WO2018217749A1 - Liants d'asphalte et compositions bitumineuses comprenant des composés oligomères - Google Patents

Liants d'asphalte et compositions bitumineuses comprenant des composés oligomères Download PDF

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Publication number
WO2018217749A1
WO2018217749A1 PCT/US2018/033886 US2018033886W WO2018217749A1 WO 2018217749 A1 WO2018217749 A1 WO 2018217749A1 US 2018033886 W US2018033886 W US 2018033886W WO 2018217749 A1 WO2018217749 A1 WO 2018217749A1
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Prior art keywords
binder
alkyl
estolide
asphalt
composition
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PCT/US2018/033886
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English (en)
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Jeremy Forest
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Biosynthetic Technologies, Llc
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Publication of WO2018217749A1 publication Critical patent/WO2018217749A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/70—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index

Definitions

  • the present disclosure relates to asphalt binders and bituminous compositions comprising oligomeric additives such as estolide compounds.
  • oligomeric additives such as estolide compounds.
  • the oligomeric compounds may be useful as rheology modifiers for use in bituminous binders in road paving applications.
  • Asphalt binder is a key ingredient in pavements, roofing and waterproofing applications.
  • the primary use of asphalt is in road construction, where it is used as the glue or binder for the aggregate particles, and accounts for approximately 80% of the asphalt consumed in the United States.
  • the most common type of flexible pavement surfacing in the United States is hot mix asphalt (HMA) that may also be known by many different names such as hot mix, asphalt concrete (AC or ACP), asphalt, blacktop or bitumen.
  • HMA hot mix asphalt
  • Additives such as polymers and rheology modifiers can be added to asphalt binder compositions in an effort to augment the overall properties of the resulting product in an effort to account for variations in the refined asphalt binder, and/or optimize the performance of the product depending on the viscoelastic properties that may be required for the resulting application. Accordingly, there remains a need to develop asphalt binder compositions comprising novel rheology modifiers.
  • compositions comprising a bituminous binder and a rheology modifier comprising at least one estolide.
  • the bituminous binder comprises bitumen and at least one elastomer or rubber.
  • asphalts comprising aggregate, a bituminous binder, and at least one rheology modifier comprising at least one estolide compound.
  • Asphaltt refers to a composite material comprising a bituminous binder and aggregate, which is generally used for paving applications. Such asphalt is also known as “asphalt concrete.” Examples of asphalt grades used in paving applications include stone mastic asphalt, soft asphalt, hot rolled asphalt, dense-graded asphalt, gap-graded asphalt, porous asphalt, mastic asphalt, and other asphalt types. Typically, the total amount of bituminous binder in asphalt is from 1 to 10 wt.% based on the total weight of the asphalt, in some cases from 2.5 to 8.5 wt.% and in some cases from 4 to 7.5 wt.%.
  • Aggregate is particulate mineral material suitable for use in asphalt. It generally comprises sand, gravel, crushed stone, and slag. Any conventional type of aggregate suitable for use in asphalt can be used. Examples of suitable aggregates include granite, limestone, gravel, and mixtures thereof.
  • Bitumen or (or a material described as “bituminous”) refers to a mixture of viscous organic liquids or semi-solids from crude oil that is black, sticky, soluble in carbon disulfide, and composed primarily of condensed aromatic hydrocarbons.
  • bitumen refers to a mixture of maltenes and asphaltenes.
  • Bitumen may be any conventional type of bitumen known to the skilled person. The bitumen may be naturally occurring. It may be crude bitumen, or it may be refined bitumen obtained as the bottom residue from vacuum distillation of crude oil, thermal cracking, or hydrocracking.
  • Performance Grade is defined as the temperature interval for which a specific asphalt product is designed. For example, an asphalt product designed to accommodate a high temperature of 64°C and a low temperature of -22°C has a PG of 64-22. Performance Grade standards are set by the National Committee of Highway and Roadway Professionals (NCHRP).
  • NCHRP National Committee of Highway and Roadway Professionals
  • the bitumen may be commercially available virgin bitumen such as paving grade bitumen, e.g., bitumen suitable for paving applications.
  • bitumen which in the penetration grade (PEN) classification system are referred to as PEN 10/20, 20/30, 30/45, 35/50, 40/60 and 70/100 or bitumen which in the performance grade (PG) classification system are referred to as PG 64-22, 58-22, 70-22 and 64-28.
  • PEN 10/20 bitumen which in the penetration grade (PEN) classification system
  • PG performance grade
  • bitumen is available from, for instance, Shell, Total, and British Petroleum (BP).
  • BP British Petroleum
  • the numeric designation refers to the penetration range of the bitumen as measured with the EN 1426 method, e.g., a 40/60 PEN bitumen corresponds to a bitumen with a penetration which ranges from 40 to 60 decimillimeters (dmm).
  • the first value of the numeric designation refers to the temperature performance and the second value refers to the low-temperature performance as measured by a method which is known in the art as the Superpave SM system.
  • bitumen may also be contained in or obtained from reclaimed asphalt shingles or reclaimed asphalt pavement, and is referred to as bitumen of RAS or RAP origin, respectively.
  • Bitumen refers to a combination of bitumen and, optionally, other components such as elastomers, non-bituminous binders, adhesion promoters, softening agents, or other suitable additives.
  • elastomers include, for example, ethylene-vinyl acetate copolymers,
  • polybutadienes ethylene-propylene copolymers, ethyl ene-propylene-diene terpolymers, butadiene- styrene block copolymers, butadiene-styrene-butadiene (i.e., butadiene end-capped) (BSB) copolymers, styrene-butadiene-styrene (SBS) block terpolymers, isoprene-styrene block copolymers and styrene-isoprene-styrene (SIS) block terpolymers, or the like.
  • BBSB butadiene end-capped
  • Exemplary polymeric materials include radial and linear block copolymers, such as those described in U.S. Patent No. 8,580,874, which is incorporated by reference in its entirety for all purposes.
  • Cured elastomer additives may include ground tire rubber materials.
  • the additional additives may be added to an asphalt binder in amounts ranging from about 0.1 wt.% to about 10 wt.%.
  • bitumen is sometimes used interchangeably with binder.
  • Recovered binder or "reclaimed binder” refers to aged binder that is present in or is recovered from reclaimed asphalt. Normally, the recovered binder is not isolated from the reclaimed asphalt. Recovered binder has a high viscosity compared with that of virgin bitumen as a result of aging and exposure to outdoor weather.
  • Aged binder includes recovered or reclaimed binder and laboratory-aged binder.
  • Aged binder can also refer to hard, poor-quality, or out-of-spec virgin binders that could benefit from combination with a rheology modifier as described herein, particularly virgin binders having a ring- and-ball softening point greater than 65°C by EN 1427 and a penetration value at 25°C by EN 1426 less than or equal to 12 dmm.
  • Virtual binder is binder that has not been used previously for road paving or "Virgin bitumen” (also known as “fresh bitumen”) refers to bitumen that has not been used, e.g., bitumen that has not been recovered from road pavement or reclaimed shingles.
  • Virgin bitumen is a component of virgin binder.
  • Virtual asphalt refers to a combination of virgin aggregate with virgin bitumen or virgin binder. Virgin asphalt has not been used previously forpaving.
  • Reclaimed asphalt generally includes reclaimed asphalt shingles (RAS), reclaimed asphalt pavement (RAP), reclaimed asphalt from plant waste, reclaimed asphalt from roofing felt, and asphalt from other applications.
  • RAS reclaimed asphalt shingles
  • RAP reclaimed asphalt pavement
  • reclaimed asphalt from plant waste reclaimed asphalt from roofing felt
  • asphalt from other applications generally includes reclaimed asphalt shingles (RAS), reclaimed asphalt pavement (RAP), reclaimed asphalt from plant waste, reclaimed asphalt from roofing felt, and asphalt from other applications.
  • RAS Reclaimed asphalt shingles
  • RAP Reclaimed asphalt pavement
  • RAP is asphalt that has been used previously as pavement.
  • RAP may be obtained from asphalt that has been removed from a road or other structure, and then has been processed by well-known methods. Prior to use, the RAP may be inspected, sized and selected, for instance, depending on the final paving application.
  • Embodision generally refers as a multiphase material in which all phases are dispersed in a continuous aqueous phase.
  • the aqueous phase may comprise surfactants, acid, base, thickeners, and other additives.
  • the dispersed phase may comprise thermoplastic natural and synthetic polymers, waxes, bitumen, other additives including rheology modifier(s), optionally petroleum based oils or mixtures thereof, herein collectively referred to as the "oil phase.
  • High shear and energy can be used to disperse the oil phase in the aqueous phase using apparatus such as colloidal mills.
  • Pavement preservation refers to a proactive maintenance of roads to prevent them from getting to a condition where major rehabilitation or reconstruction is necessary.
  • a pavement preservation application may be any of fog seal, slurry seal, micro-surfacing, chip seal, scrub seal, cape seal, and combinations thereof wherein an asphalt emulsion with optional additives is applied onto an existing road or pavement as a "seal" to seal the surface.
  • polymer is added to the asphalt emulsion to provide better mixture properties.
  • Frog seal is a pavement preservation application of an asphalt emulsion via a spray application ("fogging").
  • Slurry seal refers to a pavement preservation application wherein a mixture of water, asphalt binder, and aggregate is applied to an existing asphalt pavement surface.
  • a slurry seal is similar to a fog seal except the slurry seal has aggregates (e.g., sand) as part of the mixture for a "slurry” and slurry seals are generally used on residential streets.
  • Microsurfacing refers to a form of slurry seal, with the application of a mixture of water, bitumen binder with optional additives, aggregate (very small crushed rock), and additives to an existing asphalt concrete pavement surface.
  • a difference between slurry seal and microsurfacing is in how they "break” or harden. Slurry relies on evaporation of the water in the asphalt emulsion.
  • the asphalt emulsion used in microsurfacing contains additives which allow it to break without relying on the sun or heat for evaporation to occur, for the surface to harden quicker than with slurry seals.
  • Chip seal refers a pavement reservation application wherein first asphalt emulsion is applied then then a layer of crushed rock is applied to an existing asphalt pavement surface. "Chip seal” gets its name from the “chips” or small crushed rock placed on the surface.
  • Scrub seal refers to a pavement preservation application that is very close to a chip seal treatment where asphalt emulsion and crushed rock are placed on an asphalt pavement surface. The only difference is that the asphalt emulsion is applied to the road surface through a series of brooms placed at different angles. These brooms guide the asphalt emulsion into the pavement distresses to ensure sealing the road. These series of brooms, known as a “scrub broom”, give the treatment its title, "scrub seal.”
  • Cape seal is a combination of applications, i.e., an application of a chip or scrub seal followed by the application of slurry seal or microsurfacing at a later date.
  • Rehabilitation refers to applications carried out with pavements that exhibit distresses beyond the effectiveness of pavement preservation techniques, but not too severe to warrant the cost of complete reconstruction. As pavement ages, it will deteriorate due to weathering and traffic loading, but not to the point of complete reconstruction, so rehabilitation techniques can be performed.
  • Cold in-place recycling refers to applications involving a milling machine with a paver mixer, wherein the milling machine breaks and pulverizes a thin amount of the top layer of the old pavement.
  • the material is crushed and screened to the proper size and asphalt emulsions and/or additives including rheology modifiers or rejuvenators are mixed in to rejuvenate the material to give more life.
  • virgin aggregate can be added and spread on the existing surface.
  • the material is picked up by the paver and spread, then compacted using known methods, e.g., steel- wheel, pneumatic-tire, or vibratory rollers.
  • Rubberized asphalt refers to an asphalt mix, e.g., hot-mixed asphalt, containing crumb rubber.
  • the crumb rubber utilized is generated from recycled tires, wherein the tires are shredded and the steel enforcement and fibers are separated from the rubber.
  • the crumb rubber serves as a modifier for the asphalt and gives the asphalt greater viscosity and may improve cracking properties.
  • Rheology modifier generally refers to a composition or blend that can be used in asphalt compositions for road and pavement applications including but not limited to new construction, partial or complete re-construction, rehabilitation, preservation, CIR, e.g., in asphalt emulsion compositions, or in combination with aged binder or reclaimed asphalt (or their mixtures with virgin binder and/ or virgin asphalt) to modify flow or other properties of the aged binder or reclaimed asphalt and, in some cases, restores some or most of the original properties of virgin binder or virgin asphalt.
  • estolide compounds optionally in combination with one or more additional compononets, have not been previously described for use as rheology modifiers for bituminous binders, including reclaimed asphalt binders.
  • the use of at least one estolide compound in combination one or more other components helps to improve the high temperature properties of bituminous binders without sacrificing low-temperature performance, e.g., modifying the binders.
  • the modified binders in asphalt compositions expand the utility of reclaimed asphalt thereby helping the road construction industry reduce its reliance on virgin, non-renewable materials.
  • a dash (“-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent.
  • -C(0) H2 is attached through the carbon atom.
  • alkoxy by itself or as part of another substituent refers to a radical -OR 1 where R 1 is alkyl, cycloalkyl, cycloalkylalkyl, aryl, or arylalkyl, which can be substituted, as defined herein.
  • alkoxy groups have from 1 to 8 carbon atoms.
  • alkoxy groups have 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy, and the like.
  • Alkyl by itself or as part of another substituent refers to a saturated or unsaturated, branched, or straight-chain (linear) monovalent hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent alkane, alkene, or alkyne.
  • alkyl groups include, but are not limited to, methyl; ethyls such as ethanyl, ethenyl, and ethynyl; propyls such as propan-l-yl, propan-2-yl, prop-l-en-l-yl, prop-l-en-2-yl, prop-2-en-l-yl (allyl),
  • alkyl is specifically intended to include groups having any degree or level of saturation, i.e., groups having exclusively single carbon-carbon bonds, groups having one or more double carbon-carbon bonds, groups having one or more triple carbon-carbon bonds, and groups having mixtures of single, double, and triple carbon-carbon bonds.
  • degree or level of saturation i.e., groups having exclusively single carbon-carbon bonds, groups having one or more double carbon-carbon bonds, groups having one or more triple carbon-carbon bonds, and groups having mixtures of single, double, and triple carbon-carbon bonds.
  • alkanyl alkenyl
  • alkynyl are used.
  • an alkyl group comprises from 1 to 40 carbon atoms, in certain embodiments, from 1 to 22 or 1 to 18 carbon atoms, in certain embodiments, from 1 to 16 or 1 to 8 carbon atoms, and in certain embodiments from 1 to 6 or 1 to 3 carbon atoms.
  • an alkyl group comprises from 8 to 22 carbon atoms, in certain embodiments, from 8 to 18 or 8 to 16. 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, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 carbon atoms.
  • Aryl by itself or as part of another substituent refers to a monovalent aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system.
  • Aryl encompasses 5- and 6-membered carbocyclic aromatic rings, for example, benzene; bicyclic ring systems wherein at least one ring is carbocyclic and aromatic, for example, naphthalene, indane, and tetralin; and tricyclic ring systems wherein at least one ring is carbocyclic and aromatic, for example, fluorene.
  • Aryl encompasses multiple ring systems having at least one carbocyclic aromatic ring fused to at least one carbocyclic aromatic ring, cycloalkyl ring, or heterocycloalkyl ring.
  • aryl includes 5- and 6-membered carbocyclic aromatic rings fused to a 5- to 7-membered non-aromatic heterocycloalkyl ring containing one or more heteroatoms chosen from N, O, and S.
  • bicyclic ring systems wherein only one of the rings is a carbocyclic aromatic ring, the point of attachment may be at the carbocyclic aromatic ring or the heterocycloalkyl ring.
  • aryl groups include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexalene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene, and the like.
  • an aryl group include, but are
  • an aryl group can comprise 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
  • Aryl does not encompass or overlap in any way with heteroaryl, separately defined herein.
  • a multiple ring system in which one or more carbocyclic aromatic rings is fused to a heterocycloalkyl aromatic ring is heteroaryl, not aryl, as defined herein.
  • Arylalkyl by itself or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced with an aryl group.
  • arylalkyl groups include, but are not limited to, benzyl, 2-phenylethan-l-yl, 2-phenylethen-l-yl, naphthylmethyl, 2-naphthylethan-l-yl,
  • an arylalkyl group is C7-30 arylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the arylalkyl group is Ci-10 and the aryl moiety is C 6 -2o, and in certain embodiments, an arylalkyl group is C7-20 arylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the arylalkyl group is Ci -8 and the aryl moiety is C 6 -i2.
  • 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.
  • chiral compounds are compounds having at least one center of chirality (i.e. at least one asymmetric atom, in particular at least one asymmetric C atom), having an axis of chirality, a plane of chirality or a screw structure.
  • Achiral compounds are compounds which are not chiral.
  • Compounds and residues of Formula I-III include, but are not limited to, optical isomers of compounds and residues of Formula I-III, racemates thereof, and other mixtures thereof.
  • the single enantiomers or diastereomers i.e., optically active forms, can be obtained by asymmetric synthesis or by resolution of the racemates. Resolution of the racemates may be accomplished by, for example, chromatography, using, for example a chiral high-pressure liquid chromatography (UPLC) column.
  • UPLC chiral high-pressure liquid chromatography
  • Formula I-III cover all asymmetric variants of the compounds described herein, including isomers, racemates, enantiomers, diastereomers, and other mixtures thereof.
  • compounds of Formula I-III include Z- and E-forms (e.g., cis- and trans-forms) of compounds with double bonds.
  • the compounds of Formula I-III may also exist in several tautomeric forms including the enol form, the keto form, and mixtures thereof. Accordingly, the chemical structures depicted herein encompass all possible tautomeric forms of the illustrated compounds.
  • Cycloalkyl by itself or as part of another substituent refers to a saturated or unsaturated cyclic alkyl radical. Where a specific level of saturation is intended, the nomenclature
  • cycloalkanyl or “cycloalkenyl” is used.
  • cycloalkyl groups include, but are not limited to, groups derived from cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like.
  • a cycloalkyl group is C3-15 cycloalkyl, and in certain embodiments, C3-12 cycloalkyl or C5-12 cycloalkyl.
  • a cycloalkyl group is a C5, C 6 , C 7 , C 8 , C9, Cio, C11, C12, Ci3, Ci4, or C15 cycloalkyl.
  • Cycloalkylalkyl by itself or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced with a cycloalkyl group. Where specific alkyl moieties are intended, the nomenclature cycloalkylalkanyl, cycloalkylalkenyl, or cycloalkylalkynyl is used.
  • a cycloalkylalkyl group is C7-30 cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the cycloalkylalkyl group is Ci-10 and the cycloalkyl moiety is C 6 -2o, and in certain embodiments, a cycloalkylalkyl group is C7-20 cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the cycloalkylalkyl group is Ci -8 and the cycloalkyl moiety is C4-20 or C 6 -i2.
  • Halogen refers to a fluoro, chloro, bromo, or iodo group.
  • Heteroaryl by itself or as part of another substituent refers to a monovalent
  • heteroaromatic radical derived by the removal of one hydrogen atom from a single atom of a parent heteroaromatic ring system.
  • Heteroaryl encompasses multiple ring systems having at least one aromatic ring fused to at least one other ring, which can be aromatic or non-aromatic in which at least one ring atom is a heteroatom.
  • Heteroaryl encompasses 5- to 12-membered aromatic, such as 5- to 7-membered, monocyclic rings containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3, heteroatoms chosen from N, O, and S, with the remaining ring atoms being carbon; and bicyclic heterocycloalkyl rings containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3, heteroatoms chosen from N, O, and S, with the remaining ring atoms being carbon and wherein at least one heteroatom is present in an aromatic ring.
  • heteroaryl includes a 5- to 7-membered heterocycloalkyl, aromatic ring fused to a 5- to 7- membered cycloalkyl ring.
  • bicyclic heteroaryl ring systems wherein only one of the rings contains one or more heteroatoms, the point of attachment may be at the heteroaromatic ring or the cycloalkyl ring.
  • the heteroatoms are not adjacent to one another.
  • the total number of N, S, and O atoms in the heteroaryl group is not more than two. In certain embodiments, the total number of N, S, and O atoms in the aromatic heterocycle is not more than one. Heteroaryl does not encompass or overlap with aryl as defined herein.
  • heteroaryl groups include, but are not limited to, groups derived from acridine, arsindole, carbazole, ⁇ -carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline,
  • a heteroaryl group is from 5- to 20-membered heteroaryl, and in certain embodiments from 5- to 12- membered heteroaryl or from 5- to 10-membered heteroaryl.
  • a heteroaryl group is a 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16-, 17-, 18-, 19-, or 20-membered heteroaryl.
  • heteroaryl groups are those derived from thiophene, pyrrole,
  • benzothiophene benzofuran, indole, pyridine, quinoline, imidazole, oxazole, and pyrazine.
  • Heteroarylalkyl by itself or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced with a heteroaryl group. Where specific alkyl moieties are intended, the nomenclature heteroarylalkanyl, heteroarylalkenyl, or heteroarylalkynyl is used.
  • a heteroarylalkyl group is a 6- to 30-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the heteroarylalkyl is 1- to 10-membered and the heteroaryl moiety is a 5- to 20-membered heteroaryl, and in certain embodiments, 6- to 20-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the heteroarylalkyl is 1- to 8-membered and the heteroaryl moiety is a 5- to 12-membered heteroaryl.
  • Heterocycloalkyl by itself or as part of another substituent refers to a partially saturated or unsaturated cyclic alkyl radical in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced with the same or different heteroatom.
  • heteroatoms to replace the carbon atom(s) include, but are not limited to, N, P, O, S, Si, etc. Where a specific level of saturation is intended, the nomenclature “heterocycloalkanyl” or “heterocycloalkenyl” is used.
  • heterocycloalkyl groups include, but are not limited to, groups derived from epoxides, azirines, thiiranes, imidazolidine, morpholine, piperazine, piperidine, pyrazolidine, pyrrolidine, quinuclidine, and the like.
  • Heterocycloalkylalkyl by itself or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced with a heterocycloalkyl group. Where specific alkyl moieties are intended, the nomenclature heterocycloalkylalkanyl, heterocycloalkylalkenyl, or
  • heterocycloalkylalkynyl is used.
  • a heterocycloalkylalkyl group is a 6- to 30-membered heterocycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the
  • heterocycloalkylalkyl is 1- to 10-membered and the heterocycloalkyl moiety is a 5- to 20-membered heterocycloalkyl, and in certain embodiments, 6- to 20-membered heterocycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of the heterocycloalkylalkyl is 1- to 8-membered and the heterocycloalkyl moiety is a 5- to 12-membered heterocycloalkyl.
  • Matture refers to a collection of molecules or chemical substances. Each component in a mixture can be independently varied. A mixture may contain, or consist essentially of, two or more substances intermingled with or without a constant percentage composition, wherein each component may or may not retain its essential original properties, and where molecular phase mixing may or may not occur. In mixtures, the components making up the mixture may or may not remain distinguishable from each other by virtue of their chemical structure.
  • Parent aromatic ring system refers to an unsaturated cyclic or polycyclic ring system having a conjugated ⁇ (pi) electron system. Included within the definition of "parent aromatic ring system” are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, fluorene, indane, indene, phenalene, etc.
  • parent aromatic ring systems include, but are not limited to, aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexalene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,
  • Parent heteroaromatic ring system refers to a parent aromatic ring system in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced with the same or different heteroatom.
  • heteroatoms to replace the carbon atoms include, but are not limited to, N, P, O, S, Si, etc. Specifically included within the definition of "parent
  • heteroaromatic ring systems are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, arsindole, benzodioxan, benzofuran, chromane, chromene, indole, indoline, xanthene, etc.
  • parent heteroaromatic ring systems include, but are not limited to, arsindole, carbazole, ⁇ -carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine,
  • Substituted refers to a group in which one or more hydrogen atoms are independently replaced with the same or different substituent(s).
  • 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.
  • composition comprises at least one estolide compound of
  • 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;
  • 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;
  • n is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12;
  • Ri is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched;
  • R 2 is selected from hydrogen and optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; wherein each fatty acid chain residue of said at least one compound is independently optionally substituted.
  • the composition comprises at least one estolide compound of
  • n is an integer greater than or equal to 1 ;
  • n is an integer greater than or equal to 0;
  • Ri independently for each occurrence, is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched;
  • R 2 is selected from hydrogen and optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched;
  • R 3 and R4 independently for each occurrence, are selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • composition comprises at least one estolide compound of Formula III:
  • Ri is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched;
  • R 2 is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; wherein each fatty acid chain residue of said at least one compound is independently optionally substituted.
  • the composition comprises at least one estolide compound of Formula I, II, or III where Ri is hydrogen.
  • chain or “fatty acid chain” or “fatty acid chain residue,” as used with respect to the estolide compounds of Formula I, II, and III, refer to one or more of the fatty acid residues incorporated in estolide compounds, e.g., R or R4 of Formula II, or the structures represented by CH (CH 2 ) y CH(CH 2 )xC(0)0- in Formula I and III.
  • R or R4 of Formula II or the structures represented by CH (CH 2 ) y CH(CH 2 )xC(0)0- in Formula I and III.
  • the Ri in Formula I, II, and III at the top of each Formula shown is an example of what may be referred to as a "cap” or “capping material,” as it “caps” the top of the estolide.
  • the capping group may be an organic acid residue of general formula -OC(0)-alkyl, i.e., a carboxylic acid with a substituted or unsubstituted, saturated or unsaturated, and/or branched or unbranched alkyl as defined herein, or a formic acid residue.
  • the "cap” or “capping group” is a fatty acid.
  • the capping group regardless of size, is substituted or unsubstituted, saturated or unsaturated, and/or branched or unbranched.
  • the cap or capping material may also be referred to as the primary or alpha (a) chain.
  • the cap or capping group alkyl may be the only alkyl from an organic acid residue in the resulting estolide that is unsaturated.
  • hydrogenating the estolide may help to improve the overall stability of the molecule.
  • a fully-hydrogenated estolide such as an estolide with a larger fatty acid cap, may exhibit increased pour point temperatures.
  • the R 4 C(0)0- of Formula II or structure CH (CH2) y CH(CH 2 )xC(0)0- of Formula I and III serve as the "base” or "base chain residue" of the estolide.
  • the base organic acid or fatty acid residue may be the only residue that remains in its free-acid form after the initial synthesis of the estolide.
  • the free acid may be reacted with any number of substituents. For example, it may be desirable to react the free acid estolide with alcohols, glycols, amines, or other suitable reactants to provide the corresponding ester, amide, or other reaction products.
  • the base or base chain residue may also be referred to as tertiary or gamma ( ⁇ ) chains.
  • the estolide will be formed when a catalyst is used to produce a carbocation at the fatty acid's site of unsaturation, which is followed by nucleophilic attack on the carbocation by the carboxylic group of another fatty acid.
  • the linking residue(s) may also be referred to as secondary or beta ( ⁇ ) chains.
  • the cap is an acetyl group
  • the linking residue(s) is one or more fatty acid residues
  • the base chain residue is a fatty acid residue.
  • the linking residues present in an estolide differ from one another.
  • one or more of the linking residues differs from the base chain residue.
  • suitable unsaturated fatty acids for preparing the polyol estolides may include any mono- or polyunsaturated fatty acid.
  • suitable unsaturated fatty acids for preparing the polyol estolides may include any mono- or polyunsaturated fatty acid.
  • monounsaturated fatty acids along with a suitable catalyst, will form a single carbocation of the addition of a second fatty acid, whereby a single link between two fatty acids (e.g., between ⁇ -chain and ⁇ -chain, and ⁇ -chain and a-chain) is formed.
  • Suitable monounsaturated fatty acids may include, but are not limited to, palmitoleic (16: 1), vaccenic (18: 1), oleic acid (18: 1), eicosenoic acid (20: 1), erucic acid (22: 1), and nervonic acid (24: 1).
  • polyunsaturated fatty acids may be used to create estolides.
  • Suitable polyunsaturated fatty acids may include, but are not limited to, hexadecatrienoic acid (16:3), alpha-linolenic acid (18:3), stearidonic acid (18:4), eicosatrienoic acid (20:3), eicosatetraenoic acid (20:4), eicosapentaenoic acid (20:5),
  • heneicosapentaenoic acid (21 :5), docosapentaenoic acid (22:5), docosahexaenoic acid (22:6), tetracosapentaenoic acid (24:5), tetracosahexaenoic acid (24:6), linoleic acid (18:2), gamma-linoleic acid (18:3), eicosadienoic acid (20:2), dihomo-gamma-linolenic acid (20:3), arachidonic acid (20:4), docosadienoic acid (20:2), adrenic acid (22:4), docosapentaenoic acid (22:5), tetracosatetraenoic acid (22:4), tetracosapentaenoic acid (24:5), pinolenic acid (18:3), podocarpic acid (20:3), rumenic acid (18
  • hydroxy fatty acids may be polymerized or homopolymerized by reacting the carboxylic acid functionality of one fatty acid with the hydroxy functionality of a second fatty acid.
  • exemplary hydroxyl fatty acids include, but are not limited to, ricinoleic acid, 6- hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxy stearic acid, 9, 10-dihydroxy stearic acid, 12- hydroxy stearic acid, and 14-hydroxy stearic acid.
  • the resulting estolide polyol ester may comprise unsaturated chains and/or chains substituted with two or more fatty acids.
  • preparing a estolides from linoleic and/or linolenic acid can result in estolide substituents having two or more caps.
  • linoleic and/or linolenic acid is reacted with an organic and/or fatty acid to provide an estolide substituent having two or more caps.
  • the organic and/or fatty acid cap comprises a C1-C40 alkyl residue.
  • the organic acid cap is acetic acid.
  • the fatty acid cap comprises a C7-C17 alkyl residue.
  • the process for preparing the estolide compounds described herein may include the use of any natural or synthetic fatty acid source.
  • Suitable starting materials of biological origin may include plant fats, plant oils, plant waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, algal oils and mixtures thereof.
  • Other potential fatty acid sources may include waste and recycled food-grade fats and oils, fats, oils, and waxes obtained by genetic engineering, fossil fuel based materials and other sources of the materials desired.
  • the estolide compounds described herein may be prepared from non-naturally occurring fatty acids derived from naturally occurring feedstocks.
  • the estolides are prepared from synthetic fatty acid reactants derived from naturally occurring feedstocks such as vegetable oils.
  • the synthetic fatty acid reactants may be prepared by cleaving fragments from larger fatty acid residues occurring in natural oils such as triglycerides using, for example, a cross-metathesis catalyst and alpha-olefin(s). The resulting truncated fatty acid residue(s) may be liberated from the glycerine backbone using any suitable hydrolytic and/or transesterification processes known to those of skill in the art.
  • An exemplary fatty acid reactant includes 9-dodecenoic acid, which may be prepared via the cross metathesis of an oleic acid residue with 1-butene.
  • the estolide may be prepared from fatty acids having a terminal site of unsaturation (e.g., 9-decenoic acid), which may be prepared via the cross metathesis of an oleic acid residue with ethene.
  • the estolide comprises fatty-acid chains of varying lengths.
  • x is, independently for each occurrence, an integer selected from 0 to 20, 0 to
  • x is,
  • 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.
  • 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, 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.
  • 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. 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,
  • the estolide compound of Formula I, II, or III may comprise any number of fatty acid residues to form an " «-mer" estolide.
  • n is 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.
  • n is an integer selected from 0 to 4. In some embodiments, n is 1, wherein said at least one compound of Formula I, II, or III comprises the trimer. In some embodiments, n is greater than 1. In some embodiments, n is 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.
  • Ri of Formula I, II, or III is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • the alkyl group is a Ci to C40 alkyl, Ci to C22 alkyl or Ci to Cis alkyl.
  • the alkyl group is selected from C7 to Ci7 alkyl.
  • Ri is selected from C7 alkyl, C9 alkyl, Cn alkyl, C13 alkyl, C15 alkyl, and C 17 alkyl.
  • Ri is selected from C13 to C 17 alkyl, such as from Ci3 alkyl, C15 alkyl, and C 17 alkyl.
  • Ri is a Ci, C 2 , C 3 , C 4 , C5, C 6 , C 7 , C 8 , C9, Cio, Cn, C12, Cn, Ci4, Cis, Ci6, Cn, Ci 8 , Ci9, C20, C21, or C22 alkyl.
  • R2 of Formula I, II, or III is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • the alkyl group is a Ci to C40 alkyl, Ci to C22 alkyl or Ci to Ci 8 alkyl.
  • the alkyl group is selected from C7 to Cn alkyl.
  • R2 is selected from C7 alkyl, C9 alkyl, Cn alkyl, C13 alkyl, C15 alkyl, and C 17 alkyl.
  • R2 is selected from C13 to C 17 alkyl, such as from Ci3 alkyl, C15 alkyl, and C 17 alkyl.
  • R2 is a Ci, C 2 , C 3 , C 4 , C5, C 6 , C 7 , C 8 , C9, Cio, Cn, C12, Cn, Ci4, Cis, Ci6, Cn, Ci 8 , Ci9, C20, C21, or C22 alkyl.
  • R3 is an optionally substituted alkyl that is saturated or
  • the alkyl group is a Ci to C40 alkyl, Ci to C22 alkyl or Ci to Ci 8 alkyl.
  • the alkyl group is selected from C7 to C 17 alkyl.
  • R3 is selected from C7 alkyl, C9 alkyl, Cn alkyl, C 13 alkyl, C15 alkyl, and Cn alkyl.
  • R3 is selected from C 13 to C 17 alkyl, such as from C 13 alkyl, Cis alkyl, and C 17 alkyl.
  • R3 is a Ci, C 2 , C 3 , C 4 , C5, C 6 , C 7 , C 8 , C9, Cio, Cn, C12, Ci3, Ci4, Cis, Ci6, Cn, Ci 8 , Ci9, C20, C 21 , or C22 alkyl.
  • R is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • the alkyl group is a Ci to C40 alkyl, Ci to C22 alkyl or Ci to Cis alkyl. In some embodiments, the alkyl group is selected from C7 to C 17 alkyl.
  • R4 is selected from C7 alkyl, C9 alkyl, Cn alkyl, C 13 alkyl, C15 alkyl, and Cn alkyl. In some embodiments, R4 is selected from C 13 to C 17 alkyl, such as from C 13 alkyl, Cis alkyl, and C 17 alkyl. In some embodiments, R4 is a Ci, C 2 , C 3 , C 4 , C5, C 6 , C 7 , C 8 , C9, C10, Cn, C12, Ci3, Ci4, Cis, Ci6, Cn, Ci 8 , Ci9, C20, C 21 , or C22 alkyl.
  • the level of substitution on Ri may also be altered to change or even improve the estolides' properties.
  • polar substituents on Ri such as one or more hydroxy groups, may increase the viscosity of the estolide, while increasing pour point. Accordingly, in some
  • Ri will be unsubstituted or optionally substituted with a group that is not hydroxyl.
  • the estolide is in its free-acid form, wherein R2 of Formula I, II, or III is hydrogen.
  • R2 IS selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • the R2 residue may comprise any desired alkyl group, such as those derived from esterification of the estolide with the alcohols identified in the examples herein.
  • the alkyl group is selected from Ci to C40, Ci to C22, C3 to C20, Ci to Ci 8 , or C 6 to C12 alkyl.
  • R2 may be selected from C 3 alkyl, C4 alkyl, C 8 alkyl, C12 alkyl, Ci6 alkyl, Ci 8 alkyl, and C20 alkyl.
  • R2 may be branched, such as isopropyl, isobutyl, or 2-ethylhexyl.
  • R2 may be a larger alkyl group, branched or unbranched, comprising C12 alkyl, Ci6 alkyl, Ci 8 alkyl, or C20 alkyl.
  • Such groups at the R2 position may be derived from esterification of the free-acid estolide using the JarcolTM line of alcohols marketed by Jarchem Industries, Inc.
  • R2 may be sourced from certain alcohols to provide branched alkyls such as isostearyl and isopalmityl. It should be understood that such isopalmityl and isostearyl akyl groups may cover any branched variation of Ci6 and Ci 8 , respectively.
  • the estolides described herein may comprise highly-branched isopalmityl or isostearyl groups at the R 2 position, derived from the Fineoxocol® line of isopalmityl and isostearyl alcohols marketed by Nissan Chemical America Corporation of Houston, Texas, including Fineoxocol® 180, 180N, and 1600.
  • large, highly-branched alkyl groups e.g., isopalmityl and isostearyl
  • the compounds described herein may comprise a mixture of two or more estolide compounds of Formula I, II, and III. It is possible to characterize the chemical makeup of an estolide, a mixture of estolides, or a composition comprising estolides, by using the compound' s, mixture' s, or composition' s measured estolide number (EN) of compound or composition.
  • EN represents the average number of fatty acids added to the base fatty acid.
  • the EN also represents the average number of estolide linkages per molecule:
  • a composition comprising two or more estolide compounds may have an EN that is a whole number or a fraction of a whole number.
  • a composition having a 1 : 1 molar ratio of dimer and trimer would have an EN of 1.5
  • a composition having a 1 : 1 molar ratio of tetramer and trimer would have an EN of 2.5.
  • the compositions may comprise a mixture of two or more estolides having an EN that is an integer or fraction of an integer that is greater than 4.5, or even 5.0.
  • the EN may be an integer or fraction of an integer selected from about 1.0 to about 5.0.
  • the EN is an integer or fraction of an integer selected from 1.2 to about 4.5.
  • the 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, 5.0, 5.2, 5.4, 5.6 and 5.8.
  • 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, 5.2, 5.4, 5.6, 5.8, and 6.0.
  • the EN is selected from 1, 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, 5.0, 5.2, 5.4, 5.6, 5.8, and 6.0.
  • the chains of the estolide compounds may be independently optionally substituted, wherein one or more hydrogens are removed and replaced with one or more of the substituents identified herein. Similarly, two or more of the hydrogen residues may be removed to provide one or more sites of unsaturation, such as a cis or trans double bond. Further, the chains may optionally comprise branched hydrocarbon residues.
  • the estolides described herein may comprise at least one compound of Formula
  • n is an integer equal to or greater than 0;
  • Ri independently for each occurrence, is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched;
  • R2 is selected from hydrogen and optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched;
  • R 3 and R4 independently for each occurrence, are selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • m is 1. In some embodiments, m is an integer selected from 2, 3, 4, and 5. In some embodiments, n is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. In some embodiments, one or more R3 differs from one or more other R 3 in a compound of Formula II. In some embodiments, one or more R 3 differs from R4 in a compound of Formula II. In some embodiments, if the compounds of Formula II are prepared from one or more polyunsaturated fatty acids, it is possible that one or more of R 3 and R4 will have one or more sites of unsaturation. In some embodiments, if the compounds of Formula II are prepared from one or more branched fatty acids, it is possible that one or more of R 3 and R4 will be branched.
  • R 3 and R4 can be CH 3 (CH2)yCH(CH2)x-, where 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, and 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. Where both R 3 and R 4 are
  • the compounds may be compounds according to Formula I and III.
  • altering the EN produces estolide-containing compositions having desired viscometric properties while substantially retaining or even reducing pour point.
  • the estolides exhibit a decreased pour point upon increasing the EN value.
  • a method is provided for retaining or decreasing the pour point of an estolide base oil by increasing the EN of the base oil, or a method is provided for retaining or decreasing the pour point of a composition comprising an estolide base oil by increasing the EN of the base oil.
  • the method comprises: selecting an estolide base oil having an initial EN and an initial pour point; and removing at least a portion of the base oil, said portion exhibiting an EN that is less than the initial EN of the base oil, wherein the resulting estolide base oil exhibits an EN that is greater than the initial EN of the base oil, and a pour point that is equal to or lower than the initial pour point of the base oil.
  • the selected estolide base oil is prepared by oligomerizing at least one first unsaturated fatty acid with at least one second unsaturated fatty acid and/or saturated fatty acid.
  • the removing at least a portion of the base oil or a composition comprising two or more estolide compounds is accomplished by use of at least one of distillation, chromatography, membrane separation, phase separation, affinity separation, and solvent extraction.
  • the distillation takes place at a temperature and/or pressure that is suitable to separate the estolide base oil or a composition comprising two or more estolide compounds into different "cuts" that individually exhibit different EN values. In some embodiments, this may be accomplished by subjecting the base oil or a composition comprising two or more estolide compounds 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.
  • estolide compounds and compositions exhibit an EN that is greater than or equal to 1, such as an integer or fraction of an integer selected from about 1.0 to about 2.0.
  • the EN is an integer or fraction of an integer selected from about 1.0 to about 1.6.
  • the EN is a fraction of an integer selected from about 1.1 to about 1.5.
  • the EN is selected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9.
  • the EN is selected from a value less than 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0.
  • the EN is greater than or equal to 1.5, such as an integer or fraction of an integer selected from about 1.8 to about 2.8. In some embodiments, the EN is an integer or fraction of an integer selected from about 2.0 to about 2.6. In some embodiments, the EN is a fraction of an integer selected from about 2.1 to about 2.5. In some embodiments, the EN is selected from a value greater than 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, and 2.7. In some embodiments, the EN is selected from a value less than 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, and 2.8.
  • the EN is about 1.8, 2.0, 2.2, 2.4, 2.6, or 2.8. [093] In some embodiments, the EN is greater than or equal to about 4, such as an integer or fraction of an integer selected from about 4.0 to about 5.0. In some embodiments, the EN is a fraction of an integer selected from about 4.2 to about 4.8. In some embodiments, the EN is a fraction of an integer selected from about 4.3 to about 4.7. In some embodiments, the EN is selected from a value greater than 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, and 4.9.
  • the EN is selected from a value less than 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and 5.0. In some embodiments, the EN is about 4.0, 4.2, 4.4, 4.6, 4.8, or 5.0.
  • the EN is greater than or equal to about 5, such as an integer or fraction of an integer selected from about 5.0 to about 6.0. In some embodiments, the EN is a fraction of an integer selected from about 5.2 to about 5.8. In some embodiments, the EN is a fraction of an integer selected from about 5.3 to about 5.7. In some embodiments, the EN is selected from a value greater than 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, and 5.9. In some embodiments, the EN is selected from a value less than 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, and 6.0. In some embodiments, the EN is about 5.0, 5.2, 5.4, 5.4, 5.6, 5.8, or 6.0.
  • the EN is greater than or equal to 1, such as an integer or fraction of an integer selected from about 1.0 to about 2.0. In some embodiments, the EN is a fraction of an integer selected from about 1.1 to about 1.7. In some embodiments, the EN is a fraction of an integer selected from about 1.1 to about 1.5. In some embodiments, the EN is selected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9. In some embodiments, the EN is selected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0.
  • the EN is about 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0. In some embodiments, the EN is greater than or equal to 1, such as an integer or fraction of an integer selected from about 1.2 to about 2.2. In some embodiments, the EN is an integer or fraction of an integer selected from about 1.4 to about 2.0. In some embodiments, the EN is a fraction of an integer selected from about 1.5 to about 1.9. In some embodiments, the EN is selected from a value greater than 1.0, 1.1. 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, and 2.1.
  • the EN is selected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, and 2.2. In some embodiments, the EN is about 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, or 2.2. [096] In some embodiments, the EN is greater than or equal to 2, such as an integer or fraction of an integer selected from about 2.8 to about 3.8. In some embodiments, the EN is an integer or fraction of an integer selected from about 2.9 to about 3.5. In some embodiments, the EN is an integer or fraction of an integer selected from about 3.0 to about 3.4.
  • the EN is selected from a value greater than 2.0, 2.1, 2.2., 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.4, 3.5, 3.6, and 3.7. In some embodiments, the EN is selected from a value less than 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, and 3.8. In some embodiments, the EN is about 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, or 3.8.
  • base stocks and estolide-containing compositions exhibit certain lubricity, viscosity, and/or pour point characteristics.
  • the base oils, compounds, and compositions may exhibit viscosities that range from about 10 cSt to about 250 cSt at 40 °C, and/or about 3 cSt to about 30 cSt at 100 °C.
  • the base oils, compounds, and compositions may exhibit viscosities within a range from about 50 cSt to about 150 cSt at 40 °C, and/or about 10 cSt to about 20 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities less than about 55 cSt at 40 °C or less than about 45 cSt at 40 °C, and/or less than about 12 cSt at 100 °C or less than about 10 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities within a range from about 25 cSt to about 55 cSt at 40 °C, and/or about 5 cSt to about 11 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities within a range from about 35 cSt to about 45 cSt at 40 °C, and/or about 6 cSt to about 10 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities within a range from about 38 cSt to about 43 cSt at 40 °C, and/or about 7 cSt to about 9 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities less than about 120 cSt at 40 °C or less than about 100 cSt at 40 °C, and/or less than about 18 cSt at 100 °C or less than about 17 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 70 cSt to about 120 cSt at 40 °C, and/or about 12 cSt to about 18 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities within a range from about 80 cSt to about 100 cSt at 40 °C, and/or about 13 cSt to about 17 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities within a range from about 85 cSt to about 95 cSt at 40 °C, and/or about 14 cSt to about 16 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities greater than about 180 cSt at 40 °C or greater than about 200 cSt at 40 °C, and/or greater than about 20 cSt at 100 °C or greater than about 25 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 180 cSt to about 230 cSt at 40 °C, and/or about 25 cSt to about 31 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities within a range from about 200 cSt to about 250 cSt at 40 °C, and/or about 25 cSt to about 35 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities within a range from about 210 cSt to about 230 cSt at 40 °C, and/or about 28 cSt to about 33 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities within a range from about 200 cSt to about 220 cSt at 40 °C, and/or about 26 cSt to about 30 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities within a range from about 205 cSt to about 215 cSt at 40 °C, and/or about 27 cSt to about 29 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities less than about 45 cSt at 40 °C or less than about 38 cSt at 40 °C, and/or less than about 10 cSt at 100 °C or less than about 9 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 20 cSt to about 45 cSt at 40 °C, and/or about 4 cSt to about 10 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities within a range from about 28 cSt to about 38 cSt at 40 °C, and/or about 5 cSt to about 9 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities within a range from about 30 cSt to about 35 cSt at 40 °C, and/or about 6 cSt to about 8 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities less than about 80 cSt at 40 °C or less than about 70 cSt at 40 °C, and/or less than about 14 cSt at 100 °C or less than about 13 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 50 cSt to about 80 cSt at 40 °C, and/or about 8 cSt to about 14 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities within a range from about 60 cSt to about 70 cSt at 40 °C, and/or about 9 cSt to about 13 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities within a range from about 63 cSt to about 68 cSt at 40 °C, and/or about 10 cSt to about 12 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities greater than about 120 cSt at 40 °C or greater than about 130 cSt at 40 °C, and/or greater than about 15 cSt at 100 °C or greater than about 18 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 120 cSt to about 150 cSt at 40 °C, and/or about 16 cSt to about 24 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities within a range from about 130 cSt to about 160 cSt at 40 °C, and/or about 17 cSt to about 28 cSt at 100 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities within a range from about 130 cSt to about 145 cSt at 40 °C, and/or about 17 cSt to about 23 cSt at 100 °C.
  • estolide compounds and compositions may exhibit viscosities within a range from about 135 cSt to about 140 cSt at 40 °C, and/or about 19 cSt to about 21 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 350, or 400 cSt. at 40 °C.
  • the estolide compounds and compositions may exhibit viscosities of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30 cSt at 100 °C.
  • the estolide compounds and compositions may exhibit viscosities less than about 200, 250, 300, 350, 400, 450, 500, or 550 cSt at 0 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 200 cSt to about 250 cSt at 0 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 250 cSt to about 300 cSt at 0 °C.
  • the estolide compounds and compositions may exhibit a viscosity within a range from about 300 cSt to about 350 cSt at 0 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 350 cSt to about 400 cSt at 0 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 400 cSt to about 450 cSt at 0 °C. In some embodiments, the estolide compounds and compositions may exhibit a viscosity within a range from about 450 cSt to about 500 cSt at 0 °C.
  • the estolide compounds and compositions may exhibit a viscosity within a range from about 500 cSt to about 550 cSt at 0 °C. In some embodiments, the estolide compounds and compositions may exhibit viscosities of about 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, or 550 cSt at 0 °C.
  • estolide compounds and compositions may exhibit desirable low- temperature pour point properties. In some embodiments, the estolide compounds and compositions may exhibit a pour point lower than about -25 °C, about -35 °C, -40 °C, or even about -50 °C. In some embodiments, the estolide compounds and compositions have a pour point of about -25 °C to about -45 °C.
  • the pour point falls within a range of about -30 °C to about -40 °C, about -34 °C to about -38 °C, about -30 °C to about -45 °C, -35 °C to about -45 °C, 34 °C to about -42 °C, about -38 °C to about -42 °C, or about 36 °C to about -40 °C. In some embodiments, the pour point falls within the range of about -27 °C to about -37 °C, or about -30 °C to about -34 °C.
  • the pour point falls within the range of about -25 °C to about -35 °C, or about -28 °C to about -32 °C. In some embodiments, the pour point falls within the range of about - 28 °C to about -38 °C, or about -31 °C to about -35 °C. In some embodiments, the pour point falls within the range of about -31 °C to about -41 °C, or about -34 °C to about -38 °C. In some embodiments, the pour point falls within the range of about -40 °C to about -50 °C, or about -42 °C to about -48 °C.
  • the pour point falls within the range of about -50 °C to about -60 °C, or about -52 °C to about -58 °C.
  • the upper bound of the pour point is less than about - 35 °C, about -36 °C, about -37 °C, about -38 °C, about -39 °C, about -40 °C, about -41 °C, about -42 °C, about -43 °C, about -44 °C, or about -45 °C.
  • the lower bound of the pour point is greater than about -70 °C, about -69 °C, about -68 °C, about -67 °C, about -66 °C, about -65 °C, about -64 °C, about -63 °C, about -62 °C, about -61 °C, about -60 °C, about -59 °C, about -58 °C, about -57 °C, about -56 °C, -55 °C, about -54 °C, about -53 °C, about -52 °C, -51, about -50 °C, about -49 °C, about -48 °C, about -47 °C, about -46 °C, or about -45 °C.
  • the estolides may exhibit decreased Iodine Values (IV) when compared to estolides 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 estolide (cg/g).
  • oils having a higher degree of unsaturation may be more susceptible to creating corrosiveness and deposits, and may exhibit lower levels of oxidative stability. Compounds having a higher degree of unsaturation will have more points of unsaturation for iodine to react with, resulting in a higher IV.
  • estolide compounds and compositions described herein have an IV of less than about 40 cg/g or less than about 35 cg/g. In some embodiments, estolides 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 composition may be reduced by decreasing the estolide' s degree of unsaturation. This may be accomplished by, for example, by increasing the amount of saturated capping materials relative to unsaturated capping materials when synthesizing the estolides. Alternatively, in certain embodiments, IV may be reduced by
  • the estolide compounds and compositions described herein may be used to prepare rheology modifiers for use in, e.g., asphalt products.
  • the composition comprises at least one estolide compound selected from Formulas I, II, and III.
  • the at least one estolide compound is present in amounts of about 0 to about 100 wt. % of the composition, such as about 0.1 to about 99 wt. %.
  • the at least one estolide compound is present in amounts of about 0 to about 90, about 0 to about 80, about 0 to about 70, about 0 to about 60, about 0 to about 50, about 0 to about 40, about 0 to about 30, about 0 to about 20, or about 0 to about 10 wt. % of the composition. In certain embodiments, the at least one estolide compound is present in amounts of about 25 to about 95 wt. % of the composition, such as about 50 to about 75 wt %. In certain embodiments, the at least one estolide compound is present in amounts of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 wt.
  • the at least one estolide compound is present in amounts of about 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, or 98 wt. %.
  • the at least one polyol is contacted with the at least one estolide oligomer in the presence of a catalyst.
  • Suitable catalysts may include one or more Lewis acids and/or Bronsted acids, including, for example, AgOTf, Cu(OTf) 2 , Fe(Otf) 2 , Fe(Otf) 3 , NaOTf, LiOTf, Yb(Otf) 3 , Y(Otf) 3 , Zn(Otf) 2 , Ni(Otf) 2 , Bi(Otf) 3 , La(Otf) 3 , Sc(Otf) 3 , hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, phosphoric acid, perchloric acid, triflic acid, and p-TsOH.
  • the catalyst may comprise a strong Lewis acid such as BF
  • the catalyst may comprise a Lewis acid catalyst, such as at least one metal compound selected from one or more of titanium compounds, tin compounds, zirconium compounds, and hafnium compounds.
  • the catalyst is at least one titanium compound selected from TiCU and Ti(OCH 2 CH 2 CH 2 CH )4 (titanium (IV) butoxide).
  • the catalyst is at least one tin compound selected from Sn(0 2 CC0 2 ) (tin (II) oxalate), SnO, and SnCl 2 .
  • the catalyst is at least one zirconium compound selected from ZrCU, ZrOCl 2 , ZrO(N0 3 ) 2 , ZrO(S0 4 ), and ZrO(CH COO) 2 .
  • the catalyst is at least one hafnium compound selected from HfCl 2 and HfOCl 2 . Unless stated otherwise, all metal compounds and catalysts discussed herein should be understood to include their hydrate and solvate forms.
  • the catalyst may be selected from
  • the estolide compound may comprise a polyol estolide, such as estolides prepared from a reaction with a polyol (e.g., glycerol or polyglycerol) and a free-acid estolide.
  • the resulting estolide compound will have one or more free hydroxyl groups. Accordingly, 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.
  • the composition exhibits a hydroxyl value equal to or greater than 400 or even 500 mg KOH/g, such as about 400 to 600, about 600 to 800, about 800 to 1000, about 1000 to 1200, about 1200 to 1500, about 1500 to 2000, or even about 2000 to about 2500 mg KOH/g. In certain embodiments, that hydroxyl value may exceed 2500 mg KOH/g of composition.
  • the free hydroxyl residues of the polyol estolide may be acylated (e.g., acetic anhydride) in an effort to lower the hydroxyl value.
  • the resulting estolide polyol ester will exhibit a hydroxyl value of greater than 0 mg KOH/g.
  • the composition exhibits a hydroxyl value less than or equal to 1 mg KOH/g. 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.
  • the rheology modifier comprises at least one estolide compound. In certain embodiments, the rheology modifier comprises a polyol estolide. Optionally, in certain embodiments the rheology modifier further comprises a free fatty acid, such as a C8-C24 free fatty acid. In certain embodiments, the free fatty acid comprises 50-98 wt.%, 50-96 wt.%, 50-94 wt.%, 50-92 wt.%, 50-90 wt.%, 50-85 wt.%, 50-80 wt.%, or even 60-80 wt.%, based upon the weight of the total weight of the rheology modifier.
  • Suitable C8-C24 fatty acids are well known and commercially available. Suitable fatty acids can be saturated or unsaturated, and they can have linear or branched chains. In some aspects, the fatty acid is a C8-C20 fatty acid, a C 10 -C 18 fatty acid, or a C 14 -C 18 fatty acid.
  • Suitable fatty acids include, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, conjugated linoleic acid, linolenic acid, erucic acid, and the like, and mixtures thereof.
  • unsaturated fatty acid, and their mixtures make up the majority of the free fatty acid component (e.g., 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, 95 wt.%) or more, based upon the weight of the free fatty acid component), with the remainder being saturated fatty acids, optionally rosin acids, and unsaponifiables.
  • the saturated fatty acid content is higher than for tall oil than for pine derived fatty acids.
  • the saturated fatty acid content of tall oil fatty acid may be 10 wt.% or less (or 5 wt.% or less, or from 2 to 10 wt.%) based upon the weight of the free fatty acid, and the saturated fatty acid content of vegetable based fatty acids may be 50 wt.% or less (or 40 wt.% or less, or 30 wt.% or less, or from 5 to 30 wt.%).
  • the unsaponifiables of the free fatty acid may be up to 5 wt.% (or up to 3 wt.%), or from 0.1 to 10 wt.%), and for pine derived fatty acid, rosin acids may be 10 wt.% or less (or 5 wt.%) or less, or 3 wt.%> or less, or from 1 to 5 wt.%>) based upon the total weight of the free fatty acid.
  • the rheology modifier has an acid value of at least 100 mg KOH/g as measured by well-known titration methods, such as 150 mg KOH/g or more.
  • the rheology modifier will have an acid value of 180 mg KOH/g or at least 200 mg KOH/g, or within the range of 150 to 400 mg KOH/g or 200 to 250 mg KOH/g. In one embodiment, the rheology modifier has an acid value of 190 mg KOH/g or less, 100 to 190 mg KOH/g, 110 to 180 mg KOH/g, 120 to 170 mg KOH/g, 130 to 160 mg KOH/g or 130 to 145 mg KOH/g. In some aspects, the rheology modifier has an iodine value within the range of 80 to 200 mg I 2 /g, or 110 to 160 mg I 2 /g.
  • the rheology modifier is for use in asphalt compositions comprising aggregate and a binder composition for any of new construction, partial or complete re-construction applications.
  • the rheology modifier can be used for any of paved surfaces, road surfaces and subsurfaces, runways, shoulders, bridges, bridge abutments, gravel substitutes for unpaved roads, and the like.
  • the rheology modifier can be used in a variety of industrial applications, not limited to coatings, drilling applications, and lubricants.
  • the asphalt compositions comprise any of virgin asphalt, reclaimed asphalt, or mixtures thereof.
  • the rheology modifier is for use in asphalt compositions comprising an asphalt emulsion for use in any of rehabilitation, preservation, or CIR applications.
  • the rheology modifier is for use in any of a warm-mix composition, a hot-mix asphalt composition, e.g., mixed at a temperature around 300°F - 350°F, which then can be applied to roadways using specialized machines, compacted, and the asphalt hardens as it cools.
  • the rheology modifier is used in a cold-mix asphalt formulation with aggregate, an emulsion and water.
  • the rheology modifier is used in a modified binder composition with reclaimed asphalt suitable for use with asphalt, optionally with virgin binder and aggregate.
  • the binder composition comprises a combination of a bituminous binder and the rheology modifier comprising an estolide compound and, optionally, other components such as fatty acids.
  • Exemplary bituminous binders can come from a variety of sources, including reclaimed binders, optional virgin or performance-grade binders, or combinations thereof.
  • the reclaimed binder is from any of reclaimed asphalt pavement ("RAP binder”), reclaimed asphalt shingles ("RAS binder”), or combinations thereof.
  • the bituminous binder can include RAS binder, which is present in or recovered from RAS. Binders reclaimed from production waste during shingle manufacture can also be included.
  • the bituminous binder can include RAP binder, which is present in or recovered from RAP.
  • the bituminous binder can also include virgin binder or performance-grade binders in addition to any reclaimed binder.
  • the amount of bituminous binder in a reclaimed asphalt composition is generally known from the supplier, but it may also be determined by known methods, e.g., solvent extraction. For instance, a known amount of RAS or RAP may be treated with a suitable solvent, e.g. dichloromethane, to extract the binder. The amount of binder in the extracted fraction can be measured, thereby providing the content of binder in the RAS or RAP.
  • the amount of aged binder in the RAS or RAP depends on the source, age, history, location, any pre-treatment, and other factors. The amount of aged binder in RAS or RAP typically ranges from any of 1 to 35 wt.
  • the amount of aged binder can be up to 10 wt. %. In one embodiment of a RAS, the amount of aged binder is typically in the range of 20-25 wt. %.
  • the aged binder is isolated from the reclaimed asphalt by known methods.
  • the RAS or RAP is combined with a desirable amount of rheology modifier.
  • the rheology modifier is combined and mixed with the bituminous binder, and optionally virgin asphalt and / or RAP or RAS to give a modified asphalt product.
  • a desirable amount of rheology modifier is combined or first blended with virgin bitumen, then subsequently mixed with RAP and/ or RAS.
  • the modified binder compositions comprise any of 0.05 to 20 wt.%, 0.5 to 15 wt.% or 1 to 10 wt.%), of the rheology modifier based on the combined amounts of binder and rheology modifier.
  • the effective amount of rheology modifier needed to rejuvenate the binder in the RAS/ RAP varies and depends on the source of the binder, age, its history, and other factors.
  • the binder composition comprises 50 to 70 wt.%> of a performance-grade or virgin binder. In some aspects, the binder composition comprises any of 0.5 to 30 wt.%, 2 to 25 wt.%), or 4 to 15 wt.%), of the virgin binder. In other aspects, the bituminous binder comprises a RAS binder, a RAP binder, or a mixture thereof (100% recycled asphalt and no virgin binder). In some further aspects, the binder comprises a RAS binder.
  • DSR dynamic shear rheometry
  • bituminous binders with a rheology modifier such as estolides, the high-temperature properties of the binders can be improved with minimal impact on low- temperature performance.
  • Modified bituminous binder can also be used to improve the high- temperature performance of certain grades of asphalt binders without sacrificing low-temperature performance.
  • a performance-grade binder can be modified by including up to 20 wt. %> RAP binder.
  • binder and asphalt compositions can be made by combining components in any desired order.
  • an asphalt composition is made by combining rheology modifier with virgin binder, then blending the resulting mixture with reclaimed asphalt, e.g., RAS and/or RAP.
  • an asphalt composition is made by combining rheology modifier with RAS and/or RAP, optionally with virgin asphalt.
  • the asphalt composition comprises aggregate, RAS and/or RAP, and the rheology modifier blend described above, wherein the asphalt composition further comprises virgin asphalt.
  • the virgin asphalt comprises virgin binder and virgin aggregate.
  • the asphalt composition comprises 1 to 99 wt. % of virgin aggregate based on the combined amounts of virgin asphalt, RAS, RAP, and rheology modifier blend.
  • the asphalt composition comprises aggregate, RAS and / or RAP, and the rheology modifier.
  • the RAS / RAP binder and the rheology modifier blend form a modified binder having a PG grade at least one grade lower than that of the RAS binder without the rheology modifier.
  • a shift in the PG grade from PG 76-22 to PG 70-22 or from PG 64- 22 to PG 58-22 represents a one-grade reduction.
  • asphalt may be modified with elastomeric and plastomeric polymers such as SBS or B SB-type copolymers, optionally with ground tire rubber to increase high temperature modulus and elasticity, to increase resistance to heavy traffic loading and toughening the asphalt matrix against damage accumulation through repetitive loading.
  • elastomeric and plastomeric polymers such as SBS or B SB-type copolymers
  • ground tire rubber optionally with ground tire rubber to increase high temperature modulus and elasticity, to increase resistance to heavy traffic loading and toughening the asphalt matrix against damage accumulation through repetitive loading.
  • such polymers are usually used at 3 to 7 wt% dosages in the asphalt and can be as high as 20% for ground tire rubber.
  • the polymer is high shear blended into asphalt at high temperatures, e.g., > 180°C and allowed to "cure" at similar
  • the rheology modifier is used to compatibilize polymers and/or ground tire rubber in the asphalt.
  • the rheology modifier is added and blended into the bitumen binder before the incorporation of the polymer, or the curing stage.
  • estolide modifiers are particularly suitable for use in bitumen binders, optionally with elastomeric additives such as SBS or B SB-type block copolymers.
  • compositions described herein comprise unsubstituted estolide compounds.
  • the rheology modifier is added to a rubberized asphalt composition in any of a dry process or a wet process.
  • the crumb rubber is combined with a heated aggregate, followed by the addition of the asphalt binder and the rheology modifier.
  • the rheology modifier is mixed with bitumen and rubber particles, or blended separately with bitumen first then mixed together with rubber particles.
  • the rubberized bitumen is then mixed with asphalt.
  • the amount of rubber in the rubberized bitumen (or rubberized asphalt dispersion) is typically in the range of 1 to 25 wt.%.
  • the amount of rheology modifier is typically in the range of 1-10 wt. %.
  • the rubberized bitumen asphalt dispersion further contains 1 to 10 wt. % of a polyamide stabilizer having an amine number within the range of 50-500 mg KOH/g.
  • Asphalt Emulsions can also be used in asphalt emulsions for applications including pavement preservation, rehabilitation, and CIR applications.
  • applications or treatments using asphalt emulsions may include rejuvenating, scrub seal, fog seal, sand seal, chip seal, tack coat, bond coat, crack filler or as a material for prevention of reflective cracking of pavements.
  • Asphalt emulsions comprise globules of paving asphalt, water, an emulsifying agent or surfactant, and the rheology modifier.
  • the emulsifying agent keeps the paving asphalt globules in suspension until it is applied to the pavement surface when the water in the asphalt emulsion starts to evaporate.
  • the emulsifying agent provides a cationic, anionic, non-ionic, or neutral character to the final emulsion depending upon the desired emulsion's electrochemical properties or the intended emulsion use, for example, the surface type on which the asphalt emulsion is to be applied.
  • the rheology modifier functions to slightly soften the pavement to create a better bond when applied to an existing pavement.
  • Asphalt emulsions can optionally include a latex dispersion, e.g., a SBR latex dispersion as disclosed in US Patent No. 7,357,594, incorporated herein by reference in its entirety for all purposes.
  • the rheology modifier is used in a polymer-modified asphalt rejuvenating emulsion, which comprises an asphalt phase with an asphalt and the rheology modifier, and an aqueous phase comprising water, a polymer or copolymer (e.g., acrylics such as polychloroprene, copolymers such as styrene-butyl acrylate copolymer) and an emulsifying agent.
  • a polymer or copolymer e.g., acrylics such as polychloroprene, copolymers such as styrene-butyl acrylate copolymer
  • an emulsifying agent e.g., acrylics such as polychloroprene, copoly
  • the surfactant comprises from about 0.01 % to about 3.0% of the total weight of the emulsion.
  • the polymer or copolymer is about 1 %> to about 15% of the total weight of the emulsion.
  • the asphalt phase comprises from about 30%) to about 70%) of the total weight of the emulsion.
  • the rheology modifier comprises about 0.1 %> to about 15%) of the total weight of the emulsion.
  • the ratio of the rheology modifier to the polymer or copolymer may for example be from 1 : 10 to 5 : 1, from 1 :3 to 3 : 1, from 1 :2 to 2: 1, or about 1 : 1.
  • the surfactant comprises about 5-30 wt. %> of the rheology modifier.
  • an acid or a base may be needed to activate the emulsifying agent.
  • acid may be added to adjust the emulsion pH to between 1.0 and 7 .0.
  • Suitable acids include inorganic acids, for example hydrochloric acid and phosphoric acid.
  • anionic emulsifying agents base may be added to adjust the emulsion pH to between 7 .0 and 12.0.
  • amphoteric emulsifying agents both the cationic and anionic chemical functionality are built into the same molecule.
  • emulsifying agent is used maintain a stable emulsion, e.g., from 0.01 to about 5%> by weight of the emulsion, from 0.1 %> to about 3.0% by weight of the emulsion. Examples of emulsifying agents are disclosed in U. S. Patent Publication No.
  • Exemplary cationic emulsifying agents include polyamines, fatty amines, fatty amido- amines, ethoxylated amines, diamines, imidazolines, quaternary ammonium salts, and mixtures thereof.
  • Exemplary anionic emulsifying agents include alkali metal or ammonium salts of fatty acids, alkali metal polyalkoxycarboxylates, alkali metal N-acylsarcosinates, alkali metal
  • hydrocarbylsulphonates for example, sodium alkylsulphonates, sodium arylsulphonates, sodium alkylarylsulphonates, sodium alkylarenesulphonates, sodium lignosulphonates, sodium
  • exemplary amphoteric emulsifying agents include betaines and amphoteric imidazolinium derivatives.
  • Exemplary non-ionic emulsifying agents include ethoxylated compounds and esters, for example ethoxylated fatty alcohols, ethoxylated fatty acids, sorbitan esters, ethoxylated sorbitan esters, ethoxylated alkylphenols, ethoxylated fatty amides, glycerine fatty acid esters, alcohols, alkyl phenols, and mixtures thereof.
  • the emulsifying agent is an alkoxylated fatty amine surfactant.
  • a binder composition is first heated so that it melts, the rheology modifier is added, then an emulsifying solution comprising water and emulsifying agent is added to the molten binder composition.
  • the emulsifying solution and the molten binder are mixed under high shear (e.g. in a colloid mill) to form an emulsion.
  • the final asphalt emulsion may be applied by hand spreading, conventional spreading, spraying, or other techniques, then letting the emulsion dry.
  • An exemplary application rate may be, for example, about 0.045 to about 2.7 liters/sq. meter (about 0.01 to about 0.60 gal/sq. yd.) or about 0.14 to about 2.0 liters/sq. meter (about 0.03 to about 0.45 gal/sq. yd).
  • the present disclosure further relates to methods of making estolides according to Formula I, II, and III.
  • the reaction of an unsaturated fatty acid with an organic acid and the esterification of the resulting free acid estolide are illustrated and discussed in the following Schemes 1 and 2.
  • the particular structural formulas used to illustrate the reactions correspond to those for synthesis of compounds according to Formula I and III; however, the methods apply equally to the synthesis of compounds according to Formula II, with use of compounds having structure corresponding to R and R with a reactive site of unsaturation.
  • compound 100 represents an unsaturated fatty acid that may serve as the basis for preparing the estolide compounds described herein.
  • 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, perchloric acid, nitric acid, triflic acid, and the like.
  • Ri and R 2 are each an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched, free acid estolide 104 may be esterified by any suitable procedure known to those of skilled in the art, such as acid-catalyzed reduction with alcohol 202, to yield esterified estolide 204.
  • Other exemplary methods may include other types of Fischer esterification, such as those using Lewis acid catalysts such as BF .
  • the compounds described may be useful alone, as mixtures, or in combination with other compounds, compositions, and/or materials.
  • Estolide Number The EN was measured by GC analysis. It should be understood that the EN of a composition specifically refers to EN characteristics of any estolide compounds present in the composition. Accordingly, an estolide composition having a particular EN may also comprise other components, such as natural or synthetic additives, other non-estolide base oils, fatty acid esters, e.g., triglycerides, and/or fatty acids, but the EN as used herein, unless otherwise indicated, refers to the value for the estolide fraction of the estolide composition.
  • Iodine Value is a measure of the degree of total unsaturation of an oil. IV is expressed in terms of centigrams of iodine absorbed per gram of oil sample. Therefore, the higher the iodine value of an oil the higher the level of unsaturation is of that oil. The IV may be measured and/or estimated by GC analysis. Where a composition includes unsaturated compounds other than estolide polyol esters as set forth herein, the estolide polyol esters can be separated from other unsaturated compounds present in the composition prior to measuring the iodine value of the constituent estolides.
  • Acid Value is a measure of the total acid present in an oil. Acid value may be determined by any suitable titration method known to those of ordinary skill in the art. For example, acid values may be determined by the amount of KOH that is required to neutralize a given sample of oil, and thus may be expressed in terms of mg KOH/g of oil.
  • GC analysis was performed to evaluate the estolide number (EN) and iodine value (IV) of the polyol estolides. This analysis was performed using an Agilent 6890N series gas chromatograph equipped with a flame-ionization detector and an autosampler/injector along with an SP-2380 30 m x 0.25 mm i.d. column.
  • Measuring EN and IV by GC To perform these analyses, the fatty acid components of an polyol estolide sample were reacted with MeOH to form fatty acid methyl esters by a method that left behind a hydroxy group at sites where estolide links were once present. Standards of fatty acid methyl esters were first analyzed to establish elution times.
  • EN Calculation The EN is measured as the percent hydroxy fatty acids divided by the percent non-hydroxy fatty acids. As an example, a dimer estolide residue would result in half of the fatty acids containing a hydroxy functional group, with the other half lacking a hydroxyl functional group. Therefore, the EN would be 50% hydroxy fatty acids divided by 50% non-hydroxy fatty acids, resulting in an EN value of 1 that corresponds to the single estolide link between the capping fatty acid and base fatty acid of the dimer.
  • MWf molecular weight of the fatty compound
  • estolide compounds and compositions described herein are identified in the following examples and tables.
  • KOH (645.58 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH by volume) and added to the reactor to quench the acid. The solution was then allowed to cool for approximately 30 minutes. The contents of the reactor were then pumped through a 1 micron ( ⁇ ) filter into an accumulator to filter out the salts. Water was then added to the accumulator to wash the oil. The two liquid phases were thoroughly mixed together for approximately 1 hour. The solution was then allowed to phase separate for approximately 30 minutes. The water layer was drained and disposed of. The organic layer was again pumped through a 1 ⁇ filter back into the reactor. The reactor was heated to 60°C in vacuo (10 torr abs) until all ethanol and water ceased to distill from solution.
  • the acid catalyst reaction was conducted in a 50 gallon Pfaudler RT-Series glass-lined reactor. Oleic acid (50Kg, OL 700, Twin Rivers) and whole cut coconut fatty acid (18.754 Kg, TRC 110, Twin Rivers) were added to the reactor with 70% perchloric acid (1145 mL, Aldrich Cat# 244252) and heated to 60°C in vacuo (10 torr abs) for 24 hrs while continuously being agitated. After 24 hours the vacuum was released. 2-Ethylhexanol (34.58 Kg) was then added to the reactor and the vacuum was restored. The reaction was allowed to continue under the same conditions (60°C, 10 torr abs) for 4 more hours.
  • KOH 744.9 g was dissolved in 90% ethanol/water (5000 mL, 90% EtOH by volume) and added to the reactor to quench the acid. The solution was then allowed to cool for approximately 30 minutes. The contents of the reactor were then pumped through a 1 ⁇ filter into an accumulator to filter out the salts. Water was then added to the accumulator to wash the oil. The two liquid phases were thoroughly mixed together for approximately 1 hour. The solution was then allowed to phase separate for approximately 30 minutes. The water layer was drained and disposed of. The organic layer was again pumped through a 1 ⁇ filter back into the reactor. The reactor was heated to 60°C in vacuo (10 torr abs) until all ethanol and water ceased to distill from solution.
  • Example 1 The estolides produced in Example 1 (Ex. 1) were subjected to distillation conditions in a Myers 15 Centrifugal Distillation still at 300°C under an absolute pressure of approximately 12 microns (0.012 torr). This resulted in a primary distillate having a lower EN average (Ex. 3A), and a distillation residue having a higher EN average (Ex. 3B). Certain data are reported below in Table 1.
  • Estolides produced in Example 2 were subjected to distillation conditions in a Myers 15 Centrifugal Distillation still at 300°C under an absolute pressure of approximately 12 microns (0.012 torr). This resulted in a primary distillate having a lower EN average (Ex. 4A), and a distillation residue having a higher EN average (Ex. 4B). Certain data are reported below in Table 2. Table 2
  • Blends of RAS Binder with Rheology Modifiers are done by placing 2.0g of RAS binder and a sufficient amount of rheology modifier (e.g., Ex. 3 A and/or Ex. 4A estolides) in a 2oz. glass jar. Percent rheology modifier is determined by percent mass of binder (ex. 0.20 g rheology modifier into 2.0g of binder equals 10% rheology modifier). The jar is then placed in an oven at 177°C along with a metal spatula to pre-heat for approximately 20 minutes. The binder is stirred with the preheated spatula for 30 seconds and returned to the oven for another 20 minutes. The binder is stirred again for 30 seconds and then poured out to be tested via Dynamic Shear Rheometry ("DSR").
  • DSR Dynamic Shear Rheometry
  • Dynamic shear moduli are measured usmg 8-mm diameter parallel plate geometries with a TA Instruments AR-G2 rotational dynamic shear rheometer. Temperature sweeps are performed at 2°C intervals over a temperature range of -15°C to 200°C at a rate of 6°C/minute and an angular frequency of 10 rad/sec. Initially the temperature sweep maintains a constant torque of 5000 ⁇ up until the point at which the percent strain of the sample reaches 15%, at which time the percent strain is then held constant at 15%.
  • High- and intermediate-temperature performance parameters e.g., G*/sin 8 and G*sin d, are calculated from the measured G*, the complex modulus, and d, delta degrees.
  • the control sample is an extracted RAS binder without added rheology modifier.
  • Dynamic shear moduli are measured using 8-mm diameter parallel plate geometry with a Malvern Kinexus rotational dynamic shear rheometer. Temperature sweeps are performed at 2°C intervals over a temperature range of -15°C to 200°C and an angular frequency of 10 rad/sec.
  • Fatigue cracking resistance of an RTFO/PAV (rolling thin film oven/pressure aging vessel) aged asphalt binder can be evaluated 30 using G* sin d (a fatigue factor).
  • G* represents the binder complex shear modulus and represents the phase angle.
  • G* approximates stiffness and approximates the viscoelastic response of the binder.
  • Binder purchase specifications typically require the factor to be less than 5000 kPa. The factor is considered a measure of energy dissipation which is related to fatigue damage.
  • the critical temperature range for fatigue damage is near the midpoint between the highest and lowest service temperatures, calculated by the formula,
  • High-temperature properties High-temperature mechanical properties are evaluated by the parameter G* / sin d.
  • the factor is an indication of a binder's resistance to rutting. Binder purchase specifications typically require the factor to be greater than 2.2 kPa for RTFO aged asphalt and greater than 1 kPa before RTFO aging. In all of the tested samples, G*/sin d decreases significantly with addition of the rheology modifier.
  • DSR Dynamic shear rheometry
  • -10°C road surfaces need cracking resistance. Under ambient conditions, stiffness and fatigue properties are important.
  • roads need to resist rutting when the asphalt becomes too soft. Criteria have been established by the asphalt industry to identify rheological properties of a binder that correlate with likely paved road surface performance over the three common sets of temperature conditions.
  • G* complex modulus
  • G* at -10°C is ideally at or below 2.8 x 108 Pa.
  • the complex modulus of the modified binder can be less than or equal to the value for virgin binder.
  • G* at 20°C is ideally at or below 6.0 x 106 Pa.
  • Fatigue criteria also relates to ambient temperature performance.
  • the product of the complex modulus (G*) and the sine of the phase angle (8) measured at 10 rad/s is determined.
  • the temperature at which the value of G*sin 8 at 10 rad/s equals 5.0 x 106 Pa can be less than or equal to 20°C for modified binders comparable to 35/50 grade virgin binder.
  • the quotient G*/sin 8 is of interest.
  • the temperature at which the value of G*/sin d at 10 rad/s equals 1000 Pa can be reduced for modified binders compared with that of aged binder.
  • a composition comprising: a bituminous binder; and a rheology modifier comprising at least one estolide compound.
  • bituminous binder comprises at least one of a reclaimed asphalt pavement binder, a reclaimed asphalt shingle binder, a virgin binder, or a performance-grade binder.
  • composition according to embodiment 2, wherein the bituminous binder comprises a reclaimed asphalt pavement binder.
  • bituminous binder comprises a reclaimed asphalt shingle binder.
  • bituminous binder comprises a virgin binder.
  • bituminous binder comprises a performance-grade binder.
  • bituminous binder comprises at least one of a PG 58-28 binder, PG 52-34 binder, PG 58-34 binder, PG 64-28 binder, PG 64-22 binder, a PG 58-31 binder, a PG 58-37 binder, a PG 58-40 binder, a PG 64-25 binder, or a PG 64-31 binder.
  • bituminous binder further comprises at least one polymeric material
  • composition according to embodiment 8, wherein the polymeric material comprises at least one of an elastomer or a rubber.
  • bituminous binder comprises at least one polymeric material selected from an ethylene-vinyl acetate copolymer, a polybutadiene, an ethylene-propylene copolymer, an ethyl ene-propylene-diene terpolymer, a butadiene-styrene block copolymer, a butadiene-styrene-butadiene (BSB) block copolymer, a styrene-butadiene-styrene (SBS) block copolymer, an isoprene-styrene block copolymer, or a styrene-isoprene-styrene (SIS) block copolymer.
  • polymeric material selected from an ethylene-vinyl acetate copolymer, a polybutadiene, an ethylene-propylene copolymer, an ethyl ene-propylene-diene ter
  • n is an integer greater than or equal to 1 ;
  • n is an integer greater than or equal to 0;
  • Ri independently for each occurrence, is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched;
  • R 2 is selected from hydrogen and optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched:
  • R 3 and R4 independently for each occurrence, are selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched.
  • Ri is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched;
  • R 2 is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; wherein each fatty acid chain residue of said at least one compound is independently optionally substituted.
  • R2 is an optionally substituted Ci to C22 alkyl that is saturated or unsaturated, and branched or unbranched, wherein each fatty acid chain residue is unsubstituted.
  • Ri is selected from unsubstituted C 7 to C 17 alkyl that is unbranched and saturated or unsaturated.
  • composition according to embodiment 28, wherein said at least one estolide compound has a kinematic viscosity of 25 cSt to 55 cSt at 40 °C.

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Abstract

L'invention concerne des liants d'asphalte et des compositions bitumineuses comprenant des additifs oligomères tels que des composés d'estolides.
PCT/US2018/033886 2017-05-26 2018-05-22 Liants d'asphalte et compositions bitumineuses comprenant des composés oligomères WO2018217749A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10907353B2 (en) 2017-12-15 2021-02-02 Owens Coming Intellectual Capital, LLC Polymer modified asphalt roofing material
WO2021102157A1 (fr) * 2019-11-20 2021-05-27 Cargill, Incorporated Composition de liant comprenant un composant à base biologique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5718752A (en) * 1995-10-24 1998-02-17 Shell Oil Company Asphalt composition with improved processability
WO2015193909A1 (fr) * 2014-06-18 2015-12-23 Ranka, Seema Ajay Composés d'amide/ester d'organosilane quaternaire et leurs utilisations
US20160264464A1 (en) * 2013-11-11 2016-09-15 Collaborative Aggregates, Llc Novel Asphalt Binder Additive Compositions and Methods of Use
US20160355748A1 (en) * 2013-10-02 2016-12-08 Biosynthetic Technologies, Llc. Estolide compositions exhibiting superior high-performance properties

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5718752A (en) * 1995-10-24 1998-02-17 Shell Oil Company Asphalt composition with improved processability
US20160355748A1 (en) * 2013-10-02 2016-12-08 Biosynthetic Technologies, Llc. Estolide compositions exhibiting superior high-performance properties
US20160264464A1 (en) * 2013-11-11 2016-09-15 Collaborative Aggregates, Llc Novel Asphalt Binder Additive Compositions and Methods of Use
WO2015193909A1 (fr) * 2014-06-18 2015-12-23 Ranka, Seema Ajay Composés d'amide/ester d'organosilane quaternaire et leurs utilisations

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11028591B2 (en) 2017-12-15 2021-06-08 Owens Corning Intellectual Capital, Llc Polymer modified asphalt roofing material
US10907354B2 (en) 2017-12-15 2021-02-02 Owens Corning Intellectual Capital, Llc Polymer modified asphalt roofing material
US10934715B2 (en) 2017-12-15 2021-03-02 Owens Corning Intellectual Capital, Llc Polymer modified asphalt roofing material
US10961713B2 (en) 2017-12-15 2021-03-30 Owens Coming Intellectual Capital, LLC Polymer modified asphalt roofing material
US11028592B2 (en) 2017-12-15 2021-06-08 Owens Corning Intellectual Capital, Llc Polymer modified asphalt roofing material
US10907353B2 (en) 2017-12-15 2021-02-02 Owens Coming Intellectual Capital, LLC Polymer modified asphalt roofing material
US11035123B2 (en) 2017-12-15 2021-06-15 Owens Corning Intellectual Capital, Llc Polymer modified asphalt roofing material
US11473305B2 (en) 2017-12-15 2022-10-18 Owens Corning Intellectual Capital, Llc Polymer modified asphalt roofing material
US11746527B2 (en) 2017-12-15 2023-09-05 Owens Corning Intellectual Capital, Llc Polymer modified asphalt roofing material
US11851889B2 (en) 2017-12-15 2023-12-26 Owens Corning Intellectual Capital, Llc Polymer modified asphalt roofing material
WO2021102157A1 (fr) * 2019-11-20 2021-05-27 Cargill, Incorporated Composition de liant comprenant un composant à base biologique
CN114746376A (zh) * 2019-11-20 2022-07-12 嘉吉公司 包含生物基组分的粘结剂组合物
CN114746376B (zh) * 2019-11-20 2024-03-19 嘉吉公司 包含生物基组分的粘结剂组合物

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