CN1740291A - Lubricating oil compositions - Google Patents

Lubricating oil compositions Download PDF

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Publication number
CN1740291A
CN1740291A CNA2005100935170A CN200510093517A CN1740291A CN 1740291 A CN1740291 A CN 1740291A CN A2005100935170 A CNA2005100935170 A CN A2005100935170A CN 200510093517 A CN200510093517 A CN 200510093517A CN 1740291 A CN1740291 A CN 1740291A
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Prior art keywords
alkyl phenol
lubricating oil
alkyl
condenses
phenol aldehyde
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Inventor
L·尚巴尔
L·科西多夫斯基
M·多恩
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Infineum International Ltd
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Infineum International Ltd
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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
    • 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
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/14—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring containing at least 2 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
    • 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
    • C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/24—Epoxidised acids; Ester 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether 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
    • C10M2215/28—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
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/52—Base number [TBN]
    • 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
    • C10N2040/255—Gasoline 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

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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

Use of an oil-soluble hydrocarbyl phenol aldehyde condensate as an antiwear additive in a lubricating oil composition. The oil-soluble hydrocarbyl phenol aldehyde condensate has the following structure: wherein n is 0 to 10, preferably 1 to 8, more preferably 2 to 6, and most preferably 3 to 5; Y is a divalent bridging group, and is preferably a hydrocarbyl group, preferably having from 1 to 4 carbon atoms; and R is a hydrocarbyl group having from 4 to 30, preferably 8 to 18, and most preferably 9 to 15 carbon atoms.

Description

Lubricating oil composition
The present invention relates to lubricating oil composition, in particular for the marine diesel engine lubricating oil composition of marine diesel oil cylinder engine for example.
The lubricating oil composition that is used for the marine diesel oil cylinder engine is known marine diesel oil cylinder lubricating oil (' MDCL ') composition.They are total loss lubricants, and its objective is provides one deck strong oil film between cylinder sleeve and piston ring.Marine diesel oil cylinder lubrication agent composition needs to tolerate high operating temperature and pressure, for example 300 ℃ and higher temperature and 150 crust and higher combustion pressures.If lubricant compositions decomposes under these high operating temperatures and pressure, the inwall of cylinder sleeve will stand too high binding property abrasion (scratch just).
Target of the present invention is that a kind of lubricating oil composition that is used for cross-head diesel engine peculiar to vessel will be provided.Another one target of the present invention is that a kind of have well tolerable high temperature and pressure will be provided; for example up to 300 ℃ with the marine diesel oil lubricating oil composition of the ability of higher temperature and 150 crust and higher pressure, and can improve protection to galling of liners.
According to the present invention, the purposes of a kind of oil soluble alkyl phenol aldehyde condenses as the anti-wear additive in the lubricating oil composition is provided, this oil soluble alkyl phenol aldehyde condenses has following structure:
Figure A20051009351700041
Wherein n is 0 to 10, and is preferred 1 to 8, more preferably 2 to 6, most preferably 3 to 5; Y is a divalence bridge joint group, is preferably alkyl, preferably has 1 to 4 carbon atom; R has 4 to 30, and is preferred 8 to 18, and the alkyl of 9 to 15 carbon atoms most preferably.
The inventor is surprised to find, and in lubricating oil composition, uses oil soluble alkyl phenol aldehyde condenses, has reduced the abrasion in the marine diesel engine.Abrasion are preferably the binding property abrasion.Marine diesel engine is preferably the marine diesel oil cylinder engine.
Alkyl phenol aldehyde condenses is preferably alkyl phenol formaldehyde (PF) condenses.Alkyl phenol aldehyde condenses is containing metal not preferably.Alkyl phenol aldehyde condenses is sulfur-bearing not preferably.
Refer to that at this used term " alkyl " group of being paid close attention to mainly is made up of hydrogen and carbon atom and is connected to the rest part of molecule by carbon atom, but do not get rid of other atoms or the group that has a certain proportion of, as to be not enough to reduce group basic hydrocarbon character.Alkyl preferably only is made up of hydrogen and carbon atom.Useful is, alkyl is a fatty group, is preferably alkyl or alkenyl, alkyl particularly, what they can be for straight chain or branching.R is preferably alkyl or alkenyl.R is preferably branching.
According to the present invention, a kind of method that lubricating oil composition reduces wearing character of improving also is provided, this method comprises adds the step in the lubricating oil composition of alkyl phenol aldehyde condenses as defined above.
Lubricating oil composition preferably has the TBN above 55, preferably surpasses 60, even more preferably surpasses 65, determines according to ASTM D2896.
The weight-average molecular weight (Mw) of alkyl phenol aldehyde condenses is preferably in 800 to 4500 scope, preferred 1100 to 4200, more preferably 1300 to 4000, most preferably 1700 to 3800, measure gained by MALDI-TOF (matrix assisted laser desorption ionization-flight time, Matrix Assisted LaserDesorption Ionization-Time of Flight) mass spectrometry.
Preferably by under the situation about existing at least a aldehydes or ketones or its reactive Equivalent and at least a alkyl phenol being carried out the resulting alkyl phenol aldehyde of polycondensation condenses at acid catalyst (for example alkyl benzene sulphonate (ABS)).Product is preferably removed any unreacted alkyl phenol by separation, preferably to being less than 5.0 quality %, and more preferably to being less than 3.0 quality %, even more preferably to the unreacted alkyl phenol that is less than 1.0 quality %.Most preferred product contains and is less than 0.5%, for example is less than the unreacted alkyl phenol of 0.1 quality %.
Though can use basic catalyst, the preferred acidic catalyzer.An acidic catalyst can be selected from multiple acidic cpd, for example phosphoric acid, sulfuric acid, sulfonic acid, oxalic acid and hydrochloric acid.Acid also can exist with the form of solid matter, for example the clay of acid treatment.The amount of used acid catalyst is 0.05 to 10% or more, for example from 0.1 to 1%, and based on the total mass of reaction mixture.
Particularly, alkyl phenol aldehyde condenses is preferably the dodecylbenzene phenol formaldehyde condensate of branching, for example tetrapropylene benzene phenol formaldehyde condensate.
The amount of alkyl phenol aldehyde condenses that is used for lubricating oil composition is preferably in the scope of 0.1 to 20 quality %, more preferably from 0.2 to 15 quality %, even more preferably from 0.5 to 12 quality %, from 1 to 10 quality % most preferably is based on the quality of lubricating oil composition.
Lubricating oil composition comprises a kind of oil with lubricant viscosity.
Oil with lubricant viscosity
Oil (sometimes being called lubricating oil) with lubricant viscosity can be any lubricated oil of marine diesel engine that is suitable for.Lubricating oil can be animal, plant or mineral oil.The lubricating oil that is fit to is the lubricating oil that petroleum derivation obtains, for example cycloalkyl group, paraffin base or mixing base oil.Perhaps, lubricating oil can be synthetic lubricating oil.The ucon oil that is fit to comprises ester oil, and it comprises diester such as Octyl adipate, dioctyl sebacate and hexanodioic acid tridecyl ester, or polymeric hydrocarbon lubricating oil, for example liquid polyisobutene and poly-alpha olefins.Normally used is mineral oil.What lubricating oil generally can account for composition surpasses 60, and the typical case surpasses 70, quality %, and at 100 ℃, typical kinematic viscosity from 2 to 40, for example from 3 to 15, mm 2s -1, viscosity index from 80 to 100, for example from 90 to 95.
Another kind of lubricating oil type is a hydrocracking oil, wherein high temperature and middle pressure and exist under the situation of hydrogen in refining process will in and last running further rupture.At 100 ℃, the typical motion viscosity from 2 to 40 of hydrocracking oil, for example from 3 to 15, mm 2s -1, typical viscosity index in from 100 to 110 scope, for example from 105 to 108.
Refer to this class base oil at this used term ' bright stock ', they be from vacuum residuum through solvent extraction, the resulting product of diasphaltene, at 100 ℃, their typical kinematic viscosity from 28 to 36mm 2s -1, their typical usage ratio are less than 30, preferably are less than 20, more preferably less than 15, most preferably are less than 10, for example are less than 5, and quality % is based on the quality of composition.
In lubricating oil composition, the amount with oil of lubricant viscosity is preferably greater than 40 quality %, more preferably greater than 50 quality %, more preferably greater than 60 quality %, most preferably greater than 65 quality %, based on the quality of lubricating oil composition.
Washing agent
Lubricating oil composition preferably contains at least a metallic washing agent.Washing agent is a kind of for example additive of forming of high temperature varnish and lacquer deposit thing of piston deposit in the engine that reduces; It has acid-neutralizing property, and solid in small, broken bits is remained in the suspension.It is based on metal " soap ", and just the metal-salt of acidic organic compound sometimes is called tensio-active agent.
Washing agent contains the polar head with long hydrophobic tail.Polar head contains the metal-salt of tensio-active agent.By with excessive metallic compound, for example oxide compound or oxyhydroxide, with sour gas for example carbon dioxide reaction introduce a large amount of metal matrix to obtain a kind of high alkali cleaning agent, this washing agent contains the neutral washing agent as metal matrix (for example carbonate) micellar skin.
Metal can be alkali or alkaline-earth metal, for example sodium, potassium, lithium, calcium, barium and magnesium.Be preferably calcium.
Tensio-active agent can be salicylate, sulfonate, carboxylate salt, phenates, thiophosphate or naphthenate.Metal salicylate salt is preferred metal-salt.
Washing agent can be from surpassing a kind of metal surfactant, for example the mixture of alkylphenol calcium and alkyl sodium salicylate prepare compound/mix washing agent.Compound washing agent like this is a mixing material, wherein in the high alkalinity process, and surface active groups, for example phenates and salicylate are introduced into.Be described to the example (seeing for example WO97/46643, WO97/46644, WO97/46645, WO97/46646 and WO97/46647) of so compound washing agent in the literature.
The tensio-active agent that is used for the metallo-detergent surfactant system contains at least one alkyl, for example, and as the substituting group on the aromatic ring.Refer to that at this used term " alkyl " group of being paid close attention to mainly is made up of hydrogen and carbon atom and is connected to the rest part of molecule by carbon atom, but do not get rid of other atoms or the group that has a certain proportion of, as to be not enough to reduce group basic hydrocarbon character.According to the present invention, useful is, alkyl used in tensio-active agent is an aliphatic group, is preferably alkyl or alkenyl, alkyl particularly, what they can be for straight chain or branching.Carbonatoms total in tensio-active agent should be enough to have influence on desirable oil soluble at least.Alkyl contains from 5 to 100, and preferably from 9 to 30, more preferably from 14 to 20, carbon atom.When containing above an alkyl, in all alkyl, the average number of carbon atom preferably is at least 9 to guarantee enough oil solubles.
Washing agent can be unvulcanised or sulfurized, can be chemical modification and/or contains other substituting group.The sulfidizing that is fit to is well-known to one skilled in the art.
It is that well-known boration treatment process is by boration to one skilled in the art that washing agent can use.
The TBN of washing agent is preferably between 50 to 500, preferably 100 to 400, more preferably 150 to 350.
Available washing agent ratio is in 0.5 to 30 scope, and preferably 2 to 20, or more preferably 5 to 19, quality % is based on the quality of lubricating oil composition.
Dispersion agent
Lubricant compositions preferably contains at least a dispersion agent.Dispersion agent is a kind of additive of lubricant compositions, and in lubricant, its major function is to quicken the neutralizing effect of washing agent system acid.
Noticeable dispersion agent type is " ashless ", and the meaning is and containing metal, and the material that forms ash is thus compared, and does not have ash during formed nonmetal organic substance burning basically.Ashless powder contains a kind of generate longer-chain hydrocarbons that has polar head, and polarity produces owing to for example including O, P or N atom.Hydrocarbon is a kind of oil-soluble lipophilic group of giving, and contains for example 40 to 500 carbon atoms.Like this, ashless powder can contain to have and can and want the oily solvable polymerizing hydrocarbon main chain of the functional group of dispersed particle association.
The example of ashless powder has succinimide, for example polyisobutylene succinic anhydride; With can be by boration or not by the polymeric amide polycondensation products of boration.
The consumption of dispersion agent is in 0 to 10.0 scope, and is preferred 0.5 to 6.0, or more preferably 1.0 to 5.0, quality % is based on the quality of lubricating oil composition.
Anti-wear additive
Lubricating oil composition can comprise at least a other anti-wear additive.Dialkyl phosphorodithioic acid metal-salt is formed the anti-wear additive of a preferred type.Metal in the dialkyl phosphorodithioic acid metal-salt can be basic metal or alkaline-earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper.Preferred zinc salt, preferably in 0.1 to 1.5 scope, preferably 0.5 to 1.3, quality % is based on the total mass of lubricating oil composition.They can prepare according to known technology, at first form a kind of dialkyl phosphorodithioic acid (DDPA), pass through one or more alcohol or phenol and P usually 2S 5Reaction is used in the Zinc compounds and the synthetic DDPA of institute then.For example, phosphorodithioic acid can obtain by the mixture reaction with primary alconol and secondary alcohol.In addition, can prepare contain character be fully sechy-drocarbyl and character be fully uncle alkyl multiple phosphorodithioic acid.In order to make zinc salt, can use any alkalescence or neutral Zinc compounds, but the most frequently used be oxide compound, oxyhydroxide and carbonate.Commercial additive usually contains excessive zinc, and this is owing to used excessive alkaline Zinc compounds in neutralization reaction.
Preferred dialkyl zinc dithiophosphate is the oily soluble salt of dialkyl phosphorodithioic acid, and its available following formula is represented:
[(RO)(R 1O)P(S)S] 2Zn
Wherein R and R 1Can be identical or different alkyl, contain 1 to 18, preferred 2 to 12, carbon atom and comprising as groups such as alkyl, thiazolinyl, aryl, aralkyl, alkaryl and alicyclic groups.Especially preferably as R and R 1Be the alkyl of 2 to 8 carbon atoms.Thus, group can be, for example ethyl, n-propyl, sec.-propyl (l-propyl), normal-butyl, isobutyl-(l-butyl), sec-butyl, amyl group, n-hexyl, isohexyl (l-hexyl), n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butyl phenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.In order to obtain oil soluble, in phosphorodithioic acid (just at R and R 1In) the sum of carbon atom be generally 5 or bigger.The dialkyl zinc dithiophosphate can contain zinc dialkyl dithiophosphate thus.
The usage ratio of other anti-wear additive is in 0.1 to 1.5 scope, and is preferred 0.2 to 1.3, or more preferably 0.3 to 0.8, quality % is based on the quality of lubricating oil composition.
Lubricating oil composition also can contain at least a following additive: antioxidant, pour point depressor, defoamer, viscosity index improver, dyestuff, metal passivator, non-emulsifying agent, or its mixture.
Though optional, hope is prepared one or more additive-package or contained the enriched material of additive, it can be joined in the oil (or base oil) with lubricated concentration simultaneously to form lubricating oil composition.Can be easily by solvent and follow mild heat to mix additive-package is dissolved in the lubricating oil, but this is optional.When additive mixed with the base lubricant of predetermined amount, additive-package was formulated into the additive that contains appropriate amount usually so that desirable concentration to be provided, and/or to be implemented in desirable function in the end formulation.The amount of the activeconstituents that additive-package can contain based on additive-package, is for example from 2.5 to 90, preferably from 5 to 75, choosing from 8 to 60 is arranged most, and the additive of the proper proportion of quality %, rest part are base oils.
Usually can contain the additive-package of 5 to the 40 quality % that have an appointment in the final prescription, rest part is a base oil.
(a.i.) refer to the additive materials that is not thinner at this used term ' activeconstituents '.
Can be dissolved in the base oil under all ratios at differ definiteness compound or additive of this used term ' oil solvable '., it means that really for example solubilized applies predetermined influence to enough degree in the employed environment of oil in oil.In addition, additionally mixing of other additives also can allow to mix higher levels of special additive, if desired.
Lubricant compositions of the present invention contained before mixing one (the just separating) component with the qualification that may maybe can not keep the same chemical property afterwards.
Following embodiment is used for illustrating the present invention, but it is not constituted any restriction.
Embodiment
The preparation of alkyl phenol aldehyde condenses
Reactive component
Alkyl phenol aldehyde condenses
1158Mw 1663Mw 1839Mw 3692Mw
Dodecyl phenol 2200g 2200g 2200g 2200g
Sulfonic acid catalyst 22g 22g 22g 22g
Paraformaldehyde 170g 209g 221g 330g
Water 550g 550g 550g 550g
Heptane 831g 831g 831g 831g
Method
With dodecyl phenol, sulfonic acid catalyst, paraformaldehyde, water and heptane add in the reactor of band dividing plate of a 5L, reactor has agitator (200rpm), nitrogen curtain (600ml/min), condenser, Dean-Rodney Stark trap, temperature controlling system and Cardice/Acetone capture vacuum system.Reactive component is heated to 80 ℃ from room temperature surpasses 30 minutes, further be heated to 100 ℃ then and surpass 2 hours, and water is removed by component distillation from 80 ℃.200 ℃ and the decompression under from reaction mixture, remove residual heptane and dodecyl phenol.Reduce the temperature to 120 ℃ and add the product (Mw refer to weight-average molecular weight) of an amount of ESN 150 at last to obtain containing desired polymer concentration.
Lubricating oil composition
Use the preparation of HFRR method of testing and detect following lubricating oil composition.
The reciprocal rotating disk method of testing of HFRR or high frequency (High Frequency Reciprocating RigTest) is a kind of computer-controlled double vibrations friction and wear test macro, is used for the wear testing of the lubricant under condition of boundary lubrication.Vibrate a steel ball with an electromagnetic vibrator with little amplitude, the load with a 10N simultaneously is pressed in it on the fixed steel disc.Bottom fixed disk is with electrically heated and be installed under the lubricant during test.In 15 minutes, temperature is risen suddenly 380 ℃ from 80 ℃.Experiment finishes the back and assesses the fluidic oilness with the wearing and tearing scar on the miking steel ball.When two metallic surfaces are when testing under condition of boundary lubrication, the scar on the steel ball is shallow more, and the anti-wear protection of lubricant is good more.In addition, when temperature was raised to 380 ℃ by 80 ℃, as long as there is gratifying oil film between two metallic surfaces, frictional coefficient did not increase.When certain temperature, frictional coefficient begins rapid increase, shows that oil film is just destroyed, and the metallic surface is experiencing and directly touching such degree, to such an extent as to caused frictional coefficient along with temperature begins to increase.High more in the temperature that the frictional coefficient weight break point occurs, good more to the protection of cylinder sleeve binding property wearing and tearing.
High temperature HFRR: the abrasion protection of improvement
Prescription The comparative example 1 The comparative example 2 The comparative example 3 Embodiment 1
410BN sulfonic acid/calcium phenylate 14.00 14.00 14.00 14.00
The 258BN calcium phenylate 5.00 5.00 5.00 5.00
High borated dispersants 3.00 3.00 3.00 3.00
Uncle ZDDP (Primary ZDDP) 0.50 0.50 0.50 0.50
The C12 branched alkyl phenol 3.00
Sulfuration C12 branched alkyl phenol 3.00
The phenol aldehyde condenses, Mw 1663 3.00
Base oil 77.5 74.5 74.5 74.5
At 100 ℃ kinematic viscosity, cSt 19.00 17.79 18.98 19.45
Base number, D2896, mgKOH/g 71.1 79.9 71.6 71.8
HFRR wearing and tearing scar mean value, μ m 201.5 242 207 194
Prescription The comparative example 1 The comparative example 4 The comparative example 5 Embodiment 2
410BN sulfonic acid/calcium phenylate 14.00 14.00 14.00 14.00
The 258BN calcium phenylate 5.00 5.00 5.00 5.00
High borated dispersants 3.00 3.00 3.00 3.00
Uncle ZDDP 0.50 0.50 0.50 0.50
The C12 branched alkyl phenol 8.00
Sulfuration C12 branched alkyl phenol 8.00
The phenol aldehyde condenses, Mw 1663 8.00
Base oil 77.5 69.5 69.5 69.5
At 100 ℃ kinematic viscosity, cSt 19.00 16.85 19.20 20.54
Base number, D2896, mgKOH/g 71.1 79.0 72.4 72.6
HFRR wearing and tearing scar mean value, μ m 201.5 227.5 212.5 197.5
As implied above, in the HFRR experiment, embodiment 1 and 2 comparisons show than less wear than embodiment 1-5.
The result who is to use phenol aldehyde condenses that the following examples are showed with different weight-average molecular weight (Mw):
Prescription Embodiment 3 Embodiment 4 Embodiment 5
410BN sulfonic acid/calcium phenylate washing agent 17.40 17.40 17.40
Borated dispersants 3.00 3.00 3.00
Sanitas is to Nonylphenoxy tetraethoxy ethanol 0.80 0.80 0.80
The phenol aldehyde condenses, Mw 1158 8.00
The phenol aldehyde condenses, Mw 1839 8.00
The phenol aldehyde condenses, Mw 3692 8.00
Base oil 70.80 70.80 70.80
At 100 ℃ kinematic viscosity, cSt 20.73 21.95 23.17
Base number, D2896, mgKOH/g 73.87 73.57 72.09
HFRR, the temperature of minimized friction coefficient, ℃ 223.3 238.5 258.3
Prescription Embodiment 6 Embodiment 7 Embodiment 8
410BN sulfonic acid/calcium phenylate washing agent 17.40 17.40 17.40
Borated dispersants 3.00 3.00 3.00
Sanitas is to Nonylphenoxy tetraethoxy ethanol 0.80 0.80 0.80
The phenol aldehyde condenses, Mw 1158 3.00
The phenol aldehyde condenses, Mw 1839 3.00
The phenol aldehyde condenses, Mw 3692 3.00
Base oil 75.8 75.8 75.8
At 100 ℃ kinematic viscosity, cSt 19.30 19.83 20.53
Base number, D2896, mgKOH/g 73.31 73.05 73.35
HFRR, the temperature of minimized friction coefficient, ℃ 221.6 228.5 249.7
Prescription Embodiment 9 Embodiment 10 Embodiment 11
410BN sulfonic acid/calcium phenylate washing agent 14.00 14.00 14.00
The 258BN calcium phenylate 5.00 5.00 5.00
Borated dispersants 3.00 3.00 3.00
Uncle ZDDP 0.50 0.50 0.50
The phenol aldehyde condenses, Mw 1158 3.00
The phenol aldehyde condenses, Mw 1839 3.00
The phenol aldehyde condenses, Mw 3692 3.00
Base oil 74.5 74.5 74.5
At 100 ℃ kinematic viscosity, cSt 19.25 19.70 20.02
Base number, D2896, mgKOH/g 72.21 71.76 72.25
HFRR, the temperature of minimized friction coefficient, ℃ 362.8 363.1 375.1
Top table demonstration, along with the increase of phenol aldehyde condenses weight-average molecular weight (Mw), the temperature of minimized friction coefficient (℃) also along with rising.

Claims (10)

1. the purposes of oil soluble alkyl phenol aldehyde condenses is used as the anti-wear additive in the lubricating oil composition, and oil soluble alkyl phenol aldehyde condenses has following structure:
Figure A2005100935170002C1
Wherein n is 0 to 10, and is preferred 1 to 8, more preferably 2 to 6, most preferably 3 to 5; Y is a divalence bridge joint group, and preferred alkyl preferably has 1 to 4 carbon atom; R has 4 to 30, and is preferred 8 to 18, most preferably the alkyl of 9 to 15 carbon atoms.
2. the purposes of claim 1, wherein lubricating oil composition is used for marine diesel engine.
3. claim 1 or 2 purposes, wherein the weight-average molecular weight of alkyl phenol aldehyde condenses (Mw) is in 800 to 4500 scope, preferred 1100 to 4200, more preferably 1300 to 4000, most preferably 1700 to 3800, measure gained by MALDI-TOF (matrix assisted laser desorption ionization-flight time) mass spectrometry.
4. each purposes during aforesaid right requires, wherein condenses contains and is less than 5.0 quality %, more preferably less than 3.0 quality %, even more preferably less than the unreacted alkyl phenol of 1.0 quality %.
5. each purposes during aforesaid right requires, wherein alkyl phenol aldehyde condenses is resulting by in the presence of acid catalyst at least a aldehydes or ketones or its reactive equivalent and alkyl phenol being carried out polycondensation.
6. each purposes during aforesaid right requires, wherein the alkyl in alkyl phenol aldehyde condenses is a branching.
7. each purposes during aforesaid right requires, wherein alkyl phenol aldehyde condenses is an alkyl phenol formaldehyde (PF) condenses.
8. each purposes during aforesaid right requires, wherein alkyl phenol aldehyde condenses is the tetrapropylene benzene phenol formaldehyde condensate.
9. each purposes during aforesaid right requires, wherein lubricating oil composition contains at least a following additive: washing agent, dispersion agent, antioxidant, anti-wear additive, pour point depressor, defoamer, viscosity index improver, dyestuff, metal passivator, non-emulsifying agent, or its mixture.
10. the wearing and tearing that improve lubricating oil composition reduce the method for characteristic, and this method comprises each limited in claim 1-7 the alkyl phenol aldehyde condenses step in the lubricating oil composition.
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CN106318540A (en) * 2015-06-30 2017-01-11 英菲诺姆国际有限公司 Additive package for marine engine lubrication
CN106318540B (en) * 2015-06-30 2021-03-16 英菲诺姆国际有限公司 Additive package for marine engine lubrication

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