CN101451086A - Lubricant composition comprising a bi-modal side-chain distribution lofi - Google Patents

Lubricant composition comprising a bi-modal side-chain distribution lofi Download PDF

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Publication number
CN101451086A
CN101451086A CNA2008101816647A CN200810181664A CN101451086A CN 101451086 A CN101451086 A CN 101451086A CN A2008101816647 A CNA2008101816647 A CN A2008101816647A CN 200810181664 A CN200810181664 A CN 200810181664A CN 101451086 A CN101451086 A CN 101451086A
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distribution
lubricant compositions
lofi
side chain
hypocrystalline
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CNA2008101816647A
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CN101451086B (en
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R·A·布洛克
D·H·伯泽
D·J·马尔泰拉
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Infineum International Ltd
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Infineum International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/08—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing non-conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature

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

Abstract

The invention discloses a lubricant composition comprising a bi-modal side-chain distribution LOFI. The lubricant composition is made up of (a) an API Group III base stock; (b) one or more semi-crystalline viscosity modifier; and (c) one or more LOFIs having a side-chain distribution which satisfies the following requirements: (1) the distribution contains side chains ranging from C 8 to C 18 with an average carbon number ranging from 12.4 to 14.4; (2) the side chain distribution is bi-modal with a lower portion of the bi-modal distribution made up primarily of C 12 and an upper portion of the distribution made up primarily of C 16, C 18 or combinations thereof; (3) the total mole % of the upper portion of the distribution must be less than that of the lower portion of the distribution; and (4) the amount of C 12 on the side chain must be at least 40 mole % of the total side chain distribution.

Description

The lubricant compositions that comprises bi-modal side-chain distribution lofi
Invention field
The present invention relates to have the lubricant compositions of improved flowing property, what particularly show improved low temperature flowability comprises (API) lubricant compositions of III class oil base stock of American Petroleum Institute (API) (American Petroleum Institute).
Background of invention
Lubricant compositions is used in the various application, as automobile application, industrial application etc.Lubricant compositions is made into by oil base stock and one or more additives usually.
The various additives that are used in the lubricant compositions are as known in the art.The example of this class additive includes but not limited to, lubricating oil flow improving agent (LOFI), viscosity modifier (VM) etc.
Automaker and governability person have introduced the new stricter performance requriements to lubricant.For example to the requirement of oily volatility and fuel efficiency.These variations make the selection of used oil base stock in the lubricant than in the past much important.Because their low viscosity and low volatility, APIIII class oil base stock becomes the selection of lubricant compositions oil base stock of future generation.
The invention provides the lubricant compositions with improved low temperature flowability, it comprises (a) API III class oil base stock; (b) hypocrystalline viscosity modifier; (c) one or more have the LOFI of the side chain distribution that meets some requirement.
Summary of the invention
In a non-limiting embodiments, the present invention is a kind of lubricant compositions, and it comprises (a) API III class oil base stock; (b) hypocrystalline viscosity modifier; (c) one or more have the LOFI:(1 of the side chain distribution that meets the following requirements) to contain average carbon number be 12.4 to 14.4 C in this distribution 8To C 18The side chain of scope; (2) this side chain distribution is bimodal, wherein this bimodal distribution than lower part (lower portion of the bi-modal distribution) mainly by C 12The higher part (upper portion of the distribution) that constitutes and should distribute is mainly by C 16, C 18Or it constitutes; (3) total mole of % of the higher part of this distribution must be less than the total mole of % than lower part of this distribution; (4) C on the side chain 12Amount be necessary at least 40 moles of % of total side chain distribution.
Detailed Description Of The Invention
Unless indicate separately, used all numerical value that are expressed as component, reaction conditions, size, physical property, machined parameters etc. are interpreted as all using in all cases term " approximately " to modify in this specification sheets and the claim.Correspondingly, unless make opposite indication, numerical value listed in following specification sheets and the claim can become with the desired properties of attempting by the present invention obtains.At least, and be not the range applications doctrine of equivalents that will limit claims, each numerical value should be explained according to the significant digit of being reported with by using the common technology of rounding off at least.In addition, all scopes disclosed herein are understood to include beginning and end ranges value and wherein contained any and all subranges.For example, the described scope of " 1 to 10 " should be believed to comprise any and all subranges of between minimum value 1 and maximum value 10 (comprising end points); All subranges that just begin and finish with maximum value 10 or littler value with minimum value 1 or bigger value, for example 5.5 to 10.Any mentioning to United States Patent (USP) or patent document or reference in following specification sheets also is incorporated herein by this reference the document and be understood that to incorporate in full.
Following term used herein defines in the following manner.
Term " polymer " " comprise multipolymer, only be limited to the polymkeric substance that the polymerization by single monomer produces unless otherwise noted, and comprise branching and simple linear polymer.
Term " multipolymer " is meant the polymkeric substance that is produced by two kinds of chemically different monomeric polyreactions.With reference to the ethylene-alpha-olefin multipolymer, it being understood that this analog copolymer can be chosen wantonly contains minor amount () non-conjugated polyene for example, greater than 0 but less than 10 weight %, multipolymer is known as terpolymer sometimes in this case.With reference to the ethylene-alpha-olefin polymkeric substance, it being understood that the multipolymer of ethene and at least a other alpha-olefin and terpolymer are all included.
Term " average carbon number " is meant the average carbon number by the molar fraction weighting.
Term " lubricating oil flow improving agent " (LOFI) comprises all additives that improve size, quantity and the growth of wax crystalls in the lubricating oil (or being abbreviated as lube) in the mode of giving improved subzero treatment, pump-conveying property and/or vehicle performability (these record by the test as pour point, Mini-RotaryViscometer (MRV) and scanning brookfield's viscometer and so on).The mobile improving agent of most of lubricating oil is polymkeric substance or multipolymer, or contains polymkeric substance or multipolymer.These polymkeric substance are side chain, skeleton or its mixture normally.
Term " base oil " is meant the refining fluid that does not contain additive and be used as the component in the lubricant adulterant.
Term " oil base stock " is meant adulterant, mixture or the analogue of base oil.
Mention each " class " oil base stock, for example API III class oil base stock in this article.According to contained table in the U.S. Patent No. 6,475,963 that is incorporated herein by this reference, American Petroleum Institute (API) (API) has set up these classification.
Term " bimodal " is meant the carbon chain lengths frequency distribution with two different peaks (or mode), and each peak is a certain carbon chain lengths (or the several adjacent carbons chain lengths with regard to successive even number carbon number) that molar percentage is higher than the adjacent carbons chain length.This bimodal carbon chain length frequency distribution has " distribution than lower part " and " the higher part of distribution ".
Term " distribution than lower part " is meant the part that the mode by having the adjacent carbons chain length (with regard to successive even number carbon number with regard to) lower than low carbon chain length and molar percentage in the bimodal distribution constitutes.The high carbon chain length than in the lower part that distributes is C 14
Term " the higher part of distribution " is meant the part that the mode by having the lower adjacent carbons chain length of higher carbon chain length and molar percentage in the bimodal distribution constitutes.Minimum carbon chain lengths in the higher part that distributes is C 16
Term " mainly " is meant that the amount of a kind of component that exists in composition, the compound etc. is greater than the amount of existing any other component (with regard to component one by one).
The present invention is a kind of lubricant compositions, and it comprises (a) III class oil base stock; (b) hypocrystalline viscosity modifier; (c) one or more meet the LOFI of some specification.
According to the present invention, this lubricant compositions comprises API III class oil base stock.The III class oil base stock of API definition has unlimited viscosity index.In a non-limiting embodiments of the present invention, the viscosity index of oil base stock is higher than 120.In another non-limiting embodiments of the present invention, oil base stock has and is equal to or greater than 120 and be equal to or less than 200 viscosity index.Suitable commercially available III class oil base stock includes but not limited to: can be available from ExxonMobil (Fawley, Visom board oil base stock U.K.); Can be available from the Yubase board oil base stock of SK Corporation (Ulsan, South Korea); Can be available from the Ultra-S board oil base stock of ConocoPhillips (Westlake, LA (USA)); With can be available from Neste (Porvoo, Nexbase board oil base stock Finland).
In a non-limiting embodiments of the present invention, use gas to become liquid (" GTL ") manufactured oil base stock.GTL is used for Sweet natural gas or other hydrocarbon gas are changed into the more method for refining of long chain hydrocarbon.For example, GTL can be used for using the gas reforming that Fischer-Tropsch method will be rich in methane to become liquid fuel via direct conversion or via synthetic gas as intermediate.As known in the art, can use isomerization catalyst to make III class oil base stock with GTL.
According to the present invention, this lubricant compositions comprises the hypocrystalline viscosity modifier.Usually, the hypocrystalline viscosity modifier comprises one or more high molecular weight hydrocarbon polymers as known in the art.The example of suitable hydrocarbon polymer comprises with at least a having 3 to 30, for example 3 to 8 carbon atoms and can be the multipolymer of ethene of the other alpha olefin monomers copolymerization of straight or branched.Randomly, can there be lower concentration, for example be lower than the non-conjugated diene of about 10 weight %.In a non-limiting embodiments, these multipolymers are to comprise those of ethene and propylene.Be applicable to ethylene copolymer of the present invention comprise alternation or segmented copolymer (comprising terpolymer, tetrapolymer etc.) and as known in the art in copolymer chain and between have those of controlled composition homogeneity and/or ununiformity.This analog copolymer is described in ＂ Polymers as LubricatingOil Viscosity Modifiers ＂, G.VerStrate, M.J.Struglinski, the 15th chapter; ＂ Polymers as Rheology Modifiers ＂, D.N.Schulz and J.E.Glass edit, American Chemical Society, Washington, D.C. is in 1991.Above-mentioned article is incorporated herein by this reference on the degree that allows.
In a non-limiting embodiments of the present invention, the hypocrystalline viscosity modifier is by ethene and C 3To C 18The oil-soluble polymers that alpha-olefin constitutes, this polymkeric substance is characterised in that the following combination of parameter: (a) the average ethylene content of 60 to 80 moles of %, wherein said polymkeric substance contain no more than 1.3 weight % under 45 ℃ in n-decane insoluble polymer moieties; (b) less than 25% degree of crystallinity; (c) less than 4.0 weight-average molecular weight/number-average molecular weight ratio; (d) viscosity-average molecular weight in 10,000 to 200,000 dalton's scopes.Referring to U.S. Patent No. 3,551,336, it is incorporated herein by this reference.
In another non-limiting embodiments of the present invention, the hypocrystalline viscosity modifier is the segmented copolymer of ethene and at least a other alpha olefin monomers; Each multipolymer is that intramolecularly is inhomogeneous and intermolecular uniformly, and at least 10% at least a multipolymer segment that constitutes copolymer chain is crystallizable segment.Referring to U.S. Patent No. 4,804,794, it is incorporated herein by this reference.
In a non-limiting embodiments of the present invention, the hypocrystalline viscosity modifier is in the non-crystalline state viscosity modifier is comprised in.The example is to comprise ethene and the C with 50-95 mole % ethylene content 3To C 18First multipolymer of alpha-olefin and ethene and C with 5-80 mole % ethylene content 3To C 18The oil-soluble polymers composition of second multipolymer of high alpha-olefin more, wherein the ethylene content of first multipolymer is than the ethylene content of second polymkeric substance at least 5 moles of % greatly.Referring to U.S. Patent No. 3,697,429, it is incorporated herein by this reference.
In a non-limiting embodiments of the present invention, the hypocrystalline viscosity modifier to pass through the number-average molecular weight that gel permeation chromatography records be 20,000 to 500,000 dalton, for example 25,000 to 400,000 dalton or 30,000 to 300,000 dalton.
The hypocrystalline viscosity modifier can be present in the lubricant compositions with the amount of 0.05 to 5 weight % polymkeric substance.
According to the present invention, lubricant compositions comprises one or more LOFI with the side chain distribution that meets the following requirements:
(1) existing each side chain comprises by 8 to 18 carbochains that carbon atom constitutes, and average carbon number is 12.4 to 14.4, and for example 12.8 to 14.0 or 13.0 to 13.8;
(2) this side chain distribution is bimodal, wherein this bimodal distribution than lower part mainly by C 12The higher part (distribution that promptly has higher carbon number mode) of formation and this distribution is mainly by C 16, C 18Or it constitutes;
(3) total mole of % of the higher part of this distribution must be less than the total mole of % than lower part of this distribution; With
(4) C on the side chain 12Amount be necessary at least 40 moles of % of total side chain distribution, for example at least 50 moles of % or at least 60 moles of %.
In the basal component of bimodal distribution by (a) C 12And C 16Or (b) C 12, C 16And C 18A non-limiting embodiments constituting of mixture in, C 14Amount must be less than 20 moles of % of total side chain distribution, for example less than 10 moles of %.
In a non-limiting embodiments of the present invention, side chain comprises from C 8To C 18Even number carbon number segment, i.e. C 8, C 10, C 12, C 14, C 16, C 18
In a non-limiting embodiments, LOFI is dialkyl fumarate/vinyl-acetic ester multipolymer.This dialkyl fumarate-vinyl-acetic ester multipolymer can be that the average carbon number of 8 to 18 alcohol is 12.4 to 14.4 by carbon number, and for example 12.8 to 14.0 or 13.0 to 13.8 mixture forms.This multipolymer is to have the side chain multipolymer of methylene radical segment as side chain.
These LOFI can contain the ester side group of the mixture that is derived from alcohol, pure thus residue can be a feature with the multiple MU (methylene unit), and it is oil soluble or dispersed polymeric composition, have usually by gel permeation chromatography record 50,000 to 350,000 daltonian weight-average molecular weight.
In a non-limiting embodiments of the present invention, dialkyl fumarate-vinyl-acetic ester multipolymer has 0.3 to 1.5, for example 0.3 to 1.0 or 0.45 to 0.7 specific viscosity.In another non-limiting embodiments, the weight-average molecular weight of dialkyl fumarate-vinyl-acetic ester multipolymer is 50,000 to 350,000 dalton, for example 50,000 to 200,000 dalton or 75,000 to 120,000 dalton.
In another non-limiting embodiments, LOFI comprises poly-(alkyl methacrylate) polymkeric substance.Should comprise the multipolymer (A) that constitutes by alkyl methacrylate (a1) and one or more monomers (a2) substantially by poly-(alkyl methacrylate) polymkeric substance.Referring to U.S. Patent No. 5,891,831, it is incorporated herein by this reference.
The amount that constitutes the alkyl methacrylate (a1) of multipolymer (A) can be 30 to 99.99 weight % of multipolymer (A) weight usually.
Alkyl methacrylate (a1) can comprise the methacrylic ester (for example methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid 2-ethylhexyl, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid tridecyl ester, methacrylic acid tetradecyl ester, methacrylic acid pentadecyl ester, methacrylic acid cetyl ester, methacrylic acid stearyl) with the linear alkyl that contains 1 to 18 carbon atom usually.Wherein, preferably wherein moieties has the alkyl methacrylate of 8 to 18 carbon atoms.
Monomer (a2) is to be selected from one or more of conjugated diolefine, acetylene, replaced acetylene, alkyl vinyl ether and alkyl allyl ethers.The amount that constitutes the monomer (a2) of multipolymer (A) can be 0.01 to 10 weight % of multipolymer (A) weight, preferred 0.1 to 5 weight % usually.
In a non-limiting embodiments again, LOFI comprises poly-(alkyl acrylate) polymkeric substance.Should poly-(alkyl acrylate) polymkeric substance be to have acrylate or the alkyl acrylate copolymer derivative that disperses group.Referring to U.S. Patent No. 6,869,919, it is incorporated herein by this reference.
In another non-limiting embodiments, LOFI comprises poly-(styrene-maleic acid dialkyl) polymkeric substance.Referring to U.S. Patent No. 4,564,438, it is incorporated herein by this reference.
LOFI in the lubricant compositions and one or more other components except that oil base stock are known as " additive ".
In a non-limiting embodiments, LOFI has 50,000 to 350,000 dalton, for example 80,000 to 200, the 000 daltonian weight-average molecular weight that record by gel permeation chromatography.
In another non-limiting embodiments, LOFI has 0.3 to 1.0, for example 0.4 to 0.8 specific viscosity.
LOFI can be with 0.005 to 1.0 weight %, and for example the amount of 0.05 to 0.5 weight % is present in the lubricant compositions.
Lubricant compositions of the present invention can further comprise one or more optional components: inhibiter, oxidation retarder, friction improver, dispersion agent, antifoams, anti-wear agent, purification agent, rust-preventive agent etc.
In a non-limiting embodiments, lubricant compositions of the present invention comprises inhibiter.Inhibiter is also referred to as resist, alleviates the corrosion of the metal parts that contacts with lubricating oil composition.The example of inhibiter is the product that phosphosulfurized hydrocarbon (phosphosulfurized) and the reaction by phosphosulfurized hydrocarbon and alkaline earth metal oxide or oxyhydroxide obtain, this reaction is preferably in the presence of alkylating phenol or alkylphenol thioesters, and is also preferred in the presence of carbonic acid gas.Phosphosulfurized hydrocarbon is by making suitable hydrocarbon such as terpene, C 2To C 6The phosphorus sulfide of the heavy petroleum fractions of olefin polymer such as polyisobutene and 5 to 30 weight % reacts under the temperature of 150 ℉ to 600 ℉ (66 ℃ to 316 ℃) and prepared in 1/2 to 15 hour.The neutralization of phosphosulfurized hydrocarbon can be with U.S. Patent No. 1,969, and the mode of instruction realizes in 324.
In a non-limiting embodiments, lubricant compositions of the present invention comprises oxidation retarder.Oxidation retarder reduces the in use rotten trend of mineral oil, and this going bad can show as oxidation products such as sludge and the varnish shape settling on the metallic surface, and shows as the viscosity increase.This class oxidation retarder comprises preferably having C 5To C 12The alkaline earth salt of the alkylphenol thioesters of alkyl group side chain, for example nonyl phenol sulfurated lime, uncle's octyl phenyl barium sulphide, dioctyl phenyl amine, phenyl α ALPHA-NAPHTHYL AMINE, phosphorus sulfuration or sulfuration hydrocarbon etc.
In a non-limiting embodiments, lubricant of the present invention comprises friction improver.Friction improver is used to give lubricating oil composition, the rubbing characteristics suitable as automatic transmission fluid.The representative instance of suitable friction improver is found in U.S. Patent No. 3,933,659, and it discloses fatty acid ester and acid amides; U.S. Patent No. 4,176,074, it has described the molybdenum complex of polyisobutenyl succinic anhydride-aminoalkanol; U.S. Patent No. 4,105,571, it discloses the glyceryl ester of dimerization lipid acid; U.S. Patent No. 3,779,928, it discloses alkane phosphonic acid salt; U.S. Patent No. 3,778,375, it discloses the reaction product of phosphonic acid ester and oleylamide; U.S. Patent No. 3,852,205, it discloses S-carboxyl alkylidene group hydrocarbyl succinic imide, the acid of S-carboxyl alkylidene group hydrocarbon succinic amide and composition thereof; U.S. Patent No. 3,879,306, it discloses N-(hydroxyalkyl) alkenyl succinamic acid or succinic diamide; U.S. Patent No. 3,932,290, it discloses the reaction product of two (low-carbon alkyl) phosphorous acid esters and epoxide; With U.S. Patent No. 4,028,258, it discloses the oxirane adducts of phosphorus sulfuration N-(hydroxyalkyl) alkenyl succinimide.Preferred friction improver comprises that as U.S. Patent No. 4,344 alkyl described in 853 replaces succinate or its metal-salt of succsinic acid or acid anhydrides and thiobis alkanol, and various molybdenum compound.
In a non-limiting embodiments, lubricant compositions of the present invention comprises dispersion agent.Dispersion agent makes in use and to be kept being suspended in the fluid by produce soluble of oxidation or the compound that is insoluble in oil substantially, prevents sludge flocculation and precipitation thus or is deposited on the metal parts.Suitable dispersion agent comprises high molecular succsinic acid alkyl ester, the reaction product of oil soluble polyisobutylene succinic anhydride and ethyleneamines such as tetren and boration salt thereof.
In a non-limiting embodiments, lubricant compositions of the present invention comprises the component that foam control is provided.Can pass through polysiloxane type antifoams, provide foam control as silicone oil and polydimethylsiloxane.
In a non-limiting embodiments, lubricant compositions of the present invention comprises anti-wear agent.Anti-wear agent alleviates the wearing and tearing of metal parts shown in its title.The representative of tradition anti-wear agent is zinc dialkyl dithiophosphate and diaryl zinc dithiophosphate.
In a non-limiting embodiments, lubricant compositions of the present invention comprises purification agent and metal antirusting agent.Purification agent and metal antirusting agent comprise following metal-salt: sulfonic acid, alkylphenol, sulfenyl phenolate, alkyl salicylate, cycloalkanes acid esters and other oil soluble list-and two-carboxylic acid.High alkalinity (being parlkaline) metal-salt is often used as purification agent as high alkaline alkaline earth metal sulfonate (especially Ca and Mg salt).Representative example of this class material and preparation method thereof is found in the U.S. Patent No. 6,127,321 of the application of submitting at first based on July 11st, 1985.
Lubricant compositions of the present invention can use method well known in the art and technology manufacturing.Lubricant compositions of the present invention is usually by mixing oil base stock manufacturing with each component.For example, these components are directly added in the oil base stock by disperse or dissolve additive with the desired concn level under the temperature of room temperature or rising.
Embodiment
By the present invention of following non-limiting examples illustration.In an embodiment, lubricant compositions comprises III class oil base stock (Yubase oil base stock); Hypocrystalline viscosity modifier (from the Paratone 8451 of Chevron Oronite Company); LOFI with preparation as described below.Each lubricant compositions contains different LOFI.For example, the lubricant compositions of embodiment 1 contains LOFI 1, and the lubricant compositions of embodiment 2 contains LOFI 2, or the like.
By at first using adulterant preparation 5 kinds of dialkyl fumarate monomers (dialkyl fumarate monomer 1-5) of the alcohol that the carbon atom have as shown in Table I distributes, prepare 5 kinds of LOFI (LOFI1-5).Use the alcohol 1 preparation dialkyl fumarate monomer 1 in the Table I, use the pure II in the Table I to prepare dialkyl fumarate monomer 2, the rest may be inferred.With 232 gram fumaric acid, 824 gram certain alcohols adulterants and 0.2 gram Fascat
Figure A200810181664D0013163307QIETU
Add in the round-bottomed flask of being furnished with Dean and Stark apparatus.This slurry is stirred under nitrogen gas stream and slowly is heated to 220 ℃.By measuring the amount of the water of collecting in the Dean-Stark trap, monitor this esterification.When the generation of water stopped (common 4 to 6 hours), decantation went out the dialkyl fumarate monomer and analyzes neutralization value (2.0mg KOH/g) and saponification value (223mg KOH/g) from reactor.Form dialkyl fumarate monomer 1-5 thus.
Prepare dialkyl fumarate-vinyl-acetic ester multipolymer by (in above-mentioned steps, forming) dialkyl fumarate monomer and prepare LOFI by as described below then.Use dialkyl fumarate monomer 1 preparation dialkyl fumarate vinyl-acetic ester copolymer 1, use dialkyl fumarate monomer 2 preparation dialkyl fumarate vinyl-acetic ester multipolymers 2, the rest may be inferred.Add 150 gram dialkyl fumarate monomers (dialkyl fumarate monomer 1-5) to Parr
Figure A200810181664D0013163331QIETU
In 300 cubic centimetres of stainless steel reactors of board.With the sealing of this reactor, be heated to 50 ℃, and with nitrogen purging 10 minutes.Then 26.5 gram deoxidation vinyl-acetic esters are injected and contain the monomeric Parr of dialkyl fumarate
Figure A200810181664D0013163331QIETU
In the reactor.This mixture was stirred 15 minutes before being heated to 100 ℃ of temperature of reaction.Restrain the sad tert-butyl ester with 0.26 and be dissolved in the Blandol that 2.0 gram Sonneborn make
Figure A200810181664D0013163331QIETU
In the paraffin oil, inject this mixture then.This mixture is stirred 5 to 8 hours to finish polyreaction.Then this multipolymer is poured into round-bottomed flask and remove volatile matter from reactor at rotatory evaporator.Form dialkyl fumarate vinyl-acetic ester copolymer 1-5 thus.
With dialkyl fumarate vinyl-acetic ester copolymer 1-5 as known in the art with III class oil base stock (Yubase oil base stock) and hypocrystalline viscosity modifier (from the Paratone 8451 of Chevron Oronite Company) fusion to form the SAE5W-30 lubricant compositions of embodiment 1-5.
In following Table I, provide composition information about the LOFI side chain of embodiment 1-5.
Table I. the distribution of carbon atom among the pure 1-5
Alcohol 1 Alcohol 2 Alcohol 3 Alcohol 4 Alcohol 5
C 8[molar fraction] 0 0 0 0 .1
C 10[molar fraction] 0 0 .2 0 .3
C 12[molar fraction] .7 .708 .5 .4 0
C 14[molar fraction] .1 .084 0 .5 0
C 16[molar fraction] 0 .008 0 .1 .6
C 18[molar fraction] .2 .200 .3 0 0
Average C n 13.4 13.4 13.4 13.4 13.4
As mentioned above, the side chain of LOFI of the present invention must meet some requirement.Various requirement is listed in down in the Table II.For the various illustrative lubricant composition of making in the above described manner (embodiment 1-5), if LOFI meets the requirements, in the hurdle, occur " √ ", if LOFI is undesirable, in the hurdle, occur " X ".
Table II
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
(1) to contain average carbon number be 12.4 to 14.4 C in this distribution 8To C 18Side chain √ √ √ √ √
(2) this side chain distribution is bimodal, wherein this bimodal distribution than lower part mainly by C 12The higher part that constitutes and should distribute is mainly by C 16、C 18Or it constitutes √ √ √ X X
(3) summation of the higher part of this distribution must less than this distribution than lower part.This inevitable requirement, when the basal component of this bimodal distribution by (a) C 12And C 16Or (b) C 12, C 16And C 18Mixture when constituting, C 14Amount must be lower than 20% or be lower than 10%, and must be lower than C 16And C 18Summation √ √ √ X X
(4) C 12Amount be necessary at least 40 moles of % or at least 50 moles of % of total side chain distribution √ √ √ √ X
As can be seen, the LOFI in the lubricant compositions of embodiment 1-3 meets all requirements, and is included in the present invention.LOFI in embodiment 4 and 5 the lubricant compositions does not meet whole requirements and outside scope of the present invention.
Lubricant compositions according to 4684 couples of embodiment 1-5 of ASTM D carries out the test of MRV pump-conveying property.Test-results is presented in the Table III.
The test of Table III .MRV pump-conveying property
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Under 0.50% processing rate
Viscosity [mPa.s] 27,200 -- 24,400 161,100 54,200
Yielding stress [Pa] <35 -- <35 <350 <140
Under 0.20% processing rate
Viscosity [mPa.s] 23,800 21,400 22,400 -- --
Yielding stress [Pa] <35 <35 <35 -- --
For by MRV pump-conveying property test, lubricant compositions must show and be equal to or less than 60, the viscosity of 000mPa.s and less than the yielding stress of 35Pa.Under 0.50% processing rate, has only embodiment 1 and 3 by the test of MRV pump-conveying property.Under 0.20% processing rate, has only embodiment 1-3 by the test of MRV pump-conveying property.As implied above, embodiment 1-3 is included in the present invention.

Claims (12)

1. lubricant compositions, it comprises:
(a) API III class oil base stock;
(b) one or more hypocrystalline viscosity modifiers; With
(c) one or more have the LOFI of the side chain distribution that meets the following requirements:
(1) to contain average carbon number be 12.4 to 14.4 C in this distribution 8To C 18Side chain;
(2) this side chain distribution is bimodal, wherein this bimodal distribution than lower part mainly by C 12The higher part that constitutes and should distribute is mainly by C 16, C 18Or it constitutes;
(3) total mole of % of the higher part of this distribution must be less than the total mole of % than lower part of this distribution; With
(4) C on the side chain 12Amount be necessary at least 40 moles of % of total side chain distribution.
2. according to the lubricant compositions of claim 1, wherein the hypocrystalline viscosity modifier comprises the non-crystalline state viscosity modifier.
3. according to the lubricant compositions of claim 1, wherein LOFI is dialkyl fumarate-vinyl-acetic ester multipolymer.
4. according to the lubricant compositions of claim 1, wherein to contain average carbon number be 12.8 to 14.0 C in this distribution 8To C 18Side chain.
5. according to the lubricant compositions of claim 1, wherein the hypocrystalline viscosity modifier comprises and at least a ethylene copolymer with other alpha olefin monomers copolymerization of 3 to 30 carbon atoms.
6. according to the lubricant compositions of claim 1, wherein the hypocrystalline viscosity modifier comprises the ethylene-alpha-olefin multipolymer that contains a spot of one or more non-conjugated dienes.
7. according to the lubricant compositions of claim 1, wherein LOFI comprises poly-(alkyl methacrylate) polymkeric substance.
8. according to the lubricant compositions of claim 1, wherein LOFI comprises poly-(alkyl acrylate) polymkeric substance.
9. according to the lubricant compositions of claim 1, wherein LOFI comprises poly-(styrene-maleic acid dialkyl).
10. according to the lubricant compositions of claim 1, wherein LOFI has 0.3 to 1.0 specific viscosity.
11. according to the lubricant compositions of claim 1, wherein LOFI exists based on the amount of lubricant compositions gross weight with 0.005 weight % to 1.0 weight %.
12., further comprise one or more following components: inhibiter, oxidation retarder, friction improver, dispersion agent according to the lubricant compositions of claim 1.
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