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WO2018191585A1 - Polyols, polyesters, polyuréthanes et matériaux polymères comprenant des résidus d'estolide - Google Patents

Polyols, polyesters, polyuréthanes et matériaux polymères comprenant des résidus d'estolide Download PDF

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Publication number
WO2018191585A1
WO2018191585A1 PCT/US2018/027432 US2018027432W WO2018191585A1 WO 2018191585 A1 WO2018191585 A1 WO 2018191585A1 US 2018027432 W US2018027432 W US 2018027432W WO 2018191585 A1 WO2018191585 A1 WO 2018191585A1
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Prior art keywords
estolide
occurrence
independently
acid
certain embodiments
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PCT/US2018/027432
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English (en)
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Jeremy Forest
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Biosynthetic Technologies, Llc
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Publication of WO2018191585A1 publication Critical patent/WO2018191585A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids

Definitions

  • the present disclosure relates to polyesters, polyurethanes, and other materials comprising estolide residues, and methods of making the same.
  • Exemplary compounds include high-viscosity estolide polyesters and oligomers, and polyurethanes derived from polyol estolides such as glycerol estolides, polyglycerol estolides, and variants thereof.
  • the compounds described herein may be useful as lubricants, lubricant additives, coatings, rigid or semi-rigid polymers, or foams.
  • estolide esters provide a synthetic, stable alternative to naturally-occurring ester oils that can be engineered for certain uses.
  • estolide esters having certain functional characteristics that make them suitable for use in a variety of commercial appications.
  • estolide compounds are selected from compounds of Formula I:
  • R.5 and R6, independently for each occurrence, are selected from hydrogen, R 7 , and a residue of Formula II:
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2;
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group; n is selected from 0 or greater than 0; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20; wherein at least one R 5 or R6 is a residue of Formula II.
  • the compound is selected from compounds according to Formula
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group; n is selected from 0 to 20; x is, independently for each occurrence, selected from 7 and 8; y is, independently for each occurrence, selected from 0 to 10; and z is selected from 0 to 19.
  • the compound is selected from compounds according to Formula
  • R.5 and R6, independently for each occurrence, are selected from hydrogen, R 7 , and a residue of Formula V:
  • Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group
  • R 7 is, independently for each occurrence, selected from optionally substituted alkyl and , wherein Rio is an optionally substituted alkyl, wherein at least one R 5 or Rs is a residue of Formula V, and wherein Formula IV and Formula V are independently optionally substituted.
  • the at least one compound is selected from compounds of Formulas Via, VIb, Vic, or VId:
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group;
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2; n is 0 or greater than 0; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20; wherein at least one R 5 is a residue of Formula II.
  • the at least one compound is selected from compounds of XI:
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group;
  • R2 is, independently for each occurrence, selected from hydrogen and an optionally substituted Ci to C20 alkanyl group and an optionally substituted Ci to C20 alkenyl group;
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2;
  • Y' is selected from O and N(R 2 ); n is 0 or greater than 0; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20.
  • composition comprises:
  • estolide compound comprising at least one hydroxyl group; and at least one reactive monomer.
  • the polymers and polymeric materials described herein comprise at least one residue of Formula XII:
  • Ri is a Ci to C20 alkyl group optionally substituted with one or more of Rn, wherein Rn is, independently for each occurrence, selected from hydroxyl and
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2;
  • Y' is selected from O and N(R 2 );
  • R12 is, independently for each occurrence, a residue selected from
  • the compounds and compositions described herein may exhibit suitable properties for use in a variety of applications, such as food (e.g., chocolate, baking, and confectionaries), cosmetics (e.g., lotions and sunscreens), and pharmaceuticals (e.g., active agents, excipients, formulation coatings, etc.).
  • food e.g., chocolate, baking, and confectionaries
  • cosmetics e.g., lotions and sunscreens
  • pharmaceuticals e.g., active agents, excipients, formulation coatings, etc.
  • the amphiphilic nature of such compounds may also make them suitable for use in industrial settings, such as additives in lubricants, greases, plastics, or industrial methods (e.g., oilfield drilling muds).
  • the compounds and compositions described herein may be useful emulsifiers (e.g., surfactants), and may be implemented to prepare water-in-oil (w/o) emulsions.
  • a dash (“-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent.
  • -C(0) H2 is attached through the carbon atom.
  • alkoxy by itself or as part of another substituent refers to a radical -OR 1 where R 1 is alkyl, cycloalkyl, cycloalkylalkyl, aryl, or arylalkyl, which can be substituted, as defined herein.
  • alkoxy groups have from 1 to 8 carbon atoms.
  • alkoxy groups have 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy, and the like.
  • Alkyl by itself or as part of another substituent refers to a saturated or unsaturated, branched, or straight-chain (linear) monovalent hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent alkane, alkene, or alkyne.
  • alkyl groups include, but are not limited to, methyl; ethyls such as ethanyl, ethenyl, and ethynyl; propyls such as propan-l-yl, propan-2-yl, prop-l-en-l-yl, prop-l-en-2-yl, prop-2-en-l-yl (allyl),
  • alkyl is specifically intended to include groups having any degree or level of saturation, i.e., groups having exclusively single carbon-carbon bonds, groups having one or more double carbon-carbon bonds, groups having one or more triple carbon-carbon bonds, and groups having mixtures of single, double, and triple carbon-carbon bonds.
  • degree or level of saturation i.e., groups having exclusively single carbon-carbon bonds, groups having one or more double carbon-carbon bonds, groups having one or more triple carbon-carbon bonds, and groups having mixtures of single, double, and triple carbon-carbon bonds.
  • alkanyl alkenyl
  • alkynyl are used.
  • an alkyl group comprises from 1 to 40 carbon atoms, in certain embodiments, from 1 to 22 or 1 to 18 carbon atoms, in certain embodiments, from 1 to 16 or 1 to 8 carbon atoms, and in certain embodiments from 1 to 6 or 1 to 3 carbon atoms.
  • an alkyl group comprises from 8 to 22 carbon atoms, in certain embodiments, from 8 to 18 or 8 to 16.
  • the alkyl group comprises from 3 to 20 or 7 to 17 carbons.
  • the alkyl group comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 carbon atoms.
  • Aryl by itself or as part of another substituent refers to a monovalent aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system.
  • Aryl encompasses 5- and 6-membered carbocyclic aromatic rings, for example, benzene; bicyclic ring systems wherein at least one ring is carbocyclic and aromatic, for example, naphthalene, indane, and tetralin; and tricyclic ring systems wherein at least one ring is carbocyclic and aromatic, for example, fluorene.
  • Aryl encompasses multiple ring systems having at least one carbocyclic aromatic ring fused to at least one carbocyclic aromatic ring, cycloalkyl ring, or heterocycloalkyl ring.
  • aryl includes 5- and 6-membered carbocyclic aromatic rings fused to a 5- to 7-membered non-aromatic heterocycloalkyl ring containing one or more heteroatoms chosen from N, O, and S.
  • bicyclic ring systems wherein only one of the rings is a carbocyclic aromatic ring, the point of attachment may be at the carbocyclic aromatic ring or the heterocycloalkyl ring.
  • aryl groups include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexalene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene, and the like.
  • an aryl group include, but are
  • an aryl group can comprise 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
  • Aryl does not encompass or overlap in any way with heteroaryl, separately defined herein.
  • a multiple ring system in which one or more carbocyclic aromatic rings is fused to a heterocycloalkyl aromatic ring is heteroaryl, not aryl, as defined herein.
  • Arylalkyl by itself or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced with an aryl group.
  • arylalkyl groups include, but are not limited to, benzyl, 2-phenylethan-l-yl, 2-phenylethen-l-yl, naphthylmethyl, 2-naphthylethan-l-yl,
  • an arylalkyl group is C7-30 arylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the arylalkyl group is Ci-10 and the aryl moiety is C 6 -2o, and in certain embodiments, an arylalkyl group is C7-20 arylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the arylalkyl group is C 1-8 and the aryl moiety is G5-12.
  • Compounds refers to compounds and residues encompassed by structural Formula I- XII herein and includes any specific compounds within the formula whose structure is disclosed herein. Compounds may be identified either by their chemical structure and/or chemical name. When the chemical structure and chemical name conflict, the chemical structure is determinative of the identity of the compound.
  • the compounds described herein may contain one or more chiral centers and/or double bonds and therefore may exist as stereoisomers such as double-bond isomers (i.e., geometric isomers), enantiomers, or diastereomers.
  • any chemical structures within the scope of the specification depicted, in whole or in part, with a relative configuration encompass all possible enantiomers and stereoisomers of the illustrated compounds including the stereoisomerically pure form (e.g., geometrically pure, enantiomerically pure, or diastereomerically pure) and enantiomeric and stereoisomeric mixtures.
  • Enantiomeric and stereoisomeric mixtures may be resolved into their component enantiomers or stereoisomers using separation techniques or chiral synthesis techniques well known to the skilled artisan.
  • chiral compounds are compounds having at least one center of chirality (i.e. at least one asymmetric atom, in particular at least one asymmetric C atom), having an axis of chirality, a plane of chirality or a screw structure.
  • Achiral compounds are compounds which are not chiral.
  • Compounds and residues of Formula I-XII include, but are not limited to, optical isomers of compounds and residues of Formula I-XII, racemates thereof, and other mixtures thereof.
  • the single enantiomers or diastereomers, i.e., optically active forms can be obtained by asymmetric synthesis or by resolution of the racemates. Resolution of the racemates may be accomplished by, for example, chromatography, using, for example a chiral high-pressure liquid chromatography (UPLC) column.
  • UPLC chiral high-pressure liquid chromatography
  • Formula I-XII cover all asymmetric variants of the compounds described herein, including isomers, racemates, enantiomers, diastereomers, and other mixtures thereof.
  • compounds of Formula I-XII include Z- and E-forms ⁇ e.g., cis- and trans-forms) of compounds with double bonds.
  • the compounds of Formula I-XII may also exist in several tautomeric forms including the enol form, the keto form, and mixtures thereof. Accordingly, the chemical structures depicted herein encompass all possible tautomeric forms of the illustrated compounds.
  • Cycloalkyl by itself or as part of another substituent refers to a saturated or unsaturated cyclic alkyl radical. Where a specific level of saturation is intended, the nomenclature
  • cycloalkanyl or “cycloalkenyl” is used.
  • cycloalkyl groups include, but are not limited to, groups derived from cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like.
  • a cycloalkyl group is C3-15 cycloalkyl, and in certain embodiments, C3-12 cycloalkyl or C5-12 cycloalkyl.
  • a cycloalkyl group is a C5, C 6 , C 7 , C 8 , C9, Cio, C11, C12, Ci3, Ci4, or C15 cycloalkyl.
  • Cycloalkylalkyl by itself or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced with a cycloalkyl group. Where specific alkyl moieties are intended, the nomenclature cycloalkylalkanyl, cycloalkylalkenyl, or cycloalkylalkynyl is used.
  • a cycloalkylalkyl group is C7-30 cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the cycloalkylalkyl group is Ci-10 and the cycloalkyl moiety is C 6 -2o, and in certain embodiments, a cycloalkylalkyl group is C7-20 cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the cycloalkylalkyl group is C 1-8 and the cycloalkyl moiety is C4-20 or C 6 -i2.
  • Halogen refers to a fluoro, chloro, bromo, or iodo group.
  • Heteroaryl by itself or as part of another substituent refers to a monovalent
  • heteroaromatic radical derived by the removal of one hydrogen atom from a single atom of a parent heteroaromatic ring system.
  • Heteroaryl encompasses multiple ring systems having at least one aromatic ring fused to at least one other ring, which can be aromatic or non-aromatic in which at least one ring atom is a heteroatom.
  • Heteroaryl encompasses 5- to 12-membered aromatic, such as 5- to 7-membered, monocyclic rings containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3, heteroatoms chosen from N, O, and S, with the remaining ring atoms being carbon; and bicyclic heterocycloalkyl rings containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3, heteroatoms chosen from N, O, and S, with the remaining ring atoms being carbon and wherein at least one heteroatom is present in an aromatic ring.
  • heteroaryl includes a 5- to 7-membered heterocycloalkyl, aromatic ring fused to a 5- to 7- membered cycloalkyl ring.
  • bicyclic heteroaryl ring systems wherein only one of the rings contains one or more heteroatoms, the point of attachment may be at the heteroaromatic ring or the cycloalkyl ring.
  • the heteroatoms are not adjacent to one another.
  • the total number of N, S, and O atoms in the heteroaryl group is not more than two. In certain embodiments, the total number of N, S, and O atoms in the aromatic heterocycle is not more than one. Heteroaryl does not encompass or overlap with aryl as defined herein.
  • heteroaryl groups include, but are not limited to, groups derived from acridine, arsindole, carbazole, ⁇ -carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline,
  • a heteroaryl group is from 5- to 20-membered heteroaryl, and in certain embodiments from 5- to 12- membered heteroaryl or from 5- to 10-membered heteroaryl.
  • a heteroaryl group is a 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16-, 17-, 18-, 19-, or 20-membered heteroaryl.
  • heteroaryl groups are those derived from thiophene, pyrrole,
  • benzothiophene benzofuran, indole, pyridine, quinoline, imidazole, oxazole, and pyrazine.
  • Heteroarylalkyl by itself or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced with a heteroaryl group. Where specific alkyl moieties are intended, the nomenclature heteroarylalkanyl, heteroarylalkenyl, or heteroarylalkynyl is used.
  • a heteroarylalkyl group is a 6- to 30-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the heteroarylalkyl is 1- to 10-membered and the heteroaryl moiety is a 5- to 20-membered heteroaryl, and in certain embodiments, 6- to 20-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the heteroarylalkyl is 1- to 8-membered and the heteroaryl moiety is a 5- to 12-membered heteroaryl.
  • Heterocycloalkyl by itself or as part of another substituent refers to a partially saturated or unsaturated cyclic alkyl radical in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced with the same or different heteroatom.
  • heteroatoms to replace the carbon atom(s) include, but are not limited to, N, P, O, S, Si, etc. Where a specific level of saturation is intended, the nomenclature “heterocycloalkanyl” or “heterocycloalkenyl” is used.
  • heterocycloalkyl groups include, but are not limited to, groups derived from epoxides, azirines, thiiranes, imidazolidine, morpholine, piperazine, piperidine, pyrazolidine, pyrrolidine, quinuclidine, and the like.
  • Heterocycloalkylalkyl by itself or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced with a heterocycloalkyl group. Where specific alkyl moieties are intended, the nomenclature heterocycloalkylalkanyl, heterocycloalkylalkenyl, or
  • heterocycloalkylalkynyl is used.
  • a heterocycloalkylalkyl group is a 6- to 30-membered heterocycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the heterocycloalkylalkyl is 1- to 10-membered and the heterocycloalkyl moiety is a 5- to 20-membered heterocycloalkyl, and in certain embodiments, 6- to 20-membered heterocycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the heterocycloalkylalkyl is 1- to 8-membered and the heterocycloalkyl moiety is a 5- to 12-membered heterocycloalkyl.
  • Matture refers to a collection of molecules or chemical substances. Each component in a mixture can be independently varied. A mixture may contain, or consist essentially of, two or more substances intermingled with or without a constant percentage composition, wherein each component may or may not retain its essential original properties, and where molecular phase mixing may or may not occur. In mixtures, the components making up the mixture may or may not remain distinguishable from each other by virtue of their chemical structure.
  • Parent aromatic ring system refers to an unsaturated cyclic or polycyclic ring system having a conjugated ⁇ (pi) electron system. Included within the definition of "parent aromatic ring system” are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, fluorene, indane, indene, phenalene, etc. Examples of parent aromatic ring systems include, but are not limited to, aceanthrylene,
  • acenaphthylene acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexalene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,
  • Parent heteroaromatic ring system refers to a parent aromatic ring system in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced with the same or different heteroatom.
  • heteroatoms to replace the carbon atoms include, but are not limited to, N, P, O, S, Si, etc. Specifically included within the definition of "parent
  • heteroaromatic ring systems are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, arsindole, benzodioxan, benzofuran, chromane, chromene, indole, indoline, xanthene, etc.
  • parent heteroaromatic ring systems include, but are not limited to, arsindole, carbazole, ⁇ -carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole,
  • Substituted refers to a group in which one or more hydrogen atoms are independently replaced with the same or different substituent(s).
  • heterocycloalkyl substituted heterocycloalkyl, heteroaryl, substituted heteroaryl, heteroarylalkyl, or substituted heteroarylalkyl, or R 62 and R 63 together with the atom to which they are bonded form one or more heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, or substituted heteroaryl rings; wherein the "substituted" substituents, as defined above for R 60 , R 61 , R 62 , and R 63 , are substituted with one or more, such as one, two, or three, groups independently selected from alkyl, - alkyl-OH, -O-haloalkyl, -alkyl-NH 2 , alkoxy, cycloalkyl, cycloalkylalkyl, heterocycloalkyl, heterocycloalkylalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, -O " , -OH,
  • fatty acid refers to any natural or synthetic carboxylic acid comprising an alkyl chain that may be saturated, monounsaturated, or polyunsaturated, and may have straight (linear) or branched chains. The fatty acid may also be substituted.
  • “Fatty acid,” as used herein, includes short chain alkyl carboxylic acid including, for example, acetic acid, propionic acid, etc.
  • the present disclosure relates to polylols, polyesters, and polyurethane compounds comprising estolide residues, and methods of making the same.
  • the compounds comprise glycerol estolides and polyglycerol estolides that may be useful as components or additives of lubricants, industrial compositions, personal care and pharmaceutical products.
  • the compounds described herein may comprise one or more hydroxyl groups, making them useful starting materials for emulsifiers, additives, high-viscisity base oils, or for making polymeric materials such as coatings and foams.
  • the present disclosure relates to new methods of preparing estolide compounds exhibiting such properties.
  • the compound is selected from compounds of Formula I:
  • R.5 and R6, independently for each occurrence, are selected from hydrogen, R 7 , and a residue of Formula II:
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2;
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group; n is selected from 0 to 20; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20; wherein at least one R5 or 5 is a residue of Formula II.
  • the compound is selected from compounds according to Formula
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group; n is selected from 0 to 20; x is, independently for each occurrence, selected from 7 and 8; y is, independently for each occurrence, selected from 0 to 10; and z is selected from 0 to 19.
  • the compound is selected from compounds according to Formula
  • R5 and R5 independently for each occurrence, are selected from hydrogen, R7, and a residue of Formula V:
  • Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group
  • the at least one compound is selected from compounds of Formulas Via, VIb, Vic, or VId:
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group;
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2; n is 0 or greater than 0; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20; wherein at least one R5 is a residue of Formula II.
  • the compounds described herein comprise at least one compound of Formula XI:
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group;
  • R2 is, independently for each occurrence, selected from hydrogen and an optionally substituted Ci to C20 alkanyl group and an optionally substituted Ci to C20 alkenyl group;
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2;
  • Y' is selected from O and N(R 2 ); n is 0 or greater than 0; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20.
  • the compsition comprises: an estolide compound comprising at least one hydroxyl group; and at least one reactive monomer.
  • the polymers and polymeric materials described herein comprise at least one residue of Formula XII:
  • Ri is a Ci to C20 alkyl group optionally substituted with one or more of Rn, wherein Rn is, independently for each occurrence, selected from hydroxyl and
  • R 8 and R9 are, independently for each occurrence, selected from hydrogen, hydroxyl,
  • Y and X' are, independently for each occurrence, selected from C(Rs>) 2 ;
  • Y' is selected from O and N(R 2 );
  • Ri 2 is, independently for each occurrence, a residue selected from n is 0 or greater than 0; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20.
  • the composition comprises at least one compound or residue according to Formulas I-XII, wherein Ri is hydrogen.
  • chain or “fatty acid chain” or “fatty acid residue” or “chain residue” or “fatty acid chain residue” as used with respect to the compounds of Formulas I-X refer to one or more of the fatty acid residues comprising substituents of Formulas V, VII, and X, e.g., the structures represented by CH 3 (CH2) y CH(CH 2 )xC(0)0-.
  • the residues RiC(0)0- in Formulas II, III, V, VII, X, XI, and XII at the top of each Formula shown is an example of what may be referred to as “caps” or “capping materials,” as it “caps” the top of the estolide substituent.
  • the "caps” or “capping groups” are fatty acids.
  • the capping group may be an organic acid residue of general formula - OC(0)-alkyl, i.e., a carboxylic acid with an substituted or unsubstituted, saturated or unsaturated, and/or branched or unbranched alkyl as defined herein.
  • the capping groups regardless of size, are substituted or unsubstituted, saturated or unsaturated, and/or branched or unbranched (linear).
  • the caps or capping materials may also be referred to as the primary or alpha (a) chains.
  • the estolides are described as "poly-capped,” wherein the compounds comprise two or more primary chains.
  • the caps may be the only residues in the resulting estolide that are unsaturated.
  • Epoxidizing, sulfurizing, and/or hydrogenating may be used with various sources of the fatty-acid feedstock, which may include mono- and/or polyunsaturated fatty acids.
  • epoxidizing the estolide residue of the estolide may help to improve the solubility and/or miscibility of the compound in certain compositions, such as those containing polymeric materials.
  • epoxidizing an estolide substituent may provide for an intermediate
  • the epoxide residue may be opened by reacting it with one or more compounds or compositions.
  • the epoxide residue of an epoxy estolide substituent is opened to provide a mono-hydroxy estolide or a dihydroxy estolide.
  • exposing an epoxy estolide residue to aqueous acid conditions will provide a dihydroxy estolide.
  • reacting an epoxy estolide residue with an alcohol (e.g., fatty alcohol) under acidic conditions will provide a mono-hydroxy estolide substituted with an alkoxy group.
  • the epoxide residue may be opened by reacting the epoxy estolide residue with a carboxylic acid (e.g., fatty acid) to provide the mono-hydroxy estolide.
  • estolides having free hydroxy groups may be acylated to provide poly-capped estolides.
  • estolides having a plurality of -OH residues that can be used for further functionalization.
  • unsaturated fatty acids e.g., oleic acid, linoleic acid
  • oleic acid e.g., oleic acid, linoleic acid
  • oligomerization e.g., hydroxylated (polyol) free-acid estolides
  • estolides can then be optionally esterified with glycerol or polyglycerols to provide estolide polyol esters having -OH residues on both the glycerol/polyglycerol backbone and the estolide residue.
  • An exemplary synthesis of such compounds is set forth in Scheme 3, with glycerol/polyglycerol esterification subsequently taking place according to the procedures of Scheme 2.
  • Such compounds are generally encompassed by the compounds of Formula I.
  • the resulting compounds of Scheme 3 may be esterified with other types of monoalcohols or polyols to yield different functionalities, which would be generally encompassed by compounds of Formula XI.
  • CH (CH 2 ) y CH(CH 2 ) x C(0)0- of Formula V, VII, and X represent the "base” or "base chain residue" of the estolide substituent.
  • the base organic acid or fatty acid residue may initially remain in its free-acid form during the early stages of the compounds synthesis (i.e., free-acid estolide formation).
  • the free-acid estolide may be condensed with one or more hydroxy residues of a polyol to form the estolide polyol ester.
  • the estolide polyol ester may be prepared by condensing a free fatty acid (e.g., hydroxylated or unsaturated) with the free hydroxy group(s) of a polyol to form a polyol ester.
  • additional fatty acids may be added to the fatty acid residues of the polyol ester via, e.g., sites of hydroxylation or unsaturation, to provide an estolide polyol ester.
  • the base or base chain residue may also be referred to as tertiary or gamma ( ⁇ ) chains.
  • the structure CH (CH 2 ) y CH(CH 2 )xC(0)0- of Formula V, VII, and X represent linking residues that link the capping material and the base fatty-acid residue of the estolide substituent.
  • a linking residue may be a fatty acid and may initially be in an unsaturated form during synthesis.
  • the estolide will be formed when a catalyst is used to produce a carbocation at the fatty acid's site of unsaturation, which is followed by nucleophilic attack on the carbocation by the carboxylic group of another fatty acid.
  • the formation of the carbocation will result in a mixture of estolide isomers, wherein the bond between two fatty acid residues takes place at one of two available carbon linking sites (e.g., estolide linkage at primarily the (18: 1 n-9) and (18: 1 n-10) positions of oleic acid residues).
  • polyunsaturated fatty acids may provide multiple carbocations for the addition of two or more fatty acids to the polyunsaturated residue to provide, for example, poly-capped estolide substituents.
  • the linking residue(s) may also be referred to as secondary or beta ( ⁇ ) chains.
  • suitable unsaturated fatty acids for preparing the polyol estolides may include any mono- or polyunsaturated fatty acid.
  • suitable unsaturated fatty acids for preparing the polyol estolides may include any mono- or polyunsaturated fatty acid.
  • monounsaturated fatty acids along with a suitable catalyst, will form a single carbocation of the addition of a second fatty acid, whereby a single link between two fatty acids (e.g., between ⁇ -chain and ⁇ -chain, and ⁇ -chain and a-chain) is formed.
  • Suitable monounsaturated fatty acids may include, but are not limited to, palmitoleic (16: 1), vaccenic (18: 1), oleic acid (18: 1), eicosenoic acid (20: 1), erucic acid (22: 1), and nervonic acid (24: 1).
  • polyunsaturated fatty acids may be used to create estolides.
  • Suitable polyunsaturated fatty acids may include, but are not limited to, hexadecatrienoic acid (16:3), alpha-linolenic acid (18:3), stearidonic acid (18:4), eicosatrienoic acid (20:3), eicosatetraenoic acid (20:4), eicosapentaenoic acid (20:5),
  • heneicosapentaenoic acid (21 :5), docosapentaenoic acid (22:5), docosahexaenoic acid (22:6), tetracosapentaenoic acid (24:5), tetracosahexaenoic acid (24:6), linoleic acid (18:2), gamma-linoleic acid (18:3), eicosadienoic acid (20:2), dihomo-gamma-linolenic acid (20:3), arachidonic acid (20:4), docosadienoic acid (20:2), adrenic acid (22:4), docosapentaenoic acid (22:5), tetracosatetraenoic acid (22:4), tetracosapentaenoic acid (24:5), pinolenic acid (18:3), podocarpic acid (20:3), rumenic acid (18
  • hydroxy fatty acids may be polymerized or homopolymerized by reacting the carboxylic acid functionality of one fatty acid with the hydroxy functionality of a second fatty acid.
  • exemplary hydroxyl fatty acids include, but are not limited to, ricinoleic acid, 6- hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxy stearic acid, 9, 10-dihydroxy stearic acid, 12- hydroxy stearic acid, and 14-hydroxy stearic acid.
  • the resulting estolide polyol ester may comprise unsaturated chains and/or chains substituted with two or more fatty acids.
  • preparing a estolides from linoleic and/or linolenic acid can result in estolide substituents having two or more caps.
  • linoleic and/or linolenic acid is reacted with an organic and/or fatty acid to provide an estolide substituent having two or more caps.
  • the organic and/or fatty acid cap comprises a C1-C40 alkyl residue.
  • the organic acid cap is acetic acid.
  • the fatty acid cap comprises a C7-C17 alkyl residue.
  • the process for preparing the estolide compounds described herein may include the use of any natural or synthetic fatty acid source.
  • Suitable starting materials of biological origin may include plant fats, plant oils, plant waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, algal oils and mixtures thereof.
  • Other potential fatty acid sources may include waste and recycled food-grade fats and oils, fats, oils, and waxes obtained by genetic engineering, fossil fuel based materials and other sources of the materials desired.
  • the estolide compounds described herein may be prepared from non-naturally occurring fatty acids derived from naturally occurring feedstocks.
  • the estolides are prepared from synthetic fatty acid reactants derived from naturally occurring feedstocks such as vegetable oils.
  • the synthetic fatty acid reactants may be prepared by cleaving fragments from larger fatty acid residues occurring in natural oils such as triglycerides using, for example, a cross-metathesis catalyst and alpha-olefin(s). The resulting truncated fatty acid residue(s) may be liberated from the glycerine backbone using any suitable hydrolytic and/or transesterification processes known to those of skill in the art.
  • An exemplary fatty acid reactant includes 9-dodecenoic acid, which may be prepared via the cross metathesis of an oleic acid residue with 1-butene.
  • the estolide may be prepared from fatty acids having a terminal site of unsaturation (e.g., 9-decenoic acid), which may be prepared via the cross metathesis of an oleic acid residue with ethene.
  • the estolide polyol ester is prepared by reacting at least one polyol with at least one estolide compound, such as a free acid estolide compound.
  • the esterification of the polyol may occur via transesterification, wherein the polyol is contacted with estolide ester, such as an estolide methyl ester, in the presence of a catalyst.
  • the estolide polyol ester is prepared by contacting at least one polyol ester comprising one or more fatty acid residues having at least one reactive site.
  • one or more fatty acid residues of the polyol ester will comprise a reactive site that allows for the formation of an estolide residue when contacted with one or more free fatty acids.
  • Exemplary methods of preparing the estolide polyol esters are set forth in Schemes 1-3.
  • suitable polyols include glycerine and polyglycerine variants.
  • the polyols are selected from compounds of Formula VIII:
  • the polyol is a polyglycerol variant selected from one of the following heteroalkyl or heterocycloalkyl structures:
  • the polyol comprises other heterocycloalkyl or heteroalkyl strucutres.
  • Exemplary polyols include, but are not limited to sugars (e.g., ribose, glucose, fructose, galactose, mannose, sorbitol), ethylene glycol, polyethylene glycols (e.g., PEGs 200, 300, 400, 600, 1000, 540, 1450, 3350, 4000, 4600, 8000), polypropylene glycols, etc.
  • sugars e.g., ribose, glucose, fructose, galactose, mannose, sorbitol
  • ethylene glycol e.g., polyethylene glycols (e.g., PEGs 200, 300, 400, 600, 1000, 540, 1450, 3350, 4000, 4600, 8000), polypropylene glycols, etc.
  • polyglycerols having one or more oxygens present in the core chain of the polyol appear to impart improved properties (e.g., polarity, compatibility,
  • estolide polyol ester when compared to other estolide polyol ester compounds prepared from polyols that do not contain heteroatoms in the core chain (e.g., propanediols, butanediols, trimethylolpropane, pentaerythritol etc.).
  • heteroatoms in the core chain e.g., propanediols, butanediols, trimethylolpropane, pentaerythritol etc.
  • the compounds described herein have varying structures, wherein R 5 and R6, independently for each occurrence, are selected from hydrogen, R 7 , and residues of Formulas II and V. In certain embodiments, at least one of R 5 or Rs is a residue of Formula II or V.
  • R7 and Rio are unb substituted, and are branched or unbranched (linear).
  • at least one 5 is a residue of Formula II or Formula V, and each R 5 is independently selected from hydrogen and R7.
  • R7 and Rio independently for each occurrence, are selected from Ci alkyl, C2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, C 7 alkyl, C 8 alkyl, C 9 alkyl, C10 alkyl, Cn alkyl, C12 alkyl, C 13 alkyl, C14 alkyl, C15 alkyl, Ci6 alkyl, C 17 alkyl, Ci 8 alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22 alkyl, C2 3 alkyl, and C24 alkyl, wherein the alkyl groups are akanyl or alkenyl, branched or unbranched, and optionally substituted.
  • the estolide comprises fatty-acid chains of varying lengths.
  • x is, independently for each occurrence, an integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1 to 10, 2 to 8, 6 to 8, 7 to 10, or 4 to 6.
  • x is, independently for each occurrence, an integer selected from 7 and 8.
  • x is, independently for each occurrence, an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
  • x is an integer selected from 7 and 8.
  • y is, independently for each occurrence, an integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1 to 10, 2 to 8, 5 to 8, 6 to 8, or 4 to 6. In some embodiments, y is, independently for each occurrence, an integer selected from 7 and 8. In some embodiments, y is, independently for each occurrence, an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. In some embodiments, for at least one fatty acid chain residue, y is an integer selected from 0 to 6, or 1 and 2. In certain embodiments, y is, independently for each occurrence, an integer selected from 1 to 6, or 1 and 2. In certain embodiments, y is 0.
  • x+y is, independently for each chain, an integer selected from 0 to 40, 0 to 20, 10 to 20, or 12 to 18. In some embodiments, x+y is, independently for each chain, an integer selected from 13 to 15. In some embodiments, x+y is 15 for each chain. In some
  • x+y is, independently for each chain, an integer selected from 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24. In certain embodiments, for at least one fatty acid chain residue, x+y is an integer selected from 9 to 13. In certain embodiments, for at least one fatty acid chain residue, x+y is 9. In certain embodiments, x+y is, independently for each chain, an integer selected from 9 to 13. In certain embodiments, x+y is 9 for each fatty acid chain residue. In certain embodiments, x is 7 and y is 0, wherein x+y is 7. .
  • z is selected from 0 to 20, 1 to 19, 1 to 11, and 1 to 5. In certain embodiments, z is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. In certain embodiments, z is selected from 1 to 10. In certain embodiments, z is selected from 1 and 2.
  • n is, independently for each occurrence, an integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 0 to 12, 0 to 10, 0 to 8, or 0 to 6. In some embodiments, n is, independently for each occurrence, an integer selected from 0 to 4. In some embodiments, n is 0 for each occurrence. In some embodiments, n is, independently for each occurrence, an integer that is equal to or greater than 1. In some embodiments, n is, independently for each occurrence, an integer selected from 1 to 12, 1 to 8, or 1 to 4. In some embodiments, n is, independently for each occurrence, an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12.
  • Y and X' are, independently for each occurrence, selected from
  • R 8 is hydrogen for each occurrence.
  • at least one R9 is -OH.
  • at least one R9 is -OH for each fatty acid chain.
  • Y and X' are CH 2 for each occurrence.
  • n is, independently for each occurrence, an integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 0 to 12, 0 to 10, 0 to 8, or 0 to 6. In some embodiments, n is, independently for each occurrence, an integer selected from 0 to 4. In some embodiments, n is 0 for each occurrence. In some embodiments, n is, independently for each occurrence, an integer that is equal to or greater than 1. In some embodiments, n is, independently for each occurrence, an integer selected from 1 to 12, 1 to 8, or 1 to 4. In some embodiments, n is, independently for each occurrence, an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, and 12.
  • estolide polyol ester compounds described herein may comprise more than one estolide residue per molecule (e.g., R 5 and R6 comprise residues of Formula II).
  • compositions described herein may comprise estolide polyol ester compounds, wherein each compound comprises different estolide residues.
  • estolide polyol ester compounds wherein each compound comprises different estolide residues.
  • composition' s measured estolide number (EN).
  • EN of an estolide polyol ester represents the average number of fatty acids added to base fatty acids comprising said estolide polyol ester or mixture thereof.
  • EN also represents the average number of estolide linkages per molecule. For example, with respect to the estolide residue of Formula II:
  • a estolide polyol ester may have an EN that is a whole number or a fraction of a whole number.
  • a estolide polyol ester having a 1 : 1 ratio of dimer and trimer would have an EN of 1.5
  • a estolide polyol ester having a 1 : 1 molar ratio of tetramer and trimer would have an EN of 2.5
  • a composition comprising the following polyol estolides would have an EN of 1.5, representing the average number of linkages amongst polyol estolide Compounds A and B in the composition:
  • the compositions may comprise a mixture of two or more estolide polyol esters having an EN that is an integer or fraction of an integer that is greater than or equal to 1.
  • the EN may be an integer or fraction of an integer selected from about 1.0 to about 5.0.
  • the EN is an integer or fraction of an integer selected from 1.2 to about 4.5.
  • the estolide compounds described herein will be in there trimer form or larger, wherein the EN is greater than or equal to 2.
  • the EN is selected from an integer or fraction of an integer that is from about 2.0 to about 3.0, or from about 2.2 to about 2.8.
  • the EN is selected from an integer or fraction of an integer that is less than or equal to 2, or less than or equal to 1.5. In certain embodiments, the EN is selected from an integer or fraction of an integer that is from about 1 to about 1.5, such as about 1.0 to about 1.3. In some embodiments, the EN is selected from a value greater than 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.0.
  • the EN is selected from a value less than 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.0.
  • altering the EN produces estolides having the desired viscometric properties while substantially retaining or even reducing pour point.
  • estolide polyol esters exhibit a decreased pour point upon increasing the EN value.
  • a method is provided for retaining or decreasing the pour point of polyol estolide ester by increasing the EN of the oil, or a method is provided for retaining or decreasing the pour point of a composition comprising a estolide polyol ester by increasing the EN of the base oil.
  • the method comprises: selecting an estolide polyol ester having an initial EN and an initial pour point; and removing at least a portion of the estolide polyol ester, said portion exhibiting an EN that is less than the initial EN of the estolide polyol ester, wherein the resulting estolide polyol ester exhibits an EN that is greater than the initial EN of the base oil, and a pour point that is equal to or lower than the initial pour point of the base oil.
  • the selected estolide polyol ester is prepared by a process that includes oligomerizing at least one first unsaturated fatty acid with at least one second unsaturated fatty acid and/or saturated fatty acid.
  • the removing at least a portion of the estolide polyol ester is accomplished by distillation, chromatography, membrane separation, phase separation, affinity separation, or combinations thereof.
  • the distillation takes place at a temperature and/or pressure that is suitable to separate the estolide polyol ester into different "cuts" that individually exhibit different EN values. In some embodiments, this may be accomplished by subjecting the estolide polyol ester to a temperature of at least about 250°C and an absolute pressure of no greater than about 25 microns.
  • the distillation takes place at a temperature range of about 250°C to about 310°C and an absolute pressure range of about 10 microns to about 25 microns.
  • the estolide polyol ester compounds may exhibit glycerol/polyglycerol chain residues that exhibit differing degrees of polymerization, which may be expressed as a "glycerol number" or simply "GN", as represented by the formula z+l .
  • glycerol number or simply "GN”
  • GN glycerol number
  • a composition comprising two estolide polyol ester compounds comprising triglycerol and tetraglycerol residues, respectively would exhibit a GN of 2.5 for the composition.
  • the compositions described herein exhibit a GN of at least 2, wherein GN is the average number of glycerol residues z+l for compounds of Formula II contained in the composition.
  • the GN is about 2 to about 7.
  • the GN is about 2.5 to about 4.
  • the GN is about 2.6 to about 3.6.
  • Ri independently for each occurrence, is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • the alkyl group is a Ci to C40 alkyl, Ci to C22 alkyl or Ci to C 17 alkyl.
  • the alkyl group is selected from C7 to C 17 alkyl, C to C 13 alkyl, or C5 to Cn alkyl.
  • each Ri is independently selected from Ci alkyl, C 2 alkyl, C alkyl, C4 alkyl, C5 alkyl, C 6 alkyl, C7 alkyl, C 8 alkyl, C 9 alkyl, C10 alkyl, Cn alkyl, C12 alkyl, C 13 alkyl, C 14 alkyl, C 15 alkyl, C 16 alkyl, C17 alkyl, C 18 alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22 alkyl, C2 3 alkyl, and C24 alkyl. In some embodiments, each Ri is independently selected from Ci alkyl, C 2 alkyl, C alkyl, C4 alkyl, C5 alkyl, C 6 alkyl, C7 alkyl, C 8 alkyl, C 9 alkyl, C10 alkyl, Cn alkyl, C12 alkyl, C 13 alkyl, C 14 alkyl, C 15 alkyl, C 16 alkyl
  • Ri is methyl. In some embodiments, Ri is independently selected from C 13 to C 17 alkyl, such as from C 13 alkyl, C15 alkyl, and C 17 alkyl. In certain embodiments, Ri is unsubstituted. In certain embodiments, Ri is substituted with at least one -OH group. In certain embodiments Ri is, independently for each occurrence, selected from hydrogen and a Ci to C20 alkyl group optionally substituted with Rn, wherein Rn is, independently for each occurrence, selected from hydroxyl and
  • R2 of Formulas VII, X, and XI is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • the alkyl group is a Ci to C40 alkyl, Ci to C22 alkyl or Ci to Ci 8 alkyl.
  • the alkyl group is selected from C7 to Cn alkyl.
  • R2 is selected from C7 alkyl, C9 alkyl, Cn alkyl, C 13 alkyl, C15 alkyl, and C 17 alkyl.
  • R2 is selected from C 13 to C 17 alkyl, such as from C 13 alkyl, C15 alkyl, and C 17 alkyl.
  • R2 is a Ci, C 2 , C , C 4 , C5, C 6 , C 7 , C 8 , C9, Cio, Cn, C12, C 13 , Ci4, Ci5, Ci6, Cn, Ci 8 , Ci9, C20, C21, or C22 alkyl.
  • R2 is unsubstituted.
  • Ri is substituted with at least one -OH group.
  • estolide polyol esters comprising: providing one or more estolide oligomers, wherein the one or more estolide oligomers are derived from a process that includes reacting a first fatty acid with the double bond of a second fatty acid; and esterifying a polyol with the one or more estolide oligomers to provide an estolide polyol ester.
  • one or more estolide oligomers comprise at least one oleic- based estolide oligomer.
  • the one or more estolide oligomers are selected from compounds of Formula VII:
  • Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group
  • R 2 is selected from hydrogen, an optionally substituted alkanyl group, and an optionally substituted alkenyl group;
  • the addition of the estolide oligomer may occur in the presence of a catalyst via a simple condensation reaction (i.e., wherein R 2 is hydrogen). In certain embodiments, the addition of the estolide oligomer may occur in the presence of a catalyst via a transesterification reaction (e.g., wherein R 2 comprises an ethyl group). In certain embodiments, the esterifying is conducted in the presence of a heat greater than 50°C. In certain embodiments, the polyol is selected from at least one of a glycerol or a polyglycerol.
  • the polyclycerol is selected from compounds of Formula VIII and Formula IXa-d.
  • Exemplary polyglycerols include, but are not limited to, di glycerols, tri glycerols, tetraglycerols, pentaglycerols, hexaglycerols, heptaglycerols, octaglycerols, nonaglycerols, decaglycerols, etc., including polyglycerol
  • the estolide polyol ester compounds described herein may be suitable for use as an additive (e.g., emulsifier) in a composition comprising at least one additional component.
  • the at least one additional component is selected from fatty alcohols, fatty esters, natural esters, synthetic esters, or hydrocarbons.
  • the at least one additional component is selected from lecithins, saccharides, celluloses, alginates, glycerides, and gums.
  • the composition comprises an emulsion.
  • the emulsion comprises a water-in-oil (W/O) emulsion.
  • the at least one additional component comprises an estolide base oil.
  • the estolide base oil does not comprise an estolide polyol ester.
  • the estolide base oil may be selected from compounds of Formula X, wherein R 2 is comprises hydrogen or an unsubstituted alkyl group:
  • Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group
  • R 2 is selected from hydrogen, an unsubstituted alkanyl group, and an unsubstituted alkenyl group;
  • each fatty acid chain residue is independently optionally substituted.
  • estolide polyol esters of Formulas I, III, IV, and VI may serve as useful W/O emulsifiers for compositions comprising water and estolide base oils of Formula X.
  • the compounds described herein may be suitable for use as emulsifiers or high-viscosity base oils.
  • the base residue may be esterified, such as with a monoalcohol.
  • the hydroxyl residues of the resulting compound may be acylated (e.g, acetic anhydride) to provide a high-viscosity estolide base oil having a low hydroxyl value (e.g., ⁇ 20 mg KOH/g)
  • acylated e.g, acetic anhydride
  • the compounds described herein may be suitable for use as components for preparing polymeric materials.
  • polyhydroxy estolide compounds generally encompassed by Formula XI such as compound 302 produced in Scheme 3, may provide the basis for preparing polymeric materials, such materials comprising estolide residues generally encompassed by Formula XII.
  • the base fatty acid chain may be esterified, such as with a monoalcohol or a polyol to provide additional free hydroxyl residues for reacting with one or more reactive monomers and/or cross linkers to form a polymer.
  • the estolide compound comprises a free-acid estolide, such as compounds of Formula XI wherein Y' is O and R 2 is H.
  • the estolide compound is an estolide ester, such as a compound of Formula XI wherein Y' is O and R 2 is an optionally substituted alkyl group (- OR 2 representing the ester residue of the estolide ester).
  • R 2 is substituted with at least one hydroxyl group.
  • R 2 is a glycerol residue or a polyglycerol residue.
  • the compound comprises estolide ester, wherein the estolide residue comprises at least one hydroxyl group and the ester residue comprises as least one hydroxyl residue; that is, when applied to compounds of Formula XI, then (i) Ri is substituted with at least one hydroxyl group, or at least one R 8 or R9 comprises a hydroxyl group, and (ii) R2 is a Ci to C20 alkanyl or Ci to C20 alkenyl group, substituted with at least one hydroxyl group.
  • the at least one reactive monomer is selected from olefins, isocyanates, carboxylic acids, and esters.
  • Isocyanates include polyisocy antes such as diisocyantes.
  • Exemplary isocyantes include, but are not limited to, methylene diphenyl diisocyanate (MDI), polymeric MDI (pMDI), toluene diisocyanate (TDI), para-phenyl diisocyanate (PPDI), 4,4'- dicyclohexylmethane-diisocyanate (HMDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), triphenylmethane-4,4'4"-triisocyanate, toluene-2,4,6-triyl triisocyanate, 1,3,5- triazine-2,4,6-triisocyanate, and ethyl ester L-lysine triis
  • MDI
  • Carboxylic acids include polycarboxylic acids such as dicarboxylic acids.
  • Exemplary carboxylic acids include, but are not limited to, 1,4-terephthalic acid, 1,4-naphthalic acid, isophthalic acid, phthalic acid, 2,6- naphthalenedicarboxylic acid, diphenyldicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedionic acid, and 1,4-cyclohexanedicarboxylic acid.
  • the estolide compound and the reactive monomer are reacted in the presence of a reaction catalyst, such as a tin reaction catalyst like dibutyltin dilaruate (DBTDL) or stannous octoate.
  • a reaction catalyst such as a tin reaction catalyst like dibutyltin dilaruate (DBTDL) or stannous octoate.
  • DBTDL dibutyltin dilaruate
  • exemplary catalysts include amine catalysts, such as tertiary amine catalysts sold under the tradename Polycat® by Huntsman Petrochemical, such as Polycat® 5 (N,N,N',N",N"- pentamethyldiethylenetriamine) and Polycat® 8 ( ⁇ , ⁇ -dimethylcyclohexylamine), as well as Dabco® by Evonik Industries, such as Dabco® DC5357 and DC2585.
  • reaction mixture may further comprise a foaming (blowing) agent.
  • foaming agents include water, hydrocarbons (e.g., methane, ethane, propane, butane, pentane, optionally halogenated), and olefins.
  • foaming agents include one or more of a hydroflourocarbon (HFC) or azeotrope of two or more hydrocarbon s(HFCs), such as 1, 1, 1,3,3- pentaflourobutane (HFC-365), 1, 1, 1,2- tetraflouroethane (HFC- 134a), methoxy-nonafluorobutane (HFE-7100) and a free radical initiator comprising a nitrile, such as 2,4-Dimethyl, 2,2'-Azobis Pentanenitrile.
  • HFC hydroflourocarbon
  • HFC-365 1, 1, 1,3,3- pentaflourobutane
  • HFC- 134a 1, 1, 1,2- tetraflouroethane
  • HFE-7100 methoxy-nonafluorobutane
  • free radical initiator comprising a nitrile, such as 2,4-Dimethyl, 2,2'-Azobis Pentanenit
  • foaming agents include the HFCs Solkane® 365mfc and 134a (Solvay, Hannover, Germany), and free radical initiators Vazo 52 (DuPont, Wilmington, DE). Additionally or alternatively, azodicarbonamide can be used as an exemplary thermal decomposition agent to form pores during the manufacture of the polymeric material. Water is also commonly used to foam polyurethane/polyurea systems via the reaction between water and isocyanate producing carbon dioxide. Various combinations of foaming agents, including, but not limited to those disclosed herein, can be used to form material or media including the material and are contemplated in this disclosure. It is thought that an amount of the blowing agent/foaming agent can be important to form a polymeric foam material with desired properties.
  • the polymeric foam material is formed with less than about 5 wt. % foaming agent, or about 0 wt. % to about 3 wt. % foaming agent, or about 0 wt. % to about 1 wt. % foaming agent in the composition. Additionally or alternatively, porosity can be added during the manufacture of the polymeric material by entraining gas bubbles into the material.
  • the reaction mixture for preparing polymers may further comprise a cross linker, such as a polyol or a polyamine.
  • the cross linker may be selected from one or more of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, ethanolamine, diethanolamine, methyldi ethanolamine, phenyldi ethanolamine, glycerol, trimethylolpropane, 1,2,6- hexanetriol, triethanolamine, pentaerythritol, ⁇ , ⁇ , ⁇ ', ⁇ '- tetrakis-(2-a cross linker, such as a polyol or
  • aminoethylpropanolamine aminoethylpropanolamine, aminopropylpropanolamine, or aminohexylpropanolamine.
  • the reaction mixture may further comprise a fire retardant additive.
  • fire retardants include, but are not limited to, halogenated and non-halogenated compounds, such as: chlorinated flame retardant compounds, such as chlorinated hydrocarbons, chlorinated phosphate esters, chlorinated polyphosphates, chlorinated organic phosphonates, chloroalkyl phosphates, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans; brominated flame retardant compounds such as aliphatic brominated compounds, aromatic brominated compounds, and brominated epoxy fire retardants; phosphorous-based fire retardants such as halogenated phosphates (chlorinated phosphates, brominated phosphates and the like), non-halogenated phosphates, triphenyl phosphates, phosphate esters, polyols, phosphonium derivatives, phosphonates, phosphoric acid
  • dimethylphosphono propionamide dimethylphosphono propionamide
  • intumescent substances including ammonium polyphosphate, boric acid, chlorinated paraffin, Dl-pentaerythritol, melamine, mono-ammonium phosphate, pentaerythritol, phosphate esters, polytetrafluoroethylene, tributoxyethyl phosphate, triethyl phosphate, tris (2-ethylhexyl) phosphonate, urea, xylene and zinc borate.
  • the reaction mixture may further comprise other additives such as fillers.
  • fillers include, but are not limited to, organic and inorganic materials such as wood based materials, cork based materials, silicate based materials, glass based materials, and mineral based materials.
  • Other optional additives present may be colorants, fragrances, perfumes, and/or other substances that may be detected by scent.
  • other optional additives include surfactants such as silicone-based surfactants, such as polysiloxane
  • polyoxyalkylene block co-polymer such as B8404, B8407, B8409, and B8462 of Goldschmidt, DC- 193, DC-197, DC-5582, and DC-5598 of Air Products, L-5130, L5180, L-5340, L-5440, L-6100, L- 6900, L-6980, and L-6988 of Momentive.
  • Other exemplary silicone-based surfactants include as well as Dabco® by Evonik Industries, such as Dabco® 33-LV and BL-17.
  • non-silicone surfactants are salts of sulfonic acid, alkali metal salts of fatty acid, ammonium salts of fatty acid, oleic acid, stearic acid, dodecylbenzenedidulfonic acid,
  • exemplary additives may include one or more plasticizers, such as an estolide plasticizer selected from compounds of Formula X.
  • estolide compounds may be tailored to have a particular hydroxyl value depending on the desired properties of the resulting materials. For example, estolide compounds having a high hydroxyl value (e.g., > 200mg KOH/g) may be used to prepare polyurethanes having a high cross-link density and a higher tensile strength. In other embodiments, estolide compounds having a lower hydroxyl value (e.g., ⁇ lOOmg KOH/g) may be used to provide materials with less rigidity, such as flexible polyurethane foams.
  • estolide compounds having a high hydroxyl value e.g., > 200mg KOH/g
  • estolide compounds having a lower hydroxyl value e.g., ⁇ lOOmg KOH/g
  • the hydroxyl value of the estolide compound may range from about 1 to about 2,500 mg KOH/g, such as about 1 to about 500 mg KOH/g, about 20 to about 100 mg KOH/g, about 25 to about 90 mg KOH/g, about 40 to about 85 mg KOH/g, about 50 to about 100 mg KOH/g, about 80 to about 150 mg KOH/g, about 100 to about 1,000 mg KOH/g, about 100 to about 500 mg KOH/g, about 150 to about 400 mg KOH/g, about 1 to about 500 mg KOH/g, or about 200 to about 350 mg KOH/g.
  • the EN of the estolide compounds may be modified to help impart unique characteristics to the resulting materials.
  • the estolide oligomer may be grown to a higher EN (e.g., EN > 4).
  • EN e.g., EN > 4
  • Applicant has surprisingly discovered that doing so may help to impart unique flexibilities (e.g., good elongation) to the polymeric materials, particularly when compounds exhibit lower hydroxyl values (e.g., less than 100 mg KOH/g or even less than 50 mg KOH/g), such as Compound X, wherein n is > 5:
  • higher EN values can be used to impart a higher hydroxyl value to the estolide (e.g., > 200 mg KOH/g), which can be used to maximize linkages with the reactive monomer(s) and, thus, increase hardness and tensile strength, such as with Compound Y, wherein n is 5 or more:
  • the polymeric materials described herein may be rigid, semi-rigid, or flexible foams.
  • the foams are created by adding a foaming agent to the reaction mixture, which may create foam cells during the heating process (e.g., evaporation of hydrocarbon foaming agent) or the creation of gas bubbles in a side reaction (e.g., creation of CO2 by reaction of water with a diisocyante).
  • a foaming agent e.g., evaporation of hydrocarbon foaming agent
  • gas bubbles in a side reaction e.g., creation of CO2 by reaction of water with a diisocyante.
  • Exemplary production formulas for foams include those set forth below in Table 2:
  • polymeric materials described herein will exhibit particular hardness values, which may be reported as a Shore value according to ASTM D2240.
  • polymeric material comprises a hardness of about 0 to about 100 Shore OO as tested according to ASTM D2240, such as about about 1 to about 25, about 25 to about 50, about 50 to about 75, or about 75 to about 100.
  • polymeric material comprises a hardness of about 0 to about 100 Shore A as tested according to ASTM D2240, such as about about 1 to about 25, about 25 to about 50, about 50 to about 75, or about 75 to about 100.
  • polymeric material comprises a hardness of about 0 to about 100 Shore D as tested according to ASTM D2240, such as about about 1 to about 25, about 25 to about 50, about 50 to about 75, or about 75 to about 100.
  • Shore D as tested according to ASTM D2240
  • Other exemplary compounds that may be useful for the applications described in the instant application include, but are not limited to:
  • suitable kinematic viscosity characteristics of the base oil may range from about 2 cSt to about 10,000 cSt at 40 °C, such as about 500 cSt to about 5,000 cSt, 2 cSt to about 20 cSt at 40 °C, 20 cSt to about 50 cSt at 40 °C, 20 cSt to about 250 cSt at 40 °C, or even 250 cSt to about 500 cSt at 40 °C.
  • the compounds and compositions described herein may exhibit kinematic viscosities of at least 200 cSt at 40 °C, or at least 225 cSt at 40 °C, and/or at least 20 cSt at 100 °C or at least 25 cSt at 100 °C. In some embodiments, compounds and compositions may exhibit kinematic viscosities of at least 250 cSt at 40 °C or at least 300 cSt at 40 °C, and/or at least 30 cSt at 100 °C or at least 35 cSt at 100 °C. In some embodiments, the compounds and
  • compositions may exhibit kinematic viscosities of at least 350 cSt at 40 °C or at least 400 cSt at 40°C, and/or at least 40 cSt at 100 °C or at least 45 cSt at 100 °C. In some embodiments, the compounds and compositions may exhibit kinematic viscosities of at least 450 cSt at 40 °C or at least 525 cSt at 40°C, and/or at least 50 cSt at 100 °C or at least 55 cSt at 100 °C.
  • the compounds and compositions may exhibit kinematic viscosities of at least 600 cSt at 40 °C or at least 720 cSt at 40°C, and/or at least 60 cSt at 100 °C or at least 65 cSt at 100 °C. In some embodiments, the compounds and compositions may exhibit kinematic viscosities of at least 800 cSt at 40 °C or at least 850 cSt at 40°C, and/or at least 70 cSt at 100 °C or at least 75 cSt at 100 °C.
  • compounds described herein may exhibit desirable low-temperature pour point properties.
  • the compounds and compositions may exhibit a pour point lower than about -25 °C, about -35 °C, -40 °C, -50 °C, -60 °C, -70 °C, or even -80 °C.
  • compounds have a pour point of about -25 °C to about -45 °C.
  • the pour point falls within a range of about -30 °C to about -40 °C.
  • the pour point falls within the range of about -40 °C to about -50 °C, or about -50 °C to about -60 °C.
  • the pour point falls within the range of about -60 °C to about -70 °C, or about - 70 °C to about -80 °C. In some embodiments, the pour point falls within the range of about -80 °C to about -85 °C, or about -85 °C to about -90 °C. In some embodiments, the pour point falls within the range of about -90 °C to about -100 °C.
  • the compounds described herein may exhibit decreased Iodine Values (IV) when compared to compounds prepared by other methods.
  • IV is a measure of the degree of total unsaturation of an oil, and is determined by measuring the amount of iodine per gram of compound (cg/g).
  • oils having a higher degree of unsaturation may be more susceptible to creating corrosiveness and deposits, and may exhibit lower levels of oxidative stability.
  • Compounds having a higher degree of unsaturation will have more points of unsaturation for iodine to react with, resulting in a higher IV.
  • the compounds described have an IV of less than about 40 cg/g or less than about 35 cg/g. In some embodiments, the compounds will have an IV of less than about 30 cg/g, less than about 25 cg/g, less than about 20 cg/g, less than about 15 cg/g, less than about 10 cg/g, or less than about 5 cg/g.
  • the IV of a compound may be reduced by decreasing the estolide's degree of unsaturation. In certain embodiments, this may be accomplished by, for example, increasing the amount of saturated capping materials relative to unsaturated capping materials when synthesizing the estolides. Alternatively, in certain embodiments, IV may be reduced by
  • the at least one polyol is contacted with the at least one estolide oligomer in the presence of a catalyst.
  • Suitable catalysts may include one or more Lewis acids and/or Bronsted acids, including, for example, AgOTf, Cu(OTf) 2 , Fe(Otf) 2 , Fe(Otf) 3 , NaOTf, LiOTf, Yb(Otf) 3 , Y(Otf) 3 , Zn(Otf) 2 , Ni(Otf) 2 , Bi(Otf) 3 , La(Otf) 3 , Sc(Otf) 3 , hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, phosphoric acid, perchloric acid, triflic acid, and p-TsOH.
  • the catalyst may comprise a strong Lewis acid such as BF
  • the catalyst may comprise a Lewis acid catalyst, such as at least one metal compound selected from one or more of titanium compounds, tin compounds, zirconium compounds, and hafnium compounds.
  • the catalyst is at least one titanium compound selected from TiCU and Ti(OCH 2 CH 2 CH 2 CH )4 (titanium (IV) butoxide).
  • the catalyst is at least one tin compound selected from Sn(0 2 CC0 2 ) (tin (II) oxalate), SnO, and SnCl 2 .
  • the catalyst is at least one zirconium compound selected from ZrCU, ZrOCl 2 , ZrO(N0 3 ) 2 , ZrO(S0 4 ), and ZrO(CH COO) 2 .
  • the catalyst is at least one hafnium compound selected from HfCl 2 and HfOCl 2 . Unless stated otherwise, all metal compounds and catalysts discussed herein should be understood to include their hydrate and solvate forms.
  • the catalyst may be selected from
  • contacting the polyl with an estolide oligomer and/or any other acylating agents will result in partial esterification of the polyl.
  • the resulting estolide polyol ester will exhibit a hydroxyl value of greater than 0 mg KOH/g.
  • the composition exhibits a hydroxyl value less than or equal to 1 mg KOH/g.
  • the composition exhibits a hydroxyl value less than or equal to 5 mg KOH/g.
  • the composition exhibits a hydroxyl value less than or equal to 20 mg KOH/g, such as 5 to 10 mg KOH/g or 10 to 15 mg KOH/g.
  • the resulting estolide polyol ester will exhibit a hydroxyl value of greater than 0 mg KOH/g.
  • the composition exhibits a
  • composition exhibits a hydroxyl value greater than or equal to 20 mg KOH/g, such as 20 to 30 mg KOH/g or 30 to 40 mg KOH/g. In certain embodiments, and depending on the desired
  • the resulting compounds will exhibit very high hydroxyl values, such as greater than 50 mg KOH/g or 100 mg KOH/g.
  • the composition exhibits a hydroxyl value equal to or greater than 400 or even 500 mg KOH/g, such as about 400 to 600, about 600 to 800, about 800 to 1000, about 1000 to 1200, about 1200 to 1500, about 1500 to 2000, or even about 2000 to about 2500 mg KOH/g. In certain embodiments, that hydroxyl value may exceed 2500 mg KOH/g of composition.
  • the present disclosure further relates to methods of making compounds of Formulas I-XII.
  • the reaction of a polyol with a free-acid estolide is illustrated and discussed below.
  • Ri may represent one or more optionally substituted alkyl residues that are saturated or unsaturated and branched or unbranched.
  • Any suitable proton source may be implemented to catalyze the formation of free acid estolide 104, including but not limited to homogenous acids and/or strong acids like hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, nitric acid, triflic acid, and the like.
  • Other suitable catalysts may include dielectric heating (e.g., microwave radiation) and/or Lewis acid catalysts (e.g., iron triflate).
  • Any suitable proton source may be implemented to catalyze the formation of free acid estolide 200, including but not limited to homogenous acids and/or strong acids like hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, nitric acid, triflic acid, and the like.
  • Other suitable catalysts may include heating (e.g., microwave radiation), pressure, and/or Lewis acid catalysts (e.g., tin compounds such as stannous chloride).
  • estolide 302 is an example of a single regioisomer.
  • the capping residue of estolide 302 may retain its epoxide residue (i.e., where both Z' are taken together to form a single epoxide moiety) or result in the opening of the epoxide (i.e., where each Z' is -OH), which may be accomplished in the presence of acid and water.
  • the resulting estolide 302 may be used in place of compound 104 in Scheme 3 to yield polyglycerine estolides.
  • polyol estolide 402 is reacted with a reactive monomer (e.g., a diisocyanate and/or a diacid), optionally in the presence of a catalyst (e.g., dibutyltin dilauarate) and heat, to provide a polymeric material comprising at least one residue 404.
  • a reactive monomer e.g., a diisocyanate and/or a diacid
  • a catalyst e.g., dibutyltin dilauarate
  • polyol estolide compounds may meet or exceed one or more of the specifications for certain end-use applications, without the need for conventional additives.
  • high-viscosity lubricants such as those exhibiting a kinematic viscosity of greater than about 100 cSt at 40 °C, or even greater than about 200 cSt at 40 °C, may be desirable for particular applications such as gearbox or wind turbine lubricants.
  • Prior-known lubricants with such properties typically also demonstrate an increase in pour point as viscosity increases, such that prior lubricants may not be suitable for such applications in colder environments.
  • the counterintuitive properties of certain compounds described herein may make higher-viscosity estolides particularly suitable for such specialized applications.
  • low-viscosity oils may include those exhibiting a viscosity of lower than about 50 cSt at 40 °C, or even about 40 cSt at 40 °C. Accordingly, in certain embodiments, the low-viscosity estolides described herein may provide end users with a suitable alternative to high-viscosity lubricants for operation at lower temperatures.
  • the polyol estolides described herein may be blended with one or more additives selected from polyalphaolefins, synthetic esters, polyalkylene glycols, mineral oils (Groups I, II, and III), pour point depressants, viscosity modifiers, anti-corrosives, antiwear agents, detergents, dispersants, colorants, antifoaming agents, and demulsifiers.
  • additives selected from polyalphaolefins, synthetic esters, polyalkylene glycols, mineral oils (Groups I, II, and III), pour point depressants, viscosity modifiers, anti-corrosives, antiwear agents, detergents, dispersants, colorants, antifoaming agents, and demulsifiers.
  • the polyol estolides described herein may be co-blended with one or more synthetic or petroleum-based oils to achieve the desired viscosity and/or pour point profiles.
  • the estolides described herein also mix well with gasoline, so that they may be useful as fuel components or additives.
  • the compounds described may be useful alone, as mixtures, or in combination with other compounds, compositions, and/or materials.
  • Estolide Number The EN was measured by GC analysis. It should be understood that the EN of a composition specifically refers to EN characteristics of any estolide compounds present in the composition. Accordingly, an estolide composition having a particular EN may also comprise other components, such as natural or synthetic additives, other non-estolide base oils, fatty acid esters, e.g., triglycerides, and/or fatty acids, but the EN as used herein, unless otherwise indicated, refers to the value for the estolide fraction of the estolide composition.
  • Iodine Value is a measure of the degree of total unsaturation of an oil. IV is expressed in terms of centigrams of iodine absorbed per gram of oil sample. Therefore, the higher the iodine value of an oil the higher the level of unsaturation is of that oil. The IV may be measured and/or estimated by GC analysis. Where a composition includes unsaturated compounds other than estolide polyol esters as set forth herein, the estolide polyol esters can be separated from other unsaturated compounds present in the composition prior to measuring the iodine value of the constituent estolides.
  • a composition includes unsaturated fatty acids or triglycerides comprising unsaturated fatty acids, these can be separated from the estolide polyol ester present in the composition prior to measuring the iodine value for the one or more estolides.
  • Acid Value is a measure of the total acid present in an oil. Acid value may be determined by any suitable titration method known to those of ordinary skill in the art. For example, acid values may be determined by the amount of KOH that is required to neutralize a given sample of oil, and thus may be expressed in terms of mg KOH/g of oil.
  • GC analysis was performed to evaluate the estolide number (EN) and iodine value (IV) of the polyol estolides. This analysis was performed using an Agilent 6890N series gas chromatograph equipped with a flame-ionization detector and an autosampler/injector along with an SP-2380 30 m x 0.25 mm i.d. column.
  • Measuring EN and IV by GC To perform these analyses, the fatty acid components of an polyol estolide sample were reacted with MeOH to form fatty acid methyl esters by a method that left behind a hydroxy group at sites where estolide links were once present. Standards of fatty acid methyl esters were first analyzed to establish elution times.
  • EN Calculation The EN is measured as the percent hydroxy fatty acids divided by the percent non-hydroxy fatty acids. As an example, a dimer estolide residue would result in half of the fatty acids containing a hydroxy functional group, with the other half lacking a hydroxyl functional group. Therefore, the EN would be 50% hydroxy fatty acids divided by 50% non-hydroxy fatty acids, resulting in an EN value of 1 that corresponds to the single estolide link between the capping fatty acid and base fatty acid of the dimer.
  • pour point is measured by ASTM Method D97-96a
  • cloud point is measured by ASTM Method D2500
  • viscosity /kinematic viscosity is measured by ASTM Method D445-97
  • viscosity index is measured by ASTM Method D2270-93 (Reapproved 1998)
  • specific gravity is measured by ASTM Method D4052
  • flash point is measured by ASTM Method D92
  • evaporative loss is measured by ASTM Method D5800
  • vapor pressure is measured by ASTM Method D5191
  • acute aqueous toxicity is measured by Organization of Economic Cooperation and Development (OECD) 203.
  • the acid catalyst reaction was conducted in a 50 gallon Pfaudler RT-Series glass-lined reactor. Oleic acid (65Kg, OL 700, Twin Rivers) was added to the reactor with 70% perchloric acid (992.3 mL, Aldrich Cat# 244252) and heated to 60°C in vacuo (10 torr abs) for 24 hrs while continuously being agitated. After 24 hours the vacuum was released. At which time, KOH (645.58 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH by volume) and added to the reactor to quench the acid. The solution was then allowed to cool for approximately 30 minutes.
  • the contents of the reactor were then pumped through a 1 micron ( ⁇ ) filter into an accumulator to filter out the salts. Water was then added to the accumulator to wash the oil. The two liquid phases were thoroughly mixed together for approximately 1 hour. The solution was then allowed to phase separate for approximately 30 minutes. The water layer was drained and disposed of. The organic layer was again pumped through a 1 ⁇ filter back into the reactor. The reactor was heated to 60°C in vacuo (10 torr abs) until all ethanol and water ceased to distill from solution.
  • the acid catalyst reaction was conducted in a 50 gallon Pfaudler RT-Series glass-lined reactor. Oleic acid (50Kg, OL 700, Twin Rivers) and whole cut coconut fatty acid (18.754 Kg, TRC 110, Twin Rivers) were added to the reactor with 70% perchloric acid (1145 mL, Aldrich Cat# 244252) and heated to 60°C in vacuo (10 torr abs) for 24 hrs while continuously being agitated. After 24 hours the vacuum was released. At which time, KOH (744.9 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH by volume) and added to the reactor to quench the acid. The solution was then allowed to cool for approximately 30 minutes.
  • the contents of the reactor were then pumped through a 1 ⁇ filter into an accumulator to filter out the salts. Water was then added to the accumulator to wash the oil. The two liquid phases were thoroughly mixed together for approximately 1 hour. The solution was then allowed to phase separate for approximately 30 minutes. The water layer was drained and disposed of. The organic layer was again pumped through a 1 ⁇ filter back into the reactor.
  • the reactor was heated to 60°C in vacuo (10 torr abs) until all ethanol and water ceased to distill from solution. The remaining material was then distilled using a Myers 15 Centrifugal Distillation still at 200°C under an absolute pressure of approximately 12 microns (0.012 torr) to remove unreacted fatty acids and leaving behind free-acid estolides (Ex. 2).
  • a reactor is equipped with a mechanical stirrer, thermocouple, thermoregulator, Dean Stark trap, condenser, nitrogen sparger, and vacuum source.
  • the reactor is charged with an excess of triglycerol (4 equiv.), the free-acid estolide product of Ex. 1 (1 equiv.), and concentrated
  • the mixture is stirred at 200-300 rpm and heated to about 100°C, and the vacuum is applied at temperature to obtain a reflux, thereby removing the water and returning the acid collected in the trap to the reactor.
  • the temperature is maintained under vacuum for about 18-24 hrs.
  • the reaction mixture is then subjected to aqueous workup with sodium bicarbonate, extracted 3X with ethyl acetate, and concentrated under reduced pressure to yield a mixture of estolide polyglycerol esters and unreacted triglycerol.
  • the concentrated mixture is then subjected to purification using SiC chromatography to yield the desired estolide polyglycerol product, in which the majority of the resulting product comprises triglycerol compounds esterified with a single estolide residue.
  • Estolide polyglycerol esters are prepared according to the method set forth in Example 3, except an excess of the free-acid estolide product prepared according to the method of Ex. 1 (6 equiv.) is reacted with triglycerol (1 equiv.) to yield triglycerol compounds each having a plurality of estolide residues.
  • Estolide polyglycerol esters prepared in accordance with the method of Example 3 (1 equiv.) and pyridine (10 equiv.) are added to a roundbottom flask fitted with a mechanical stirrer, nitrogen sparger, condenser, and dropping funnel.
  • Acetic anhydride (6 equiv.) is slowly added by the dropping funnel, and the reaction was refluxed under stirring for 4-6 hrs.
  • the reaction mixture is allowed to cool to ambient temperature, and then a cold 10% aqueous sodium bicarbonate solution is added and the mixture was allowed to stir for 10-15 minutes. Aliquots of 50% aqueous sodium bicarbonate solution are added to the stirred organic layer until the aqueous layer tests basic using litmus paper.
  • estolide polyglycerol esters comprising a single estolide residue and a plurality of acetate residues.
  • Polyol estolides are prepared according to the methods set forth in Examples 3-5, except the free-acid estolide of Example 1 is replaced with the free-acid estolide product of Example 2.
  • Free-acid estolides are prepared according to the method set forth in Example 1, except the oleic acid feedstock is replaced with 9-decenoic acid feedstock.
  • Free-acid estolides are prepared according to the methods set forth in Example 2, except the oleic acid feedstock is replaced with 9-decenoic acid feedstock.
  • Free-acid estolides are prepared according to the method set forth in Example 8, except the coconut fatty acid feedstock is replaced with acetic acid.
  • Polyol estolides are independently prepared according to the methods set forth in Examples 3-6, except the free-acid estolide products of Examples 1 and 2 are independently replaced with the free-acid estolides prepared according to Examples 7, 8, and 9.
  • Example 11 [0134] Oleic acid (1 equiv.) (100 g, 0.354 mol), Na 2 W0 4 2H 2 0 (0.02 equiv.), Stark's catalyst (0.2 equiv.), and H 2 0 2 (30% w/w, 5.4 equiv.) are charged into a 3-neck round bottom flask equipped with a mechanical stirrer and reflux condenser. The mixture is heated at 100°C over stirring for 24 hrs. The resulting mixture is then transferred to a separatory funnel to allow to cool, and to allow the organic and aqueous layers to separate. The aqueous layer together with any aqueous precipitate is separated from the organic layer and is discarded. The organic layer is then diluted with
  • hydroxylated free-acid estolide compounds also referred to as polyol free-acid estolides, having a high hydroxyl value (e.g., >200 mg KOH/g).
  • Polyol free-acid estolides (5g) are made according to the method set forth in Ex. 11 and are added to a roundbottom flask and are dissolved in chloroform (25 ml). The roundbottom flask was purged with nitrogen to remove any moisture that may exist, and then 4,4' -methylene diphenyl diisocyanate (MDI) (3.9 g) was added to the reaction mixture, such that the hydroxyl to isocyanate (OH/NCO) ratio achieved is about 1.3. The reaction mixture is then heated to about 60°C under reflux conditions for 24 hours.
  • MDI 4,4' -methylene diphenyl diisocyanate
  • R.5 and R6, independently for each occurrence, are selected from hydrogen, R 7 , and a residue of Formula II:
  • R 8 and R9 are, independently for each occurrence, selected from hydrogen and hydroxyl
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2;
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group; n is selected from 0 to 20; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20; wherein at least one R5 or 5 is a residue of Formula II.
  • Ri is selected from, independently for each occurrence, unsubstituted C7 to C 17 alkanyl and a C7 to C 17 alkanyl substituted with at least one hydroxyl group.
  • composition comprising at least one compound according to any one of the preceding embodiments.
  • composition exhibits an GN of at least 2, wherein GN is the average number of glycerol residues z+1 for compounds of Formula II contained in the composition.
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group; n is selected from 0 to 20; x is, independently for each occurrence, selected from 7 and 8; y is, independently for each occurrence, selected from 0 to 10; and z is selected from 0 to 19.
  • composition comprising at least one compound according to any one of embodiments 29-38.
  • composition according to any one of embodiments 29-42, wherein the composition exhibits an GN of about 2.5 to about 4, wherein GN is the average number of glycerol residues z+1 for compounds of Formula III contained in the composition.
  • R.5 and R6, independently for each occurrence, are selected from hydrogen, R 7 , and and a residue of Formula V:
  • Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group
  • Ri is selected from, independently for each occurrence, optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group.
  • Ri is selected from, independently for each occurrence, Ci to C20 alkanyl group optionally substituted with at least one hydroxyl group.
  • composition comprising at least one compounds according to any one of embodiments 45-57.
  • composition according to embodiment 58 wherein the composition exhibits an EN of about 2 to about 6, wherein EN is the average number of linkages n+1 for compounds of Formula V contained in the composition.
  • composition according to any one of embodiments 58-59, wherein the composition exhibits an GN of at least 2, wherein GN is the average number of glycerol residues z+1 for compounds of Formula IV contained in the composition.
  • composition according to any one of embodiments 58-60, wherein the composition exhibits an GN of about 2 to about 7, wherein GN is the average number of glycerol residues z+1 for compounds of Formula IV contained in the composition.
  • composition according to any one of embodiments 58-61, wherein the composition exhibits an GN of about 2.5 to about 4, wherein GN is the average number of glycerol residues z+1 for compounds of Formula IVcontained in the composition.
  • composition according to any one of embodiments 58-62, wherein the composition exhibits an GN of about 2.6 to about 3.6, wherein GN is the average number of glycerol residues z+1 for compounds of Formula IV contained in the composition.
  • GN is the average number of glycerol residues z+1 for compounds of Formula IV contained in the composition.
  • 64. At least one compound selected from Formulas Via, VIb, Vic, or VId:
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group;
  • R 8 and R9 are, independently for each occurrence, selected from hydrogen and hydroxyl
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2; n is 0 or greater than 0; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20; wherein at least one R5 is a residue of Formula II.
  • Ri is an optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group;
  • R2 is, independently for each occurrence, selected from hydrogen and an optionally substituted Ci to C20 alkanyl group and an optionally substituted Ci to C20 alkenyl group;
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2;
  • Y' is selected from O and N(R 2 ); n is 0 or greater than 0; x is, independently for each occurrence, selected from 0 to 20; and y is, independently for each occurrence, selected from 0 to 20.
  • 78. The compound according to embodiment 77, wherein at least one R9 is not hydrogen. [0218] 79. The compound according to any one of embodiments 77-78, wherein at least one R9 is hydroxyl.
  • Ri is a Ci to C20 alkanyl group substituted with at least one hydroxyl group or at least one epoxide residue.
  • composition according to embodiment 92 further comprising at least one cross linker.
  • composition according to embodiment 93, wherein the at least one cross linker is selected from one or more polyols or polyamines.
  • the at least one cross linker is selected from one or more of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3- butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, ethanolamine, diethanolamine, methyldiethanolamine, phenyldiethanolamine, glycerol,
  • aminoethylpropanolamine aminoethylpropanolamine, aminopropylpropanolamine, or aminohexylpropanolamine.
  • composition according to embodiment 92-95 wherein the at least one reactive monomer is selected from one or more of olefins, isocyanates, carboxylic acids, or esters.
  • MDI methylene diphenyl diisocyanate
  • 2,4-TDI
  • composition according to embodiment 101 wherein the at least one reaction catalyst is selected from one or more of tin catalysts or amine catalysts.
  • the at least one reactive monomer is a polycarboxylic acid.
  • composition according to embodiment 103 wherein the at least one reactive monomer is selected from one or more of 1,4-terephthalic acid, 1,4-naphthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedionic acid, or 1,4-cyclohexanedicarboxylic acid.
  • the at least one reactive monomer is selected from one or more of 1,4-terephthalic acid, 1,4-naphthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedionic acid, or 1,4-cyclohexanedicarboxylic acid.
  • composition according to embodiment 108, wherein the estolide ester compound comprises a plurality of hydroxyl groups.
  • estolide compound has a hydroxyl value of about 150 to about 400 mg KOH/g.
  • composition according to any one of embodiments 92-112, wherein the estolide compound is selected from at least one compound according to any one of embodiments 1-91.
  • Ri is a Ci to C20 alkyl group optionally substituted with one or more of Rn, wherein R11 is, independently for each occurrence, selected from hydroxyl and
  • Y and X' are, independently for each occurrence, selected from C(Rs>)2;
  • Y' is selected from O and N(R 2 );
  • R12 is, independently for each occurrence, a residue selected from
  • composition according to embodiment 130, wherein the at least one foaming agent is water.
  • composition according to any one of embodiments 92-124 and 130-133, further comprising a fire retardant.
  • composition according to any one of embodiments 92-124 and 130-134, further comprising a filler.
  • composition according to any one of embodiments 92-124 and 130-135, further comprising a surfactant.
  • x" is selected from 0 to 20;
  • y' is selected from 0 to 20;

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Abstract

L'invention concerne des polyols, des polyesters et des polyuréthanes comprenant des résidus d'estolide, et leurs procédés de fabrication. Des exemples de composés comprennent des estolides de polyol, des estolides de glycérol, des estolides de polyglycérol, et des matériaux polymères dérivés de ceux-ci.
PCT/US2018/027432 2017-04-14 2018-04-13 Polyols, polyesters, polyuréthanes et matériaux polymères comprenant des résidus d'estolide WO2018191585A1 (fr)

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Publication number Priority date Publication date Assignee Title
EP4134410A1 (fr) * 2021-08-13 2023-02-15 Oleon N.V. Additif de lubrification
US11633333B2 (en) 2018-06-12 2023-04-25 Gattefossé SAS Surfactant for water-in-oil emulsion
FR3154997A1 (fr) * 2023-11-06 2025-05-09 Ingrebeauce Nouveaux estolides, leur procédé de préparation et leurs utilisations, notamment pour la préparation d’esters de polyglycérol

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US20160229790A1 (en) * 2013-07-09 2016-08-11 Biosynthetic Technologies, Llc Polyol estolides and methods of making and using the same

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11633333B2 (en) 2018-06-12 2023-04-25 Gattefossé SAS Surfactant for water-in-oil emulsion
EP4134410A1 (fr) * 2021-08-13 2023-02-15 Oleon N.V. Additif de lubrification
WO2023017057A1 (fr) * 2021-08-13 2023-02-16 Oleon Nv Additif lubrifiant
FR3154997A1 (fr) * 2023-11-06 2025-05-09 Ingrebeauce Nouveaux estolides, leur procédé de préparation et leurs utilisations, notamment pour la préparation d’esters de polyglycérol
WO2025099381A1 (fr) * 2023-11-06 2025-05-15 Ingrebeauce Nouveaux estolides, leur procédé de préparation et leurs utilisations, notamment pour la préparation d'esters de polyglycérol

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