EP2694630A1 - Dérivés étholides utiles comme biolubrifiants - Google Patents

Dérivés étholides utiles comme biolubrifiants

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Publication number
EP2694630A1
EP2694630A1 EP12724265.9A EP12724265A EP2694630A1 EP 2694630 A1 EP2694630 A1 EP 2694630A1 EP 12724265 A EP12724265 A EP 12724265A EP 2694630 A1 EP2694630 A1 EP 2694630A1
Authority
EP
European Patent Office
Prior art keywords
acid
mixture
carbon atoms
product
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12724265.9A
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German (de)
English (en)
Inventor
Daniele Vinci
Jochem Kersbulck
Martin R. Greaves
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP2694630A1 publication Critical patent/EP2694630A1/fr
Withdrawn legal-status Critical Current

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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

Definitions

  • the invention relates to biolubricant compositions. More particularly, the invention relates to estolide derivatives of fatty acids that have a high level of renewable raw materials and are useful as lubricants.
  • the lubricants (engine and non-engine) and process fluids industries today are searching for materials that are biodegradable.
  • Biodegradability means that the lubricants and process fluids (hereinafter “fluids") degrade over a period of time, which may be measured by tests such as those promulgated by the Organization of Economic Co-Operation and Development (OECD), including OECD 301 B and OECD 301 F.
  • OECD Organization of Economic Co-Operation and Development
  • Renewable products contain, by definition, high levels of renewable carbons, and standards are being set to encourage increasingly greater levels of renewability.
  • the European Ecolabel now requires that hydraulic fluids must contain at least 50 percent by weight renewable carbons.
  • Estolides are oligomeric fatty acids which may be formed by condensation of two or more fatty acid units to yield an ester linkage. Typically this condensation is accomplished by reacting a carboxylic acid moiety onto a double bond via acid catalysis.
  • estolides An example of work on estolides is disclosed in United States (US) Patent 6,018,063 (Isbell, et al.), which relates to esters of estolides derived from oleic acids. This patent discloses a synthesis of estolides involving homopolymerization of castor oil fatty acids or 12-hydroxystearic acid under thermal or acid catalyzed conditions.
  • the invention provides a process for preparing a composition comprising a mixture of esters, the process comprising the ordered steps of: (1 -a) oligomerizing a mixture of at least two hydroxylated fatty acids or fatty esters to form a mixture of hydroxylated fatty acid or fatty ester oligomers; (1 -b) capping the hydroxylated fatty acid or fatty esters oligomers with an acid, acid anhydride or ester to form a mixture of capped fatty acid or fatty ester oligomers; and (1 -c) transesterifying the capped fatty acid or fatty esters oligomers with an alcohol to form the mixture of esters; or the ordered steps of (2-a) transesterifying a mixture of hydroxylated fatty acids or fatty esters with an alcohol to form a mixture of hydroxylated fatty esters; (2-b) oligomerizing the hydroxylated fatty esters to form a mixture of hydroxylated fatty este
  • the invention provides a process for preparing a composition comprising a mixture of esters, the process comprising either the ordered steps of (1 -a) through (1 - c), or of (2-a) through (2-c), the ordered steps being either: (1 -a) oligomerizing a mixture of at least two hydroxylated fatty acids or fatty esters using a tin-containing, titanium-containing or nitrogen- containing catalyst and removing formed alcohol, optionally by using one or more of an entrainer, reduced pressure and nitrogen sparging, to yield a product 1 -X with distribution of compounds represented by Formula 1 :
  • R is an alkyl group that contains from 1 to 12 carbon atoms
  • R 1 is hydrogen or a methyl radical
  • x is a rational number from 0 to 12
  • n is a rational number from 1 to 20, and the formed alcohol having the formula R 1 OH
  • (1 -a1 ) optionally recovering product 1 -X from residual R 1 OH and, when used, the entrainer
  • (1 -b) reacting product 1 -X with an acid that contains from 2 to 12 carbon atoms, an ester that contains from 3 to 13 carbon atoms, or an acid anhydride that contains from 4 to 24 carbon atoms, optionally using an additional amount of a tin-containing, titanium-containing or nitrogen-containing catalyst, and removing formed alcohol to yield a product 1 -Y with a distribution of compounds represented by Formula 2:
  • R, R 3 , x and n are as defined above, and R 2 is an alkyi group that contains from 1 to 20 carbon atoms; (1 -c1 ) optionally recovering product 1 -Z from alcohol and residual R 1 OH added during (1 -c) and acid formed during reaction of 1 -Y with the acid, acid anhydride or ester added in (1 -b) ; or the ordered steps being: (2-a) reacting a mixture of at least two hydroxylated fatty acids or fatty esters with an alcohol to form product 2-X with a distribution of compounds represented by Formula 4:
  • R is an alkyi group that contains from 1 to 12 carbon atoms
  • R 2 is an alkyi group that contains from 1 to 20 carbon atoms
  • x is a rational number from 0 to 12
  • the invention provides a composition comprising a distribution of compounds represented by Formula 3:
  • R is an alkyi group that contains from 1 to 12 carbon atoms
  • R 2 is an alkyi group that contains from 1 to 20 carbon atoms
  • R 3 is an alkyi group that contains from 1 to 1 1 carbon atoms
  • x is a rational number from 0 to 12 and n is a rational number from 1 to 20, wherein at least two compounds in the distribution of compounds have different values of x.
  • the invention provides an improved process to prepare certain estolide derivatives that exhibit useful friction and wear properties, desirably low pour points, good thermo-oxidative stability, and are based on a renewable resource, such that the material may be classified as bio-based.
  • estolide derivatives may be carried out beginning with a mixture of hydroxylated fatty acids or fatty esters. It has surprisingly been found that starting from such mixtures according to the processes of the invention, estolide derivatives may be prepared that exhibit favorable properties, including very low pour points. As a result, the estolide derivatives may be suitable for use in a wide range of applications, including those requiring performance at very low temperatures.
  • the mixture of starting hydroxylated fatty acids or a fatty esters comprises two or more hydroxylated ( C 24 fatty acids, alternatively two or more hydroxylated C r C 20 fatty acids (or their esters).
  • the mixture comprises a short chain hydroxylated fatty acid, such as hydroxylated C C ⁇ COOH (or its ester) and a long chain hydroxylated fatty acid, such as hydroxylated C 12 -C 20 -COOH (or its ester).
  • the mixture of hydroxylated fatty acids or fatty esters may be, conveniently, a 12-hydroxy fatty acid, such as 12-hydroxystearic acid, or its methyl ester, and lactic acid.
  • the synthesis may be via a three-step process which includes a oligomerization, a transesterification, and a capping, but it has surprisingly been found that variation in the order of these steps, though ultimately still resulting in formation of a double ester of the starting hydroxylated material, affects the overall properties of the double ester, which is generally obtained as a mixture of final products.
  • the three steps are ordered as a oligomerization, a capping, and a transesterification.
  • the mixture of hydroxylated fatty acids or fatty esters is first oligomerized to form a mixture of hydroxylated fatty acid or fatty ester oligomers.
  • This oligomerization is desirably carried out in the presence of a tin-, titanium-, or nitrogen-containing catalyst and any forming water/alcohol is concurrently removed.
  • the water/alcohol removal may be accomplished by means of an entrainer, reduced pressure, and/or nitrogen sparging.
  • the result of this step is a mixture of hydroxylated fatty acid or fatty ester oligomers which includes a distribution of compounds of Formula 1 , as defined hereinabove.
  • the mixture of hydroxylated fatty acid or fatty ester oligomers is then recovered from excess alcohol, residual methanol and/or the entrainer, and then capped by reacting with an acid that contains from 2 to 12 carbon atoms, an ester that contains from 3 to 13 carbon atoms, or an acid anhydride that contains from 4 to 24 carbon atoms, to form a mixture of capped fatty acid or fatty ester oligomers. Additional tin-, titanium-, or nitrogen-containing catalyst may optionally be employed for this capping.
  • the distribution of product capped fatty acid or fatty ester oligomers may be represented by Formula 2, as defined hereinabove.
  • the capped material may be recovered from excess acid, acid anhydride or ester.
  • the mixture of capped fatty acid or fatty ester oligomers are reacted with an alcohol having from 2 to 20 carbon atoms.
  • the alcohol may be selected from 2-ethylhexanol, 2-(2-butoxy-propoxy)propan-1 -ol (DPnB), 1 -octanol, 2-octanol, and combinations thereof. Additional tin-, titanium-, or nitrogen- containing catalyst may be employed at this point, and formed methanol is removed, yielding a double estolide ester represented by a distribution of compounds represented by Formula 3, as defined hereinabove.
  • the composition comprising a mixture of esters may be prepared by a process wherein a transesterification step is conducted first, followed by oligomerization and, finally, capping steps.
  • the mixture of hydroxylated fatty acids or fatty esters is first transesterified by reacting with an alcohol to form a product 2-X with a distribution of compounds represented by Formula 4, as defined hereinabove;
  • (2-a1 ) optionally recovering product 2-X from excess alcohol ;
  • (2- b1 ) optionally recovering product 2-Y from residual R 2 OH and, when used, the entrainer;
  • (2-c) reacting product 2-Y with an acid that contains
  • Illustrative anhydrides include isobutyric anhydride.
  • the invention provides a composition comprising a distribution of compounds represented by Formula 3:
  • R is an alkyi group that contains from 1 to 12 carbon atoms
  • R 2 is an alkyi group that contains from 1 to 20 carbon atoms
  • R 3 is an alkyi group that contains from 1 to 1 1 carbon atoms
  • x is a rational number from 0 to 12 and n is a rational number from 1 to 20, wherein at least two compounds in the distribution of compounds have different values of x.
  • x is a rational number from 0 to 12. In some embodiments, x is a rational number from 2.5 to 10. Since the Formulae 1 , 2, 3, 4, 5, and 6 distribution of compounds are prepared from a mixture of hydroxylated fatty acids or fatty esters, at least two compounds in the distribution have differing values of x.
  • a person of ordinary skill in the art can readily calculate the value of x in the distribution of compounds based on which starting acids or esters were used and their quantities, or they can determine the value using known analytical methods such saponification and LC-MS.
  • R 1 in the distribution of compounds of Formulae 1 and 2 described above is a methyl radical.
  • R in the distribution of compounds of Formulae 1 , 2, 3, 4, 5, and 6 is
  • CrCe alkyi In some embodiments, it is a methyl radical or a hexanyl radical.
  • n in the Formulae 1 , 2, 3, 5, and 6 is a fraction between 1 and 20.
  • the mixed esters prepared by the inventive process are novel compositions and may exhibit a number of properties that make them useful and/or desirable for a variety of applications. These applications may include, but are not limited to, plasticizers for resins, power transmission fluids for hydraulics, heat transfer fluids, thickening agents, solvents, and surfactants. Furthermore, these compositions may also be useful in the production of polyurethanes, including foams, elastomers, coatings, and adhesives.
  • the ester compositions may exhibit properties including at least one of a pour point that is less than or equal to -10 °C, alternatively -15 S C or less, or alternatively -20 S C or less (measured according to ASTM D97) ; a viscosity index that is greater than or equal to 130; a kinematic viscosity at 40 °C that is 25 centistokes (cSt) or greater (0.000025 square meters per second (m 2 /second)) (measured according to ASTM D445) ; a total acid number that is less than 1 milligram of potassium hydroxide per gram (mg KOH/g), and in particular embodiments less than 0.5 mg KOH/g; and an iodine number that is less than 3 weight percent (wt%), indicating full saturation.
  • a pour point that is less than or equal to -10 °C, alternatively -15 S C or less, or alternatively -20 S C or less
  • a viscosity index that is greater than or equal
  • the double esters may have a pour point that is less than -30 °C, and a kinematic viscosity at 40 °C that is at least 29 cSt (0.000029 m 2 /second) and preferably greater than 45 cSt (0.000045 m 2 /second). They may also have a hydroxyl number of less than or equal to 1 0, preferably less than 8, more preferably less than 5, still more preferably less than 4, and even more preferably less than 3; and an iodine number that is less than 3 weight percent (wt%), indicating full saturation. They may also exhibit desirable levels of thermo-oxidative stability (measured according to ASTM D2893), and renewable carbons (at least 50 percent by weight, measured according to ASTM D6866-08).
  • the temperature for the oligomerization (alternatively referred to as condensation) of the mixture of hydroxylated fatty acid or ester compounds, and also for the azeotropic distillation of the methanol formed during the reaction is desirably from 70 °C to 220 °C, more desirably from 120 °C to 210 °C, and still more desirably from 180 °C to 200 °C.
  • the temperature for the transesterification reaction may be accomplished at a temperature from 70 °C to 220 °C, and in certain particular embodiments from 120 °C to 210 °C, still more particularly from 180 °C to 200 °C.
  • the branched alcohol is desirably present in an amount sufficient to provide at least one molar equivalent of alcohol for each molar equivalent of the oligomerized ester or the hydroxylated fatty acid or fatty acid ester (depending upon the embodiment).
  • the capping of the estolide ester is desirably carried out at a temperature from 80 °C to 160 °C, more preferably from 100 °C to 140 °C, and still more desirably from 1 10 °C to 130 °C.
  • Optional step (1 -a1 ), recovering product 1 -X from residual methanol formed during step (1 - a) and, when used, an entrainer may be accomplished via conventional procedures such as azeotropic distillation with the entrainer, preferably using an aliphatic compound having from 7 to 1 0 carbon atoms, most preferably 9 carbon atoms. Entrainment and removal of both residual methanol and the entrainer preferably occurs via distillation under reduced pressure (for example, 4 kilopascals (kPa)).
  • the temperature is preferably within a range of from 100 °C to 200 °C, more preferably from 120 °C to 190 S C, and still more preferably from 150°C to 180°C.
  • Optional step (1 -b1 ), recovering product 1 -Y from excess step (1 -b) alcohol and residual methanol from step (1 -a), may be accomplished via conventional procedures such as fractionated distillation.
  • Step (1 -b1 ) preferably involves distillation under reduced pressure (for example, 4 kPa) to effect recovery of product 1 -Y.
  • the temperature is preferably within a range of from 70 °C to 350 °C, more preferably from 120 °C to 250 °C, and still more preferably from 150 ⁇ to 180 °C.
  • Optional step (1 -c1 ), recovering product 1 -Z from excess acid, acid anhydride or ester added as a reactant in step (1 -b) and acid formed during reaction of product 1 -Y with the acid, acid anhydride or ester preferably includes one or more of (1 ) use of reduced pressure to remove volatile materials, (2) washing one or more times with a base, such as an aqueous solution of sodium hydrogen carbonate (NaHC0 3 ), (3) use of absorbent materials such as magnesium silicate, activated carbon and magnesium sulfate (MgS0 4 ), and (4) filtration.
  • a base such as an aqueous solution of sodium hydrogen carbonate (NaHC0 3 )
  • absorbent materials such as magnesium silicate, activated carbon and magnesium sulfate (MgS0 4 )
  • numeric ranges used in this specification are inclusive of the numbers defining the range. Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.
  • Step 1 A glass reactor equipped with a temperature controller, overhead stirrer and Dean- Stark apparatus is charged with 12-hydroxy-stearic acid (450.4 grams (g)), lactic acid (37.1 g), 2- ethylhexanol (487.8 g) and tin(l l)-2-ethylhexanoate (1 .9 g). The mixture is then heated to 190 °C for a period of 6 hours, while removing water via fractional distillation. Excess 2-ethylhexanol is removed by distillation under reduced pressure at 160 °C and then the reactor is cooled to 120 °C.
  • Step 2 To the product of step 1 (584.7 g) tin(ll)-2-ethylhexanoate (1 .2 g) is added. The mixture is heated with stirring, to a set point temperature of 200 °C for a period of three hours. Excess 2-ethylhexanol is removed from the reactor contents by distillation under reduced pressure (20 mbar) and then the reactor is cooled to 120 °C.
  • Step 3 Isobutyric anhydride (120.4 g) is added to the product of step 2 (466.2 g). The reactor is stirred at this temperature for 2 hours. Excess anhydride and acid formed during capping are removed under reduced pressure. Temperature is then increased to 160 °C and reduced pressure maintained for two hours. The reactor contents are then cooled to a set point temperature of 70 °C and NaHC0 3 aqueous solution (100 ml_, 1 M) is added to the reactor with stirring. After stirring for 1 hour, water is removed under reduced pressure.
  • Magnesium silicate (1 % w/w), activated carbon (1 % w/w) and MgS0 4 (1 % w/w) are added to the reactor, then the material is filtered using a filter paper coated with 8 % of magnesium silicate to yield the final product, which is a light yellow liquid.
  • Step 1 A glass reactor equipped with a temperature controller, overhead stirrer and Dean- Stark apparatus is charged with 12-hydroxy-stearic acid (407.0 g), lactic acid (67.6 g), 2- ethylhexanol (520.2 g) and tin(ll)-2-ethylhexanoate (2.0 g). The mixture is heated to a set point temperature of 190 °C and maintained with stirring for a period of 6 hours, removing water via fractional distillation. Excess 2-ethylhexanol is removed by distillation under reduced pressure at 160 °C and then the reactor is cooled to 120 °C.
  • Step 2 Tin(ll)-2-ethylhexanoate (1 .3 g) is added to the step 1 product (565.8 g), and the mixture is heated with stirring, to a set point temperature of 200 °C for a period of three hours. 2- Ethylhexanol formed during the reaction is removed from the reactor contents by distillation under reduced pressure (20 mbar) and then the reactor is cooled to 120 °C.
  • Step 3 Isobutyric anhydride (144.3 g) is added to the product of step 2 (445.0 g). The reactor is stirred at this temperature for 2 hours. Excess anhydride and acid formed during capping are removed under reduced pressure. Temperature is then increased to 160 °C and reduced pressure maintained for two hours. The reactor contents are then cooled to a set point temperature of 70 °C and NaHC0 3 aqueous solution (100 ml_, 1 M) is added to the reactor with stirring. After stirring for 1 hour, water is removed under reduced pressure.
  • Magnesium silicate (1 % w/w), activated carbon (1 % w/w) and MgS0 4 (1 % w/w) are added to the reactor, then the material is filtered using a filter paper coated with 8 % of magnesium silicate to yield the final product, which is a light yellow liquid.
  • Step 1 A glass reactor equipped with a temperature controller, overhead stirrer and Dean- Stark apparatus is charged with methyl-12-hydroxy-stearate (5296.2 grams (g)), nonane fraction (793.4 g) and tin(l l)-2-ethylhexanoate (15.9 g). The mixture is then heated to 190 °C for a period of 20 hours, removing methanol by azeotropic distillation with nonane. Residual nonane fraction is distilled under reduced pressure (20 millibar (mbar), 2 kilopascals (kPa)) at 160 °C, and then the reactor is cooled to 120 °C.
  • mbar millibar
  • kPa kilopascals
  • Step 2 To the product of step 1 (463.29 g), isobutyric anhydride (93.49 g) is added. The reactor is stirred at this temperature for 2 hours. Excess anhydride and acid formed during capping are removed under reduced pressure. Temperature is then increased to 160 °C and reduced pressure is maintained for two hours, the reactor contents are then cooled to a set point temperature of 70 °C, and a NaHC0 3 aqueous solution (100 milliliters (ml_), 1 molar (M)) is added to the reactor with stirring. After stirring for 1 hour, water is removed under reduced pressure.
  • ml_ milliliters
  • M molar
  • Magnesium silicate (1 percent by weight (% w/w)), activated carbon (1 % w/w) and MgS0 4 (1 % w/w) is added to the reactor, then the material is filtered using a filter paper coated with 8 percent (%) of magnesium silicate to yield the final product.
  • Step 3 A Vigreux distillation column is placed between the reactor and the Dean-Stark apparatus, then 2-ethylhexanol (77.72 g) and tin(ll)-2-ethylhexanoate (0.02 g) are added to the product of step 2 (357.2 g) and the mixture is heated to 190 °C for a period of 6 hours, removing methanol by fractional distillation. Excess 2-ethylhexanol is removed by distillation under pressure at 160 °C and then the reactor is cooled to 20 °C. The resulting product is a light yellow liquid.
  • Example 4 Comparative
  • Step 1 A glass reactor equipped Vigreux distillation column placed between the reactor and the Dean-Stark apparatus is charged with methyl-12-hydroxy-stearate (2921 .8 g), 2- ethylhexanol (2363.2 g) and tin(ll)-2-ethylhexanoate (18.7 g). The mixture is heated to a set point temperature of 190 °C and maintained with stirring for a period of time, removing methanol via fractional distillation. Excess 2-ethylhexanol is removed by distillation under reduced pressure at 160 °C and then the reactor is cooled to 120 °C.
  • Step 2 The Vigreux column is then removed from the reactor and tin(ll)-2-ethylhexanoate (6.0 g) is added to the step 1 product (900.0 g), and the mixture is heated with stirring, to a set point temperature of 200 °C for a period of three hours. Excess 2-ethylhexanol is removed from the reactor contents by distillation under reduced pressure (20 mbar) and then the reactor is cooled to 120 °C.
  • Step 3 Isobutyric anhydride (188.05 g) is added to the product of step 2 (754.02 g). The reactor is stirred at this temperature for 2 hours. Excess anhydride and acid formed during capping are removed under reduced pressure. Temperature is then increased to 160 °C and reduced pressure maintained for two hours. The reactor contents are then cooled to a set point temperature of 70 °C and NaHC0 3 aqueous solution (100 ml_, 1 M) is added to the reactor with stirring. After stirring for 1 hour, water is removed under reduced pressure.
  • Magnesium silicate (1 % w/w), activated carbon (1 % w/w) and MgS0 4 (1 % w/w) are added to the reactor, then the material is filtered using a filter paper coated with 8 % of magnesium silicate to yield the final product, which is a light yellow liquid.
  • compositions prepared from mixtures of fatty acids or esters according to the invention exhibit considerably more favorable pour points that compositions prepared from single fatty acids or esters (comparative Examples 3 and 4).

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Abstract

L'invention porte sur une composition comprenant un mélange d'esters préparé par un procédé en trois étapes comprenant les étapes d'oligomérisation, de transestérification et de coiffage. La composition est utile dans un grand nombre d'applications, notamment comme biolubrifiant ayant un niveau élevé de carbones renouvelables, et elle peut présenter des propriétés particulièrement souhaitables en ce qui concerne le point d'écoulement, la stabilité vis-à-vis d'une dégradation thermo-oxydative et le comportement viscosimétrique en raison de niveaux réduits ou supprimés d'insaturation dans les esters doubles finaux.
EP12724265.9A 2011-06-28 2012-05-18 Dérivés étholides utiles comme biolubrifiants Withdrawn EP2694630A1 (fr)

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CN102906155A (zh) 2010-04-29 2013-01-30 陶氏环球技术有限责任公司 低聚酯烷氧基化物组合物
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US8236194B1 (en) * 2011-06-17 2012-08-07 Lubrigreen Biosynthetics, Llc Refrigerating fluid compositions comprising estolide compounds
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ES2590220B1 (es) 2015-05-18 2017-12-18 Neol Biosolutions, S.A. Producción de aceites microbianos con alto contenido en acido oleico

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US20140100150A1 (en) 2014-04-10
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