Binder Compositions Including Bio-Based Components

Abstract

Various embodiments relate to binder compositions containing bio-based components and preblends for forming the binder composition. The binder composition includes at least 10% by weight of the binder composition of an oligomerized bio-renewable oil. The binder composition also includes an asphaltene additive including at least 20% to 100% by weight of asphaltenes, where the asphaltene additive is at least 8% by weight of the binder composition.

Description

[Background technology]

[0001] Bitumen, or asphalt, is typically derived from petroleum-based materials used in a variety of applications, including the binder phase for roofing shingles and asphalt concrete, also known as bituminous materials or asphalt pavement. Due to concerns such as declining supplies of petroleum-based materials and their rising costs, pollution, and climate change, binder compositions comprising non-petroleum-derived materials are attractive. Summary of the Invention

[0002] In various aspects, the present invention provides a binder composition comprising at least 10 wt% of an oligomerized biorenewable oil, the binder composition also comprising an asphaltene additive comprising at least 20 wt% to 100 wt% asphaltenes, the asphaltene additive comprising at least 8 wt% of the binder composition.

[0003] In various embodiments, the present invention provides a binder composition. The binder composition comprises an oligomerized biorenewable oil that has been oligomerized by sulfidation, and the binder composition comprises 20% to 45% by weight of the binder composition, with the oligomer molecules comprising, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% by weight of the oligomerized biorenewable oil. The binder composition also comprises an asphaltene additive, which is Gilsonite, and the asphaltene additive comprises 10% to 45% by weight of the binder composition. The binder composition also comprises bitumen, which is added to the bitumen contained in the asphaltene additive, which comprises 15% to 90% by weight of the binder composition.

[0004] In various embodiments, the present invention provides an asphalt emulsion. The asphalt emulsion includes a binder composition. The binder composition includes at least 10% by weight of the binder composition of an oligomerized biorenewable oil. The binder composition also includes an asphaltene additive including at least 20% to 100% by weight of asphaltenes, the asphaltene additive being at least 8% by weight of the binder composition. The asphalt emulsion also includes water emulsified with the binder composition.

[0005] In various embodiments, the present invention provides an asphalt pavement. The asphalt pavement includes a binder composition. The binder composition includes at least 10% by weight of the binder composition of an oligomerized biorenewable oil. The binder composition also includes an asphaltene additive including at least 20% to 100% by weight of asphaltenes, the asphaltene additive being at least 8% by weight of the binder composition. The asphalt pavement also includes aggregate blended with the binder composition. In some embodiments, the asphalt pavement includes recycled asphalt pavement, where the bitumen in the binder composition includes recycled or aged bitumen, and the aggregate includes aggregate from a recycled asphalt composition, or a combination thereof.

[0006] In various embodiments, the present invention provides a roofing shingle. The roofing shingle includes a binder composition. The binder composition includes at least 10% by weight of the binder composition of an oligomerized biorenewable oil. The binder composition also includes an asphaltene additive including at least 20% to 100% by weight of asphaltenes, the asphaltene additive being at least 8% by weight of the binder composition. The roofing shingle also includes a substrate.

[0007] In various aspects, the present invention provides methods of making a binder composition, the method comprising forming a binder composition comprising an oligomerized biorenewable oil, at least 10 wt% of the binder composition, an asphaltene additive comprising at least 20 wt% to 100 wt% asphaltenes, wherein the asphaltene additive is at least 8 wt% of the binder composition, and bitumen, in addition to any bitumen included in the asphaltene additive.

[0008] In various aspects, the present invention provides methods for making asphalt emulsions. The methods include emulsifying a binder composition and an aqueous phase (e.g., water). The binder composition includes an oligomerized biorenewable oil that is at least 10% by weight of the binder composition. The binder composition also includes an asphaltene additive that includes at least 20% to 100% by weight of asphaltenes, and the asphaltene additive is at least 8% by weight of the binder composition.

[0009] In various aspects, the present invention provides methods for making asphalt pavement. The methods include combining a binder composition with aggregate. The binder composition includes at least 10% by weight of the binder composition of an oligomerized biorenewable oil. The binder composition also includes an asphaltene additive including at least 20% to 100% by weight of asphaltenes, the asphaltene additive being at least 8% by weight of the binder composition. In some aspects, the asphalt pavement can include recycled asphalt pavement, where the bitumen in the binder composition includes recycled or aged bitumen, and the aggregate includes aggregate from a recycled asphalt composition, or a combination thereof.

[0010] In various aspects, the present invention provides a method for producing an asphalt pavement. The method includes combining aggregate with a binder composition. The binder composition includes an oligomerized bio-renewable oil that has been oligomerized by sulfidation and that accounts for 20% to 45% by weight of the binder composition, with the oligomer molecules comprising, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% by weight of the oligomerized bio-renewable oil. The binder composition includes an asphaltene additive, which is Gilsonite, that accounts for 10% to 45% by weight of the binder composition. The binder composition also includes bitumen, which is added to the bitumen contained in the Gilsonite, which accounts for 15% to 90% by weight of the binder composition. In some aspects, the asphalt can include pavement, recycled asphalt pavement, the bitumen in the binder composition includes recycled or aged bitumen, and the aggregate includes aggregate from a recycled asphalt composition, or a combination thereof.

[0011] In various aspects, the present invention provides a method for making roof shingles. The method includes combining a binder composition with a substrate. The binder composition includes at least 10% by weight of the binder composition of an oligomerized biorenewable oil. The binder composition also includes an asphaltene additive including at least 20% to 100% by weight of asphaltenes, wherein the asphaltene additive is at least 8% by weight of the binder composition.

[0012] Various embodiments of the present invention have certain advantages over other binder compositions, asphalt emulsions, asphalt paving, roofing shingles, and methods of making them, at least some of which are unexpected. For example, in various embodiments, the binder compositions have maintained or improved rheological profiles, thermal stability, oxidative stability, and / or adhesion compared to corresponding petroleum-based bitumen compositions that do not contain oligomerized biorenewable oils. In various embodiments, the binder compositions of the present invention can provide significantly larger effective temperature intervals for performance ratings and significantly superior desirable performance ratings while maintaining or improving ΔTc values, a measure of binder compatibility and durability, without compromising thermal and oxidative stability. In various embodiments, the binder compositions of the present invention provide unique, high-content biorenewable or non-petroleum-based binders that can offset or replace fossil-based bitumen. In various embodiments, the binder compositions incorporate higher-than-typical amounts of asphaltene-rich material, which is often considered an undesirable by-product that cannot be used to form useful binder compositions. In various aspects, the binder compositions of the present invention can provide a unique alternative in terms of bio-renewable content and rheological and aging performance for paving, roofing, and industrial applications.

[0013] In various aspects, the binder compositions of the present invention can be formed by blending a mixture comprising bitumen and oligomerized bio-renewable oil with an asphaltene additive at a lower mixing temperature, shorter time, or a combination thereof, compared to other blending processes that combine asphaltene additives with bitumen. In various aspects, pre-blending the asphaltene additive with the oligomerized bio-renewable oil can incorporate a higher content of asphaltene additive into the bitumen than typically used. In various aspects, the oligomerized bio-renewable oil of the binder compositions of the present invention can enable the incorporation of higher than typical amounts of polymer modifier or acid modifier, providing superior elasticity and toughness. DETAILED DESCRIPTION OF THE INVENTION

[0014] Reference will now be made in detail to certain aspects of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0015] Throughout this document, values ​​expressed in range format should be interpreted flexibly to include not only the numerical values ​​explicitly recited as the limits of the range, but also all individual numerical values ​​or subranges subsumed within that range, as if each numerical value and subrange were explicitly recited. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also individual values ​​(e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the stated range. A statement "about X to Y" has the same meaning as "about X to about Y" unless otherwise indicated. Similarly, a statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z" unless otherwise indicated.

[0016] In this document, the terms "a," "an," or "the" are used to include one or more unless the context clearly dictates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. "At least one of A and B" or "at least one of A or B" have the same meaning as "A, B, or A and B." Furthermore, it should be understood that phraseology or terminology used herein and not otherwise defined is for purposes of description only and not of limitation. Any use of section headings is intended to aid in the reading and comprehension of the document and should not be construed as limiting. Information associated with a section heading may be found within that particular section or outside that section.

[0017] In the methods described herein, acts may be performed in any order without departing from the principles of the invention, unless a temporal or operational order is explicitly recited. Moreover, certain acts may be performed in parallel unless express "claim" language recites them separately. For example, a claimed act of doing X and a claimed act of doing Y may be performed simultaneously in a single operation, with the resulting process falling within the literal scope of the claimed process.

[0018] As used herein, the term "about" can allow for a degree of variation within a value or range, for example, within 10%, within 5%, or within 1% of the specified value or the limits of a specified range, and includes the exact specified value or range.

[0019] As used herein, the term "substantially" refers to a majority or majority portion, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. As used herein, the term "substantially free" can mean that the amount of material present does not affect or has no effect on the material properties of the composition including the material, such that about 0% to about 5% by weight of the composition is about 0% to about 1%, or about 5% by weight or less, or less than or equal to about 4.5%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01% by weight, or about 0.001% by weight or less, or about 0% by weight of the material.

[0020] As used herein, the term "polymer" refers to a molecule that has at least one repeat unit within the backbone of the polymer (e.g., at least one monomer that is repeated within the backbone of the polymer) and can include copolymers.

[0021] As used herein, "asphalt," "asphalt binder," and "bitumen" refer to the binder phase of an asphalt pavement. The binder used in this invention can be a material obtained from oxidized and aged asphalt obtained from asphalt-producing refineries, solvents, refinery vacuum tower bottoms, pitch, and other residues from processing vacuum tower bottoms, as well as recycled asphalt compositions such as reclaimed asphalt pavement (RAP) and recycled asphalt shingles (RAS). Asphalt or bitumen can also be from naturally occurring sources, such as "lake asphalt." Without being bound by any particular theory, the following explanation of the chemical structure of conventional asphalt is provided. Asphalt or bitumen comprises a complex continuum of compounds covering a range of molecular weights, functionality, polarity, and heteroatom content. As a result, asphalt or bitumen is often conveniently fractionated with respect to reactivity and solubility using a set of solvents. Researchers have used several models to describe the interactions between defined fractions, including the colloidal model. In the colloidal model, the medium or continuous phase is defined as containing primarily relatively low-polarity naphthenic aromatic compounds (or "solvent phase") and paraffinic compounds, which may include a crystalline fraction. The dispersion of highly polar micelles at various levels of intermolecular association in the continuous medium provides many of the mechanical and rheological properties of asphalt or bitumen. The components of the micelles are often defined as a highly polar and high molecular weight "asphaltene" fraction surrounded by a less polar "resin" ("polar aromatic") fraction, which has a high affinity for both the neutral aromatic and polar asphaltene fractions.

[0022] Asphalt "ages" through a combination of mechanisms, primarily oxidation and volatilization. Aging increases the asphalt's modulus, reduces its viscous dissipation and stress relaxation, and makes it more brittle at temperatures where performance is lower. As a result, asphalt becomes more susceptible to cracking and damage accumulation.

[0023] As used herein, "asphalt concrete" or "asphalt pavement" refers to a blend comprising an asphalt binder and aggregate. The asphalt concrete or pavement may be recycled asphalt concrete, such that the bitumen in the binder comprises recycled or aged bitumen, and the aggregate comprises aggregate from a recycled asphalt composition, or a combination thereof.

[0024] As used herein, "asphaltenes" are substances containing primarily carbon and hydrogen, including numerous naphthenic and aromatic ring structures, and additionally containing heteroatoms and functional groups primarily based on sulfur, nitrogen, and oxygen. Asphaltenes can be n-heptane-insoluble components of carbonaceous materials as defined in ASTM D3279. In bitumen or asphalt, asphaltenes are generally the components with the highest molecular weight and highest density of the four "SARA" fractions (saturates, aromatics, resins, and asphaltenes), and contain the most polar portions. The other three fractions (n-heptane-soluble fractions) are collectively referred to as the "maltene" phase, which can be defined using the MK-6S thin-layer chromatography method by adapting the principles described in ASTM D4142 for fractionation of bitumen, using n-pentane to elute the "saturates" and a 90:10 blend of toluene and chloroform to elute the "cyclic" or "aromatic" fractions. The data can be interpreted by assigning the peak areas in the retention time range (stated as a percentage of the total rod scan time) from 0.01 to 0.250 to "saturates," 0.251 to 0.400 to "cyclics," and the remainder (0.401 to 0.510) to the "resin" fraction. Asphaltenes are often components of vacuum tower residues resulting from the refining of crude oil, particularly heavy crude oil. Certain processes in the crude oil refining process can result in materials that are particularly rich in asphaltenes, such as solvent deasphalted pitch or residual oil supercritical extraction process (ROSE®) pitch. Naturally occurring materials rich in asphaltenes can come from sources including "gilsonite" or "uintarite," commonly identified from deposits in Utah's Uintar Basin, and Trinidad Lake asphalt (TLA).

[0025] As used herein, "aggregate" refers to the rock phase of an asphalt pavement. In asphalt pavement, aggregates are bound together by binders. Aggregates may be materials obtained from RAP and RAS sources and / or may be virgin materials not previously used in asphalt applications.

[0026] As used herein, "recycled asphalt" or "recycled bitumen" includes RAP, RAS, or asphalt obtained from a solvent deasphalting process. Recycled asphalt or recycled bitumen may include aggregates containing recycled materials, such as aggregates derived from recycled or aged asphalt compositions. Sources of recycled asphalt or recycled bitumen may include asphalt pavement, asphalt shingles, roofing membranes, asphalt coatings, or other bitumen-containing formulations. Recycled asphalt or recycled bitumen may include binders containing recycled materials, such as recycled or aged bitumen. The content of such recycled asphalt may include initial recycled content and / or multiple recycled content.

[0027] As used herein, an "oligomer" is a polymer molecule having a molecular weight greater than 400. In contrast, monomers include monoacylglycerides (MAGs), diacylglycerides (DAGs), triacylglycerides (TAGs), and free fatty acids (FFAs).

[0028] As used herein, "oligomerized bio-renewable oil" includes one or more bio-renewable oils that have been oligomerized via sulfurization, thickening, blowing, or a combination thereof. The oligomerized bio-renewable oils of the present invention typically have a number average molecular weight of at least 800, preferably at least 1000, e.g., at least 1200, preferably 1200 to 1750. Binder Composition

[0029] In various aspects, the present invention provides a binder composition. The binder composition can include bitumen in addition to any bitumen included in the asphaltene additive, or the binder composition can be substantially free of bitumen other than the bitumen included in the asphaltene additive. The binder composition can include at least 10% by weight of the binder composition of oligomerized biorenewable oil. The binder composition can also include an asphaltene additive including at least 20% to 100% by weight of asphaltenes, with the asphaltene additive being at least 8% by weight of the binder composition. The binder composition can partially or completely replace an asphalt binder combined with aggregate to form an asphalt pavement. The binder composition itself is substantially free of aggregate (e.g., contains about 0% by weight of aggregate). The binder composition, even in embodiments of the binder composition that are substantially free of bitumen, can be referred to as an "asphalt," "asphalt composition," or "asphalt binder composition." A composition comprising a combination of a binder composition and aggregate may be referred to as an "asphalt pavement" or "asphalt concrete," even in embodiments of the binder composition that are substantially free of bitumen.

[0030] The binder composition can be utilized in asphalt mixes for road applications, such as asphalt paving, pothole repair mixes, cold mix, hot mix, and hot recycle mixes. The binder composition can be utilized in pavement preservation applications, where the binder composition may or may not be emulsified, particularly applications that typically use bitumen, such as crack sealants, joint sealers, chip seals, fog seals, scrub seals, slurry seals, reclaim seals, and microsurfacing. The binder composition can be utilized for construction purposes, such as tack coats, prime coats, and cold recycle, where the binder composition may or may not be emulsified. The binder composition can be utilized in various roofing applications where bitumen may be used, including shingles, roofing mats, laminate roofs, and the like. The binder composition can be utilized in coating applications, particularly applications where bitumen may be used, including, but not limited to, corrosion inhibitors, paints, waterproofing agents, fertilizer coatings, pipe coatings, and other industrial coating applications.

[0031] The asphaltene additive may be any suitable one or more additives comprising at least 20 wt% to 100 wt% asphaltenes, 30 wt% to 90 wt%, 50 wt% to 80 wt% asphaltenes, or 20 wt% or more, or less than or equal to 25 wt%, 30, 35, 40, 45, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, or 85 wt% asphaltenes, or less than 90 wt% asphaltenes, or less than 90 wt%, 85, 80, or 75 wt% asphaltenes in the asphaltene additive. The asphaltene additive is substantially free of low molecular weight and low polarity naphthenic and aromatic molecules and saturates. The low molecular weight and low polarity naphthenic and aromatic molecules and saturates fraction is about 0 wt% to about 40 wt% of the asphaltene additive, preferably less than 35 wt%, more preferably less than 30 wt% of the asphaltene additive, or about 0 wt% to about 50 wt%, 0 wt% to 40 wt%, 0 wt% to 5 wt%, 0 wt% to 3 wt%, 0 wt% to 1 wt%, 0 wt% to 0.5 wt%, 0 wt% to 0.1 wt%, or 0 wt% or greater, or less than or equal to 0.0001 wt%, 0.001, 0.01, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35 wt%, or 40 wt% or less of the asphaltene additive. In contrast, bitumen generally has significant concentrations of low molecular weight and low polarity naphthenic and aromatic molecules, and a significant amount of saturated fractions. Preferably, the asphaltene additive can be gilsonite, unitalite, residual oil supercritical extract, or a combination thereof. More preferably, the asphaltene additive can include or be gilsonite. The asphaltene additive can form any suitable proportion of the binder composition, such as at least 10 wt.% of the binder composition, 8 wt.% to 60 wt.%, 10 wt.% to 45 wt.%, 8 wt.% or more of the binder composition, less than or equal to 10 wt.%, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 45, 50, or 55 wt.% of the binder composition, or less than or equal to 60 wt.%.

[0032] The total asphaltenes content of the binder composition can be at least 1, 2, 3, 4, 5, 8, 10, 12, 15, 20 wt%, 30, 40, or at least 50 wt%, or between 1 wt% and 70 wt%, between 2 wt% and 60 wt%, or between 3 wt% and 50 wt%, or less than or equal to 1 wt%, 2 wt%, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50, 55, 60, 65 wt%, or up to about 70 wt%.

[0033] In the binder composition comprising bitumen added to the bitumen contained in the asphaltene additive, the bitumen can be any suitable bitumen. The bitumen can comprise or be virgin bitumen. The bitumen can comprise or be recycled bitumen, whereby the binder composition is a recycled binder composition. The recycled bitumen can be bitumen obtained from RAP or RAS, bitumen-type material can be obtained via a solvent deasphalting process, such as propane precipitation bitumen obtained from the bottom of a solvent deasphalting process, or a combination thereof. The bitumen can form any suitable proportion of the binder composition, such as 0%, 10% to 90%, 15% to 90%, 60% to 90%, 15% to 40%, 10% to 15%, or 0% or more, or less than or equal to 1%, 2, 4, 6, 8, 10, 12, 14, 15%, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by weight of the binder composition, or 90% or less.

[0034] The biorenewable oil can be any suitable biorenewable oil, such as animal-based oil, algae-based oil, vegetable oil, or a combination thereof. The animal-based oil can be any suitable oil extracted from or derived from an animal source, such as animal fats (e.g., lard, tallow), lecithin (phospholipids), and combinations and crude streams thereof. The algae-based oil can be any suitable oil extracted or derived from an algae source. The vegetable-based oil can be any suitable vegetable-based oil. Vegetable-based oils can include soybean oil, linseed oil, canola oil, rapeseed oil, castor oil, tall oil, cottonseed oil, sunflower oil, palm oil, peanut oil, safflower oil, corn oil, corn stillage oil, and lecithin (phospholipids), as well as combinations thereof, distillates thereof, derivatives thereof, and crude streams thereof. The vegetable-based oil can be a vegetable oil. Vegetable-based oils can include partially hydrogenated oils, oils with conjugated bonds, and thickened oils without heteroatoms, but can also include, for example, diacylglycerides, monoacylglycerides, or free fatty acids (and their distillate streams), alkyl esters of free fatty acids (e.g., methyl, ethyl, propyl, and butyl esters), and mixtures and derivative streams thereof. Examples of vegetable-based oils can include used cooking oil or other used oils. In contrast, petroleum-based oils include a wide range of hydrocarbon-based compositions and refined petroleum products with different chemical compositions, which are obtained from recovered and refined oils from fossil-based sources and are considered non-renewable because the starting materials take millions of years to produce.

[0035] The oligomerized bio-renewable oil comprises one or more bio-renewable oils that have been oligomerized via sulfurization, thickening, blowing, or a combination thereof. In some embodiments, the oligomerized bio-renewable oil is not blended with any non-oligomerized oils (e.g., any non-oligomerized bio-renewable oils) after oligomerization. In other embodiments, the oligomerized bio-renewable oil is blended with non-oligomerized bio-renewable oils after oligomerization. The oligomeric molecules (e.g., oligomerized biorenewable oil molecules) can be any suitable percentage of the oligomerized biorenewable oil, such as 5% to 100% by weight of the oligomerized biorenewable oil, 65% to 75% by weight of the oligomerized biorenewable oil, or 5% by weight or more, or less than or equal to 10%, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 62, 64, 65, 66, 68, 70, 72, 74, 75, 76, 78, 80, 85, 90, or 95% by weight, or up to 100% by weight. The oligomerized biorenewable oil can form any suitable percentage of the binder composition, such as 10% to 80%, 10% to 60%, 20% to 45% by weight of the binder composition, or at least 10%, at least 15%, at least 20%, at least 40%, at least 50% by weight, or 10% or less, or less than or equal to 12%, 15, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 45, 46, 48, 50, 55, 60, 65, 70, or 75% by weight, or 80% or more by weight.

[0036] Oligomerized biorenewable oils can include modified or functionalized biorenewable oils. Examples of pre-modified oils include those that have been pre-vulcanized or oligomerized by other oligomerization techniques, such as those modified with maleic anhydride or acrylic acid, hydrogenated, modified with dicyclopentadiene, conjugated via reaction with iodine, transesterified, or treated to change the acid value, hydroxyl value, or other properties. Such modified oils can be blended with unmodified biorenewable oils or animal-based oils, fatty acids, glycerin, and / or lecithin. Examples of functionalized oils include those with the introduction of heteroatoms (oxygen, nitrogen, sulfur, phosphorus).

[0037] The oligomerized biorenewable oils can be oligomerized via various techniques, such as sulfurization, as described in WO 2016 / 138377, blowing and stripping, as described in U.S. Patent Application Publication Nos. 2016 / 0369203 and WO 2016 / 149102.

[0038] The oligomerized biorenewable oil can include modified biorenewable oligomerized oil, unmodified biorenewable oligomerized oil, or a combination thereof. The modified oil can include oil modified with maleic anhydride, acrylic acid, hydrogen, dicyclopentadiene, conjugation via reaction with iodine, or transesterification, or a combination thereof.

[0039] The oligomerized bio-renewable oil can include sulfurized bio-renewable oil. The oligomerized bio-renewable oil can include modified sulfurized bio-renewable oil. The oligomerized bio-renewable oil can include unmodified sulfurized bio-renewable oil.

[0040] In some aspects, the binder composition can further comprise a bio-renewable oil, a modified bio-renewable oil, an unmodified bio-renewable oil, an oligomerized bio-renewable oil, a petroleum-based oil, a modified petroleum-based oil, an unmodified petroleum-based oil, an unoligomerized petroleum-based oil, or a combination thereof.

[0041] In some embodiments, the binder composition is selected from the group consisting of elastomers (e.g., rubbers such as ground-mounted tire rubbers), thermoplastic elastomers (e.g., styrene-butadiene-styrene polymers, styrene-butadiene-rubber polymers, styrene-isoprene-styrene polymers, styrene-ethylene-butadiene-styrene polymers, ethylene-propylene-diene polymers, isobutene-isoprene polymers, polybutadiene, polyisoprene), thermoplastic polymers (e.g., ethylene vinyl acetate, ethylene methyl acrylate, ethylene butyl acrylate, polypropylene, polyethylene, polyvinyl chloride, polystyrene, functionalized polyolefins), thermosetting polymers (e.g., epoxy resins, polyurethane resins, acrylic resins, phenolic resins), and the like. resins), warm mix additives (e.g., amines, oils, waxes, zeolites), fibers (e.g., cellulose, alumina-magnesium silicate, glass fibers, asbestos, polyester, polypropylene), emulsifiers, adhesion promoters (e.g., organic amines, amides, organosilanes), anti-stripping additives, polyphosphates, fillers (e.g., carbon black, hydrated lime, lime, fly ash), rheology modifiers (e.g., aromatic, naphthenic, and paraffinic distillates, base oils, rerefined engine oils and residual oils, waste oils), cutback, oils, resins, waxes (e.g., Fischer-Tropsch wax, montan wax, amide wax), surfactants, waste plastics, pigments, or combinations thereof.

[0042] The binder composition may be free of polymer modifiers and / or polymer modifications using polymer modifiers. In some embodiments, the binder composition may include a polymer modifier and / or may be polymer modified using a polymer modifier such as polystyrene, poly(divinylbenzene), poly(indene), styrene-butadiene-styrene polymers, polyolefins, copolymers thereof, or combinations thereof. The polymer modifier may include or be a styrene-butadiene-styrene polymer. The polymer modifier may be a crosslinked or non-crosslinked polymer modifier. The polymer modifier can be any suitable percentage of the binder composition, such as 0.01% to 30%, 0.5% to 10%, 1% to 6%, or 0.01% or more by weight of the binder composition, or less than or equal to 0.05, 0.1, 0.2, 0.5, 0.6, 0.8, 1, 1.5, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, or 28% by weight of the binder composition, or less than or equal to 30% by weight.

[0043] The binder composition may be free of an acid modifier and / or acid modified using an acid modifier. In some embodiments, the binder composition may include an acid modifier and / or may be acid modified using an acid modifier such as polyphosphoric acid. The acid modifier may be any suitable percentage of the binder composition, such as 0.3% to 8%, 1% to 5%, 1% to 3%, or 0.3% or more by weight of the binder composition, or less than or equal to 0.4%, 0.5, 0.6, 0.8, 1, 1.5, 2, 2.5, 3, 4, 5, 6, or 7% by weight of the binder composition, or 8% or more by weight.

[0044] In some aspects, the binder composition can include a bio-based filler, which can be any bio-based filler (e.g., in addition to any bio-based filler present in the asphaltene additive), such as lignin (e.g., in addition to any lignin present in the asphaltene additive), lignin-based by-products, rosin, rosin-based by-products, bio-based fibers, biomass, pyrolysis products, biochar from pyrolysis of biomass, tall oil pitch, cellulosic materials from agricultural by-products, or combinations thereof.

[0045] The binder composition can have any suitable performance grade as determined in accordance with AASHTO M320-10, where the performance grade (PG) can be written as "PGAB," where A is the high service temperature performance grade and B is the low service temperature performance grade. For example, PG52-34 indicates a high service temperature performance grade of 52°C and a low service temperature performance grade of -34°C. The binder composition can have any suitable performance grade, such as a performance grade of PG52-34, PG58-28, PG58-34, PG64-22, PG64-28, PG70-16, PG70-22, or PG76-22. The binder composition can have a performance grade of PG52-34, PG58-28, PG64-22, or PG70-16.

[0046] The binder composition can have a high service temperature performance rating, such as 34 to 122°C, or 46 to 82°C, or 52 to 70°C, or 30°C or greater, or less than or greater than 34, 40, 46, 52, 58, 64, 70, 76, 82, 88, or 94°C, or less than or equal to 122°C, as determined in accordance with AASHTO M320-10.

[0047] The binder composition can have a low temperature use temperature performance rating, such as -46 to 22°C, or -40 to -10°C, or -46°C or greater, or less than or greater than -40°C, -37, -34, -28, -22, -16, -10, -4, 2, or 6°C, or less than or equal to 22°C, as determined in accordance with AASHTO M320-10.

[0048] The term UTI refers to the difference between the high temperature performance rating and the low temperature performance rating, which is the effective temperature interval, as determined using AASHTO M320. The binder composition can have an effective temperature interval, such as 86-120°C, or 92-104°C, or 86°C or greater, or less than or greater than 88°C, 90, 92, 94, 96, 98, 100, 102, 104, 106, or 108°C, or less than or equal to 120°C, as determined in accordance with AASHTO M320.

[0049] The term O-DSR refers to the high temperature performance rating of an unaged ("original") asphalt binder as measured using a dynamic shear rheometer (DSR) in accordance with ASTM D7175 and AASHTO M320. The binder composition can have an O-DSR of 34-122°C, or 52-70°C, or 30°C or greater, or less than or greater than 34°C, 40, 46, 52, 58, 64, 70, 76, 82, 88, or 94°C, or less than or equal to 122°C, as determined in accordance with ASTM D7175 and AASHTO M320.

[0050] The term R-DSR refers to the high temperature performance rating of a rolled thin film oven aged (RTFO per ASTM D2872) asphalt binder as measured using a dynamic shear rheometer (DSR) per ASTM D7175 and AASHTO M320. The binder composition can have an R-DSR of 34-122°C, or 52-70°C, or 30°C or greater, or less than or greater than 35°C, 40, 45, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 75, 80, 85, 90, or 95°C, or less than or equal to 100°C, as determined per ASTM D7175 and AASHTO M320.

[0051] The term S-BBR refers to a low temperature performance rating controlled by the creep stiffness parameter ("S") measured on an asphalt binder using a bending beam rheometer in accordance with ASTM D6648 and AASHTO M320, and conditioned using both a rolled thin film oven or "RTFO" (ASTM D2872) and a pressure aging vessel or "PAV" (ASTM D6521). The binder composition can have an S-BBR from -46 to 22°C, or from -40 to -10°C, or above -46°C, or below or above -40°C, -37, -34, -28, -22, -16, -10, -4, 2, or 6°C, or below 22°C, as determined in accordance with AASHTO M320-10.

[0052] The binder composition may have an m-BBR between -46 and 22°C, or between -40 and -10°C, or greater than -46°C, or less than or greater than -40°C, -37, -34, -28, -22, -16, -10, -4, 2, or 6°C, or less than or equal to 22°C, as determined in accordance with AASHTO M320-10. The term m-BBR refers to the low temperature performance rating controlled by the creep stiffness parameter ("m" value) measured on asphalt binders using a bending beam rheometer in accordance with ASTM D6648 and AASHTO M320, and conditioned using both a rolled thin film oven (ASTM D2872) and a pressure aging vessel (ASTM D6521).

[0053] The ASTM D5 standard describes the penetration testing of bitumen using a penetrometer. Penetration is reported in units of dmm. Higher penetration values ​​generally indicate lower viscosity or stiffness at the test temperature. The binder composition can have an undegraded penetration, determined according to ASTM D5, of 15 to 220 dmm, or 30 to 100 dmm, or 15 dmm or greater, or less than or equal to 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, or 210 dmm, or less than or equal to 220 dmm. The binder composition can have an RTFO penetration of 15 to 220 dmm, 30 to 100 dmm, or 15 dmm or more, or less than or equal to 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, or 210 dmm, or less than or equal to 220 dmm, as determined according to ASTM D5.

[0054] ASTM D3461 describes performing the dropping point or "softening point" test using a Mettler dropping point tester. Dropping point values ​​correlate closely with, and are typically statistically equivalent to, the ASTM D36 softening point test. In this invention, results, conclusions, and discussions based on the ASTM D3461 dropping point also represent the ASTM D36 softening point. The binder composition can have an undegraded softening point determined in accordance with ASTM D3461 of 35 to 190°C, or 40 to 90°C, or 35°C or greater, or less than or greater than 40°C, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, or 185°C, or less than or equal to 190°C. The binder composition can have an RTFO softening point of 30 to 190°C, or 40 to 90°C, or 45 to 65°C, or greater than or equal to 30°C, or less than or equal to 35°C, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, or 185°C, or less than or equal to 190°C, as determined according to ASTM D3461 and ASTM D2872.

[0055] The binder composition can be a roofing shingle component, such as a roofing shingle, comprising a binder composition and a substrate as described herein. The binder composition can be a roofing shingle flux, which can be blown to form a shingle coating. In some embodiments of binder compositions suitable for use in roofing shingle components, the binder composition can be a blown binder composition having an unaged penetration and / or RTFO penetration, as determined according to ASTM D5, of 3 to 40 dmm, or 5 to 30 dmm, or 10 to 20 dmm, or 3 dmm or greater, but less than or equal to 4, 6, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 32, 34, 36, or 38 dmm, or 40 dmm or less. The binder composition can be a blown binder composition having an unaged softening point and / or RTFO softening point of 100-190°C, or 110-130°C, or 115-125°C, or greater than or equal to 100°C, or less than or equal to 102°C, 104, 106, 108, 110, 112, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 128, 130, 132, 134, 136, 140, 145, 150, 155, 160, 165, 170, 175, 180, or 185°C, or less than or equal to 190°C, as determined in accordance with ASTM D3461 and ASTM D2872.

[0056] In various aspects, the binder compositions of the present invention have an effective property balance and can provide a very large performance grade effective temperature interval and excellent desirable performance grades without including other useful properties.

[0057] In some embodiments, the roofing shingle component or roofing flux comprises a binder composition that is a 50:50 blend of oligomerized bio-renewable oil and Gilsonite, wherein the binder is substantially free of Gilsonite. In some embodiments, the roofing shingle component or roofing flux comprises a binder composition that is a 48:48:4 blend of oligomerized bio-renewable oil, Gilsonite, and one or more suitable additives. Asphalt emulsion

[0058] In various aspects, the present invention provides asphalt emulsions. The asphalt emulsions include a binder composition described herein and water emulsified with the binder composition. For example, the binder composition can include bitumen in addition to any bitumen included in the asphaltene additive, or the binder composition can be substantially free of bitumen other than the bitumen included in the asphaltene additive. The binder composition can include at least 10% by weight of the binder composition of oligomerized biorenewable oil. The binder composition can also include an asphaltene additive including at least 20% to 100% by weight of asphaltenes, where the asphaltene additive is at least 8% by weight of the binder composition.

[0059] The aqueous phase and binder composition can be individually present in any suitable proportion in the asphalt emulsion. Asphalt pavement

[0060] In various aspects, the present invention provides an asphalt pavement. The asphalt pavement comprises the binder composition described herein blended with a binder composition. For example, the binder composition can include bitumen in addition to any bitumen included in the asphaltene additive, or the binder composition can be substantially free of bitumen other than the bitumen included in the asphaltene additive. The binder composition can include at least 10% by weight of the binder composition of oligomerized biorenewable oil. The binder composition can also include an asphaltene additive comprising at least 20% to 100% by weight of asphaltenes, with the asphaltene additive being at least 8% by weight of the binder composition.

[0061] The aggregate and binder composition can be individually present in any suitable proportion in the asphalt pavement. In some aspects, the binder composition can be a recycled binder composition, and the bitumen (if present in the binder composition) added to the bitumen contained in the asphaltene additive can include or be bitumen from RAP or RAS, where the bitumen is obtained via a solvent deasphalting process, such as propane precipitated bitumen obtained from the bottom of a solvent deasphalting process, or a combination thereof. In some aspects, the aggregate can include or be virgin aggregate. In some aspects, the asphalt can be recycled pavement, where the bitumen includes recycled or aged bitumen, and the aggregate includes aggregate derived from a recycled asphalt composition, such as recycled or aged asphalt concrete or shingles, or a combination thereof.

[0062] The aggregate can be any suitable aggregate used in asphalt paving, such as sand, gravel, crushed stone, slag, recycled concrete, aggregate obtained from recycled asphalt compositions, aggregate obtained from RAP or RAS, geosensitic additives, or combinations thereof.

[0063] In some embodiments, the pavement comprises a binder composition that is a 50:50 blend of oligomerized bio-renewable oil and Gilsonite, wherein the binder is substantially free of additives. In some embodiments, the pavement comprises a binder composition that is a 48:48:4 blend of oligomerized bio-renewable oil, Gilsonite, and one or more suitable additives. Roof shingles

[0064] In various aspects, the present invention provides roofing shingles. The roofing shingles include a binder composition and a substrate as described herein. For example, the binder composition can include bitumen in addition to any bitumen included in the asphaltene additive, or the binder composition can be substantially free of bitumen other than the bitumen included in the asphaltene additive. The binder composition can include at least 10% by weight of the binder composition of oligomerized biorenewable oil. The binder composition can also include an asphaltene additive including at least 20% to 100% by weight of asphaltenes, where the asphaltene additive is at least 8% by weight of the binder composition. The binder composition can be a shingle coating.

[0065] The substrate and binder composition can be individually present in any suitable proportion in the roof shingle. The substrate can be any suitable substrate for the shingle. The substrate can include organic materials, fiberglass, or a combination thereof. The organic materials can include paper, cellulose, wood fiber, or a combination thereof.

[0066] In some embodiments, the roofing shingle binder composition can be a blown binder composition having an unaged penetration and / or RTFO penetration of 3 to 40 dmm, or 5 to 30 dmm, or 10 to 20 dmm, or 3 dmm or greater, but less than or equal to 4, 6, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 32, 34, 36, or 38 dmm, or 40 dmm or less, as determined according to ASTM D5. The binder composition can be a blown binder composition having an unaged softening point and / or RTFO softening point of 100-190°C, or 110-130°C, or 115-125°C, or greater than or equal to 100°C, or less than or equal to 102°C, 104, 106, 108, 110, 112, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 128, 130, 132, 134, 136, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185°C, or less than or equal to 190°C, as determined in accordance with ASTM D3461 and ASTM D2872. Method for making a binder composition

[0067] In various aspects, the present invention provides methods of making a binder composition. The methods include forming a binder composition described herein. For example, the methods can include forming a binder composition comprising at least 10% by weight of the binder composition of an oligomerized biorenewable oil and an asphaltene additive comprising at least 20% to 100% by weight of asphaltenes, wherein the asphaltene additive is at least 8% by weight of the binder composition. The binder composition can include bitumen in addition to any bitumen included in the asphaltene additive, or the binder composition can be substantially free of bitumen other than the bitumen included in the asphaltene additive.

[0068] The binder composition can include bitumen added to the bitumen contained in the asphaltene additive. The components of such binder compositions can be combined in any suitable order. For example, an asphaltene additive containing at least 20% to 100% by weight of asphaltenes (e.g., Gilsonite) can be added to a blend of bitumen and oligomerized biorenewable oil. In another embodiment, the asphaltene additive containing at least 20% to 100% by weight of asphaltenes and the oligomerized biorenewable oil can be pre-blended into a mixture. The asphaltene additive containing at least 20% to 100% by weight of asphaltenes can be present in the finished mixture in any suitable form, such as suspended or dissolved. The pre-blended mixture can then be combined with bitumen to form the binder composition. In some embodiments, the use of a preblend comprising an asphaltene additive comprising at least 20 wt% to 100 wt% asphaltenes and an oligomerized bio-renewable oil can improve homogenization of the binder composition and allow for the formation of the binder composition at lower temperatures, less shear, or a combination thereof, compared to forming the binder composition by adding an asphaltene additive comprising at least 20 wt% to 100 wt% asphaltenes to a blend of bitumen and oligomerized bio-renewable oil.

[0069] In various aspects, the present invention provides preblends for use in forming binder compositions containing bitumen, which are added to bitumen contained in an asphaltene additive. The preblends can include a mixture of oligomerized biorenewable oil and an asphaltene additive containing at least 20% to 100% asphaltenes by weight. The preblends can be substantially free of bitumen other than any bitumen contained in the asphaltene additive. The preblends can include any suitable ratio of oligomerized biorenewable oil and asphaltene additive suitable for forming the binder compositions described herein. For example, the oligomerized biorenewable oil can be 7% to 55% by weight of the preblend, or 9% to 40% by weight, or 7% or more, or less than or equal to 8, 10, 15, 20, 25, 30, 35, 40, 45, 50% by weight, or up to 55% by weight. The asphaltene additive, which contains at least 20 wt% to 100 wt% asphaltenes, can be 9 wt% to 72 wt% of the preblend, or 20 wt% to 40 wt%, or 9 wt% or more, or less than or equal to 10 wt%, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 wt%, or 72 wt% or less.Preblends may include elastomers (e.g., rubbers such as ground tire rubber), thermoplastic elastomers (e.g., styrene-butadiene-styrene polymers, styrene-butadiene-rubber polymers, styrene-isoprene-styrene polymers, styrene-ethylene-butadiene-styrene polymers, ethylene-propylene-diene polymers, isobutene-isoprene polymers, polybutadiene, polyisoprene), thermoplastic polymers (e.g., ethylene vinyl acetate, ethylene methyl acrylate, ethylene butyl acrylate, polypropylene, polyethylene, polyvinyl chloride, polystyrene, functionalized polyolefins), thermosetting polymers (e.g., epoxy resins, polyurethane resins, acrylic resins, phenolic resins), warm mix additives (e.g., amines, oils, waxes, zeolites), fibers (e.g., cellulose, alumina-magnesium The preblend may optionally include any one or more of the other compositions described as suitable for inclusion in the binder composition, such as additives such as cellulose silicates, glass fibers, asbestos, polyester, polypropylene), emulsifiers, adhesion promoters (e.g., organic amines, amides, organosilanes), anti-stripping additives, polyphosphates, fillers (e.g., carbon black, hydrated lime, lime, fly ash), rheology modifiers (e.g., aromatic, naphthenic, and paraffinic distillates, base oils, rerefined engine oils and residual oils, waste oils), cutback, oils, resins, waxes (e.g., Fischer-Tropsch wax, montan wax, amide wax), surfactants, waste plastics, pigments, or combinations thereof; polymer modifiers and / or polymer modifications; acid modifiers and / or acid modifications; bio-based fillers; or combinations thereof. The preblend may be the same as the binder composition described herein substantially free of bitumen other than any bitumen included in the asphaltene additive, and may have the same or different properties as the binder composition described herein. Method for making asphalt emulsion

[0070] In various aspects, the present invention provides methods for making asphalt emulsions. The methods include emulsifying a binder composition described herein and an aqueous phase (e.g., water). For example, the binder composition can include bitumen in addition to any bitumen included in the asphaltene additive, or the binder composition can be substantially free of bitumen other than the bitumen included in the asphaltene additive. The binder composition can include at least 10% by weight of the binder composition of oligomerized biorenewable oil. The binder composition can also include an asphaltene additive comprising at least 20% to 100% by weight of asphaltenes, where the asphaltene additive is at least 8% by weight of the binder composition.

[0071] The aqueous phase and binder composition can be individually present in any suitable proportion in the asphalt emulsion. Emulsification of the aqueous phase and binder composition can be accomplished via any suitable emulsification technique. Method for producing asphalt pavement

[0072] In various aspects, the present invention provides methods for producing asphalt pavements. The methods include combining a binder composition described herein with aggregate. For example, the binder composition can include bitumen in addition to any bitumen included in the asphaltene additive, or the binder composition can be substantially free of bitumen other than the bitumen included in the asphaltene additive. The binder composition can include at least 10% by weight of the binder composition of oligomerized biorenewable oil. The binder composition can also include an asphaltene additive including at least 20% to 100% by weight of asphaltenes, where the asphaltene additive is at least 8% by weight of the binder composition.

[0073] The aggregate and binder composition can be individually present in any suitable proportion in the asphalt pavement. In some aspects, the binder composition can include a recycled binder component, and the bitumen added to the bitumen included in the asphaltene additive can include or be bitumen from RAP or RAS, where the bitumen is obtained via a solvent deasphalting process, such as propane precipitated bitumen obtained from the bottom of a solvent deasphalting process, or a combination thereof. In some aspects, the aggregate can include or be virgin aggregate. In some aspects, the asphalt pavement can be a recycled pavement, and the aggregate can include aggregate from a recycled asphalt composition (e.g., RAP or RAS), and the bitumen can include bitumen from a recycled asphalt composition, such as recycled or aged asphalt concrete or shingles, or a combination thereof.

[0074] The aggregate can be any suitable aggregate used in asphalt paving, such as sand, gravel, crushed stone, slag, recycled concrete, aggregate obtained from RAP or RAS, geosynthetic additives, or combinations thereof. How to Make Roof Shingles

[0075] In various aspects, the present invention provides methods for making roof shingles. The methods include combining a binder composition described herein with a substrate. For example, the binder composition can include bitumen in addition to any bitumen included in the asphaltene additive, or the binder composition can be substantially free of bitumen other than the bitumen included in the asphaltene additive. The binder composition can include at least 10% by weight of the binder composition of oligomerized biorenewable oil. The binder composition can also include an asphaltene additive including at least 20% to 100% by weight of asphaltenes, where the asphaltene additive is at least 8% by weight of the binder composition.

[0076] The substrate and binder composition can be individually present in any suitable proportions in a roof shingle. The substrate can be any suitable substrate for a shingle. The substrate can be any suitable substrate for a shingle. The substrate can include organic materials, fiberglass, or a combination thereof. The organic materials can include paper, cellulose, wood fiber, or a combination thereof.

[0077] The binder composition can be a shingle coating, and a method for making roofing shingles can include applying the coating to a substrate. For such applications, the binder composition can be air-blown to a high softening point. The binder composition can be air-blown alone or in a blend with bitumen, optionally in addition to the asphaltene additive, and thus can withstand harsh air-blower conditions at temperatures ranging from about 200°C to 250°C. The binder composition can include oligomerized bio-renewable oil, where the oligomerization is achieved by sulfidation. The binder composition can be added in part or in its entirety before the start of the blowing process or at some point before the end of the blowing process, such as when the catalyst is added. The binder composition can be pre-blended with the catalyst. [Example]

[0078] Various aspects of the present invention may be better understood by reference to the following examples, which are provided by way of illustration and not limitation. The present invention is not limited to the examples set forth herein.

[0079] The term ΔTc refers to the difference between BBR S grade and BBR m grade (S-BBR-m-BBR) at 20 hours of PAV aging. A trend toward low or negative ΔTc values ​​is considered in the literature to roughly indicate a decrease in bitumen compatibility, colloidal stability, and durability. An increasing trend toward high or positive values ​​is desirable.

[0080] Using AASHTO M320, bitumen performance grades are determined as a range defining the lower of two DSR grades and the higher of two BBR grades.

[0081] PG64-22, with a high-temperature rating of 64°C and a low-temperature rating of -22°C, is one of the most common paving grade bitumen grades (PG64-22). Other grades commonly used in paving are PG58-28 and PG52-34. These grades, ranging from 64°C to -34°C, cover the majority of paving worldwide and are comparable to the most commonly used grades in other regions of the world. In some very warm regions, grades such as PG64-16 and PG70-16 are used, and very rarely, PG70-10. In colder regions, PGXX-34 or PG46-40 may be used, with the XX indicating that the high-temperature grade may vary from batch to batch, between 46°C and 52°C.

[0082] The numerical difference between grades is called the "effective temperature interval" or "UTI." Typical paving-grade bitumen has a UTI above 86°C. Several premium grades have higher UTI values, such as PG76-22, PG70-22, PG64-28, PG64-34, PG58-34, and PG52-40. While less common, such grades are highly desirable for their broader temperature range coverage, thus offering greater flexibility and reliability in their applications. These grades are also offered at a significantly higher price point due to the costs and difficulties associated with their manufacture and typically contain approximately 1-3% by weight of a polymer, such as styrene-butadiene-styrene, or 0.5-1.0% PPA. High-temperature grades above 76°C are unusual for paving-grade bitumen, but are not problematic when paired with a sufficiently low-temperature grade (e.g., -16 or -22°C).

[0083] Conversely, bitumens with grades such as PG64-16 and PG70-10 have a low UTI of 80° C. and are often considered less desirable. Such binders also often suffer from negative ΔTc values.

[0084] The Performance Grade (PG) system of bitumen grading is used primarily in North America and a few other countries, but all bitumen worldwide can be graded in this manner, and therefore its use in this patent is not meant to exclude the applicability of these examples to a particular region or geographic area. Many countries use some combination of needle penetration, softening point, and viscosity as the basis for grading (i.e., energy grading or viscosity grading). For example, a Pen 50 / 70 grade (with a needle penetration of 50-70 dmm at 25°C) is typically graded as PG 64-22 in the PG system, and Pen 70 / 100 is often graded as PG 58-28. Other grades that may be used are Pen 40 / 60, which is typically close to PG 64-16 or PG 70-16, and Pen 160 / 220, which is close to PG XX-34.

[0085] In producing asphalt coatings for roofing shingles by blowing roofing flux, a high softening point is targeted and controlled throughout the blowing process. The penetration of the resulting coating must be higher than a certain minimum penetration value to ensure flexibility and durability of the shingle coating.

[0086] Based on Gilsonite literature, blending temperatures of 185-220°C and blending times of 4-6 hours are often required to fully incorporate Gilsonite into bitumen. Such temperatures are higher than typical bitumen processing temperatures and can be detrimental to bitumen quality due to the volatilization of certain low-boiling fractions (i.e., lower molecular weight cyclic molecules, such as those defined as the "aromatic" fraction) that provide bitumen flexibility.

[0087] In the following examples using Gilsonite, blending times and temperatures were used: a low temperature of 155°C for 1 hour and a high temperature of 180°C for 2 hours. The Gilsonite used in the examples was a fine black powder manufactured by American Gilsonite. 100% of the material passed through a standard ASTM #16 mesh, about 11% by weight was retained on a #30 mesh, and about 65% by weight was retained on a #100 mesh. Example 1. Compositions containing oligomerized biorenewable oil and Gilsonite

[0088] Sulfurized refined soybean oil was reacted with 7.0 wt. % elemental sulfur at 160°C for 19 hours under a nitrogen purge. The sulfurized refined soybean oil had 70.8 wt. % oligomers and is referred to herein as "MO#1." MO#1 was blended with Gilsonite at 155°C using a benchtop low shear drill mixer at 200 RPM for 1 hour to form a binder composition. No bitumen was used in the binder composition. [Table 1]

[0089] Gilsonite is completely dissolved and incorporated into the resulting binder composition, which is visually similar to bitumen. Furthermore, the composition can be easily blended with other bitumen to create new grades, providing an efficient and thermally stable method for incorporating Gilsonite into bitumen with less stringent blending energies. Example 2. Compositions containing oligomerized biorenewable oil and Gilsonite

[0090] A diluted sulfurized refined soybean oil was formed comprising a blend of "MO#1" and refined soybean oil. This resulted in an oil having an oligomer content of approximately 45%, which is referred to herein as "MO#2." "MO#2" and Gilsonite were heated to 180°C and blended for 2 hours at 500 RPM using a benchtop low-shear drill mixer to form a binder composition. No bitumen was used in the binder composition. [Table 2]

[0091] Gilsonite was completely dissolved and incorporated into the resulting binder composition, which was visually similar to bitumen and exhibited some of the rheological properties of bitumen. Furthermore, the composition can be easily blended with other bitumen to create new grades, providing an efficient and thermally stable method for incorporating Gilsonite into bitumen with less stringent blending energies. Example 3. Binder Composition Comprising Oligomerized Biorenewable Oil, Gilsonite, and Bitumen

[0092] A binder composition was formed containing Gilsonite, neat asphalt binder graded as PG64-22 (PG64.88-24.7), and sulfurized refined soybean oil, previously identified as "MO#1." The ingredients were blended at 155°C for 1 hour using a benchtop low-shear drill mixer at 200 RPM. Performance rating testing was performed in accordance with AASHTO M320. Table 1 shows the blends and the resulting performance ratings. [Table 3]

[0093] BB#1 is one of the most common paving-grade bitumen grades (PG64-22). Therefore, it is used both as the base for the blends and as a comparison standard for the other blends. As the results show, increasing the Gilsonite content (Blends BB#1, #3, and #4) resulted in a significant increase in the high-temperature grades (O-DSR and R-DSR) and a decrease in the low-temperature grades, i.e., an overall hardening of the binder. Furthermore, the ΔTc values ​​became increasingly negative with increasing Gilsonite content. In the case of Blend #5, a performance grade of PG88-10 was achieved, which is not typical of paving-grade binders due to its excessive stiffness.

[0094] Meanwhile, the incorporation of MO#1 balanced this trend across the board in all noted properties. In the case of Binder Blend #5, the binder composition meets (and improves upon) the base and control bitumen (BB#1) while significantly improving at low temperatures. The resulting grade, PG64-34, is an ultra-premium grade that meets the climatic requirements for most North American grades. Furthermore, Blends #6 and #7 also incorporate significant amounts of both Gilsonite and oligomerized biorenewable oil while occupying a highly desirable portion of the relevant typical performance temperature range (64 to -34°C). Example 4. Binder Composition Comprising Oligomerized Biorenewable Oil, Gilsonite, and Propane Precipitated Bitumen (PPB)

[0095] A binder composition was formed containing "MO#1", Gilsonite, and propane-precipitated bitumen obtained from the bottom of a solvent deasphalting process. The components were blended into the bitumen at 155°C for 1 hour using a benchtop low-shear drill mixer at 200 RPM. Performance rating testing was performed in accordance with AASHTO M320. Tables 4 and 5 show the blends and the resulting performance ratings.

[0096] For Binder Blend #11, Gilsonite was introduced through the use of a binder composition previously identified as "Binder Blend #1," which is Gilsonite dissolved in MO#1 oligomerized biorenewable oil. The resulting incorporation process significantly simplifies the process, eliminating the need to incorporate powdered Gilsonite and instead reducing the complexity of a multi-additive blending process to a simple blend of two binders, which is very typical of industry paving-grade bitumen blending processes. Results show statistically similar rheological properties (penetration and softening point) between Blend #10 and Blend #11, confirming the equivalence of the resulting products. [Table 4] [Table 5] Example 5. Binder Composition Comprising Oligomerized Biorenewable Oil, Gilsonite, and Polyphosphate-Modified Bitumen

[0097] A binder composition was formed containing "MO#1", Gilsonite, asphalt binder BB#1, and polyphosphoric acid (PPA).

[0098] For Binder Blend #12, bitumen was first blended with PPA, followed by the addition of oligomerized bio-renewable oil and Gilsonite. The components were blended for 2 hours at 180°C using a benchtop low-shear drill mixer at 500 RPM. However, the resulting blend was a surprisingly non-sticky granular binder. It is hypothesized that the interaction between PPA and Gilsonite resulted in rapid gelation of Gilsonite, preventing effective compatibilization with the oligomerized bio-renewable oil. It should be noted that while the material exhibited interesting properties and could be a potential industrial application, it was deemed unsuitable for asphalt pavement applications.

[0099] To address this issue, for Binder Blend #13, Gilsonite was introduced through the use of a binder composition previously identified as "Binder Blend #1," which is Gilsonite dissolved in MO#1 oligomerized biorenewable oil. Because the incorporation of this blend is easier than using Gilsonite directly, the blending temperature and conditions were lowered compared to Blend #12 by blending at 155°C for 1 hour using a benchtop low-shear drill mixer at 200 RPM. The resulting mixture appeared smooth and completely homogenized, demonstrating a significant increase in softening point, highlighting the utility of the aforementioned aspect of the invention, in which complete digestion of Gilsonite into oligomerized biorenewable oil provides a compatible and thermally stable means of incorporating large amounts of Gilsonite into the binder composition. These results demonstrate the synergistic effect of using a PPA in combination with an asphaltene additive such as Gilsonite, which increases the binder's modulus. [Table 6]

[0100] The terms and expressions employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions to exclude any equivalents of the features or portions thereof shown and described, but it is recognized that various modifications are possible within the scope of the aspects of the present invention. Thus, while the present invention has been specifically disclosed by certain embodiments and optional features, it will be understood that modifications and variations of the concepts disclosed herein may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of the aspects of the present invention. Exemplary Embodiments

[0101] The following exemplary aspects are provided, the numbering of which should not be construed as designating a level of importance.

[0102] Aspect 1 is an oligomerized bio-renewable oil that is at least 10% by weight of the binder composition; and an asphaltene additive comprising at least 20 wt% to 100 wt% asphaltenes, wherein the asphaltene additive is at least 8 wt% of the binder composition.

[0103] Aspect 2 provides the binder composition of aspect 1, wherein the binder composition comprises bitumen added to bitumen contained in an asphaltene additive, wherein the low molecular weight and low polarity naphthenic or aromatic molecules and saturates fraction is from about 0 wt % to about 40 wt % of the asphaltene additive, and the asphaltenes are from about 1 wt % to about 70 wt % of the binder composition, or a combination thereof.

[0104] Aspect 3 provides the binder composition of any one of Aspects 1-2, wherein the asphaltenes are 30% to 90% by weight of the asphaltene additive, or wherein the asphaltenes are 50% to 80% by weight of the asphaltene additive.

[0105] Aspect 4 provides the binder composition of any one of Aspects 1-3, wherein the asphaltene additive is at least 10 wt. % of the binder composition.

[0106] Aspect 5 provides the binder composition of any one of Aspects 1 to 4, wherein the asphaltene additive is 8% to 60% by weight of the binder composition.

[0107] Aspect 6 provides the binder composition of any one of Aspects 1 to 5, wherein the asphaltene additive is 10% to 45% by weight of the binder composition.

[0108] Example 7 provides the binder composition of any one of Examples 1-6, wherein the asphaltene additive is gilsonite, unitarite, residual oil supercritical extract, or a combination thereof.

[0109] Example 8 provides the binder composition of any one of Examples 1 to 7, wherein the asphaltene additive is gilsonite.

[0110] Example 9 provides the binder composition of any one of Examples 1-8, wherein the binder composition comprises a bitumen in addition to any bitumen included in the asphaltene additive, and the additional bitumen comprises virgin bitumen.

[0111] Example 10 provides the binder composition of any one of Examples 1-9, wherein the binder composition comprises a bitumen additional to any bitumen included in the asphaltene additive, and the additional bitumen comprises recycled bitumen.

[0112] Example 11 provides the binder composition of any one of Examples 1 to 10, wherein the binder composition comprises bitumen in addition to any bitumen included in the asphaltene additive, and the additional bitumen is between 10% and 90% by weight of the binder composition.

[0113] Example 12 provides the binder composition of any one of Examples 1 to 11, wherein the binder composition includes bitumen in addition to any bitumen included in the asphaltene additive, and the additional bitumen is between 15% and 90% by weight of the binder composition.

[0114] Example 13 provides the binder composition of any one of Examples 1-12, wherein the oligomerized biorenewable oil is not blended with any non-oligomerized oil after oligomerization.

[0115] Example 14 provides the binder composition of any one of Examples 1 to 13, wherein the oligomeric molecules are between 5% and 100% by weight of the oligomerized biorenewable oil.

[0116] Example 15 provides the binder composition of any one of Examples 1 to 14, wherein the oligomeric molecules are 65% to 75% by weight of the oligomerized biorenewable oil.

[0117] Example 16 provides the binder composition of any one of Examples 1-15, wherein the oligomerized bio-renewable oil is blended with non-oligomerized bio-renewable oil after oligomerization.

[0118] Example 17 provides the binder composition of any one of Examples 1-16, wherein the oligomerized bio-renewable oil comprises bio-renewable oil oligomerized via sulfidation, thickening, blowing, or a combination thereof.

[0119] Example 18 provides the binder composition of any one of Examples 1 to 17, wherein the oligomerized biorenewable oil comprises a sulfurized biorenewable oil.

[0120] Example 19 provides the binder composition of any one of Examples 1 to 18, wherein the oligomerized bio-renewable oil comprises a modified sulfurized bio-renewable oil.

[0121] Example 20 provides the binder composition of any one of Examples 1-19, wherein the oligomerized bio-renewable oil comprises an unmodified sulfurized bio-renewable oil.

[0122] Example 21 provides the binder composition of any one of Examples 1 to 20, wherein the oligomerized bio-renewable oil comprises a modified oligomerized bio-renewable oil.

[0123] Example 22 provides the binder composition of any one of Examples 1 to 21, wherein the oligomerized biorenewable oil is between 10% and 80% by weight of the binder composition.

[0124] Example 23 provides the binder composition of any one of Examples 1 to 22, wherein the oligomerized biorenewable oil is 20% to 45% by weight of the binder composition.

[0125] Example 24 provides the binder composition of any one of Examples 1-23, further comprising a bio-renewable oil, a modified bio-renewable oil, an unmodified bio-renewable oil, an oligomerized bio-renewable oil, a petroleum-based oil, a modified petroleum-based oil, an unmodified petroleum-based oil, a non-oligomerized petroleum-based oil, or a combination thereof.

[0126] Example 25 provides the binder composition of any one of Examples 1 to 24, further comprising an elastomer, a thermoplastic elastomer, a thermoplastic polymer, a thermoset polymer, a warm mix additive, a fiber, an emulsifier, an adhesion promoter, an anti-peeling additive, polyphosphate, a filler, a rheology modifier, cutback, an oil, a resin, a wax, a surfactant, waste plastic, a pigment, or a combination thereof.

[0127] Example 26 provides the binder composition of any one of Examples 1 to 25, wherein the binder composition does not include aggregate.

[0128] Example 27 provides the binder composition of any one of Examples 1 to 26, wherein the binder composition comprises a polymer modifier, wherein the binder composition has been modified using the polymer modifier or a combination thereof.

[0129] Example 28 provides the binder composition of example 27, wherein the polymer modifier is 0.01% to 30% by weight of the binder composition.

[0130] Example 29 provides the binder composition of any one of Examples 27-28, wherein the polymer modifier is 0.5% to 10% by weight of the binder composition.

[0131] Example 30 provides the binder composition of any one of Examples 27-29, wherein the polymer modifier is polystyrene, poly(divinylbenzene), poly(indene), a styrene-butadiene-styrene polymer, a polyolefin, a copolymer thereof, or a combination thereof.

[0132] Example 31 provides the binder composition of any one of Examples 27-30, wherein the polymer modifier is a styrene-butadiene-styrene polymer.

[0133] Example 32 provides the binder composition of any one of Examples 1 to 31, wherein the binder composition comprises an acid modifier, wherein the binder composition has been modified using the acid modifier or a combination thereof.

[0134] Example 33 provides the binder composition of any one of Examples 32, wherein the acid modifier is 0.3% to 8% by weight of the binder composition.

[0135] Example 34 provides the binder composition of any one of Examples 32-33, wherein the acid modifier is 1% to 3% by weight of the binder composition.

[0136] Example 35 provides the binder composition of any one of Examples 32 to 34, wherein the acid modifier is polyphosphoric acid.

[0137] Example 36 provides the binder composition of any one of Examples 1 to 35, further comprising a bio-based filler.

[0138] Example 37 provides the binder composition of example 36, wherein the bio-based filler comprises lignin, a lignin-based product, rosin, a rosin-based product, a bio-based fiber, biomass, a pyrolysis product, biochar from pyrolysis of biomass, tall oil pitch, cellulosic material from agricultural by-products, or a combination thereof.

[0139] Example 38 provides the binder composition of any one of Examples 1 to 37, wherein the binder composition has a high use temperature performance rating of 34 to 122°C as determined in accordance with AASHTO M320-10.

[0140] Example 39 provides the binder composition of any one of Examples 1 to 38, wherein the binder composition has a high use temperature performance rating of 46 to 82°C as determined in accordance with AASHTO M320-10.

[0141] Example 40 provides the binder composition of any one of Examples 1 to 39, wherein the binder composition has a high use temperature performance rating of 52-70° C. as determined according to AASHTO M320-10.

[0142] Example 41 provides the binder composition of any one of Examples 1 to 40, wherein the binder composition has a low temperature use temperature performance rating of −46 to 22° C. as determined in accordance with AASHTO M320-10.

[0143] Example 42 provides the binder composition of any one of Examples 1 to 41, wherein the binder composition has a low temperature use temperature performance rating of −40 to −10° C. as determined according to AASHTO M320-10.

[0144] Example 43 provides the binder composition of any one of Examples 1 to 42, wherein the binder composition has an effective temperature interval of 86 to 110° C. as determined according to AASHTO M320.

[0145] Example 44 provides the binder composition of any one of Examples 1 to 43, wherein the binder composition has an effective temperature interval of 92 to 104° C. as determined according to AASHTO M320.

[0146] Example 45 provides the binder composition of any one of Examples 1 to 44, wherein the binder composition has an O-DSR of 34 to 122° C. as determined according to ASTM D7175 and AASHTO M320.

[0147] Example 46 provides the binder composition of any one of Examples 1 to 45, wherein the binder composition has an O-DSR of 52 to 70° C. as determined according to ASTM D7175 and AASHTO M320.

[0148] Example 47 provides the binder composition of any one of Examples 1 to 46, wherein the binder composition has an R-DSR of 34 to 122°C as determined according to ASTM D7175 and AASHTO M320.

[0149] Example 48 provides the binder composition of any one of Examples 1 to 47, wherein the binder composition has an R-DSR of 52 to 70° C. as determined according to ASTM D7175 and AASHTO M320.

[0150] Example 49 provides the binder composition of any one of Examples 1 to 48, wherein the binder composition has an S-BBR of −46 to 22° C. as determined by ASTM D6648 and AASHTO M320.

[0151] Example 50 provides the binder composition of any one of Examples 1 to 49, wherein the binder composition has an S-BBR of −40 to −10° C. as determined by ASTM D6648 and AASHTO M320.

[0152] Example 51 provides the binder composition of any one of Examples 1 to 50, wherein the binder composition has an m-BBR of −46 to 22° C. as determined by ASTM D6648 and AASHTO M320.

[0153] Example 52 provides the binder composition of any one of Examples 1 to 51, wherein the binder composition has an m-BBR of −40 to −10° C. as determined according to ASTM D6648 and AASHTO M320.

[0154] Example 53 provides the binder composition of any one of Examples 1 to 52, wherein the binder composition has an undegraded penetration of 15 to 220 dmm as determined according to ASTM D5.

[0155] Example 54 provides the binder composition of any one of Examples 1 to 53, wherein the binder composition has an undegraded penetration of 30 to 100 dmm as determined according to ASTM D5.

[0156] Example 55 provides the binder composition of any one of Examples 1 to 54, wherein the binder composition has an RTFO penetration of 15 to 220 dmm as determined according to ASTM D5.

[0157] Example 56 provides the binder composition of any one of Examples 1 to 55, wherein the binder composition has an RTFO penetration of 30 to 100 dmm determined according to ASTM D5.

[0158] Example 57 provides the binder composition of any one of Examples 1 to 56, wherein the binder composition has an unaged softening point of 35 to 190° C. as determined according to ASTM D3461.

[0159] Example 58 provides the binder composition of any one of Examples 1 to 57, wherein the binder composition has an undegraded softening point of 40 to 90° C. as determined by ASTM D3461.

[0160] Example 59 provides the binder composition of any one of Examples 1 to 58, wherein the binder composition has an RTFO softening point of 30 to 190° C. as determined according to ASTM D3461 and ASTM D2872.

[0161] Example 60 provides the binder composition of any one of Examples 1 to 59, wherein the binder composition has an RTFO softening point of 40 to 90° C. as determined according to ASTM D3461 and ASTM D2872.

[0162] Example 61 provides the binder composition of any one of Examples 1 to 60, wherein the binder composition has an RTFO softening point of 45 to 65° C. as determined according to ASTM D3461 and ASTM D2872.

[0163] Example 62 provides the binder composition of any one of Examples 1 to 61, wherein the binder composition is an asphalt binder.

[0164] Example 63 provides the binder composition of any one of Examples 1 to 62, wherein the binder composition is a roofing shingle component.

[0165] Embodiment 64 provides a binder composition, the binder composition comprising: an oligomerized bio-renewable oil that has been oligomerized by sulfurization and that is 20% to 45% by weight of the binder composition, wherein the oligomer molecules are at least 10% by weight (e.g., at least 40% by weight, or at least 60% by weight) of the oligomerized bio-renewable oil; an asphaltene additive that is Gilsonite, wherein the asphaltene additive is 10% to 45% by weight of the binder composition; and bitumen added to the bitumen contained in the asphaltene additive, which is 15% to 90% by weight of the binder composition.

[0166] Aspect 65 is A binder composition according to any one of aspects 1 to 64; and and water.

[0167] Aspect 66 is A binder composition according to any one of aspects 1 to 64; and and an aggregate.

[0168] Example 67 provides the asphalt pavement of Example 66, wherein the asphalt pavement comprises recycled asphalt pavement, the bitumen in the binder composition comprises recycled or aged bitumen, and the aggregate comprises aggregate from a recycled asphalt composition or a combination thereof.

[0169] Aspect 68 is A binder composition according to any one of aspects 1 to 64; and a substrate; and

[0170] Example 69 provides the roof shingle of Example 68, wherein the substrate comprises an organic material, fiberglass, or a combination thereof.

[0171] Example 70 provides the roof shingle of Example 69, wherein the organic material comprises paper, cellulose, wood fiber, or a combination thereof.

[0172] Embodiment 71 provides a method of making a binder composition, the method comprising: forming a binder composition, the binder composition comprising: an oligomerized bio-renewable oil that is at least 10% by weight of the binder composition; an asphaltene additive comprising at least 20 wt% to 100 wt% asphaltenes, wherein the asphaltene additive is at least 8 wt% of the binder composition.

[0173] Example 72 provides the method of claim 71, comprising combining a bio-renewable oil with an asphaltene additive to form a mixture, and combining the mixture with bitumen in addition to any bitumen included in the asphaltene additive to form a binder composition.

[0174] Embodiment 73 provides a method of making an asphalt emulsion, the method comprising: The method includes emulsifying the binder composition of any one of aspects 1 to 64 and an aqueous phase.

[0175] Embodiment 74 provides a method of making an asphalt pavement, the method comprising: The method includes combining the binder composition of any one of aspects 1-64 with aggregate.

[0176] Example 75 provides the method of example 74, wherein the asphalt pavement comprises recycled asphalt pavement, the bitumen in the binder composition comprises recycled or aged bitumen, and the aggregate comprises aggregate from a recycled asphalt composition or a combination thereof.

[0177] Example 76 provides the method of any one of Examples 74-75, wherein the asphalt pavement comprises recycled asphalt pavement and the binder composition comprises bitumen added to the bitumen contained in the asphaltene additive, the bitumen comprising recycled bitumen.

[0178] Embodiment 77 is a method of making an asphalt pavement, the method comprising: combining the aggregate with a binder composition, the binder composition comprising: an oligomerized bio-renewable oil that has been oligomerized by sulfurization and that is 20% to 45% by weight of the binder composition, wherein the oligomer molecules are at least 60% by weight (e.g., at least 40% by weight, or at least 60% by weight) of the oligomerized bio-renewable oil; an asphaltene additive that is Gilsonite, wherein the asphaltene additive is 10% to 45% by weight of the binder composition; and bitumen added to the bitumen contained in the asphaltene additive, which is 15% to 90% by weight of the binder composition.

[0179] Embodiment 78 provides a method of making a roof shingle, the method comprising: The method includes combining the binder composition of any one of embodiments 1-64 with a substrate.

[0180] Embodiment 79 provides a preblend for forming the binder composition of any one of embodiments 1-64, the preblend comprising: an oligomerized bio-renewable oil; an asphaltene additive comprising at least 20 wt.% to 100 wt.% asphaltenes; The preblend is substantially free of bitumen other than any bitumen contained in the asphaltene additive.

[0181] Example 80 provides a binder composition, preblend, asphalt emulsion, asphalt pavement, roof shingle, or method of making thereof, according to any one or any combination of Examples 1-79, optionally configured such that all listed elements or options are available for use or selection.

Claims

1. 1. A binder composition comprising: an oligomerized bio-renewable oil that is at least 10% by weight of the binder composition; an asphaltene additive that is gilsonite, wherein the asphaltene additive is at least 8 wt% of the binder composition.

2. 10. The binder composition of claim 1, wherein the low molecular weight and low polarity naphthenic or aromatic molecules and saturates fraction is less than about 30 weight percent of the asphaltene additive.

3. 2. The binder composition of claim 1, wherein the binder composition comprises a bitumen added to the bitumen contained in the asphaltene additive, the added bitumen comprising virgin bitumen and / or recycled bitumen.

4. 10. The binder composition of claim 1, wherein the asphaltene additive is 8% to 60% by weight of the binder composition.

5. 10. The binder composition of claim 1, wherein the oligomerized bio-renewable oil is not blended with any non-oligomerized oil after oligomerization.

6. 10. The binder composition of claim 1, wherein the oligomerized bio-renewable oil is 10% to 80% by weight of the binder composition.

7. The binder composition of claim 1 , wherein the binder composition comprises a polymeric modifier, and the binder composition has been modified using the polymeric modifier or a combination thereof.

8. The binder composition of claim 1 , wherein the binder composition comprises an acid modifier, the binder composition being modified using the acid modifier or a combination thereof.

9. 10. The binder composition of claim 1, wherein the binder composition has a high use temperature performance rating of 34 to 122°C as determined in accordance with AASHTO M320-10, a low use temperature performance rating of -46 to 22°C as determined in accordance with AASHTO M320-10, or a combination thereof.

10. 10. The binder composition of claim 1, wherein the binder composition has a performance rating of PG 52-34, PG 58-28, PG 58-34, PG 64-22, PG 64-28, PG 70-16, PG 70-22, or PG 76-22 as determined in accordance with AASHTO M320-10.

11. 1. A binder composition comprising: an oligomerized bio-renewable oil that has been oligomerized by sulfurization and that is 20% to 45% by weight of the binder composition, wherein oligomeric molecules are at least 10% by weight of the oligomerized bio-renewable oil; an asphaltene additive that is Gilsonite, said asphaltene additive being 10% to 45% by weight of said binder composition; and bitumen added to the bitumen contained in the asphaltene additive, the bitumen being 15% to 90% by weight of the binder composition.

12. The binder composition of claim 1; An asphalt emulsion comprising: water;

13. The binder composition of claim 1; and an asphalt pavement comprising: an aggregate;

14. The binder composition of claim 1; a substrate; and a roof shingle.

15. 1. A method for making a binder composition, comprising: A method comprising forming the binder composition of claim 1.

16. 10. A preblend for forming the binder composition of claim 1, said preblend comprising: The oligomerized bio-renewable oil; an asphaltene additive that is Gilsonite; A preblend, wherein the preblend is substantially free of bitumen other than the bitumen contained in the asphaltene additive.

17. 1. A method for making an asphalt emulsion, comprising: A method comprising emulsifying the binder composition of claim 1 and an aqueous phase.

18. 1. A method for making an asphalt pavement, comprising: A method comprising combining the binder composition of claim 1 with aggregate.

19. 1. A method for making an asphalt pavement, comprising: combining aggregate with a binder composition, the binder composition comprising: an oligomerized bio-renewable oil that has been oligomerized by sulfurization and that is 20% to 45% by weight of the binder composition, wherein oligomeric molecules are at least 10% by weight of the oligomerized bio-renewable oil; an asphaltene additive that is Gilsonite, said asphaltene additive being 10% to 45% by weight of said binder composition; and bitumen, which is 15% to 90% by weight of said binder composition.

20. 1. A method for making a roof shingle, comprising: A method comprising combining the binder composition of claim 1 with a substrate.

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