POLYOLS, POLYESTERS, POLYURETHANES, AND POLYMERIC MATERIALS COMPRISING ESTOLIDE RESIDUES

FIELD

[001] 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.

BACKGROUND

[002] A variety of commercial uses for fatty esters such as triglycerides have been described. However, naturally-occurring fatty esters are typically deficient in one or more areas, including stability, availability, and/or flexibility for use in multiple applications. Estolide esters provide a synthetic, stable alternative to naturally-occurring ester oils that can be engineered for certain uses. However, there remains a need to provide estolide esters having certain functional characteristics that make them suitable for use in a variety of commercial appications.

SUMMARY

[003] Described herein are polyesters, polyurethanes, and other materials comprising estolide residues. In certain embodiments, such compounds and compositions may be useful as lubricants, lubricant additives, coatings, rigid or semi-rigid polymers, or foams. In certain embodiments, the estolide compounds are selected from compounds of Formula I:

Formula I wherein z is selected from 0 to 20; and

R.5 and R6, independently for each occurrence, are selected from hydrogen, R ₇ , and a residue of Formula II:

Formula II wherein

R ₇ is, independently for each occurrence, selected from optionally substituted alkyl and -C(=0)Rio, wherein Rio is an optionally substituted alkyl;

R ₈ and R9 are, independently for each occurrence, selected from hydrogen, hydroxyl, and -OC(=0)Rio, wherein Rio is an optionally substituted alkyl;

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. In certain embodiments, the compound is selected from compounds according to Formula

Formula III wherein

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.

[005] In certain embodiments, the compound is selected from compounds according to Formula

IV:

Formula IV wherein z is selected from 0 to 20; and

R.5 and R6, independently for each occurrence, are selected from hydrogen, R ₇ , and a residue of Formula V:

Formula V wherein x is, independently for each occurrence, an integer selected from 0 to 20; y is, independently for each occurrence, an integer selected from 0 to 20; n is an integer equal to or greater than 0; and

Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group; and

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.

[006] In certain embodiments, the at least one compound is selected from compounds of Formulas Via, VIb, Vic, or VId:

Formula Via Formula VIb

Formula Vic Formula VId wherein R ₅ is selected from, independently for each occurrence, hydrogen, R ₇ , and a residue of Formula II:

Formula II wherein

R ₇ is, independently for each occurrence, selected from optionally substituted alkyl and -C(=0)Rio, wherein Rio is an optionally substituted alkyl;

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, hydroxyl, and -OC(=0)Rio, wherein Rio is an optionally substituted alkyl;

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.

In certain embodiments, the at least one compound is selected from compounds of XI:

Formula XI wherein

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, hydroxyl, and -OC(=0)Rio, wherein Rio is an optionally substituted alkyl;

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.

[008] Also described are methods and compositions for making polymers and polymeric materials. In certain embodiments, the composition comprises:

an estolide compound comprising at least one hydroxyl group; and at least one reactive monomer.

[009] In certain embodiments, the polymers and polymeric materials described herein comprise at least one residue of Formula XII:

Formula XII

wherein

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, R.2 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 -OC(=0)R ₁₂ ;

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

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. DETAILED DESCRIPTION

[010] 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.). 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). Thus, in certain embodiments, 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. In other embodiments, they may be suitable for producing high-viscosity lubricants, or serve as the basis for preparing oligomeric/polymeric materials, solid and semi-solid polymers, and rigid or flexible foams. [Oil] As used in the present specification, the following words, phrases and symbols are generally intended to have the meanings as set forth below, except to the extent that the context in which they are used indicates otherwise. The following abbreviations and terms have the indicated meanings throughout:

[012] A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -C(0) H2 is attached through the carbon atom.

[013] "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. In some embodiments, alkoxy groups have from 1 to 8 carbon atoms. In some embodiments, 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.

[014] "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. Examples of 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),

prop-l-yn-l-yl, prop-2-yn-l-yl, etc. butyls such as butan-l-yl, butan-2-yl, 2-methyl-propan-l-yl, 2-methyl-propan-2-yl, but-l-en-l-yl, but-l-en-2-yl, 2-methyl-prop-l-en-l-yl, but-2-en-l-yl, but-2-en-2-yl, buta-l,3-dien-l-yl, buta-l,3-dien-2-yl, but-l-yn-l-yl, but-l-yn-3-yl, but-3-yn-l-yl, etc. ; and the like.

[015] Unless otherwise indicated, the term "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. Where a specific level of saturation is intended, the terms "alkanyl," "alkenyl," and "alkynyl" are used. In certain embodiments, 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. In certain embodiments, an alkyl group comprises from 8 to 22 carbon atoms, in certain embodiments, from 8 to 18 or 8 to 16. In some embodiments, the alkyl group comprises from 3 to 20 or 7 to 17 carbons. In some embodiments, 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.

[016] "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. For example, 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. For such fused, 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. Examples of 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. In certain embodiments, an aryl group can comprise from 5 to 20 carbon atoms, and in certain embodiments, from 5 to 12 carbon atoms. In certain

embodiments, 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, however, does not encompass or overlap in any way with heteroaryl, separately defined herein. Hence, 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.

[017] "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. Examples of arylalkyl groups include, but are not limited to, benzyl, 2-phenylethan-l-yl, 2-phenylethen-l-yl, naphthylmethyl, 2-naphthylethan-l-yl,

2-naphthylethen-l-yl, naphthobenzyl, 2-naphthophenylethan-l-yl, and the like. Where specific alkyl moieties are intended, the nomenclature arylalkanyl, arylalkenyl, or arylalkynyl is used. In certain embodiments, 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.

[018] Estolide "base oil" and "base stock", unless otherwise indicated, refer to any composition comprising one or more estolide compounds. It should be understood that an estolide "base oil" or "base stock" is not limited to compositions for a particular use, and may generally refer to compositions comprising one or more estolides, including mixtures of estolides. Estolide base oils and base stocks can also include compounds other than estolides.

[019] "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. Accordingly, 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.

[020] For the purposes of the present disclosure, "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.

[021] 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. In such embodiments, 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. However, unless otherwise stated, it should be assumed that Formula I-XII cover all asymmetric variants of the compounds described herein, including isomers, racemates, enantiomers, diastereomers, and other mixtures thereof. In addition, 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.

[022] "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. Examples of cycloalkyl groups include, but are not limited to, groups derived from cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like. In certain embodiments, a cycloalkyl group is C3-15 cycloalkyl, and in certain embodiments, C3-12 cycloalkyl or C5-12 cycloalkyl. In certain embodiments, a cycloalkyl group is a C5, C ₆ , C ₇ , C ₈ , C9, Cio, C11, C12, Ci3, Ci4, or C15 cycloalkyl.

[023] "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. In certain embodiments, 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.

[024] "Halogen" refers to a fluoro, chloro, bromo, or iodo group.

[025] "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. For example, heteroaryl includes a 5- to 7-membered heterocycloalkyl, aromatic ring fused to a 5- to 7- membered cycloalkyl ring. For such fused, 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. In certain embodiments, when the total number of N, S, and O atoms in the heteroaryl group exceeds one, the heteroatoms are not adjacent to one another. In certain

embodiments, 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.

[026] Examples of heteroaryl groups include, but are not limited to, groups derived from acridine, arsindole, carbazole, β-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, tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like. In certain embodiments, 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. In certain embodiments, a heteroaryl group is a 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16-, 17-, 18-, 19-, or 20-membered heteroaryl. In certain embodiments heteroaryl groups are those derived from thiophene, pyrrole,

benzothiophene, benzofuran, indole, pyridine, quinoline, imidazole, oxazole, and pyrazine.

[027] "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. In certain embodiments, 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.

[028] "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. Examples of 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. Examples of heterocycloalkyl groups include, but are not limited to, groups derived from epoxides, azirines, thiiranes, imidazolidine, morpholine, piperazine, piperidine, pyrazolidine, pyrrolidine, quinuclidine, and the like.

[029] "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. In certain embodiments, 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.

[030] "Mixture" 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.

[031] "Parent aromatic ring system" refers to an unsaturated cyclic or polycyclic ring system having a conjugated π (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,

trinaphthalene, and the like.

[032] "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. Examples of 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. Examples of parent heteroaromatic ring systems include, but are not limited to, arsindole, carbazole, β-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, tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like.

[033] "Substituted" refers to a group in which one or more hydrogen atoms are independently replaced with the same or different substituent(s). Examples of substituents include, but are not limited to, -R ⁶⁴ , -R ⁶⁰ , -0\ -OH, =0, -OR ⁶⁰ , -SR ⁶⁰ , -S\ =S, - R ⁶⁰ R ⁶¹ , = R ⁶⁰ , -CN, -CF ₃ , -OCN, -SCN, -NO, -N0 ₂ , =N ₂ , -N ₃ , -S(0) ₂ 0\ -S(0) ₂ OH, -S(0) ₂ R ⁶⁰ , -OS(0 ₂ )0 ^" , -OS(0) ₂ R ⁶⁰ , - P(0)(0 ) ₂ , -P(O)(OR ⁶⁰ )(O ), -OP(O)(OR ⁶⁰ )(OR ⁶¹ ), -C(0)R ⁶⁰ , -C(S)R ⁶⁰ , -C(0)OR ⁶⁰ , - C(O)NR ⁶⁰ R ⁶¹ , -C(0)0 ^" , -C(S)OR ⁶⁰ , -NR ⁶² C(O)NR ⁶⁰ R ⁶¹ , -NR ⁶² C(S)NR ⁶⁰ R ⁶¹ , - NR ⁶² C(NR ⁶³ )NR ⁶⁰ R ⁶¹ , -C(NR ⁶² )NR ⁶⁰ R ⁶¹ , -S(0) ₂ , NR ⁶⁰ R ⁶¹ , -NR ⁶³ S(0) ₂ R ⁶⁰ , -NR ⁶³ C(0)R ⁶⁰ , and - S(0)R ⁶⁰ ; wherein each -R ⁶⁴ is independently a halogen; each R ⁶⁰ and R ⁶¹ are independently alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl, or substituted heteroarylalkyl, or R ⁶⁰ and R ⁶¹ together with the nitrogen atom to which they are bonded form a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, or substituted heteroaryl ring, and R ⁶² and R ⁶³ are independently alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, substituted arylalkyl, cycloalkyl, substituted cycloalkyl,

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, =0, -O-alkyl, -O-aiyl, - O-heteroaiylalkyl, -O-cycloalkyl, -O-heterocycloalkyl, -SH, -S ^" , =S, -S-alkyl, -S-aryl, -S- heteroarylalkyl, -S-cycloalkyl, -S-heterocycloalkyl, - H ₂ , = H, -CN, -CF , -OCN, -SCN, -NO, - N0 ₂ , =N ₂ , -N ₃ , -S(0) ₂ 0-, -S(0) ₂ , -S(0) ₂ OH, -OS(0 ₂ )0 ^" , -S0 ₂ (alkyl), -S0 ₂ (phenyl), - S0 ₂ (haloalkyl), -S0 ₂ NH ₂ , -S0 ₂ NH(alkyl), -S0 ₂ NH(phenyl), -P(0)(0 ) ₂ , -P(0)(0-alkyl)(0 ), - OP(0)(0-alkyl)(0-alkyl), -C0 ₂ H, -C(0)0(alkyl), -CON(alkyl)(alkyl), -CONH(alkyl), -CONH ₂ , -C(0)(alkyl), -C(0)(phenyl), -C(0)(haloalkyl), -OC(0)(alkyl), -N(alkyl)(alkyl), -NH(alkyl), -N(alkyl)(alkylphenyl), -NH(alkylphenyl), -NHC(0)(alkyl), -NHC(0)(phenyl),

-N(alkyl)C(0)(alkyl), and -N(alkyl)C(0)(phenyl).

[034] As used in this specification and the appended claims, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

[035] The term "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.

[036] All numerical ranges herein include all numerical values and ranges of all numerical values within the recited range of numerical values.

[037] The present disclosure relates to polylols, polyesters, and polyurethane compounds comprising estolide residues, and methods of making the same. In certain embodiments, 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. In certain embodiments, 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. In certain embodiments, the present disclosure relates to new methods of preparing estolide compounds exhibiting such properties.

[038] In certain embodiments, the compound is selected from compounds of Formula I:

Formula I wherein z is selected from 0 to 20; and

R.5 and R6, independently for each occurrence, are selected from hydrogen, R ₇ , and a residue of Formula II:

Formula II wherein

R ₇ is, independently for each occurrence, selected from optionally substituted alkyl -C(=0)Rio, wherein Rio is an optionally substituted alkyl; R.8 and R9 are, independently for each occurrence, selected from hydrogen, hydroxyl, and -OC(=0)Rio, wherein Rio is an optionally substituted alkyl;

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. In certain embodiments, the compound is selected from compounds according to Formula

Formula III wherein

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.

[040] In certain embodiments, the compound is selected from compounds according to Formula

IV:

Formula IV wherein z is selected from 0 to 20; and

R5 and R5, independently for each occurrence, are selected from hydrogen, R7, and a residue of Formula V:

Formula V wherein x is, independently for each occurrence, an integer selected from 0 to 20; y is, independently for each occurrence, an integer selected from 0 to 20; n is an integer equal to or greater than 0; and

Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group; and

R ₇ is, independently for each occurrence, selected from optionally substituted alkyl and - C(=0)Rio, 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.

[041] In certain embodiments, the at least one compound is selected from compounds of Formulas Via, VIb, Vic, or VId:

Formula Via Formula VIb

Formula Vic Formula VId wherein R ₅ is selected from, independently for each occurrence, hydrogen, R ₇ , and a residue of Formula II:

Formula II wherein R.7 is, independently for each occurrence, selected from optionally substituted alkyl and -C(=0)Rio, wherein Rio is an optionally substituted alkyl;

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, hydroxyl, and -OC(=0)Rio, wherein Rio is an optionally substituted alkyl;

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.

[042] In certain embodiments, the compounds described herein comprise at least one compound of Formula XI:

Formula XI wherein

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, hydroxyl, and -OC(=0)Rio, wherein Rio is an optionally substituted alkyl;

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.

[043] Also described are methods and compsositions for making polymers. In certain embodiments, the compsition comprises: an estolide compound comprising at least one hydroxyl group; and at least one reactive monomer.

[044] In certain embodiments, the polymers and polymeric materials described herein comprise at least one residue of Formula XII:

Formula XII

wherein

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,

R ₂ is, independently for each occurrence, selected from hydrogen and a Ci to C ₂ o alkyl group optionally substituted with Rn, wherein Rn is, independently for each occurrence, selected from hydroxyl and -OC(=0)Ri ₂ ;

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.

[045] In certain embodiments, the composition comprises at least one compound or residue according to Formulas I-XII, wherein Ri is hydrogen.

[046] The terms "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-.

[047] 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. In certain embodiments, the "caps" or "capping groups" are fatty acids. Similarly, 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. In certain embodiments, 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. In certain embodiments the estolides are described as "poly-capped," wherein the compounds comprise two or more primary chains.

[048] Depending on the manner in which the estolide is synthesized, the caps may be the only residues in the resulting estolide that are unsaturated. In certain embodiments, it may be desirable to use saturated organic or fatty-acid caps to increase the overall saturation of the estolide and/or to increase the resulting estolide's stability. For example, in certain embodiments, it may be desirable to provide a saturated capped estolide by epoxidizing, sulfurizing, and/or hydrogenating an unsaturated cap using any suitable methods available to those of ordinary skill in the art.

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.

[049] Without being bound to any particular theory, in certain embodiments, 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. Alternatively, in certain embodiments, epoxidizing an estolide substituent may provide for an intermediate

compound, wherein the epoxide residue may be opened by reacting it with one or more compounds or compositions. For example, in certain embodiments, the epoxide residue of an epoxy estolide substituent is opened to provide a mono-hydroxy estolide or a dihydroxy estolide. In certain embodiments, exposing an epoxy estolide residue to aqueous acid conditions will provide a dihydroxy estolide. In certain embodiments, 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. In certain embodiments, 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. In certain embodiments, estolides having free hydroxy groups may be acylated to provide poly-capped estolides.

[050] In other embodiments, epoxidation can be implemented to form estolides having a plurality of -OH residues that can be used for further functionalization. For example, in certain embodiments unsaturated fatty acids (e.g., oleic acid, linoleic acid) may be epoxidized, and then exposed to conditions that allow for self-reaction and oligomerization to form hydroxylated (polyol) free-acid estolides (see, e.g., Scheme 3). These hydroxylated 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. Alternatively, 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.

[051] In certain embodiments, it may be desirable to provide a method of preparing a saturated capped estolide residue by hydrogenating one or more of the unsaturated caps using any suitable methods available to those of ordinary skill in the art. Hydrogenation may be used with various sources of the fatty-acid feedstock, which may include mono- and/or polyunsaturated fatty acids. Without being bound to any particular theory, in certain embodiments, hydrogenating the estolide residues may help to improve the overall stability of the estolide molecule. However, a fully- hydrogenated estolide, such as an estolide with a larger fatty acid cap, may exhibit increased pour point temperatures. In certain embodiments, it may be desirable to offset any loss in desirable pour- point characteristics by using shorter, saturated capping materials.

[052] The structure 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. Depending on the manner in which the estolide is synthesized, 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).

Subsequently, the free-acid estolide may be condensed with one or more hydroxy residues of a polyol to form the estolide polyol ester. Alternatively, in certain embodiments, 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. Subsequently, 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 (γ) chains.

[053] 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. Depending on the manner in which the estolide polyol ester is prepared, a linking residue may be a fatty acid and may initially be in an unsaturated form during synthesis. In some embodiments, 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. In certain embodiments, 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). In certain embodiments, 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. In some embodiments, it may be desirable to have a linking fatty acid that is monounsaturated so that when the fatty acids link together, all of the sites of unsaturation are eliminated. The linking residue(s) may also be referred to as secondary or beta (β) chains.

[054] As noted above, in certain embodiments, suitable unsaturated fatty acids for preparing the polyol estolides may include any mono- or polyunsaturated fatty acid. For example,

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 β-chain and γ-chain, and β-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). In addition, in certain embodiments, 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 (18:2), alpha-calendic acid (18:3), beta-calendic acid (18:3), jacaric acid (18:3), alpha- eleostearic acid (18:3), beta-eleostearic (18:3), catalpic acid (18:3), punicic acid (18:3), rumelenic acid (18:3), alpha-parinaric acid (18:4), beta-parinaric acid (18:4), and bosseopentaenoic acid (20:5). In certain embodiments, 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.

[055] Because polyunsaturated fatty acids have more than one site of unsaturation, the resulting estolide polyol ester may comprise unsaturated chains and/or chains substituted with two or more fatty acids. For example, preparing a estolides from linoleic and/or linolenic acid can result in estolide substituents having two or more caps. In certain embodiments, linoleic and/or linolenic acid is reacted with an organic and/or fatty acid to provide an estolide substituent having two or more caps. In some embodiments, the organic and/or fatty acid cap comprises a C1-C40 alkyl residue. In some embodiments, the organic acid cap is acetic acid. In some embodiment, the fatty acid cap comprises a C7-C17 alkyl residue.

[056] The process for preparing the estolide compounds described herein may include the use of any natural or synthetic fatty acid source. However, it may be desirable to source the fatty acids from a renewable biological feedstock. 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.

[057] In certain embodiments, the estolide compounds described herein may be prepared from non-naturally occurring fatty acids derived from naturally occurring feedstocks. In certain embodiments, the estolides are prepared from synthetic fatty acid reactants derived from naturally occurring feedstocks such as vegetable oils. For example, 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. In certain embodiments, 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.

[058] In certain embodiments, 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. In certain embodiments, 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.

Alternatively, in certain embodiments, 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. For example, in certain embodiments, 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.

[059] In certain embodiments, suitable polyols include glycerine and polyglycerine variants. In certain embodiments, the polyols are selected from compounds of Formula VIII:

Formula VIII wherein z is selected from 0 to 20, 1 to 19, 1 to 1 1, and 1 to 5. In certain embodiments, the polyol is a polyglycerol variant selected from one of the following heteroalkyl or heterocycloalkyl structures:

Formula IXa Formula IXb

H

Formula IXc Formula IXd

[060] In certain embodiments, 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. In certain embodiments, it has been surprisingly discovered that estolide polyol esters derived from heterocycloalkyl or heteroalkyl polyols exhibit superior characteristics when compared to other polyols. For example, and without being bound to any particular scientific theory, it has been surprisingly discovered that certain polyols described herein (e.g., polyglycerols) having one or more oxygens present in the core chain of the polyol appear to impart improved properties (e.g., polarity, compatibility,

emulsification) to the resulting 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.).

[061] In certain embodiments, 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. In certain embodiments, R ₇ is, independently for each occurrence, selected from optionally substituted alkyl and -C(=0)Rio, wherein Rio is an optionally substituted alkyl. In certain embodiments, R ₇ is, independently for each occurrence, selected from optionally substituted Ci to C20 alkyl and -C(=0)Rio, wherein Rio is an optionally substituted Ci to C20 alkyl. In certain embodiments, R7 and Rio are unb substituted, and are branched or unbranched (linear). In certain embodiments, at least one 5 is a residue of Formula II or Formula V, and each R ₅ is independently selected from hydrogen and R7. In certain embodiments, R7 is, independently for each occurrence, selected from -C(=0)Rio, wherein Rio is an optionally substituted Ci to C20 alkyl. In certain embodiments, 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.

[062] In some embodiments, the estolide comprises fatty-acid chains of varying lengths. In some embodiments, 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. In some embodiments, x is, independently for each occurrence, an integer selected from 7 and 8. In some embodiments, 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. In certain embodiments, for at least one fatty acid chain residue, x is an integer selected from 7 and 8.

[063] In some embodiments, 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.

[064] In some embodiments, 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

embodiments, 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. .

[065] In certain embodiments, 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.

[066] In some embodiments, 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.

[067] In certain embodiments, R ₈ is, independently for each occurrence, selected from -OH, hydrogen, and -OC(=0)Rio. In certain embodiments, Y and X' are, independently for each occurrence, selected from C(R9) ₂ , wherein R9 is selected from -OC(=0)Rio, hydrogen and -OH. Thus, in certain embodiments, Y and X' are, independently for each occurrence, selected from

CHOH and CH ₂ . In certain embodiments, R ₈ is hydrogen for each occurrence. In certain embodiments, at least one R9 is -OH. In certain embodiments, at least one R9 is -OH for each fatty acid chain. In certain embodiments, Y and X' are CH ₂ for each occurrence.

[068] In some embodiments, the estolide residue of the estolide polyol ester compounds may comprise any number of fatty acid residues to form one or more "«-mer" estolide residues. That is, the compounds described herein may comprise one or more estolide residues in their dimer (n=0), trimer (n=l), tetramer (n=2), pentamer (n=3), hexamer (n=4), heptamer (n=5), octamer (n=6), nonamer (n=7), or decamer (n=8) form. Thus, in some embodiments, 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.

[069] In certain embodiments, the 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).

Similarly, in certain embodiments, compositions described herein may comprise estolide polyol ester compounds, wherein each compound comprises different estolide residues. Hence, it is possible to characterize the chemical makeup of a estolide polyol ester, a mixture of estolide polyol esters, or a composition comprising estolide polyol esters by using the compound' s, mixture' s, or

composition' s, measured estolide number (EN). The 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. The EN also represents the average number of estolide linkages per molecule. For example, with respect to the estolide residue of Formula II:

EN = n+1 wherein n is the number of secondary (β) fatty acids. Accordingly, a single estolide residue will have an EN that is a whole number, for example for dimers, trimers, and tetramers: dimer EN = 1 trimer EN = 2 tetramer EN = 3

However, a estolide polyol ester, or mixture of estolide polyol esters, may have an EN that is a whole number or a fraction of a whole number. For example, a estolide polyol ester having a 1 : 1 ratio of dimer and trimer would have an EN of 1.5, while a estolide polyol ester having a 1 : 1 molar ratio of tetramer and trimer would have an EN of 2.5. Similarly, 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:

"Compound A" EN = 1.33 "Compound B" EN = 1.67

[070] In some embodiments, 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. In some embodiments, the EN may be an integer or fraction of an integer selected from about 1.0 to about 5.0. In some embodiments, the EN is an integer or fraction of an integer selected from 1.2 to about 4.5. In some embodiments, the estolide compounds described herein will be in there trimer form or larger, wherein the EN is greater than or equal to 2. Thus, in some embodiments, 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. In certain embodiments, 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. In some embodiments, 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.

[071] Without being bound to any particular theory, in certain embodiments, altering the EN produces estolides having the desired viscometric properties while substantially retaining or even reducing pour point. For example, in some embodiments estolide polyol esters exhibit a decreased pour point upon increasing the EN value. Accordingly, in certain embodiments, 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. In some embodiments, 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. In some embodiments, 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. In some embodiments, 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. In some embodiments, 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. In some

embodiments, 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.

[072] Similar to EN, in certain embodiments 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 . For example, for a single estolide polyol ester compound comprising a triglycerol residue would have a GN of 3, whereas a composition comprising two estolide polyol ester compounds comprising triglycerol and tetraglycerol residues, respectively, would exhibit a GN of 2.5 for the composition. Thus, in certain embodiments, 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. In certain embodiments, the GN is about 2 to about 7. In certain embodiments, the GN is about 2.5 to about 4. In certain embodiments, the GN is about 2.6 to about 3.6.

[073] In some embodiments, Ri, independently for each occurrence, is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched. In some embodiments, the alkyl group is a Ci to C40 alkyl, Ci to C22 alkyl or Ci to C ₁₇ alkyl. In some embodiments, the alkyl group is selected from C7 to C ₁₇ alkyl, C to C ₁₃ alkyl, or C5 to Cn 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, 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 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

-OC(=0)Ri2, wherein R12 is independently for each occurrence a residue selected from

and R

[074] In some embodiments, R2 of Formulas VII, X, and XI is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched. In some embodiments, the alkyl group is a Ci to C40 alkyl, Ci to C22 alkyl or Ci to Ci ₈ alkyl. In some embodiments, the alkyl group is selected from C7 to Cn alkyl. In some embodiments, R2 is selected from C7 alkyl, C9 alkyl, Cn alkyl, C ₁₃ alkyl, C15 alkyl, and C ₁₇ alkyl. In some embodiments, R2 is selected from C ₁₃ to C ₁₇ alkyl, such as from C ₁₃ alkyl, C15 alkyl, and C ₁₇ alkyl. In some embodiments, 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. In certain embodiments, R2 is unsubstituted. In certain embodiments, Ri is substituted with at least one -OH group. In certain embodiments R2 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 -OC(=0)R ₁₂ , wherein R12 is independently for each occurrence a residue selected

from and 2 [075] As noted above, also described herein are methods of making 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. In certain embodiments, one or more estolide oligomers comprise at least one oleic- based estolide oligomer. In certain embodiments, the one or more estolide oligomers are selected from compounds of Formula VII:

Formula VII

wherein

x is, independently for each occurrence, an integer selected from 0 to 20; y is, independently for each occurrence, an integer selected from 0 to 20; n is an integer equal to or greater than 0;

Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group; and

R ₂ is selected from hydrogen, an optionally substituted alkanyl group, and an optionally substituted alkenyl group;

wherein each fatty acid chain residue is independently optionally substituted. [076] In certain embodiments, 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. In certain embodiments, 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

compositions available from Solvay Chemicals, Inc. and described below in Table 1 :

Table 1

[077] In certain embodiments, 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. In certain embodiments, the at least one additional component is selected from fatty alcohols, fatty esters, natural esters, synthetic esters, or hydrocarbons. In certain embodiments, the at least one additional component is selected from lecithins, saccharides, celluloses, alginates, glycerides, and gums. In certain embodiments, the composition comprises an emulsion. In certain embodiments, the emulsion comprises a water-in-oil (W/O) emulsion.

[078] In certain embodiments, the at least one additional component comprises an estolide base oil. In certain embodiments, the estolide base oil does not comprise an estolide polyol ester. For example, the estolide base oil may be selected from compounds of Formula X, wherein R ₂ is comprises hydrogen or an unsubstituted alkyl group:

Formula X

wherein

x is, independently for each occurrence, an integer selected from 0 to 20; y is, independently for each occurrence, an integer selected from 0 to 20; n is an integer equal to or greater than 0;

Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group; and

R ₂ is selected from hydrogen, an unsubstituted alkanyl group, and an unsubstituted alkenyl group;

wherein each fatty acid chain residue is independently optionally substituted.

In certain embodiments, 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.

[079] In certain embodiments, the compounds described herein may be suitable for use as emulsifiers or high-viscosity base oils. In certain embodiments, polyhydroxy (polyol) estolide compounds generally encompassed by Formula XI, such as compound 302 produced in Scheme 3, may provide the basis for preparing high-viscosity oils, such as when n = 3 or greater than 3, such as 10-20. In certain embodiments, the base residue may be esterified, such as with a monoalcohol. Further, in certain embodiments, 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)

[080] In certain embodiments, the compounds described herein may be suitable for use as components for preparing polymeric materials. In certain embodiments, 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. In certain embodiments, 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.

[081] Thus, in certain embodiments are described methods of making polymeric materials comprising contacting an estolide compound with at least one reactive monomer. In certain embodiments, the estolide compound comprises a free-acid estolide, such as compounds of Formula XI wherein Y' is O and R ₂ is H. In certain embodiments, 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). In certain embodiments, R ₂ is substituted with at least one hydroxyl group. In certain embodiments, R ₂ is a glycerol residue or a polyglycerol residue. In certain embodiments 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.

[082] In certain embodiments, 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 triisocyanate. 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. In certain embodiments, 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. Other 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 (Ν,Ν-dimethylcyclohexylamine), as well as Dabco® by Evonik Industries, such as Dabco® DC5357 and DC2585.

[083] In certain embodiments are described rigid, semi-rigid, or flexible foams. Thus, in certain embodiments the reaction mixture may further comprise a foaming (blowing) agent. Exemplary foaming agents include water, hydrocarbons (e.g., methane, ethane, propane, butane, pentane, optionally halogenated), and olefins. For example, 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. Particular 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. In accordance with some embodiments of the disclosure, 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.

[084] In certain emodiments, the reaction mixture for preparing polymers may further comprise a cross linker, such as a polyol or a polyamine. In certain embodiments, 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, Ν,Ν,Ν',Ν'- tetrakis-(2-hydroxypropyl)- ethylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, ethylenediamine, 1,2- propanediamine, 1,6- hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5- dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'- dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine,

aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine,

aminoethylpropanolamine, aminopropylpropanolamine, or aminohexylpropanolamine.

[085] In certain embodiments, the reaction mixture may further comprise a fire retardant additive. Exemplary 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 esters and phosphate esters; metal hydroxide fire retardants including inorganic hydroxides, such as aluminum hydroxide, magnesium hydroxide, aluminum trihydroxide (ATH) and hydroxycarbonate; non-halogenated melamine-based fire retardants such as melamine(2,4,6-triamino-l,3,5 triazine), melamine derivatives (including salts with organic or inorganic acids, such as boric acid, cyanuric acid, phosphoric acid or pyro/poly- phosphoric acid), and melamine homologues; borate fire retardant compounds include zinc borate, borax (sodium borate), ammonium borate, and calcium borate; silicon-based materials include linear and branched chain-type silicone with (hydroxy or methoxy) or without (saturated hydrocarbons) functional reactive groups; phosphonic acid derivatives include phosphonic acid, ethylenediamine salt of phosphonic acid, tetrakis hydroxymethyl phosphonium chloride and n-methyl

dimethylphosphono propionamide; and 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.

[086] In certain embodiments, the reaction mixture may further comprise other additives such as fillers. Exemplary 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. In certain embodiments, 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. [087] Exemplary 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,

dinaphthylmetanedissulfonic acid, ricinoleic acid, an oxyethylated alkylphenol, an oxyethylated fatty alcohol, a paraffin oil, a caster oil ester, a ricinoleic acid ester, turkey red oil, groundnut oil, a paraffin fatty alcohol, and combinations thereof. Other exemplary additives may include one or more plasticizers, such as an estolide plasticizer selected from compounds of Formula X.

[088] In certain embodiments, 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. Thus, in certain embodiments 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.

[089] In other embodiments, and optionally in addition to the hydroxyl value, the EN of the estolide compounds may be modified to help impart unique characteristics to the resulting materials. For example, in certain embodiments, the estolide oligomer may be grown to a higher EN (e.g., EN > 4). Without being bound to any particular theory, 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:

Compound X

[090] Also surprisingly, in other embodiments, 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:

Compound Y

[091] In certain embodiments, the polymeric materials described herein may be rigid, semi-rigid, or flexible foams. In certain embodiments, 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). Exemplary production formulas for foams include those set forth below in Table 2:

Table 2

[092] In certain embodiments, the polymeric materials described herein will exhibit particular hardness values, which may be reported as a Shore value according to ASTM D2240. In certain embodments, 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. In certain embodments, 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. In certain embodments, 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. [093] Other exemplary compounds that may be useful for the applications described in the instant application include, but are not limited to:

52

53

[094] In other embodiments, the compounds described herein will exhibit certain lubricity, viscosity, and/or pour point characteristics. For example, in certain embodiments, 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.

[095] In some embodiments, 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. In some embodiments, 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.

[096] In certain embodiments, compounds described herein may exhibit desirable low-temperature pour point properties. In some embodiments, 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. In some embodiments, compounds have a pour point of about -25 °C to about -45 °C. In some embodiments, the pour point falls within a range of about -30 °C to about -40 °C. In some embodiments, the pour point falls within the range of about -40 °C to about -50 °C, or about -50 °C to about -60 °C. In some embodiments, 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.

[097] In addition, in certain embodiments, 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). In certain instances, 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. Thus, in certain embodiments, it may be desirable to reduce the IV of the compounds in an effort to increase the oil's oxidative stability, while also decreasing harmful deposits and the corrosiveness of the oil.

[098] In some embodiments, 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

hydrogenating compounds having unsaturated caps.

[099] Also described herein are methods of making estolide esters and estolide base oils. In certain embodiments, 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. In certain embodiments, the catalyst may comprise a strong Lewis acid such as BF etherate. In certain embodiments, the reaction is conducted in the presence of dielectric heating, such as microwave radiation.

[0100] In some embodiments, 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. In certain embodiments, the catalyst is at least one titanium compound selected from TiCU and Ti(OCH ₂ CH ₂ CH ₂ CH )4 (titanium (IV) butoxide). In certain embodiments, the catalyst is at least one tin compound selected from Sn(0 ₂ CC0 ₂ ) (tin (II) oxalate), SnO, and SnCl ₂ . In some embodiments, 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 . In certain embodiments, 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. For example, in certain embodiments, the catalyst may be selected from

ZrOCl ₂ 8H ₂ 0 and ZrOCl ₂ 2THF, or HfOCl ₂ 2THF and HfOCl ₂ 8H ₂ 0.

[0101] In certain embodiments, contacting the polyl with an estolide oligomer and/or any other acylating agents (e.g., acetic anhydride, wherein at least one of R5 or R6 represents -C(=0)CH ) will result in partial esterification of the polyl. Accordingly, in certain embodiments, the resulting estolide polyol ester will exhibit a hydroxyl value of greater than 0 mg KOH/g. In certain embodiments, the composition exhibits a hydroxyl value less than or equal to 1 mg KOH/g. In certain embodiments, the composition exhibits a hydroxyl value less than or equal to 5 mg KOH/g. In certain embodiments, 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. In certain embodiments, the

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

characteristics, the resulting compounds will exhibit very high hydroxyl values, such as greater than 50 mg KOH/g or 100 mg KOH/g. In certain embodiments, 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.

[0102] The present disclosure further relates to methods of making compounds of Formulas I-XII. By way of example, the reaction of a polyol with a free-acid estolide is illustrated and discussed below.

Scheme 1

[0103] In Scheme 1, wherein x is, independently for each occurrence, an integer selected from 0 to 20, y is, independently for each occurrence, an integer selected from 0 to 20, n is an integer greater than or equal to 0, and Ri is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched, unsaturated fatty acid 100 may be combined with compound 102 and a catalyst to form free acid estolide 104. In certain embodiments, compound 102 is not included, and unsaturated fatty acid 100 may be exposed alone to catalystic conditions to form free acid estolide 104, wherein Ri would represent an unsaturated alkyl group. In certain embodiments, if compound 102 is included in the reaction, 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).

Scheme 2

[0104] In Scheme 2, wherein x is, independently for each occurrence, an integer selected from 0 to 20, y is, independently for each occurrence, an integer selected from 0 to 20, z is, independently for each occurrence, an integer selected from 0 to 20, n is an integer greater than or equal to 0, Ri is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched, free acid estolide 104 and polyglycerol 200 are combined under catalytic conditions to form estolide polyol 202. In certain embodiments, polyglycerine 200 undergoes partial esterification with free acid estolide 104, such that one or more of the hydroxyl hydrogen of polyglycerine 200 are replaced with a residue of estolide 104. 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).

Scheme 3

[0105] In Scheme 3, wherein x is, independently for each occurrence, an integer selected from 0 to 20, y is, independently for each occurrence, an integer selected from 0 to 20, and n is an integer greater than or equal to 0, unsaturated fatty acid 300 is expoxidized and exposed to ring-opening conditions to yield estolide 302, wherein each Z' is a -OH group, or both of Z' are taken together to form an epoxide residue. Any suitable epoxidation source may be used to form the epoxidized intermediate, with ring opening catalyzed by the addition of a first epoxidized fatty acid molecule to a second epoxidized fatty acid molecule. In certain embodiments the synthesis may be conducted in a one-pot manner by using an epoxidizing agent (e.g., H2O2) in the presence of a catalyst (e.g.,

Na ₂ W04 ) and a phase transfer catalyst. It should be understood that the oligomerization may be non-specific, resulting in different regioisomers depending on which side the ring opening occurs. Estolide 302 is an example of a single regioisomer. Depending on the synthetic conditions, 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.

Scheme 4

[0106] In Scheme 4, wherein x is, independently for each occurrence, an integer selected from 0 to 20, y is, independently for each occurrence, an integer selected from 0 to 20, and Z' independently for each occurrence is selected from C(R ₂ ) ₂ and N(R ₂ ), wherein each R ₂ is independently selected from hydrogen and an optionally substituted alkyl, 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.

[0107] In certain embodiments, polyol estolide compounds may meet or exceed one or more of the specifications for certain end-use applications, without the need for conventional additives. For example, in certain instances, 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. However, in certain embodiments, the counterintuitive properties of certain compounds described herein (e.g., increased EN provides estolides with higher viscosities while retaining, or even decreasing, the oil's pour point) may make higher-viscosity estolides particularly suitable for such specialized applications.

[0108] Similarly, the use of prior-known lubricants in colder environments may generally result in an unwanted increase in a lubricant's viscosity. Thus, depending on the application, it may be desirable to use lower-viscosity oils at lower temperatures. In certain circumstances, 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.

[0109] In some embodiments, it may be desirable to prepare lubricant compositions comprising a estolide polyol ester. For example, in certain embodiments, 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. In addition, or in the alternative, in certain embodiments, 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. In certain embodiments, the estolides described herein also mix well with gasoline, so that they may be useful as fuel components or additives.

[0110] In all of the foregoing examples, the compounds described may be useful alone, as mixtures, or in combination with other compounds, compositions, and/or materials.

[0111] Methods for obtaining the novel compounds described herein will be apparent to those of ordinary skill in the art, suitable procedures being described, for example, in the examples below, and in the references cited herein.

EXAMPLES

Analytics

[0112] Nuclear Magnetic Resonance: MR spectra were collected using a Bruker Avance 500 spectrometer with an absolute frequency of 500.113 MHz at 300 K using CDCh as the solvent. Chemical shifts were reported as parts per million from tetramethylsilane. The formation of a secondary ester link between fatty acids, indicating the formation of estolide, was verified with ¾ NMR by a peak at about 4.84 ppm.

[0113] Estolide Number (EN): 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.

[0114] Iodine Value (IV): The 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. For example, if 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.

[0115] Acid Value: The 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.

[0116] Gas Chromatography (GC): 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.

[0117] The parameters of the analysis were as follows: column flow at 1.0 mL/min with a helium head pressure of 14.99 psi; split ratio of 50: 1; programmed ramp of 120-135°C at 20°C/min, 135-265°C at 7°C/min, hold for 5 min at 265°C; injector and detector temperatures set at 250°C.

[0118] 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.

[0119] Sample Preparation: To prepare the samples, 10 mg of polyol estolide was combined with 0.5 mL of 0.5M KOH/MeOH in a vial and heated at 100°C for 1 hour. This was followed by the addition of 1.5 mL of 1.0 M FFiSC /MeOH and heated at 100°C for 15 minutes and then allowed to cool to room temperature. One (1) mL of Η ₂ 0 and ImL of hexane were then added to the vial and the resulting liquid phases were mixed thoroughly. The layers were then allowed to phase separate for 1 minute. The bottom H ₂ 0 layer was removed and discarded. A small amount of drying agent (Na ₂ S04 anhydrous) was then added to the organic layer after which the organic layer was then transferred to a 2 mL crimp cap vial and analyzed.

[0120] 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.

[0121] IV Calculation: The iodine value is estimated by the following equation based on ASTM Method D97 (ASTM International, Conshohocken, PA):

Af = fraction of fatty compound in the sample

MWi = 253.81, atomic weight of two iodine atoms added to a double bond db = number of double bonds on the fatty compound MWf = molecular weight of the fatty compound

[0122] The properties of exemplary polyol estolide compounds and compositions described herein are identified in the following examples and tables.

[0123] Other Measurements: Except as otherwise described, 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, and acute aqueous toxicity is measured by Organization of Economic Cooperation and Development (OECD) 203.

Example 1

[0124] 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 (μ) 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 1μ 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. 1).

Example 2

[0125] 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 1μ 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 1μ 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).

Example 3

[0126] 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

methanesulfonic acid (0.1 equiv.). 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.

Example 4

[0127] 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.

Example 5

[0128] 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. The organic layer is then washed with aliquots of 10% aqueous copper sulfate until the color of the aqueous layer indicated the absence of pyridine. The organic layer is dried over sodium sulfate, and the mixture is concentrated under reduced pressure to yield estolide polyglycerol esters comprising a single estolide residue and a plurality of acetate residues.

Example 6

[0129] 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.

Example 7

[0130] 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.

Example 8

[0131] 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.

Example 9

[0132] 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.

Example 10

[0133] 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

dichloromethane and isdried over MgS04. The solvent is removed in vacuo to provide a

hydroxylated free-acid estolide compounds, also referred to as polyol free-acid estolides, having a high hydroxyl value (e.g., >200 mg KOH/g).

Example 12

[0135] 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. After 24 hours, about 75-85% of the chloroform is removed in vacuo, and the resulting polyurethane mixture is poured into a pre-heated mold at 60°C and is cured in an oven for 24 hrs to provide a solid polyurethane product.

Example 13

[0136] The method according to Ex. 3 is repeated, except the free-acid estolide product of Ex. 1 is replaced with the polyol free-acid estolide of Ex. 11, to provide polyol estolide esters having a high hydroxyl value (e.g., > 300 mg KOH/g).

Example 14

[0137] The method according to Ex. 13 is repeated, except triacylglycerol is replaced with glycerine to provide polyol estolide esters (e.g., > 250 mg KOH/g).

Example 15

[0138] The method according to Ex. 12 is repeated, except the polyol free-acid estolide is replaced with the polyol estolide esters prepared according to Ex. 13 to provide a solid polyurethane product. Example 16

[0139] The method according to Ex. 13 is repeated, except the polyol free-acid estolide is replaced with the polyol estolide esters prepared according to Ex. 13 to provide a solid polyurethane product.

Additional Embodiments

[0140] 1. At least one compound according to Formula I:

Formula I wherein z is selected from 0 to 20; and

R.5 and R6, independently for each occurrence, are selected from hydrogen, R ₇ , and a residue of Formula II:

Formula II wherein

R.7 is, independently for each occurrence, selected from optionally substituted alkyl and -C(=0)Rio, wherein Rio is an optionally substituted alkyl;

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.

[0141] 2. The at least one compound according to embodiment 1, wherein x is, independently for each occurrence, selected from 0 to 10.

[0142] 3. The at least one compound according to any of the preceding embodiments, wherein x is, independently for each occurrence, selected from 7 and 8.

[0143] 4. The at least one compound according to any of the preceding embodiments, wherein y is, independently for each occurrence, selected from 0 to 10. [0144] 5. The at least one compound according to any of the preceding embodiments, wherein y is 0 for each occurrence.

[0145] 6. The at least one compound according to any of embodiments 1-4, wherein y is, independently for each occurrence, selected from 7 and 8.

[0146] 7. The at least one compound according to any of the preceding embodiments, wherein x+y is 15 for at least one chain.

[0147] 8. The at least one compound according to any one of embodiments 1-7, wherein z is 1 to 10.

[0148] 9. The at least one compound according to any of the preceding embodiments, wherein z is selected from 1 and 2.

[0149] 10. The at least one compound according to any of the preceding embodiments, wherein at least one Ri is substituted with at least one hydroxyl group.

[0150] 1 1. The at least one compound according to any of the preceding embodiments, wherein at least one of R ₈ or R9 is a hydroxyl group.

[0151] 12. The at least one compound according to any of the preceding embodiments, wherein R ₈ is hydrogen for each occurrence.

[0152] 13. The at least one compound according to any of the preceding embodiments, wherein at least one R9 is a hydroxyl group.

[0153] 14. The at least one compound according to any one of embodiments 1-12, wherein R9 is hydrogen for each occurrence. [0154] 15. The at least one compound according to any one of the preceding embodiments, wherein Ri is selected from, independently for each occurrence, unsubstituted Ci to C20 alkanyl group and a Ci to C20 alkanyl group substituted with at least one hydroxyl group.

[0155] 16. The at least one compound according to any one of embodiments 1-14, wherein 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.

[0156] 17. The compound according to any one of the preceding embodiments, wherein Ri is linear for each occurrence.

[0157] 18. The compound according to any one of embodiments 1-9, wherein R5 is hydrogen for each occurrence.

[0158] 19. The compound according to any of the preceding embodiments, wherein at least one R5 is a residue of Formula II.

[0159] 20. The compound according to any of the preceding embodiments, wherein 5 is a residue of Formula II for each occurrence.

[0160] 21. The compound according to any one of embodiments 1-20, wherein one R5 is a residue of Formula II, and the other 5 is hydrogen.

[0161] 22. The compound according to any of the preceding embodiments, wherein at least one R5 is a residue of Formula II.

[0162] 23. A composition comprising at least one compound according to any one of the preceding embodiments. [0163] 24. The composition according to embodiment 23, 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 II contained in the composition.

[0164] 25. The composition according to embodiment 24, 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 II contained in the composition.

[0165] 26. The composition according to embodiment 24, 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 II contained in the composition.

[0166] 27. The composition according to any one of embodiments 24, 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 II contained in the composition.

[0167] 28. The composition according to any one of embodiments 23-27, further comprising at least one to compound according Formula X, wherein R ₂ is selected from hydrogen and unsubstituted alkyl.

[0168] 29. At least one compound according to Formula III:

Formula III wherein

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.

[0169] 30. The compound according to embodiment 29, wherein Ri is an optionally substituted Ci to C20 alkanyl group. [0170] 31. The compound according to any one of embodiments 29-30, wherein Ri is substituted with at least one hydroxyl group.

[0171] 32. The compound according to any one of embodiments 29-31, wherein y is, independently for each occurrence, selected from 7 and 8.

[0172] 33. The compound according to any one of embodiments 29-32, wherein x+y is 15 for each chain.

[0173] 34. The compound according to embodiment 29-31, wherein y is 0 for each occurrence.

[0174] 35. The compound according to any one of embodiments 29-34, wherein Ri is linear.

[0175] 36. The compound according to any one of embodiments 29-35, wherein n is selected from 0 to 8.

[0176] 37. The compound according to embodiment 36, wherein n is selected from 1 to 6.

[0177] 38. The compound according to any one of embodiments 29-37, wherein z is 1 to 10.

[0178] 39. A composition comprising at least one compound according to any one of embodiments 29-38.

[0179] 40. The composition according to embodiment 29, 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 III contained in the composition.

[0180] 41. The composition according to any one of embodiments 29-40, wherein the composition exhibits an GN of at least 2, wherein GN is the average number of glycerol residues z+l for compounds of Formula III contained in the composition. [0181] 42. The composition according to any one of embodiments 29-41, 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 III contained in the composition.

[0182] 43. The 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.

[0183] 44. The composition according to any one of embodiments 29-33, 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 III contained in the composition.

[0184] 45. At least one compound according to Formula IV:

Formula IV wherein z is selected from 0 to 20; and

R.5 and R6, independently for each occurrence, are selected from hydrogen, R ₇ , and and a residue of Formula V:

Formula V wherein x is, independently for each occurrence, an integer selected from 0 to 20; y is, independently for each occurrence, an integer selected from 0 to 20; n is an integer equal to or greater than 0; and

Ri is an optionally substituted alkanyl group or an optionally substituted alkenyl group; and

R ₇ is, independently for each occurrence, selected from optionally substituted alkyl and - C(=0)Rio, 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.

[0185] 46. The at least one compound according to embodiment 45, wherein Formula IV and Formula V are unsubstituted. [0186] 47. The at least one compound according to any one of embodiments 45-46, wherein x is, independently for each occurrence, selected from 7 and 8.

[0187] 48. The at least one compound according to any one of embodiments 45-47, wherein x+y is 15 for each chain.

[0188] 49. The at least one compound according to any one of embodiments 45-47, wherein y is, independently for each occurrence, selected from 7 and 8.

[0189] 50. The at least one compound according to any one of embodiments 45-48, wherein y is 0 for each occurrence.

[0190] 51. The at least one compound according to any one of embodiments 45-50, wherein z is 1 to 10.

[0191] 52. The at least one compound according to any one of embodiments 45-51, wherein Ri is selected from, independently for each occurrence, optionally substituted Ci to C20 alkanyl group or an optionally substituted C2 to C20 alkenyl group.

[0192] 53. The at least one compound according to any one of embodiments 45-51, wherein Ri is selected from, independently for each occurrence, Ci to C20 alkanyl group optionally substituted with at least one hydroxyl group.

[0193] 54. The at least one compound according to any one of embodiments 45-51, wherein Ri is selected from, independently for each occurrence, unsubstituted Ci to C20 alkanyl group.

[0194] 55. The compound according to any one of embodiments 45-54, wherein Ri is linear for each occurrence. [0195] 56. The compound according to any one of embodiments 45-55, wherein R ₅ is hydrogen for each occurrence.

[0196] 57. The compound according to any one of embodiments 45-56, wherein at least one R6 is a residue of Formula II.

[0197] 58. A composition comprising at least one compounds according to any one of embodiments 45-57.

[0198] 59. The 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.

[0199] 60. The 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.

[0200] 61. The 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.

[0201] 62. The 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.

[0202] 63. The 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. [0203] 64. At least one compound selected from Formulas Via, VIb, Vic, or VId:

Formula Via Formula VIb

Formula Vic Formula VId wherein R ₅ is selected from, independently for each occurrence, hydrogen, R ₇ , and a residue of Formula II:

Formula II wherein

R.7 is, independently for each occurrence, selected from optionally substituted alkyl and -C(=0)Rio, wherein Rio is an optionally substituted alkyl;

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.

[0204] 65. The compound according to embodiment 64, wherein x is, independently for each occurrence, selected from 7 and 8.

[0205] 66. The compound according to any one of embodiments 64-65, wherein x+y is 15 for each chain.

[0206] 67. The compound according to embodiment 64-66, wherein y is, independently for each occurrence, selected from 7 and 8.

[0207] 68. The compound according to any one of embodiments 64-66, wherein y is 0 for each occurrence. [0208] 69. The compound according to any one of embodiments 64-68, wherein Ri is selected from Ci to C20 alkanyl substituted with at least one hydroxyl group.

[0209] 70. The compound according to any one of embodiments 64-68, wherein Ri is selected from unsubstituted Ci to C20 alkanyl.

[0210] 71. The compound according to any one of embodiments 64-70, wherein Ri is linear.

[0211] 72. The compound according to any one of embodiments 64-71, wherein n is selected from 0 to 8.

[0212] 73. The compound according to any one of embodiments 64-72, wherein n is selected from 1 to 6.

[0213] 74. The compound/composition according to any one of embodiments 1-28 and 64-73, wherein Y and X' are, independently for each occurrence, selected from CH ₂ and CHOH.

[0214] 75. The compound/composition according to embodiment 74, wherein at least one Y or X' is CHOH.

[0215] 76. The compound/composition according to embodiment 74, wherein Y and X' are CH ₂ for each occurrence.

[0216] 77. At least one compound of Formula XI:

Formula XI wherein

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, hydroxyl, and -OC(=0)Rio, wherein Rio is an optionally substituted alkyl;

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.

[0219] 80. The compound according to any one of embodiments 77-79, wherein R ₈ is hydrogen for each occurrence.

[0220] 81. The compound according to any one of embodiments 77-80, wherein at least one R9 on each fatty acid chain residue is hydroxyl.

[0221] 82. The compound according to any one of embodiments 77-81, wherein, for each fatty acid chain residue, R9 is a hydroxyl group for a single occurrence.

[0222] 83. The compound according to any one of embodiments 77-82, wherein Ri is a Ci to C20 alkanyl group substituted with at least one hydroxyl group or at least one epoxide residue.

[0223] 84. The compound according to any one of embodiments 77-83, wherein Ri is a Ci to C20 alkanyl group substituted with two hydroxyl groups.

[0224] 85. The compound according to any one of embodiments 77-84, wherein Y' is O.

[0225] 86. The compound according to any one of embodiments 77-85, wherein R ₂ is a Ci to C20 alkanyl group substituted with at least one hydroxyl group, or a Ci to C20 alkenyl group substituted with at least one hydroxyl group.

[0226] 87. The compound according to any one of embodiments 77-86, wherein R2 is a glycerol residue or a polyglycerol residue.

[0227] 88. The compound according to any one of embodiments 77-87, wherein (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. [0228] 89. The compound according to embodiment 88, wherein R ₂ is a Ci to C20 alkanyl group substituted with at least one hydroxyl group.

[0229] 90. The compound according to any one of embodiments 77-89, wherein n is from 0 to 8. [0230] 91. The compound according to any one of embodiments 77-90, wherein n is from 1 to 6. [0231] 92. A composition for producing a polymer comprising: an estolide compound comprising at least one hydroxyl group; and

at least one reactive monomer.

[0232] 93. The composition according to embodiment 92, further comprising at least one cross linker.

[0233] 94. The composition according to embodiment 93, wherein the at least one cross linker is selected from one or more polyols or polyamines.

[0234] 95. The process according to any one of embodiments 93-94, wherein 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,

trimethylolpropane, 1,2,6-hexanetriol, tri ethanolamine, pentaerythritol, Ν,Ν,Ν',Ν'- tetrakis-(2- hydroxypropyl)-ethylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine,

ethylenediamine, 1,2-propanediamine, 1,6- hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'- dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine,

aminoethylpropanolamine, aminopropylpropanolamine, or aminohexylpropanolamine.

[0235] 96. The 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.

[0236] 97. The composition according to any one of embodiments 92-96, wherein the at least one reactive monomer is selected from one or more of polyisocyanates or polycarboxylic acids.

[0237] 98. The composition according to any one of embodiments 92-97, wherein the at least one reactive monomer is a polyisocyanate.

[0238] 99. The composition according to any one of embodiments 92-98, wherein the at least one reactive monomer is a diisocyanate.

[0239] 100. The composition according to any one of embodiments 92-98, wherein the at least one reactive monomer is selected from one or more of methylene diphenyl diisocyanate (MDI), 2,4- toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-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, l,3,5-triazine-2,4,6-triisocyanate, or ethyl ester L-lysine triisocyanate.

[0240] 101. The composition according to any one of embodiments 92-100, further comprising at least one reaction catalyst.

[0241] 102. The composition according to embodiment 101, wherein the at least one reaction catalyst is selected from one or more of tin catalysts or amine catalysts. [0242] 103. The composition according to any one of embodiments 92-97, wherein the at least one reactive monomer is a polycarboxylic acid.

[0243] 104. The composition according to embodiment 103, wherein the at least one reactive monomer is a dicarboxylic acid.

[0244] 105. The 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.

[0245] 106. The composition according to any one of embodiments 103-105, further comprising a reaction catalyst.

[0246] 107. The composition according to any one of embodiments 103-105, further comprising a tin reaction catalyst.

[0247] 108. The composition according to any one of embodiments 92-107, wherein the estolide compound comprises an estolide ester.

[0248] 109. The composition according to embodiment 108, wherein the estolide ester compound comprises a plurality of hydroxyl groups.

[0249] 110. The composition according to any one of embodiments 108-109, wherein the ester residue of the estolide ester comprises at least one hydroxyl group.

[0250] 111. The composition according to any one of embodiments 108-110, wherein the estolide residue of the estolide ester comprises at least one hydroxyl group, and the ester residue of the estolide ester comprises at least one hydroxyl group. [0251] 112. The composition according to any one of embodiments 108-111, wherein the estolide residue of the estolide ester comprises two or more hydroxyl groups, and the ester residue of the estolide ester comprises two or more hydroxyl groups.

[0252] 113. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 1 to about 2,500 mg KOH/g.

[0253] 114. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 1 to about 500 mg KOH/g.

[0254] 115. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 20 to about 100 mg KOH/g.

[0255] 116. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 25 to about 90 mg KOH/g.

[0256] 117. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 40 to about 85 mg KOH/g.

[0257] 118. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 50 to about 100 mg KOH/g.

[0258] 119. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 80 to about 150 mg KOH/g.

[0259] 120. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 100 to about 1,000 mg KOH/g.

[0260] 121. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 100 to about 500 mg KOH/g. [0261] 122. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 150 to about 400 mg KOH/g.

[0262] 123. The composition according to any one of embodiments 92-112, wherein the estolide compound has a hydroxyl value of about 200 to about 350 mg KOH/g.

[0263] 124. The 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.

[0264] 125. A polymeric material comprising a residue of Formula XII:

Formula XII

wherein

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

-OC(=0)R ₁₂ ;

R ₈ and R9 are, independently for each occurrence, selected from hydrogen, hydroxyl, R.2 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 -OC(=0)R ₁₂ ;

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

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.

[0265] 126. The polymeric material of embodiment 125, wherein Ri and/or R2 are substituted with at least one -OC(=0)Ri ₂ .

[0266] 127. The polymeric material of any one of embodiments 125-126, wherein at least one R ₈ or

[0267] 128. The polymeric material of any one of embodiments 125-127, wherein at least one R12

R ₂

N ?

comprises the residue . [0268] 129. The polymeric material according to any one of embodiments 125-128, wherein R ₂ for residue R12 is a hydrogen for each occurrence.

[0269] 130. The composition according to any one of embodiments 92-124, further comprising at least one foaming agent.

[0270] 131. The composition according to embodiment 130, wherein the at least one foaming agent is water.

[0271] 132. The composition according to any one of embodiments 130-131, wherein the at least one foaming agent comprises a hydrocarbon.

[0272] 133. The composition according to any one of embodiments 130-131, wherein the at least one foaming agent comprises a halogenated hydrocarbon.

[0273] 134. The composition according to any one of embodiments 92-124 and 130-133, further comprising a fire retardant.

[0274] 135. The composition according to any one of embodiments 92-124 and 130-134, further comprising a filler.

[0275] 136. The composition according to any one of embodiments 92-124 and 130-135, further comprising a surfactant.

[0276] 137. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 1 to about 50 Shore OO as tested according to ASTM D2240. [0277] 138. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 50 to about 75 Shore 00 as tested according to ASTM D2240.

[0278] 139. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 75 to about 90 Shore OO as tested according to ASTM D2240.

[0279] 140. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 90 to about 100 Shore OO as tested according to ASTM D2240.

[0280] 141. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 1 to about 30 Shore A as tested according to ASTM D2240.

[0281] 142. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 30 to about 60 Shore A as tested according to ASTM D2240.

[0282] 143. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 60 to about 80 Shore A as tested according to ASTM D2240.

[0283] 144. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 80 to about 100 Shore A as tested according to ASTM D2240. [0284] 145. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 1 to about 30 Shore D as tested according to ASTM D2240.

[0285] 146. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 30 to about 60 Shore D as tested according to ASTM D2240.

[0286] 147. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 60 to about 80 Shore D as tested according to ASTM D2240.

[0287] 148. The polymeric material according to any one of embodiments 125-129, wherein the polymeric material comprises a hardness of about 80 to about 100 Shore D as tested according to ASTM D2240.

[0288] 149. A compound according to any one of embodiments 77-91, wherein the compound of Formula XI is selected from compounds of Formula XIII:

Formula XIII wherein

x" is selected from 0 to 20;

y' is selected from 0 to 20; and

Z' are independently selected from -OH and -OC(=0)Rio, or each of Z' are taken together to form an epoxide residue.

[0289] 150. A compound of embodiment 149, wherein x is, independently for each occurrence, selected from 6 or 7.

[0290] 151. A compound of embodiment 150, wherein x is, independently for each occurrence, selected from 6 or 7.

[0291] 152. A compound according to any one of embodiments 149-151, wherein x" is 7. [0292] 153. A compound according to any one of embodiments 149-152, wherein y' is 7.