CN103649282A - Estolide derivatives useful as biolubricants - Google Patents

Estolide derivatives useful as biolubricants Download PDF

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CN103649282A
CN103649282A CN201280032090.1A CN201280032090A CN103649282A CN 103649282 A CN103649282 A CN 103649282A CN 201280032090 A CN201280032090 A CN 201280032090A CN 103649282 A CN103649282 A CN 103649282A
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acid
ester
mixture
product
alcohol
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D·芬奇
J·科尔斯布尔克
M·R·格瑞维斯
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Dow Global Technologies LLC
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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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/08—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with fatty acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/14—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material
    • 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
    • C10N2020/013—Iodine value
    • 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
    • C10N2020/065—Saturated Compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/081—Biodegradable compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/64—Environmental friendly compositions
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Abstract

A composition comprising a mixture of esters prepared by a three-step process comprising the steps of a oligomerization, a transesterification, and a capping, The composition is useful in a variety of applications, including as a biolubricant having a high level of renewable carbons, and may exhibit particularly desirable properties relating to pour point, thermo-oxidative stability, and viscometric behavior due to reduced or eliminated levels of unsaturation in the final double esters.

Description

Can be used as the anhydride ester derivs of biological lubricants
the cross reference of related application
The application requires the right of priority of the provisional application that the sequence number of submission on June 28th, 2011 is 61/501,802, and described application is incorporated to herein by reference with its full content.
Invention field
The present invention relates to biological lubricants composition.More particularly, the present invention relates to acid anhydrides (estolide) derivative of lipid acid, it has high-caliber renewable starting material and can be used as lubricant.
Background technology
At present, biodegradable material is being searched in lubricant (engine and non-engine with) and process fluid industry.Biodegradable refers to that lubricant and process fluid (being called for short below " fluid ") degrade within for some time, it can be measured by testing, the test of for example (OECD) being promulgated by the Organization for Economic Cooperation and Development (Organization of Economic Co-Operation and Development), comprises OECD301B and OECD301F.Recently, for not only interest biodegradable but also reproducible fluid is more and more higher.According to definition, renewable product comprises high-caliber renewable carbon, and is setting up standard to encourage day by day higher levels of recyclability.For example, European Union's eco-label (European Ecolabel) requires hydraulic fluid must contain at least 50% renewable carbon by weight now.
Researchist has attempted, by comprise various types of natural and synthetic oils in their fluid preparation, meeting requirement or suggestion aspect biodegradable and recyclability two.Unfortunately, many these bill of material reveal too high and can not use the pour point in some important application.Pour point is the minimum temperature that fluid can be mobile, and conventionally need to lower than 0 degree Celsius (℃), ideally lower than-10 ℃, better lower than-15 ℃, even lower than the pour point of-25 ℃.In many cases, these materials also have at high temperature (for example, over 90 ℃) bad shortcoming of thermo-oxidative stability, and this may be that the amount of the nonsaturation that exists in the acid moieties of their chemical structure causes in some cases.
In order to obtain these character, acid anhydrides is studied.Acid anhydrides is oligomeric fatty acids, and it can form to produce ester bond by the condensation of two or more fatty acid units.Conventionally, this condensation by reacting carboxylic acid integral part to realize through acid catalysis on two keys.
An example about the work of acid anhydrides is disclosed in the U.S. (US) patent 6,018,063(Isbell etc.) in, it relates to the ester of the acid anhydrides that stems from oleic acid.This patent discloses the synthetic of acid anhydrides, and it comprises oligomeric under heat or acid catalysis condition of Castor Oil Fatty Acid or 12-oxystearic acid.
Another example is United States Patent (USP) 6,407,272(Nelson etc.), it has been taught by alcohol ester is reacted under organo-metallic transesterification catalyst exists with secondary alcohol, prepares the secondary alcohol ester (for example ricinoleate of secondary alcohol) of alcohol acid.
Another example can (WO) find in 2008/040864 in Patent Cooperation Treaty open (Patent Cooperation Treaty Publication), and it relates to the synthetic method of the acid anhydride ester with specific oligomeric level and low residue acid number.Described method comprises that saturated hydroxy acid is carried out to low coalescence carries out esterification by monohydroxy-alcohol to alcohol acid simultaneously.
Yet, aforesaid method all show to produce and there is low pour point (in or lower than-10 ℃), the complete saturated material of the desirable combination of thermo-oxidative stability and renewable carbon (by weight at least 50%).Therefore, in the art, for meeting these, require and show simultaneously other required or appointment oilness and viscometric properties, to can be used in the novel composition of lubricant applications, exist demand.
Summary of the invention
In one embodiment, the invention provides the method for preparing the composition that comprises ester mixture, described method comprises following sequential steps: (1-a) that the mixture of at least two kinds of hydroxylation lipid acid or fatty acid ester is oligomeric, to form the mixture of hydroxylation lipid acid or fatty acid ester oligopolymer; (1-b) with hydroxylation lipid acid or fatty acid ester oligopolymer described in acid, acid anhydrides or ester end-blocking, to form the lipid acid of end-blocking or the mixture of fatty acid ester oligopolymer; (1-c) lipid acid of described end-blocking or fatty acid ester oligopolymer and alcohol are carried out to transesterify, to form the mixture of ester; Or following sequential steps: (2-a) mixture of hydroxylation lipid acid or fatty acid ester and alcohol are carried out to transesterify, to form the mixture of hydroxylation fatty acid ester; (2-b) oligomeric described hydroxylation fatty acid ester, to form the mixture of hydroxylation fatty acid ester oligopolymer; (2-c) with hydroxylation fatty acid ester oligopolymer described in acid, acid anhydrides or ester end-blocking, to form the mixture of described ester.By this any composition of preparing of two kinds of methods, represent another embodiment of the invention.
In another embodiment, the invention provides the method for the preparation of the composition that comprises ester mixture, described method comprises (1-a) to (1-c) or (2-a) to the sequential steps of (2-c), described sequential steps is: (1-a) use stanniferous, titaniferous or nitrogenous catalyzer that the mixture of at least two kinds of hydroxylation lipid acid or fatty acid ester is oligomeric, and remove the alcohol of formation, optionally, by using one or more means in entrainer, decompression and nitrogen jet, to obtain, there is the product 1-X being distributed by the represented compound of formula 1:
Figure BDA0000448182590000031
Wherein R is the alkyl that contains 1 to 12 carbon atom, R 1be hydrogen or methyl, x is 0 to 12 rational number, and n is 1 to 20 rational number, and the alcohol of described formation has formula R 1oH; (1-a1) optional from remaining R 1in OH and if you are using described entrainer, reclaim product 1-X; (1-b) product 1-X and the acid that contains 2 to 12 carbon atoms, the ester that contains 3 to 13 carbon atoms or the acid anhydrides that contains 4 to 24 carbon atoms are reacted, optionally use stanniferous, titaniferous or the nitrogenous catalyzer of additional quantity, and remove the alcohol of formation, to obtain, there is the product 1-Y being distributed by the represented compound of formula 2:
Wherein R, R 1, x and n as defined above, and R 3it is the alkyl that contains 1 to 11 carbon atom; (1-b1) in excess acid, acid anhydrides or the ester optionally adding as reactant, reclaim product 1-Y from step (1-b); And (1-c) product 1-Y is reacted with alcohol, to form, there is the product 1-Z being distributed by the represented compound of formula 3:
Figure BDA0000448182590000033
Figure BDA0000448182590000041
Wherein R, R 3, x and n as defined above, R 2it is the alkyl that contains 1 to 20 carbon atom; (1-c1) optionally from alcohol with the remaining R adding (1-c) 1in the acid forming between the reaction period of OH and the described acid, acid anhydrides or the ester that add at 1-Y and (1-b), reclaim product 1-Z; Or following sequential steps: (2-a) at least two kinds of hydroxylation lipid acid or fatty acid ester are reacted with alcohol, there is to form the product 2-X being distributed by the represented compound of formula 4:
Figure BDA0000448182590000042
Wherein R is the alkyl that contains 1 to 12 carbon atom, R 2be the alkyl that contains 1 to 20 carbon atom, x is 0 to 12 rational number; (2-a1) optionally from R remaining or that form 2in OH, reclaim product 2-X; (2-b) use stanniferous, titaniferous or nitrogenous catalyzer that product 2-X is oligomeric, and remove the R of described formation 2oH, optionally by using one or more means in entrainer, decompression and nitrogen jet, has to obtain the product 2-Y being distributed by the represented compound of formula 5:
Figure BDA0000448182590000043
Wherein R, R 2with x as defined above, and n is 1 to 20 rational number; (2-b1) optional from remaining R 2in OH and if you are using described entrainer, reclaim product 2-Y; And (2-c) product 2-Y and the acid that contains 2 to 12 carbon atoms, the ester that contains 3 to 13 carbon atoms or the acid anhydrides that contains 4 to 24 carbon atoms are reacted, optionally use stanniferous, titaniferous or the nitrogenous catalyzer of additional quantity, to obtain, there is the product 2-Z being distributed by the represented compound of formula 6:
Figure BDA0000448182590000044
Wherein R, R 2, R 3, x and n as defined above; (2-c1) optionally from (2-b), as excess acid, acid anhydrides or the ester of reactant interpolation and in the alcohol adding as reactant (2-c), reclaim product 2-Z.
In another embodiment, the invention provides the composition that comprises the compound distribution being represented by formula 3:
Figure BDA0000448182590000051
Wherein R is the alkyl that contains 1 to 12 carbon atom, R 2it is the alkyl that contains 1 to 20 carbon atom; R 3it is the alkyl that contains 1 to 11 carbon atom; X is that 0 to 12 rational number and n are 1 to 20 rational numbers, and at least two kinds of compounds during wherein said compound distributes have different x values.
Embodiment
The invention provides the modification method of some anhydride ester derivs of preparation, described anhydride ester derivs shows useful friction and wear character, desirable low pour point, good thermo-oxidative stability, and be based on renewable resources, therefore described material can be classified as bio-based materials.
The preparation of anhydride ester derivs can be started by the mixture of hydroxylation lipid acid or fatty acid ester to carry out.Unexpected discovery, the method according to this invention, from such mixture, can preparation table reveals favourable character, comprises the anhydride ester derivs of low-down pour point.Therefore, described anhydride ester derivs goes for the application of broad range, comprises those application that require the performance at low-down temperature.
In some embodiments, the mixture of initial hydroxylation lipid acid or fatty acid ester comprises two or more hydroxylation C 1-C 24lipid acid, or two or more hydroxylation C 1-C 20lipid acid (or their ester).In some embodiments, described mixture comprises short-chain hydroxyl lipid acid, for example hydroxylation C 1-C 4-COOH(or its ester) and long-chain hydroxylation lipid acid, for example hydroxylation C 12-C 20-COOH(or its ester).In a preferred embodiment, the mixture of hydroxylation lipid acid or fatty acid ester can be 12-hydroxy fatty acid, for example 12-oxystearic acid easily, or its methyl esters, and lactic acid.
In general, synthetic can be oligomeric by comprising, three one step process of transesterify and end-blocking, but find surprisingly, variation on the order of these steps, although finally still cause forming the dibasic acid esters of initial hydroxylation material, the gross properties of the dibasic acid esters that the general mixture as end product of impact obtains.
In embodiments of the present invention, the order of described three steps is oligomeric, end-blocking and transesterify.In more detail, the mixture of described hydroxylation lipid acid or fatty acid ester is first oligomeric, forms the mixture of hydroxylation lipid acid or fatty acid ester oligopolymer.This oligomericly carry out under the catalyzer of stanniferous, titanium or nitrogen exists ideally, and remove the water/alcohol of any formation simultaneously.Removing of water/alcohol can utilize the mode of entrainer, decompression and/or nitrogen jet to realize.The result of this step is the mixture of hydroxylation lipid acid or fatty acid ester oligopolymer, and it compound that comprises formula 1 as hereinbefore defined distributes.
Then from excessive alcohol, residual methanol and/or entrainer, reclaim the mixture of described hydroxylation lipid acid or fatty acid ester oligopolymer, then by the acid with containing 2 to 12 carbon atoms, the ester that contains 3 to 13 carbon atoms or the anhydride reaction that contains 4 to 24 carbon atoms, carry out end-blocking, to form the lipid acid of end-blocking or the mixture of fatty acid ester oligopolymer.For this end-blocking, can optionally use the catalyzer of additional stanniferous, titanium or nitrogen.The distribution of the lipid acid of end-blocking or fatty acid ester oligomer product can be represented by the formula 2 above defining.Can from excessive acid, acid anhydrides or ester, reclaim the material of end-blocking.
Finally, in step of transesterification, the mixture of the lipid acid of end-blocking or fatty acid ester oligopolymer is reacted with the alcohol with 2 to 20 carbon atoms.In some ideal and non-limiting embodiment, described alcohol can be selected from 2-Ethylhexyl Alcohol, 2-(2-butoxy-propoxy-) propane-1-alcohol (DPnB), 1-octanol, sec-n-octyl alcohol and combination thereof.Now can use the catalyzer of additional stanniferous, titanium or nitrogen, and remove the methyl alcohol of formation, produce and there are defined formula 3 represents the compound represented two acid anhydride esters that distribute above.
In yet another embodiment of the present invention, first the composition that comprises ester mixture can be by wherein carrying out step of transesterification, then carries out oligomericly, is finally prepared by the method for termination procedure.In this embodiment, (2-a) first the mixture of hydroxylation lipid acid or fatty acid ester is carried out to transesterify to form the product 2-X having by the represented compound of defined formula 4 distributes above by reacting with alcohol; (2-a1) optionally from alcohol excess, reclaim product 2-X; (2-b) use stanniferous, titaniferous or nitrogenous catalyzer to carry out part to product 2-X oligomeric, and remove the alcohol of formation, optionally use one or more means in entrainer, decompression and nitrogen jet, to obtain, there is above the product 2-Y that the represented compound of formula 5 of definition distributes; (2-b1) optional from remaining R 2in OH and if you are using entrainer, reclaim product 2-Y; (2-c) product 2-Y and the acid that contains 2 to 12 carbon atoms, the ester that contains 3 to 13 carbon atoms or the acid anhydrides that contains 4 to 24 carbon atoms are reacted, optionally use stanniferous, titaniferous or the nitrogenous catalyzer of additional quantity, to obtain, there is the product 2-Z that the represented compound of formula 6 of above definition distributes; (2-c1) optionally from (2-b), as excess acid, acid anhydrides or the ester of reactant interpolation and in the alcohol adding as reactant (2-c), reclaim product 2-Z.
In aforesaid method, in some embodiments, described termination procedure can be carried out with the acid anhydrides of formula 7:
Figure BDA0000448182590000071
R wherein 3as above formula 2 is defined.Exemplary acid anhydrides comprises isobutyric anhydride.
In another embodiment, the invention provides the composition that comprises the compound distribution being represented by formula 3:
Figure BDA0000448182590000072
Wherein R is the alkyl that contains 1 to 12 carbon atom, R 2it is the alkyl that contains 1 to 20 carbon atom; R 3it is the alkyl that contains 1 to 11 carbon atom; X is that 0 to 12 rational number and n are 1 to 20 rational numbers, and at least two kinds of compounds during wherein said compound distributes have different x values.
During the formula 1,2,3,4,5 of describing in the above and 6 compounds distribute, x is 0 to 12 rational number.In some embodiments, x is 2.5 to 10 rational number.Because formula 1,2,3,4,5 and the distribution of 6 compounds are what to prepare from the mixture of hydroxylation lipid acid or fatty acid ester, at least two kinds of compounds in described distribution have different x values.
Those of ordinary skills can be according to the starting acid using or ester and their amount, easily calculate the x value of described compound in distributing, or they can utilize known analytical method, and for example saponification and LC-MS determine described value.
In some preferred implementations, the R during above-described formula 1 and 2 compound distribute 1it is methyl.
In some embodiments, formula 1,2,3,4,5 and 6 the compound R in distributing is C 1-C 6alkyl.In some embodiments, it is methyl or hexyl.
In some embodiments, the n in formula 1,2,3,5 and 6 is the mark between 1 and 20.
In some embodiments, the mixed ester of preparing by method of the present invention is new composition, and may show their useful and/or desirable many character concerning various application of sening as an envoy to.These application can include but not limited to the softening agent for resin, hydraulic transmission fluid, heat-transfer fluid, thickening material, solvent and tensio-active agent.In addition, these compositions also may, for urethane, comprise the production of foam, elastomerics, coating and tackiness agent.
Described ester composition can show and comprise following at least one character: less than or equal to-10 ℃ or-15 ℃ or lower or-20 ℃ or lower pour point (measuring according to ASTM D97); Be more than or equal to 130 viscosity index; Kinematic viscosity in the time of 40 ℃ is 25 centistokes(cst)s (cSt) or larger (0.000025 square metre of (m per second 2/ second)) (according to ASTM D445, measuring); Be less than every gram, 1 milligram of potassium hydroxide (mg KOH/g) and in specific implementations, be less than the total acid value of 0.5mg KOH/g; And show the completely saturated 3%(wt% by weight that is less than) iodine number.In specific implementations, described dibasic acid esters can have the pour point lower than-30 ℃, and the kinematic viscosity at 40 ℃ is 29cSt(0.000029m at least 2/ second), be preferably greater than 45cSt(0.000045m 2/ second) kinematic viscosity.They also can have and are less than or equal to 10, are preferably less than 8, are more preferably less than 5, are more preferably less than 4, are more preferably less than 3 hydroxyl value; And show the completely saturated 3%(wt% by weight that is less than) iodine number.They also can show the thermo-oxidative stability (measuring according to ASTM D2893) of desired level and renewable carbon (by weight at least 50%, according to ASTM D6866-08 measurement).
Carry out institute's described method with the end-blocking acid anhydride ester for the preparation of the present composition in, those skilled in the art should be able to easily find out applicable reaction scheme and condition.Yet, can notice, for oligomeric (being called as alternatively condensation) of hydroxy fatty acid or ester cpds, and also for the temperature of the component distillation of the methyl alcohol that forms between the reaction period, be desirably 70 ℃ to 220 ℃, better be 120 ℃ to 210 ℃, better be 180 ℃ to 200 ℃.
For the temperature of transesterification reaction can be at 70 ℃ to 220 ℃ and in some specific implementations, be 120 ℃ to 210 ℃, be more particularly at the temperature of 180 ℃ to 200 ℃ and realize.Ideally, branched-chain alcoho be take is enough to provide the amount of the alcohol of at least 1 molar equivalent to exist as the oligomer ester of every molar equivalent or hydroxy fatty acid or fatty acid ester (depending on embodiment).
The end-blocking of acid anhydride ester ideally 80 ℃ to 160 ℃, more preferably at the temperature of 100 ℃ to 140 ℃, better 110 ℃ to 130 ℃, carry out.
Optional step (1-a1), the residual methanol forming during step (1-a) and reclaim product 1-X entrainer if you are using, can for example realize with the component distillation of entrainer by conventional procedure, described entrainer preferably use there are 7 to 10 carbon atoms, the aliphatic cpd of 9 carbon atoms most preferably.Carrying secretly or removing of remaining methyl alcohol and entrainer, preferably for example, is undertaken by distillation under decompression (4 kPas (kPa)).Temperature preferably 100 ℃ to 200 ℃, more preferably 120 ℃ to 190 ℃, more preferably in the scope of 150 ℃ to 180 ℃.
Optional step (1-b1) reclaims product 1-Y from the alcohol of excessive step (1-b) and the residual methanol from step (1-a), can by conventional procedure for example fractional distillation realize.Step (1-b1) is for example preferably included in, under decompression (4 kPas (kPa)) distills to carry out the recovery of product 1-Y.Temperature preferably 70 ℃ to 350 ℃, more preferably 120 ℃ to 250 ℃, more preferably in the scope of 150 ℃ to 180 ℃.
Optional step (1-c1), in excess acid, acid anhydrides or the ester adding as reactant and the acid that forms between the reaction period of product 1-Y and described acid, acid anhydrides or ester, reclaim product 1-Z from step (1-b), preferably include following one or more: (1) is used decompression to remove volatile matter, and (2) are with alkali, for example sodium bicarbonate (NaHCO 3) solution washing one or many, (3) are used sorptive material for example Magnesium Silicate q-agent, gac and magnesium sulfate (MgSO 4), and filter (4).
Unless otherwise noted or apparent, the numerical range of using has in this manual comprised the numerical value that defines described scope.Unless otherwise, otherwise ratio, percentage, umber etc. by weight.
The present invention will be described for the following examples, but do not limit its scope.
Embodiment
embodiment 1
Step 1: the glass reactor that is equipped with temperature regulator, overhead type stirrer and Dean-Stark device loads 12-hydroxyl-stearic acid (450.4 grams (g)), lactic acid (37.1g), 2-Ethylhexyl Alcohol (487.8g) and 2 ethyl hexanoic acid tin (II) (1.9g).Then described mixture is heated to 190 ℃ and reaches 6 hours, is removed and is anhydrated simultaneously by fractionation.Excessive 2-Ethylhexyl Alcohol is removed by underpressure distillation at 160 ℃, then described reactor cooling to 120 ℃.
Step 2: the product (584.7g) to step 1 adds 2 ethyl hexanoic acid tin (II) (1.2g).Under agitation heat described mixture and reach three hours to 200 ℃ of set point temperatures.By underpressure distillation (20 millibars), from reactor content, remove excessive 2-Ethylhexyl Alcohol, then by reactor cooling to 120 ℃.
Step 3: the product (466.2g) to step 2 adds isobutyric anhydride (120.4g).At this temperature, stirred reactor is 2 hours.The acid forming during excessive acid anhydrides and end-blocking is removed in decompression.Then temperature is brought up to 160 ℃, and kept this decompression two hours.Then reactor content is cooled to the set point temperatures of 70 ℃, and under agitation to described reactor, adds NaHCO 3the aqueous solution (100ml, 1M).After stirring 1 hour, decompression is except anhydrating.To reactor, add Magnesium Silicate q-agent (1%w/w), activated carbon (1%w/w) and MgSO 4(1%w/w), then utilize material described in the filter paper filtering scribble 8% Magnesium Silicate q-agent, to obtain final product, it is light yellow liquid.
embodiment 2
Step 1: the glass reactor that is equipped with temperature regulator, overhead type stirrer and Dean-Stark device loads 12-hydroxyl-stearic acid (407.0g), lactic acid (67.6g), 2-Ethylhexyl Alcohol (520.2g) and 2 ethyl hexanoic acid tin (II) (2.0g).Described mixture is heated to the set point temperatures of 190 ℃, and keeps stirring 6 hours, by fractionation, is removed and is anhydrated.Excessive 2-Ethylhexyl Alcohol is removed by underpressure distillation at 160 ℃, then described reactor cooling to 120 ℃.
Step 2: add 2 ethyl hexanoic acid tin (II) (1.3g) to step 1 product (565.8g), and described mixture is under agitation heated to the set point temperatures of 200 ℃ reaches three hours.By underpressure distillation (20 millibars), from reactor content, remove the 2-Ethylhexyl Alcohol forming between the reaction period, then by reactor cooling to 120 ℃.
Step 3: the product (445.0g) to step 2 adds isobutyric anhydride (144.3g).At this temperature, stirred reactor is 2 hours.The acid forming during excessive acid anhydrides and end-blocking is removed in decompression.Then temperature is brought up to 160 ℃, and kept decompression two hours.Then reactor content is cooled to the set point temperatures of 70 ℃, and under agitation to described reactor, adds NaHCO 3the aqueous solution (100ml, 1M).After stirring 1 hour, decompression is except anhydrating.To reactor, add Magnesium Silicate q-agent (1%w/w), activated carbon (1%w/w) and MgSO 4(1%w/w), then utilize material described in the filter paper filtering scribble 8% Magnesium Silicate q-agent, to obtain final product, it is light yellow liquid.
embodiment 3(comparison)
Step 1: the glass reactor that is equipped with temperature regulator, overhead type stirrer and Dean-Stark device loads 12-hydroxyl-methyl stearate (5296.2 grams (g)), nonane fraction (793.4g) and 2 ethyl hexanoic acid tin (II) (15.9g).Then described mixture is heated to 190 ℃ and reaches 20 hours, removes methyl alcohol with nonane component distillation.At 160 ℃, remaining nonane fraction is distilled in decompression (20 millibars (mbar), 2 kPas (kPa)), then by reactor cooling to 120 ℃.
Step 2: the product (463.29g) to step 1 adds isobutyric anhydride (93.49g).At this temperature, stirred reactor is 2 hours.The acid forming during excessive acid anhydrides and end-blocking is removed in decompression.Then temperature is brought up to 160 ℃, and kept decompression two hours, then reactor content is cooled to the set point temperatures of 70 ℃, and under agitation to described reactor, add NaHCO 3the aqueous solution (100 milliliters (ml), 1 mole (M)).After stirring 1 hour, decompression is except anhydrating.To reactor, add Magnesium Silicate q-agent (1 % by weight (%w/w)), activated carbon (1%w/w) and MgSO 4(1%w/w), then utilize and scribble percent 8(%) material described in the filter paper filtering of Magnesium Silicate q-agent, to obtain final product.
Step 3: Vigreux distillation column is placed between reactor and Dean-Stark device, then to the product (357.2g) of step 2, add 2-Ethylhexyl Alcohol (77.72g) and 2 ethyl hexanoic acid tin (II) (0.02g), and described mixture is heated to 190 ℃ reaches 6 hours, by fractionation, remove methyl alcohol.Excessive 2-Ethylhexyl Alcohol is removed by underpressure distillation at 160 ℃, then described reactor cooling to 20 ℃.The product generating is light yellow liquid.
Embodiment 4(comparison)
Step 1: the glass reactor that is placed on the outfit Vigreux distillation column between reactor and Dean-Stark device loads 12-hydroxyl-methyl stearate (2921.8g), 2-Ethylhexyl Alcohol (2363.2g) and 2 ethyl hexanoic acid tin (II) (18.7g).Described mixture is heated to the set point temperatures of 190 ℃, and keeps stirring for some time, by fractionation, removes methyl alcohol.Excessive 2-Ethylhexyl Alcohol is removed by underpressure distillation at 160 ℃, then described reactor cooling to 120 ℃.
Step 2: then remove Vigreux post and add 2 ethyl hexanoic acid tin (II) (6.0g) to step 1 product (900.0g) from described reactor, and described mixture is under agitation heated to 200 ℃ of set point temperatures time of three hours.By underpressure distillation (20 millibars), from reactor content, remove excessive 2-Ethylhexyl Alcohol, then by reactor cooling to 120 ℃.
Step 3: the product (754.02g) to step 2 adds isobutyric anhydride (188.05g).At this temperature, stirred reactor is 2 hours.The acid forming during excessive acid anhydrides and end-blocking is removed in decompression.Then temperature is brought up to 160 ℃, and kept decompression two hours.Then reactor content is cooled to the set point temperatures of 70 ℃, and under agitation to described reactor, adds NaHCO 3the aqueous solution (100ml, 1M).After stirring 1 hour, decompression is except anhydrating.To reactor, add Magnesium Silicate q-agent (1%w/w), activated carbon (1%w/w) and MgSO 4(1%w/w), then utilize material described in the filter paper filtering scribble 8% Magnesium Silicate q-agent, to obtain final product, it is light yellow liquid.
The physical properties of the product of test implementation example 1 and embodiment 2 and comparative example 3 and 4, result is presented in table 1.
Table 1
1pPM
2grams per liter
As can be seen from Table 1, the composition of preparing from fatty acid or ester mixture of the present invention (embodiment 1 and 2) shows obviously more favourable pour point than the composition (comparative example 3 and 4) of preparing from single fat acid or ester.

Claims (7)

1. for the preparation of the method for the composition that comprises ester mixture, described method comprises
Following sequential steps:
(1-a) mixture of at least two kinds of hydroxylation lipid acid or fatty acid ester is oligomeric at least partly, to form the mixture of hydroxylation lipid acid or fatty acid ester oligopolymer;
(1-b) mixture of hydroxylation lipid acid or fatty acid ester oligopolymer described in use acid, acid anhydrides or ester end-blocking, to form the lipid acid of end-blocking or the mixture of fatty acid ester oligopolymer; With
(1-c) lipid acid of described end-blocking or fatty acid ester oligopolymer and alcohol are carried out to transesterify, to form the mixture of ester;
Or
Following sequential steps:
(2-a) mixture of at least two kinds of hydroxylation lipid acid or fatty acid ester and alcohol are carried out to transesterify, to form the mixture of hydroxylation fatty acid ester;
(2-b) oligomeric described hydroxylation fatty acid ester, to form the mixture of hydroxylation fatty acid ester oligopolymer; With
(2-c) with hydroxylation fatty acid ester oligopolymer described in acid, acid anhydrides or ester end-blocking, to form the mixture of described ester.
2. the process of claim 1 wherein
Step (1-a) also comprises utilizes stanniferous, titaniferous or nitrogenous catalyzer, and forms the alcohol as secondary product, and removes formed alcohol;
Step (1-b) also comprises utilizes acid, the ester that contains 3 to 13 carbon atoms that contains 2 to 12 carbon atoms or the acid anhydrides that contains 4 to 24 carbon atoms, and utilize stanniferous, titaniferous or nitrogenous catalyzer, and reclaim the lipid acid of end-blocking or the mixture of fatty acid ester oligopolymer in the excessive described acid, described acid anhydrides or the described ester that optionally add from step (1-b);
Step (1-c) also comprises utilizes stanniferous, titaniferous or nitrogenous catalyzer;
Step (2-a) also comprises the mixture that utilizes stanniferous, titaniferous or nitrogenous catalyzer and optionally reclaim hydroxylation fatty acid ester from alcohol remaining or that form;
Step (2-b) also comprises utilizes stanniferous, titaniferous or nitrogenous catalyzer, and removes formed alcohol, optionally by utilizing one or more of entrainer, decompression and nitrogen jet; With
Step (2-c) also optionally comprises from step (2-b) in the alcohol adding as reactant in excessive described acid, acid anhydrides or the ester that add as reactant and step (2-c) and reclaims described ester mixture.
3. the method for the composition that preparation comprises ester mixture, described method comprises (1-a) to (1-c) or (2-a) to the sequential steps of (2-c), the step of described order is:
(1-a) utilize stanniferous, titaniferous or nitrogenous catalyzer that the mixture of at least two kinds of hydroxylation lipid acid or fatty acid ester is oligomeric, and remove the alcohol of formation, optionally by using one or more of entrainer, decompression and nitrogen jet, to produce product 1-X, its compound distributes and is represented by formula 1:
Figure FDA0000448182580000021
Wherein R is the alkyl that contains 1 to 12 carbon atom, R 1be hydrogen or methyl, x is that 0 to 12 rational number and n are 1 to 20 rational numbers, and formed alcohol has formula R 1oH;
(1-a1) optional from remaining R 1in OH and if you are using described entrainer, reclaim product 1-X;
(1-b) by product 1-X and the acid, the ester that contains 3 to 13 carbon atoms that contain 2 to 12 carbon atoms or the anhydride reaction that contains 4 to 24 carbon atoms, optionally use stanniferous, titaniferous or the nitrogenous catalyzer of additional quantity, and remove the alcohol of formation to produce product 1-Y, its compound distributes and is represented by formula 2:
Figure FDA0000448182580000022
Wherein R, R 1, x and n as above define, and R 3it is the alkyl that contains 1 to 11 carbon atom;
(1-b1) optionally from the excessive acid, acid anhydrides or the ester that add as reactant, reclaim product 1-Y step (1-b);
With
(1-c) product 1-Y is reacted with alcohol, form product 1-Z, its compound distributes and is represented by formula 3:
Wherein R, R 3, x and n as above define, R 2it is the alkyl that contains 1 to 20 carbon atom;
(1-c2) optional alcohol and the remaining R from adding during (1-c) 1in the acid that OH and 1-Y and the acid, acid anhydrides or the ester that add formed between the reaction period, reclaim product 1-Z in (1-b);
Or the step of described order is:
(2-a) mixture of at least two kinds of hydroxylation lipid acid or fatty acid ester is reacted with alcohol, form product 2-X, its compound distributes and is represented by formula 4:
Figure FDA0000448182580000032
Wherein R is the alkyl that contains 1 to 12 carbon atom, R 2be the alkyl that contains 1 to 20 carbon atom, x is 0 to 12 rational number;
(2-a1) optionally from R remaining or that form 2in OH, reclaim product 2-X;
(2-b) use stanniferous, titaniferous or nitrogenous catalyzer that product 2-X is oligomeric, and remove the R of formation 2oH, optionally, by use entrainer, decompression and nitrogen jet one or more, produces product 2-Y, and its compound distributes and represented by formula 5:
Figure FDA0000448182580000033
Wherein R, R 2with x as defined above, and n is 1 to 20 rational number;
(2-b1) optional from remaining R 2in OH and if you are using described entrainer, reclaim product 2-Y; With
(2-c) by product 2-Y and the acid, the ester that contains 3 to 13 carbon atoms that contain 2 to 12 carbon atoms or the anhydride reaction that contains 4 to 24 carbon atoms, optional stanniferous, titaniferous or the nitrogenous catalyzer that uses additional quantity, to produce product 2-Z, its compound distributes and is represented by formula 6:
Figure FDA0000448182580000041
Wherein R, R 2, R 3, X and n as defined above; With
(2-c1) optionally from (2-b), as excessive acid, acid anhydrides or the ester of reactant interpolation with in the alcohol adding as reactant (2-c), reclaim product 2-Y.
4. the composition that comprises ester mixture, prepared by its method by claim 1 or claim 3.
5. the composition of claim 4, it shows and comprises following at least one character: pour point is less than or equal to-10 ℃ (according to ASTM D97, measuring); Viscosity index is more than or equal to 150; The kinematic viscosity of 40 ℃ surpasses 15 centistokes(cst)s (cSt) (measuring according to ASTM D445); Total acid value is less than 1 milligram of potassium hydroxide/gram (mg KOH/g); Hydroxyl value is less than or equal to 10; Iodine number is less than 3 % by weight; Be at least 50 % by weight (measuring according to ASTM6866-08) with renewable carbon level.
6. the composition of claim 5, wherein said pour point is less than-15 ℃; The kinematic viscosity of 40 ℃ is greater than 20cSt; Total acid value is less than 0.5mg KOH/g; Be less than 5 with hydroxyl value.
7. the composition that comprises the compound distribution of formula 3 expressions:
Figure FDA0000448182580000042
Wherein R is the alkyl that contains 1 to 12 carbon atom, R 2it is the alkyl that contains 1 to 20 carbon atom; R 3it is the alkyl that contains 1 to 11 carbon atom; X is that 0 to 12 rational number and n are 1 to 20 rational numbers, and at least two kinds of compounds during wherein said compound distributes have different x values.
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