CN101945981A - Be used for the marine diesel cylinder lubrication agent of improved fuel efficiency - Google Patents

Be used for the marine diesel cylinder lubrication agent of improved fuel efficiency Download PDF

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Publication number
CN101945981A
CN101945981A CN2008801267192A CN200880126719A CN101945981A CN 101945981 A CN101945981 A CN 101945981A CN 2008801267192 A CN2008801267192 A CN 2008801267192A CN 200880126719 A CN200880126719 A CN 200880126719A CN 101945981 A CN101945981 A CN 101945981A
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Prior art keywords
acid
oil
composition
lubricant
engine
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S·J·库克
A·梅修
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Lubrizol Corp
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Lubrizol Corp
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Priority claimed from PCT/US2008/085617 external-priority patent/WO2010016856A1/en
Publication of CN101945981A publication Critical patent/CN101945981A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/402—Castor oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Comprise the lubricant compositions of organic friction modifiers of the oil of lubricant viscosity and 0.01-5 weight %, be applicable to and lubricate the oil engine that in steam jacket, is higher than 150 ℃ of operations, marine diesel engine for example, the essentially no molybdenum compound of described lubricant compositions.

Description

Be used for the marine diesel cylinder lubrication agent of improved fuel efficiency
Background technology
The present invention relates to be used for the lubricant of oil engine, and particularly marine diesel cylinder lubrication agent.
The improvement fuel economy is the interest place from relatively little petrol power engine to the operation of nearly all engine of big marine diesel engine.There are economy and environmental advantages simultaneously for the improved fuel economy in the shipping-trade, maximum influence perhaps comes from the improvement in marine diesel cylinder lubrication agent (MDCL) technology, for example by the contact between piston ring and the steam jacket in these engines of improvement.Particularly in shipping-trade, on the improvement fuel economy, finished extensive work by engineering method by original equipment manufacturers.
In petrol engine and less diesel motor, improve efficient by means of in engine, reducing friction and expended significant effort by modified lubricant.Yet, when being applied to the lubricant that is used for marine diesel engine with this method, trial has other challenge, because the temperature that runs into usually with lubricant in littler engine is 100 ℃ or lower comparing according to appointment, the quite higher service temperature of this engine, usually surpass 150 ℃, for example in the zone (being steam jacket) lubricated, be 175-275 ℃ by the agent of marine diesel cylinder lubrication.Natural gas fueled engines (stationary engine) also will at high temperature be moved usually.
United States Patent (USP) 4,683,069 discloses the glyceryl ester that the comprises 0.05-0.2 weight % economy additive that acts as a fuel.Disclosed glyceride type comprises GMO.Lubricating oil composition is applicable to gasoline or diesel motor.
U.S. Patent application 2003/134758 discloses the heavy duty diesel engine lubricating oil composition in the fuel economy that is used for improving heavy duty diesel engine, under mixed lubrication or condition of boundary lubrication, can reduce the purposes of one or more compounds of the significant quantity of frictional coefficient.Embodiment 1 comprises glyceryl monooleate.
U.S. Patent application 2003/134758 discloses the heavy duty diesel engine lubricating oil composition that is used to improve fuel economy.Processing rate can be 0.01-5.0 weight %, is preferably 0.15-0.5 weight %.Embodiment 1 discloses the composition of the glyceryl monooleate with 0.3 quality %, and embodiment 2 comprises three nuclear molybdenum dithiocarbamates as low friction compound simultaneously.
United States Patent (USP) 6,074,993 disclose the lubricating composition that shows improved fuel economy.Said composition also comprises at least a organic oil dissolubility friction modifiers except that other material.Claim 12 discloses ethoxylated amine.Lubricating composition can be used in the preparaton of crankcase oil.Heavy duty diesel engine is mentioned as possible crankcase oil with oil.
U.S. Patent application 2007/0015672 discloses the driving mechanism with regard to the fuel economy that is used for gasoline and diesel motor, and it has caused the level of used organic friction modifiers in the lubricating oil composition to improve; Regrettably, between friction modifiers and over-based detergent such as high alkaline calcium sulfonate, there is compatibling problem.Therefore, this invention relates to and improves the consistency between the friction modifiers and over-based detergent in the lubricating oil composition.Wherein embodiment comprises the purposes of GMO and/or ethoxylated tallow amine.
United States Patent (USP) 6,333,298 disclose by adopting at least a friction modifiers to show the no molybdenum lube oil composition of improved fuel economy and fuel economy maintain property.Claim 8 regulation friction modifiers is an ethoxylated amine.Lubricating oil composition is applicable to heavy duty diesel engine.
United States Patent (USP) 6,074,993 disclose the lubricating oil composition that shows improved fuel economy and humid clutch nature of friction, and described composition comprises: the oil of lubricant viscosity; At least a high alkalinity calcium; At least a organic oil dissolubility friction improver; With at least a dialkyl phosphorodithioic acid zn cpds, the TBN of wherein said composition is at least 3.6.Ethoxylated amine is disclosed in the claim 12.The crankcase that lubricating oil composition is suitable for being used for spark-ignited and compression ignition engine is with lubricating oil (being bus engine oil, heavy duty diesel engine oil and passenger vehicle diesel engine oil).
U.S. Patent application 2006/276354 discloses the automobile engine oil of combination of the mixture that is used for comprising adhoc basis oil plant or oil base stock and antifriction additive to improve the fuel economy and the lubricant compositions in fuel economy life-span of automobile engine oil.Antifriction additive is specific part polyol ester and can comprises specific saturated primary amide.The regulation motor car engine comprises gasoline and heavy-duty diesel oil.Embodiment discloses the GMO in the specific group compound.
U.S. Patent application 2006/183647 disclose comprise tartaric acid derivatives lubricant compositions as fuel economy improvers in the crankcase oil and anti-wear agent.Tartaric acid derivatives comprises tartrates, winestone acid imide and tartaroyl amine.Lubricating oil has low-sulfur, phosphorus and ash content.The purposes that these lubricant compositions are used for automobile and truck engine, 2 two-stroke engines, aviation piston engine, peculiar to vessel and rail diesel engine is further disclosed.
U.S. Patent application 2006/079413 discloses the lubricant formulation agent of using the tartarize compound to reduce wearing and tearing and rub and improve fuel economy in low-sulfur, low ash and low-phosphorous lubricant.The disclosure content has further been put down in writing the purposes of lubricant in automobile and truck engine, 2 two-stroke engines, aviation piston engine, peculiar to vessel and rail diesel engine.The combination that tartarize compound and other are selected from the friction modifiers of glyceryl monooleate class, oleoyl amine, di-alcohol fat amine and composition thereof is also disclosed.
SAE Special Publication SP-1550, " Topics in Lubricants ", 225-231 page or leaf, people such as Sasak, 2000, disclose by the 5W-30 that comprises molybdenum dithiocarbamate is provided the development that complete synthetic oil prolongs the high-performance heavy duty diesel engine oil of oil draining period.
There's a widespread conviction that molybdenum compound is suitable uniquely is used for the lubricant that high-temperature engine is used as friction modifiers for people.Yet, because comprise expense and reduce the various reasons that heavy metal enters the output of environment, wish to prepare the lubricant of avoiding using molybdenum compound, consume lubricating oil and discharge its products of combustion because high-temperature engine such as marine diesel are typically designed to.
Therefore, the invention provides the method that a kind of lubricant that the good lubrication performance still can be provided by the lubricant that does not comprise molybdenum compound is provided improves the fuel economy of high-temperature engine such as marine diesel.
Lubricating composition of the present invention can be used for explosive motor, for example diesel-fueled engine, gasoline engines, natural gas fueled engines or blend gasoline/alcohol fuel engine.In one embodiment, explosive motor is the 4-stroke and is the 2-two-stroke engine in another embodiment.In one embodiment, the output rating of engine is at least 1600 kilowatts.In one embodiment, diesel-fueled engine is a marine diesel engine.In some marine diesel engine, lubricant is produced specifically that to be used for and to offer cylinder wall be steam jacket, so that the interface of lube pistons and cylinder wall, rather than is provided for or from crankcase.Because marine diesel engine is operated under comparatively high temps usually, operating period the temperature of steam jacket can be generally 150 ℃ or higher, for example 175 ℃-300 ℃.For this lubricating condition, specially designed lubricant is desirable.
Summary of the invention
In one embodiment, the invention provides be applicable to lubricated to be higher than the lubricant compositions of the engine of 150 ℃ of operations at the steam jacket place, it comprises the oil of lubricant viscosity and organic friction modifiers of 0.01-5 weight %, and described lubricant compositions does not have molybdenum compound substantially.
The present invention also is provided for lubricating provides this paper aforesaid lubricant compositions to be higher than the method for the engine of 150 ℃ of operations at the steam jacket place, to comprise to it.
Detailed Description Of The Invention
Various preferable feature and embodiment will be described below by non-limitative illustration.
Lubricant described herein comprises the oil of lubricant viscosity.The oil of lubricant viscosity can have the SAE level of SAE 30, SAE 40, SAE 50 or SAE 60.In one embodiment, the oil of lubricant viscosity can be SAE 50 oil.SAE 50 oil have 16.3mm usually at 100 ℃ 2/ s-21.9mm 2The kinematic viscosity of/s.
Oil also is called base oil, any base oil among the group I-V that stipulates among the Base Oil Interchangeability Guidelines of optional comfortable American Petroleum Institute (API) (API).5 kinds of base oil groups are as follows:
Base oil kind sulphur (%) saturation ratio (%) viscous index
The 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 all polyalphaolefins of IV (PAO)
Group V be not included in group all among I, II, III or the IV other
Group I, II and III are mineral oil basis oil plant.Then, the oil of lubricant viscosity can comprise natural or ucon oil and composition thereof.Usually use the mixture of mineral oil and synthetic oil, particularly poly-a-olefin oil and polyester oil.
That natural oil comprises mineral lubricating oils such as liquid petroleum and solvent treatment or acid-treated paraffinic hydrocarbons, naphthenic hydrocarbon or blended paraffinic hydrocarbons-naphthenic hydrocarbon type mineral lubricating oils.The oil of hydrotreatment or hydrocracking is included in the scope of oil of useful lubricant viscosity.
Oil derived from the lubricant viscosity of coal or shale also is useful.Ucon oil comprises that hydrocarbon-type oil and halogenated hydrocarbon oil is as olefines of polymerization and copolymerization and composition thereof, alkyl benzene, polyphenyl class (for example biphenyl class, Terphenyls and alkylation polyphenyl class), alkylation diphenyl ether and alkylation diphenyl sulfide class and their derivative, analogue and homologue thereof.Oxygen ethene polymers and multipolymer and derivative thereof, and wherein terminal hydroxyl group constitutes the known ucon oil of spendable other kind for example by esterification or etherification modified those.The ucon oil of spendable another suitable species comprises the ester of dicarboxylic acid and by C 5-C 12Those that monocarboxylic acid and polyvalent alcohol or polyol ethers make.
The ester class, polymeric tetrahydrofuran derivatives, silicon-based oil that other ucon oil comprises phosphorated acid as poly-alkyl-, poly-aryl-, poly-alkoxyl group-or poly-aryloxy-silicone oil and silicic acid ester oil.
The cycloalkane oil of hydrotreatment also is known and can be used, and by the oil that fischer-tropsch gas-liquid synthetic method prepares, comprises fischer-tropsch wax or other wax of hydroisomerization.
The above openly not refining of type, refining and refining oil or natural or synthetic (and mixture of two or more any of theses) can be used in the composition of the present invention again.Refining oil is not directly to obtain and be not further purified those of processing from natural or synthetic source.Refining oil is similar to not refining oil, except they are further handled in one or more purification steps and improve one or more character.Refining oil is to obtain by such method being applied to used refining oil again, and promptly it is to be used to obtain those of refining oil similar.This refining oil is more often processed in addition by the technology that is used to remove exhausted additive and oil decomposition product.
Lubricant compositions described herein also will comprise organic friction modifiers.It is as well known to those skilled in the art that friction modifiers is generally.The catalogue of useful friction modifiers is included in United States Patent (USP) 4,792, in 410.The inventory of organic friction modifiers comprises:
(i) aliphatic phosphites class
(ii) fatty acid acyl amine
(iii) aliphatic epoxide
(iv) boration aliphatic epoxide
(v) fatty amine
(vi) glyceride type
(vii) boration glyceride type
(viii) alkoxylated fats amine
(ix) boration alkoxylated fats amine
(x) fatty acid metal salt (amount is at least 2 or 3% in certain embodiments)
(xi) olefine sulfide class
(xii) aliphatics imidazolines
(xiii) condensation product of carboxylic acid and polyalkylene polyamine
(xiv) metal-salt of alkyl salicylate
(xv) amine salt of alkylphosphonic acid carboxylic acid
(xvi) tartaric acid derivatives
(xvii) fatty acid
And composition thereof.
Being represented as separately of these type friction modifiers is known and commercially available.For example, (i) the aliphatic phosphites class is generally formula (RO) 2PHO.Exemplary dialkyl phosphites shown in preceding formula usually with formula (RO) on a small quantity (HO) the monoalkyl phosphorous acid ester of PHO exist.In these structures, term " R " typically refers to alkyl.Certainly, might alkyl actual for thiazolinyl and therefore term used herein " alkyl " and " alkylation " will comprise the unsaturation alkyl in phosphorous acid ester.Phosphorous acid ester will have enough alkyl usually so that the enough oleophylics of phosphorous acid ester.Alkyl can be nonbranched substantially.Many suitable phosphorous acid esters are commercially available and can be as United States Patent (USP) 4,752, put down in writing in 416 synthetic.Phosphorous acid ester can comprise 8-24 carbon atom in each R group.Aliphatic phosphites can comprise 12-22 carbon atom or 16-20 carbon atom in each aliphatic group.In one embodiment, aliphatic phosphites can be formed by the oil base group, thereby has 18 carbon atoms in each aliphatic group.
(iv) the boration aliphatic epoxide is from Canadian Patent 1,188, and is known in 704.These oil soluble boron-containing compositions are by making boric acid or boron trioxide and at least a aliphatic epoxide prepared in reaction with following formula under 80 ℃-250 ℃ temperature:
Figure BPA00001197609100071
R wherein 1, R 2, R 3And R 4Respectively do for oneself hydrogen or aliphatic group, or its any two form cyclic group with epoxy carbon atom or atom that they connected.Aliphatic epoxide can comprise at least 8 carbon atoms.
(iii) non-boration aliphatic epoxide also can be used as friction modifiers.
The boration amine is usually from United States Patent (USP) 4,622, and is known in 158.Boration amine friction modifiers (comprising (ix) boration alkoxylated fats amine) is usually by aforesaid boron compound and corresponding amine reaction preparation easily.Amine can be the tertiary amines of simple aliphatic amide or hydroxyl.The boration amine can be by adding aforesaid boron reactant in the amine reactant and at 50 ℃-300 ℃, follows stirring heating gained mixture under preferred 100 ℃-250 ℃ or 150 ℃-230 ℃ and prepare.The continuation reaction stops to emit the demonstration reaction up to water byproduct and finishes from reaction mixture.
Comprise known and industrial alkoxylated fats amine that buy from Akzo Nobel at the amine that is used for preparing the boration amine with the trade mark " ETHOMEEN ".These ETHOMEEN TMThe representative example of material is ETHOMEEN TMC/12 (two [2-hydroxyethyl] coco amine); ETHOMEEN TMC/20 (polyoxyethylene [10] coco amine); ETHOMEEN TMS/12 (two [2-hydroxyethyl] soybean amine); ETHOMEEN TMT/12 (two [2-hydroxyethyl]-tallow amine); ETHOMEEN TMT/15 (polyoxyethylene-[5] tallow amine); ETHOMEEN TM0/12 (two [2-hydroxyethyl] oleyl amine); ETHOMEEN TM18/12 (two [2-hydroxyethyl] octadecylamine); And ETHOMEEN TM18/25 (polyoxyethylene [15] octadecylamine).The fatty amine of fat amine and ethoxylation also is documented in United States Patent (USP) 4,741, in 848.
(viii) oxyalkylated fatty amine is with (v) fatty amine itself (for example oleyl amine) is usually as friction modifiers.This amine is commercially available.
The boration of glycerine and not the boration fatty acid ester the two all can be used as friction modifiers.(vii) the boration fatty acid ester of glycerine carries out boration and removes the water that reacts preparing by fatty acid ester and boric acid with glycerine.In certain embodiments, have capacity boron, thus boron separately will with 1.5-2.5 the hydroxyl reaction that is present in the reaction mixture.Reaction can be under 60 ℃-135 ℃ temperature, carries out not having or exist under the condition of any suitable organic solvent such as methyl alcohol, benzene, dimethylbenzene, toluene or oil.
(vi) the fatty acid ester of glycerine itself can be by prepared in various methods well known in the art.Many these ester classes, for example glyceryl monooleate and glycerine list butter acid esters are with the production of industry rule film.Useful ester class is oil-soluble and can be from for example C8-C22 lipid acid of discovery and following more write up or its mixture preparation natural product.Although use glycerol fatty acid monoester usually, also can use single-and the mixture of diester class.For example, the industry glycerol monoleate is considered to comprise the chemical substance " glyceryl monooleate " of about 60 ± 5 weight %, and 35 ± 5% glycerol dioleate and be lower than about 5% trioleate and oleic acid.Amount as this material described herein is the amount of technical grade material.
Lipid acid (xvii) can be used as friction modifiers or they can be used for preparing above-mentioned glyceride type; They also can be used for preparing their (x) metal-salt (for example Ca, Mg or Na salt, if for example expect ashless additive, it is any also can be excluded), (ii) amides and (xii) imidazolines, its any friction modifiers that can be used as.Fatty acid comprises and contains 6-24, for example those of 8-18 carbon atom.Acid can be branching or straight chain, saturated or undersaturated.Suitable acid comprises 2 ethyl hexanoic acid, capric acid, oleic acid, stearic acid, Unimac 5680, palmitinic acid, tetradecanoic acid, Zoomeric acid, linolic acid, lauric acid and linolenic acid, and from the acid of natural product tallow, plam oil, sweet oil, peanut oil, Semen Maydis oil and neat's foot oil.The example of fatty acid mixt is known as ready denier oil acid.Lipid acid, for example C18 acid can provide with another component such as over-based detergent.Lipid acid can be used for preparing some over-based detergent.
The suitable amide class comprise by with ammonia or with uncle or those of secondary amine class such as diethylamine and diethanolamine condensation prepared.The aliphatics imidazolines is the cyclic condensation product of acid and diamines or polyamines such as multiethylene polyamine.Imidazolines is represented by following structure usually:
Figure BPA00001197609100091
Wherein R is that alkyl and R ' are the alkyl of hydrogen or alkyl or replacement, comprises-(CH 2CH 2NH) n-group.In one embodiment, friction modifiers is the condensation product of C8-C24 lipid acid and polyalkylene polyamine, for example the product of Unimac 5680 and tetren.The condensation product of carboxylic-acid and polyalkylene amine (xiii) can be imidazolines or amides usually.
Olefine sulfide class (xi) is the industrial raw material as friction modifiers as everyone knows.Suitable olefine sulfide is according to United States Patent (USP) 4,957, those of 651 and 4,959,168 detailed instruction preparation.Wherein record for two or more are selected from the covulcanization mixture of the reactant of following material: the fatty acid ester of (1) at least a polyvalent alcohol, (2) at least a lipid acid, the fatty acid ester of (3) at least a alkene and (4) at least a monohydroxy-alcohol.Reactant (3), olefin component comprises at least a alkene and can be the aliphatic olefin that contains 4-40 carbon atom.Mixture and the sulphur source prepared in reaction of the covulcanization mixture of two or more reactants by making suitable reactants.
The metal-salt of alkyl salicylate (xiv) comprises salicylic calcium and other salt that long-chain (for example C12-C16) alkyl replaces.
The amine salt of alkylphosphonic acid carboxylic acid (xv) comprises the oil base of phosphoric acid and the salt of the amine of other long-chain ester class and following record.In this respect, useful amine is with trade(brand)name Primene TMUncle's aliphatic primary amine of selling.
The friction modifiers of these and other type for example is documented in the U.S. and openly applies among the 2006-0172899.
Be suitable for some friction modifiers of the present invention comprise with as above the record glyceride type (vi), its representative comprises glyceryl monooleate; The tartaric acid derivatives of following record; The fatty amine of ethoxylation, for the oxyalkylated fatty amine substance of as above record (viii) and the cocoa amine that comprises for example ethoxylation (from the Ethomeen of Akzo Chemical TM.C/12), the tallow amine (Ethomeen of ethoxylation TM.T12), the hydrogenated tallow amine (Ethomeen of ethoxylation TM18/12) and the fatty amine of boration ethoxylation (3 moles of Ethomeen for example TM.T-12 with the reaction product of 2 moles of boric acid); And as in above fatty acyl amide in (ii), for example oleylamide.
Generally speaking, tartaric acid derivatives is the representative derived from the compound of hydroxycarboxylic acid, and it can be used as friction modifiers usually.Therefore, in one embodiment, organic anti-wear agent is derived from least a hydroxycarboxylic acid diester, hydroxycarboxylic acid diamide, hydroxycarboxylic acid imide, hydroxycarboxylic acid ester-acid amide, hydroxycarboxylic acid esters-imide and hydroxycarboxylic acid imide-acid amides.In one embodiment, ash-free antiwear agent is derived from least a hydroxycarboxylic acid diester, hydroxycarboxylic acid diamide and hydroxycarboxylic acid ester-acid amide.
The example of suitable hydroxycarboxylic acid comprises citric acid, tartrate, oxysuccinic acid (or hydroxy succinic acid), lactic acid, oxyacetic acid, hydroxy-propionic acid, hydroxyl pentanedioic acid or its mixture.In one embodiment, ash-free antiwear agent is derived from tartrate, citric acid, hydroxy succinic acid, the acid of dihydroxyl list, monohydroxy diacid or its mixture.In one embodiment, ash-free antiwear agent comprises derived from tartaric compound.U.S. Patent application 2005/198894 discloses suitable hydroxy carboxylic acid compound and its method of preparation.Canadian Patent 1183125; U.S. Patent Publication No. 2006/0183647 and US-2006-0079413; U.S. Patent application 60/867402; With English Patent 2 105 743 A, the example of suitable tartaric acid derivatives is all disclosed.
In one embodiment, diester class, diamide, ester-acid amide or imide compound are derived from following formula (1a) and/or compound (1b).The detailed description (by making tartrate and primary amine reaction) that is used to prepare the suitable imido method of winestone is disclosed in United States Patent (USP) 4,237, in 022.The example of this winestone acid imide comprises by tartrate and hexylamine, lauryl amine, Semen Myristicae amine, palmitamide, stearylamine, Semen Myristicae oleyl amine (myristoleylamine), palm oleyl amine (palmitoleylamine), oleyl amine or inferior oleyl amine (linoleylamine) or its mixture condensation and forming.In one embodiment, ash-free antiwear agent comprises tartaric acid imide, diester class, diamide and ester-acid amide derivative.
In one embodiment, ash-free antiwear agent is represented by formula (1a) and/or compound (1b):
Figure BPA00001197609100111
Wherein
N is 0-10,0-6,0-4,1-4 or 1-2;
P is 1-5 or 1-2 or 1;
Y and Y ' be independently-O-,＞NH,＞NR 3Perhaps comprise by the R between two＞C=O group 1The different ring texturees (1c) of the imide group that-N＜group forms;
X is-CH independently 2-,＞CHR 4Or＞CR 4R 5,＞CHOR 6Or＞C (CO 2R 6) 2
R 1And R 2Be alkyl independently, comprise 1-150,4-30,6-20, a 10-20 or 11-18 carbon atom usually;
R 3Be alkyl;
R 4And R 5Be ketone group, ester group or alkyl independently; And
R 6Be hydrogen or alkyl independently, comprise a 1-150 or 4-30 carbon atom usually.
In one embodiment, the compound of formula (1b) comprises imide group, and it can be by making the combination of Y and Y ' group and form R between two＞C=O group 1-N＜group and forming.In one embodiment, formula (1a) and/or (1b) n, X and the R of compound 1, R 2And R 6As give a definition: n is 1-2, and X is＞CHOR 6And R 1, R 2And R 6Independently for containing the alkyl of 4-30 carbon atom.In one embodiment, Y and Y ' are-O-.In one embodiment, formula (1a) and/or (1b) n, X, Y, Y ' and the R of compound 1, R 2And R 6As give a definition: n is that 1-2, X are＞CHOR 6Y and Y ' are-O-, and R 1, R 2And R 6Independently for containing the alkyl of 4-30 carbon atom.
Formula (1a) and/or (1b) and/or (1c) diester class, diamide, ester-acid amide or imide compound can choose wantonly in the presence of known esterifying catalyst and amine or pure prepared in reaction by making dicarboxylic acid (for example tartrate).Amine or alcohol have enough carbon atoms usually, to satisfy R 1And/or R 2Requirement as definition in formula (1a) and/or (1b).
In one embodiment, R 1And R 2Be straight chain or branched hydrocarbyl radical independently.In one embodiment, alkyl is a branching.In one embodiment, alkyl is a straight chain.R 1And R 2Can be by amine or pure drawing-in system (1a) and/or (1b).Alcohol comprise monohydroxy-alcohol and polyvalent alcohol the two.The example of suitable branching alcohol comprises 2-Ethylhexyl Alcohol, different tridecyl alcohol, Guerbet alcohol or its mixture.The example of monohydroxy-alcohol comprises methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, hendecanol, dodecanol, tridecyl alcohol, tetradecanol, pentadecylic alcohol, cetyl alcohol, heptadecanol, Stearyl alcohol, nonadecanol, eicosanol or its mixture.In one embodiment, monohydroxy-alcohol comprises 5-20 carbon atom.Alcohol comprises monohydroxy-alcohol or polyvalent alcohol.Suitable examples of polyhydric alcohols comprises ethylene glycol, propylene glycol, 1,3-butyleneglycol, 2,3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, glycerine, sorbyl alcohol, tetramethylolmethane, TriMethylolPropane(TMP), starch, glucose, sucrose, methyl glucoside or its mixture.In one embodiment, polyvalent alcohol and monohydroxy-alcohol one are used from the mixture.Usually, in this combination, monohydroxy-alcohol constitutes 60mol% at least, or the mixture of 90mol% at least.
The example of ester class comprises by those of tartrate and for example long-chain monohydroxy-alcohol condensation prepared.These comprise independent alcohol, straight chain or branching, and the mixture of various alcohol.The example of straight chain alcohol comprises those with 8-20 carbon atom, for example the straight chain alcohol of 8-10,8-12,12-14, a 12-16 and 14-18 carbon.The example of branching alcohol comprises those with 8-20 carbon atom, for example 8 carbon atoms (as 2-Ethylhexyl Alcohol) or 12-14 or 13 or 16 or 18 or the branching alcohol of 14-18 carbon.Therefore, the ester class can be derived from the mixture of all straight chain alcohols or all branching alcohols or the mixture of straight chain and branching alcohol, for example straight chain C 8-14 is pure and the mixture of the mixture of branching C8 alcohol or straight chain C 12-14 alcohol and branching C13 alcohol or straight chain C 14-18 alcohol and branching C18 alcohol, and the mixture of the mixture of C18 and C12 straight chain alcohol and C13 and C8 branching alcohol and other this type of combination.Straight chain is not special limit to another kind of straight chain alcohol or a kind of branching alcohol to the ratio of another kind of branching alcohol in any this type of combination to relative weight ratio or a kind of straight chain alcohol of branching alcohol, but in certain embodiments, can be 10～95: 90～5 or 50～90: 50～10, for example about 95: 5 or 90: 10 or 80: 20 or 70: 30 or 50: 50 or 30: 70.
In one embodiment, organic anti-wear agent is derived from tartrate.The tartrate that is used to prepare tartrate of the present invention can be commercially available (for example obtaining from Sargent Welch), and may be with one or more isomeric forms such as d-tartrate, l-tartrate, d, l-tartrate (racemize) or mesotartaric acid exist, and often depend on source (natural) or synthetic method (for example from toxilic acid).These derivatives also can be from conspicuous diacid preparation, for example ester class, acyl chloride or the anhydrides of being equal to of those skilled in the art.
When formula (1a) and/or compound deriving (1b) during from tartrate, depend on used certain alcohols in the preparation tartrate, formed tartrate can be solid, semisolid or or oily.For be used as additive in the oleaginous composition that comprises lubricated and fuel composition, tartrate advantageously is soluble and/or stably is dispersed in this oleaginous composition.For example, be intended for use in composition in the oil and be generally molten and/or stable can being dispersed in their oil to be used wherein of oil.The term that uses in specification sheets and the claims " oil molten " might not represent all described compositions with all proportions can be miscible in or dissolve in all oil.On the contrary, it is to be used for representing that composition is solvable in oil (mineral, synthetic etc.), and wherein it plays a role to allowing that solution shows the degree of one or more desirable propertieses.Similarly, this type of " solution " must be not true solution on the physics of strictness or chemical sense.For the purpose of the present invention, they can be microemulsion or colloidal dispersion, show enough those character near true solution, they can be exchanged in fact in the context of the present invention.
Be suitable for equally as friction modifiers for vegetables oil, for example Viscotrol C (based on the triglyceride of the main ingredient of ricinolic acid, hydroxyl unsaturated acid) or sunflower oil.
The amount that is present in the friction modifiers in the lubricant described herein can be 0.01-5 weight % or 0.01-2% or 0.02-1.2% or 0.03-1%.
Composition of the present invention can be essentially no or not be had a molybdenum compound.Molybdenum compound has been used as oxidation inhibitor, friction modifiers in lubricant compositions, and is used for various other functions, for example anti-wear agent.For example United States Patent (USP) 4,285,822 disclose and comprise the lubricating oil composition that contains molybdenum and sulphur composition, and it prepares by following steps: (1) makes polar solvent, acid molybdenum compound and oil soluble basic nitrogen compound contain the molybdenum mixture in conjunction with formation and mixture is contacted with dithiocarbonic anhydride form with (2) and contain molybdenum and sulphur composition.The agent of this lubricant formulation comprises seldom or does not comprise molybdenum, for example is lower than 500 or be lower than 300 or be lower than 150 or be lower than 100 or be lower than 50 or be lower than 20 or be lower than 10 or be lower than 5 or be lower than the Mo of 1ppm by weight, perhaps with the amount of 0.1-50ppm or 1-5ppm.Perhaps, the amount of molybdenum can be to be lower than and effectively provides remarkable lubricant active amount in this lubricant.
Composition of the present invention also can not have or does not have substantially zn cpds.Zn cpds, for example zinc phosphate, thiophosphoric acid zinc (particularly zinc dialkyl dithiophosphate) and other zn cpds such as zinc oleate often are used as in lubricant and resistance to wear or oxidation inhibitor.Lubricant of the present invention even can well use not having under the situation of these zn cpdss.Therefore, the amount of zinc in composition can be 0-1000 or 0-100 or 1-20 by weight or is lower than 20 or be lower than 10 or be lower than 5ppm.
Also can comprise dispersion agent as composition described herein.Dispersion agent is well-known in field of lubricant and mainly comprises ashless dispersant and the polymeric dispersant that everybody was familiar with.Ashless dispersant is so named, and is that they do not comprise metal because of the form as supply, can not contribute to the vitriol ash usually in the time of therefore in adding lubricant.Yet, in case when being added into them in the lubricant that comprises the containing metal material, they certainly can to around metal influential.Being characterized as on the hydrocarbon chain that polar group is attached to higher molecular weight of ashless dispersant.Ashless dispersant generally includes the long-chain alkylidene group succinimide class that N-replaces, and has to generally include the various chemical structures that comprise following structure:
Figure BPA00001197609100141
R wherein 1Being alkyl independently of one another, usually is the polyisobutylene group of 500-5000 for molecular weight, and R 2Be alkylidene group, be generally ethylidene (C 2H 4) group.This quasi-molecule is usually derived from the reaction of thiazolinyl acylating agent and polyamines, and the multiple keyed jointing between two structure divisions may comprise various amidess and quaternary ammonium salt on the next door of above-mentioned simple imide structure.Simultaneously, R 1The various connection modes of group on imide structure are possible, comprise various ring-type keyed jointings.The carbonyl of acylating agent can be 1 to the ratio of the nitrogen-atoms of amine: 0.5-1: 3, and be 1 in other cases: 1-1: 2.75 or 1: 1.5-1: 2.5.The more abundant United States Patent (USP) 4,234 that is documented in of succinimide dispersants is in 435 and 3,172,892.
The ashless dispersant of other kind is the high-molecular weight ester class.These materials are similar to the succinimide class of above-mentioned record, except they can be regarded as by alkyl acylating agent and multi-aliphatic alcohol such as glycerine, tetramethylolmethane or sorbyl alcohol prepared in reaction.This type of material is documented in United States Patent (USP) 3,381 in more detail, in 022.
Another kind of ashless dispersant is a Mannich dispersant.The material that these form for phenol, alkylene polyamine and aldehyde such as formaldehyde condensation by more high-molecular weight alkyl replacement.This material can have formula:
Figure BPA00001197609100151
(comprising various isomer etc.) and be documented in United States Patent (USP) 3,634 in more detail is in 515.
Other dispersion agent comprises the polymeric dispersant additive, it typically is the hydrocarbyl polymers that comprises the polar functional group of giving the polymer dispersed characteristic.
Dispersion agent also can carry out aftertreatment by reacting with any all ingredients.Comprise succinyl oxide class, nitrile, epoxide, boron compound and phosphorus compound that urea, thiocarbamide, dimercaptothiodiazole class, dithiocarbonic anhydride, aldehydes, ketone, carboxylic-acid, hydrocarbon replace in these.The reference of describing this type of processing in detail is listed in United States Patent (USP) 4,654, in 403.Borated dispersants has been found that for this lubricant useful.Usually, borated dispersants will comprise the boron of 0.1%-5% or 0.5%-4% or 0.7%-3 weight %.In one embodiment, borated dispersants is the boration acylated amine, for example the boration succinimide dispersants.Borated dispersants is by making one or more dispersion agents and one or more boron compound prepared in reaction and being documented in United States Patent (USP) 3,000,916; 3,087,936; 3,254,025; 3,282,955; 3,313,727; 3,491,025; 3,533,945; In 3,666,662 and 4,925,983.
If be present in this composition, the amount of dispersion agent or borated dispersants (or both combinations) can be 0.1 or 0.2-5 weight % or 0.4-4 weight % or 0.5-3 weight % or 0.5-1.8 weight %.
The agent of this lubricant formulation also can comprise one or more over-based detergents.Overbased material perhaps is called high alkalinity or hyperalkaline salt, is generally homogeneous newton system, it is characterized by metal content surpass the specific acidic organic compound that reacts according to metal with metal be used for that the neutral stoichiometry exists those.Overbased material is by making acidic substance (being generally mineral acid or low-grade carboxylic acid, for example carbonic acid gas) and comprising acidic organic compound, comprise the mixture reaction preparation of the excessive metal base of reaction medium, the stoichiometry of at least a inert organic solvents (for example mineral oil, petroleum naphtha, toluene, dimethylbenzene) that is used for described acid organic materials and promotor such as phenol or pure and mild optional ammonia.Acid organic materials has the carbon atom of enough numbers usually, for example is hydrocarbyl substituent, so that rational solubleness to be provided in oil.The amount of excess metal is represented with term metal ratio usually.Term " metal ratio " is that the metal total yield is to the normal ratio of acidic organic compound.The metal ratio of neutral metal salt is 1.Have and be present in the normal salt 4.5 times salt of amount of metal will to have 3.5 normal metals excessive, or than being 4.5.
Over-based detergent is a feature with total basicnumber (TBN) often.TBN is expressed as potassium hydroxide equivalent (sample of mgKOH/g) for the amount of the required strong acid of basicity (perchloric acid or hydrochloric acid) of all overbased material that need neutralize.Because to comprise a certain amount of thinning oil, for example the form of 40-50% oil provides over-based detergent usually, will depend on the amount of this thinning oil of existence for the actual TBN value of this sanitising agent, no matter " intrinsic " basicity of overbased material.For the present invention, the TBN of over-based detergent will be scaled no oil base.Therefore, for example having unadjusted total basicnumber is that the cleanser compositions of 300 and 40% oil-contg can have 500 TBN (no oil base).Useful in the present invention sanitising agent has the TBN (no oil base) of 100-800 usually, and in one embodiment, for 150-750 and in another embodiment, is 400-700.If adopt multiple sanitising agent, total TBN of detergent components (i.e. the mean value of all specific sanitising agents) usually will be in above-mentioned scope.
Total TBN of bag butyraceous composition will be derived from the TBN contribution of independent component such as dispersion agent, sanitising agent and other basic material.Total TBN for the lubricant that is used as the agent of marine diesel cylinder lubrication will for example be 31-100 or 35-80 or 40-70 for greater than 30 usually.Total TBN of other lubricant can be at least 7 or at least 10, or sometimes even be at least 20.Most of TBN is contributed by the over-based detergent component usually.
The metallic compound that is used to prepare alkaline metal salt is generally the compound (the CAS version of the periodic table of elements) of the metal of any family 1 or family 2.The metallic compound of family's 1 metal comprises the 1a of family basic metal such as sodium, potassium and lithium, and the 1b of family metal such as copper.Family's 2 metals of metallic matrix comprise the 2a of family alkaline-earth metal such as magnesium, calcium and barium, and the 2b of family metal such as zinc or cadmium.
This overbased material is well-known to those skilled in the art.Record is used to prepare sulfonic acid, carboxylic acid, (alkyl replaces) phenol, phosphonic basic salt and any two or more patent of technology of mixture comprises United States Patent (USP) 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; With 3,629,109.
In one embodiment, lubricant of the present invention can comprise the overbased sulfonate sanitising agent.Suitable sulfonic acid comprises sulfonic acid and thiosulfonic acid.That sulfonic acid comprises is single-or polynuclear aromatic or alicyclic sulfoacid compound.Oil-soluble sulfonic acid salt can be by a kind of expression in the following formula: R 2-T-(SO 3-) aAnd R 3-(SO 3-) b, wherein T is that ring nucleus is as being generally benzene; R 2Be aliphatic group such as alkyl, thiazolinyl, alkoxyl group or alkoxyalkyl; (R 2)-T comprises at least 15 carbon atoms altogether usually; And R 3For comprising the aliphatic hydrocarbyl of at least 15 carbon atoms usually.R 3Example be alkyl, thiazolinyl, alkoxyalkyl and carbonylic alkoxy alkyl.The R group can be mixing straight chain or branching or straight chain and branching group.Group T, R 2And R 3Also can comprise other inorganic or organic substituent such as hydroxyl, sulfydryl, halogen, nitro, amino, nitroso-group, sulfide or disulphide.In above structural formula, a and b are at least 1.
Another overbased material that can exist is a high alkalinity phenates sanitising agent.The phenol that is used to prepare the phenates sanitising agent can be by formula (R 1) a-Ar-(OH) bExpression, wherein R 1For having the aliphatic hydrocarbyl of 4-400 carbon atom or 6-80 or 6-30 or 8-25 or 8-15 carbon atom; Ar is aromatic group (it can be phenyl or other aromatic group such as naphthalene); A and b are at least one quantity independently, and the sum of a and b is by interchangeable hydrogen number decision on the aromatic ring of Ar or nuclear.In one embodiment, a and b are to 4 independently, or 1-2.R 1Usually make by R with a 1Group provides the mean value of at least 8 aliphatic carbon atoms to each oxybenzene compound.The phenates sanitising agent also provides sometimes as disulfide-bridged material.
In one embodiment, overbased material is the over-based detergent that is selected from high alkalinity salixarate sanitising agent, high alkalinity bigcatkin willow alcohol sanitising agent, high alkaline salicylate sanitising agent and high alkalinity glyoxylate sanitising agent and composition thereof.High alkalinity bigcatkin willow alcohol sanitising agent is generally the high alkalinity magnesium salts based on the saligenol derivative.
The common example of this saligenol derivative can be expressed from the next:
Figure BPA00001197609100181
Wherein X comprise-CHO or-CH 2OH, Y comprise-CH 2-or-CH 2OCH 2-, and wherein this-CHO group comprises X and the Y group of 10mol% at least usually; M is the key (valence) of hydrogen, ammonium or metal ion, R 1For containing the alkyl of 1-60 carbon atom, m is that 0-is common 10, and p is 0,1,2 or 3 independently of one another, and condition is that at least one aromatic ring comprises R 1Substituting group and carbon atom are at all R 1Add up at least 7 in the group.When m is 1 or when bigger, one of X group can be hydrogen.In one embodiment, M is the mixture of Mg ionic key or Mg and hydrogen.Other metal comprises basic metal such as lithium, sodium or potassium; Alkaline-earth metal such as calcium or barium; With other metal such as copper, zinc and tin.The saligenol sanitising agent is disclosed in United States Patent (USP) 6,310 in more detail, in 009, is specifically related to their synthetic method (the 8th hurdle and embodiment 1) and the preferred amounts (the 6th hurdle) of the various materials of X and Y.
The structure of the described chemical substance of this formula ordinary representation " represented " to be meant in term used herein by formula.Yet well-known is to produce less variation, particularly comprises position isomerismization, i.e. the location of different positions on those the aromatic ring that shows in structure of X, Y and R group.This variation " represented " obviously to comprise in term by formula.
The overbased material of salixarate sanitising agent for representing by the unitary basic straight chain compound that comprises at least a formula (I) or formula (II):
Figure BPA00001197609100191
Each end of compound has formula (III) or end group (IV):
Figure BPA00001197609100192
This group is by divalent bridging group A keyed jointing, and it can be identical or different for each keyed jointing; Wherein in formula (I)-(IV), R 3Be hydrogen or alkyl; R 2For hydroxyl or alkyl and j are 0,1 or 2; R 6Be hydrogen, alkyl or the assorted alkyl that replaces; Perhaps R 4Be hydroxyl and R 5And R 7Be hydrogen, alkyl or the assorted alkyl that replaces, perhaps R independently 5And R 7The two is hydroxyl and R 4Be hydrogen, alkyl or the assorted alkyl that replaces; Condition is R 4, R 5, R 6And R 7In at least one is the alkyl that comprises at least 8 carbon atoms; And wherein molecule on average comprises at least one unit (I) or (III) and at least one unit (II) or (IV), and unit (I) and sum (III) are about 0.1 to the ratio of unit (II) and sum (IV) in the composition: about 2: 1 of 1-.In each situation, can be identical or different divalent bridging group " A ", comprise-CH 2-(methylene bridge) and-CH 2OCH 2-(ether bridge), its arbitrary can be derived from formaldehyde or formaldehyde equivalent (for example polyoxymethylene, formalin).Salixarate derivative and preparation method thereof is documented in United States Patent (USP) 6,200 in more detail, 936 and the open WO01/56968 of PCT in.There's a widespread conviction that the salixarate derivative mainly has straight chain for people, but not macrocyclic structure, although two kinds of structures comprise by term " salixarate ".
The glyoxylate sanitising agent is the similar overbased material based on anionic group, in one embodiment, can have following structure:
Figure BPA00001197609100201
Wherein R is independently of one another for comprising at least 4, and the alkyl of preferred at least 8 carbon atoms, condition be in all this R groups carbon atom add up at least 12, preferably at least 16 or 24.Perhaps, the R olefin polymer substituting group of can respectively doing for oneself.When by its preparation high alkalinity glyoxylate sanitising agent, acidic substance are the condensation product of hydroxyaromatic material such as alkyl substituted phenol and carboxyl reaction thing such as oxoethanoic acid and other ω-oxo alkane acid.High alkalinity oxoethanoic acid sanitising agent and preparation method thereof is disclosed in United States Patent (USP) 6,310 in more detail, 011 and the reference wherein quoted in.
Over-based detergent also can be high alkaline salicylate.Alkylsalicylate can be and can pass through an alkali metal salt or the alkaline earth salt of Cole Bai-Shi Mite reaction by the alkyl salicylate of alkylphenol preparation.Alkylphenol can be by having for example alpha-olefin and the phenol reactant preparation of 8-30 carbon atom (average quantity).Perhaps, calcium salicylate can be by the direct neutralization of alkylphenol and carbonating production subsequently.Therefore Whitfield's ointment can be the Whitfield's ointment that alkyl replaces, the Whitfield's ointment that replaces of aliphatic hydrocrbon for example, and wherein each substituting group comprises at least 8 carbon atoms of each substituting group and each molecule 1-3 substituent mean value.Substituting group can be the polyolefine substituting group, and wherein polyolefine comprises the monomeric homopolymer of polymerizable olefin and the multipolymer of 2-16 or 2-6 or 2-4 carbon atom.Alkene can be monoene hydro carbons such as ethene, propylene, 1-butylene, iso-butylene and 1-octene; Or the polyolefine monomer, diolefinic monomer for example is as 1,3-butadiene and different the eleventh of the twelve Earthly Branches diene.In one embodiment, the hydrocarbyl substituent on Whitfield's ointment comprises 7-300 carbon atom and can be the alkyl that molecular weight is 150-2000.Polyolefins and poly-alkyl group prepare by ordinary method, and the replacement of this group on Whitfield's ointment can realize by currently known methods.High alkaline salicylate sanitising agent and preparation method thereof is disclosed in United States Patent (USP) 4,719, in 023 and 3,372,116.
Detergent components also can be mixture or so-called " the hybridization thing sanitising agent " of sanitising agent, also is called mixture sanitising agent or mixed-matrix sanitising agent.In one embodiment, the hybridization thing can be high alkalinity phenates-salicylate sanitising agent.The method for preparing high alkalinity phenates-salicylate sanitising agent is disclosed among EP 123 6791 A1 and EP 123 6792 A1.In one embodiment, the hybridization thing can be by making alkyl aromatic sulfonic acid and at least a alkylphenol (for example alkylphenol, aldehyde coupled alkylphenol, sulfurized alkylphenol) and optional alkyl salicylate prepared in reaction in the presence of suspension and the agent of acidifying high alkalinity.The preparation of this material also is disclosed among the WO97046643.
Therefore this lubricant can comprise 20 weight % at the most, the high alkalinity alkylphenol sulfurated lime sanitising agent of (or 0.1-19 or 0.5-18 or 1-17 or 0.1-10 or 0.5-7 or 1-5 weight %) (has any amount of high basicity, high or low TBN) or at the most the relative high alkalinity linear alkyl benzene sulphonic acid sanitising agent of 20 weight % (or 0.1-17.5 or 0.1-17 or 0.5-15 or 1-17 or 0.5-15 or 2-12 or 6-10 weight %), promptly not having oily TBN is 400-900 or these mixtures of material.In preparaton of the present invention, the total amount of over-based detergent is generally at least 0.6 weight % on oil-free basis.In other embodiments, it can 0.7-20 weight % or the amount of 1-18 weight % or 3-13 weight % exist.In one embodiment, detergent components is formed (and not having sulfonate) by the salicylate sanitising agent.In another embodiment, detergent components is formed (and not having phenates) by sulfonate detergents.
Lubricant described herein also can comprise one or more and be generally used for preparing lubricant, particularly other material of marine diesel cylinder lubrication agent.Usually, other performance additive comprises metal passivator, oxidation inhibitor, anti-wear agent, corrosion inhibitor, rumbling compound, extreme pressure agent, froth suppressor, emulsion splitter, viscosity modifier, pour point reducer and composition thereof.Usually, the lubricating oil of preparation will comprise one or more these performance additive fully.
Antioxidant compound is known and for example comprises olefine sulfide class, alkylated diphenylamine class (being generally dinonyldiphenylamine, octyl diphenylamine, dioctyl diphenylamine), Hinered phenols and composition thereof.Molybdenum compound is sometimes also as oxidation inhibitor, but as mentioned above, the Mo compound is not included in this composition usually.
Hindered phenol antioxygen comprises sec-butyl and/or the tertiary butyl usually as space steric hindrance group.Phenolic groups is further replaced by the bridged group of alkyl and/or keyed jointing second aryl usually.The example of suitable hindered phenol antioxygen comprises 2,6 di t butyl phenol, 4-methyl-2,6 di t butyl phenol, 4-ethyl-2,6-DI-tert-butylphenol compounds, 4-propyl group-2,6-DI-tert-butylphenol compounds or 4-butyl-2,6 di t butyl phenol or 4-dodecyl-2,6 di t butyl phenol.In one embodiment, hindered phenol is ester and for example can comprises the Irganox that derives from Ciba TML-135.The suitable hindered phenol antioxygen chemical descriptor that comprises ester be documented in United States Patent (USP) 6,559 in more detail, in 105.
Viscosity modifier comprises alkenyl aryl conjugated diene copolymer, the polyolefins of different the eleventh of the twelve Earthly Branches diene polymer, polymethacrylate, polyacrylate(s), polyoxyethylene alkylphenyl vinyl, the hydrogenation of vinylbenzene-different the eleventh of the twelve Earthly Branches diene polymer, the hydrogenation of hydrogenation multipolymer, ethylene-propylene copolymer, polyisobutene, the hydrogenation of vinylbenzene and divinyl, the ester class of maleic anhydride olefin copolymer, and the ester class of maleic anhydride-styrene copolymers.
The example of anti-wear agent comprises ash-free antiwear agent, the metal dialkyl dithiophosphate (zinc dialkyl dithiophosphate for example of boron-containing compound such as boration ester class or boration alcohols, phosphoric acid ester, olefine sulfide class, sulfur-bearing; it also can not be present in this preparaton as mentioned above), contain the compound of sulfo-carbamate; for example thiocarbamates, alkylidene group link coupled thiocarbamates, and two-(S-alkyl Dithiocarbamyl) disulphide.Anti-wear agent can be based on 0 weight %-15 weight % or the 0.1 weight %-10 weight % or the 1 weight %-8 weight % existence of lubricating composition.
Boration ester class or boration alcohols can be basic identical, except boration alcohol has at least one nonesterified hydroxyl.Therefore, term used herein " boration ester " is used in reference to boration ester or boration alcohol.Boration ester class or boration alcohols can have formula B (OR ') 3Or for it comprises＞derivative of B-O-B＜group, wherein R ' can be hydrogen or alkyl, comprises 1-40 or 1-20 carbon atom usually on each R '.When R ' was hydrogen, the compound of boracic was a boration alcohol.When R ' was alkyl, boron-containing compound was the boration ester.The boration ester can be by making boron compound, and for example boric acid, boron oxide or halogenation boron are with at least a epoxy compounds, halohydrin compound, epihalohydrin compound, alcohols and composition thereof the prepared in reaction that is selected from.Alcohols comprises dibasic alcohol, trivalent alcohol or higher alcohols more, and its precondition is in the embodiment, and hydroxyl is adjacent, promptly on the Lin Jin carbon atom.As mentioned above, some boron-containing compounds also can be used as friction modifiers.
The compound that contains dithiocar-bamate can be by making dithiocarbamic acid or salt and unsaturated compound prepared in reaction.The compound that contains dithiocar-bamate also can be by making amine, dithiocarbonic anhydride and unsaturated compound prepared in reaction simultaneously.Usually, be reflected under 25 ℃-125 ℃ the temperature and carry out.United States Patent (USP) 4,758,362 and 4,997,969 have put down in writing dithiocar-bamate compound and preparation method thereof.
The example that can vulcanize the suitable alkene that forms olefine sulfide comprises propylene, butylene, iso-butylene, amylene, hexane, heptene, octane, nonene, decene, undecylene, dodecylene, undecyl, tridecylene, tetradecene, 15 carbenes, cetene, heptadecene, vaccenic acid, octadecenene, 19 carbenes, eicosylene or its mixture.In one embodiment, cetene, heptadecene, vaccenic acid, octadecenene, 19 carbenes, eicosylene or its mixture and their dipolymer, trimer and tetramer are useful especially alkene.Perhaps, alkene can be the diels-alder adduct of diolefine such as 1,3-butadiene and unsaturated ester such as butyl acrylate.The olefine sulfide of other kind comprise lipid acid and they the ester class and with the mixture of alpha-olefin.Lipid acid often obtains from vegetables oil or animal oil and comprises 4-22 carbon atom usually.
Extreme pressure (EP) agent comprises EP agent, chlorinated hydrocarbon EP agent and the phosphorus EP agent of sulfur-bearing and chlorine sulphur.The example of this EP agent comprises chlorinated wax; Organic sulfide and polysulphide such as diphenyl-methyl disulphide, two (chlorophenylmethyl) disulphide, dibutyl tetrasulfide, oleic sulfuration methyl esters, sulfenyl phenolate, sulfuration limonene, sulfuration terpenes and sulfurized diels-Alder reaction adducts; The reaction product of phosphosulfurized hydrocarbon such as phosphoric sulfide and turps or Witconol 2301; Phosphide (phosphorus ester) class is as two hydrocarbon and three hydrocarbon phosphorous acid esters, for example dibutyl phosphite, phosphorous acid diheptyl ester, phosphorous acid dicyclohexyl ester, phosphorous acid amyl group phenylester; The phenol phosphorous acid ester that phosphorous acid diamyl phenylester, phosphorous acid tridecyl ester, phosphorous acid distearyl ester and polypropylene replace; Metal thiocarbamate such as dioctyl zinc dithiocarbamate and heptylphenol diacid barium; The amine salt of alkyl and dialkyl group phosphoric acid for example comprises the amine salt of the reaction product of dialkyl dithiophosphoric acid and propylene oxide; And composition thereof.
Other performance additive such as corrosion inhibitor are included in those that put down in writing in the 5-8 section of U. S. application 2005-038319, octylame octanoate, the condensation product of laurylene base succsinic acid or acid anhydrides and lipid acid such as oleic acid and polyamines.In one embodiment, corrosion inhibitor comprises Synalox
Figure BPA00001197609100241
Corrosion inhibitor.Synalox
Figure BPA00001197609100242
Corrosion inhibitor is generally the homopolymer or the multipolymer of propylene oxide.Synalox
Figure BPA00001197609100243
Corrosion inhibitor is documented in the product brochure of the Form No.118-01453-0702 AMS that is published by Dow Chemical Company in more detail.Product brochure title is " SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications ".
Metal passivator comprises derivative (being generally tolytriazole), the dimercaptothiodiazole derivative, 1,2 of benzotriazole category, 4-triazole species, benzimidazoles, 2-alkyl dithio benzimidazoles or 2-alkyl dithio benzothiazoles.Froth suppressor comprises the multipolymer of ethyl propenoate and 2-EHA and optional vinyl-acetic ester.Emulsion splitter comprises trialkylphosphate, polyoxyethylene glycol, polyoxyethylene, polyoxytrimethylene and (epoxy ethane-epoxy propane) polymkeric substance.Pour point reducer comprises ester class, polymethacrylate, polyacrylate(s) or the polyacrylamide of maleic anhydride-styrene.
Ji Zai lubricant also can comprise titaniferous additive such as titanium alcohol salt or titanium modification dispersion agent herein, for example is documented in more detail as among the U. S. application 2006-0217271.
Term used herein " hydrocarbyl substituent " or " alkyl " use with its common meaning well-known to those skilled in the art.Particularly, it is meant the carbon atom of the rest part with direct link molecule and the group that mainly has the hydrocarbon characteristic.The example of alkyl comprises:
Hydrocarbon substituent, promptly aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl, cycloalkenyl group) substituting group, and aromatics-, aliphatic series-and the aromatic substituent of alicyclic replacement, and wherein encircle the cyclic substituents of finishing (for example two substituting groups form ring together) by the other parts of molecule;
The hydrocarbon substituent that replaces promptly comprises the substituting group (for example halogen (particularly chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulphur oxygen base (sulfoxy)) of the non-alkyl that does not change substituent main hydrocarbon character in the context of the present invention;
Assorted substituting group, promptly such substituting group if not it comprises non-carbon atom in ring of so being made up of carbon atom in the context of the present invention or chain, has main hydrocarbon characteristic simultaneously.Heteroatoms comprises sulphur, oxygen, nitrogen, and comprises substituting group such as pyridyl, furyl, thienyl and imidazolyl.Usually, per ten carbon atoms in alkyl will exist at the most two or non-hydrocarbon substituent at the most; Usually, in alkyl, incite somebody to action hydrocarbon substituent nothing but.
Well-known more aforesaid materials can interact in final preparaton, so that the component of final preparaton can be different from initial interpolation those.For example, metal ion (as sanitising agent) can migrate to other acidity or the anionic sites of other molecule.The product of Xing Chenging comprises when adopting composition of the present invention with the product that its desired use forms thus, may be not easy explanation.Yet all these type of modifications and reaction product comprise within the scope of the invention; The present invention includes by mixing the composition of component preparation as mentioned above.
Embodiment
The agent of " well " benchmark lubricant formulation is that feature prepares with the agent of marine diesel cylinder lubrication.In the mineral oil of API group I, lubricant comprises:
12.5% the high alkalinity Phenylsulfonic acid calcium and the mixture of phenates sanitising agent are given the TBN of lubricant about altogether 69; With
0.67 the boration succinimide dispersants of weight %.
Notice that some industrial component can comprise a spot of other component such as stearic acid or dispersion agent, to help their production.
Above-mentioned lubricant is not having and is having a frictional coefficient of estimating under the situation of various organic friction modifiers as temperature function.Evaluation is at the CameronPlint with pin platen (pin-on-plate) geometry TMCarry out on the testing table.Before test, each lubricant is partly used sulfuric acid (3.5% acid) neutralization.Lubricant is carried out the 100N load, and simultaneous temperature rises to 300 ℃ from room temperature.In 2.5 hours test, per 10 seconds records frictional coefficient, contact potential (contact potential) and sample temperatures.The frictional coefficient that comprises the lubricant of various additives is recorded as the mean value under each temperature range in table 1.
Figure BPA00001197609100261
The result shows and respectively tests organic friction modifiers agent provides the friction that significantly reduces to lubricant formulation, particularly under 150 ℃ and above high temperature.The performance that is provided by known containing metallic additive thiocarbamate molybdenum is provided in organic no metal friction properties-correcting agent demonstration under the high temperature.
Embodiment 11. repeats to comprise the preparaton of the embodiment 6 of glyceryl monooleate, except that the corresponding non-boration succinimide dispersants that the boration succinimide dispersants is replaced by equivalent.Carry out identical as mentioned above rub(bing)test, the result shows below:
The result shows, compares with using non-borated dispersants, and the use of borated dispersants can provide improved high temperature friction performance in the target lubricant.
Above-mentioned each document is incorporated herein for reference.The mentioning of any file is not to recognize that this document is qualified as prior art or constitute those skilled in the art's common practise with any authority.Except that in an embodiment, perhaps wherein other clearly marked, the numerical quantities of all specified material amounts, reaction conditions, molecular weight, carbonatoms etc. will be interpreted as by speech " pact " and limit in this specification sheets.Except as otherwise noted, each chemical substance as referred to herein or composition should be interpreted as the technical grade material that can comprise isomer, by product, derivative and be generally understood as other this type of material that exists with technical grade.Yet the amount of each chemical composition is disregarded any solvent or the thinning oil that is present in usually in the Industrial materials.Except as otherwise noted, the upper and lower bound that is interpreted as amount, scope and ratio that this paper proposes can be made up independently.Similarly, can use with the scope or the amount of any other composition for the scope and the amount of each composition of the present invention.Term used herein " substantially by ... form " allow and comprise and do not influence the basis of the composition in the research and the material of new feature in fact.

Claims (14)

1. a lubricant compositions is applicable to lubricate at the steam jacket place to be higher than 150 ℃ of oil engines of operation down, and it comprises the oil of lubricant viscosity and organic friction modifiers of 0.01-5 weight %, and described lubricant compositions does not have molybdenum compound substantially.
2. according to the composition of claim 1, it has the total basicnumber greater than 30.
3. according to the composition of claim 1 or 2, wherein organic friction modifiers is selected from fatty amine, fatty acid and the fatty acyl amide of glyceryl monooleate, tartaric acid derivatives, ethoxylation.
4. according to each composition among the claim 1-3, wherein friction modifiers is a glyceryl monooleate.
5. according to each composition among the claim 1-4, it does not have zn cpds substantially.
6. according to each composition among the claim 1-5, it further comprises the borated dispersants of 0.1-5 weight %.
7. according to each composition among the claim 1-6, it further comprises the high alkalinity alkylphenol sulfurated lime sanitising agent of 0.1-17 weight %.
8. according to each composition among the claim 1-7, the high alkalinity linear alkyl benzene sulphonic acid sanitising agent that its TBN that further comprises 0.5-15 weight % is 400-900.
9. require the composition of each component preparation among the 1-8 by hybrid right.
10. lubricating method is used for being higher than at the steam jacket place 150 ℃ of engines of operation down, and it comprises the lubricant compositions that each is provided among the claim 1-9 to it.
11. according to the method for claim 10, wherein engine is a marine diesel engine.
12. according to the method for claim 10 or 11, wherein engine is the 2-two-stroke engine.
13. according to each method among the claim 10-12, wherein lubricant compositions is provided for the cylinder of engine.
14. according to each method among the claim 10-13, wherein lubricant is not provided for crankcase.
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