB Mn = 2200; 14 TBN 4 4 Abrasion resistance agent: mixed C ₃ -C ₆ secondary zinc dialkyl dithiophosphate (ZDDP) (10% oil) 0.2 0.2 Anti-wear agent: C ₆ Secondary ZDDP (8% oil) 0.66 0.66 Diarylamine antioxidant 0.8 0.9 Hindered phenol ester antioxidant 0.45 0.35 Vulcanized olefin antioxidant 0.2 0.2 Fat amide friction modifier 0.1 0.1 300 TBN Ca sulphonate (42% oil) 0.88 0.88 400 TBN Ca sulphonate (42% oil) 0.4 0.4 450 TBN Na sulfonate (31% oil) 0.25 0.25 Silicone defoamer 0.009 0.009 Pour Point Depressant: Esterified maleic anhydride-styrene copolymer 0.25 0.25 Polymer 1 (86% oil) [oil-free amount] 5.25 [0.73] Comp OCP (91% oil) [oil-free amount] 7 [0.63]

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

ASTM Sequence IIIG test results EO No.1 Comp EP Viscosity grade 5W-30 5W-30 Base oil viscosity at 100 캜 (cSt) 4.8 4.9 Lubricating composition, kinematic viscosity at 100 DEG C (cSt) 9.83 10.3 High temperature high shear viscosity (cP) ASTM D4683 2.87 3.02 Low temperature cranking simulator (cP at -30 ° C) ASTM D4684 6324 6152 Viscosity increase 76.9% 138% Weighted piston sediment assessment 4.05 3.88

The results of these tests show a significant decrease in the enrichment of the engine oil and a significant increase in the piston sediment evaluation when using EO No.1 compared to Comp EO.

While the invention has been described in terms of various aspects, it is to be understood that various modifications thereof may become apparent to those skilled in the art through this disclosure. It is, therefore, to be understood that the invention includes all such modifications as fall within the scope of the appended claims.

The amount of each chemical component described is the amount excluding any solvent or diluent oil that may normally be present in a commercial product (i.e., on an active chemical basis), unless otherwise indicated, e.g., the amount of oil is not indicated. However, unless otherwise indicated, each chemical or composition referred to herein should be interpreted to be a commercially available material that may contain isomers, by-products, derivatives and other materials that are generally understood to be present on a commercial grade .

It is known that some of the foregoing materials may interact in the final formulation, so that the components of the final formulation may differ from those initially added. For example, metal ions (e.g., metal ions of a detergent) can migrate to other acidic or anionic sites of other molecules. The product thus formed, for example, the product formed when the present invention is used for its intended use, may not be easy to explain. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; The present invention includes a composition prepared by mixing the aforementioned components.

Each of the foregoing documents is incorporated herein by reference, including any prior applications claiming priority, whether specifically listed above. Any reference to any such document is not an admission that such document is prior art and constitutes the general knowledge of a person skilled in the art under any or all jurisdiction. It should be understood that the term "about" is used throughout this specification to specify amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc., unless the context clearly dictates otherwise. It is to be understood that the amounts, ranges and limitations of the upper and lower limits set forth herein may be combined independently. Likewise, the scope and amount of each element of the invention may be used with a range or amount to any other element. As used herein, the expression "consisting essentially of" allows inclusion of materials that do not materially affect the basic properties and novel properties of the composition under consideration.

Claims (27)

Oils having a lubricating viscosity of at least 60% by weight;
0.001 to 2% by weight of a viscosity index improving polymer,
From 5 mol% to 10 mol% of structural units derived from ethylene,
60 mol% to 70 mol% of structural units derived from propylene, and
From 15 mol% to 30 mol% of structural units derived from butylene,
A number average molecular weight of 150,000 to 250,000 and a molecular weight distribution Mw / Mn of 2 to 2.5;
0.01 to 20% by weight of a succinimide dispersant; And
0.05 to 5% by weight of a detergent, comprising an overbased calcium, magnesium, or sodium sulfonate, wherein the sulfonate is a detergent having a total base in the range of 250 to 600
≪ / RTI > The composition of claim 1, wherein the polymer has a viscosity index enhancement amount of 0.5 to 2% by weight. 3. The composition of claim 1 or 2 wherein the dispersant comprises a polyisobutene substituted succinimide dispersant. 3. The composition of claim 1 or 2, wherein the overbased sulfonate is present in the lubricant composition in an amount to provide TBN in the range of 1 to 10 (total base). 3. The composition of claim 1 or 2, further comprising at least one of an antiwear agent, an antioxidant, a friction modifier, a pour point depressant, or a defoamer. The composition according to any one of claims 1 to 3, further comprising at least one additive selected from the group consisting of at least one metal deactivator, an additional auxiliary viscosity modifier, an auxiliary detergent, a corrosion inhibitor, a dispersant viscosity modifier, an extreme pressure agent, an anti-emulsifier, a seal swelling agent or a mixture of two or more thereof Composition. 3. The composition of claim 1 or 2, wherein the oil of lubricating viscosity comprises a Group II oil. 3. The composition according to claim 1 or 2, wherein the oil of lubricating viscosity has a kinematic viscosity at 100 DEG C of less than 5 cSt and a viscosity index of less than 130. 3. A composition according to claim 1 or 2, Polymerizing ethylene, propylene, and butylene in the presence of a catalyst capable of stereoregular polymerization in an isotactic configuration or a syndiotactic configuration;
A propylene-derived structural unit of 60 mol% to 70 mol%, and a butylene-derived structural unit of 15 mol% to 30 mol%, wherein the number average molecular weight is 150,000 to 250,000 and the molecular weight distribution Mw / Mn is from 2 to 2.5.
≪ / RTI > of claim 1, wherein the lubricating composition is a lubricating composition. The production process according to claim 9, wherein the catalyst is a metallocene catalyst capable of performing steric polymerization in an isotactic arrangement. delete 3. The composition according to claim 1 or 2, wherein the sulfur content is 1 wt% or less, the phosphorus content is 0.2 wt% or less, and the sulfated ash content is in the range of 0.3 to 1.2 wt%. A method for lubrication of an internal combustion engine, comprising feeding the lubricating composition of any one of claims 1 or 2 to the engine. A method for reducing the piston sediment level of an internal combustion engine, comprising lubrication of the engine with the lubricating composition of claim 1 or claim 2. delete delete delete delete delete delete delete delete delete delete delete delete delete