CN106459818A - Multigrade lubricating compositions - Google Patents

Multigrade lubricating compositions Download PDF

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Publication number
CN106459818A
CN106459818A CN201580033464.5A CN201580033464A CN106459818A CN 106459818 A CN106459818 A CN 106459818A CN 201580033464 A CN201580033464 A CN 201580033464A CN 106459818 A CN106459818 A CN 106459818A
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Prior art keywords
weight
lubricant
oil
viscosity
lubricating composition
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CN201580033464.5A
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Chinese (zh)
Inventor
J·G·卢普
M·加里克拉古兹
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Lubrizol Corp
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Lubrizol Corp
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Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Priority to CN202210757995.0A priority Critical patent/CN115093893A/en
Publication of CN106459818A publication Critical patent/CN106459818A/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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2207/26—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
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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—Overbased sulfonic acid 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
    • 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
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/52—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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • 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

The invention relates to a method of lubricating a mechanical device (such as an internal combustion engine) with a lubricating composition. The invention further relates to the use of the lubricating composition for an internal combustion engine to provide improved fuel economy and providing at least one of (i) wear reduction, (ii) control of corrosion, (iii) cleanliness, and (iv) soot control.

Description

Multistage lubricating composition
Invention field
The technology relates to the lubricating composition of large diesel engine, and which is used for improved fuel economy and does not reduce Durability (i.e. wear-resistant) performance of electromotor.This can be by being applied in combination height with ashless dispersant and parlkaline containing metal detergent Viscosity index (VI) base oil and realize.
Background of invention
Lubricant oil composite is used for the smooth operation of internal combustion engine.It is used in particular for for the engine oil of internal combustion engine：I () lubricates Between piston ring and cylinder liner, in the bearing of crank axle and connecting rod and valve driving mechanism, including in cam and valve tappet Various sliding interfaces, (ii) cools down electromotor, (iii) cleaning and disperses combustion products, and therefore (iv) prevent from corroding and Rust is formed.In recent years, the strict demand with regard to high-performance enginer mean with regard in this kind of electromotor with lubricator relatively Big requirement.
There is the interest of raising in terms of the fuel efficiency of internal combustion engine is improved.Vehicular manufacturer is improved by electromotor design Fuel economy, using the improvement of the lubricating oil of the friction for providing higher oxygen stability, abrasion protection and reduction.Heavy bavin The operator of oily vehicle is difficult to improve fuel economy using low viscosity grade engine oil；Durability, that is, keep vehicle on road The time of upper prolongation and mileage are for mainly worrying and remaining main misgivings.Therefore, for highway heavy diesel vehicle Most widely used viscosity grade is SAE 15W-40.In recent years, the fuel efficiency for improving heavy diesel vehicle is increasingly promoted.Cause This, need to improve the fuel economy of diesel engine and do not jeopardize durability or the negative effect lubricant properties of electromotor, bag Include deposit and flue dust control and non-oxidizability and anticorrosive property.This is especially in regard to the viscosity lighter than SAE 15W-40 etc. Level, such as 10W-30.
Generally polymer viscosity index improver is added in lubricating base oil, including high refined mineral oil, to improve lubrication The viscosity-temperature profile of compositionss and/or low-temperature viscosity profiles.Viscosity index (VI) is usually as lubricating base oil and lubricating composition Viscosity-temperature profile is assessed, and the performance with regard to low-temperature viscosity profiles assessment is usually pour point, cloud point and freezing point.Polymer glues Degree index improver is also related in deposit is formed.
Summary of the invention
The purpose of invention described herein includes to provide improved fuel economy, at the same also provide following at least one：(i) The abrasion (such as cam wear or tappet abrasion) of reduction, the deposit that (ii) reduces is formed, and (iii) improved flue dust is processed, (iv) lead for reducing or copper corrosion, improved seal compatibility in the non-oxidizability that (v) is improved, and/or (vi) internal combustion engine.Example Such as, the purpose of the present invention includes to provide improved fuel economy, at the same also provide following at least one：I abrasion that () reduces Or the deposit that (ii) reduces is formed, especially in compression ignition (i.e. diesel oil) electromotor.
Invention described herein provides multistage lubricating composition, and which includes：Have at least 110 or 120 to 140 or 150 The oil with lubricant viscosity of viscosity index (VI)；Ashless dispersant；With overbased metal detersive, wherein lubricating composition is comprising few In 0.01 weight % polymer viscosity index improver.Lubricant compositions have the SAE viscosity grade of XW-Y, and wherein X is permissible For 0,5 or 10；And Y can be 16,20,26,30 or 40.
The present invention further provides lubricating composition as described herein, wherein Multistage crankshaft case lubricant be SAE 0W-16, 0W-20,0W-26,5W-16,5W-20,5W-26,5W-30,10W-16,10W-30, or 10W-40 lubricant.
The present invention further provides lubricating composition as described herein, wherein ashless dispersant is derived from 500-5000 Number-average molecular weight polyolefin.
The present invention further provides lubricating composition as described herein, wherein overbased detergent containing metal include sulfonic acid One or more in calcium, Calcium carbolate, sulfonic acid magnesium or phenol magnesium.
The present invention further provides lubricating composition as described herein, wherein overbased detergent containing metal is to be supplied to group The amount of compound at least 4TBN is present.
The present invention further provides lubricating composition as described herein, wherein lubricating composition have at least 130 or at least 135 viscosity index (VI).In one embodiment, lubricating composition has 130-230,135-195, or 140-175's is viscous Degree index.
The present invention further provides lubricating composition as described herein, the wherein oil with lubricant viscosity have at least 124 Viscosity index (VI).
The present invention further provides lubricating composition as described herein, wherein has the oil of lubricant viscosity comprising 0.1 weight The oil of the hydroisomerization derived from high-content wax feed stream of amount weight % of % to 20.
The present invention further provides lubricating composition as described herein, wherein has the oil of lubricant viscosity comprising 0.5 weight The oil of the hydroisomerization derived from high-content wax feed stream of amount weight % of % to 5.
The present invention further provides the method for lubrication compression-ignition engine, which feeds as this paper institute in including to electromotor State lubricant compositions.
The present invention further provides the method for the fuel economy of compression-ignition engine, which feeds in including to electromotor SAE 0W-16,0W-20,0W-26,5W-16,5W-20,5W-30,10W-16,10W-30 or 10W-40 lubricant, wherein lubricates Oil with lubricant viscosity of the agent comprising the viscosity index (VI) with least 115, ashless dispersant and overbased detergent, wherein moisten Sliding compositionss are comprising less than 0.01 weight % polymeric viscosity modifier.
The present invention further provides the Multistage crankshaft case lubricant combination of the viscosity index (VI) with least 130 as described herein Thing, which includes the oil with lubricant viscosity of the viscosity index (VI) with least 115, and ashless dispersant, overbased metal are peace and quiet Agent, wherein lubricating composition are comprising less than 0.1 weight % ethylene-olefin base co-polymer.
The present invention further provides lubricant compositions as described herein, wherein in ethylenic copolymer, ethylene is constituted For preparing 50 moles of % to 90 mole of % of the monomer of copolymer.
The present invention further provides lubricant compositions as described herein, wherein ethylene-olefin copolymer have 5,000- The molecular weight of 40,000Mn.
The present invention further provides lubricant compositions as described herein, wherein not more than 50% overbased detergent bag Soap containing salicylate.
Detailed description of the invention
Illustrate below by indefiniteness and describe each preferred feature and embodiment.Unless otherwise indicated, as this paper institute With the referring to for amount of the additive with regard to being present in the lubricating composition is quoted based on the amount of oil-free, i.e. active substance.
Oil with lubricant viscosity
The present invention has the oil of lubricant viscosity and may be defined as API II+ group base oil.API II+ group base oil is known and retouches It is set forth in for example entitled " Design Practice：The SAE of Passenger Car Automatic Transmissions " goes out Version thing, the 4th edition, AE-29, publishes, in the 12-9 page for 2012.API II+ group is also defined as by US 8,216,448 to be had greatly In or viscosity index (VI) equal to 110 and less than 120 " II+ group base oil ".
The present invention have lubricant viscosity oil can have at least 110 or 115 or 120 to 140 or 150 viscosity refer to Number (VI).In one embodiment, viscosity index (VI) can be at least 130, or at least 135.In another embodiment, glue Degree index can be at least 124.
The present invention have the example of the oil of lubricant viscosity include with registrar name of an article Ultra-S,The base oil that Petrocanada and Chevron neutral oil 110RLV sells.
The present invention has the oil of lubricant viscosity can be with 60 weight % of lubricating composition to 97.5 weight %, or 70 weights Weight % of % to 95 is measured, or 80 weight % are present to 95 weight %.
The oil that the present invention has lubricant viscosity also (can be different from present invention definition with the conventional oil with lubricant viscosity Oil with lubricant viscosity) mixing, condition is that base oil continues to show viscosity index (VI) as described above.Conventional have lubrication The oil of viscosity can be as American Petroleum Institute (API) Base Oil Interchangeability Define described in Guidelines.Five groups of base oils are as follows：I group (sulfur content>0.03 weight %, and/or<90 weight % saturates, glue Degree index 80-120)；II group (sulfur content≤0.03 weight %, and >=90 weight % saturates, viscosity index (VI) 80-120)；III Group (sulfur content≤0.03 weight %, and >=90 weight % saturates, viscosity index (VI) >=120)；IV group (all polyalphaolefins (PAO))；With V group (all other base oil not included in I, II, III or IV group).Oil with lubricant viscosity includes API I group, II group (different from the oil with lubricant viscosity of present invention definition), III group, IV group, V group oil or its mixture.
Generally, the oil that routine has lubricant viscosity is API I group, II group is (different from gluing with lubrication for present invention definition The oil of degree), III group, IV group oil or its mixture.Alternatively, the conventional oil with lubricant viscosity is usually API II group (no Be same as the oil with lubricant viscosity of present invention definition), oily or its mixture of III group or IV group.I, II and III group is mineral Oily base stock.Oil with lubricant viscosity may include naturally occurring or synthetic oil and its mixture.Mineral oil and artificial oil can be used Mixture, such as poly-a-olefin oil and/or polyester oil.
API II group and III group base oil is made to stand hydrotreating to reduce/remove aromatic compounds and improve viscosity index (VI). III group base oil is made to stand harsh hydroprocessing technique condition to produce the oil of the viscosity index (VI) with least 120.Implement at one In scheme, lubricating composition of the present invention comprising having at least 110, at least 120, at least 130, or even at least 140 viscosity The strict hydrotreating base oil of index.In one embodiment, lubricating composition includes III group base oil.Some high viscositys refer to Number III group base oil is produced partially by high-content wax feed stream is included so as to is stood hydroisomerization and is referred to producing high viscosity Number iso-paraffinic base oils.
Natural oil includes animal oil and vegetable oil (such as plant acid esters) and mineral lubricating oil, such as liquid petroleum, with And the solvent of alkane, cycloalkane or mixing paraffmic-naphthenic types is processed or acid treatment mineral lubricating oil.Hydrotreating or plus Hydrogen cracked oil is also the useful oil with lubricant viscosity.The oil with lubricant viscosity derived from coal or shale is also useful 's.
Artificial oil includes hydrocarbon ils and halo hydrocarbon ils, such as polymerization and copolyalkenamer and its mixture, alkylbenzene, polyphenyl, alkane Base diphenyl ether and alkylated diphenyl sulfides and its derivant, analog and homologue.Oxyalkylene polymer and copolymer and its Derivant and terminal hydroxyl by be for example esterified or etherification modified those for other classifications synthetic lubricant fluid.Other are suitable Synthetic lubricant fluid include the ester of dicarboxylic acids and by C5-C12Those of monocarboxylic acid and polyhydric alcohol or polyol ethers preparation.Other close Become lubricating oil include the liquid ester of phosphoric acid, PolyTHF, silicon-based oil such as poly- alkyl-, poly- aryl-, poly-alkoxyl-or poly- virtue Epoxide-silicone oil, and silicic acid ester oil.
Other artificial oils include those for preparing by fischer-tropsch reaction, the Fischer-Tropsch hydrocarbon of usual hydroisomerization or wax.One In individual embodiment, oil can pass through Fischer-Tropsch gas to the preparation of liquid (gas-to-liquid) synthesis program and other gas to liquid oil.
In one embodiment, the base oil with lubricant viscosity is comprising 0.1 weight % to 20 weight % derived from height The base oil fraction of the hydroisomerization of wax feed stream and/or the base oil of the hydroisomerization derived from Fischer-Tropsch wax feed stream.? Adding derived from high-content wax feed stream of the oil comprising 0.5 weight % to 5 weight % in one embodiment, with lubricant viscosity The base oil fraction of hydrogen isomerization and/or the base oil of the hydroisomerization derived from Fischer-Tropsch wax feed stream.In one embodiment, Wax of the lubricating composition without (or being substantially free of) hydroisomerization derives base oil.
The naturally occurring or synthetic non-refine of above-disclosed type, refine and refined oil (and its mixture) again can be used. Non- refined oil is without further purification processes and direct by those that originates and obtain naturally occurring or synthetic.Refined oil is similar to not essence They are except for the difference that processed to improve one or more performance in one or more purification step by oil refining further.Smart again Oil refining is obtained by being applied to have been used to similar to the method for obtaining refined oil the refined oil of service.Generally will also refine again Oil processing is to remove useless additive and oil decomposition product.
The amount of the oil with lubricant viscosity for existing is usually the amount for deducting performance additive of the present invention from 100 weight % And remaining surplus later.
Lubricating composition can be concentrate and/or the form for preparing lubricant completely.If performance additive of the present invention Form for concentrate (which can be combined with other oil completely or partially to form final lubricant), then performance additive and tool Have lubricant viscosity oil and/or with the ratio of flux oil be:99-99:1 weight meter, or 80:20-10:90 weight meters.
Ashless dispersant
Dispersant is typically known in field of lubricant, and mainly includes referred to as ashless dispersant and polymer dispersion Agent.Ashless dispersant is so called to be because that they are not comprising metal, therefore usual when adding in lubricant when providing Sulfate ash is not contributed.However, add them into include in lubricant containing metal species when, they may be with environment metal Interact.Ashless dispersant is characterized in that the polar group being connected on higher molecular weight hydrocarbon chain.Typical ashless dispersant Replace long chain alkenyl succinimides including the N- with multiple chemical constitutions, those for representing including formula (I)：
Wherein each R1Alkyl independently is, is typically based on the molecular weight (M that polyisobutylene precursor has 500-5000n) Polyisobutylene group, and R2For alkylidene, usual ethylidene (C2H4).
This quasi-molecule is typically derived from the reaction of alkenyl acylating agent and polyamines, and except simple imide structure illustrated above Outward, the multiple keys between two structure divisions are possible, including multiple amide and quaternary ammonium salt.In upper formula (I), amine moiety shows Alkylene polyamine is shown as, but can also use other aliphatic series and aromatics list-and polyamines.In addition, R1Group is on imide structure Multiple key patterns are possible, including various ring keys.The carbonyl of acylating agent can be 1 with the ratio of the nitrogen-atoms of amine:0.5-1:3, In other cases 1:1-1:2.75 or 1:1.5-1:2.5.Succinimide dispersants are described more fully below in United States Patent (USP) 4, In 234,435 and 3,172,892 and EP 0355895.
In certain embodiments, dispersant is prepared by the method for being related to the presence of a small amount of chlorine or other halogens, such as beautiful (referring to the 4th hurdle 18-60 row and preparation embodiment A) described in state's patent 7,615,521.This kind of dispersant generally replaces in alkyl In base and the connection of acid or amide " head " group, there are some carbocyclic ring structure.In other embodiments, dispersant is by relating to And " alkene " reaction and do not use the thermal means of any chlorine or other halogens to prepare, such as United States Patent (USP) 7, described in 615,521；With this Dispersant prepared by mode is typically derived from high vinylidene (i.e. more than 50% terminal vinylidene) polyisobutylene (referring to the 4th The 61st row of hurdle to the 30th row of the 5th hurdle and prepares embodiment B).This kind of dispersant is typically free of above-mentioned carbocyclic ring structure at junction point. In certain embodiments, dispersant is poly- with the free radical catalysis of olefinic unsaturated acyl agent by high vinylidene polyisobutylenes Close and prepare, such as United States Patent (USP) 8, described in 067,347.
Dispersant can be derived from as the polyolefinic high vinylidene with more than 50,70 or 75% terminal vinylidene Polyisobutylene (α and beta isomer).In certain embodiments, succinimide dispersants can pass through direct alkylation route system Standby.In other embodiments, it can include the mixture of direct alkylation and chloro- route dispersant.
Include succinimide dispersants for the suitable dispersant in the present composition.In one embodiment, Dispersant can be present as single dispersant.In one embodiment, dispersant can be used as two or three different dispersion The mixture of agent is present, and wherein at least one can be succinimide dispersants.
Succinimide dispersants can be derivant or its mixture of aliphatic polyamines.Aliphatic polyamines can be many for aliphatic series Amine such as ethylene, propylidene polyamines, butylidene polyamines or its mixture.In one embodiment, aliphatic polyamines are permissible For ethylene.In one embodiment, aliphatic polyamines are selected from by ethylenediamine, diethylenetriamines, triethylene four The group of amine, tetren, penten, polyamines kettle residual and its mixture composition.
Succinimide dispersants can be the derivant of aromatic amine, aromatic polyamine or its mixture.Aromatic amine can be 4-ADPA (ADPA) (also referred to as N- phenyl phenylenediamine), the derivant of ADPA are (as United States Patent (USP) discloses 2011/ Described in 0306528 and 2010/0298185), nitroaniline, aminocarbazole, amino-indazole quinoline ketone, aminopyrimidine, 4- (4- nitro Phenylazo) aniline or its combination.In one embodiment, dispersant is the derivant of aromatic amine, and wherein aromatic amine has At least 3 discontinuous aromatic rings.
Succinimide dispersants can be the derivant of polyetheramine or polyether polyamine.Typical polyether amine compound includes At least one ether unit and with least one amine structure part chain termination.Polyether polyamine can be based on derived from C2-C6Epoxide Polymer as ethylene oxide, propylene oxide and butylene oxide.The example of polyether polyamine withTrademark Soynatto is simultaneously And it is commercially available by the Hunstman Corporation for being located at Houston, Texas.
Another kind of ashless dispersant is high-molecular weight ester.These materials similar to above-mentioned butanimide, except for the difference that it Can be considered by alkyl acylating agent and multi-aliphatic alcohol such as glycerol, tetramethylolmethane or Sorbitol reaction and prepare.This kind of material Material is described in greater detail in United States Patent (USP) 3,381,022.Aromatics succinate also can disclose 2010/ as United States Patent (USP) Prepare described in 0286414.
Succinic based dispersants (butanimide, succinamide, succinate and its mixture) can be by any method Those (such as chloro method or thermal means) make maleic anhydride or its reactive equivalent such as acid or ester react with hydrocarbon chain as described above And formed.Other acid or its equivalent can be used to replace maleic anhydride.These include fumaric acid, itaconic acid, itaconic anhydride, lemon health The acid of acid, citraconic anhydride and cinnamic acid and other ethylenic unsaturated acids, such as acrylic or methacrylic；Reactivity with them Equivalent.
Another kind of ashless dispersant is Mannich base.These are many by higher molecular weight alkyl substituted phenol, alkylidene Amine and aldehyde such as formaldehyde condensation and the material that formed.These materials can have the general structure as shown in formula (II)：
(including multiple isomers etc.) and it is described in greater detail in United States Patent (USP) 3,634,515.
Another kind of ashless dispersant includes the dispersant comprising quaternary ammonium salt.Quaternary ammonium salt includes the product of following material： The compound of (i) comprising at least one tertiary amino；(ii) it is suitable to for the tertiary amino of compound (i) to change into the quaternized of quaternary nitrogen Agent.The example of suitably quaternary ammonium salt includes：(i) acid imide quaternary ammonium salt, (ii) Mannich quaternaries, (iii) polyalkylene replaces Amine quaternary ammonium salt, (iv) amidoquat salt, (v) ester quat, (vi) polyester quaternary ammonium salt, or (vii) its any combinations.
These various types of quaternary ammonium salts can be prepared in a variety of ways, but generally by on-quaternised nitrogen-containing compound with Quaternizing agent reacts and prepares.Different on-quaternised nitrogen used in each its preparation comfortable of the different types of quaternary ammonium salt Compound, but generally on-quaternised nitrogen-containing compound comprising can be quaternized tertiary carbon (or the primary or secondary of tertiary carbon can be alkylated into Nitrogen-atoms, the tertiary carbon then can be quaternized) and hydrocarbyl substituent.The preparation of quaternary ammonium dispersant and using being described in detail in the U.S. In patent 7,951,211 and United States Patent (USP) 7,906,470.
Also can by dispersant by conventional method by with plurality of reagents in any one reaction and post processing.Wherein, this A little is boron compound, urea, thiourea, dimercaptothiodiazole, Carbon bisulfide, aldehyde, ketone, carboxylic acid, the succinic anhydrides of hydrocarbon replacement, maleic acid Acid anhydride, nitrile, epoxide and phosphorus compound.
Dispersant can also show the basicity as measured by total base number (TBN).TBN can be determined by ASTM D2896. This is particularly, and prepared by dispersant amine such as polyamines and amine is comprising one or more amino not reacted with the acidic-group of dispersant Situation.In some embodiments, the TBN of dispersant can be 1-110, or 5-50, or 10-40 or 30-70.So And, in some embodiments, dispersant can not show basicity (having 0 or almost 0 TBN).In one embodiment, Dispersant has the TBN for being measured as zero by D2896.This is probably the situation that there is no basic nitrogen on dispersant.
Dispersant can be with 0.01 weight % of lubricating composition to 20 weight %, or 0.1 weight % is to 15 weight %, Or 0.1 weight % to 10 weight %, or 0.5 weight % is to 8 weight %, or 1.0 weight % are present to 6.5 weight %.
Metal overbased detergent
The further referred to as metal overbased detergent of overbased detergent, overbased detergent containing metal or hyperalkaline salt It is characterized in that tenor exceedes according to metal and the stoichiometry with the specific acidic organic compound (i.e. substrate) of metal reaction Amount needed for neutralization.Overbased detergent can include without thiophenol salt, sulfur-bearing phenates, sulfonate, salicylate and its mixture In one or more.
The amount of excessive metal is generally according to substrate:Metal is than representing.Term " metal ratio " is used in prior art and herein Total chemical equivalent of metal and salt in overbased salt are defined in the known chemical reactivity according to two kinds of reactants and stoichiometry Middle expection replaces organic acid by alkyl；Waited the reaction that alkalizes between alkyl fortified phenol or its mixture and alkali metal compound Stoichiometric ratio of the metal of generation.Therefore, in normal salt or neutral salt (i.e. soap), metal ratio is 1, in overbased salt, Metal ratio is more than 1 especially greater than 1.3.Overbased detergent of the present invention can be with 5-30 metal ratio, or the gold of 7-22 Category ratio, or at least 11 metal ratio.
" mixing " detersive for being formed by mixed surfactant system, the system bag be may also include containing metal detergent Containing phenates and/or sulfonate component, such as phenates/salicylate, sulfonate/phenates, sulfonate/salicylate, sulfonate/phenol Salt/salicylate, such as United States Patent (USP) 6,429,178；6,429,179；6,153,565；With described in 6,281,179.If For example using mixing sulfonate/phenate detergents, then it is assumed that this mixes detersive and is equal to phenates and the sulphur for introducing similar quantity respectively The independent phenates of hydrochlorate soap and the amount of sulfonate detergent.Parlkaline phenates and salicylate generally have the total of 180-450TBN Base number.Overbased sulfonates generally have 250-600, or the total base number of 300-500.Overbased detergent be in this area Know.
Alkylphenol is typically used as the component in overbased detergent and/or construction unit.Alkylphenol can be used to prepare Phenates, salicylate, salixarate or salicin detersive or its mixture.Suitably alkylphenol may include that para-position takes The hydrocarbylphenol in generation.Alkyl can be with 1-60 carbon atom, 8-40 carbon atom, 10-24 carbon atom, 12-20 carbon Atom, or the linear or branched aliphatic group of 16-24 carbon atom.In one embodiment, alkylphenol parlkaline is clear Net agent is by the alkylphenol for not containing or being substantially free of (i.e. comprising less than 0.1 weight %) p- dodecyl phenol or its mixing Prepared by thing.In one embodiment, lubricating composition of the present invention is comprising less than 0.3 weight % alkylphenol, less than 0.1 weight Amount % alkylphenol, or it is less than 0.05 weight % alkylphenol.
Parlkaline can be alkali metal or alkali salt containing metal detergent.In one embodiment, parlkaline is clear Net agent can be sodium salt, calcium salt, magnesium salt or its mixing of phenates, sulfur-bearing phenates, sulfonate, salixarate and salicylate Thing.In one embodiment, overbased detergent is calcium detersive, magnesium detersive or its mixture.In an embodiment In, parlkaline calcium detersive can be supplied to lubricating composition at least 500 weight ppm calcium and not more than 3000 weight ppm calcium, Or at least 1000 weight ppm calcium, or at least 2000 weight ppm calcium, or the amount presence of not more than 2500 weight ppm calcium. In one embodiment, overbased detergent can be deposited with being supplied to the amount of lubricating composition not more than 500 weight ppm magnesium , or not more than 330 weight ppm, or not more than 125 weight ppm, or not more than 45 weight ppm.In an embodiment party In case, lubricating composition is substantially free of the magnesium that (i.e. comprising less than 10ppm) is caused by overbased detergent.In an embodiment In, overbased detergent is to be supplied to lubricating composition at least 200 weight ppm magnesium, or at least 450 weight ppm magnesium, Huo Zhezhi The amount of few 700 weight ppm magnesium is present.In one embodiment, calcic and detersive containing magnesium all may be present in lubricating composition In.There may be calcium and magnesium detersive to cause calcium be 10 with the weight ratio of magnesium:1-1:10, or 8:3-4:5, or 1:1-1:3.? In one embodiment, overbased detergent is not contained or is substantially free of sodium.
In one embodiment, sulfonate detergent can predominantly have the linear alkyl benzene of at least 8 metal ratio Sulfonate detergent, such as United States Patent (USP) disclose [0026th]-[0037] of 2005/065045 (and authorizing as US 7,407,919) Duan Suoshu.Linear alkyl benzene sulfonate detersive can be used in particular for help and improve fuel economy.Linear alkyl can be along alkane Any position of the linear chain of base is connected with phenyl ring, but on 2,3 or 4 generally in linear chain, in some cases, is mainly existed On 2, linear alkyl benzene sulfonate detersive is produced.
Salicylate detergent and parlkaline salicylate detergent can be prepared in the way of at least two is different.To alkane The carbonylation (also referred to as carboxylation) of base phenol is described in many lists of references, including United States Patent (USP) 8,399,388.Carbonylation it After can be alkalization, to form parlkaline salicylate detergent.Suitably alkylphenol is included with 1-60 carbon original Those of the linear and/or branched hydrocarbyl radical of son.Salicylate detergent also can pass through alkylation of salicylic acid, thereafter cross alkalization and Prepare, such as United States Patent (USP) 7, described in 009,072.The salicylate detergent being prepared can be by containing 6-50 carbon atom, 10- 30 carbon atoms, or linear and/or branched-alkyl agent (the usual 1- alkene) preparation of 14-24 carbon atom.In a reality Apply in scheme, overbased detergent of the present invention is salicylate detergent.In one embodiment, salicylate of the present invention is clear Net agent is without unreacted to alkylphenol (i.e. containing less than 0.1 weight %).In one embodiment, salicylic acid of the present invention Salt detersive is prepared by alkylation of salicylic acid.
Overbased detergent can be with 0.2 weight % to 15 weight %, or 0.3 weight % is to 10 weight %, or 0.3 Weight % is to 8 weight %, or 0.4 weight % is present to 3 weight %.For example, in large diesel engine, detersive can be with profit 2 weight % of sliding compositionss are present to 3 weight %.For bus engine, detersive can be with 0.2 weight of lubricating composition Amount weight % of % to 1 is present.
Overbased detergent containing metal is generally provided to lubricating composition TBN.In one embodiment, parlkaline is peace and quiet Agent is being supplied to the lubricating composition at least TBN of 4mg KOH/g, or is supplied to lubricating composition 4-15mg KOH/g, or The amount of the TBN of 5-9mg KOH/g is present.
Lubricating composition sulfate ash is contributed to containing metal detergent.Sulfate ash can be determined by ASTM D874.One In individual embodiment, lubricating composition of the present invention contains comprising the amount for being supplied to total composition at least 0.4 weight % sulfate ash Metal detergent.In another embodiment, containing metal detergent to be supplied to lubricating composition at least 0.6 weight % sulfate Ash, or at least 0.75 weight % sulfate ash, or the amount presence of even at least 0.9 weight % sulfate ash.
Outside ash disposal and TBN, overbased detergent contributes to lubricating composition detersive soap, also referred to as neutral detergents salt. Soap (for the slaine of substrate) can serve as surfactant in lubricating composition.In one embodiment, lubricating composition Comprising 0.05 weight % to 1.5 weight % detersive soaps, or 0.1 weight % is to 0.9 weight % detersive soap.Implement at one In scheme, lubricating composition includes not more than 0.5 weight % detersive soap.Overbased detergent can have 5:1-1:2.3, or 3.5:1-1:2, or 2.9:1-1:1:7 ash:Soap weight ratio.
Other performance additive
The present composition can optionally include one or more other performance additive.These other performance additives can be wrapped Include one or more metal deactivator, detersive, friction improver, antiwear additive, corrosion inhibitor, flue dust dispersing additive, spy Pressure agent, antioxidant, foam inhibitor, demulsifier, pour-point depressant, sealing sweller and its any combinations or mixture.Generally, Lubricating oil is prepared completely comprising one or more in these performance additive, the bag of usual multiple performance additive.
In one embodiment, the present invention provides lubricating composition, and which changes comprising antiwear additive, dispersant viscosity further Enter agent, friction improver, viscosity improver, antioxidant, overbased detergent, dispersant (different from the present invention's) or its group Close, wherein listed additive can be each the mixture of two or more in such additive.In one embodiment, The present invention provides lubricating composition, and which includes antiwear additive, dispersant viscosity modifiers, friction improver, viscosity modified further Agent (usual olefin copolymer, such as ethylene-propylene copolymer), excessively antioxidant (including phenols and amine antioxidants), alkali Property detersive (including overbased sulfonates and phenates) or its combination, wherein listed additive each can be such additive in The mixture of two or more.
Another additive is antiwear additive.The example of antiwear additive includes phosphorous wear-resistant/extreme pressure agent, such as metal thiophosphate phosphoric acid Salt, phosphate ester and its salt, phosphorus-containing carboxylic acid, ester, ether and amide, and phosphite.In certain embodiments, phosphorus antiwear additive is permissible To provide the amount presence of 0.01-0.2 or 0.015-0.15 or 0.02-0.1 or 0.025-0.08% phosphorus.Generally, wear-resistant Agent is zinc dialkyl dithiophosphate (ZDP).
Depending on the structure of alcohol used in its preparation, zinc dialkyl dithiophosphate can be described as primary dialkyl dithio phosphorus Sour zinc or secondary zinc dialkyl dithiophosphate.In some embodiments, the present composition includes primary dialkyl dithio phosphorus Sour zinc.In some embodiments, the present composition includes secondary zinc dialkyl dithiophosphate.In some embodiments, Mixture of the present composition comprising primary and secondary zinc dialkyl dithiophosphate.In some embodiments, component (b) is primary With the mixture of secondary zinc dialkyl dithiophosphate, wherein primary zinc dialkyl dithiophosphate and secondary zinc dialkyl dithiophosphate Ratio (based on weight) be at least 1:1, or even at least 1:1.2, or even at least 1:1.5 or 1:2, or 1:10.? In some embodiments, component (b) is the mixture of primary and secondary zinc dialkyl dithiophosphate, and the mixture is at least 50 weights Amount % primary, or even at least 60,70,80, or even 90 weight % primary.In some embodiments, component (b) does not contain primary Zinc dialkyl dithiophosphate.
Phosphorus antiwear additive can be with 0 weight % of lubricating composition to 3 weight %, or 0.1 weight % is to 1.5 weight %, Or 0.5 weight % exist to 0.9 weight %.
Another kind of antiwear additive includes oil-soluble titanium, such as United States Patent (USP) No.7,727,943 Hes Described in US20060014651.Oil-soluble titanium may act as antiwear additive, friction improver, antioxidant, sediment monitoring and add Plus it is more than one in agent or these functions.In one embodiment, oil-soluble titanium can be titanium (IV) alkoxide. Titanium alkoxides can be formed by monohydric alcohol, polyhydric alcohol or its mixture.Unitary alkoxide can be with 2-16, or 3-10 carbon atom. In one embodiment, Titanium alkoxides can be isopropyl titanate (IV).In one embodiment, Titanium alkoxides can be 2- ethyl hexyl Alcohol titanium (IV).In one embodiment, alkoxide of the titanium compound comprising vincial faces 1,2- glycol or polyhydric alcohol.In an embodiment party In case, the glycerinated fatty-acid monoester of 1,2- vincial faces glycol bag, usual fatty acid can be Oleic acid.In one embodiment, Oil-soluble titanium can be carboxylic acid titanium.In one embodiment, carboxylic acid titanium (IV) can be neodecanoic acid titanium.In a reality Apply in scheme, oil-soluble titanium can be to provide weight ppm of 10ppm to 1500 titanium or weight ppm of 25ppm to 150 titanium institute The amount for needing is present in lubricating composition.
In one embodiment, the present invention provides lubricating composition, and which includes ashless antioxidant further.Ashless anti- Oxidant can include arylamine, diaryl amine, alkylated aryl amine, alkylation diaryl amine, phenol, hindered phenol, olefine sulfide Or one or more in its mixture.In one embodiment, lubricating composition is comprising antioxidant or its mixture.Anti- Oxidant can be with 0 weight % of lubricating composition to 15 weight %, or 0.1 weight % is to 10 weight %, or 0.5 weight Amount weight % of % to 5, or 0.5 weight % is to 3 weight %, or 0.3 weight % is present to 1.5 weight %.
Diaryl amine or alkylation diaryl amine can be phenyl-a-naphthylamine (PANA), alkylated diphenylamine, or alkyl Change nonox or its mixture.Alkylated diphenylamine may include two-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, Dioctylated diphenylamines, didecylated diphenylamines, decyl diphenylamine and its mixture.In one embodiment, diphenylamines can Including nonyl diphenylamine, dinonyldiphenylamine, octyl diphenylamine, dioctyl diphenylamine or its mixture.In an embodiment In, alkylated diphenylamine may include nonyl diphenylamine or dinonyldiphenylamine.Alkylation diaryl amine may include octyl group, two pungent Base, nonyl, dinonyl, decyl or didecyl nonox.
Diarylamine antioxidant of the present invention can be with the weight based on lubricating composition as 0.1% to 10%, 0.35% To 5%, or even 0.5% to 2% is present.
Phenol antioxidant can be monoalkyl benzene phenol, hindered phenol or be coupled oxybenzene compound.
Hindered phenol antioxidant generally comprises sec-butyl and/or the tert-butyl group as steric group.Phenolic groups can be further The bridge linkage group being connected by alkyl (generally linear or branched-alkyl) and/or with the second aromatic group replaces.Suitable hindered phenol The example of antioxidant includes 2,6- di-t-butyl phenol, 4- methyl -2,6- di-t-butyl phenol, 4- ethyl two-uncle of -2,6- Butylphenol, 4- propyl group -2,6- di-t-butyl phenol or 4- butyl -2,6- di-t-butyl phenol, 4- dodecyl -2,6- Di-t-butyl phenol, or 3- (3,5- di-tert-butyl-hydroxy phenyl) butyl propionate.In one embodiment, hindered phenol Antioxidant can be ester, and may include the Irganox for example from CibaTML-135.
Being coupled phenol 2 alkylphenols being coupled with alkylidene is generally comprised to form bisphenol compound.Suitably it is coupled The example of oxybenzene compound includes 4,4' methylene bis-(2,6- di-t-butyl phenol), 4- methyl -2,6- di-t-butyl benzene Phenol, 2,2'- pair-(the 6- tert-butyl group -4- heptylphenol)；4,4'- double (2,6- di-t-butyl phenol), 2,2' methylene bis (4- Methyl-6-tert-butylphenol) and 2,2' methylene bis (4- ethyl -6- tert-butyl phenol).
Phenol of the present invention also includes polyhydric aromatic compound and its derivant.The example bag of suitable polyhydric aromatic compound Include gallic acid, 2,5- resorcylic acid, 2,6- resorcylic acid, 1,4- dihydroxy-2-naphthoic acid, 3,5- dihydroxy naphthlene Formic acid, the ester of 3,7- dihydroxy naphthlene formic acid and amide and its mixture.
In one embodiment, phenol antioxidant includes hindered phenol.In another embodiment, hindered phenol derived from 2,6 di t butyl phenol.
In one embodiment, lubricating composition of the present invention includes 0.01 weight % of lubricating composition to 5 weight %, Or 0.1 weight % to 4 weight %, or 0.2 weight % to 3 weight %, or the phenols of 0.5 weight % to 2 weight % resists Oxidant.
Olefine sulfide be known to commercial materials, and be substantially free of nitrogen, i.e., those of not nitrogenous sense are readily available. Vulcanizable olefin(e) compound is multiple in nature.They include at least one olefinic double bonds, and which is defined as non-aromatic double Key；That is, connect the double bond of two aliphatic carbon atoms.These materials generally have with 1-10, such as 1-4 or 1 or 2 sulfur original The sulfide linkage of son.
Ashless antioxidant can be used dividually or in combination.In one embodiment of the invention, two are applied in combination Plant or more kinds of different antioxidants so that there is each at least two antioxidants of at least 0.1 weight %, and The combined amount of wherein ashless antioxidant is 0.5-5 weight %.In one embodiment, there may be at least 0.25-3 weight % Each ashless antioxidant.
In one embodiment, the present invention provides the lubricating composition comprising molybdenum compound further.Molybdenum compound can Selected from molybdenum dialkyl-dithiophosphate, molybdenum dithiocarbamate, the amine salt of molybdenum compound, dispersant containing molybdenum and its mixture The group of composition.The example of commercially available molybdenum compound includes Sakura-lubeTM525 and Sakura-lubeTM710, which all can be by Adeka Corporation is obtained；With can be obtained by Vanderbilt Chemicals, LLC855.Molybdenum Compound is provided to lubricating composition 0-1000ppm, or 5-1000ppm, or 10-750ppm, or 5ppm to 300ppm, Or 20ppm to 250ppm molybdenum.In one embodiment, molybdenum compound be to be supplied to lubricating composition 300ppm extremely The molybdenum dithiocarbamate compound that the amount of 750ppm molybdenum is present.
In one embodiment, lubricating composition of the present invention includes flue dust dispersing additive further.Flue dust dispersion adds Plus agent can be with 0 weight % of lubricating composition to 5 weight %, or 0 weight % is to 4 weight %, or 0.05 weight % is to 2 Weight % is present.
Suitably flue dust dispersing additive includes functionalization low-molecular-weight polyolefin, and the number for example having less than 20,000 is equal Molecular weight (Mn) with acylating agent such as maleic anhydride and amine, the preferably amine-functionalized ethylene-propylene copolymer of aromatics.Other flue dust Dispersing additive can be prepared by the acylated polyisobutylene amine-functionalized with aromatics (many).The more detailed description of flue dust dispersing additive It is disclosed in United States Patent (USP) 4,863,623；5,182,041；7,790,661；8,557,753；In 8,637,437.In a reality Apply in scheme, flue dust dispersing additive may include United States Patent (USP) 7,790,661 or United States Patent (USP) 8, described in 557,753 those.
In one embodiment, the present invention provides the lubricating composition comprising friction improver further.Friction is improved The example of agent includes long-chain fatty acid derivative, fatty ester or the epoxide of amine；Fatty imidazolines, such as carboxylic acid and poly- alkylene The condensation product of Quito amine；The amine salt of alkyl phosphoric acid；Alpha-hydroxy-carbonyl compound such as tartaric acid, malic acid, citric acid, hydroxyl Acetic acid, the fatty ester of lactic acid and mandelic acid, amide and/or acid imide.As used herein, term fat is can refer to C8-22Line Property alkyl.
Friction improver may also include material such as sulfurized fatty compound and alkene, molybdenum dialkyl-dithiophosphate, two sulfur Monoesters for carbamic acid molybdenum, Oleum helianthi or polyhydric alcohol and aliphatic carboxylic acid.
In one embodiment, friction improver be selected from by the long-chain fatty acid derivative of amine, long-chain fat ester or Long chain fatty epoxide；Fatty imidazolines；The amine salt of alkyl phosphoric acid；Tartaric acid fatty alkyl ester；Fatty alkyl tartaroyl Asia Amine；Group with fatty alkyl tartramide composition.Friction improver can with 0 weight % of lubricating composition to 6 weight %, or 0.05 weight % of person is to 4 weight %, or 0.1 weight % is present to 2 weight %.
In one embodiment, friction improver can be long-chain fatty acid ester.In another embodiment, long-chain fat Fat acid esters can be monoesters or diester or its mixture, and in another embodiment, long-chain fatty acid ester can be glycerol three Ester.
Other performance additive U. S. application US05/ as disclosed in corrosion inhibitor is included as WO2006/047486 Described in 038319 5-8 section those, the contracting of octyl group caprylamide, dodecenyl succinic acid or acid anhydride and fatty acid such as Oleic acid and polyamines Close product.In one embodiment, corrosion inhibitor includes(the note of The Dow Chemical Company Volume trade mark) corrosion inhibitor.Corrosion inhibitor can be homopolymer or the copolymer of propylene oxide.Corrosion inhibitor is described in greater detail in the product manual Form of Dow Chemical Company publication In No.118-01453-0702AMS.The product manual entitled " SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications”.
Lubricating composition can further include metal deactivator, including the derivative of benzotriazole (usually tolyl-triazole) Thing, dimercaptothiodiazole derivant, 1,2,4- triazole, benzimidazole, 2- alkyl dithio benzimidazole or 2- alkyl dithio Benzothiazole；Foam inhibitor, the copolymer and ethyl acrylate including ethyl acrylate and 2-EHA and propylene Sour 2- Octyl Nitrite and the copolymer of vinyl acetate；Demulsifier, including trialkylphosphate, Polyethylene Glycol, polyoxyethylene Alkene, polypropylene oxide and (ethylene oxide-propylene oxide) polymer；And pour-point depressant, including maleic anhydride-styrene Ester, polymethacrylates, polyacrylate or polyacrylamide.
Lubricating composition can further include polyether compound.Polyether compound can be polyethers, polyetheramine, (gathering) alcoxyl Base amine, ethoxylated alcohol or its mixture.Polyethers can be by formula RO [CH2CH(R1)O]xH represents, wherein R is alkyl；R1It is selected from The group being made up of hydrogen, the alkyl with 1-14 carbon atom and its mixture；And x is the number of 2-50.Alkyl R is univalence hydrocarbyl, With one or more carbon atoms, and including with 7-30 carbon atom is amounted to, such as amounting to 9-25 carbon atom, or amounting to The alkyl of 11-20 carbon atom and alkyl phenyl.Repeated oxidation alkene unit can derive ethylene oxide, propylene oxide or oxidation fourth Alkene.The number x of oxyalkylene units can be 10-35, or 18-27.Polyethers of the present invention can be prepared by the method known to various, Including generally making 1 mol of alcohol or alkylphenol and 2 moles or more moles of oxyalkylene, oxyalkylene in the presence of base catalyst Mixture, or be condensed with several oxyalkylenes in a sequential manner.The offer of United States Patent (USP) No.5,094,667 prepares the anti-of polyethers Answer condition.Suitably polyethers is commercially available by Chemicals, Huntsman, ICI, and including from Bayer's Series.Suitably ethoxylate includesEthoxylate, such as Surfonic L24-5, which can be by Huntsman International LLC is obtained.
There may be polymeric viscosity modifier, condition is that they are less than lubricating composition in one embodiment 0.1 weight %.In one embodiment, polymeric viscosity modifier is deposited with the amount less than 0.01 weight % of lubricating composition ?.Suitably viscosity improver includes ethylene-olefin copolymer, especially ethylene-propylene；Maleic anhydride-styrene is alternately altogether Polymers and its ester, polymethacrylates (including random, block and hub-and-spoke configuration), hydrogenated styrene-butadiene block copolymerization Thing, hydrogenated styrene isoprene radial direction and/or block copolymer or its mixture.In one embodiment, polymer glues Degree modifier includes ethylene-olefin base co-polymer.In some embodiments, ethylene is constituted based on for preparing ethylene-olefin 50 weight % of the molal quantity of the monomer of base co-polymer are to 90 weight % or 65 weight % to 85 weight %.In another embodiment In, ethylene constitutes at least 70 weight % for the monomer for preparing copolymer.In one embodiment, ethylene-olefin copolymerization Thing has the molecular weight of 5,000-40,000Mn.
Can be used for pour-point depressant in the present composition and further include polyalphaolefin, maleic anhydride-styrene Ester, poly- (methyl) acrylate, polyacrylate or polyacrylamide.
Commercial Application
As described above, the method that the present invention provides lubricating internal combustion engines, methods described is fed as herein in including to internal combustion engine The lubricating composition.In general, adding lubricant in the lubricating system of internal combustion engine, then the lubricating system is grasped at which During work being supplied to lubricating composition needs the electromotor critical component of lubrication.
Above-mentioned lubricating composition can be used in internal combustion engine.Engine pack can with steel or aluminium surface (usual steel surface), And also can for example scribble diamond-like-carbon (DLC) coating.
Aluminium surface may include aluminium alloy, and which can be for eutectic or hypereutectic aluminium alloy (for example derived from aluminium silicate, aluminum oxidation Those of thing or other ceramic materials).Aluminium surface may be present in cylinder block with aluminium alloy or aluminum complex, cylinder boring or work On plug ring.
Internal combustion engine can be provided with emission control systems, oil mist separator or turbocharger.The example of emission control systems Including diesel particulate filters (DPF), or the system using SCR (SCR).
Inventive combustion engine is different from gas turbine.In internal combustion engine, single combustion incident is by bar and bent axle by straight Line reciprocating force is transformed into driving torque.Conversely, in gas turbine (which is alternatively referred to as jet engine), continuous burning process is even Produce driving torque continuously and do not change, but also thrust can be developed at waste gas outlet.Gas turbine and the operation of internal combustion engine These differences of condition cause different operating environments and stress.
Any engine lubricant be may be adapted to for the lubricant compositions of internal combustion engine but regardless of sulfur, p and ses hydrochlorate ash (ASTM D-874) content.The sulfur content of engine oil lubricants can be 1 weight % or less, or 0.8 weight % or more Few, or 0.5 weight % or less, or 0.3 weight % or less.In one embodiment, sulfur content can be 0.001 Weight % is to 0.5 weight %, or 0.01 weight % is to 0.3 weight %.Phosphorus content can be 0.2 weight % or less, or 0.12 weight % or less, or 0.1 weight % or less, or 0.085 weight % or less, or 0.08 weight % or more Few, or even 0.06 weight % or less, 0.055 weight % or less, or 0.05 weight % or less.Implement at one In scheme, phosphorus content can be 100ppm to 1000ppm, or 200ppm to 600ppm.Total sulfate ash content can be 2 weights Amount % or less, or 1.5 weight % or less, or 1.1 weight % or less, or 1 weight % or less, or 0.8 Weight % or less, or 0.5 weight % or less, or 0.4 weight % or less.In one embodiment, sulfate Ash content can be 0.05 weight % to 0.9 weight %, or 0.1 weight % to 0.2 weight % or to 0.45 weight %.
In one embodiment, lubricating composition can be engine oil, and the wherein feature of lubricating composition can be With following at least one：(i) 0.5 weight % or less sulfur content, (ii) 0.1 weight % or less phosphorus content, and (iii) 1.5 weight % or less sulfate ash content, or its combination.
Embodiment
Following examples provide the elaboration to the present invention.These embodiments are exhaustive, and are not intended to limit the present invention Scope.
Embodiment：
A series of 10W-30 diesel fuel lubricity compositionss are prepared according to table 1 below.Compositionss are by component as shown in table 1 to be mixed into Prepare in lubricant.Amount in table 1 is based on oil-free.
1 lubricating composition of table
1.Ultra-S(S-Oil)VHVI-8cSt；VI=131
2.Ultra-S (S-Oil) VHVI-4cSt (29.64%) (VI=125)/Ultra-S (S-Oil) VHV-8cSt (46.36%) VI=131
3.PIB butanimide
4. low metal ratio (<3) and high metal ratio (>10) combination of alkylbenzenesulfonate
5. low metal ratio (<2) and high metal ratio (>5) sulfur is coupled the combination of phenates
6. it is acylated with maleic anhydride and the ethylene-propylene copolymer (Mn 7000) with nitroaniline functionalization
7. other additives include matal deactivator, surfactant, ashless antioxidant and foam inhibitor
In GM 6.5L roller follower wear test (RFWT) (ASTM D5966), the abrasion of assessment lubricating composition is protected Shield.Abrasion in the test measurement camshaft roller follower pin is to determine engine oil control mill in the presence of soot load oil The ability of damage.Acquired results are summarized in table 2 below.
In addition, assessing lubricating composition also in Volvo D12D fuel economy engine test；The test assessment is waited Oil phase is selected for the fuel economy benefit of baseline oil (HVES 540).Baseline lubricant is business SAE 15W-40API CJ-4 Heavy-duty diesel oil.Acquired results collect in table 2 below.
The abrasion of table 2 and fuel economy test result
The embodiment of the present invention 1 Comparative example 1
Base oil viscosity@100C 5.80 7.11
KV100 10.5 11.5
VI(D2270) 137 159
Calcium (weight %) 0.29 0.29
Phosphorus (weight %) 0.11 0.11
Sulfur (weight %) 0.38 0.38
HTHS(cP)(D4683) 3.3 3.3
RFWT–GM 6.5L
Average abrasion (mil) 0.10 0.24
D12D FE screen analysis
Average FE improves (%) 0.71 0.47
Acquired results prove that lubricating composition described herein provides improved fuel economy performance and do not sacrifice abrasion and protect Shield.This can realize in the compositionss without polymer viscosity index improver.
Unless otherwise noted, the amount of each chemical constituent is expressed as eliminating generally and may be present in commercial materials Any solvent or flux oil, i.e. based on active chemistry.However, unless otherwise noted, each chemical substance for being mentioned above Or compositionss should be understood to can containing isomer, by-product, derivant and generally it should be understood that be present in commerical grade its The commercial grade material of its this kind of material.
As used herein, term " hydrocarbyl substituent " or " alkyl " are made with its conventional meaning well known to those skilled in the art With.Specifically, it refers to there is the carbon atom being connected directly between on molecule remainder and the main group with hydrocarbon property.Hydrocarbon The example of base includes：
Hydrocarbon substituent, i.e. aliphatic (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group) substituent group, and virtue Race-, aliphatic series-and alicyclic substituted aromatic substituent, and its medium ring completes (such as two by another part of the molecule Substituent group forms ring together) cyclic substituents；
Substituted hydrocarbon substituent, i.e., the non-alkyl containing the main hydrocarbon property for not changing substituent group in the context of the present invention Group (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxyl, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfinyl (sulphoxy) substituent group)；
Miscellaneous substituent group, i.e., in the context of the present invention, in the ring being made up of carbon atom while with main hydrocarbon property Or containing the substituent group for being different from carbon in chain, and including substituent group such as pyridine radicals, furyl, thienyl and imidazole radicals.Hetero atom Including sulfur, oxygen and nitrogen.Generally, for per 10 carbon atoms, no more than 2 in alkyl, preferably no more than 1 nonhydrocarbon Substituent group；Alternatively, there are no substituents in alkyl.
Some above-mentioned materials known may be interacted in final preparaton so that the component of final preparaton may be with Originally those for adding are different.For example, metal ion (such as detersive) can migrate to other molecules other are acid or cloudy Ion position.The product being consequently formed, may not allow including the product through being formed using the present composition with its intended use Easily describe.However, all such is improved and product is included within the scope of the present invention；The present invention is included by will be above-mentioned The compositionss that component mixes and prepares.
As mentioned below, the molecular weight of above-mentioned material uses known method, and such as gpc analysis use polystyrene standard Determine.Determine polymer molecular weight method be known to.Method is described in for example：(i) P.J.Flory, " Principles Of star polymer Chemistry ", Cornell University Press 91953), chapter vii, 266-315 Page；Or (ii) " Macromolecules, an Introduction to star polymer Science ", F.A.Bovey And F.H.Winslow, editor, Academic Press (1979), in the 296-312 page.As used herein, the weight of the material All obtained by the area for combining under peak corresponding to meaningful material with number-average molecular weight, do not include with diluent, impurity, It is not coupled the peak of star-type polymer chain and other additives.
Here by above-mentioned each file, including any earlier application for claiming priority (no matter hereinbefore whether It is expressly recited) it is incorporated by reference into the present invention.Mentioning not for any file is that this document obtains prior art qualification or to appoint What authority constitutes the accreditation of the general knowledge of technical staff.Except in embodiment, or in addition clearly state outer, describe material in this manual All quantity of the amount of material, reaction condition, molecular weight, carbon number etc. should be understood modified by the term " about.It should be understood that this The upper and lower bound of the text amount, scope and ratio independently can be combined.Similarly, the scope of each element of the present invention and amount are permissible It is used together with the scope of any other element or amount.
As used herein, the transitional term "comprising" synonymous with " including ", " containing " or " being characterized in that ... " be inclusive or Open and be not excluded for other unstated elements or method and step.However, in each description of "comprising" herein, it is intended to Used as optional embodiment, the term also includes phrase " substantially by ... constitute " and " Consists of ", wherein " Consists of " are not Including any element for not describing or step, " substantially by ... constitute " allows to include the compositionss not considered by substantial effect Or other of the important or basic and new features of method do not describe element or step.
Although showing some representative embodiment and details to illustrate the present invention, those skilled in the art learn can not Deviate the scope of the present invention and make various changes and the improvement of this paper.On this point, the scope of the present invention only receives following power Sharp claim is limited.

Claims (15)

1. multigrade lubricant compositionss, which includes：
A the oil of () with lubricant viscosity, which has at least 110 or 120 to 140 or 150 viscosity index (VI)；
(b) ashless dispersant；With
(c) overbased detergent,
Wherein lubricating composition is comprising less than 0.01 weight % polymer viscosity index improver；
Wherein lubricant compositions have the SAE viscosity grade of XW-Y, and wherein X can be 0,5 or 10；And Y can be 16,20, 26th, 30 or 40.
2. lubricant compositions according to claim 1, wherein Multistage crankshaft case lubricant are SAE OW-16,0W-20,0W- 26th, 5W-16,5W-20,5W-26,5W-30,10W-16,10W-30, or 10W-40 lubricant.
3. lubricating composition according to claim 1, wherein ashless dispersant is derived from the number-average molecular weight with 500-000 Polyolefin.
4. lubricating composition according to claim 1, wherein overbased detergent containing metal include sulfoacid calcium, Calcium carbolate, sulfonic acid One or more in magnesium or phenol magnesium.
5. lubricating composition according to claim 4, wherein overbased detergent containing metal is to be supplied to compositionss at least 4TBN Amount exist.
6. lubricating composition according to claim 1, wherein lubricating composition have at least 130 or at least 135 viscosity index (VI).
7. lubricant according to claim 1, wherein has viscosity index (VI) of the oil of lubricant viscosity with least 124.
8. lubricant compositions according to claim 1, wherein have the oil of lubricant viscosity comprising 0.1 weight % to 20 weight % The hydroisomerization derived from high-content wax feed stream oil.
9. lubricant compositions according to claim 1, wherein have the oil of lubricant viscosity comprising 0.5 weight % to 5 weight % The hydroisomerization derived from high-content wax feed stream oil.
10. the method for lubricating compression-ignition engine, which feeds lubricant according to claim 1 in including to the electromotor Compositionss.
The method of 11. fuel economies for improving compression-ignition engine, which feeds SAE OW-16, OW- in including to electromotor 20th, OW-26,5W-16,5W-20,5W-26,5W-30,10W-16,10W-30, or 10W-40 lubricant, wherein lubricant bag Contain：
A the oil of () with lubricant viscosity, which has at least 115 viscosity index (VI)；
(b) ashless dispersant, and
(c) overbased metal detersive,
Wherein lubricating composition is comprising less than 0.01 weight % polymeric viscosity modifier.
The 12. Multistage crankshaft case lubricant compositions with least 130 viscosity index (VI), which includes：
A the oil of () with lubricant viscosity, which has at least 115 viscosity index (VI)；
(b) ashless dispersant；With
(c) overbased detergent,
Wherein lubricating composition is comprising less than 0.1 weight % ethylene-olefin base co-polymer.
13. lubricant compositions according to claim 12, wherein in ethylene-olefin base co-polymer, ethylene constitutes 50 and rubs The monomer for preparing copolymer of your % to 90 mole of %.
14. lubricant compositions according to claim 13, wherein ethylene-olefin copolymer have dividing for 5,000-40,000Mn Son amount.
15. lubricant compositions according to claim 12, wherein not more than 50% overbased metal detersive includes bigcatkin willow Hydrochlorate soap.
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