PRODUCING THEM

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial Nos. 62/044,028, filed August 29, 2014, and 62/046,105, filed September 4, 2014, which are hereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

[0002] The present invention relates to improved asphalt products and materials and methods of producing them.

BACKGROUND OF THE INVENTION

[0003] Asphalt or flexible pavement is typically built with several layers to form a layered system with better materials at the top where the stress intensity is high and inferior materials at the bottom where the stress intensity is low. The top layer, called the surface course, is typically made of an asphalt mixture. All types of failure or distress can be classified by whether they are structural or functional failures and load associated or non-load associated distresses. Surface course aging is considered a non-load associated distress caused by climate/environmental effects. Many environmental factors can cause surface course aging damage, such as ozone, UV rays, oxygen, and thermal radiation. Oxidative aging causes the asphalt binder to become harder and more brittle. Aging can be characterized as two parts, short-term aging and long-term aging.

[0004] Most of the short-term aging that occurs in asphalt begins with the blending of the aggregate with asphalt binders. The blending temperature in the asphalt plant primarily controls the oxidative aging rate of the asphalt. The short-term aging for the asphalt binder in the mixture continues until the end of the pavement construction. Methods such as warm mix asphalt and cold mix asphalt are the main solutions to reduce the short-term aging via heating and constructing the asphalt mixture at lower temperatures compared with hot mix asphalt.

[0005] During the service life, the long-term oxidative aging begins and occurs at a much slower rate than the rate of aging during mixing and construction. The brittleness of the asphalt mixture gradually increases due to physico-chemical changes in the binder. Exudation, evaporation, oxidation, and physical aging are all related to asphalt binder aging, while oxidation and physical hardening (steric hardening) are the most important direct consequences. Physical aging is a reversible process, which can produce changes in rheological, electrical, and caloric properties, etc., without altering the chemical composition of the material. The oxidation of asphalt binder caused by chemical reactions causes transformations in the asphalt components. Asphalt oxidation is the main cause of long-term deterioration and eventually results in cracking in asphalt pavements. The asphalt can be separated into four generic fractions namely:

asphaltenes, polar aromatics, naphthene aromatics, and saturates. Each fraction provides different properties. Asphaltenes mainly contribute to the viscosity (hardening effect), and the aromatics and saturates are correlated to the ductility (elastic effect). Many researchers have compared the fractions of aged asphalt with fractions of unaged asphalt. It was found that the oxidation of asphalt had an effect on chemical properties and, consequently, on the rheological properties. While asphalt is aging, the viscosity increases due to the oxidative conversion of polar aromatics to asphaltenes. This transformation between the components during oxidation can be described as follows: Aromatics Resins Asphaltenes. The polymerization or condensation of the asphaltenes create larger molecules with long chained structures which harden the asphalt. The oxidation causes a great increase in the asphaltenes, including those with high molecular weight. This asphalt hardening theory can be used to explain a condition known as the air-blown asphalt phenomena. An antioxidant is added to stop or delay the oxidative processes that convert aromatic fractions.

[0006] Historically, growth of bio-based chemical products in the world market has typically been limited due to their higher production costs compared to crude petroleum derived products. However due to the variability of crude petroleum pricing, increasing demand for environmentally friendly products from a growing population and limited amount of nonrenewable resources, growth for bio-based chemical products has increased. This market growth has propelled the number and size of bio-refineries to increase in the past ten years. Depending on the production process, bio-refineries can produce a sizable amount of material with surfactant characteristics. These materials are candidates for use as bio-based warm mix asphalt (WMA) additive technologies.

[0007] U.S. Patent No. 8,007,657 to Mentink et al, for example, describes the use of esters of glycolic, lactic and glucaric acids, methylic, ethylic and isobutylic esters of glutaric, succinic and adipic acids, and ethers or esters of a product of an internal dehydration of a sugar or an hydrogenated sugar. Dimethyl isosorbide is identified as a particularly preferred example of an ether prepared from an internal dehydration product (isosorbide) from a sugar alcohol (sorbitol), being already found in commercial use in personal care products (e.g., lotions), and is said to be useful as a fluxing agent especially in combinations with the methyl esters of vegetable oils or in compositions for cleaning bituminous materials in combination with terpenic compounds. SUMMARY OF THE INVENTION

[0008] One aspect of the present invention relates to a method of producing an improved asphalt. The method includes providing an asphalt and providing a reaction product of a sorbitol to isosorbide conversion process. The asphalt is mixed with the reaction product of a sorbitol to isosorbide conversion process under conditions effective to produce an improved asphalt.

[0009] Another aspect of the invention relates to an asphalt product. The asphalt product includes an asphalt and a non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process, mixed with the asphalt.

[0010] A further aspect of the present invention relates to a method of making an asphalt material. The method includes providing an improved asphalt product comprising an asphalt and a non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process, mixed with the asphalt. The method further includes mixing the improved asphalt product with a mineral aggregate at a temperature of 150 °C or lower, to coat the mineral aggregate and produce a heated paving material which, at a warm mix temperature, has a compaction production temperature at least 15-50 °C lower than that of the improved asphalt material absent the reaction product of a sorbitol to isosorbide conversion process. The heated paving material is applied to a surface to be paved to form an applied paving material. The applied paving material is compacted to a void fraction of less than 8%, at a compacting temperature of 140 °C or lower to form a paved surface.

[0011] Isosorbide compounds have shown potential as warm mix asphalt (WMA) additives in preliminary laboratory testing. WMA additives reduce the mixing and compaction temperature of Hot Mix Asphalt (HMA) by approximately 30° F to 100° F. The benefits of WMA additives include reduced emissions, savings in fuel costs associated with reduced plant temperatures, construction benefits such as longer haul distances, cooler weather paving, and reduced compaction effort.

[0012] For laboratory testing, an unmodified Montana crude source supplied by Jebro, with a performance grade ("PG") of 58-28 was used as a first binder along with a polymer modified form of this binder as a second binder— the PG 58-28 binder polymer modified with 1.5% styrene-butadiene-styrene (SBS) to achieve a PG 64-28 binder. The WMA additive was an isosorbide product mixture. The dosage levels chosen were 0.5%, and 0.75% for addition of each of isosorbide mixtures. Binder testing included specific gravity, dynamic shear rheometer (DSR) testing on original and aged binders as well as bending beam rheometer tests. Aging included both rolling thin film oven (RTFO) and pressure aging vessel (PAV) aging which simulate short and long term aging of the asphalt, respectively. Mass loss of the binder was measured after RTFO testing. All binder testing followed American Association of State Highway and Transportation Officials (AASHTO) protocols. Asphalt mix testing included moisture sensitivity testing and rutting at high temperature using the Hamburg Wheel Tracking test, and low temperature testing was done by using the Semi-circular Bend test to determine the resistance to cracking/fatigue.

[0013] WMA is asphalt concrete that is mixed and compacted at substantially lower temperatures that those used to produce hot mix asphalt (HMA). WMA technologies are known best for their ability to reduce asphalt binder viscosity, and decrease mixing and compaction temperatures for asphalt mixtures. With WMA use mixing and compaction temperatures can be decreased by as much as 20°C to 55°C. A temperature decrease makes it possible to save on cost because fuel usage is lowered. An additional benefit is that emissions of greenhouse gases (GHG) are reduced as well, thus improving air quality and lowering the exposure of workers to fumes. Lower compaction temperatures and improved mix compactibility are achieved, because of reduced asphalt binder viscosity. With lower compaction temperatures, contractors can extend their paving season in colder climates. Increased use of reclaimed asphalt pavement in WMA mixtures is also possible because the asphalt binder viscosity is reduced. Button et al., "A Synthesis of Warm Mix Asphalt," Rep No FHWA/TX-07/0-5597-1, College Station, TX. : Texas Transportation Institute (2007); D'Angelo et al, "Warm-Mix Asphalt: European Practice," Publication FHWA-PL-08-007: FHWA, U.S. Dept. of Transportation, Washington, D.C. (2008); Gandhi T., "Effects of Warm Asphalt Additives on Asphalt Binder and Mixture Properties: Ph.D. dissertation," Clemson Univ., Clemson, South Carolina (2008); Hassan M., "Life-Cycle Assessment of Warm-Mix Asphalt: An Environmental and Economic Perspective,"

Transportation Research Board 88th Annual Meeting, Washington, D.C. (2009); Hurley et al, "Evaluation of Evotherm for Use in Warm Mix Asphalt," Rep No 06-02. Auburn, Alabama: National Center for Asphalt Technology (2006); Jenkins et al., "Half-Warm Foamed Bitumen Treatment, a New Process," 7th Conference on Asphalt Pavements for Southern Africa (CAPSA 99) (1999); Kristjansdottir 0., "Warm-Mix Asphalt for Cold Weather Paving," Seattle,

Washington: Univ. of Washington (2006); Kristjansdottir et al, "Assessing Potential for Warm- Mix Asphalt Technology Adoption," Transp Res Rec. 2040:91-9 (2007); Larsen et al, "WAM Foam Asphalt Production at Lower Operating Temperatures as an Environmental Friendly Alternative to HMA," 3rd Eurasphalt & Eurobitume Congress: Foundation Eurasphalt,

Breukelen, Netherlands (2004); Perkins S.W., "Synthesis of Warm Mix Asphalt Paving

Strategies for use in Montana Highway Construction," Rep No FHWA/MT-09-009/8117-38. Helena, Montana: Western Transportation Institute (2009); Prowell et al, "Field Performance of Warm-Mix Asphalt at the NCAT Test Track," Transportation Research Board 86th Annual Meeting: Washington, D.C. (2007); and Kim et al., "Influence of Warm Mix Additives on PMA Mixture Properties," Journal of Transportation Engineering 138(8): 991-7 (2012), all of which are hereby incorporated by reference in their entirety.

[0014] There are four categorized groups of WMA technologies: (1) foaming - water based; (2) foaming - water bearing additive; (3) chemical additive; and (4) organic/bio-derived additives. Isosorbide Distillation Bottoms (IDB) has now been derived as a warm mix asphalt additive co-produced from the conversion of sorbitol to isosorbide where sorbitol is derived by hydrogenating glucose from corn biomass. IDB is produced from the conversion of sorbitol to isosorbide by using sorbitan to perform a dehydration reaction. Sorbitol is produced by hydrogenating glucose from corn biomass Werpy et al., "Top Value Added Chemicals From Biomass: I. Results of Screening for Potential Candidates from Sugars and Synthesis Gas,"

(2004), which is hereby incorporated by reference in its entirety. IDB has surfactant properties Werpy et al, "Top Value Added Chemicals From Biomass: I. Results of Screening for Potential Candidates from Sugars and Synthesis Gas," (2004), which is hereby incorporated by reference in its entirety. Past research with IDB has showed that there was improvement in low temperature binder performance using the bending beam rheometer (BBR). Podolsky J.,

"Investigation of Bio-Derived Material and Chemical Technologies as Sustainable Warm Mix Asphalt Additives," Iowa State University, Ames, Iowa (2014) and Podolsky et al.,

"Comparative Performance of Bio-Derived/Chemical Additives in Warm Mix Asphalt at Low Temperature," Mater Struct. 1-13 (2014), both of which are hereby incorporated by reference in their entirety. Due to this observation it is hypothesized that softening could be occurring at high temperatures decreasing the resistance to rutting and stripping for the warm mix asphalt (WMA) mixtures modified with bio-derived/chemical additives as compared to a hot mix control.

[0015] These additives help to decrease emissions produced during HMA production.

This allows the asphalt industry the opportunity to reduce their carbon footprint, save money associated with increased plant temperatures and lessen fumes workers are exposed to during production and construction. D'Angelo et al., "Warm-Mix Asphalt: European Practice," Publication FHWA-PL-08-007: FHWA, U.S. Dept. of Transportation, Washington, D.C. (2008), which is hereby incorporated by reference in its entirety. Reducing asphalt plant temperatures helps protect plant equipment from wear and tear. These combined benefits help to make asphalt a more sustainable product for the environment, the contractor, and the general public.

[0016] As the cost of crude petroleum and asphalt prices continue to trend upward, saving money by using WMA additives becomes increasingly important for maintaining a competitive edge in the market. As base material costs increase, WMA can help contractors save money because of the reduced fuel costs and higher percentages of recycled asphalt pavement that can be incorporated in WMA mixes. In addition to savings, WMA has been shown to produce a quality asphalt product. In many field produced mixes, there has been no performance difference between the WMA and control pavement sections. Laboratory tests have shown concern regarding moisture susceptibility in WMA. This is likely due to incomplete drying of aggregates. Hurley et al, "Evaluation of Evotherm for Use in Warm Mix Asphalt," Rep No 06- 02. Auburn, AL.: National Center for Asphalt Technology (2006), which is hereby incorporated by reference in its entirety. Overall, WMA has shown promise and is quickly being

implemented by owner-agencies around the country.

[0017] In particular contrast to the teachings of U.S. Patent No. 8,007,657 to Mentink et al., no further esterification or etherification is found to be necessary of the reaction product in order for the same to be useful as a warm mix additive. This distinction between the materials of Mentink et al. and the present inventive materials will be understood as captured within the description of the inventive materials as "non-esterified and non-etherified", though it will equally be appreciated that this terminology should not be taken as excluding the presence of a very small amount of esters and/or ethers of sorbitans (i.e., less than 0.1 wt%, preferably less than 0.05 wt%, more preferably less than 0.01 wt% esters and ethers of sorbitans in total), such as may be incidentally formed and then not removed in the dehydration of sorbitol to produce isosorbide.

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] FIG. 1 is a schematic diagram of a process for manufacturing isosorbide from sorbitol in accordance with U.S. Patent No. 7,439,352 to Moore et al, which is hereby incorporated by reference in its entirety.

[0019] FIG. 2 is a schematic diagram of the process of FIG. 1, modified to include the chromatographic separation of inorganic salts and other ionic materials from a crude dehydration product mixture prior to a refining of the crude dehydration product mixture to provide an isosorbide product.

[0020] FIG. 3 illustrates a proposed dehydration and degradation reaction pathway for the sulfuric acid-catalyzed dehydration of sorbitol. This figure is based on information obtained by liquid chromatography/mass spectroscopy, gas chromatography/mass spectroscopy, and ion chromatography of a crude dehydration product.

DETAILED DESCRIPTION OF THE INVENTION [0021] One aspect of the present invention relates to a method of producing an improved asphalt. The method includes providing an asphalt and providing a non-esterified and non- etherified reaction product of a sorbitol to isosorbide conversion process. The asphalt is mixed with the non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process under conditions effective to produce an improved asphalt.

[0022] Asphalt includes material in which the predominating constituents are bitumens, which occur in nature or are obtained in petroleum processing. Bitumens include solid, semisolid, or viscous substances, natural or manufactured, composed principally of high molecular weight hydrocarbons. The asphalt used in the present invention is not particularly limited, and various kinds of asphalts may be used in the present invention. Examples of the asphalt includes straight asphalts such as petroleum asphalts for pavements, as well as polymer- modified asphalts produced by modifying asphalt with a polymer material including a thermoplastic elastomer such as styrene/butadiene block copolymers (SBS), styrene/isoprene block copolymers (SIS), and ethylene/vinyl acetate copolymers (EVA).

[0023] Suitable grades of asphalt include, but are not limited to, the following: PG52-22,

PG58-22, PG64-22, PG67-22, PG70-22, PG76-22, PG82-22, PG52-28, PG58-28, PG64-28, PG67-28, PG70-28, PG76-28, PG52-34, PG58-34, PG64-34, PG64-16, PG67-16, PG70-16, PG76-16, PG64-10, PG67-10, PG70-10, PG76-10, pen grade 40-50, pen grade 60-70, pen grade 85-100, pen grade 120-150, AR4000, AR8000, AC10 grade, AC20 grade, and AC30 grade. Roberts et al, "Hot Mix Asphalt Materials, Mixture Design, and Construction," NAPA Research and Education Foundation (2nd ed.) (1996), which is hereby incorporated by reference in its entirety.

[0024] Non-esterified and non-etherified reaction products of a sorbitol to isosorbide conversion process (i.e., isosorbide distillation bottoms and other isosorbide mixtures) are WMA additives that improve low temperature binder performance of asphalt. For asphalt pavements, both short and long term aging can cause deterioration and eventually result in cracking, rutting, and stripping. The present invention relates to WMAs including non-esterified and non- etherified reaction products for utilization as an additive in asphalt. Using these reaction products in asphalt production represents an economical alternative to conventional asphalt production methods. This is achieved while being conscious of the environment, improving worker safety, lowering compaction temperatures, improving mix compactibility, reducing asphalt binder viscosity, and increasing the longevity and performance of asphalt pavements. As a pavement ages, it becomes stiffer and more susceptible to failure. The use of WMAs as an asphalt additive is an attractive way to increase the longevity and enhance the performance of asphalt pavements. [0025] A variety of processes have been described in the literature for converting sorbitol to isosorbide, conventionally involving the removal of two water molecules from sorbitol in the presence of an acid catalyst. A variety of acid catalysts have been proposed, but since isosorbide has been used for pharmaceutical applications and proposed for use in a variety of polymers, the main of inventive activity has centered around the manufacture of very pure isosorbide. As will be evident from the discussion and examples following, however, useful non-esterified and non- etherified reaction products for purposes of asphalt modification include components of a crude dehydration product that would ordinarily be unsuitable for the usual applications for which isosorbide has been prepared and can, in one embodiment, comprise the crude dehydration product mixture as a whole. Examples of known processes for converting sorbitol to isosorbide include U.S. Patent No. 7,439,352 to Moore et al, WO/2014/070371 to Hagberg et al,

WO/2014/070369 to Stensrud et al., and WO/2014/070370 to Stensrud et al, all of which are hereby incorporated by reference in their entirety.

[0026] As described herein, the non-esterified and non-etherified reaction product may more particularly be comprised of one or more sorbitans (i.e., sorbitol minus one water molecule), isosorbide (sorbitol minus two water molecules), or the dimers, trimers, and/or oligomers of sorbitans and isosorbide. In one embodiment, asphalt is combined with a composition predominantly comprised on a weight percentage basis of isosorbide. In another embodiment, asphalt is combined with a composition predominantly comprised of one or more sorbitan isomers. In another embodiment, asphalt is combined with a composition predominantly comprised of isosorbide and one or more sorbitan isomers. In another embodiment, asphalt is combined with a composition predominantly comprised of isosorbide and one or more sorbitan isomers. In another embodiment, the asphalt is combined with a mixture comprising any unconverted sorbitol, isosorbide, and one or more sorbitan isomers. Alternatively, in yet another embodiment, asphalt is combined with a mixture comprising unconverted sorbitol, isosorbide, one or more sorbitan isomers, and one or more condensation products of sorbitol, isosorbide, and sorbitans. In still another embodiment, asphalt is combined with a crude sorbitol dehydration product mixture without any prior step to remove any fraction thereof. In another embodiment, asphalt is combined with a crude sorbitol dehydration product mixture without any prior step to remove any fraction thereof and without any neutralization of the crude dehydration product mixture. Preferably, in another embodiment, the reaction product is at least 40% isosorbide and optionally includes unconverted sorbitol, unreacted sorbitol, isosorbide, one or more sorbitan isomers, and one or more condensation products of sorbitol, isosorbide, and sorbitans.

[0027] It is also contemplated that the present invention may find optimal application in the context of an existing, ongoing process for making isosorbide for previously known end uses, for example, for use in the manufacture or various polymers. Accordingly, in still other embodiments, asphalt may be mixed with compositions or streams produced within such an existing, ongoing process, generally and preferably without any derivatization or other modification thereof.

[0028] Whatever the particular source of the reaction product, the inventive materials, when combined with asphalt, produce a shear energy of between 0.1 and 100 kJ/m ² , and more particularly between 0.1 and 10 kJ/m ² . For example, the shear energy of the improved asphalt is 3.48, 2.96, 3.10, 3.19, 3.97, 3.96, 3.77, or 3.80 kJ/m ² . Moreover, the compaction force index may be between 100 and 5,000, and more particularly between 500 and 2,000 at temperatures ranging from 100 °C to 140 °C. For example, the compaction force index is 750, 775, 924.1, 960.5, 990.1, 1150, 1263.1, 1266.1, 1350.3, 1525, 1550, or 1613.3. In one embodiment, the asphalt product has a compaction force index of 1550 at a temperature ranging from 100 °C to 140 °C. In another embodiment, the asphalt product has a compaction force index of 750 at a temperature ranging from 100 °C to 140 °C. In yet another embodiment, the asphalt product has a compaction force index of 1525 at a temperature ranging from 100 °C to 140 °C. In yet another embodiment, the asphalt product has a compaction force index of 775 at a temperature ranging from 100 °C to 140 °C. The number of gyrations to achieve 7% air voids in the isosorbide product mixture with asphalt can range from 25 to 200. For example, the number of gyrations can be 49, 54, 56, 58, 70, 75, 80, or 11 1.

[0029] For example, in the context of one known process for producing isosorbide from sorbitol illustrated schematically in FIG. 1, a process 10 is shown as originally described in U.S. Patent No. 7,439,352 to Moore et al., which is hereby incorporated by reference in its entirety. In process 10, sorbitol 12 is supplied to reactor 14. Sorbitol 12 is first heated to a molten state, then dehydrated in reactor 14 in the presence of a catalyst for facilitating dehydration to isosorbide, producing water effluent 16 and a dehydration product mixture 18 which includes isosorbide. Dehydration product mixture 18 is then subjected to a first distillation step in first distillation apparatus 20 to form first isosorbide distillate 22 and first distillate bottom 24. First isosorbide distillate 22 is then subjected to a second distillation in second distillation apparatus 26 to form purified isosorbide product 28 and second distillate bottom 30.

[0030] In one embodiment of the present invention adapted to a process as illustrated in

FIG. 1, asphalt is mixed with either or both of first distillate bottom 24 and second distillate bottom 30. The isosorbide distillation bottoms additive, when combined with asphalt, can produce a shear energy of between 0.1 and 10 kJ/m ² . For example, the shear energy may be 3.48, 2.96, 3.06, 3.97, 3.96, or 3.66 kJ/m ² . Moreover, the compaction force index may be between 500 and 2000. More specifically, the compaction force index may be 881.3, 924.1, 1150, 1350.3, 1407.1, or 1613.3. The number of gyrations to achieve 7% air voids in the isosorbide distillation bottoms with asphalt can range from 25 to 200. For example, the number of gyrations can be 47, 49, 58, 80, 97, or 1 11.

[0031] In the first step of the process 10 of FIG. 1, the sorbitol is melted by standard methods that are known in the art. For example, the sorbitol can be melted by placing it in a 3- neck round bottom flask equipped with an agitator, temperature probe, and vacuum line.

Preferably, the sorbitol is heated to at least about 100°C to about 200°C. For sorbitol powder, to provide a specific example, a preferred melting temperature is from 98°C to 105°C, while an even more preferred melting temperature is from 98°C to 100°C. Once molten, the sorbitol is subject to stirring. One of skill in the art would be familiar with the specific melting points of other sugar alcohols and monoanhydrosugar alcohols. Generally, they fall between about 60°C. and about 200°C.

[0032] A catalyst that will facilitate the dehydration of the sorbitol is then added to the molten starting material. Typically acid catalysts have been used to facilitate the dehydration of sugar alcohols such as sorbitol, including, for example, soluble acids, acidic ion exchange resins, and inorganic ion exchange materials. Sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and p-methanesulfonic acid are given as examples of soluble acids that may be used, though one of skill in the art would recognize that other soluble acids with similar properties would be useful as well.

[0033] Zeolite powders are examples of inorganic ion exchange materials that could be used; specifically an acidic zeolite powder such as a type ZSM-5 ammonium form zeolite powder may be used.

[0034] In some embodiments, the acid catalyst comprises an acidic ion exchange resin, specifically a sulfonated divinylbenzene/styrene co-polymer acidic ion exchange resin.

[0035] The amount of catalyst used is indicated as generally being on the order of from

0.01 equivalents to 0.15 equivalents by weight. A preferred amount of catalyst is 0.1 equivalents by weight.

[0036] It is possible to perform one or more dehydrations of the starting sugar alcohol during the reaction, producing, for example, a mono- or dianhydrosugar alcohol. The reaction may also be controlled to produce a combination of mono- and dianhydrosugar alcohols by adjusting either the reaction conditions or the starting materials, which as those of skill in the art will appreciate, could contain both sugar alcohols and monoanhydrosugar alcohols.

[0037] The dehydration can be carried out under a vacuum, at elevated temperatures, and with stirring of the reaction mixture. The vacuum can range over a pressure of from 0.05 Torr to 40 Torr, with preferred pressures of from 1 Torr to 10 Torr. As a specific example, a preferred pressure for the dehydration of sorbitol to isosorbide is from 1 Torr to 10 Torr. The temperature for the dehydration can be from 90°C to 140°C. In certain embodiments, the dehydration temperature can be from 98°C to 130°C, especially, from 120°C to 130°C. The dehydration can be carried out over a period of approximately two hours at such temperatures. The water can be pulled off of the melted sorbitol/catalyst mixture under a vacuum of from 1 Torr to 10 Torr. The dehydration reaction is preferably performed in a reactor which can run in a batch or continuous mode. In embodiments, where the acid catalyst is a solid acid catalyst (e.g., acidic ion exchange resin), the reactor can preferably hold or contain baskets to which the solid acid catalyst can be added.

[0038] Following the dehydration procedure, dehydration product mixture 18 is purified.

In one embodiment, a vacuum distillation is used. In a more specific embodiment, the vacuum distillation is performed using a film evaporator, specifically a wiped film evaporator. One example of a wiped film evaporator apparatus that is useful is a vertical agitated thin- film processor. Advantages of using a wiped film evaporator include handling of viscous solutions, improved product purity, and low residence time, which leads to a reduction or elimination of product degradation. Specifically with respect to production of isosorbide from sorbitol, use of a wiped film evaporator was said to provide approximately an 80% yield on distillation, negligible water loss during distillation (which results in reduced polymerization), and further recovery of isosorbide and sorbitan from the residue. The distillation process results in first isosorbide distillate 22.

[0039] The pot temperature and vacuum used for the first distillation apparatus 20 can vary, but vapor temperatures of from 140°C to 190°C are preferred. More preferred vapor temperatures are from 160°C to 170°C, especially from 165°C to 170°C. The vacuum pressure can be from 0.05 Torr to 40 Torr, preferably being from 1 Torr to 10 Torr. For the vacuum distillation of isosorbide, a vacuum pressure of from 1 Torr to 10 Torr, a pot temperature of

180°C, and a vapor temperature of from 160°C to 170°C are preferred. Alternative purification methods of the anhydrosugar alcohol mixture such as filtration of the anhydrosugar alcohol mixture, or the addition of activated charcoal with subsequent crystallization of the anhydrosugar alcohol mixture, are also useful.

[0040] First isosorbide distillate 22 is then preferably subjected to a second vacuum distillation in second distillation apparatus 26, for example, by means of a second wiped film evaporator, providing purified isosorbide product 28 and second distillate bottoms 30. The second wiped film evaporator can be of the same type as, or different than, the first wiped film evaporator. The conditions (e.g., vacuum pressure and temperature) of the second vacuum distillation can be the same as, or different than, the conditions of the first vacuum distillation, the parameters of which are described above. The use of two film evaporators allows for production and purification of isosorbide without the use of potentially harmful organic solvents.

[0041] In an alternate embodiment described in U.S. Patent No. 7,439,352 to Moore et al., which is hereby incorporated by reference in its entirety, first isosorbide distillate 22 is subjected to melt crystallization where first isosorbide distillate 22 is heated until molten (isosorbide's melting point is about 65°C), and then cooled over time until the crystallization point is reached, but not so much that the material solidifies. In fact, a slurry-like consistency is preferred, so that the material can be centrifuged. As used herein, the term "slurry-like consistency" refers to a material that is a mixture of liquid with several finely divided particles. The centrifugation is performed at a relatively high speed for a relatively short period of time in order to avoid solidification of the material, and also to avoid having the desired isosorbide product drawn off with the impurities. For example, the centrifugation can be performed at 3000 to 4000 rpm for 5 minutes, though those skilled in the art will appreciate that the duration of centrifugation will ideally vary depending on the amount of material to be purified. The resultant isosorbide in any case is indicated as being at least 98% pure, and in most cases being greater than 99% pure (depending upon the solidity of the "slurry").

[0042] Alternatively, first isosorbide distillate 22 can be subjected to solvent

recrystallization. See U.S. Patent No. 7,439,352 to Moore et al, which is hereby incorporated by reference in its entirety.

[0043] Further purification of first isosorbide distillate 22 can involve subjecting first distillate 22 to a solvent wash, followed by filtration. See U.S. Patent No. 7,439,352 to Moore et al., which is hereby incorporated by reference in its entirety.

[0044] The process according to any of the aforementioned embodiments described in

U.S. Patent No. 7,439,352 to Moore et al, which is hereby incorporated by reference in its entirety, may be modified to include one or both of ion exchange and ion exclusion to remove ionic species before the further purification of the remainder of a crude dehydration product mixture, for example, by successive distillation steps as shown in FIG. 1. See WO/2014/070371 to Hagberg et al, WO/2014/070369 to Stensrud et al, and WO/2014/070370 to Stensrud et al, all of which are hereby incorporated by reference in their entirety.

[0045] An example of such a modified process 32 is schematically illustrated in FIG. 2, in which crude isosorbide impurity removal system 34 is deployed upstream of first distillation apparatus 20, with the other elements of process 32 being prior to system 34, as previously described in respect of FIG. 1. In the particular embodiment of system 34 depicted in FIG. 2 and described herein, nanofiltration or ultrafiltration, ion exclusion, ion exchange and carbon or resin bed adsorption work together in combination to remove substantially all ionic species from crude dehydration product mixture 18 in FIG. 1, as well as removing other species (or the precursors of such species).

[0046] In quantitative terms, preferably not more than 1000 ppm of total ionic species remain in the crude dehydration product mixture, on an overall weight basis, after crude isosorbide impurity removal system 34. More preferably, no more than 100 ppm remain, and most preferably no more than 50 ppm remain.

[0047] Alternatively, given the numbers of dehydration and degradation products that may be made in the dehydration of sorbitol (as partly demonstrated in FIG. 3), many color- associated, as well as other, impurities can be considered as having been separated when no more than 100 ppm remains of formic acid, more preferably no more than 10 ppm of formic acid remains after the crude isosorbide impurity removal system 34, and most preferably no more than 1 ppm remains.

[0048] As shown in FIG. 2, where both ion exclusion and ion exchange are used, either can be used before the other, with carbon or resin bed adsorption optionally, but preferably, following to remove nonionic oligomeric and polymeric impurities. As further shown in FIG. 2, nanofiltration or ultrafiltration may optionally be used upstream of an ion exclusion step, an ion exchange step or both, primarily to protect the resins from fouling with especially higher molecular weight, oligomeric or polymeric species as may be formed in the crude dehydration product mixture 18, for example, by the proposed reaction pathways shown in FIG. 3.

[0049] Molten sorbitol 12 may, in one embodiment, be dehydrated in reactor 14 using sulfuric acid to produce crude dehydration product mixture 18. Mixture 18 is typically neutralized with a strong base such as sodium hydroxide, then diluted with water to a 65 percent solution. Neutralized crude dehydration product mixture 18 is then supplied to crude isosorbide impurity removal system 34.

[0050] Crude isosorbide impurity removal system 34 includes first, nanofiltration or ultrafiltration step 36 to remove at least those higher molecular weight, oligomeric or polymeric impurities in crude dehydration product mixture 18 (as indicated by retentate 38) that tend to precipitate out and foul subsequent ion exchange and/or ion exclusion resins. For the crude isosorbide product mixtures, membranes having a molecular weight cut-off of about 1,000 to 10,000 were satisfactory.

[0051] Where fouling of subsequent ion exchange and/or ion exclusion resins is a concern, other measures may be considered as well as alternatives to the use of nanofiltration or ultrafiltration membranes. The inclusion of nanofiltration or ultrafiltration 36 is effective in preventing fouling. [0052] Following nanofiltration or ultrafiltration step 36, ion exclusion step 40 may be employed for removing ionic species 42 from filtered crude dehydration product mixture 18 through simulated moving bed chromatography using at least one strong acid cation exchange resin. Preferred resins are chromatographic grade, gel type resins with a volume median diameter between 290-317 μιη, where more than 80% of the particle size range is between 280- 343 μιη and more than 60% of the particle size range is between 294-392 μιη. Such resins are characterized by a crosslink density of less than 12%, more preferably less than 8%, and most preferably less than 6%. The resins are in the cation form corresponding to the highest cation concentration present in crude dehydration product mixture 18.

[0053] Ion exclusion step 40 may be followed by ion exchange step 44 to remove additional ionic impurities 46, through the use of preferably a fixed bed arrangement including at least one highly crosslinked strong acid cation exchange resin in the hydrogen form and one macroporous, highly crosslinked strong base anion exchange resin in the hydroxide form.

[0054] Carbon or resin bed adsorption step 48 may then be used to remove further nonionic oligomeric and polymeric impurities and/or color bodies 50 that may remain.

Preferably, a fixed bed arrangement with one or more activated carbons is used. Remainder 52 of crude dehydration product mixture 18 following crude isosorbide impurity removal system 34 may be filtered to remove any of the resin(s) and carbon(s) from system 34 that are carried over in remainder 52. Remainder 52 may be further processed to ultimately yield a finished isosorbide product 28' which is enriched in the desired isosorbide material compared to crude dehydration product mixture 18 and which can be used for making additional products or sold. In the particular embodiment shown FIG. 2, water is initially removed from filtered remainder 52 in a dewatering step and remainder 52 is degassed of light gases. Thereafter, enrichment in the isosorbide can be conventionally achieved by known refining methods, for example, through successive distillations in first and second distillation devices 20 and 26, respectively, with first and second distillation devices 20 and 26 preferably making use of thin or wiped film

evaporation to minimize further heat history on desired isosorbide product 28'.

[0055] The removal of impurities via system 34 in advance of distilling a crude isosorbide product has been found to provide significantly higher yields (through the prevention of yield losses to, for example, various degradation products formed in the manner suggested by FIG. 3 or otherwise) with lower intrinsic color and improved color stability as compared to where system 34 is not used, and a crude isosorbide product containing the impurities is distilled. The removal of the impurities also enables a further yield-enhancing refinement, in that isosorbide distillation bottoms 24' and 30' are combined to provide isosorbide distillation bottoms stream 54 which can be recycled to the front of the process. This permits unconverted sorbitol and sorbitan partial dehydration products to be used in making additional isosorbide. Previously, the isosorbide distillation bottoms have not been recycled in this manner, because impurities removed by system 34 have tended to adversely affect dehydration reactor 14. FIG.3 illustrates the reaction pathways of the conversion of sorbitol to isosorbide reaction product, depicting the intermediate products such as various sorbitans such as 3,6-sorbitan, 1,4-sorbitan, 1,5-sorbitan, and 2,5-sorbitan.

[0056] In one embodiment, the isosorbide distillation bottoms containing some sorbitans can be dehydrated separately and not recycled. This optimizes dehydration of sorbitans rather than sorbitol. In another alternative embodiment, the isosorbide distillation bottoms may be used directly in certain isosorbide product end uses and applications. In yet another alternative embodiment, sorbitans are themselves useful products for certain applications, so that at least some portion of the sorbitans may be removed for these applications from the isosorbide distillation bottoms before recycling the remainder. The reaction product of the present invention can be drawn from any of these processes.

[0057] The non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process may alternatively be derived from a process of internal dehydration product of a hydrogenated sugar as described in U.S. Patent No. 8,008,477 to Fuertes, which is hereby incorporated by reference in its entirety.

[0058] The molecular weight of the condensation products of sorbitol, isosorbide, and sorbitans may be up to 5,000. In particular, the molecular weight of the condensation products of sorbitol, isosorbide, and sorbitans may be less than 5,000, less than 4,500, less than 4,000, less than 3,500, less than 3,000, less than 2,500, less than 2,000, less than 1,500, less than 1,000, less than 900, less than 800, less than 700, less than 600, less than 500, less than 400, less than 300, less than 200, and less than 100. In one embodiment, the one or more condensation products of sorbitol, isosorbide and sorbitans have a molecular weight of less than about 5,000.

[0059] The asphalt of the present invention may contain anywhere from 0.1% to 100% by weight non-esterified and non-etherified reaction product. More preferably, the asphalt contains from about 3% to about 40% by weight reaction product. For example, the asphalt may contain about 0.1, 0.25, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 25%, 40%, 50%, 60%, 70%, 80%, 90, or 100% by weight reaction product. In one embodiment, the non-esterified and non- etherified reaction product is mixed in an amount of 0.1 to 5.0 wt.% with the asphalt. In one embodiment, a composition of matter is produced by the methods described above.

[0060] In the present invention, the term asphalt product includes a warm-melt flowable mixture of warm-mix binder of bituminous type optionally together with mineral filler. An asphalt product does not need to be roller compacted when implemented. It should thus be easily cast and spread. Examples of asphalt products include in particular asphalts, sealants, pavement seals and heat sealing materials.

[0061] The improved asphalt may optionally include a polymer additive, such as polyethylenes, oxidized polyethylenes, polyolefins, PE homopolymers, and the like. The polymer additive can include low molecular weight polymers, such as low, medium, or high density polyethylenes having a maximum viscosity of 1000 cps at 140°C. Other suitable polymers would include ethylenes and polypropylenes with melting points below 140°C. The polymer additive is preferably added at a concentration of up to about 1%, 5%, 10%, 15%, 20%, 25%, and 50% by weight of the improved asphalt.

[0062] The asphalt binder can be polymer-modified asphalt, preferably a styrene- butadiene type polymer-modified asphalt. Styrene-butadiene type polymers preferably include SB rubber, SBS linear type, SBS radial type, and SB sulphur linked type polymers, and the like. The asphalt binder optionally includes up to about 5% by weight styrene-butadiene type polymer. Any suitable polymer or mixture of different polymers can be used in producing polymer-modified asphalt. Non-limiting examples of suitable polymers include polyethylene, polypropylene, styrene/butadiene/styrene triblock copolymer, styrene/ethylene-butylene/styrene triblock copolymer, epoxy modified acrylate copolymer, ethylene/vinyl acetate copolymer, or mixture thereof.

[0063] Another aspect of the invention relates to an asphalt product. The asphalt product includes an asphalt and a non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process, mixed with the asphalt.

[0064] This asphalt and non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process used in this aspect of the present invention are described above. The asphalt product of the present aspect may have a viscosity of between 0.01 and 0.5 Pa ^» s at a temperature ranging from 130 °C to 165 °C. For example, the viscosity at a temperature ranging from 130 °C to 165 °C may be 0.01 Pa ^» s, between 0.01 and 0.05 Pa ^» s, between 0.01 and 0.1 Pa ^» s; between 0.01 and 0.2 Pa ^» s; between 0.1 and 0.3 Pa ^» s; between 0.1 and 0.4 Pa ^» s; and between 0.1 and 0.5 Pa ^» s. The temperature may be, for example, 130 °C, between 130 °C and 140 °C, between 130 °C and 150 °C, between 130 °C and 160 °C, or between 130 °C and 165 °C. In one embodiment, the asphalt product has a viscosity of 0.23-0.33 Pa ^» s at a temperature ranging from 130 °C to 150 °C. In another embodiment, the asphalt product has a viscosity of 0.13-0.21 Pa ^» s at a temperature ranging from 150 °C to 165 °C.

[0065] According to the present invention, the asphalt product may have a compaction energy of 3.11 kJ/m ² at a temperature ranging from 120 °C when used with neat binder. The asphalt product may have a compaction energy of 3.77 kJ/m2 at a temperature ranging of 120 °C. Compaction energy may be evaluated through use of a Pine AFG2 gyratory compactor and may include moment, height, pressure and angle of gyration. Abed, A.H., "Enhanced Aggregate- Asphalt Adhesion and Stability of Local Hot Mix Asphalt," Engineering and Technical Journal 29(10):2044-59 (2011); DelRio-Prat et al, "Energy Consumption During Compaction with a Gyratory Intensive Compactor Tester. Estimation Models," Construction and Building Materials 25(2): 979-86 (201 1); Faheem et al., "Estimating Results of a Proposed Simple Performance Test for Hot-Mix Asphalt from Superpave Gyratory Compactor Results," Transportation Research Record: Journal of the Transportation Research Board 1929: 104-13 (2005); Mo et al.

"Laboratory Investigation of Compaction Characteristics and Performance of Warm Mix Asphalt Containing Chemical Additives," Construction and Building Materials 37:239-47 (2012);

Sanchez-Alonso et al, "Evaluation of Compactability and Mechanical Properties of Bituminous Mixes with Warm Additives," Construction and Building Materials 25(5):2304-l (2011), all of which are hereby incorporated by reference in its entirety.

[0066] In one embodiment of the present invention, the asphalt product further includes a mineral aggregate. A mineral aggregate may be added to the asphalt product to modify its rheology and temperature susceptibility. In an alternative embodiment, the asphalt product includes asphalt concrete used in pavement. The asphalt binder is mixed with mineral aggregate typically composed of sand, gravel, limestone, crushed stone, slag, and mixtures thereof. The mineral aggregate particles of the present invention include calcium based aggregates, for example, limestone, siliceous based aggregates and mixtures thereof. Aggregates can be selected for asphalt paving applications based on a number of criteria, including physical properties, compatibility with the bitumen to be used in the construction process, availability, and ability to provide a finished pavement that meets the performance specifications of the pavement layer for the traffic projected over the design life of the project.

[0067] In one embodiment, the asphalt product is in the form of an asphalt mixture. The asphalt mixture may further include fiberglass and a mineral aggregate including at least one of lime dust and granular ceramic material.

[0068] Mineral aggregates of the present invention may include elements of less than

0.063 mm and optionally aggregates originating from recycled materials, sand with grain sizes between 0.063 mm and 2 mm and optionally grit, containing grains of a size greater than 2 mm, and optionally alumino-silicates. Aluminosilicates are inorganic compounds based on aluminium and sodium silicates or other metal such as potassium or calcium silicates.

Aluminosilicates reduce the viscosity of the warm-mix and are in form of a powder and/or granulates. The term granulates refers to mineral and/or synthetic granulates, especially coated material aggregates, which are conventionally added to bituminous binders for making mixtures of materials for road construction.

[0069] In another embodiment, the asphalt material includes roofing shingles. For a roofing-grade asphalt material, roofing granules can be applied to a surface of a coated base material. The roofing granules can be used for ultraviolet radiation protection, coloration, impact resistance, fire resistance, another suitable purpose, or any combination thereof. The roofing granules can include inert base particles that are durable, inert inorganic mineral particles, such as andesite, boehmite, coal slag, diabase, metabasalt, nephaline syenite, quartzite, rhyodacite, rhyolite, river gravel, mullite-containing granules, another suitable inert material, or any combination thereof. See U.S. Patent Publ. No. 2013/0160674 to Hong et al, which is hereby incorporated by reference in its entirety.

[0070] Roofing granules may also include one or more surface coatings over the shingle.

The surface coating can cover at least approximately 75% of the surface of the shingle, and may cover at least approximately 90% of the surface of the shingle and may or may not have a uniform thickness. If more than one surface coating is used, a surface coating closer to the shingle can include a binder that can be inorganic or organic. An inorganic binder can include a silicate binder, a titanate binder, a zirconate binder, an aluminate binder, a phosphate binder, a silica binder, another suitable inorganic binder, or any combination thereof. An organic binder can include a polymeric compound. In a particular embodiment, an organic binder can include an acrylic latex, polyurethane, polyester, silicone, polyamide, or any combination thereof. One or more additional organic binders of the same or different composition can be used.

[0071] A surface coating may also or alternatively include a solar reflective material that helps to reflect at least some of the solar energy. For example, UV radiation can further polymerize or harden the asphalt within roofing product being fabricated. A solar reflective material can include titanium dioxide, zinc oxide, or the like. Alternatively, the solar reflective material can include a polymeric material. In an embodiment, a polymer can include a benzene- modified polymer (e.g., copolymer including a styrene and an acrylate), a fluoropolymer, or any combination thereof. Other solar reflective materials are described in U.S. Pat. No. 7,241,500 to Shiao et al. and U.S. Publ. Nos. 2005/00721 10 to Shiao et al. and 2008/0220167 to Wisniewski et al, all of which are incorporated by reference for their teachings of materials that are used to reflect radiation (e.g., UV, infrared, etc.) from the sun.

[0072] A surface coating can also or alternatively include an algaecide or another biocide to help reduce or delay the formation of algae or another organic growth. The algaecide or other biocide can include an organic or inorganic material. The algaecide or other biocide can include a triazine, a carbamate, an amide, an alcohol, a glycol, a thiazolin, a sulfate, a chloride, copper, a copper compound, zinc, a zinc compound, another suitable biocide, or any combination thereof. In a particular embodiment, the algaecide or other biocide can be included within a polymeric binder. The polymeric binder can include polyethylene, another polyolefin, an acid-containing polyolefin, ethylene vinyl acetate, an ethylene-alkyl acrylate copolymer, a polyvinylbutyral, polyamide, a fluoropolymer, an acrylic, a methacrylate, an acrylate, polyurethane, another suitable binder material, or any combination thereof. The algaecide or other biocide can be an inorganic material that is included within an inorganic binder, for example, within an alkali metal silicate binder. An exemplary inorganic algaecide or other biocide can include a metal (by itself), a metal oxide, a metal salt, or any combination thereof. The metallic element used within the metal, metal oxide, or salt may include copper, zinc, silver, or the like. The metal salt can include a metal sulfate, a metal phosphate, or the like.

[0073] A surface coating can include a colorant or another material to provide a desired optical effect. The colorant or other material can include a metal oxide compound, such as titanium dioxide (white), zinc ferrite (yellow), red iron oxides, chrome oxide (green), and ultramarine (blue), silver oxide (black), zinc oxide (dark green), or the like. In another embodiment, the colorant or other material may not be a metal-oxide compound. For example, the colorant may include carbon black, zinc or aluminum flake, or a metal nitride.

[0074] The asphalt containing the WMA reaction product is mixed with fiberglass and mineral aggregate typically composed of lime dust and/or granular ceramic material, such as manufactured ceramic material to form roofing shingles. The shingles can also include manufactured sand, e.g., crushed and washed mined aggregate, and also a blend of ceramic material and manufactured sand. The roofing shingles can also include modified asphalt containing a Fischer-Tropsch wax, polyethylene wax, and/or oxidized polyethylene wax. Wax modifiers that can be usefully employed in the context of the invention include, but are not limited to waxes of vegetable (e.g., carnuba wax), animal (e.g., beeswax) mineral (e.g.,

Montan™ wax from coal, Fischer Tropsch wax from coal) or petroleum (e.g., paraffin wax, polyethylene wax, Fischer-Tropsch wax from gas) origin including oxidized waxes; amide waxes (e.g., ethylene bis stearamide, stearyl amide, stearyl stearamide); fatty acids and soaps of waxy nature (e.g., aluminum stearate, calcium stearate, fatty acids); other fatty materials of waxy nature (fatty alcohols, hydrogenated fats, fatty esters etc) with the ability to stiffen asphalt, and the like. The above products are basically soluble in the asphalt at the temperatures of the warm mix, to make a homogeneous binder, and/or will melt at the temperature of the mix and the ingredients will disperse/dissolve into the mixture. The wax and resin ingredients will generally act to improve cohesion properties of the asphalt, while the adhesion promoter will improve the adhesion of the asphalt to the aggregate. Together the ingredients provide improved resistance to water damage. The invention may employ a Fischer Tropsch Wax derived from coal or natural gas or any petroleum feedstock. The process entails the gasification of the above feedstock by partial oxidation to produce carbon monoxide under high temperature and pressure and reaction of the resultant carbon monoxide with hydrogen under high temperature and pressure in the presence of a suitable catalyst (such as iron compound or cobalt compound) for example as in the case of processes employed by Shell and Sasol. The congealing point of the wax is between 68°C and 120°C with a Brookfield viscosity at 135°C in the range of 8 to 20 cPs. For example, the congealing point of the wax may be between 80° C and 120° C. Alternatively, the congealing point of the wax may be between 68°C and 105°C. See U.S. patent Publ. No.

2013/0186302 to Naidoo et al, which is hereby incorporated by reference in its entirety.

[0075] A further aspect of the present invention relates to a method of making an asphalt material. The method includes providing an improved asphalt product comprising an asphalt and a non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process, mixed with the asphalt. The method further includes mixing the improved asphalt product with a mineral aggregate at a temperature of 150 °C or lower, to coat the mineral aggregate and produce a heated paving material which, at a warm mix temperature, has a compaction production temperature at least 15-50 °C lower than that of the improved asphalt material absent the reaction product of a sorbitol to isosorbide conversion process. The heated paving material is applied to a surface to be paved to form an applied paving material. The applied paving material is compacted to a void fraction of less than 8%, at a compacting temperature of 140 °C or lower to form a paved surface.

[0076] This asphalt and non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process of the present aspect are in accordance with the previously described aspects.

[0077] The mixing step may be may be carried out at a temperature of, for example, 150

°C, 140 °C, 130 °C, 120 °C, 1 10 °C, 100 °C, 90 °C, 80 °C, 70 °C, 60 °C, 50 °C, 40 °C, 30 °C, 20 °C, 10 °C, 5 °C, 4 °C, 3 °C, 2 °C, 1 °C or any temperature in between. In one embodiment, mixing is carried out at 110-140 °C.

[0078] The compacting step may be carried out at a temperature of, for example, 140 °C, 130 °C, 120 °C, 110 °C, 100 °C, 90 °C, 80 °C, 70 °C, 60 °C, 50 °C, 40 °C, 30 °C, 20 °C, 10 °C, 9 °C, 8 °C, 7 °C, 6 °C, 5 °C, 4 °C, 3 °C, 2 °C, 1 °C, or any temperature in between. In one embodiment, compacting is carried out at 100-130 °C.

[0079] The present invention further relates to the asphalt material product of this method. In one embodiment, the asphalt material can be mixed with water and a surfactant and mechanically agitated, in for example, a shear mill, to form an emulsion. Suitable emulsion- forming surfactants are known to those of skill in the art. The emulsified asphalt material can be used as weather-proofing sealant or as an adhesive bonding layer between two surfaces.

[0080] The fracture energy of the asphalt material of the present aspect may be between

5% to 100% greater than that of the improved asphalt material without the non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process. For example, the fracture energy may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or even 100% greater than when the non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process is present in the asphalt material. In one embodiment, the asphalt material has a fracture energy, at a temperature ranging from -24 to -6 °C, between 10% and 50% greater than that of the improved asphalt material absent the non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process. A semi-circular bend (SCB) test carried out in accordance with AASHTO TP 105 - 13 is one method for determining fracture energy and may be used herein. See Chong et al, "New Specimen for Fracture Toughness Determination for Rock and Other Materials," International Journal of Fracture 26(2): R59-R62 (1984); Semi-Circular Bending Test: A Practical Crack Growth Test Using Asphalt Concrete Cores. RILEM PROCEEDINGS, CHAPMAN & HALL (1996); Li et al, "Using Semi Circular Bending Test to Evaluate Low Temperature Fracture Resistance for Asphalt Concrete," Experimental Mechanics 50(7):867-76 (2010); Li et al, "Evaluation of the Low Temperature Fracture Resistance of Asphalt Mixtures Using the Semi Circular Bend Test (with Discussion)," Journal of the Association of Asphalt Paving Technologists 73 (2004); Lim et al, "Stress Intensity Factors for Semi-Circular

Specimens under Three-Point Bending," Engineering Fracture Mechanics 44(3):363-82 (1993); Marasteanu et al., "National Pooled Fund Study -Phase Ii: Final Report - Investigations of Low Temperature Cracking in Asphalt Pavements," MN/RC 2012-23, (2012); Low Temperature Fracture Test for Asphalt Mixtures. Fifth International RILEM Conference on Reflective Cracking in Pavements (2004) RILEM Publications SARL; and Teshale et al, "Low- Temperature Fracture Behavior of Asphalt Concrete in Semi-Circular Bend Test," University of Minnesota (2012), all of which are hereby incorporated by reference in their entirety.

[0081] The stiffness of the asphalt material of the present aspect may be between 5% to 100% less than that of an asphalt material without the non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process. For example, the stiffness may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or even 100% less than when the non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process is absent from the asphalt material. In one embodiment, the asphalt material has a stiffness, at a temperature ranging from -24 °C to -6 °C, that is reduced by 10% to 30% compared to that of the improved asphalt material absent the non- esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process. A semi-circular bend (SCB) test carried out in accordance with AASHTO TP 105 - 13 is one method for determining stiffness and may be used herein.

[0082] The Hamburg Steel Wheel Test Stripping Inflection Point may be increased by

1% to 90% compared to that of the improved asphalt material absent the non-esterified and non- etherified reaction product of a sorbitol to isosorbide conversion process. For example, the Hamburg Steel Wheel Test Stripping Inflection Point may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or even 90% higher than when the non-esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process is absent from the asphalt material. In one

embodiment, the asphalt material has a Hamburg Steel Wheel Test Stripping Inflection Point that is increased by 2% to 40% compared to that of the improved asphalt material absent the non- esterified and non-etherified reaction product of a sorbitol to isosorbide conversion process. The Hamburg Steel Wheel Tester (HSWT) may be carried out in accordance with AASHTO T324. See AASHTO. T 324 - Hamburg Wheel-Track Testing of Compacted Hot Mix Asphalt (HMA) AASHTO T 324 - 11. Washington, D.C.: American Association of State Highway and

Transportation Officials (2011), which is incorporated by reference in its entirety.

[0083] The above disclosure generally describes the present invention. A more specific description is provided below in the following examples. The examples are described solely for the purpose of illustration and are not intended to limit the scope of the present invention.

Changes in form and substitution of equivalents are contemplated as circumstances suggest or render expedient. Although specific terms have been employed herein, such terms are intended in a descriptive sense and not for purposes of limitation.

EXAMPLES Example 1 - Isosorbide Product Mixture

[0084] Description of Blend Ingredients - For laboratory testing, an unmodified Montana crude source asphalt supplied by Jebro, with a performance grade ("PG") of 58-28 was used as a first binder while a polymer modified form of this binder was used as a second binder - the PG 58-28 binder polymer modified with 1.5% styrene-butadiene-styrene (SBS) was used to make the PG 64-28 binder. The polymer modified PG 64-28 was blended by the binder supplier. The WMA additive was an isosorbide product mixture supplied by Archer Daniels Midland (Decatur, Illinois). The IPM is comprised of isosorbide at 66.74%, 1,4-sorbitan at 1.28%, 2,5-sorbitan isomer A at 2.17%, 3,6-sorbitan at 0.40%, and 2,5 sorbitan isomer B at 4.48%. The balance is composed of a mixture of sorbitan/isosorbide dimers to polymers, furfural and other furanics, dehydration products of sorbitan or isosorbide, sodium sulfate and organic sulfate esters as described in Fig 3.

[0085] To construct the test specimens that make up one half of each HWTD test specimen, a 10 million ESAL design level surface mix approved by the Iowa Department of Transportation (DOT) was used. Each specimen was procured with air voids at 7% ± 1%, diameter 150 mm and a set height of 61±1 mm. Each individual aggregate's gradation, the blended aggregate gradation, and source information used to produce this mix design are shown in Table 1. The Iowa DOT job mix formula was also verified for each source aggregate's gradation in the laboratory.

Table 1. Mix Design Gradation and Supplier Information

[0086] Methods - Binder rheology testing was completed according to industry standard testing, which is further described in Table 2, below. Table 2. List of Standards Used in Binder Rheology Testing

[0087] The Isosorbide Product Mixture (IPM) was blended with the unmodified and polymer modified asphalt with a Silverson shear mill at 140°C at 3000rpm for one hour. The dosage levels chosen were 0.5%, and 0.75% for addition of each of the IPMs. For example, the IPM was blended at 0.5% by total weight of the total blend and at 0.75% by total weight of the total blend.

[0088] The developed blends were then tested in accordance with ASTM and/or

AASHTO standards described above in Table 2 for viscosity, specific gravity, mass loss, performance grade, and separation. Table 3 contains the data for the IPM. The dosage rates were chosen based on ranges for other commercially available WMA additives. Binder testing included specific gravity, dynamic shear rheometer (DSR) testing on original and aged binders as well as bending beam rheometer tests. Aging included both rolling thin film oven (RTFO) and pressure aging vessel (PAV) aging which simulate short and long term aging of the asphalt, respectively. Mass loss of the binder was measured after RTFO testing. All binder testing followed the American Association of State Highway and Transportation Officials (AASHTO) M320 standard. Asphalt mix testing included moisture sensitivity testing and rutting at high temperature using the Hamburg Wheel Tracking test, and low temperature testing using the Semi-circular Bend test to determine the resistance to cracking/fatigue.

Table 3. Summary of Results for Asphalt Binders Modified with IPM

[0089] Results - The data in Table 3 shows that the IPM provides a lower stiffness at the lower temperatures tested for viscosity and performance grading in the dynamic shear rheometer and bending beam rheometer. The specific gravity of the blends did not change from the base asphalts. The mass loss due to the IPM demonstrated there was not a concern. The separation testing demonstrated the IPM did not separate after blending with the asphalt binders.

[0090] The developed blends of the IPM and asphalt binders (unmodified and polymer modified) at the 0.75% IPM addition rate were then subsequently mixed with aggregate from Martin Marietta (Ames, Iowa), Hallett Materials (Ames, Iowa), Manatts (Ames, Iowa), and OldCastle Materials Group (Johnston, Iowa) at approximately 5% by total weight of the mix. The warm mix asphalt (WMA) groups were mixed and compacted at 120°C, while the hot mix asphalt (HMA) control groups were mixed and compacted at 140°C. All specimens from each group were compacted to a set height to achieve 7% air voids.

[0091] The samples were evaluated during compaction and after compaction for low temperature performance, and moisture sensitivity/stripping with the data presented in Table 4.

Table 4. Summary of Results for Mix Testing with IPM Modified Asphalt Binders

N/T is not tested.

[0092] Compaction evaluation data was collected using a Pine AFG2 gyratory compactor and included moment, height, pressure and angle of gyration for subsequent calculations and evaluation. This included the number of gyrations to achieve 7% air voids, shear energy, and compaction force index. Low temperature testing was done on the samples using the semicircular bend (SCB) test (AASHTO TP 105) and the disk compact tension (DCT) test (ASTM D7317). Moisture susceptibility/stripping evaluation on the samples were with the Hamburg Steel Wheel Tester (HSWT) in accordance with AASHTO T324.

[0093] The evaluation of the mix testing shows the IPM has improved compactibility over the control asphalts (unmodified and polymer modified).

[0094] The IPM blends showed equal or better low temperature performance over the control asphalt binders and the comparative examples in the SCB and DCT test results, respectively. The IPM blends showed improved moisture susceptibility/stripping performance in the HSWT as compared to the base asphalts (unmodified and polymer modified). These mix performance results are summarized in Table 4 above.

Example 2 - Isosorbide Product Mixture

[0095] Description of Blend Ingredients - For laboratory testing, an unmodified Montana crude source of asphalt was supplied by Jebro, with a performance grade ("PG") of 58-28 was used as a first binder along with a polymer modified form of this binder was used as a second binder - the PG 58-28 binder polymer modified with 1.5% styrene-butadiene-styrene (SBS) was used to make the PG 64-28 binder. The polymer modified PG 64-28 was blended by the binder supplier. The WMA additive was an isosorbide product mixture supplied by Archer Daniels Midland (Decatur, Illinois). This IPM is comprises of isosorbide at 66.92%, 1,4-sorbitan at 3.12%, 2,5-sorbitan isomer A at 1.81%, 2,5-sorbitan isomer B at 3.63%, and the balance as described in FIG. 3 and in Example 1 above.

[0096] Methods - The Isosorbide Product Mixture (IPM) was blended with the unmodified and polymer modified asphalt with a Silverson shear mill at 140°C at 3000rpm for one hour. The dosage levels chosen were 0.5%, and 0.75% for addition of each of the IPMs. For example, the IPM was blended at 0.5% by total weight of the total blend and at 0.75% by total weight of the total blend.

[0097] The developed blends were then tested in accordance with ASTM and/or

AASHTO as described in Table 2 above for viscosity, specific gravity, mass loss, performance grade, and separation. Table 5 contains the data for this IPM.

Table 5. Summary of Results for Asphalt Binders Modified with IPM

N/T is not tested.

[0098] Results - This data in Table 5 shows that the IPM provides a lower stiffness at the lower temperatures tested for viscosity and performance grading in the dynamic shear rheometer and bending beam rheometer. The specific gravity of the blends did not change from the base asphalts. The mass loss due to the IPM demonstrated there was not a concern. The separation testing demonstrated the IPM did not separate after blending with the asphalt binders.

[0099] The developed blends of the IPM and asphalt binders (unmodified and polymer modified) at the 0.75% IPM addition rate were then subsequently mixed with aggregate from Martin Marietta (Ames, Iowa), Hallett Materials (Ames, Iowa), Manatts (Ames, Iowa) and OldCastle Materials Group (Johnston, Iowa) at approximately 5% by total weight of the mix. The warm mix asphalt (WMA) groups were mixed and compacted at 120°C, while the hot mix asphalt (HMA) control groups were mixed and compacted at 140°C. All specimens from each group were compacted to a set height to achieve 7% air voids.

[00100] The samples were evaluated during compaction and after compaction for low temperature performance, and moisture sensitivity/stripping with the data presented below in Table 6.

Table 6. Summary of Results for Mix Testing with IPM Modified Asphalt Binders

Binder PG 58-28 PG 58- PG 58- PG 64- PG 64- PG 64-

WMA 28 HMA 28 28 28 HMA 28

WMA WMA WMA

Modifier Dosage (%) 0 0 0.75 0 0 0.75

# Gyrations to achieve 58 49 56 80 11 1 75

7% Air Voids

N/T is not tested.

[00101] Compaction evaluation data was collected using a Pine AFG2 gyratory compactor and included moment, height, pressure, and angle of gyration for subsequent calculations and evaluation. This included the number of gyrations to achieve 7% air voids, shear energy, and compaction force index. Low temperature testing was done on the samples using the semicircular bend (SCB) test (AASHTO TP 105) and the disk compact tension (DCT) test (ASTM D7317). Moisture susceptibility/stripping evaluation on the samples were with the Hamburg Steel Wheel Tester (HSWT) in accordance with AASHTO T324.

[0102] The evaluation of the mix testing shows the IPM has improved compactibility over the control asphalts (unmodified and polymer modified). The IPM blends showed equal or better low temperature performance over the control asphalt binders and the comparative examples in the SCB and DCT test results, respectively. The IPM blends showed improved moisture susceptibility/stripping performance in the HSWT as compared to the base asphalts (unmodified and polymer modified). These mix performance results are summarized in Table 6 above.

Example 3 (Comparative Example) - Isosorbide Distillation Bottoms

[0103] Description of Blend Ingredients - For laboratory testing, an unmodified Montana crude source of asphalt was supplied by Jebro, with a performance grade ("PG") of 58-28 was used as a first binder along with a polymer modified form of this binder as a second binder - the PG 58-28 binder polymer modified with 1.5% styrene-butadiene-styrene (SBS) to achieve a PG 64-28 binder. The polymer modified PG 64-28 was blended by the binder supplier. The WMA additive was isosorbide distillation bottoms supplied by Archer Daniels Midland (Decatur, Illinois). The isosorbide distillation bottoms are comprised of isosorbide at 35.4%, sorbitans at 14%, organic sulfate esters at 4.9%, and the balance is the coproducts described in FIG. 3, dimers to polymers of isosorbide/sorbitan, furanics, and other dehydration products of isosorbide and sorbitan. [0104] Methods - The Isosorbide Distillation Bottoms (IDB) was blended with the unmodified and polymer modified asphalt with a Silverson shear mill at 140°C at 3000rpm for one hour. The IDB was blended at 0.5% by total weight of the total blend. The IDB was also blended at 0.75% by total weight of the total blend.

[0105] The developed blends were then tested in accordance with ASTM and/or

AASHTO for viscosity, specific gravity, mass loss, performance grade, and separation. Table 7 contains the data for the IDB.

Table 7. Summary of Results for Asphalt Binders Modified with IDB

N/T is not tested.

[0106] Results - This data in Table 7 shows that the IDB provides a lower stiffness at the lower temperatures tested for viscosity and performance grading in the dynamic shear rheometer and bending beam rheometer. The specific gravity of the blends did not change from the base asphalts. The mass loss due to the IDB demonstrated there was not a concern. The separation testing demonstrated the IDB did not separate after blending with the asphalt binders.

[0107] The developed blends of the IDB and asphalt binders (unmodified and polymer modified) at the 0.75% IDB addition rate were then subsequently mixed with aggregate from Martin Marietta (Ames, Iowa), Hallett Materials (Ames, Iowa), Manatts (Ames, Iowa), and OldCastle Materials Group (Johnston, Iowa) at approximately 5% by total weight of the mix. The warm mix asphalt (WMA) groups were mixed and compacted at 120°C, while the hot mix asphalt (HMA) control groups were mixed and compacted at 140°C. All specimens from each group were compacted to a set height to achieve 7% air voids. [0108] The samples were evaluated during compaction and after compaction for low temperature performance, and moisture sensitivity/stripping with the data presented in Table 8.

Table 8. Summary of Results for Mix Testing with IDB Modified Asphalt Binders

N/T is not tested.

[0109] Compaction evaluation data was collected using a Pine AFG2 gyratory compactor and included moment, height, pressure and angle of gyration for subsequent calculations and evaluation. This included the number of gyrations to achieve 7% air voids, shear energy, and compaction force index. Low temperature testing was done on the samples using the semicircular bend (SCB) test (AASHTO TP 105) and the disk compact tension (DCT) test (ASTM D7317). Moisture susceptibility/stripping evaluation on the samples were with the Hamburg Steel Wheel Tester (HSWT) in accordance with AASHTO T324.

[0110] The evaluation of the mix testing shows the IDB has improved compactibility over the control asphalts (unmodified and polymer modified). The IDB blends showed equal or better low temperature performance over the control asphalt binders and the comparative examples in the SCB and DCT test results, respectively. The IDB blends showed improved moisture susceptibility/stripping performance in the HSWT as compared to the base asphalts (unmodified and polymer modified). These mix performance results are summarized above in Table 8.

[0111] Although preferred embodiments have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions, and the like can be made without departing from the spirit of the invention and these are therefore considered to be within the scope of the invention as defined in the claims which follow.