Granted Patent
B2
US 12,595,369 · App. 18/085,753 · Granted Apr 7, 2026
Algae-resistant bitumen-containing materials
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Abstract
A modified bitumen composition includes bitumen, biomass oil including one or more phenolic compounds, and added sulfur. The modified bitumen composition includes between about 5 wt % and about 25 wt % of the added sulfur, at least some of the added sulfur is present as polysulfide chains, and at least some of the one or more phenolic compounds are configured to covalently bind to the polysulfide chains. Making a modified bitumen includes combining bitumen and elemental sulfur to yield sulfur-extended bitumen, and combining the sulfur-extended bitumen with biomass oil including one or more phenolic compounds to yield the modified bitumen.
Claims (23)
1 . A modified bitumen composition comprising:
bitumen;
biomass oil comprising one or more phenolic compounds; and
added sulfur,
wherein the modified bitumen composition comprises between about 5 wt % and about 25 wt % of the added sulfur, at least some of the added sulfur is present as polysulfide chains, the added sulfur comprises about 70 wt % to about 90 wt % crystalline sulfur, and at least some of the one or more phenolic compounds are configured to covalently bind to the polysulfide chains.
2 . The composition of claim 1 , wherein the modified bitumen composition comprises between about 10 wt % and about 20 wt % of the added sulfur.
3 . The composition of claim 1 , wherein the biomass oil comprises plant-based bio-oil.
4 . The composition of claim 3 , wherein the plant-based bio-oil comprises castor oil, corn stover oil, miscanthus oil, wood pellet oil, vegetable oil, or a combination thereof.
5 . The composition of claim 1 , wherein the one or more phenolic compounds comprise one or more of 2,6-dimethoxy phenol, 5-tert-butylpyrogallol, homosyringaldehyde, trans-isoeugenol, 4-ethylphenol, 2-methoxy phenol, or a combination thereof.
6 . A roadway comprising the modified bitumen of claim 1 .
7 . A building material comprising the modified bitumen of claim 1 .
8 . The building material of claim 7 , wherein the building material comprises roofing shingles.
9 . The building material of claim 8 , wherein the roofing shingles demonstrate self-regenerative sulfur blooms during use.
10 . The building material of claim 8 , wherein the roofing shingles are algae-resistant relative to roofing shingles comprising unmodified bitumen.
11 . Roofing shingles comprising the modified bitumen of claim 1 .
12 . A method of making a modified bitumen, the method comprising:
combining bitumen and elemental sulfur to yield sulfur-extended bitumen; and
combining the sulfur-extended bitumen with biomass oil comprising one or more phenolic compounds to yield the modified bitumen,
wherein the modified bitumen comprises between about 5 wt % and about 25 wt % of the added sulfur, at least some of the elemental sulfur is present as polysulfide chains, the elemental sulfur comprises about 70 wt % to about 90 wt % crystalline sulfur, and at least some of the one or more phenolic compounds are configured to covalently bind to the polysulfide chains.
13 . The method of claim 12 , wherein the biomass oil comprises plant-based bio-oil.
14 . The method of claim 13 , wherein the plant-based bio-oil comprises castor oil, corn stover oil, miscanthus oil, wood pellet oil, vegetable oil, or a combination thereof.
15 . The method of claim 12 , wherein the modified bitumen comprises between about 10 wt % and about 20 wt % of the elemental sulfur.
16 . The method of claim 12 , wherein the one or more phenolic compounds comprise one or more of 2,6-dimethoxy phenol, 5-tert-butylpyrogallol, homosyringaldehyde, trans-isoeugenol, 4-ethylphenol, and 2-methoxy phenol.
Assignments (2)
CONFIRMATORY LICENSE
Recorded Feb 3, 2025
From: ARIZONA STATE UNIVERSITY-TEMPE CAMPUS
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 070085/0323 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Dec 21, 2022
From: FINI, ELHAM; PAHLAVAN, FARIDEH; HUNG, ALBERT
To: ARIZONA BOARD OF REGENTS ON BEHALF OF ARIZONA STATE UNIVERSITY
Reel/Frame 062168/0288 →
Continuity (2)
Provisional Application
63292680
· Dec 22, 2021
References Cited (95)
US 2182837A
· Bacon
· 1939
[cited by applicant]
US 2686166A
· Taylor
· 1954
[cited by applicant]
US 3803066A
· Petrossi
· 1974
[cited by applicant]
US 4145322A
· Maldonado
· 1979
[cited by applicant]
US 9243409B2
· Kalkanoglu
· 2016
[cited by applicant]
US 20190106637A1
· Oswald et al.
· 2019
[cited by applicant]
US 20230242820A1
· Fini
· 2023
[cited by applicant]
US 20230374310A1
· Fini
· 2023
[cited by applicant]
AU 2015213412A1
· 2015
[cited by applicant]
CN 113145069A
· 2021
[cited by applicant]
DE 102015013981A1
· 2017
[cited by applicant]
GB 579368A
· 1946
[cited by examiner]
GB 610629A
· 1948
[cited by examiner]
GB 1507332A
· 1978
[cited by applicant]
GB 2205104A
· 1988
[cited by examiner]
WO WO2009016381A2
· 2009
[cited by applicant]
WO 2015127561A1
· 2015
[cited by applicant]
WO WO2019074499A1
· 2019
[cited by applicant]
Amić, Ana, et al. “Free radical scavenging potency of quercetin catecholic colonic metabolites: Thermodynamics of 2H +/2e-processes.” Food chemistry 218 (2017): 144-151.
[cited by applicant]
Amorati, Riccardo, et al. “Effect of ortho-SR Groups on O—H Bond Strength and H-Atom Donating Ability of Phenols: A Possible Role for the Tyr-Cys Link in Galactose Oxidase Active Site?.” Journal of the American Chemical…
[cited by applicant]
Becke, Axel D. “Density-functional thermochemistry. III. The role of exact exchange. 98 (7): 5648-5652.” The Journal of Chemical Physics. doi: https://doi. org/10.1063/1.464913 (1993).
[cited by applicant]
Bordwell, F. G., et al. “Assessment of the importance of changes in ground-state energies on the bond dissociation enthalpies of the OH bonds in phenols and the SH bonds in thiophenols.” Journal of the American Chemical…
[cited by applicant]
Bukowski, J., et al. “An alternative asphalt binder, sulfur-extended asphalt (SEA).” No. FHWA-HIF-12-037. United States. Federal Highway Administration, 2012, pp. 1-13.
[cited by applicant]
Chen, Y., et al. “Structure-thermodynamics-antioxidant activity relationships of selected natural phenolic acids and derivatives: An experimental and theoretical evaluation.” PLoS One 10.3 (2015): e0121276, pp. 1-20.
[cited by applicant]
Chung, W.J., et al. “The use of elemental sulfur as an alternative feedstock for polymeric materials.” Nature chemistry 5.6 (2013): 518-524.
[cited by applicant]
De Heer, Martine I., et al. “Hydrogen atom abstraction kinetics from intramolecularly hydrogen bonded ubiquinol-0 and other (poly) methoxy phenols.” Journal of the American Chemical Society 122.10 (2000): 2355-2360.
[cited by applicant]
Dizhbite, T., et al. “Characterization of the radical scavenging activity of lignins—natural antioxidants.” Bioresource technology 95.3 (2004): 309-317.
[cited by applicant]
D'Melo, D., et al. “Self-assembly of amorphous sulphur in bitumen-sulphur mixtures and its impact on properties.” Construction and Building Materials 126 (2016): 976-982.
[cited by applicant]
Fan, G., et al. “Growth inhibition of harmful cyanobacteria by nanocrystalline Cu-MOF-74: efficiency and its mechanisms.” Journal of hazardous materials 367 (2019): 529-538.
[cited by applicant]
Farhoosh, R., et al. “Structure—antioxidant activity relationships of o-hydroxyl, o-methoxy, and alkyl ester derivatives of p-hydroxybenzoic acid.” Food chemistry 194 (2016): 128-134.
[cited by applicant]
Fini, Elham H., et al. “Chemical characterization of biobinder from swine manure: Sustainable modifier for asphalt binder.” Journal of Materials in Civil Engineering 23.11 (2011): 1506-1513.
[cited by applicant]
Frisch, “Gaussian 16,” Expanding the limits of computational chemistry, 2016, 2 pages.
[cited by applicant]
Gawel, Irena. “Sulphur-modified asphalts.” Developments in petroleum science. vol. 40. Elsevier, 2000. 515-535.
[cited by applicant]
Gladkikh, V., et al. “Viscosity of plasticized sulfur-extended asphalt: Two-factor sequential optimization.” MATEC Web of Conferences. vol. 106. EDP Sciences, 2017, pp. 1-7.
[cited by applicant]
Gonzalez, C., et al. “An improved algorithm for reaction path following.” The Journal of Chemical Physics 90.4 (1989): 2154-2161.
[cited by applicant]
Gonzalez, C., et al. “Reaction path following in mass-weighted internal coordinates.” Journal of Physical Chemistry 94.14 (1990): 5523-5527.
[cited by applicant]
Hosseinnezhad, S., et al. “Physiochemical characterization of synthetic bio-oils produced from bio-mass: a sustainable source for construction bio-adhesives.” RSC advances 5.92 (2015): 75519-75527.
[cited by applicant]
Hung, Albert M., et al. “Effects of water exposure on bitumen surface microstructure.” Construction and Building Materials 135 (2017): 682-688.
[cited by applicant]
Jacobsen, Heiko. “Localized-orbital locator (LOL) profiles of chemical bonding.” Canadian Journal of Chemistry 86.7 (2008): 695-702.
[cited by applicant]
Jin, X., et al. “Fast-rate-constant-rate oxidation kinetics model for asphalt binders.” Industrial & Engineering Chemistry Research 50.23 (2011): 13373-13379.
[cited by applicant]
Jongberg, S., et al. “Phenolic antioxidant scavenging of myosin radicals generated by hypervalent myoglobin.” Journal of agricultural and food chemistry 60.48 (2012): 12020-12028.
[cited by applicant]
Lee, Dah-yinn. “Modification of asphalt and asphalt paving mixtures by sulfur additives.” Industrial & Engineering Chemistry Product Research and Development 14.3 (1975): 171-177.
[cited by applicant]
Lee, C., et al. “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.” Physical review B 37.2 (1988): 785-789.
[cited by applicant]
Leopoldini, M., et al. “Structure, conformation, and electronic properties of apigenin, luteolin, and taxifolin antioxidants. A first principle theoretical study.” The Journal of Physical Chemistry A 108.1 (2004): 92-96.
[cited by applicant]
Leopoldini, M., et al. “The molecular basis of working mechanism of natural polyphenolic antioxidants.” Food chemistry 125.2 (2011): 288-306.
[cited by applicant]
Liu, Gang, et al. “α-Sulfur crystals as a visible-light-active photocatalyst.” Journal of the American Chemical Society 134.22 (2012): 9070-9073.
[cited by applicant]
Lucarini, M., et al. “Bond dissociation enthalpies of polyphenols: the importance of cooperative effects.” The Journal of organic chemistry 67.3 (2002): 928-931.
[cited by applicant]
Makowska, M., et al. “The oxidation of bitumen witnessed in-situ by infrared spectroscopy.” Materials and structures 50 (2017): 1-17.
[cited by applicant]
Martínez-Estrada, A., et al. “Comparative study of the effect of sulfur on the morphology and rheological properties of SB- and SBS-modified asphalt.” Journal of Applied Polymer Science 6.115 (2009): 3409-3422.
[cited by applicant]
Meyer, B. “Elemental sulfur.” Chemical Reviews 76.3 (1976): 367-388.
[cited by applicant]
Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications,” (2009) Second Edition, CRC press, 796 pages.
[cited by applicant]
Mousavi, M., et al. “Sustainability implications of regenerative sulfur blooms in bituminous composites.” ACS Sustainable Chemistry & Engineering 9.28 (2021): 9486-9493.
[cited by applicant]
Mousavi, M., et al. “Phenolic compounds to amplify the effect of sulfur on Bitumen's thermomechanical properties.” Fuel 287 (2021): 119532, pp. 1-10.
[cited by applicant]
Mutlu, H., et al. “Sulfur chemistry in polymer and materials science.” Macromolecular rapid communications 40.1 (2019): 1800650, pp. 1-51.
[cited by applicant]
Ochterski, J., et al. “A comparison of model chemistries.” Journal of the American Chemical Society 117.45 (1995): 11299-11308.
[cited by applicant]
Ordoudi, S. A., et al. “Structure—DPPH⋅ scavenging activity relationships: Parallel study of catechol and guaiacol acid derivatives.” Journal of agricultural and food chemistry 54.16 (2006): 5763-5768.
[cited by applicant]
Papirer, E., et al. “Structural modes of sulphur in sulphur-bitumen composites as studied by electron microscopy.” Fuel 59.9 (1980): 617-620.
[cited by applicant]
Petersen, J. Claine. “A review of the fundamentals of asphalt oxidation: chemical, physicochemical, physical property, and durability relationships.” Transportation research circular E-C140 (2009), pp. 1-78.
[cited by applicant]
Petrossi, U., et al. “Reactions and technological properties of sulfur-treated asphalt.” Industrial & Engineering Chemistry Product Research and Development 11.2 (1972): 214-219.
[cited by applicant]
Pfaendtner, J., et al. “Elucidation of structure—reactivity relationships in hindered phenols via quantum chemistry and transition state theory.” Chemical engineering science 62.18-20 (2007): 5232-5239.
[cited by applicant]
Reza N., et al. “Antioxidant properties of Aloe vera components: a DFT theoretical evaluation.” Free radical research 53.8 (2019): 922-931.
[cited by applicant]
Rodríguez-Bonilla, P., et al. “Comparative study of the antioxidant capacity of four stilbenes using ORAC, ABTS+, and FRAP techniques.” Food Analytical Methods 10 (2017): 2994-3000.
[cited by applicant]
Sakib, N., et al. “A review of the evolution of technologies to use sulphur as a pavement construction material.” International Journal of Pavement Engineering 22.3 (2021): 392-403.
[cited by applicant]
Sathe, P., et al. “Removal and regrowth inhibition of microalgae using visible light photocatalysis with ZnO nanorods: A green technology.” Separation and Purification Technology 162 (2016): 61-67.
[cited by applicant]
Shankar, S., et al. “Preparation of sulfur nanoparticles and their antibacterial activity and cytotoxic effect.” Materials Science and Engineering: C 92 (2018): 508-517.
[cited by applicant]
Singh, N., et al. “Mechanistic aspects of hydrogen abstraction for phenolic antioxidants. Electronic structure and topological electron density analysis.” Physical Chemistry Chemical Physics 7.4 (2005): 614-619.
[cited by applicant]
Siquet, C., et al. “Antioxidant profile of dihydroxy- and trihydroxyphenolic acids—A structure-activity relationship study.” Free radical research 40.4 (2006): 433-442.
[cited by applicant]
Strickland, D., et al. “Study of the low-temperature properties of sulphur extended asphalt mixtures.” Proceedings of the fifty-third annual conference of the Canadian technical asphalt association (CTAA) Canadian techn…
[cited by applicant]
Syroezhko, A. M., et al. “Modification of paving asphalts with sulfur.” Russian journal of applied chemistry 76 (2003): 491-496.
[cited by applicant]
Tejero, I., et al. “Tunneling in green tea: Understanding the antioxidant activity of catechol-containing compounds. A variational transition-state theory study.” Journal of the American Chemical Society 129.18 (2007): …
[cited by applicant]
Tobolsky, A.V., et al. “Equilibrium polymerization of sulfur.” Journal of the American Chemical Society 81.4 (1959): 780-782.
[cited by applicant]
Vaquero, MJ Rodríguez, et al. “Antibacterial effect of phenolic compounds from different wines.” Food control 18.2 (2007): 93-101.
[cited by applicant]
Veselinović, J. B., et al. “Antioxidant properties of selected 4-phenyl hydroxycoumarins: Integrated in vitro and computational studies.” Chemico-biological interactions 214 (2014): 49-56.
[cited by applicant]
Wen, G., et al. “Vulcanization characteristics of asphalt/SBS blends in the presence of sulfur.” Journal of applied polymer science 82.4 (2001): 989-996.
[cited by applicant]
Wen, G., et al. “Improved properties of SBS-modified asphalt with dynamic vulcanization.” Polymer Engineering & Science 42.5 (2002): 1070-1081.
[cited by applicant]
Wright, J. S., et al. “Theoretical calculation of substituent effects on the O—H bond strength of phenolic antioxidants related to vitamin E.” Journal of the American Chemical Society 119.18 (1997): 4245-4252.
[cited by applicant]
Wright, J. S., et al. “Predicting the activity of phenolic antioxidants: theoretical method, analysis of substituent effects, and application to major families of antioxidants.” Journal of the American Chemical Society …
[cited by applicant]
Zhang, Y., et al. “Inverse vulcanization of elemental sulfur and styrene for polymeric cathodes in Li—S batteries.” Journal of Polymer Science Part A: Polymer Chemistry 55.1 (2017): 107-116.
[cited by applicant]
Zhang, J., et al. “Characterization of crack growth rate of sulfur-extended asphalt mixtures using cyclic semicircular bending test.” Journal of Materials in Civil Engineering 30.12 (2018): 04018311, pp. 1-11.
[cited by applicant]
Zhang, Yueyan, et al. “Recent advances in the polymerization of elemental sulphur, inverse vulcanization and methods to obtain functional Chalcogenide Hybrid Inorganic/Organic Polymers (CHIPs).” Polymer Chemistry 10.30 …
[cited by applicant]
Zhang, J., et al. “Characterisation of rheological properties of sulfur-extended asphalt with/without crumb rubber.” International Journal of Pavement Engineering 23.5 (2022): 1491-1499.
[cited by applicant]
Zhou, T., et al. “Effect of sulfur on bio-modified rubberized bitumen.” Construction and Building Materials 273 (2021): 122034, pp. 1-11.
[cited by applicant]
Cocurullo, A.; Grenfell, J.; Yusof, N. I. M.; Airey, G. In Fatigue characteristics of sulphur modified asphalt mixtures, 7th RILEM International Conference on Cracking in Pavements, Springer: 2012; pp. 783-792.
[cited by applicant]
Fritschy, G.; Papirer, E.; Chambu, C., Sulfur modified bitumen: A new binder. Rheologica Acta 1981, 20 (1), 78-84.
[cited by applicant]
Abdullah et al., “Identification of Hydrophilic Phenolic Compounds Derived from Palm Oil Products,” Journal of Oil Palm Research, Jun. 2020, 32(2):258-270.
[cited by applicant]
Maria et al., “Peanut oil: Compositional data,” Review Article European Journal of Lipid Science and Technology, Jul. 2010, 112(7):697-707.
[cited by applicant]
Ng et al., “Detection of cis-Vaccenic Acid in Palm Oil by 13C NMR Spectroscopy,” Lipids, 1988, 23:140-143.
[cited by applicant]
Pomerantz et al., “Sulfur speciation in kerogen and bitumen from gas and oil shales,” Organic Geochemistry, Dec. 2013, 68(31):5-12.
[cited by applicant]
Simone Alves da Silva, Polycyclic aromatic hydrocarbons content and fatty acids profile in coconut, safflower, evening primrose, and linseed oils, 2018, Food Chemistry (Elsevier), 798-805. (Year: 2018).
[cited by applicant]