CN101451086B - 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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CN101451086B
CN101451086B CN2008101816647A CN200810181664A CN101451086B CN 101451086 B CN101451086 B CN 101451086B CN 2008101816647 A CN2008101816647 A CN 2008101816647A CN 200810181664 A CN200810181664 A CN 200810181664A CN 101451086 B CN101451086 B CN 101451086B
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distribution
lofi
side chain
lubricant compositions
mole
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CN101451086A (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

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 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 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 oil base stock used in lubricant than in the past much important.Due to 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 of formation and this distribution divides (upper portion of the distribution) mainly by C 16, C 18Or it constitutes; (3) higher part of this distribution divide total % by mole must less than this distribution than total % by mole of lower part; (4) C on side chain 12Amount be necessary at least 40 % by mole of total side chain distribution.
Detailed Description Of The Invention
Unless indicate separately, in this specification sheets and claim, all numerical value that are expressed as component, reaction conditions, size, physical property, machined parameters etc. used are interpreted as all using in all cases term " approximately " to modify.Correspondingly, unless make opposite indication, numerical value listed in following specification sheets and 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 reporting 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 contained any and all subranges wherein.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 namely begin with minimum value 1 or larger value and finish with maximum value 10 or less 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 to incorporate in full.
Following term used herein defines in the following manner.
Term " polymer " " comprise multipolymer, only be limited to unless otherwise noted the polymkeric substance that the polymerization by single monomer produces, and comprise branching and simple linear polymer.
Term " multipolymer " refers to the polymkeric substance by the polyreaction generation of two kinds of chemically different monomers.With reference to the ethylene-alpha-olefin multipolymer, it being understood that this analog copolymer can choose the non-conjugated polyene that contains minor amount (for example, greater than 0 but less than 10 % by weight) wantonly, 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 " refers to the average carbon number by the molar fraction weighting.
The mode that term " lubricating oil flow improving agent " (LOFI) comprises 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) is improved all additives of size, quantity and the growth of wax crystalls in lubricating oil (or being abbreviated as lube).Most of lubricating oil flow improving agent is polymkeric substance or multipolymer, or contains polymkeric substance or multipolymer.These polymkeric substance are side chain, skeleton or its mixture normally.
The refining fluid that term " base oil " refers to not contain additive and is used as the component in the lubricant adulterant.
Term " oil base stock " refers to adulterant, mixture or the analogue of base oil.
Mention in this article each " class " oil base stock, for example API III class oil base stock.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 " refers to have the carbon chain lengths frequency distribution at two different peaks (or mode), and each peak is that molar percentage is higher than a certain carbon chain lengths (or the several adjacent carbons chain lengths with regard to continuous even number carbon number) of adjacent carbons chain length.This bimodal carbon chain length frequency distribution has " distribution than lower part " and " higher part of distribution is divided ".
Term " distribution than lower part " refers to the part that the mode by having than low carbon chain length and the lower adjacent carbons chain length (with regard to continuous even number carbon number) of molar percentage in bimodal distribution consists of.The high carbon chain length than in lower part that distributes is C 14
Term " higher part of distribution is divided " refers to the part that the mode by having the lower adjacent carbons chain length of higher carbon chain length and molar percentage in bimodal distribution consists of.Minimum carbon chain lengths during the higher part that distributes is divided is C 16
Term " mainly " refers to that the amount of a kind of component of existing in composition, 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 the Visom board oil base stock of ExxonMobil (Fawley, 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 the Nexbase board oil base stock of Neste (Porvoo, Finland).
In a non-limiting embodiments of the present invention, use gas to become liquid (" GTL ") legal system and make oil base stock.GTL is 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 together 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 lower than the non-conjugated diene of about 10 % by 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 consists of, this polymkeric substance is characterised in that the following combination of parameter: (a) the average ethylene content of 60 to 80 % by mole, wherein said polymkeric substance contain no more than 1.3 % by 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 be in molecule inhomogeneous and intermolecular uniformly, and at least 10% at least a multipolymer segment that consists of 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 included together with the non-crystalline state viscosity modifier.The example is to comprise ethene and the C with 50-95 % by mole of ethylene content 3To C 18The first multipolymer of alpha-olefin and ethene and C with 5-80 % by mole of ethylene content 3To C 18The oil-soluble polymers composition of the second multipolymer of high alpha-olefin more, wherein the ethylene content of the first multipolymer is than at least 5 % by mole greatly of the ethylene content of the second polymkeric substance.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 number-average molecular weight that records by gel permeation chromatography of hypocrystalline viscosity modifier is 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 lubricant compositions with the amount of 0.05 to 5 % by 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 consists of, 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 of formation and this distribution divides (distribution that namely has higher carbon number mode) mainly by C 16, C 18Or it constitutes;
(3) higher part of this distribution divide total % by mole must less than this distribution than total % by mole of lower part; With
(4) C on side chain 12Amount be necessary at least 40 % by mole of total side chain distribution, for example at least 50 % by mole or at least 60 % by mole.
In the basal component of bimodal distribution by (a) C 12And C 16Or (b) C 12, C 16And C 18A non-limiting embodiments consisting of of mixture in, C 14Amount must be less than 20 % by mole of total side chain distribution, for example less than 10 % by mole.
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.The average carbon number that this dialkyl fumarate-vinyl-acetic ester multipolymer can be 8 to 18 alcohol by carbon number is 12.4 to 14.4, and for example 12.8 to 14.0 or 13.0 to 13.8 mixture forms.This multipolymer is to have the methylene radical segment as the side chain multipolymer of side chain.
These LOFI can contain the ester side group of the mixture that is derived from alcohol, pure residue can be take the MU (methylene unit) that repeats as feature thus, and it is oil soluble or dispersed polymeric composition, usually have 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 is substantially consisted of by alkyl methacrylate (a1) and one or more monomers (a2) 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 consists of the alkyl methacrylate (a1) of multipolymer (A) can be 30 to 99.99 % by weight of multipolymer (A) weight usually.
alkyl methacrylate (a1) can comprise methacrylic ester with the linear alkyl that contains 1 to 18 carbon atom (methyl methacrylate for example usually, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, 2-Ethylhexyl Methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid tridecyl ester, methacrylic acid tetradecyl ester, methacrylic acid pentadecyl ester, the methacrylic acid cetyl ester, the methacrylic acid stearyl).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 consists of the monomer (a2) of multipolymer (A) can be 0.01 to 10 % by weight of multipolymer (A) weight, preferred 0.1 to 5 % by 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 lubricant compositions and one or more other components except 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 % by weight, and for example the amount of 0.05 to 0.5 % by weight is present in 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 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 under alkylating phenol or alkylphenol thioesters exist, also preferably under carbonic acid gas exists.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 % by weight reacts at 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 trend that mineral oil in use goes bad, 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, such as 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 for giving lubricating oil composition, rubbing characteristics as suitable in 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 as U.S. Patent No. 4,344, the alkyl replacement succsinic acid described in 853 or succinate or its metal-salt of 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 by produce soluble of oxidation or the compound that substantially is insoluble in oil and keeps being suspended in fluid, prevents thus sludge flocculation and precipitation or is deposited on 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 the 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 as 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, naphthenic 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 by dispersing or dissolving during additive directly adds oil base stock to the desired concn level at 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, etc.
Prepare 5 kinds of dialkyl fumarate monomers (dialkyl fumarate monomer 1-5) by the adulterant that at first uses the alcohol that the carbon atom have as shown in Table I distributes, prepare 5 kinds of LOFI (LOFI 1-5).Use the alcohol 1 preparation dialkyl fumarate monomer 1 in Table I, use the pure II in 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 Add in the round-bottomed flask of being furnished with Dean and Stark apparatus.This slurry is stirred under nitrogen gas stream and slowly be heated to 220 ℃.By measuring the amount of the water of collecting in 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 thus dialkyl fumarate monomer 1-5.
Then prepare dialkyl fumarate-vinyl-acetic ester multipolymer by (forming) dialkyl fumarate monomer prepare LOFI in above-mentioned steps by as described below.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.150 gram dialkyl fumarate monomers (dialkyl fumarate monomer 1-5) are added to
Figure G2008101816647D0010102602QIETU
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 to contain the dialkyl fumarate monomer
Figure G2008101816647D0010102616QIETU
In reactor.This mixture was stirred 15 minutes before being heated to 100 ℃ of temperature of reaction.0.26 gram is crossed the sad tert-butyl ester be dissolved in that 2.0 gram Sonneborn make
Figure G2008101816647D0010102629QIETU
In paraffin oil, then inject this mixture.This mixture is stirred 5 to 8 hours to complete polyreaction.Then this multipolymer is poured into round-bottomed flask and remove volatile matter at rotatory evaporator from reactor.Form thus dialkyl fumarate vinyl-acetic ester copolymer 1-5.
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 SAE 5W-30 lubricant compositions of embodiment 1-5.
In lower Table I, provide the composition information about the LOFI side chain of embodiment 1-5.
Table I. the distribution of carbon atom in 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 lower Table II.For the various illustrative lubricant composition of making in the above described manner (embodiment 1-5), if LOFI meets the requirements, occur in the hurdle " √ ", if LOFI is undesirable, occur in the hurdle " * ".
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 of formation and this distribution is divided mainly by C 16、C 18Or it constitutes √ √ √ × ×
(3) higher part of this distribution summation of dividing 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 consisting of, C 14Amount must be lower than 20% or lower than 10%, and must be lower than C 16And C 18Summation √ √ √ * *
(4) C 12Amount be necessary at least 40 % by mole or at least 50 % by mole of total side chain distribution √ √ √ √ *
Can find out, 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 lubricant compositions does not meet whole requirements and outside scope of the present invention.
Carry out the test of MRV pump-conveying property according to the lubricant compositions of 4684 couples of embodiment 1-5 of ASTM D.Test-results is presented in 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 the viscosity that is equal to or less than 60,000mPa.s and less than the yielding stress of 35Pa.Under 0.50% processing rate, only has embodiment 1 and 3 by the test of MRV pump-conveying property.Under 0.20% processing rate, only has 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. a preparation is by the method for satisfying of forming of III class oil base stock according to the lubricant compositions of the requirement of the MRV pump-conveying property test of ASTM D4684, and it comprises the following at least component of mixing:
(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 of formation and this distribution is divided mainly by C 16, C 18Or it constitutes;
(3) higher part of this distribution divide total % by mole must less than this distribution than total % by mole of lower part; With
(4) C on side chain 12Amount be necessary at least 40 % by mole of total side chain distribution, wherein said lubricant compositions shows the viscosity that is equal to or less than 60,000mPa.s and less than the yielding stress of 35Pa when carrying out the test of MRV pump-conveying property according to ASTM D4684.
2. according to claim 1 method, wherein the hypocrystalline viscosity modifier comprises the non-crystalline state viscosity modifier.
3. according to claim 1 method, wherein LOFI is dialkyl fumarate-vinyl-acetic ester multipolymer.
4. according to claim 1 method, wherein to contain average carbon number be 12.8 to 14.0 C in this distribution 8To C 18Side chain.
5. according to claim 1 method, 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 claim 1 method, wherein the hypocrystalline viscosity modifier comprises the ethylene-alpha-olefin multipolymer that contains one or more a small amount of non-conjugated dienes.
7. according to claim 1 method, wherein LOFI comprises poly-(alkyl methacrylate) polymkeric substance.
8. according to claim 1 method, wherein LOFI comprises poly-(alkyl acrylate) polymkeric substance.
9. according to claim 1 method, wherein LOFI comprises poly-(styrene-maleic acid dialkyl).
10. according to claim 1 method, wherein LOFI has 0.3 to 1.0 specific viscosity.
11. method according to claim 1, wherein LOFI exists based on the amount of lubricant compositions gross weight with 0.005 % by weight to 1.0 % by weight.
12. method according to claim 1 further comprises and mixes one or more following components: inhibiter, oxidation retarder, friction improver, dispersion agent.
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