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US20110009300A1 - Synthesis of biolubricant esters from unsaturated fatty acid derivatives - Google Patents

Synthesis of biolubricant esters from unsaturated fatty acid derivatives Download PDF

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Publication number
US20110009300A1
US20110009300A1 US12/498,663 US49866309A US2011009300A1 US 20110009300 A1 US20110009300 A1 US 20110009300A1 US 49866309 A US49866309 A US 49866309A US 2011009300 A1 US2011009300 A1 US 2011009300A1
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species
diester
group
isomeric mixture
isomeric
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US12/498,663
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Inventor
Saleh A. Elomari
Stephen Joseph Miller
Zhen Zhou
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Chevron USA Inc
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Chevron USA Inc
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Priority to US12/498,663 priority Critical patent/US20110009300A1/en
Assigned to CHEVRON U.S.A. INC. reassignment CHEVRON U.S.A. INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ELOMARI, SALEH A., MILLER, STEPHEN JOSEPH, ZHOU, ZHEN
Priority to CN2010800283373A priority patent/CN102471715A/zh
Priority to PCT/US2010/039809 priority patent/WO2011005604A2/en
Priority to MX2011013030A priority patent/MX2011013030A/es
Priority to BR112012000171A priority patent/BR112012000171A2/pt
Priority to EP10797618A priority patent/EP2451907A4/en
Priority to AU2010270827A priority patent/AU2010270827B2/en
Priority to CA2765723A priority patent/CA2765723A1/en
Publication of US20110009300A1 publication Critical patent/US20110009300A1/en
Priority to US13/553,611 priority patent/US8481465B2/en
Priority to US13/553,658 priority patent/US8507423B2/en
Priority to US13/938,547 priority patent/US9267090B2/en
Abandoned 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
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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
    • 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
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • This invention relates to ester-based lubricants, and specifically to diester-based lubricants and their manufacture—particularly wherein they are made from at least one biologically-derived precursor.
  • Esters have been used as lubricating oils for over 50 years. They arc used in a variety of applications ranging from jet engines to refrigeration. In fact, esters were the first synthetic crankcase motor oils in automotive applications. However, esters gave way to polyalphaolefins (PAOs) due to the lower cost of PAOs and their formulation similarities to mineral oils. In full synthetic motor oils, however, esters are almost always used in combination with PAOs to balance the effect on seals, additives solubility, volatility reduction, and energy efficiency improvement by enhanced lubricity.
  • PAOs polyalphaolefins
  • Ester-based lubricants in general, have excellent lubrication properties due to the polarity of the ester molecules of which they are comprised.
  • the polar ester groups of such molecules adhere to positively-charged metal surfaces creating protective films which slow down the wear and tear of the metal surfaces.
  • Such lubricants are less volatile than the traditional lubricants and tend to have much higher flash points and much lower vapor pressures.
  • Ester-based lubricants are excellent solvents and dispersants, and can readily solvate and disperse the degradation by-products of oils. Therefore, they greatly reduce sludge buildup.
  • ester-based lubricants are stable to thermal and oxidative processes, the ester functionalities give microbes a handle to do their biodegrading more efficiently and more effectively than their mineral oil-based analogues.
  • the preparation of esters is more involved and more costly than the preparation of their PAO counterparts.
  • diester-based lubricants and their manufacture have been recently reported, wherein the diester species have a general formula:
  • R′ 1 , R′ 2 , R′ 3 , and R′ 4 are the same or independently selected from a C 2 to C 17 carbon fragment. See commonly-assigned U.S. patent application Ser. No. 11/673,879 (Miller et al.), filed Feb. 12, 2007 and published as United States Patent Publication No. US 20080194444 on Aug. 14, 2008; and Ser. No. 12/023,695 (Miller et al.), filed Jan. 31, 2008. Note that the two ester groups are vicinal in their attachment to the aliphatic backbone of the diester species.
  • the present invention is generally directed to diester-based lubricant compositions, such compositions generally comprising one or more isomeric mixtures of diester species.
  • the present invention is also directed to methods of making these and other similar lubricant compositions.
  • the methods for making such diester-based lubricants make at least partial use of one or more biomass precursor species as reagents in the synthesis of such diester species. Indeed, in some embodiments such diester-based lubricants can be entirely bio-derived.
  • lubricant precursor species can also be sourced or otherwise derived from Fischer-Tropsch (FT) reaction products/byproducts.
  • FT Fischer-Tropsch
  • the present invention is directed to at least one lubricant composition
  • at least one lubricant composition comprising a quantity of at least one isomeric mixture of diester species, the diester species (1a) and (1b) having the following structures:
  • the isomeric diester species, of which the at least one isomeric mixture is comprised have a molecular mass that is from at least about 400 atomic mass units (a.m.u.) to at most about 1100 a.m.u., and more typically between 450 a.m.u. and 1000 a.m.u.
  • the kinematic viscosity of the above-described composition at a temperature of 100° C. is at least 3 mm 2 /s, i.e., 3 centistokes (cSt).
  • said composition has a pour point of less than ⁇ 20° C.
  • such properties are such that, in at least some embodiments, the compositions can be used as lubricants in one or more of a variety of applications and environments.
  • the above-described composition comprises quantities of at least two different isomeric mixtures of diester species—typically with large variability in relative amounts.
  • said composition further comprises a base oil selected from the group consisting of Group I oils, Group II oils, Group III oils, and combinations thereof. Additionally or alternatively, in some embodiments, said composition further comprises one or more monoester and/or triester species.
  • the present invention is directed to methods of making the above-described composition(s), such methods comprising the steps of: (A) converting a quantity of mono-unsaturated free lipid species (e.g., mono-unsaturated fatty acid(s) and/or ester(s)), having a carbon number of from 10 to 22, to an isomeric mixture of diol species having the same carbon number as the free lipid species from which they were derived, wherein said converting proceeds via an epoxide intermediate species; and (B) esterifying the isomeric mixture of diol species with an esterifying species to form an isomeric mixture of diester species, wherein the isomeric mixture of diester species comprises isomerically-related structures 1a and 1b, and wherein R 1 , R 2 , R 3 , and R 4 are the same or independently selected from C 2 to C 20 hydrocarbon groups, and wherein n and m are the same or independently selected from the group of integers 2 to 20.
  • A converting a quantity of
  • the step of converting comprises the following sub-steps: (Substep A) epoxidizing the quantity of mono-unsaturated free lipid species to yield a quantity of epoxidized lipid species; and (Substep B) reducing the epoxidized lipid species to yield an isomeric mixture of diol species—which is subsequently esterified to yield an isomeric mixture of diester species.
  • the step of converting comprises the following alternate (variational) substeps: (Alt. Substep A) reducing the quantity of mono-unsaturated free lipid species to yield a quantity of mono-unsaturated fatty alcohol species; (Alt. Substep B) epoxidizing the quantity of mono-unsaturated fatty alcohol species to yield a quantity of epoxidized alcohol species; and (Alt. Substep C) reducing the epoxidized alcohol species to yield an isomeric mixture of diol species.
  • FIG. 1 depicts four exemplary isomeric diester pairs 2a-5a and 2b-5b, suitable for use as lubricants and/or lubricant components, in accordance with some embodiments of the present invention
  • FIG. 2 is a flow diagram describing how isomeric mixtures of diester species are prepared, in accordance with some embodiments of the present invention
  • FIG. 3 is a chemical flow diagram illustrating some representative methods of making (synthesizing) a diester-based lubricant composition (or at least a diester component thereof), in accordance with some embodiments of the present invention, wherein oleic acid is used as a representative mono-unsaturated fatty acid;
  • FIG. 4 is a chemical flow diagram illustrating one or more alternate methods of making a diester-based lubricant composition (or at least a diester component thereof), in accordance with some embodiments of the present invention, wherein oleic acid is used as a representative mono-unsaturated fatty acid;
  • FIG. 5 is a chemical flow diagram illustrating methods of making a diester-based lubricant composition (or at least a diester component thereof) from oleic acid, in accordance with some embodiments of the present invention, and as illustrated in Examples 1-4; and
  • FIG. 6 (Table 1) lists lubrication and physical properties of isomeric diester mixture 4a/4b, as prepared in Example 4.
  • the present invention is generally directed to diester-based lubricant compositions comprising isomeric mixtures of diester species.
  • the present invention is also directed to methods (processes) of making these and other similar lubricant compositions.
  • the methods for making such diester-based lubricants utilize one or more biomass precursor species, wherein it is typically at least the lipid components utilized in such methods that are obtained from biomass sources (e.g., vegetable oil and/or algae).
  • biomass sources e.g., vegetable oil and/or algae
  • Other chemical components used in such methods can be similarly derived from biomass, or they can be derived from other sources such as, but not limited to, Fischer-Tropsch (FT) synthesis products and/or by-products.
  • FT Fischer-Tropsch
  • diester lubricants described herein in at least some embodiments, are that they can be entirely bio-derived; i.e., all of the reagents used in their synthesis (generally exclusive of solvents and catalysts) can be derived from a biological precursor material. Additionally, methods for producing such lubricants make use of olefins already present in vegetable/crop oils, thereby streamlining the synthetic process. Additionally still, as opposed to conventional biolubricants, i.e., triglycerides, the diester-based lubricants described herein have, in at least some embodiments, excellent low temperature properties without having carbon-carbon double bonds, the presence of such bonds generally compromising the lubricant composition's oxidation stability.
  • “Lubricants,” as defined herein, are substances (usually a fluid under operating conditions) introduced between two moving surfaces so to reduce the friction and wear between them.
  • Base oils used as motor oils are generally classified by the American Petroleum Institute as being mineral oils (Group I, II, and III) or synthetic oils (Group IV and V). See American Petroleum Institute (API) Publication Number 1509.
  • Pul point represents the lowest temperature at which a fluid will pour or flow. See, e.g., ASTM Standard Test Method D 5950-02 (R 2007).
  • Cloud point represents the temperature at which a fluid begins to phase separate due to crystal formation. See, e.g., ASTM Standard Test Method D 5771-05.
  • Oxidation stability generally refers to a composition's resistance to oxidation.
  • Oxidator BN is a convenient way to measure the oxidation stability of base oils, and it is the method used to evaluate the oxidation stability of at least some of the lubricant compositions described herein.
  • the Oxidator BN test is described by Stangeland et al. in U.S. Pat. No. 3,852,207, which issued on Dec. 3, 1974.
  • the Oxidator BN test measures an oil's resistance to oxidation by means of a Dornte-type oxygen absorption apparatus. See Dornte “Oxidation of White Oils,” Industrial and Engineering Chemistry, vol. 28, pp. 26-30, 1936. Normally, the conditions are one atmosphere of pure oxygen at 340° F. (171° C.). the results are reported in hours to absorb 1000 mL (1 L) of O 2 by 100 grams of oil.
  • R x refers to a hydrocarbon group, wherein the molecules and/or molecular fragments can be linear and/or branched, and unless stated otherwise, groups identified by different “x” identifiers can be the same or different.
  • carbon number As defined herein, “carbon number,” as it relates to a hydrocarbon molecule or fragment (e.g., an alkyl group), is an integer denoting the total number of carbon atoms in the fragment or molecule. Carbon number with such a fragment or molecule can also be denoted as “C y ” where “y” is the total number of carbon atoms within that particular fragment or molecule.
  • Triglyceride refers to class of molecules having the following molecular structure:
  • x′, y′, and z′ can be the same or different, and wherein one or more of the branches defined by x′, y′, and z′ can have unsaturated regions.
  • a “carboxylic acid” or “fatty acid,” as defined herein, is a class of organic acids having the general formula:
  • R n is generally a saturated (alkyl) hydrocarbon chain or a mono- or polyunsaturated (alkenyl) hydrocarbon chain.
  • Lipids as defined herein, broadly refers to the class of molecules comprising fatty acids, and tri-, di-, and mono-glycerides.
  • “Hydrolysis” of triglycerides yields free fatty acids and glycerol, such fatty acid species also commonly referred to as carboxylic acids (see above).
  • Transesterification refers to the reaction between a fatty acid or ester (e.g., a triglyceride) and an alcohol to yield an ester species.
  • a fatty acid or ester e.g., a triglyceride
  • mono-unsaturated free lipid species refers to mono-unsaturated fatty acids and/or mono-unsaturated fatty esters—typically such species being derived from triglyceride species via hydrolysis and/or transesterification, wherein at least some of the triglyceride species comprise at least one mono-unsaturated fatty chain, i.e., a hydrocarbon chain having a single carbon-carbon double bond.
  • bio refers to an association with a renewable resource of biological origin, such as resource generally being exclusive of fossil fuels.
  • bio-derived refers to derivation from a renewable biological resource, organism, or entity; and it generally precludes derivation from fossil fuels, the latter not being deemed “renewable.”
  • biomass precursor species and “biomass precursor material,” as used (interchangeably) herein, refer to biomass or biomass derivatives from which bio-derived reagents and/or products can be synthesized or otherwise manufactured.
  • Fischer-Tropsch products refer to molecular species derived from a catalytically-driven reaction between CO and H 2 (i.e., “syngas”). See, e.g., Dry, “The Fischer-Tropsch process: 1950-2000,” vol. 71(3-4), pp. 227-241, 2002; Schulz, “Short history and present trends of Fischer-Tropsch synthesis,” Applied Catalysis A, vol. 186, pp. 3-12, 1999.
  • “Isomeric mixtures,” as defined herein, refers to a mixture of quantities of at least two different molecular species having the same chemical formula and molecular weight, but having a different structural arrangements—in terms of the atoms making up the at least two different molecular species.
  • the present invention is generally directed to diester-based lubricant compositions comprising a quantity of at least one isomeric mixture of diester species having the following chemical structures:
  • R 1 , R 2 , R 3 , and R 4 are the same or independently selected from C 1 to C 20 hydrocarbon groups, and wherein n and m are the same or independently selected from the group of integers 2 to 20.
  • the kinematic viscosity of the resulting composition at a temperature of 100° C. is at least 3 mm 2 /s. Additionally or alternatively, in some such compositional embodiments, said composition has a pour point of less than ⁇ 20° C.
  • diester structures are selected, and additional components present (if at all), so as to provide for a lubricant composition having such aforementioned properties.
  • R 1 and R 2 are independently selected to have a carbon number from at least about 1 to at most about 15. Additionally or alternatively, in some such embodiments, R 3 and R 4 are independently selected to have a carbon number from at least about 1 to at most about 15. In some or other such embodiments, n is an integer from 5 to 10. In some or still other such embodiments, m is an integer from 5 to 10.
  • the isomeric diester species, of which the at least one isomeric mixture is comprised each having a molecular mass that is from at least about 400 atomic mass units (a.m.u.) to at most about 1100 a.m.u., and more typically between 450 a.m.u. and 1000 a.m.u.
  • the at least one isomeric mixture of diester species is selected from the group of isomeric diester pairs consisting of octadecane-1,9-diyl dihexanoate (2a) and octadecane-1,10-diyl dihexanoate-(2b); octadecane-1,9-diyl bis(decanoate) (3a) and octadecane-1,10-diyl bis(decanoate) (3b); octadecane-1,9-diyl dioctanoate (4a) and octadecane-1,10-diyl dioctanoate (4b); ocatadecane-1,9-diyl didodecanoate (5a) and ocatadecane-1,10-diyl didodecanoate (5b); and mixtures thereof
  • compositions are not limited to a single isomeric diester pair.
  • such lubricant compositions comprise at least two (i.e., two or more) different isomeric mixtures of diester species.
  • a particular lubricant composition may comprise quantities of both diester mixture 4a/4b and 5a/5b.
  • the relative amount of one isomeric mixture of diester species can vary considerably from that of another isomeric mixture of diester species within a given lubricant composition.
  • compositions are not limited (at least in terms of their ester-component) to diesters in the form of isomeric mixtures of such species.
  • such lubricant compositions additionally comprise one or more ester species selected from the group consisting of monoesters, diesters, triesters, and combinations thereof.
  • ester species selected from the group consisting of monoesters, diesters, triesters, and combinations thereof.
  • Types of such additional diester species include, but are not limited to, vicinal diesters such as those described in commonly-assigned U.S. patent application Ser. No. 11/673,879 (Miller et al.), filed Feb. 12, 2007 and published as United States Patent Publication No. US 20080194444 on Aug. 14, 2008; and Ser. No. 12/023,695 (Miller et al.), filed Jan. 31, 2008.
  • Types of such triester species include, but are not limited to, those described in commonly-assigned U.S. Pat. No. 7,544,645, issued
  • such lubricant compositions comprise, individual diester isomers 1a and 1b, of which the isomeric mixture of diester species is comprised, differ in relative amount by not more than 5 percent. In some or other such embodiments, 1a and 1b differ in relative amount by not more than 3 percent. In some or still other such embodiments, 1a and 1b differ in relative amount by not more than 1 percent.
  • At least one of the at least one isomeric diester mixtures take the form of 6a and 6b below, wherein R 1 , R 2 , R 3 , and R 4 are selected as described above for 1a and 1b.
  • the above-described diesters and their compositions are not used as lubricants by themselves, but are used as components and/or blending stocks for more complex lubricant compositions or mixtures. Accordingly, in some such embodiments, the above-described compositions further comprise a base oil selected from the group consisting of Group I oils, Group II oils, Group III oils, and combinations thereof (vide supra). As such, esters with higher pour points may also be used as blending stocks with other lubricant oils since they are very soluble in hydrocarbons and hydrocarbon-based oils.
  • the present invention is additionally directed to methods of making the above-described (Section 3) lubricant compositions and/or the diester-based compositions contained therein.
  • processes/methods for making at least the isomeric diester mixtures of the above-mentioned diester-based compositions comprise the following steps: (Step 201 ) converting a quantity of mono-unsaturated free lipid species, having a carbon number of from 10 to 22, to an isomeric mixture of diol species having the same carbon number as the free lipid species from which they were derived, wherein said converting proceeds via an epoxide intermediate species; and (Step 202 ) esterifying the isomeric mixture of diol species with an esterifying species to form an isomeric mixture of diester species, wherein the isomeric mixture of diester species comprises the following isomerically-related structures:
  • R 1 , R 2 , R 3 , and R 4 are the same or independently selected from C 2 to C 20 hydrocarbon groups, and wherein n and m are the same or independently selected from the group of integers 2 to 20.
  • the step of converting comprises the following sub-steps: (Substep 201 a ) epoxidizing the quantity of mono-unsaturated free lipid species to yield a quantity of epoxidized lipid species; and (Substep 201 b ) reducing the epoxidized lipid species to yield an isomeric mixture of diol species.
  • the substep of epoxidizing utilizes a reagent (i.e., an epoxidizing agent/species) selected from one or more species such as, but not limited to, peroxides and peroxy acids.
  • a reagent i.e., an epoxidizing agent/species
  • species such as, but not limited to, peroxides and peroxy acids.
  • the above-described mono-unsaturated free lipid species e.g., oleic acid
  • a peroxide e.g., H 2 O 2
  • a peroxy acid e.g., peroxyacetic acid
  • Substep 201 a Another exemplary peroxy acid for use in Substep 201 a is meta-chloro-peroxybenzoic acid (mCPBA).
  • mCPBA meta-chloro-peroxybenzoic acid
  • the substep of reducing utilizes a metal-hydride reducing agent.
  • a metal-hydride reducing agent in some embodiments, lithium aluminum hydride (LiAlH 4 ) is used as a reducing agent to effect such reduction.
  • catalytic hydrogenation may be employed using, for example, copper- or zinc-based catalysts. See, e.g., U.S. Pat. No. 4,880,937; Scrimgeour, “Chemistry of Fatty Acids,” in Bailey's Industrial Oil and Fat Products, 6 th Edition, Vol. 1, pp. 1-43, F. Shahidi (Ed.), J. Wiley & Soils, New York, 2005.
  • the step of esterifying the isomeric mixture of diol species with an esterifying species first involves conversion of one or more fatty acid species to one or more corresponding esterification species selected from the group consisting of acyl halide species, it/they selected from the group consisting of acyl chlorides, acyl bromides, acyl iodides, and combinations thereof; and acyl anhydride species.
  • the esterification species can react with the —OH groups of the diols to form diester species.
  • the step of esterifying the isomeric mixture of diol species with an esterifying species involves a catalyst selected from the group consisting of an acid catalyst and a base catalyst.
  • an acid can be used to catalyze the reaction between the —OH groups of the diol and the carboxylic acid(s).
  • Suitable acids include, but are not limited to, sulfuric acid (Munch-Peterson, Org. Synth., Coll. Vol. 5, p. 762, 1973), sulfonic acid (Allen and Sprangler, Org Synth., Coll. Vol. 3, p. 203, 1955), hydrochloric acid (Eliel et al., Org Syndi., Coll. Vol. 4, p. 169, 1963), and phosphoric acid (among others).
  • the carboxylic acid used in this step is first converted to an acyl chloride (or another acyl halide) via, e.g., thionyl chloride or PCl 3 .
  • an acyl chloride or other acyl halide could be employed directly.
  • an acid catalyst is not needed and a base such as pyridine, 4-dimethylaminopyridine (DMAP) or triethylamine (TEA) is typically added to react with an HCl produced.
  • DMAP 4-dimethylaminopyridine
  • TAA triethylamine
  • esterification steps can also be base-catalyzed. See, e.g., Fersht et al., “Acetylpyridinium ion intermediate in pyridine-catalyzed hydrolysis and acyl transfer reactions of acetic anhydride. Observation, kinetics, structure-reactivity correlations, and effects of concentrated salt solutions.” J. Am. Chem. Soc., vol. 92(18), pp. 5432-5442, 1970; and Höfle et al., “4-Dialkylaminopyradines as Highly Active Acylation Catalysts,” Angew. Chem. Int. Ed. Engl., vol. 17, pp. 569-583, 1978. Additionally or alternatively, the carboxylic acid could be converted into an acyl anhydride and/or such species could be employed directly.
  • one or more other ester species selected from the group consisting of triesters, diesters, monoesters, and combinations thereof.
  • Such one or more other ester species need not be provided as isomeric mixtures.
  • the isomeric mixture of diester species is entirely bio-derived, meaning that the synthesis of said species uses (exclusive of solvents and catalysts) only bio-derived reagents.
  • bio-derived isomeric mixtures of diester species are subsequently mixed or blended with other components and/or mixtures not entirely of bio-derivation to yield lubricant compositions that are only partially bio-derived.
  • lubricant compositions made by such methods and comprising such diester species have a viscosity of 3 mm 2 /s (centistokes) or more at a temperature of 100° C. and they typically have a pour point of less than ⁇ 20° C., and selection of reagents and/or mixture components is typically made with this objective.
  • compositions comprising at least one isomeric mixture of diester species selected from among the following isomeric diester pairs: octadecane-1,9-diyl dihexanoate (2a) and octadecane-1,10-diyl dihexanoate (2b); octadecane-1,9-diyl bis(decanoate) (3a) and octadecane-1,10-diyl bis(decanoate) (3b); octadecane-1,9-diyl dioctanoate (4a) and octadecane-1,10-diyl dioctanoate (4b); ocatadecane-1,9-diyl didodecanoate (5a) and ocatadecane-1,10-diyl didodecanoate (5b); and mixtures thereof.
  • diester pairs selected from among the following isomeric diester pairs
  • the lubricant compositions produced by such methods comprise individual diester isomers 1a and 1b that differ in relative amount by not more than 5 percent. In some or other such embodiments, 1a and 1b differ in relative amount by not more than 3 percent. In some or still other such embodiments, 1a and 1b differ in relative amount by not more than 1 percent. While not intending to be bound by theory, deviation from equivalent isomer amounts in a given isomeric mixture of diester species can be attributed to one or more scenarios including, but not limited to, rearrangements, solvent effects on transition state, and statistical factors.
  • the mono-unsaturated free lipid species can be a bio-derived fatty acid (or ester) formed by hydrolysis (or esterification) of one or more triglyceride-containing vegetable oils such as, but not limited to, palm oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and the like.
  • triglyceride-containing vegetable oils such as, but not limited to, palm oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and the like.
  • Other sources of triglycerides, for which hydrolysis can yield unsaturated fatty acids include, but are not limited to, algae, animal tallow, and zooplankton. See, e.g., Bajpai et al., “Biodiesel: Source, Production, Composition, Properties and Its Benefits,” J. Oleo Sci., vol.
  • hydrolyzed triglyceride sources contain mixtures of saturated fatty acids, mono-unsaturated fatty acids, and poly-unsaturated fatty acids
  • one or more techniques may be employed to isolate, concentrate, or otherwise separate the mono-unsaturated fatty acids from the other fatty acids in the mixture. See, e.g., commonly-assigned U.S. patent application by Miller entitled, “Isolation and Subsequent Utilization of Saturated Fatty Acids and ⁇ -Olefins in the Production of Ester-Based Biolubricants,” Ser. No. 12/122,894, filed May 19, 2008.
  • partial hydrogenation of polyunsaturated fatty acids can yield mono-unsaturated fatty acids for use in methods of the present invention.
  • Post hydrogenation such mono-unsaturated fatty acids may be subjected to one or more of the above-mentioned separation/isolation techniques. See, e.g., Falk et al., “The Effect of Fatty Acid Composition on Biodiesel Oxidative Stability,” Eur. Journal of Lipid Sci. & Technol., vol. 106(12), pp. 837-843, 2004.
  • oleic acid (7) is epoxidized with an epoxidizing agent (e.g., a peroxy acid) to yield epoxy-lipid (epoxy-fatty acid) species 8 (Step 301 ).
  • an epoxidizing agent e.g., a peroxy acid
  • epoxy-lipid species 8 is reduced, using a reducing agent (e.g., LiAlH 4 ), to an isomeric mixture of diol species (9a/9b) (Step 302 ).
  • a reducing agent e.g., LiAlH 4
  • the carboxylic acids (or their acyl derivatives) used in the above-described methods are derived from biomass. In some such embodiments, this involves the extraction of some oil (e.g., triglyceride) component from the biomass and hydrolysis of the triglycerides of which the oil component is comprised so as to form free carboxylic acids.
  • oil e.g., triglyceride
  • Other sources of such carboxylic acids include, but are not limited to, those derived (directly or indirectly) from FT synthesis.
  • the step of converting comprises the following alternate (variational) sub-steps: (Alt. Substep 201 a ′) reducing the quantity of mono-unsaturated free lipid species to yield a quantity of mono-unsaturated fatty alcohol species; (Alt. Substep 201 b ′) epoxidizing the quantity of mono-unsaturated fatty alcohol species to yield a quantity of epoxidized alcohol species; and (Alt. Substep 201 c ′) reducing the epoxidized alcohol species to yield an isomeric mixture of diol species.
  • the variational substeps of reducing the quantity of mono-unsaturated free lipid species and reducing the epoxidized alcohol species utilize one or more metal-hydride reducing agents.
  • the variational substep of epoxidizing the quantity of mono-unsaturated fatty alcohol species utilizes an oxidizing agent selected from the group consisting of peroxides and peroxy acids.
  • oleic acid (7) is reduced with a representative reducing agent/species (LiAlH 4 ) to yield oleoyl alcohol 11 (Step 401 ).
  • Oleoyl alcohol 11 is then epoxidized with an epoxidizing agent (mCPBA) to yield epoxy-alcohol species 12 (Step 402 ) and the epoxy-alcohol species 12 is reduced with a reducing species to yield an isomeric mixture of diol species 9a and 9b (Step 403 ).
  • the isomeric mixture of diester species 9a and 9b is reacted with esterification agent 10 to yield an isomeric mixture of diester species 6a and 6b (Step 404 ).
  • compositions produced by such method variations will, naturally, be variations themselves. Generally, all such variations fall within the scope of the compositions and methods described herein.
  • molecular averaging can be employed to generate greater molecular homogeneity in the resulting compositions (at least in terms of die diester species contained therein) by furthering the homogeneity of the quantity of mono-unsaturated free lipid species—if not already in a fairly homogeneous state.
  • Such molecular averaging techniques involve olefin metathesis and are generally described in the following commonly-assigned U.S. Pat. No. 6,566,568 by Chen, issued May 20, 2003; U.S. Pat. No. 6,369,286 by O'Rear, issued Apr. 9, 2002; and U.S. Pat. No. 6,562,230 by O'Rear et al., issued May 13, 2003.
  • the resulting lubricant compositions additionally comprise more highly branched diester species.
  • more highly branched diester species can be added so as to provide for lubricant compositions comprising additional diester species (vide supra).
  • This Example serves to illustrate synthesis of mono-unsaturated fatty alcohol 11, in accordance with some embodiments of the present invention, and en route to the formation of isomeric diester mixture 4a/4b.
  • oleic acid 7 was reduced to the corresponding oleoyl alcohol 11 (Step 501 ) as follows.
  • the reaction progress was monitored by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies for the disappearance of the acid carbonyl group.
  • IR infrared
  • NMR nuclear magnetic resonance
  • This Example serves to illustrate the synthesis of epoxy-alcohol species 12 (oleoyl epoxide), en route to the synthesis of isomeric diester mixture 4a/4b and in accordance with some embodiments of the present invention.
  • epoxy-alcohol species 12 was prepared from oleoyl alcohol 11 (Step 502) according to the following procedure.
  • the filtrate was rinsed once with 150 mL of 10 wt % NaSO 3 aqueous solution, once with 200 mL of saturated KHCO 3 solution, and three times with 300 mL of water.
  • the organic layer was dried over MgSO 4 , filtered, and concentrated on a rotary evaporator to give the product as a waxy, solid material in 93% yield (48 grams) with high purity according to GC/MS analysis. Note that methyl oleate was also epoxidized using the same epoxidation procedure to give the corresponding epoxy methyl oleate.
  • this Example serves to illustrate how the epoxy-alcohol species 12 is converted (reduced) to an isomeric mixture of diol species 9a/9b (Step 503 ), in accordance with some embodiments of the present invention.
  • Isomeric mixture 9a/9b was prepared according to the procedure that follows.
  • the resulting two phase mixture (liquid layer+white precipitate) was filtered and the filtrate dried over MgSO 4 , then filtered again and concentrated to give an isomeric mixture of diol species 9a/9b as a white powder in 88% yield (41 grams).
  • the diols 9a and 9b were identified by spectral analysis (IR, NMR and GCMS). Note that epoxy methyl oleate was similarly reduced with lithium aluminum hydride according to the procedure above to give the diols 9a and 9b described above.
  • This Example serves to illustrate the synthesis of isomeric diester mixture 4a/4b, in accordance with some embodiments of the present invention.
  • the synthesis of octadecane-1,9-diyl dioctanoate/octadecane-1,10-diyl dioctanoate (4a/4b) was carried out via the esterification of diol mixture 9a/9b (Step 504 ) as follows.
  • the mixture was distilled under a vacuum of 10 mm Hg (Torr) to remove excess octanoic acid.
  • the desired diester product 4a/4b was obtained in 75% yield.
  • the lubrication and physical properties of diester product 4a/4b are shown in Table 1 ( FIG. 6 ).
  • the present invention provides for diester-based lubricant compositions comprising isomeric mixtures of diester species.
  • the present invention also provides for methods (processes) of making these and other similar lubricant compositions.
  • the methods for making such diester-based lubricants utilize a biomass-derived precursor comprising mono-unsaturated fatty acids and/or esters, wherein such mono-unsaturated fatty acids/esters are converted to one or more isomeric diol species en route to the synthesis of diester-based lubricant compositions. Subsequent steps on the path to such synthesis may employ carboxylic acids and/or acyl halides/anhydrides derived from biomass and/or Fischer-Tropsch synthesis.
  • at least the isomeric mixtures of diester species, of which the diester-based lubricant compositions are comprised are entirely bio-derived.

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BR112012000171A BR112012000171A2 (pt) 2009-07-07 2010-06-24 composição lubrificante, e, método
PCT/US2010/039809 WO2011005604A2 (en) 2009-07-07 2010-06-24 Synthesis of biolubricant esters from unsaturated fatty acid derivatives
MX2011013030A MX2011013030A (es) 2009-07-07 2010-06-24 Sintesis de esteres biolubricantes a partir de derivados de acidos grasos insaturados.
CN2010800283373A CN102471715A (zh) 2009-07-07 2010-06-24 由不饱和脂肪酸衍生物合成生物润滑酯
EP10797618A EP2451907A4 (en) 2009-07-07 2010-06-24 SYNTHESIS OF BIOFUEL ESTERS FROM DERIVATIVE UNSATURATED FATTY ACIDS
AU2010270827A AU2010270827B2 (en) 2009-07-07 2010-06-24 Synthesis of biolubricant esters from unsaturated fatty acid derivatives
US13/553,611 US8481465B2 (en) 2009-07-07 2012-07-19 Synthesis of biolubricant esters from unsaturated fatty acid derivatives
US13/553,658 US8507423B2 (en) 2009-07-07 2012-07-19 Synthesis of biolubricant esters from unsaturated fatty acid derivatives
US13/938,547 US9267090B2 (en) 2009-07-07 2013-07-10 Synthesis of biolubricant esters from unsaturated fatty acid derivatives

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CA2765723A1 (en) 2011-01-13
US8481465B2 (en) 2013-07-09
US8507423B2 (en) 2013-08-13
US20130296209A1 (en) 2013-11-07
EP2451907A4 (en) 2013-01-23
US20130017983A1 (en) 2013-01-17
MX2011013030A (es) 2012-02-08
AU2010270827B2 (en) 2015-03-26
US20120283160A1 (en) 2012-11-08
EP2451907A2 (en) 2012-05-16
CN102471715A (zh) 2012-05-23
AU2010270827A1 (en) 2012-01-19
BR112012000171A2 (pt) 2016-03-15
WO2011005604A2 (en) 2011-01-13
US9267090B2 (en) 2016-02-23

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