The method of lubricant and improvement low speed pre-ignition with high alkalinity calcium and high alkalinity magnesium detergent

文档序号：1759985 发布日期：2019-11-29 浏览：32次中文

阅读说明：本技术 具有高碱性钙和高碱性镁清洁剂的润滑剂和改进低速早燃的方法 (The method of lubricant and improvement low speed pre-ignition with high alkalinity calcium and high alkalinity magnesium detergent ) 是由克里斯汀·弗莱彻丽莎·丁韦尔于 2017-11-09 设计创作，主要内容包括：一种润滑油组合物和运行增压型内燃发动机的方法。所述润滑油包括大于50重量％的基础油、一种或多种高碱性含钙清洁剂、一种或多种高碱性含镁清洁剂和一种或多种钼化合物并且与参考油的LSPI相比,使得LSPI减少大于60％并通过球锈蚀测试。来自所述高碱性清洁剂的钙的重量％与来自所述高碱性清洁剂的镁的重量％的比率小于11.9。镁的总ppm与所述润滑油的以mg KOH/g计的总TBN的比率大于19。钙的总ppm与所述润滑油的总TBN的比率小于222。相对于市售润滑油,所述油和方法可以减少增压型内燃机的低速早燃事件。(A kind of method of lubricant oil composite and operation boosting type internal combustion engine.The lubricating oil include greater than 50 weight % base oil, one or more high alkalinity calcic detergents, one or more high alkalinity detergents containing magnesium and one or more molybdenum compounds and compared with the LSPI of reference oil so that LSPI reduce be greater than 60% and by ball corrosion test.The ratio of the weight % of the weight % and magnesium from the over-based detergent of calcium from the over-based detergent is less than 11.9.The ratio of total TBN in terms of mg KOH/g of the total ppm and lubricating oil of magnesium is greater than 19.The ratio of total TBN of the total ppm and lubricating oil of calcium is less than 222.Relative to commercially available lubricating oil, the oil can reduce the low speed pre-ignition event of supercharged combustion engine with method.)

1. a kind of lubricant oil composite, it includes:

With the total weight of the lubricant oil composite, the base oil of the lubricant viscosity greater than 50 weight %；

Enough one or more high alkalinity calcic detergents have and are greater than as measured by the method for ASTM D-2896 The total base number of 225mg KOH/g, to provide the calcium for being greater than 1000ppm to the lubricant oil composite；

One or more high alkalinity detergents containing magnesium have and are greater than 225mg as measured by the method for ASTM D-2896 The total base number of KOH/g, wherein the magnesium provided from one or more high alkalinity detergents containing magnesium to the lubricant oil composite Total amount be 50-1500ppm；With

One or more molybdenum compounds provide the total amount of the molybdenum of 25-1000ppm to the lubricating composition；

Wherein the weight % of the calcium from one or more high alkalinity calcic detergents in the lubricant oil composite with The ratio of the weight % of the magnesium from one or more high alkalinity detergents containing magnesium in the lubricant oil composite is less than 11.9；

As measured by the method for ASTM D-2896, total ppm of the magnesium in the lubricant oil composite with the lubricating oil group The ratio for closing total TBN of the lubricant oil composite of the mg KOH/g meter of object is greater than 19；

As measured by the method for ASTM D-2896, total ppm of the calcium in the lubricant oil composite with the lubricating oil group The ratio of total TBN of the lubricant oil composite of the mg KOH/g meter of object is closed less than 222；

Relative to the low speed pre-ignition event number in the same engine lubricated with reference lubricating oil R-1, the lubricating oil composition Object, which is effectively reduced the quantity of low speed pre-ignition event, is greater than 60%, such as under steady state conditions, a reactor, in the speed of about 1750rpm and big 4 hours 2.0 liter of 4 cylinder EcoBoost turbocharging gasoline direct of Ford is run under 80% maximum brake mean-effective pressure In engine, four 4 hour stages each 175,000 cycle of engine of stage is undergone to be measured；And

The lubricant oil composite is corroded by ball to be tested.

2. lubricant oil composite according to claim 1, wherein one or more high alkalinity calcic detergents include Detergent selected from sulfoacid calcium and calcium phenoxide detergent.

3. lubricant oil composite according to claim 1, wherein one or more high alkalinity detergents containing magnesium include Sulfonic acid magnesium detergent.

4. lubricant oil composite according to claim 3, wherein in the lubricant oil composite from described a kind of or The weight % of the calcium of a variety of high alkalinity calcic detergents in the lubricant oil composite from described one or more high-alkali The ratio of the weight % of the magnesium of property detergent containing magnesium is less than 10.

5. lubricant oil composite according to claim 3, wherein in the lubricant oil composite from described a kind of or The weight % of the calcium of a variety of high alkalinity calcic detergents in the lubricant oil composite from described one or more high-alkali Property the detergent containing magnesium magnesium weight % ratio be 0.5 to 9.

6. lubricant oil composite according to claim 3, wherein as measured by the method for ASTM D-2896, the profit Total ppm of magnesium in sliding oil composition is total in terms of lubricant oil composite described in mg KOH/g with the lubricant oil composite The ratio of TBN is greater than 25.

7. lubricant oil composite according to claim 3, wherein as measured by the method for ASTM D-2896, the profit Total ppm of magnesium in sliding oil composition is total in terms of lubricant oil composite described in mg KOH/g with the lubricant oil composite The ratio of TBN is 30-90.

8. lubricant oil composite according to claim 2, wherein as measured by the method for ASTM D-2896, the profit Total ppm of calcium in sliding oil composition is total in terms of lubricant oil composite described in mg KOH/g with the lubricant oil composite The ratio of TBN is less than 215.

9. lubricant oil composite according to claim 2, wherein as measured by the method for ASTM D-2896, the profit Total ppm of calcium in sliding oil composition is total in terms of lubricant oil composite described in mg KOH/g with the lubricant oil composite The ratio of TBN is 125-210.

10. lubricant oil composite according to claim 3, the amount of one or more of them high alkalinity calcic detergent is to institute It states lubricant oil composite and the calcium for being greater than 1000ppm to less than 2000ppm is provided.

11. lubricant oil composite according to claim 3, the amount of one or more of them high alkalinity calcic detergent is to institute It states lubricant oil composite and the calcium of 1050ppm to 1900ppm is provided.

12. lubricant oil composite according to claim 3, wherein one or more high alkalinity detergents containing magnesium are to institute It states lubricant oil composite and the magnesium of 100-1200ppm is provided.

13. lubricant oil composite according to claim 3, wherein one or more high alkalinity detergents containing magnesium are to institute It states lubricant oil composite and the magnesium of 200-800ppm is provided.

14. lubricant oil composite according to claim 3, wherein one or more molybdenum compounds are to the lubrication group It closes object and the molybdenum of 50-800ppm is provided.

15. lubricant oil composite according to claim 1, wherein with the total weight of the lubricant oil composite, it is described The amount of boron in lubricant oil composite is 150 to 600ppm.

16. lubricant oil composite according to claim 2, wherein one or more overbased calcium sulfonate detergents tools There is the total base number of at least 250mg KOH/g.

17. lubricant oil composite according to claim 1, wherein as measured by the method for ASTM D-2896, it is described Lubricant oil composite has the total base number for being less than lubricant oil composite described in 10mg KOH/g.

18. lubricant oil composite according to claim 1, wherein as measured by the method for ASTM D-2896, it is described The TBN that one or more calcic detergents are contributed to the lubricant oil composite is lubricating oil group described in 2.5-5.0mg KOH/g Close object.

19. lubricant oil composite according to claim 1, wherein as measured by the method for ASTM D-2896, it is described The combination of one or more calcic detergents and one or more detergents containing magnesium is contributed to the lubricant oil composite TBN is lubricant oil composite described in 4.0-8.0mg KOH/g.

20. lubricant oil composite according to claim 1, wherein relative to the identical hair lubricated with reference lubricating oil R-1 The quantity of low speed pre-ignition event in motivation, the lubricant oil composite are effectively reduced the quantity of low speed pre-ignition event 60%.

21. lubricant oil composite according to claim 1 also includes one or more selected from the group being made up of Component: friction improver, antiwear agents, dispersing agent, antioxidant and viscosity index improver.

22. lubricant oil composite according to claim 1, wherein the base oil greater than 50 weight % be selected from by The group of consisting of: II class, Group III, IV class, V class base oil and it is aforementioned in the combination of two or more, and its Described in be greater than the base oil of 50% weight and be not due to provide additive component or viscosity to the lubricant oil composite Index improver and the flux oil generated.

23. a kind of method for reducing the quantity of the low speed pre-ignition event in boosting type internal combustion engine, it includes following steps It is rapid:

Boosting type internal combustion engine is lubricated with lubricant oil composite according to claim 1, and

Run the engine lubricated with the lubricant oil composite.

24. according to the method for claim 24, wherein the lubricating step makes to be provided with turbocharger or booster Spark-ignition direct injection (sidi) engines or the spark ignition fuel port injection type IC engine for being provided with turbocharger or booster Combustion chamber or cylinder wall lubrication.

25. according to the method for claim 25, also including the internal combustion for measuring and being lubricated with the lubricant oil composite The step of quantity of the low speed pre-ignition event of engine.

Technical field

This disclosure relates to contain the lubricant oil composite and this lubricating oil composition of one or more oil soluble additives The purposes of object improvement low speed pre-ignition.

Background technique

Turbocharged engine or supercharged engine (i.e. boosting type or forcing induction internal combustion engine) are likely to occur title For the abnormal combustion phenomenon of random pre-ignition or low speed pre-ignition (or " LSPI ").LSPI is a kind of pre-ignition event, may include non- Normal high pressure peak, the pre-ignition and pinking occurred during inappropriate crankshaft angles.It is all these, individually and with Combining form may cause engine degradation and/or be badly damaged.However, because LSPI event is only even in an uncontrollable manner So occur, so being difficult to identify the cause of this phenomenon and being difficult to develop the solution for containing it.

Pre-ignition is a kind of combustion type, be the indoor air fuel mixture of burning it is desired by igniter by air The result that fuel mixture burns before lighting.The problem of pre-ignition is typically during high engine speeds are run, because of hair A part of combustion chamber can be heated to being enough lighting the temperature of air fuel mixture at the time of contact by the heat that motivation operation generates.This The pre-ignition of seed type is sometimes referred to as hot spot pre-ignition.

Recently, intermittent abnormal combustion is observed in the boosting type internal combustion engine in low speed in high load capacity. For example, the phase run in engine with 3,000rpm or smaller, underload, at least 10 bars of brake mean-effective pressure (BMEP) Between, low speed pre-ignition (LSPI) may occur with a kind of random and random manner.During low speed engine operation, compression stroke Time longest.

Use, the engine design, engine coatings, piston-shaped, fuel of several open studies have shown that turbocharger Selection, and/or oil additives may cause the increase of LSPI event.A kind of theory thinks, from piston gap (Piston volume tube Space between top and top land) spontaneous combustion of machine oil drop that enters engine chamber may be one of LSPI event Cause.Therefore, it is necessary to effectively reduce or eliminate the oil additives component of the LSPI in boosting type internal combustion engine and/or group It closes.

In addition it is also necessary to which the lubricating component of pressurization h type engine h is reduced or prevented to get rusty to maintain engine performance.It reduces A kind of mode of LSPI event is to reduce the total amount of detergent.But since detergent often has anti-corrosion effects, The amount for reducing detergent can increase corrosion.Therefore, it is necessary to can not only efficiently reduce or eliminate LSPI but also maintain boosting type The oil additives component and/or combination of the anti-corrosion effect of desired level in internal combustion engine.

Summary of the invention

This disclosure relates to a kind of method of lubricant oil composite and operation boosting type internal combustion engine.Lubricant oil composite packet It includes with the base oil of the lubricant viscosity greater than 50 weight % of the total weight of lubricant oil composite；Enough is one or more high Alkaline calcic detergent has the total base number for being greater than 225mg KOH/g as measured by the method for ASTM D-2896, with The calcium for being greater than 1000ppm is provided to lubricant oil composite；One or more high alkalinity detergents containing magnesium have and pass through ASTM It is greater than the total base number of 225mg KOH/g measured by the method for D-2896, wherein by one or more high alkalinity detergents containing magnesium The total amount for being supplied to the magnesium of lubricant oil composite is 50-1500ppm；With one or more molybdenum compounds, to lubricating composition The total amount of the molybdenum of 25-1000ppm is provided.Calcium in lubricant oil composite from one or more high alkalinity calcic detergents Weight % and the ratio of the weight % of the magnesium in the lubricant oil composite from one or more high alkalinity detergents containing magnesium are less than 11.9.Total ppm of magnesium in the lubricant oil composite as measured by the method for ASTM D-2896 and lubricant oil composite it is total The ratio of TBN (in terms of the mg KOH/g of lubricant oil composite) is greater than 19.The lubrication as measured by the method for ASTM D-2896 The ratio of total TBN (in terms of the mg KOH/g of lubricant oil composite) of total ppm and lubricant oil composite of calcium in fluid composition Less than 221.Relative to the low speed pre-ignition event number in the same engine lubricated with reference lubricating oil R-1, the lubricating oil The quantity of low speed pre-ignition event is effectively reduced 60% by composition, such as under steady state conditions, a reactor, in about 1750rpm speed and is greater than 4 hours 2.0 liter of 4 cylinder EcoBoost turbocharging gasoline direct injection of Ford is run under 80% maximum brake mean-effective pressure In motivation, four 4 hour stages each 175,000 cycle of engine of stage is undergone to be measured.In addition, lubricant oil composite is logical Cross ball corrosion test.

Disclosed method is a kind of for reducing the side of the quantity of the low speed pre-ignition event in boosting type internal combustion engine Method comprising following steps: boosting type internal combustion engine is lubricated with the lubricant oil composite of the disclosure, and lubricating oil is used in operation The engine of composition lubrication.In method, lubricating step, which can lubricate, is provided with turbocharger or booster (is included in whirlpool The channel that finds in wheel booster or booster, bushing and other components) spark-ignition direct injection (sidi) engines or be provided with turbine The combustion chamber of the spark ignition fuel port injection type IC engine of booster or booster and/or cylinder wall.It states in each of front In embodiment, method may also include the quantity of the low speed pre-ignition event of the internal combustion engine of measurement lubricant oil composite lubrication Step.Herein in each embodiment of the method, engine in operation can be less than 3000 revs/min (rpm) it is horizontal that engine speed generates the brake mean-effective pressure (BMEP) greater than 1,500kPa, or with the hair of 2000rpm Motivation speed generates the BMEP of 1,800kPa.

In each embodiment of method, the quantity of low speed pre-ignition event can be based on about 175,000 cycle of engine The low speed pre-ignition of period counts.In each embodiment of method, engine can be at about 1750 revs/min and greater than maximum system The lower operation of the 80% of dynamic mean effective pressure.

It states in embodiment in each of front, one or more high alkalinity calcic detergents include that can be selected from sulfoacid calcium and calcium phenoxide The detergent of detergent.It states in embodiment in each of front, one or more high alkalinity detergents containing magnesium may include sulfonic acid magnesium cleaning Agent.

It states in embodiment in each of front, the calcium in the lubricant oil composite from one or more high alkalinity calcic detergents Weight % and the ratio of weight % of the magnesium in the lubricant oil composite from one or more high alkalinity detergents containing magnesium can Less than 10.It states in embodiment in each of front, the calcium in the lubricant oil composite from one or more high alkalinity calcic detergents Weight % and the ratio of weight % of the magnesium in the lubricant oil composite from one or more high alkalinity detergents containing magnesium can To be 0.5 to 9.

It states in embodiment in each of front, the magnesium in the lubricant oil composite as measured by the method for ASTM D-2896 The ratio of total TBN (in terms of the mg KOH/g of lubricant oil composite) of total ppm and lubricant oil composite can be greater than 25.In each of front It states in embodiment, the total ppm and lubricating oil composition of the magnesium in the lubricant oil composite as measured by the method for ASTM D-2896 The ratio of total TBN (in terms of the mgKOH/g of lubricant oil composite) of object can be 30 to 90.

It states in embodiment in each of front, the calcium in the lubricant oil composite as measured by the method for ASTM D-2896 The ratio of total TBN (in terms of the mg KOH/g of lubricant oil composite) of total ppm and lubricant oil composite is smaller than 215.Each In previous embodiment, the total ppm and lubricating oil group of the calcium in the lubricant oil composite as measured by the method for ASTM D-2896 The ratio for closing total TBN (in terms of the mgKOH/g of lubricant oil composite) of object can be 125 to 210.

It states in embodiment in each of front, the amount of one or more high alkalinity calcic detergents can be provided to lubricant oil composite Greater than the calcium of 1000ppm to less than 2000ppm.It states in embodiment in each of front, one or more high alkalinity calcic detergents Amount can provide the calcium of 1050ppm to 1900ppm to lubricant oil composite.

It states in embodiment in each of front, one or more high alkalinity detergents containing magnesium can provide 100- to lubricant oil composite The magnesium of 1200ppm.It states in embodiment in each of front, one or more high alkalinity detergents containing magnesium can be provided to lubricant oil composite The magnesium of 200-800ppm.It states in embodiment in each of front, one or more molybdenum compounds can provide 50- to lubricating composition The molybdenum of 800ppm or 70-550ppm.

It states in embodiment in each of front, lubricant oil composite, which can contain, is no more than 100ppm, or is no more than 50ppm, or not The calcium introduced using low alkalinity/neutrality calcic detergent more than 25ppm.It states in embodiment in each of front, lubricant oil composite It can be without low alkalinity/neutrality calcic detergent of addition.

It states in embodiment in each of front, lubricant oil composite, which can contain, is no more than 200ppm, or is no more than 1000ppm, or The alkaline-earth metal introduced using low alkalinity/mild detergent no more than 75ppm.It states in embodiment in each of front, lubricating oil group Closing object can be without low alkalinity/mild detergent of addition.

It states in embodiment in each of front, with the total weight of lubricant oil composite, the amount of boron can appoint in lubricant oil composite Selection of land is 150 to 600ppm.

It states in embodiment in each of front, one or more overbased calcium sulfonate detergents can have at least 250mgKOH/g's Total base number.

It states in embodiment in each of front, as measured by the method for ASTM D-2896, lubricant oil composite can have small In the total base number of the lubricant oil composite of 10mg KOH/g.

It states in embodiment in each of front, it is clear by one or more calcics as measured by the method for ASTM D-2896 The TBN of clean dose of contribution to lubricant oil composite can be the lubricant oil composite of 2.5-5.0mg KOH/g.

It states in embodiment in each of front, it is clear by one or more calcics as measured by the method for ASTM D-2896 Clean dose is contributed the TBN to lubricant oil composite can be for 4.0-8.0mg KOH/g's with combining for one or more detergents containing magnesium Lubricant oil composite.

It states in embodiment in each of front, relative to the low speed pre-ignition in the same engine lubricated with reference lubricating oil R-1 The quantity of low speed pre-ignition event effectively can be reduced 60% or more by the quantity of event, lubricant oil composite.

It states in embodiment in each of front, lubricant oil composite can be also comprising one or more selected from the group being made up of Component: friction improver, antiwear agents, dispersing agent, antioxidant and viscosity index improver.

It states in embodiment in each of front, the base oil greater than 50 weight % can be selected from the group being made up of: Group II, The combination of Group III, Group IV, Group V base oil and two or more base oils above-mentioned, and wherein it is greater than 50% The base oil of weight is not due to provide additive component or viscosity index improver to lubricant oil composite and the dilution that generates Oil.

It states in embodiment in each of front, lubricant oil composite may include the group iv base oils no more than 10 weight %, V Group base oil or combinations thereof.It states in embodiment in each of front, lubricant oil composite may include the Group V basis less than 5 weight % Oil.

It states in embodiment in each of front, high alkalinity calcic detergent optionally excludes calcium salicylate detergent.

It states in embodiment in each of front, lubricant oil composite can be free of any group iv base oils.

It states in embodiment in each of front, lubricant oil composite can be free of any Group V base oil.

Following term is provided to define to illustrate the meaning of certain terms used herein.

Think term " fluid composition ", " lubricating oil composition ", " lubricant oil composite ", " lubricating oil ", " lubricant combination Object ", " lubricating composition ", " lubricant compositions prepared completely ", " lubricant ", " crankcase oils ", " crankcase lubricant ", " machine oil ", " engine lubricant ", " machine oil " and " motor lubricant " are the synonymous terms of complete interchangeable, all refer to and include Greater than the finished product lubricity product of 50 weight % base oils and a small amount of additive composition.

As used herein, it is believed that term " additive packet ", " multifunctional additive for lubricating oils ", " compositions of additives ", " machine oil addition Agent packet ", " oil additives concentrate ", " crankcase additive packet ", " crankcase multifunctional additive for lubricating oils ", " oil additives Packet ", " machine oil concentrate " are the synonymous terms of complete interchangeable, all refer to the exclusion of lubricant oil composite greater than 50 weight %'s The part of feed of base oil mixture.Additive packet may include or may not include viscosity index improver or pour-point depressant.

Term " high alkalinity " is related to metal salt, such as the metal salt of sulfonate, carboxylate, salicylate and/or phenolate, Present in metal amount be more than stoichiometry amount.This kind of salt can have the level of conversion more than 100% (that is, it may include 100% or more of theoretical metal amount needed for converting its " normal ", " neutrality " salt for acid)." metal ratio " is expressed usually to contract It is written as MR, for indicating that total chemical equivalent of metal is in high alkalinity salt according to known chemical reactivity and stoichiometry Stoichiometric ratio of metal in property salt.In normal or neutral salt, metal ratio one, and in high alkalinity salt, MR is big Yu Yi.It is commonly known as high alkalinity, hyperalkaline or superbased salt, and can be organic sulfuric acid, carboxylic acid, salicylate And/or the salt of phenol.In the disclosure, overbased calcium phenate's detergent has the TBN greater than 170mg KOH/g, and high alkalinity Calcium sulfonate detergents have the TBN greater than 225mg KOH/g, as measured by the method for ASTM D-2896.

In some cases, " high alkalinity " can be abbreviated as " OB ", and in some cases, and " low alkalinity/neutrality " can contract It is written as " LB/N ".

Term " total metal " refers to total metal, metalloid or transition metal in lubricant oil composite, including lubricating oil group Close the metal that the detergent components of object are contributed.

As used herein, term " hydrocarbyl substituent " or " alkyl " or " alkyl " are with its institute to those skilled in the art Well known common meaning uses.Specifically, it refers to the carbon atom that is directly attached to molecule rest part and main Group with hydrocarbon feature.The example of alkyl includes:

(a) hydrocarbon substituent, i.e. aliphatic (for example, alkyl or alkenyl), alicyclic (for example, naphthenic base, cycloalkenyl) replace Base, and through aromatic series, aliphatic and alicyclic substituted aromatic substituents and its middle ring be complete by another part of molecule At cyclic substituents (such as two substituent groups are formed together cycloaliphatic moiety)；

(b) hydrocarbon substituent being substituted, i.e., containing the nonhydrocarbon for not changing main hydrocarbon substituent in the context of the disclosure Base (such as halogen (especially chloro and fluorine-based), hydroxyl, alkoxy, sulfydryl, alkyl thiol, nitro, nitroso, amino, alkyl Amino and sulphur oxygroup) substituent group；With

(c) miscellaneous substituent group, although there is main hydrocarbon feature that is, in the context of the disclosure, in script by carbon atom structure At ring or chain in the substituent group containing atom in addition to carbon.Hetero atom may include sulphur, oxygen and nitrogen, and cover substituent group, Such as pyridyl group, furyl, thienyl and imidazole radicals.Generally, for every ten carbon atoms in alkyl, it will be present and not surpass Two are crossed, for example, being no more than a substituents；In general, will be not present substituents in alkyl.

Unless expressly stated otherwise, otherwise term " weight % " as used herein means that the component accounts for entire lubricating oil The percentage of the weight of composition.In addition, unless expressly stated otherwise, otherwise term " ppm " refers to lubricant oil composite Hundred a ten thousandth weight (ppmw) of total weight.

The term as used herein " solubility ", " oil-soluble " or " dispersibility " can with but not necessarily indicate compound or add Add agent to dissolve in, can be dissolved in, being miscible in or can be suspended in oil by all proportions.However, preceding terms mean really It for example dissolves in, can be suspended in, is dissolvable in water or can steadily be scattered in oil, and degree is enough in the environment using oil Play its predictive role.In addition, if needing, being in addition incorporated to other additives may also allow for being incorporated to higher levels of specific addition Agent.

As used herein, term " TBN " for indicate as measured by ASTM D-2896 method with mg KOH/g group Close the total base number of object meter.

As used herein, term " alkyl " refers to the straight chain of about 1 to about 100 carbon atom, branch, ring-type and/or through taking The saturation chain part in generation.

As used herein, term " alkenyl " refers to the straight chains of about 3 to about 10 carbon atoms, branch, ring-type and/or is substituted Unsaturated chain part.

As used herein, term " aryl " refers to monocycle and polycyclc aromatic compound, may include alkyl, alkenyl, alkane Aryl, amino, hydroxyl, alkoxy, halogenic substituent and/or hetero atom, including but not limited to nitrogen, oxygen and sulphur.

The lubricant of this specification, the combination of component or single component are applicable to various types of internal combustion engines.It closes Suitable engine type may include but be not limited to heavy-duty diesel engine, passenger car, underloading diesel engine, medium seed diesel engine, peculiar to vessel start Machine or motorcycle engine.Internal combustion engine can start for diesel-fueled engine, gasoline engines, gas fuel Machine, bio-fuel engine, diesel oil/bio-fuel mixed fuel engine, gasoline/bio fuel mixed fuel engine, alcohol Or mixtures thereof engine fuel, gasoline/alcohol mixed fuel engine, compressed natural gas (CNG) engine fuel.Diesel engine Machine can be compression ignition engine.Diesel engine can be the compression ignition engine assisted with spark ignition.Gasoline engine Machine can be spark ignition engine.Internal combustion engine can also be applied in combination with electric supply or battery supply.Configured in this way Engine is commonly known as compound engine.Internal combustion engine can be 2 strokes, 4 strokes or rotary engine.In suitable Burn engine includes marine diesel engine (such as inland is peculiar to vessel), aviation piston engine, underload diesel engine and motor Vehicle, automobile, locomotive and truck engine.

Internal combustion engine can containing have one of the following or multiple components: aluminium alloy, lead, tin, copper, cast iron, Magnesium, ceramics, stainless steel, composite material and/or its mixture.The component, which can be, is coated with such as diamond-like carbon coating, profit Sliding coating, contains molybdenum coating, equadag coating, contains nanoparticle coating and/or its mixture phosphorus-containing coatings.Aluminium alloy may include silicon Sour aluminium, aluminium oxide or other ceramic materials.In one embodiment, aluminium alloy is silicic acid aluminium surface.As used herein, term " aluminium alloy " is intended to synonymous with " aluminium composite material " and describes component or surface comprising aluminium and another component, the aluminium with Another component is mutually mixed or is reacted on microcosmic or approximate microscopic scale, regardless of its detailed construction.This will include having to remove Any Conventional alloys of metal except aluminium, and the composite material with nonmetalloid or compound or alloy spline structure, Such as Ceramic Like material.

Lubricant oil composite for internal combustion engine is suitably adapted for any engine, regardless of sulphur, phosphorus or sulfate ash How is (ASTM D-874) content.The sulfur content of oil lubricating agent can be about 1 weight % or less, or about 0.8 weight % or more It is few, or about 0.5 weight % or less, or about 0.3 weight % or less, or about 0.2 weight % or less.In one embodiment In, sulfur content can be within the scope of about 0.001 weight % to about 0.5 weight %, or about 0.01 weight % to about 0.3 weight %.Phosphorus Content can be about 0.2 weight % or less, or about 0.1 weight % or less, or about 0.085 weight % or less, or about 0.08 Weight % or less, or even about 0.06 weight % or less, about 0.055 weight % or less, or about 0.05 weight % or more It is few.In one embodiment, phosphorus content can be about 50ppm to about 1000ppm or about 325ppm to about 850ppm.Overall sulfate Content of ashes can be about 2 weight % or less, or about 1.5 weight % or less, or about 1.1 weight % or less, or about 1 weight Measure % or less, or about 0.8 weight % or less, or about 0.5 weight % or less.In one embodiment, sulfate ash Content can be about 0.05 weight % to about 0.9 weight %, or about 0.1 weight % or about 0.2 weight % to about 0.45 weight %.In In another embodiment, sulfur content can be about 0.4 weight % or less, and phosphorus content can be about 0.08 weight % or less, and sulphur Acidification ash content is about 1 weight % or less.In another embodiment, sulfur content can be about 0.3 weight % or less, and phosphorus content is About 0.05 weight % or less, and sulfate ash can be about 0.8 weight % or less.ASTM D4951 is a kind of covering eight It plants element and the test method of element composition data can be provided.ASTM D5185, which can be used for measuring, to be used and not used profit 22 kinds of elements in lubricating oil and base oil and it can provide the screening using oil with indicating wear.

In some embodiments, total TBN of lubricant oil composite as can be as measured by ASTM D-2896 method to Few 6.0mg KOH/g, or such as measured by ASTM D-2896 method 6.4 to 10mgKOH/g or 6.5 to 9.5mg KOH/g.

In one embodiment, lubricant oil composite is machine oil, and wherein lubricant oil composite can have (i) about 0.5 weight Measure % or less sulfur content, (ii) about 0.1 weight % or less phosphorus content, and (iii) about 1.5 weight % or less sulphur It is acidified content of ashes.

In some embodiments, lubricant oil composite is suitble to (such as contain the combustion of about 1% to about 5% sulphur with by low-sulphur fuel Material) provide power engine be used together.Vehicle on highway fuel contains about 15ppm sulphur (or about 0.0015% sulphur).Profit Sliding oil composition is suitble to be used together with boosting type internal combustion engine, and the boosting type internal combustion engine includes turbocharging internal combustion Engine or booster-type internal combustion engine.

In addition, the lubricant of this specification is suitably adapted for meeting one or more industry specification requirements, as ILSACGF-3, GF-4、GF-5、GF-6、PC-11、CI-4、CJ-4、CK-4、FA-4、ACEAA1/B1、A2/B2、A3/B3、A3/B4、A5/B5、 C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro 5/6, Jaso DL-1, low SAPS, middle SAPS or original equipment manufacturer Specification, such asMB ratify 229.51/229.31, MB- approval 229.71, VW 502.00, 503.00/503.01、504.00、505.00、506.00/506.01、507.00、508.00、509.00、BMW Longlife- 04、Porsche C30、PeugeotAutomobile B71 2290, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM6094-M, Chrysler MS-6395, or it is unmentioned herein PCMO the or HDD specification in any past or future.In some embodiments, passenger car machine oil (PCMO) is applied, product stream The amount of phosphorus is 1000ppm or less or 900ppm or less or 800ppm or less in body.

Other hardware may be not suitable for being used together with disclosed lubricant." functional fluid " is to cover various fluids Term, the fluid includes but is not limited to dragger hydraulic fluid；Power transmitting fluids: including automatic transmission fluids, stepless change Fast device fluid and manual transmission fluid；Hydraulic fluid, including dragger hydraulic fluid；Some gear oils；Electronic-controlled power steering fluid； For wind turbine, the fluid of compressor；Some industrial fluids and fluid relevant to power system part.It should be noted that In In each such as automatic transmission fluid in these fluids, due to the various transmission devices with different designs, there are various Different types of fluid, this results in the need for the fluid with dramatically different functional characteristic.This and term " lubricating fluid " are formed pair Than " lubricating fluid " is not used in generation or transmission power.

About dragger hydraulic fluid, for example, these fluids are in addition to owning in the lubrication external dragger of engine The universal product of lubricant application.These lubrication applications may include gear-box, power output and one or more clutches, rear-wheel Axis, reduction gearing, the lubrication of wet brake and hydraulic services.

When functional fluid is automatic transmission fluids, automatic transmission fluids must have it is enough rub so that from Clutch plate transmits power.However, the coefficient of friction of fluid has the tendency of decline, because of temperature caused by fluid heats during operation Degree influences.Dragger hydraulic fluid or automatic transmission fluids maintain its great friction coefficient particularly significant at high temperature, otherwise make Dynamic system or automatic transmission may break down.This is not the function of machine oil.

Tractor fluids and for example super dragger oil universal (STUO) or general dragger transmission oil (UTTO) can be by machines The performance of oil is combined with speed changer, differential mechanism, whole transmission planetary gear, wet brake and hydraulic performance.Although many is used for Prepare UTTO or STUO fluid additive it is functionally similar, if but merging it is improper, may have illeffects.For example, The some wear-resistant and EP agent used in machine oil can have extremely strong corrosivity to the copper component in hydraulic pump.For The detergent and dispersing agent of gasoline or diesel engine performance can be unfavorable for wet brake performance.It is exclusively used in eliminating wet braking Thermal stability needed for the friction improver of device noise can lack machine oil performance.Each in these fluids, either function Property, dragger or lubrication, be all to meet specifically and stringent manufacturer requires and designs.

The disclosure provides the new lubricant blend prepared and be used as vehicle crankcase lubricant.Embodiment of the disclosure can It provides and is suitable for crankcase application and there is the improved lubricating oil of following characteristics: is aerating processing, alcohol fuel compatibility, anti-oxidant Property, wear resistance, bio-fuel compatibility, foam reduce performance, antifriction, fuel economy, pre-ignition prevention, antirust, sludge And/or cigarette ash dispersibility, piston cleanliness, deposit are formed, turbocharger deposit is formed and water resistance.

It can be by the way that one or more additives (as described in detail later) be added in suitable basic oil formulation To prepare the machine oil of the disclosure.Additive can be combined in the form of additive packet (or concentrate) with base oil or alternatively, can It is individually combined with base oil (or both mixture).Additive and its corresponding ratio based on addition, are prepared completely Machine oil can express improved performance.

The other details and advantage of the disclosure will illustrate partially in the following description, and/or can be by practicing this public affairs It opens and learns.The details and advantage of the disclosure can be realized by means of the element that is particularly pointed out in the appended claims and combination and It obtains.It should be understood that foregoing general description and following detailed description are all only exemplary and illustrative, it is not to requiring The limitation of the disclosure of protection.

Specific embodiment

The various embodiments of the disclosure provide lubricant oil composite and can be used for reducing low in boosting type internal combustion engine The method of the quantity of fast pre-ignition event (LSPI).Specifically, the boosting type internal combustion engine of the disclosure include turbocharging and Booster-type internal combustion engine.Boosting type internal combustion engine includes spark-ignition direct-injection and/or spark ignition fuel port injecting type hair Motivation.Spark ignition IC engine can be petrol engine.

Composition of the invention includes the lubricating oil composition of the base oil containing lubricant viscosity and special additive composition Object.Disclosed method uses the lubricant oil composite containing compositions of additives.As described in greater detail below, lubricating oil group Closing object may for reducing the quantity of low speed pre-ignition event in the boosting type internal combustion engine lubricated using lubricant oil composite Unexpectedly effectively.

Lubricant oil composite includes with the base of the lubricant viscosity greater than 50 weight % of the total weight of lubricant oil composite Plinth oil；Enough one or more high alkalinity calcic detergents have and are greater than as measured by the method for ASTM D-2896 The total base number of 225mg KOH/g, to provide the calcium for being greater than 1000ppm to lubricant oil composite；One or more high alkalinities contain magnesium Detergent has the total base number for being greater than 225mg KOH/g as measured by the method for ASTM D-2896, wherein by one kind Or it is 50-1500ppm that a variety of high alkalinity detergents containing magnesium, which are supplied to the total amount of the magnesium of lubricant oil composite,；With one or more molybdenums Compound provides the total amount of the molybdenum of 25-1000ppm to lubricating composition.From one or more high alkalinity calcic detergents Lubricant oil composite in calcium weight % and the lubricant oil composite from one or more high alkalinity detergents containing magnesium in Magnesium weight % ratio less than 11.9.Magnesium in the lubricant oil composite as measured by the method for ASTM D-2896 The ratio of total TBN (in terms of the mg KOH/g of lubricant oil composite) of total ppm and lubricant oil composite is greater than 19.Pass through ASTM Total ppm of calcium in lubricant oil composite measured by the method for D-2896 and total TBN of lubricant oil composite are (with lubricating oil group Close object mg KOH/g meter) ratio less than 221.Relative to the low speed in the same engine lubricated with reference lubricating oil R-1 Pre-ignition event number, the quantity of low speed pre-ignition event is effectively reduced 60% or more by the lubricant oil composite, such as in stable state Under the conditions of, run under about 1750rpm speed and greater than 80% maximum brake mean-effective pressure 4 hours Ford 2.0L liters 4 In cylinder EcoBoost turbocharging gasoline direct injection engine, undergo each 175,000 cycle of engine of stage of four-stage It is measured.It is tested in addition, lubricant oil composite is corroded by ball.

Optionally, method of the invention may include the low speed pre-ignition of the internal combustion engine of measurement lubricant oil composite lubrication The step of quantity of event.In such method, the reduction of the quantity of LSPI event can reduce 50% or bigger, or reduce It greater than 60% or reduces greater than 70%, or reduces and be greater than 80%.The par of LSPI event can be about 175,000 times and start Machine recycle during the quantity that counts of LSPI, wherein engine about 1750 revs/min speed and be greater than 80% maximum braking It is run under mean effective pressure.

As described in greater detail below, embodiment of the disclosure can provide significant and be gone out in terms of reducing LSPI event The improvement of people's will material, while maintaining relatively high calcium detergent concentration in lubricant oil composite.Embodiment of the disclosure can be with Come in conjunction with LSPI event is reduced through ball corrosion test.

Ball corrosion test mentioned herein is carried out using the method for ASTM-D-6557.Ball corrosion test (BRT) is to use In the program of the resistance to corrosion of assessment fluid lubricant.According to ASTM D6557, ball bearing is immersed in the oil.It will saturation There is the air of acid contaminant to be bubbled 18 hours at 49 DEG C by oil.After 18 hours reaction phases, removed from test oil Ball, and use the etching extent on light reflection technology quantization ball.The amount of reflected light is reported as average gray value (AGV).For new The AGV for not corroding ball is about 140.The ball corroded completely has the AGV result less than 20.The lubricating oil of given at least 100 AGV Composition passes through BRT.The lubricant oil composite of the given AGV less than 100 cannot pass through BRT.

Detergent

Lubricant oil composite includes that one or more high alkalinity calcic detergents and one or more high alkalinities are cleaned containing magnesium Agent.Specifically, lubricant oil composite includes enough one or more high alkalinity calcic detergents, has and passes through ASTM D- It is greater than the total base number of 225mg KOH/g measured by 2896 method, to provide to lubricant oil composite greater than 1000ppm's Calcium, and lubricant oil composite includes enough one or more high alkalinity detergents containing magnesium, has and passes through ASTM D-2896 Method measured by be greater than 225mg KOH/g total base number, with to lubricant oil composite provide 50-1500ppm magnesium.Lubrication Fluid composition optionally includes other detergents, and such as one or more over-based detergents or one or more low alkalinities/in Property detergent.

Suitable detergent matrix includes phenolate, sulfur-bearing phenolate, sulfonate, calixarenes alkoxide, salicylic acid alkoxide, water Poplar hydrochlorate, carboxylic acid, phosphoric acid, single thiophosphate and/or phosphordithiic acid, alkyl phenol, sulphur coupling alkylphenol compound or methylene Bridging phenol.Suitable detergent and preparation method are more fully described in many patent disclosures, including US7,732,390 with And references cited therein.Detergent matrix can be used alkali or alkaline earth metal salt such as, but not limited to, below: calcium, Or mixtures thereof magnesium, potassium, sodium, lithium, barium.In some embodiments, detergent not baric.Suitable detergent may include petroleum sulphur The alkali or alkaline earth metal salt of acid and long-chain list or di alkylaryl sulfonic acid, wherein the aryl be benzyl, tolyl and Xylyl.

The example of suitable detergent includes but is not limited to calcium phenoxide, sulfur-bearing calcium phenoxide, sulfoacid calcium, calixarenes alcohol calcium, water Poplar acid alcohol calcium, calcium salicylate, calcium carboxylates, calcium phosphate, single thiophosphate calcium and/or phosphordithiic acid calcium, alkyl phenol calcium, sulphur coupling Alkyl phenol calcium compound, methylene-bridged phenol calcium, phenol magnesium, magnesium containing phenylmercaptan, sulfonic acid magnesium, calixarenes magnesium alkoxide, salicylic acid magnesium alkoxide, Magnesium salicylate, magnesium carboxylates, magnesium phosphate, single thiophosphate magnesium and/or phosphordithiic acid magnesium, alkyl phenol magnesium, sulphur are coupled alkyl phenol magnesium Compound, methylene-bridged phenol magnesium, sodium phenate, sulfur-bearing sodium phenate, sodium sulfonate, calixarenes sodium alkoxide, salicylic acid sodium alkoxide, salicylic acid Sodium, carboxylic acid sodium, sodium phosphate, single thiophosphate sodium and/or phosphordithiic acid sodium, alkyl phenol sodium, sulphur coupling alkyl phenol sodium compound, Or methylene-bridged phenol sodium.

Over-based detergent is well known in the art, and can be cleaned for alkali or alkaline earth metal high alkalinity Agent.Such detergent can be prepared by oxidizing metal object or metal hydroxides and matrix and carbon dioxide gas precursor reactant. Matrix is typically acid, such as following acid, such as by sulfonic acid that aliphatic replaces, the carboxylic acid replaced by aliphatic, or by aliphatic Substituted phenol.

Term " high alkalinity " is related to metal salt, such as the metal salt of sulfonate, carboxylate and phenolate, present in metal Amount be more than stoichiometry amount.This kind of salt can have the level of conversion more than 100% (that is, it may include converting it for acid 100% or more of theoretical metal amount needed for " normal ", " neutrality " salt).Expression " metal ratio " is commonly abbreviated as MR, is used for table Show according to known chemical reactivity and stoichiometry, the change of total chemical equivalent of metal and metal in neutral salt in high alkalinity salt Learn the ratio of equivalent.In normal or neutral salt, metal ratio one, and in high alkalinity salt, MR is greater than one.It is usually claimed For high alkalinity, hyperalkaline or superbased salt, and it can be the salt of organic sulfuric acid, carboxylic acid or phenol.

The TBN of over-based detergent as measured by ASTM D-2896 method as that can be greater than 170mg KOH/g, or work For other examples, TBN about 250mg KOH/g or bigger or TBN about 300mg KOH/g or bigger or TBN about 350mg KOH/g Or bigger or TBN about 375mg KOH/g or bigger or TBN about 400mg KOH/g or bigger.

In any previous embodiment, one or more overbased sulfonate detergents are at least 225mg KOH/g's Total base number.It states in embodiment in each of front, one or more overbased sulfonate detergents can have at least 250mg KOH/g's Total base number.It states in embodiment in each of front, one or more overbased sulfonate detergents can have 260-450mg KOH/g's Total base number.

The example of suitable high alkalinity calcic detergent includes but is not limited to overbased calcium phenate, high alkalinity containing phenylmercaptan Calcium, high alkaline calcium sulfonate, high alkalinity calixarenes alcohol calcium, high alkalinity bigcatkin willow acid alcohol calcium, overbased calcium salicylate, high alkalinity carboxylic acid Calcium, high alkalinity calcium phosphate, high alkalinity single thiophosphate and/or phosphordithiic acid calcium, high alkalinity alkyl phenol calcium, the coupling of high alkalinity sulphur Alkyl phenol calcium compound and high alkalinity methylene-bridged phenol calcium.The example of suitable high alkalinity detergent containing magnesium includes high alkalinity benzene Phenol magnesium, high alkalinity magnesium containing phenylmercaptan, overbased magnesium sulphonates, high alkalinity calixarenes magnesium alkoxide, high alkalinity bigcatkin willow acid alcohol magnesium, very alkaline water Poplar acid magnesium, high alkalinity magnesium carboxylates, high alkalinity magnesium phosphate, high alkalinity single thiophosphate magnesium and/or phosphordithiic acid magnesium, high alkalinity alkane Base phenol magnesium, high alkalinity sulphur coupling alkyl phenol magnesium compound or high alkalinity methylene-bridged phenol magnesium.

The metal of over-based detergent and the ratio of matrix can be 1.1: 1 or 2: 1 or 4: 1 or 5: 1 or 7: 1 or 10: 1。

In some embodiments, detergent effectively reduces or prevents within the engine to get rusty.

With the total weight of lubricant oil composite, existing total detergent can be up to 10 weight %, or about at most 8 weights Measure %, or at most about 4 weight %, or greater than about 1 weight % to about 8 weight %, or greater than about 1.1 weight % are to about 2.5 weights Measure %.

The total amount of detergent can exist with the amount to lubricant oil composite offer about 1100 to about 3500ppm metal.In In other embodiments, detergent can provide about 1100 to about 3000ppm metal to lubricant oil composite, or about 1250 to about The metal of 2500ppm, or about 1400 to about 2500ppm metal.In some embodiments, metal is the combination of only calcium and magnesium.

The disclosure further includes following methods: such lubricant oil composite is used in method, or by using lubricating oil composition Object lubrication engine and the method for lubricating engine for running engine.

In certain embodiments, the amount of one or more high alkalinity calcic detergents can provide big to lubricant oil composite In the calcium of 1000ppm to less than 2000ppm.It states in embodiment in each of front, the amount of one or more high alkalinity calcic detergents The calcium of 1050ppm to 1900ppm can be provided to lubricant oil composite.

In some embodiments, one or more high alkalinity detergents containing magnesium can provide 100- to lubricant oil composite The magnesium of 1200ppm or 200-800ppm.

In certain embodiments, the total amount of one or more high alkalinity calcics and the detergent containing magnesium can be mentioned to finished fluid For the combination of about 900 to about 2400ppm calcium and magnesium.As another example, one or more high alkalinity calcics and containing magnesium it is clear Clean dose can be to provide the combination of about 900 to about 2500ppm calcium and magnesium to lubricant oil composite, or about 1100 to about The combination of the calcium and magnesium of 2500ppm, or about 1200 to 2450ppm calcium and magnesium combination, or about 1400 to 2400ppm calcium and The combined amount of magnesium exists.

The lubricant oil composite of the disclosure optionally includes low alkalinity/mild detergent, has at most 170mg KOH/g, or the TBN of at most 150mg KOH/g.Low alkalinity/mild detergent may include calcic detergent.Low alkalinity neutrality calcic Detergent can be selected from calcium sulfonate detergents, calcium phenoxide detergent and calcium salicylate detergent.In some embodiments, low alkali Property/mild detergent be calcic detergent or calcic detergent mixture.In some embodiments, low alkalinity/neutrality cleaning Agent is calcium sulfonate detergents or calcium phenoxide detergent.

The lubricant oil composite of the disclosure may include low alkalinity/mild detergent, and amount is total in lubricant oil composite At least 2.5 weight % of detergent.In some embodiments, at least 4 weight % of total detergent in lubricant oil composite, or At least 6 weight %, or at least 8 weight %, or at least 10 weight %, or at least 12 weight % or at least 20 weight % be can be optional Ground is low alkalinity/neutrality calcic detergent low alkalinity/mild detergent.

In certain embodiments, with the total weight of lubricant oil composite, one or more low alkalinities/neutrality calcic cleaning Agent can provide about 50 to about 1000ppm calcium to lubricant oil composite.In some embodiments, with the gross weight of lubricant oil composite Meter, one or more low alkalinities/neutrality calcic detergent can provide 75 to less than 800ppm or 100 to lubricant oil composite Calcium to 600ppm or 125 to 500ppm.

In some preferred embodiments, lubricant oil composite contains no more than 100ppm, or is no more than 50ppm, or do not surpass Cross low alkalinity/neutrality calcic detergent of 25ppm.It states in embodiment in each of front, lubricant oil composite can be without addition Low alkalinity/neutrality calcic detergent.

In some preferred embodiments, lubricant oil composite contains no more than 100ppm, or is no more than 50ppm, or do not surpass Cross low alkalinity/mild detergent of 25ppm.It states in embodiment in each of front, lubricant oil composite can be without the low alkali of addition Property/mild detergent.

In some embodiments, one or more high alkalinity calcic detergents include to be selected from sulfoacid calcium and calcium phenoxide detergent Detergent.One or more high alkalinity detergents containing magnesium may include sulfonic acid magnesium detergent.

In certain embodiments, the weight of the calcium in lubricant oil composite from one or more high alkalinity calcic detergents The ratio of the weight % of the magnesium in % and the lubricant oil composite from one or more high alkalinity detergents containing magnesium is measured less than 10 It or is 0.5 to 9.

In some embodiments, total ppm of the magnesium in the lubricant oil composite as measured by the method for ASTM D-2896 25 can be greater than with the ratio of total TBN (in terms of the mg KOH/g of lubricant oil composite) of lubricant oil composite or for 30 to 90.

In certain embodiments, total ppm of the calcium in the lubricant oil composite as measured by the method for ASTM D-2896 215 are smaller than with the ratio of total TBN (in terms of the mg KOH/g of lubricant oil composite) of lubricant oil composite or for 125 to 210.

In certain embodiments, as measured by the method for ASTM D-2896, pass through one or more calcic detergents Contributing the TBN to lubricant oil composite can be the lubricant oil composite of 2.5-5.0mg KOH/g.

Lubricant oil composite is optionally free of overbased calcium salicylate detergent.

In any embodiment of the disclosure, with the total weight of lubricant oil composite, the amount of sodium can in lubricating composition It is limited to the sodium no more than 150ppm, or is no more than the sodium of 50ppm with the total weight of lubricant oil composite.

Base oil

It can be selected from American Petroleum Institute (API) (American Petroleum for the base oil of lubricant oil composite herein Institute, API) any one of base oil in I-V group specified in base oil interchangeability guide.Five kinds of base oils Group is as follows:

Table 1

I, II and III group are that mineral oil processes raw material.Group iv base oils contain pure synthetic molecules substance, the homozygosis It is prepared at molecular substance by the polymerization of alkene system unsaturated hydrocarbons.Many Group V base oils are also pure synthetic product, and can be wrapped Diester, polyol ester, polyalkylene glycol, alkylated aromatic hydrocarbon, polyphosphate, polyvinylether and/or polyphenyl ether etc. are included, but It can also be naturally occurring oil, such as vegetable oil.Although should be noted that Group III base oil is derived from mineral oil, these fluid institutes The stringent processing of experience is so that its physical characteristic is very similar to some pure synthetics, such as PAO.Therefore, it is derived from Group III base The oil of plinth oil is referred to alternatively as complex fluids in the industry.

For the base oil in disclosed lubricant oil composite can for mineral oil, animal oil, vegetable oil, synthetic oil or its Mixture.Suitable oil can derived from hydrocracking, hydrogenation, hydrofinishing, do not refine, refine and refined oil and its mixing again Object.

Non- refined oil is derived from those of natural, mineral or synthesis source, and there is no or almost no further purifying Processing.Refined oil is similar to non-refined oil, and the exception is that it is handled in one or more purification steps, this can draw Play the improvement of one or more characteristics.The example of suitable purification technique is solvent extraction, second distillation, acid or alkali extraction, mistake Filter, diafiltration etc..The oil for being refined to edible quality may be applicable in or may be not suitable for.Edible oil is also referred to as white oil.Some In embodiment, lubricant oil composite is free of edible oil or white oil.

Refined oil is also referred to as reclaimed oil or reprocessed oils again.Using same or similar technique, similarly with refined oil Obtain these oil.Usually these oil, which pass through, is directed to the technology further processing for removing useless additive and oil decomposition product.

Mineral oil may include by probing or the oil obtained from plant and animal or its any mixture.For example, this kind of oil It may include but be not limited to castor oil, lard, olive oil, peanut oil, corn oil, soybean oil and linseed oil and mineral lubricant Oil, such as the mine of liquid petroleum and alkane, cycloalkane or mixed paraffinic-naphthenic handled through solvent or handled through acid Object lubricating oil.This kind of oil when necessary can partly or completely perhydrogenating.Oil derived from coal or shale is also possible to useful.

Useful synthetic lubricant fluid may include hydrocarbon ils, such as polymerization, oligomeric or mutual polyolefin (for example, polybutene, polypropylene, Propylene/isobutylene copolymers)；The trimer or oligomer of poly- (1- hexene), poly- (1- octene), 1- decene, for example, poly- (the 1- last of the ten Heavenly stems Alkene), substance of this kind is commonly referred to as alpha-olefin and its mixture；Alkylbenzene (such as detergent alkylate, Tetradecylbenzene, dinonyl Benzene, two-(2- ethylhexyl)-benzene)；Polyphenyl (for example, biphenyl, terphenyl, alkylated polyphenyls)；Diphenyl alkane, alkylation two Phenyl alkanes, alkylated diphenyl ethers and alkylation or mixtures thereof diphenylsulfide and its derivative, analog and homologue. Polyalphaolefin is usually hydrogenation material.

Other synthetic lubricant fluids include polyol ester, diester, phosphoric acid liquid ester (for example, tricresyl phosphate, phosphoric acid The diethylester of three monooctyl esters and decane phosphonic acids) or polymerizing tetrahydrofuran.Synthetic oil can be prepared by Fischer-Tropsch reaction, and described Synthetic oil generally can be the fischer-tropsch hydrocarbon or wax of hydroisomerization.In one embodiment, oil can pass through Fischer-Tropsch gas-liquid systhesis journey It is prepared by sequence and other solution-air oil.

The base oil greater than 50 weight % for including in lubricating composition can be selected from the group being made up of: Group I, II group, Group III, Group IV, Group V and two or more combination above-mentioned, and wherein greater than 50 weight %'s Base oil is not the base oil generated by providing additive component or viscosity index improver in the composition.In another implementation In example, the base oil greater than 50 weight % for including in lubricating composition can be selected from the group being made up of: Group II, the III group, Group IV, Group V and two or more combination above-mentioned.Also, base oil can be selected from Group II to Group V The mixture of base oil or its any two or more.With the total weight of lubricant oil composite, greater than the base of 50 weight % Plinth oil can not be the flux oil generated from providing additive component or viscosity index improver to composition.

The amount of the oil of existing lubricant viscosity can be to subtract from 100 weight % including viscosity index improver and/or pour point depression Remaining surplus after the summation of the amount of the performance additive of agent and/or other pre-treatment additives.For example, may be present in finished product The oil of lubricant viscosity in fluid can be primary amount, such as larger than about 50 weight %, greater than about 60 weight %, greater than about 70 weights Measure %, greater than about 80 weight %, greater than about 85 weight %, or greater than about 90 weight %.

Lubricant oil composite may include the group iv base oils no more than 10 weight %, Group V base oil or combinations thereof.In In each previous embodiment, lubricant oil composite may include less than the Group V base oil of 5 weight %.The lubrication of some embodiments Fluid composition is without containing any group iv base oils and/or does not contain any Group V base oil.

Containing molybdenum component

Lubricant oil composite herein contains molybdenum.Specifically, one or more molybdenum compounds are provided to lubricating composition The total amount of molybdenum is the molybdenum of 25-1000ppm or 50-800ppm or 70-550ppm or 75-500ppm to lubricant oil composite.

Soluble molybdenum compounds can have the functional performance of or mixtures thereof antiwear agents, antioxidant, friction improver. Soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyl-dithiophosphate, phosphonodithious acid molybdenum, molybdenum chemical combination The amine salt of object, xanthic acid molybdenum, Thioxanthate molybdenum, molybdenum sulfide, carboxylic acid molybdenum, molybdenum alkoxide, three core organic molybdenums, and/or its Mixture.Molybdenum sulfide includes molybdenum disulfide.Molybdenum disulfide can be in stabilising dispersions form.In one embodiment, oil-soluble molybdenum Compound can be selected from the group being made up of: molybdenum dithiocarbamate, molybdenum dialkyl-dithiophosphate, molybdenum compound amine Salt and its mixture.In one embodiment, soluble molybdenum compounds can be molybdenum dithiocarbamate.

The suitable example of workable molybdenum compound includes the commercial materials sold with following trade (brand) name: from model Derby that The Molyvan 822 of special Co., Ltd (R.T.Vanderbilt Co., Ltd.)^TM、Molyvan^TM A、Molyvan 2000^TMWith Molyvan 855^TMWith the Sakura-Lube for being purchased from Chinese mugwort Dicon A/S (Adeka Corporation)^TMS-165、S-200、 S-300, S-310G, S-525, S-600, S-700 and S-710 and its mixture.Suitable molybdenum component is described in US 5,650, 381；US RE 37,363E1；In US RE38,929E1 and US RE 40,595E1, it is incorporated herein in entirety by reference In.

In addition, molybdenum compound can be acidic molybdenum compound.Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other molybdic acids Alkali metal salt and other molybdenum salt, such as molybdic acid hydrogen sodium, MoOCl₄、MoO₂Br₂、Mo₂O₃Cl₆, molybdenum trioxide or similar acidity Molybdenum compound.Alternatively, composition can provide molybdenum by molybdenum/sulfide complex of basic nitrogen compound, such as example in U.S. Patent No. No. 4,263,152, No. 4,285,822, No. 4,283,295, No. 4,272,387, No. 4,265,773, the 4,261st, Described in No. 843, the 4th, 259, No. 195 and the 4th, 259, No. 194 and U.S. Patent Publication case the 2002/0038525th, Which is incorporated herein by reference in its entirety.

Another kind of suitable organic molybdenum is tri-nuclear molybdenum compound, such as formula Mo₃S_kL_nQ_zThose of and its mixture, Wherein S indicates that sulphur, L indicate that having for independent choice is enough that compound is made to be soluble or dispersible in the amount of carbon atom in oil The ligand of organic group, n are that 1 to 4, k changes between 4 to 7, and Q is selected from neutral supplied for electronic compound such as water, amine, alcohol, phosphine and ether Group, and z is in 0 to 5 range, and including non-stoichiometry value.It may be present in total in the organic group of all ligands At least 21 carbon atoms, such as at least 25, at least 30 or at least 35 carbon atoms.In addition it is special to be described in the U.S. for suitable molybdenum compound In benefit the 6th, 723,685, which is incorporated herein by reference in its entirety.

Lubricant oil composite may also include one or more optional components selected from the various additives being described below.

Antioxidant

Lubricant oil composite herein also optionally contains one or more antioxidants.Anti-oxidant compounds are It is known and including such as phenolate, phenol sulfide, olefine sulfide, phosphorus vulcanize terpene, sulfurised ester, aromatic amine, alkylation Diphenylamines (for example, nonyl diphenylamine, dinonyldiphenylamine, octyl diphenylamine, dioctyl diphenylamine), phenyl-α-naphthylamine, alkyl Change phenyl-α-naphthylamine, the non-aromatic amine that is obstructed, phenol, hindered phenol, soluble molybdenum compounds, macromolecular antioxidant or its mixing Object.Anti-oxidant compounds can be used alone or in combination.

Hindered phenol antioxidant can contain sec-butyl and/or tert-butyl as space steric hindrance group.Phenolic group can further by Alkyl and/or the bridged group for being connected to the second aromatic group replace.The example of suitable hindered phenol antioxidant includes 2, 6- di-tert-butylphenol, 4- methyl -2,6- di-tert-butylphenol, 4- ethyl -2,6- di-tert-butylphenol, 4- propyl -2,6- di-t-butyl Phenol or 4- butyl -2,6- di-tert-butylphenol or 4- dodecyl -2,6- di-tert-butylphenol.In one embodiment, hindered phenol is anti- Oxidant can be ester, and may include the IRGANOX for being for example purchased from BASF (BASF)^TML-135 is derived from 2,6-, bis- uncle The addition product of butylphenol and alkyl acrylate, wherein alkyl can contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms.Another commercially available hindered phenol antioxidant can be ester, and may include being purchased from The ETHANOX of refined treasured (Albemarle Corporation)^TM4716。

Useful antioxidant may include diaryl amine and high molecular weight phenol.In one embodiment, lubricant oil composite Mixture containing diaryl amine and high molecular weight phenol, so that with the total weight of lubricant oil composite, every kind of antioxidant Can exist with the amount for being enough to provide at most about 5 weight %.In one embodiment, with the total weight of lubricant oil composite, Antioxidant can be about the mixture of 0.3 to about 1.5 weight % diaryl amine and about 0.4 to about 2.5 weight % high molecular weight phenol.

Can vulcanize the example to form the suitable alkene of olefine sulfide include propylene, butylene, isobutene, polyisobutene, amylene, Hexene, heptene, octene, nonene, decene, hendecene, laurylene, tridecylene, tetradecene, ten pentaenes, hexadecylene, 17 alkene, ten Or mixtures thereof eight alkene, 19 alkene, icosa alkene.In one embodiment, hexadecylene, 17 alkene, octadecylene, 19 alkene, 20 Or mixtures thereof alkene and its dimer, trimer and tetramer are the alkene being particularly useful.Alternatively, alkene can be diene Diels-Alder (Diels-A1der) adduct of (such as 1,3-butadiene) and beta-unsaturated esters (such as butyl propyleneglycol acid esters).

Another kind of olefine sulfide includes sulfide aliphatic acid and its ester.Fatty acid is usually obtained from vegetable oil or animal oil and leads to Often contain about 4 to about 22 carbon atoms.The example of suitable fat acid and its ester includes triglycerides, oleic acid, linoleic acid, palm Or mixtures thereof oleic acid.In general, fatty acid is obtained from lard, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower oil or it is mixed Close object.Fatty acid and/or ester can be mixed with alkene (such as alpha-olefin).

One or more antioxidants can be with the about 0.0 weight % to about 5.0 weight % or about 0.1 of lubricating composition The range of weight % to about 3.0 weight % or about 0.2 weight % to about 2.5 weight % exists.

Antiwear agents

Lubricant oil composite herein also optionally contains one or more antiwear agents.Suitable antiwear agents Example includes but is not limited to thiophosphoric acid metal salt；Dialkyl dithiophosphoric acid metal salt；Phosphate or its salt；Phosphate；It is sub- Phosphate；Phosphorus-containing carboxylic acid ester, ether or amide；Olefine sulfide；Compound containing thiocarbamate, including thiocarbamic acid Ester, alkylidene link sulfo carbamate and bis- (two thiocarbamoyl of S- alkyl) disulphide；And its mixture.Properly Antiwear agents can be molybdenum dithiocarbamate.Phosphorous antiwear agents are more fully described in European patent 612839. Metal in dialkyl disulfides based phosphates can be alkali metal, alkaline-earth metal, aluminium, lead, tin, molybdenum, manganese, nickel, copper, titanium or Zinc.Applicable antiwear agents can be zinc dialkyl dithiophosphate.

Other examples of suitable antiwear agents include the oil of titanium compound, tartrate, tartrimide, phosphorus compound Dissolubility amine salt, olefine sulfide, phosphite ester (such as dibutyl phosphite), phosphonate ester, the compound containing thiocarbamate are (such as Thiocarbamate, thiocarbamate amide, thiocarbamic acid ether, alkylidene link sulfo carbamate and double (two thiocarbamoyl of S- alkyl) disulphide).Tartrate or tartrimide can contain alkyl group, wherein alkyl In carbon atom summation can be at least 8.In one embodiment, antiwear agents may include citrate.

Antiwear agents can with include lubricant oil composite about 0.0 weight % to about 10 weight %, or about 0.0 weight % To about 5.0 weight %, or about 0.05 weight % to about 5.0 weight %, or about 0.1 weight % is to about 3 weight % or less than 2.0 weights The range for measuring % exists.

Wear-resistant compound can be dihydrocarbyl dithiophosphate trbasic zinc phosphate (ZDDP), and the ratio of P:Zn is about 1: 0.8 to about 1: 1.7.The dialkyl of ZDDP can be formed by the mixture of C3 and C6 alcohol.

Boron-containing compound

Lubricant oil composite herein optionally contains one or more boron-containing compounds.With the total of lubricant oil composite Poidometer, the amount of boron is less than 600ppm in lubricant oil composite, or with the total weight of lubricant oil composite, the amount of boron is smaller than 200ppm, or it is less than 100ppm, or be less than 50ppm or 150ppm to less than 600ppm or 200ppm to less than 500ppm, or 200ppm to 350ppm.

The example of boron-containing compound include borate, borated fatty amine, boration epoxides, boration detergent and Borated dispersants, such as boration succinimide dispersant, as disclosed in U.S. Patent No. 5,883,057.

Dispersing agent

Lubricant oil composite optionally further includes or mixtures thereof one or more dispersing agents.Dispersing agent is commonly referred to as For ashless type dispersants, because before being mixed in lubricant oil composite, without containing the metal for forming ash content and when addition It does not facilitate any ash content usually when into lubricant.The feature of ashless type dispersants is that polar group is connected to relatively high score Son amount hydrocarbon chain.Typical ashless dispersant includes that N- replaces long-chain alkenyl succimide.N- replaces long-chain alkenyl succinyl sub- The example of amine includes polyisobutene succinimide, and wherein the number-average molecular weight of polyisobutene substituent group is about 350 to about 50, 000 or to about 5,000 or in about 3,000 ranges.Succinimide dispersant and its preparation are disclosed in such as U.S. Patent No. In No. 7,897,696 or U.S. Patent No. 4,234,435.Polyolefin can by containing about 2 to about 16 or about 2 to about 8 or The polymerisable monomer preparation of about 2 to about 6 carbon atoms.Succinimide dispersant is usually by polyamine, usually poly- (ethylidene Amine) formed acid imide.

In embodiment, the disclosure further includes at least one polyisobutene succinimide dispersing agent, is derived from Number average molecular weight is about 350 to about 50,000 or to about 5000 or to the polyisobutene in about 3000 ranges.Polyisobutene Succimide can use individually or with other dispersant packages.

In some embodiments, polyisobutene (when included) can have greater than 50mol%, greater than 60mol%, be greater than 70mol%, greater than 80mol% or greater than the terminal double bond of 90mol% content.This kind of PIB is also referred to as highly reactive property PIB ("HR-PIB").HR-PIB of the number-average molecular weight in about 800 to about 5000 ranges is suitable for embodiment of the disclosure.It is conventional PIB be typically below 50mol%, less than 40mol%, less than 30mol%, less than 20mol% or less than 10mol% content Terminal double bond.

HR-PIB of the number-average molecular weight in about 900 to about 3000 ranges can be suitable.This kind of HR-PIB is commercially available Or can be synthesized by polymerizeing isobutene in the presence of non-chlorinated catalyst (such as boron trifluoride), such as in the beauty of Boerzel et al. Described in U.S. Patent No. 5,739,355 of state's patent the 4,152,499th and Gateau et al..When for aforementioned hot alkene When reaction, HR-PIB is since increased reactivity can make the conversion ratio of reaction higher, and the amount for forming sediment is less.It closes Suitable method is described in U.S. Patent No. 7,897,696.

In one embodiment, the disclosure further includes at least one derived from polyisobutylene butanedioic anhydride The dispersing agent of (" PIBSA ").PIBSA every polymer that is averaged can have the succinic acid part between about 1.0 and about 2.0.

Usable chromatographic technique determines the active % of alkenyl or dialkyl succinylsuccinate acid anhydride.The method is described in U.S. Patent No. 5, In No. 334,321 the 5th columns and the 6th column.

The hundred of polyolefin is calculated by active % using the equation in U.S. Patent No. 5,334,321 the 5th columns and the 6th column Percent conversion.

Unless otherwise stated, otherwise all percentages are by weight percentage and all molecular weight are several equal molecules Amount.

In one embodiment, dispersing agent can be derived from polyalphaolefin (PAO) succinic anhydride.

In one embodiment, dispersing agent can be derived from alkene copolymer-maleic anhydride.As example, dispersing agent can be retouched It states as poly- PIBSA.

In embodiment, dispersing agent can be derived from the acid anhydrides being grafted with ethylene-propylene copolymer.

A kind of suitable dispersing agent can be Mannich base (Mannich base).Mannich base is by higher molecular weight alkyl The substance that the condensation of substituted phenol, polyalkylene polyamine and aldehyde (such as formaldehyde) is formed.Mannich base is described in greater detail in the U.S. In patent the 3,634,515th.

A kind of suitable dispersing agent can be high-molecular weight ester or half esteramides.

Suitable dispersing agent can also by conventional method by with any post-reaction treatment in various reagents.In these For boron, urea, thiocarbamide, dimercaptothiodiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon replaced succinate acid anhydride, maleic anhydride, nitrile, epoxy Compound, carbonic ester, cyclic carbonate, hindered phenolic ester and phosphorus compound.US 7,645,726；US 7,214,649；With US 8, 048,831 is incorporated herein by reference in its entirety.

Other than carbonic ester and boric acid post-process, two kinds of compounds are all available to be designed to improve or assign different characteristics A variety of post treatment methods post-processing or further work-up.This kind of post-processing includes in the beauty being incorporated herein by reference Those of summarized in the column 27-29 that state's patent the 5,241,003rd.Such processing includes being handled with following:

Inorganic phosphorous acid or dehydrate (such as U.S. Patent No. No. 3,403,102 and No. 4,648,980)；

Organic phosphorus compound (such as U.S. Patent No. 3,502,677)；

Phosphoric sulfide；

Boron compound (such as U.S. Patent No. No. 3,178,663 and No. 4,652,387) as has been mentioned above；

Carboxylic acid, polycarboxylic acids, acid anhydrides and/or acid halide (such as U.S. Patent No. 3,708,522 and the 4,948,386th Number)；

Epoxides, polyepoxide or thioepoxide (such as U.S. Patent No. 3,859,318 and the 5,026th, No. 495)；

Aldehydes or ketones (such as U.S. Patent No. 3,458,530)；

Carbon disulfide (such as U.S. Patent No. 3,256,185)；

Glycidol (such as U.S. Patent No. 4,617,137)；

Urea, thiocarbamide or guanidine (such as U.S. Patent No. 3,312,619；No. 3,865,813 and British patent GB1,065, 595)；

Organic sulfonic acid (such as U.S. Patent No. 3,189,544 and British patent GB 2,140,811)；

Alkenyl cyanide (such as U.S. Patent No. No. 3,278,550 and No. 3,366,569)；

Diketene (such as U.S. Patent No. 3,546,243)；

Diisocyanate (such as U.S. Patent No. 3,573,205)；

Alkane sultone (such as U.S. Patent No. 3,749,695)；

1,3- dicarbonyl compound (such as U.S. Patent No. 4,579,675)；

The sulfate (such as U.S. Patent No. 3,954,639) of alcohol alcoxylates or phenol；

Annular lactone (such as U.S. Patent No. 4,617,138；No. 4,645,515；No. 4,668,246；4th, No. 963,275；With No. 4,971,711)；

Cyclic carbonate or the linear monocarbonate of sulfocarbonate or polycarbonate or chloro-formate (such as United States Patent (USP) No. 4,612,132；No. 4,647,390；No. 4,648,886；No. 4,670,170)；

Containing nitronic acid (such as U.S. Patent No. 4,971,598 and British patent GB 2,140,811)；

The chlorine dicarbapentaborane oxo-compound (such as U.S. Patent No. 4,614,522) of hydroxyl protection；

Lactams, sulphur lactams, thiolactone or two thiolactones (such as U.S. Patent No. 4,614,603 and the 4,666th, No. 460)；

Cyclic carbonate or the linear monocarbonate of sulfocarbonate or polycarbonate or chloro-formate (such as United States Patent (USP) No. 4,612,132；No. 4,647,390；No. 4,646,886；With No. 4,670,170)；

Containing nitronic acid (such as U.S. Patent No. 4,971,598 and British patent GB 2,440,811)；

The chlorine dicarbapentaborane oxo-compound (such as U.S. Patent No. 4,614,522) of hydroxyl protection；

Lactams, sulphur lactams, thiolactone or two thiolactones (such as U.S. Patent No. 4,614,603, the 4th, 666, No. 460)；

Cyclic carbamate, cyclothiocarbamate or Cyclic Dithio carbamate (such as United States Patent (USP) No. 4,663,062 and No. 4,666,459)；

Hydroxyaliphatic carboxylic acids (such as U.S. Patent No. 4,482,464；No. 4,521,318；4,713,189th Number)；

Oxidant (such as U.S. Patent No. 4,379,064)；

The combination (such as U.S. Patent No. 3,185,647) of phosphorus pentasulfide and polyalkylene polyamine；

The combination of carboxylic acid or aldehydes or ketones and sulphur or sulfur chloride (such as U.S. Patent No. 3,390,086；3,470,098th Number)；

The combination (such as U.S. Patent No. 3,519,564) of hydrazine and carbon disulfide；

The combination of aldehyde and phenol (such as U.S. Patent No. 3,649,229；No. 5,030,249；No. 5,039,307)；

The combination (such as U.S. Patent No. 3,865,740) of the O- diester of aldehyde and phosphordithiic acid；

The combination (such as U.S. Patent No. 4,554,086) of hydroxyaliphatic carboxylic acids and boric acid；

Hydroxyaliphatic carboxylic acids, the then combination (such as U.S. Patent No. 4,636,322) of formaldehyde and phenol；

The combination (such as U.S. Patent No. 4,663,064) of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acid；

The combination (such as U.S. Patent No. 4,699,724) of formaldehyde and phenol and then glycolic；

Hydroxyaliphatic carboxylic acids or oxalic acid, and then combination (such as the U.S. Patent No. 4,713,191 of diisocyanate Number)；

Combination (such as the United States Patent (USP) of inorganic acid or acid anhydrides of phosphorus or part thereof or whole sulfur analogs and boron-containing compound No. 4,857,214)；

Organic diacid, then unsaturated fatty acid with then nitroso aromatic amine, optionally subsequent boron compound and Then the combination (such as U.S. Patent No. 4,973,412) of glycolated reagent；

The combination (such as U.S. Patent No. 4,963,278) of aldehyde and triazole；

Aldehyde and triazole, the then combination (such as U.S. Patent No. 4,981,492) of boron compound；

The combination (such as U.S. Patent No. No. 4,963,275 and No. 4,971,711) of annular lactone and boron compound；With On the patent that refers to be incorporated in its entirety herein.

The TBN of suitable dispersing agent can be about 10 to about 65 on oil-free basis, be equivalent to containing about 50% flux oil Dispersing agent sample measurement when be about 5 to about 30TBN.

With the total weight of lubricant oil composite, can be come with the amount for being enough to provide at most about 20 weight % using dispersing agent (if present).With the total weight of lubricant oil composite, another amount for the dispersing agent that can be used can be 0.0 weight % to about 12.0 weight, or about 0.1 weight % to about 12 weight %, or about 2.0 weight % to about 10.0 weight %, or about 1.0 weight % To about 8.5 weight %, or about 4.0 weight % to about 8.0 weight %.In some embodiments, lubricant oil composite utilizes mixing Dispersant system.The dispersing agent of the single type dispersing agent or two or more seed types by any desired ratio can be used Mixture.

Friction improver

Lubricant oil composite herein also optionally contains one or more friction improvers.Suitable friction improves Agent may include containing metal and metal-free frictionIt improvesAgent, and may include but be not limited to imidazoline, amide, amine, succinyl Imines, alkoxylated amines, alkoxylate ether amines, amine oxide, amidoamines, nitrile, glycine betaine, quaternary amine, imines, amine salt, amino Guanidine, alkanolamide, phosphonate ester, metal-containing compound, glyceride, sulfurized fatty compound and alkene, other are naturally deposited sunflower oil Plant or animal oil, dicarboxylic ester, the ester of polyalcohol or partial ester and one or more aliphatic or aromatic carboxylic acid etc..

Suitable friction improver contains the alkyl selected from or mixtures thereof straight chain, branch or aromatic hydrocarbyl, and It can be saturated or unsaturated.Alkyl can be made of carbon and hydrogen or hetero atom (such as sulphur or oxygen).Alkyl can be about 12 to about In the range of 25 carbon atoms.In some embodiments, friction improver can be long-chain fatty acid ester.In another embodiment In, long-chain fatty acid ester can be monoesters or diester or (three) glyceride.Friction improver can be higher fatty acid amide, long-chain rouge Fat ester, long chain fatty epoxide derivative or long-chain imidazoline.

Other suitable friction improvers may include organic, ashless (without metal), not nitrogenous organic friction modifiers.This Class friction improver may include the ester by forming carboxylic acid and acid anhydrides and reaction of alkanol, and generally includes covalently bonded and arrive The polar terminal group (for example, carboxyl or hydroxyl) of lipophilic hydrocarbon chain.The example of organic ashless unazotized friction improver is big Glyceryl monooleate (GMO) is known as on body, monoesters, diester and three esters containing oleic acid.Other suitable frictions improve Agent is described in U.S. Patent No. 6,723,685, and which is incorporated herein by reference in its entirety.

Amine friction improver may include amine or polyamine.This kind of compound can have linear saturated or unsaturated alkyl or Its mixture, and about 12 to about 25 carbon atoms can be contained.The other example of suitable friction improver includes alkoxylate Amine and alkoxylate ether amines.This kind of compound can have or mixtures thereof saturated or unsaturated linear alkyl.It can be containing about 12 to about 25 carbon atoms.Example includes ethoxylated amine and ethoxylation ether amines.

Amine and amide can use as former state or with boron compound such as boron oxide, boron halide, metaboric acid esters, boric acid, or The form of mono-, two- or three-boron alkyl acid esters adducts or reaction product uses.Other suitable friction improvers are described in In U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

Friction improver is optionally with for example, about 0.01 weight % to about 5.0 weight % or about 0.01 weight % to about The range of 3.0 weight % or 0.02 weight % to about 1.5 weight % or about 0.1 weight % to about 1.4 weight % exists.

Compound containing transition metal

In another embodiment, oil-soluble compounds can be compound or metalloid containing transition metal.Transition metal can Including but not limited to titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten etc..Suitable metalloid includes but is not limited to boron, silicon, antimony, tellurium etc..

In one embodiment, the oil-soluble that can be used in the Ca/M weight ratio in about 0.8: 1 to about 70: 1 range Closing object is titanium-containing compound, and wherein M is total metal in lubricant compositions as described above.The titanium-containing compound can rise anti- Abrasion agent, friction improver, antioxidant, sediment monitoring Additive or these it is active more than one.

The titanium-containing compound of oil-soluble material that is workable or can be used for preparing disclosed technology in disclosed technology It is various Ti (IV) compound, such as titanium oxide (IV)；Titanium sulfide (IV)；Titanium Nitrate (IV)；Titanium (IV) alkoxide, such as methanol titanium, second Alcohol titanium, titanium propanolate, isopropyl titanate, butanol titanium, 2-Ethylhexyl Alcohol titanium；And other titanium compounds or complex compound, including but it is unlimited In phenol titanium；Carboxylic acid titanium, such as 2- ethyl -1-3- adipic acid titanium or Titanium Citrate or oleic acid titanium；(triethanolamine acid group) isopropyl Alcohol titanium (IV).Unitary alkoxide can have 2 to 16 or 3 to 10 carbon atoms.In embodiment, titanium compound can be 1,2- glycol Or the alkoxide of polyalcohol.In embodiment, 1,2- glycol includes fatty mono glyceride, such as oleic acid.In embodiment, oil-soluble Titanium compound can be carboxylic acid titanium.In embodiment, carboxylic acid titanium (IV) can be neodecanoic acid titanium.

The titanium for covering the other forms in disclosed technology includes titanium phosphate, if phosphordithiic acid titanium is (for example, dioxane Base phosphordithiic acid titanium) and sulfonic acid titanium (for example, alkyl benzene sulphonate titanium), or usually titanium compound is formed with various acidic materials The reaction product of salt such as oil-soluble salt.Therefore titanium compound can especially be derived from organic acid, pure and mild glycol.Ti compound can also be with Exist with dimerization or oli-gomeric forms, contains Ti--O--Ti structure.This kind of titanium material is commercially available or can be easy through this field skill Art personnel appropriate synthetic technology preparation apparent easy to know.It exists in solid or liquid form at room temperature, this depends on specific Compound.It can also be provided in the form of in the solution in appropriate atent solvent.

In one embodiment, titanium can be supplied as the modified dispersing agent of Ti, such as succinimide dispersant.This kind of material can By forming titanium mixed acid anhydride between Titanium alkoxides and the succinic anhydride (such as alkenyl-(or alkyl) succinic anhydride) replaced through alkyl To prepare.Gained titanate-succinate intermediate can be used directly, or can react with any one of many kinds of substance, such as (a) With it is free, can be condensed -- the succimide based on polyamine/amide dispersing agent of NH functional group；(b) based on polyamine Succimide/amide dispersing agent component, i.e. alkenyl-(or alkyl -) succinic anhydride and polyamine, (c) fourth by being substituted The hydroxyl polyester dispersants for reacting preparation of dicarboxylic anhydride and or mixtures thereof polyalcohol, amino alcohol, polyamine.Alternatively, metatitanic acid Salt-succinate intermediate can with other reagents, such as alcohol, amino alcohol, ether alcohol, Aethoxy Sklerol or polyalcohol or fatty acid response, and And directly using its product to assign Ti to lubricant, or further reacted as described above with succinic acid dispersing agent.As Example, the succinic anhydride that 1 part of (in mol) tetraisopropyl titanate can replace with about 2 parts (in mol) through polyisobutene exist It is reacted 5 to 6 hours at 140 DEG C -150 DEG C, to provide titanium modified dispersing agent or intermediate.Obtained material (30g) can be further With from the succinic anhydride replaced through polyisobutene succinimide dispersant and polyethylenepolyamine mixture (127 grams+dilution Oil) it is reacted 1.5 hours at 150 DEG C, to generate titanium modified succinimides dispersing agent.

Another titanium-containing compound can be Titanium alkoxides and C₆To C₂₅The reaction product of carboxylic acid.Reaction product can be by following formula table Show:

Wherein n is the integer selected from 2,3 and 4, and R is the alkyl containing about 5 to about 24 carbon atoms, or by following formula table Show:

Wherein m+n=4 and n is in 1 to 3 range, R₄For the moieties with the carbon atom within the scope of 1-8, R₁Choosing From the alkyl for containing about 6 to 25 carbon atoms, and R₂And R₃It is identical or different and selected from containing about 1 to 6 carbon atom hydrocarbon Base, or be expressed from the next:

Wherein x is in 0 to 3 range, R₁Selected from the alkyl for containing about 6 to 25 carbon atoms, R₂And R₃Identical or different and choosing From the alkyl for containing about 1 to 6 carbon atom, and R₄Selected from the group being made up of: H or C₆To C₂₅Carboxylic moiety.

Suitable carboxylic acid can include but is not limited to caproic acid, octanoic acid, lauric acid, myristic acid, palmitinic acid, stearic acid, flower Raw acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexane-carboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid etc..

In one embodiment, oil-soluble titanium can be to provide by weight 0 to 3000ppm titanium or 25 to about The amount of 1500ppm titanium or about 35ppm to 500ppm titanium or about 50ppm to about 300ppm titanium is present in lubricant oil composite.

Viscosity index improver

Lubricant oil composite herein also optionally contains one or more viscosity index improvers.Suitable viscosity Index improver may include polyolefin, olefin copolymer, ethylene/propene copolymer, polyisobutene, hydrogenated styrene-isoamyl two Alkene polymer, styrene/maleate copolymer, hydrogenated styrene/butadiene copolymer, hydrogenated isoprene polymer, α- Alkene copolymer-maleic anhydride, polymethacrylates, polyacrylate, alkyl styrenes, hydrogenated alkenyl aryl conjugation two Or mixtures thereof alkene copolymer.Viscosity index improver may include star polymer, and to be described in the U.S. special for suitable example In benefit the 8,999,905B2nd.

Other than viscosity index improver or viscosity index improver is replaced, lubricant oil composite herein can also appoint Selection of land contains one or more dispersing agents viscosity index improver.Suitable viscosity index improver may include functionalization polyene Hydrocarbon, for example, having used the functionalized ethylene-propylene copolymer of reaction product of acylating agent (such as maleic anhydride) and amine；With amine function The polymethacrylates of change, or the esterification maleic anhydride-styrene copolymers reacted with amine.

The total amount of viscosity index improver and/or dispersant viscosity index improvers can be about the 0 of lubricant oil composite Weight % to about 20 weight %, about 0.1 weight % are to about 15 weight %, about 0.1 weight % to about 12 weight % or 0.25 weight Measure % to about 10 weight %, or about 0.5 weight % to about 10 weight %, or about 3.0 weight % to about 9.5 weight %.

Other optional additives

Other additives may be selected to be lubricated one or more functions of fluid needs.Further, mentioned One of additive is a variety of to be polyfunctional, and other than function specified herein or is different from referred to herein Fixed function also provides other functions.

According to the lubricant oil composite of the disclosure optionally including other performance additive.Other performance additive can be Additive other than the special additive of the disclosure and/or may include one of following or a variety of: matal deactivator, viscous Spend index improver, ashless tbn synergist, friction improver, antiwear agents, corrosion inhibitor, antirust agent, dispersing agent, dispersion Agent viscosity index improver, extreme pressure agent, antioxidant, foam in hibitors, demulsifier, emulsifier, pour-point depressant, sealing sweller and Its mixture.In general, the lubricating oil prepared completely will contain one of these performance additives or a variety of.

Suitable matal deactivator may include that benzotriazole derivatives (usually tolyl-triazole), dimercaptothiodiazole spread out Biology, 1,2,4- triazoles, benzimidazole, two Thiobenzimidazole of 2- alkyl or the thio benzothiazole of 2- alkyl two；Foam inhibits Agent, the copolymer including ethyl acrylate and 2-EHA and optional vinyl acetate；Demulsifier, including phosphoric acid Trialkyl ester, polyethylene glycol, polyethylene oxide, polypropylene oxide and (epoxy ethane-epoxy propane) polymer；Pour-point depressant, packet Include ester, polymethacrylates, polyacrylate or the polyacrylamide of maleic anhydride-styrene.

Suitable foam in hibitors includes the compound based on silicon, such as siloxanes.

Suitable pour-point depressant may include or mixtures thereof polymethyl methacrylate.With the total weight of lubricant oil composite Meter, pour-point depressant can be to be enough to provide about 0 weight % to about 5 weight %, about 0.01 weight % to about 1.5 weight %, or about The amount of 0.02 weight % to about 0.4 weight % exists.

Suitable antirust agent can be single compound or compound with the characteristic for inhibiting ferrous metal surface corrosion Mixture.The non-limiting example of available antirust agent includes oil-soluble high molecular weight organic acid herein, such as 2 ethyl hexanoic acid, the moon Cinnamic acid, myristic acid, palmitinic acid, oleic acid, linoleic acid, linolenic acid, behenic acid and cerinic acid；And including dimeric dibasic acid and three Those of the oil-soluble polycarboxylic acids of polyacids, such as generated by ready denier oil acid, oleic acid and linoleic acid.Other suitable corrosion inhibit Agent includes long-chain alpha, omega-dicarboxylic acid of the molecular weight in about 600 to about 3000 ranges, and wherein alkenyl contains about 10 or more The alkenyl succinic acid of a carbon atom, such as tetrapropylene base succinic acid, tetradecene base succinic acid and hexadecylene base succinic acid.It is another available The sour corrosion inhibitor of type is the alkenyl succinic acid and alcohol (such as poly- second two in alkenyl with about 8 to about 24 carbon atoms Alcohol) half ester.The correspondence half amide of this kind of alkenyl succinic acid is also suitable.Available antirust agent is high molecular weight organic acid.One In a little embodiments, machine oil is free of antirust agent.

It, can be to be enough to provide about 0 weight % to about 5 weight %, about 0.01 weight with the total weight of lubricant oil composite % to about 3 weight % is measured, the amount of about 0.1 weight % to about 2 weight % were come using antirust agent (if present).

In a general sense, suitable crankcase lubricant may include the additive component in the range of being listed in the table below.

Table 2

The percentage of every kind of component is indicated with the weight percent of every kind of component of total weight of lubricant oil composite above. The rest part of lubricant oil composite is made of one or more base oils.

The additive for being used to prepare composition described herein can be blended into base oil individually or in the form of various sub-portfolios In.However, all components, which are blended, simultaneously using multifunctional additive for lubricating oils (i.e. additive adds diluent, such as hydrocarbon solvent) can be properly 's.

The disclosure is provided as being used as the novel lubricating oil blend of automotive engine lubrication agent and particular formulation.The disclosure Embodiment can provide the lubricating oil for being suitable for engine application, and the lubricating oil provides changing for following one or more features Into: low speed pre-ignition event, inoxidizability, wear resistance, rust-preventing characteristic, fuel economy, water tolerance, air entrainment, sealing Protection, deposit are reduced and foam reduces characteristic.

The lubricant prepared completely usually contains additive packet, herein referred to as dispersant/inhibitor packet or DI packet, Feature needed for formulation will be supplied.Suitable DI packet is described in such as U.S. Patent No. 5,204,012 and the 6,034th, In No. 040.The additive types for including in additive packet can for dispersing agent, sealing sweller, antioxidant, foam in hibitors, Lubricant, antirust agent, corrosion inhibitor, demulsifier, viscosity index improver etc..Some in these components are art technologies Personnel with convention amount and additive as described herein with composition it is well known that and be usually used together.

The disclosure is provided as being used as the novel lubricating oil blend of automotive engine lubrication agent and particular formulation.The disclosure Embodiment can provide the lubricating oil suitable for engine application, provide the improvement of following one or more features: low speed pre-ignition thing Part, antioxidant, wear resistance, rust-preventing characteristic, fuel economy, water tolerance, air entrainment, seal protection, deposit subtract It is few, test is corroded by ball and foam reduces characteristic.

Following instance is illustrated and noted limit to disclosed method and composition.To usually being encountered in this field And be the other suitable modifications and adjustment of various conditions apparent to those skilled in the art and parameter all in this public affairs In the scope opened.

Example

The lubricant oil composite prepared completely containing conventional additives is prepared, and the low speed for measuring lubricant oil composite is early The quantity of combustion event.Add the total weight of viscosity index improver with lubricant oil composite, conventional disperse agent inhibitor (DI) packet, Every kind of lubricant oil composite contains the major amount of base oil greater than 50 weight %, wherein DI packet (viscosity index improver is less) About 8 to 13% lubricant oil composite is provided.DI includes dispersing agent, antiwear additive, defoaming agent and the antioxygen of convention amount Agent, as illustrated in the following table 3.Specifically, DI includes succinimide dispersant, the dispersion of boration succimide Agent, molybdate compound, friction improver, one or more antioxidants and one or more antiwear agents are (unless otherwise rule It is fixed).It include one or more viscosity index improvers of about 4 to about 10 weight % in the lubricant oil composite of every kind of test.Base Plinth oil is used as the flux oil of viscosity index improver.The component of variation indicates in the discussion of following table and example.Unless otherwise rule Fixed, all values otherwise listed in table 3 illustrate to be with lubricant oil composite (that is, active constituent adds flux oil, if deposited ) total weight weight percent of the component in lubricant oil composite.

Table 3-DI packet compositing range

Component	Weight %
		Antioxidant	0.5 to 2.5
Antiwear agents, including any metal dialkyl dithiophosphate	0.7 to 5.0
		Defoaming agent	0.001 to 0.01
Detergent *	0.0
		Dispersing agent	2.0 to 6.0
Metalliferous friction improver	0.05 to 1.25
		Metal-free friction improver	0.01 to 0.5
Pour-point depressant	0.05 to 0.5
		Processing oil	0.25 to 1.0

* it is different in following experiment first detergent, therefore for the purpose of basic formula object, it will be clear in basic DI packet Clean dosage is set as zero.

Measure the low speed pre-ignition in 2.0 liter of 4 cylinder Ecotec turbocharging gasoline direct (TGDi) engine of Ford (LSPI) event.One complete LSPI igniter motor test contains 4 test iteration.Each test iteration is in limit Under run 4 hours under the speed of about 1750rpm and maximum brake mean-effective pressure (BMEP) greater than 80%.For each Stage collects about 175, the data of 000 cycle of engine.Therefore, LSPI igniter motor test complete for one, it is typical Ground generates the data of about 700,000 cycle of engine in total and for assessing more oily and oil of the invention performance.This is surveyed Method for testing is expected to be included into International Lubricants standardization and the examination & approval committee's (ILSAC) GF-6 engine oil specifications and American Petroleum Industry (API) SN machine oil class.

It is measured by monitoring peak cylinder pressure (PP) and when in combustion chamber 2% combustible material burns (MFB02) LSPI event.In single cycle of engine, LSPI event is recorded when exceeding the threshold value of PP and MFB02.LSPI event can be with Many modes are reported.Report that every cycle of engine counts the ambiguity being related to remove, wherein different igniter motors are surveyed Different cycle of engine quantity can be used to carry out for examination, and the more oily opposite LSPI event with oil of the invention is to be based on being set as 1.0 Reference oil R-1 " LSPI ratio " form report.It clearly proves to be changed relative to some normal responses in this way Into.

In the examples below, several different additives are tested with basic components to combine.LSPI ratio is with test oil LSPI event relative to reference oil " R-1 " LSPI event ratio form report.R-1 be using basic DI packet and in for Lubricant oil composite provides the lubricant oil composite that the high alkalinity calcium detergent of the amount of about 2400ppm Ca is prepared.Ginseng is given below Examine the more detailed formulation information of oily R-1.

Therefore, the LSPI ratio of R-1 reference oil is considered as 1.00.It is big when being reduced relative to reference oil R-1 LSPI event When 60% (that is, LSPI ratio is less than 0.4), it can be appreciated that improved to sizable LSPI.When relative to reference oil R-1 LSPI Event is reduced when being greater than 70% (that is, LSPI ratio is less than 0.3), it can be appreciated that further improvement.When relative to reference oil R-1 LSPI event is reduced when being greater than 75% (that is, LSPI ratio is less than 0.25), it can be appreciated that being even further improved, when relative to ginseng Oily R-1 LSPI event is examined to reduce when being greater than 80% (that is, LSPI ratio is less than 0.20), it can be appreciated that even further improvement, and And when reducing relative to reference oil R-1 LSPI event greater than 90% (that is, LSPI ratio is less than 0.10), it can be appreciated that even It is further improved.

Ball corrosion test is carried out according to the method for ASTM D-6557.

The TBN measured value provided in following table is made using the program of ASTM-D-2896.

Tank oil R-1 is included as the reference oil for showing state of the art.Reference oil R-1 is by about 80.7 weight % Group III base oil, 12.1 weight % are purchased from Afton Chemical Corporation's11150PCMO adds Agent packet and 7.2 weight %35SSI ethylene/propene copolymer viscosity index improvers is added to prepare.11150 passenger cars Oil additives packet is the DI packet of API SN, ILSAC-GF-5 and ACEAA5/B5 quality.Reference oil R-1 is commercially available machine oil, Meet all ILSAC GF-5 performance requirements, including passing through for ball discussed below corrosion test.

Reference oil R-1 also shows following and characteristic and Partial Elements analysis:

Reference oil R-1

Table 4

Table 5

As shown in table 4-5, by the way that reference example oil R-1 is compared with invention example 1-6, the present composition LSPI performance has a significant improvement, as LSPI event reduces shown at least 60%.The calcic that reference oil R-1 contains 1.95 weight % is clear Clean dose, amount is relatively large compared with the total amount of the calcic detergent in present example 1-6.However, when control detergent, When the amount of calcium, magnesium and molybdenum is to provide following, even if LSPI performance is of the invention real under significant lower total calcium detergent concentration It is improved in example 1-6:

(a) the weight % of the calcium in lubricant oil composite from one or more high alkalinity calcic detergents with come from one It plants or the ratio of the weight % of the magnesium in the lubricant oil composite of a variety of high alkalinity detergents containing magnesium is less than 11.9,

(b) the total ppm and lubricating oil composition of the magnesium in the lubricant oil composite as measured by the method for ASTM D-2896 The ratio of total TBN (in terms of mg KOH/g) of object is greater than 19；With

(c) the total ppm and lubricating oil composition of the calcium in the lubricant oil composite as measured by the method for ASTM D-2896 The ratio of total TBN (in terms of mg KOH/g) of object is less than 222.

Data are also shown that when example 1-6 of the invention to be compared with comparative example A-C, obtain LSPI ratio Improvement, wherein ratio A-C respectively has in the ratio being given above except ratio (a)-(c) range.Therefore, Ke Yixuan The adequate rate for selecting Ca-Mg-Mo allows average LSPI event to reduce 60% or more, and formulation still can pass through Ball corrosion test.This demonstrates the need for appropriately combined including Ca, Mg and Mo within the scope of prescribed concentration

Comparative example C and present example 6 have similar Ca and Mo concentration, but the addition of Mg provide LSPI ratio and The unexpected improvement of ball corrosion test.

Comparative example A and present example 4 show Ca, Mg and Mo it is appropriately combined cause LSPI ratio reduce and Ball corrosion test is passed through.

Comparative example A and present example 2 have similar Ca concentration, but lead to LSPI ratio to the adjusting of Mg and Mo The improvement performance of both tests is corroded with ball.

Many places refer to multiple United States Patent (USP)s and other files in entire this specification.All such reference documents are clear Ground is incorporated in the disclosure for the specific purposes of reference document in entirety by reference or at least, as sufficiently explained herein It states general.

After considering the practice of this specification and embodiment disclosed herein, the other embodiments of the disclosure are to this The technical staff in field is apparent from aobvious.As used in entire disclosure and claims, "one" and/or "an" can Refer to one (kind) or more than one (kind).Unless otherwise instructed, what is otherwise used in the present specification and claims is all Express ingredient, characteristic amount number, such as molecular weight, percentage, ratio, reaction condition, it is thus understood that in all examples It is modified by term " about ", no matter term " about " whether there is.Therefore, unless providing on the contrary, otherwise this specification and right are wanted Seeking the numerical parameter illustrated in book is that can depend on the approximation for attempting to change by the desirable properties that the disclosure obtains. Minimally, and it is not intended to limit application of the equivalent principle to Claims scope, each numerical parameter is answered Number according at least to the effective digital reported and technology is generally rounded up by application to explain.Although illustrating this public affairs The broad range of numberical range and parameter opened are approximations, but the numerical value illustrated in specific example is reported as precisely as possible Report.It is necessarily caused however, any numerical value inherently contains certain standard deviations as found in its corresponding test measured value Error.Wish only to be considered as this specification and example illustratively, wherein the true scope of the disclosure and spirit are by following Claims indicate.

Previous embodiment is easy to produce sizable variation when practicing.Therefore, embodiment is not intended to be limited to explain above The concrete example stated.On the contrary, previous embodiment is within the spirit and scope of the appended claims, including it can be used as law and asks The equivalent of topic.

Patentee, which is not intended to, contributes to the public for any disclosed embodiment, and any to a certain extent disclosed repairs Changing or changing may not be the range that claims are fallen on literal, think that it is one of this paper under equivalent principle Point.

It should be understood that every kind of component, compound, substituent group or parameter disclosed herein should be interpreted that disclosure to be used alone Or it is used with one of each other components, compound, substituent group or parameter disclosed herein or multiple combinations.

It should also be understood that every kind of component disclosed herein, compound, each amounts/values of substituent group or parameter or amounts/values Range should be interpreted that also with each amounts/values disclosed in any other component disclosed herein, compound, substituent group or parameter or The range combinations of amounts/values disclose, and therefore, and for the purpose of this description, two or more components disclosed herein are changed Any combination for closing the range of the amounts/values or amounts/values of object, substituent group or parameter is also disclosed in the form of combination with one another.

It is also to be understood that each range disclosed herein should be interpreted that has identical significant figure within the scope of the disclosed The disclosure of each occurrence of number of words.Therefore, the range of 1-4 shall be interpreted as clearly disclosing for value 1,2,3 and 4.

It should also be understood that each lower limit of each range disclosed herein should be interpreted that and identical group disclosed herein Point, each certain combinations of values in each upper limit and each range of each range of compound, substituent group or parameter discloses.Cause This, will appreciate in view of this disclosure that for by by each upper limit of each lower limit of each range and each range or in each range Each certain combinations of values, or by by institute derived from each certain combinations of values in each upper limit of each range and each range There is the disclosure of range.

In addition, this specification or component disclosed in example, compound, substituent group or parameter specific amounts/values should solve It is interpreted as the lower limit of a certain range or the disclosure of the upper limit, and therefore can be with the lower limit or the upper limit or the application of any other range In same composition, compound, substituent group or parameter disclosed in other places the combination of specific amounts/values, with formed the component, The range of compound, substituent group or parameter.

30页详细技术资料下载

上一篇：一种医用注射器针头装配设备

下一篇：基于醚的润滑剂组合物、方法和用途

The method of lubricant and improvement low speed pre-ignition with high alkalinity calcium and high alkalinity magnesium detergent

相关技术

网友询问留言