CA2976950C - Rejuvenating compositions for asphalt applications & methods of manufacturing the same - Google Patents

Abstract

Disclosed herein are rejuvenating compositions for asphalt applications. In one aspect, the rejuvenating composition comprises a polymerized oil having a polymeric distribution ranging from about 2 to about 80 wt% oligomer content and Hildebrand solubility ranging from about 6 to about 12. In another aspect, the rejuvenating composition comprises an oil having a Hildebrand solubility ranging from about 6 to about 12 and a flash point ranging from about 100°C to about 400°C. In yet another aspect, the rejuvenating composition comprises a modified oil having a Hildebrand solubility ranging from about 6 to about 12 and a flash point ranging from about 100°C to about 400°C.

Description

[0001]

[0002] REJUVENATING COMPOSITIONS FOR ASPHALT APPLICATIONS & METHODS OF MANUFACTURING THE SAME (intentionally left blank) TECHNICAL FIELD This disclosure relates to rejuvenating compositions for asphalt applications and methods of manufacturing the same.

BACKGROUND

[0003] Recent technical challenges facing the asphalt industry have created opportunities for the introduction of agriculture-based products for the overall performance enhancement of asphalt. Such performance enhancements may include expanding the useful temperature interval (UTI) of asphalt, rejuvenating aged asphalt, and compatibilizing the various chemical fractions in asphalt with each other as well as with other additives such as elastomeric thermoplastic polymers in asphalt.

SUMMARY

[0004] Disclosed herein are rejuvenating compositions for asphalt applications. In one aspect, the rejuvenating composition comprises a polymerized oil having a polymeric distribution ranging from about 2 to about 80 wt% oligomer content and Hildebrand solubility ranging from about 6 to about 12. In another aspect, the rejuvenating composition comprises an unmodified/non-polymerized oil having a Hildebrand solubility ranging from about 6 to about 12 and a flash point ranging from about 100°C to about 400°C. In yet another aspect, the rejuvenating composition comprises a modified oil having a Hildebrand 1830873.1 1 Date Re9ue/Date Received 2022-05-19 2 solubility ranging from about 6 to about 12 and a flash point ranging from about 100°C to about 400°C. [0004a] According to an aspect of the invention is a rejuvenating composition for asphalt applications, the composition comprising a polymerized oil comprising a starting oil crosslinked with elemental sulfur, the polymerized oil having a polymeric distribution ranging from about 2 wt% to about 80 wt% oligomer content, wherein the oligomer is defined as a polymer having a number average molecular weight (Mn) larger than 1000, and a Hildebrand solubility ranging from about 6 to about 12. [0004b] According to an aspect of the invention is a rejuvenating composition for asphalt applications, the composition comprising an oil crosslinked with elemental sulfur and having a Hildebrand solubility ranging from about 6 to about 12 and a flash point ranging from about 100°C to about 400°C. [0004c] According to an aspect of the invention is a rejuvenating composition for asphalt applications, the composition comprising: a modified oil crosslinked using sulfurization to achieve polymerization, the polymerized modified oil having a polymeric distribution ranging from about 2 wt% to about 80 wt% oligomer content, the oligomer being a polymer having a number average molecular weight (Mn) larger than 1000, having a Hildebrand solubility ranging from about 6 to about 12 and a flash point ranging from about 100°C to about 400°C.

FIGURES

[0005] Figure 1 illustrates various oils that may be used in the rejuvenating composition and compares oligomer content against Hildebrand solubility.

DETAILED DESCRIPTION [0006] "Flash Point" or "Flash Point Temperature" is a measure of the minimum temperature at which a material will initially flash with a brief flame. It is measured according to the method of ASTM D-92 using a Cleveland Open Cup and is reported in degrees Celsius (°C). [0007] "Oligomer" is defined as a polymer having a number average molecular weight (Mn) larger than 1000. A monomer makes up everything else and includes monoacylgyclerides (MAG), diacylglycerides (DAG), triacylglycerides (TAG), and free fatty acids (FFA). 2a [0008] "Performance Grade" (PG) is defined as the temperature interval for which a specific asphalt product is designed. For example, an asphalt product designed to accommodate a high temperature of 64°C and a low temperature of -22°C has a PG of 64- 22. Performance Grade standards are set by the America Association of State Highway and Transportation Officials (AASHTO) and the American Society for Testing Materials (ASTM). [0009] "Polydispersity Index" (also known as "Molecular Weight Distribution") is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). The polydispersity data is collected using a Gel Permeation Chromatography instrument equipped with a Waters 510 pump and a 410 differential refractometer.

Samples are prepared at an approximate 2% concentration in a THF solvent. A flow rate of 1 ml/minute and a temperature of 35°C are used. The columns consist of a PhenogelTM 5 micron linear/mixed Guard column, and 300 x 7.8 mm PhenogelTM 5 micron columns (styrene-divinylbenzene copolymer) at 50, 100, 1000, and 10000 Angstroms. Molecular weights were determined using the following standards: Standard Mono- Diolein ARcof™ Trio-lein Epoxidized AccJaimTM Mult- Acclaim™ olein LHT240 Soybean 2200 ranol Oil 3400 Molecular 356 620 707 878 950 2000 3000 8000 Weight (Daltons) [00010] "Useful Temperature Interval" (UTI) is defined as the interval between the highest temperature and lowest temperature for which a specific asphalt product is designed. For example, an asphalt product designed to accommodate a high temperature of 64 °C and a low temperature of -22°C has a UTI of 86. For road paving applications, the seasonal and geographic extremes of temperature will determine the UTI for which an asphalt product must be designed. UTI of asphalt is determined by a series of AASHTO and ASTM standard tests developed by the Strategic Highway Research Program (SHRP) also known as the "Performance Grading" (PG) specification.

Asphalt and Bituminous Materials

[00011] For the purpose of this invention asphalt, asphalt binder, and bitumen refer to the binder phase of an asphalt pavement, roofing, coatings or other industrial applications. Bituminous material may refer to a blend of asphalt binder and other material such as mineral aggregate or filler. The binder used in this invention may be material acquired from asphalt producing refineries, flux, refinery vacuum tower bottoms, pitch, and other residues of processing of vacuum tower bottoms, as well as oxidized and aged asphalt from recycled bituminous material such as reclaimed asphalt pavement (RAP), and recycled asphalt shingles (RAS) or in the surface layer of existing pavements.

[00012] For the purpose of this invention, emulsion is defined as a multiphase material in which all phases are dispersed in a continuous aqueous phase. The aqueous phase may be comprised of surfactants, acid, base, thickeners, and other additives. The dispersed phase may comprise of the polymerized oil, thermoplastic natural and synthetic polymers, waxes., asphalt, and other additives and oils, herein collectively referred to as the "oil phase". High shear and energy is often necessary to disperse the oil phase in the aqueous phase using apparatus such as colloidal mills. 3 Date Re9ue/Date Received 2022-05-19 Description o.f._Qil

[00013] The rejuvenating composition for asphalt applications described herein comprises an oiL The oil in the rejuvenation composition may be a biorenewable oil {umnodified/non-polymel'ized), a petroleum based oil (unmodlfied/non-polyrneri7..ed), or polymerizations or modifications thereof.

[00014] Biorenewable oils can in dude oils isolated from plants, animals, and algae. l00015] Examples of plant-based oils may include but are not limited to soybean oil, linseed oil, cunola oil, rapeseed oil, castor oil, taH oil, cottonseed oil, sunflower oil, palm oii, peanut oil, safflower oii, com oil, com stillage oil, lecithin (phospholipids) and combinations, distillates, derivatives, and crude streams thereof.

[00016] Examples of animal-based oils may include but are not limited to animal fat (e.g., lard, tallow) and lecithin (phospholipids), and combinations, distillates, derivatives, and crude streams thereof.

[00017] Biorenewable oils can also include partially hydrogenated oils, oils with conjugated bonds, and bodied oils wherein a hetcroatom is not introduced, for example but not limited to, diacylglycerides, monoacylglycerides, free fatty acid;..: (and distillate streams thereof), alkyl esters of fatly acids (e.g., methyl, ethyl, pmpyl, and butyl esters), diol and trio! esters (e,g., ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane), and mixtures and derivative streams thereof. An example ofbiorenewable oils may be waste cooking oil or other used oils.

[00018] Petroleum based oil includes a broad range of hydrocarbon-based compositions and refined petroleum products; having a variety of different chemical compositions which are obtained from recovery and refining oils of fossil based original and considered non-renewable in that it takes millions of year to generate crude starting material.

[00019] Tht~ aforementioned biorenewable or petroleum based oils may be polymeriwd wherein polymerization is achieved through crosslinking of the fatty acid chains and/or the glyceride fraction of the tri-glyceride molecules contained in the starting oil material utilizing sulfurization, bodying, blowing, or polyol ester (for example, polyglycerol ester or a castor oil ester, or estolides) polymerization techniques to achieve a targeted oligomeriza:tion and/or Hildebrand solubility parameter, It. shall also be understood that polymerized oil versions may also be blended with straight (i.e., non- 4 polymerized/unmodified) biorenewable or petroleum based oil or modified variations thereof.

[00020] Modified oils can include biorenewable or petroleum based oils modified utilizing maleic anhydride, acrylic acid, hydrogen, dicyclopentadiene, a conjugation via reaction with iodine, or interesterification.

[00021] Despite the oil utilize.d in the rejuvenating composition (biorenewable oil, petroleum based, or polymerization or modifications thereof), the oil has a Hildebrand solubility ranging from about 6 to about 12. Figure 1 illustrates various oils that may be used in the rejuvenating composition and compares oligomer content against Hildebrand solubility.

[00022] Further, the oil utilized in the rejuvenating compositions has a flash point, as measured using the Cleve land Open Cup method. of at least about 1 ()O<'C and no more than about 400°C. In some aspects, the flash point is between about 200°C and about 350°C. In other aspects, the flash point is between about 220°C and about 300°C. In yet other aspects, the flash point is between about 245°C and about 27S°C.

[00023] Specifically regarding a polymerized version ofbiorenewable or petroleum based oil, the viscosity of the polymerized oil will vary based on the type of starting oil material, but generally ranges from about l cSt to about 100 cSt at 100°C, Further, the polymeric distribution ranging from about 2 wt% and about 80 wt% oligomers (20 wt% to 98 wt% monomers), and more preferably betv.·een about l :S wt% to about 60 wt% oligomers (40 wt% to 85 wt~/,, monomers), and even more preferably between about 20 wt%, to about 60 wt% oligomers (40 wt% to 80 ·wt% monomers) is achieved. In even more preferred aspects, the polymeric distribution ranges from about 50 wt% to about 7.5 'Wt°/4 oligomers and about 25 wt"/., to about 50 vvt% monomers, Rejuvenation . .of A_g_ed Bituminous Material

[00024] Asphalt "ages" through a combination of mechanisms, ma.inly oxidation and volatilization. Aging increases asphalt modulus, decreases viscous dissipation and stress relaxation, and increases brittleness at lower performance temperatures. As a result, the asphalt becomes more susceptible to cracking and damage accumulation. The increasing usage of recycled and reclaimed bituminous materials which contain highly aged asphalt binder from sources such as reclaimed asphalt pavements (RAP) and recycled asphalt shingles (RAS) have created a necessity for "rejuvenators" capable of partially or completely restoring the rheological and fracture properties of the aged asphalt. Aging of asphalt has also been shown to increase colloidal instability and phase incompatibility, by increasing the content of high molecular weight and highly polar insoluble "asphalternl' fraction which may increasingly associate, The use of the oils described herein are particularly useful for RAP and RAS applications. The oils described int.his document act as a cornpatibilizer of the asphalt fractions, especially in aged and mddized asphalt, resulting in a balanced and stable asphalt binder with restored pe1formance and durability, [00025) During plant production the asphalt is exposed to high temperatures (usually between 150 to ] 90•:•q and exposure to air during which significant oxidation and voiatil ization ofiighte; fractions can occur leading to an increase in modulus and a decrease in viscous behavior. The aging process is simulflted using a Rolling Thin Film Oven (ASTM D2872) during which a rolling thin film of asphalt is subjected a jet of heated air at about l63"C for about 85 minutes. The rheological properties are measured before and after the aging procedure using a Dynamic Shear Rheometer following ASTM D7175 using the ratio of the IG*!/sino after to before aging, in ,vhich G* is the complex modulus and o is the phase angle, The larger the ratio of the (IG*l/sino) after aging to the (IG*l/sino) before aging, the higher the effect of oxidative aging and volatilization rm the tested asphalt.

[00026] Using this procedure it is shown that asphalts treated with the oils described herein have a lower ratio, thus showing a lower tendency for change in rhe.ologi.cal properties as a result of oxidative aging and volatili.zation.

[00027] Accordingly, the oils described herein have been shown to be capable of rejuvenating aged asphalt binder, and modify the rheological properties of the asphalt binder, As a result, small dosages of the t1il can be used to incorporate high content of aged recycled asphalt material into pavements and other applications resulting in significant economic savings and possible reduction in the environmental impact of the pavement through reduction of use of fresh resources. [000281 Additional components may be added to the oil described herein, for exarnple but not limited to them1oplastlc elastomeric and plastomeric polymers, polyphosphodc acid, anti-snipping additives, warm mix additives. emulsifiers, and/or fibers.

[00029] Notably, the oils described herein may be used to make an emu fr.ion for use in asphalt rejuvenation applications. The emulsion comprises an oil phase and an aqueous phase. The oil phase comprises the oil described herein and may further comprise of asphalt 6 binder and other additives and modifiers, wherein the oil is about O. l to 1 OU vmfo of the oil phase. 111e aqueous phase often comprises a surfactant and may further comprise natural and synthetic polymers (such as Styrene Butadiene Rubber and latex) and/or water phase thickeners.

[00030] The oil phase makes up about 15 to 85 wt.% of the emulsion with the aqueous phase making up the remaining balance. It is unden,tood by those skilled in the art that emulsions are sometimes fuither diluted with water at time of application, thus the effective t)H phase content of the diluted emulsion may be reduced indefinitely. [0003 l J Fmi.her contemplated herein is a method c.omprising applying the emulsion to the surface of an existing pavement or applying the emulsion to treat RAS or RAP and further mixing the treated RAS or RAP with vfrgin asphalt thereby obtaining a 1·ejuvenat.ed asphalt blend.

[00032] The emulsion may also be used as patt of a cold patching material, a high perf ormancc cold patch or cold mix application that contains recycled asphalt thereby obtaining treated RAS or RAP. [00033] rn other aspects, the emulsion may be used for cold-in~place recycling of milled asphalt pavements or hotNin-place recycling of mHled asphalt pavements.

EXAMPLES

[00034] The following examples are presented to illustrate the present invention and to assist one of ordinary skill in making and using same. The examples are not intended in any way to otherwise limit the scope of the invention.

F:xperimental Method

[00035] A charge of precipitated sulfur (mass ranges between 6.S grams to 56.5 grams) is added to a 1 liter round bottom flask containing 650 grams of biorenewable oil.

The reactor is then heated to the target reaction temperature using a heating mantle, taking care not to over shoot the target tempetature by more than 5°C, The reaction mixture is agitated using a motorized stirrer with a stir shaft and blade. The reaction is continuously sparged with nitrogen at 2-i2 standard cubic feet per hour (SCFH). A condenser and l'eceiving flask is used to collect any distillate.

[00036] It is noted that the reaction will create foam around 110-115°C when the sulfur melts into the oil. The reaction is monitored using GPC, to measure the oligomer 7 content and distribution, and viscosity is measured at 40°C following ASTM D44S. The reaction is considered complete when the desired oligomer content and Polydispersity Index has been achieved. The reactor is then cooled to 60°C.

Example 1: Cationic Emulsion of Asphalt Containing Sulfurized Soybean Oil Blend # 1

[00037] A modified asphalt binder comprising: • 95.0% by weight of neat asphalt binder graded as PG64-22 (PG 64.88-24.7) • 5.0% by weight of a blend having: • 59.0% by weight of a sulfurized soybean oil reacted with 7.0% by weight of elemental sulfur at l 60°C for 19 hrs under a Nitrogen sparge. This resulted in a modifier with 70.8% oligomer • 41.0% by weight of straight soybean oil ■ Blend of the sulfurized oil and the soybean oil had about 45.6% oligomer content and a PDI of approximately 3.95.

[00038] The modifier was blended into the asphalt after the binder had been annealed at 150°C for 1 hour.

[00039] The modified asphalt was used as the oil component to make a latex modified cationic rapid set emulsion. The oil phase was 65.0% by total weight of the emulsion. The aqueous phase consisted of the following components: • 0. 70% by weight of emulsion of a cationic quick set imidazoline emulsifier (Anova™ 1620 manufactured by Cargill) • 2.0% by weight of emulsion of Latex (UltraPave™) • HCI in sufficient content to achieve a pH of 2.6

[00040] Incorporation of the polymerized oil in this formulation enables use of this product in rejuvenating surface applications used for pavement maintenance and preservation, especially rejuvenating scrub seal applications, and rejuvenating fog seals and sand seals. Furthermore, the emulsified solution enables use in low unheated paving applications (known as ncold Mixesn) such as cold in place recycling, cold patch, and cold mix pavement layers. Use of rapid-setting surfactant formulations, such as that used in this example, enable rapid buildup of aggregate retention and traffic resistance. As a result, in ideal conditions the road can be opened to traffic within 30 minutes to an hour of the application. The content of polymerized oil will vary depending on the grade of the base oil and the final desired properties. 8 Date Reyue/Date Received 2022-05-19 l\¥w1n?J~J,UDiitimu~tsiaj:t()fA~~twlt;Qtlt'MfifiiVlt•h'JltiJtljiiz$d §6,ftia,htl (>H ·Mlij, Recovetx<LCorn Oil.Blend

[00041] This example demonstrates the use of another polymerized oil that may be used in appl lcations similar to that described in Example# 1.

[00042] A modified asphalt binder comprising: • 95.0% by weight of neat asphalt binder gr-aded as PG64-22 (PG 64.88-24.7) • 5.0% by weight of a blend having: " 59.0% hy weight of a sulfurized soybean oil reacted with 7.00/4 by weight of elemental sulfur at 160°C for 19 hrs under a Nitrogen sparge. This resulted in a modifier with 70,8% oligomer 11 41.0% by weight of recovered com oil 11 Blend of the ~.mlforized oil and the recovered corn oil had about 46.31 % oligomer content and a PDI of approximately 4.40. [00043 J The modifier was blended into the asphalt after the binder had been anneak.>d at 150°C for 1 hour.

[00044] The modified asphalt was used as the oil phase in a latex modified cationic rapid set emuision, The oil phase was 65.0% by total weight of the emulsion. The aqueous phase consisted of the following components: 111 0. 70% by weight of emulsion of a a cationic quick set imidazoline emulsifier (Anova 1620 manufactured by Cargill) • 2.0% by weight of emulsion of Latex (UltraPave) • HCl in sufficient content to achieve a pH of 2.6

[00045] The content of Polymerized Oil win vary depending on the grade of the base oil and the final desired pmperties. t;lQtrn,clv:Catipni0 &nlJ.Jl&lOUQfAspha1t Cm1tainin~ajzcyl So~l OU1}lend #2

[00046] This example demonstrates the use of another polymerized oil that may be used in applications similar to that described in Example #1. [0004 7] A modified asphalt binder comprising: • 95.0% by weight ofneat asphalt binder graded as PG64~22 (PG 64.88-24.7) • 5.0%, by weight of a blend having: 9 11 14.5% by weight ofa. sulfurized soybean oil niacted with 7.0% by weight of elemental sulfur at 160°C for 19 hrs under a. Nitrogen sparge. This resulted in a modifier with 70.8% oligmners "' 85.5% by weight of straight soybean oil "' Blend of the sulfori:7.,ed oil and the straight soybean oil had about 16.59% oligomer content and a PDI of approximately 2.44.

[00048] The modifier was blended into the asphalt after the binder had been annealed at l 50°C for l hour.

[00049] The modified asphalt was used as the oil phase in a latex modified cationic rapid set emulsion. The oil phase was 65.0% by total weight of the emulsion. The aqueous phase consisted of the following components: " 0. 70% by weight of emt1 ls ion of a cationic quick set imidazoline emulsifier (A nova 1620 manufactured by Cargill) • 2.0% by weight of emulsion of Latex (UltraPave) 111 HCI in sufficient content to achieve a pH of 2.6

[00050] The content of Polymer.ized Oil wm vary depending on the grade of the base oil and the final desired properties. i~J.lll\.n1~.¾;.JJ.!l!.9l\!~Jn:a.ffi~i~n)6J1~tthalit~,1#fai1iih~•;~l!!~J~t:lt.~5L~t~hew1,Q!H·l~!¥f••ff:2,

[00051] A modified asphalt binder comprising: • 97.5% by weight of neat asphalt binder graded as PG58-28 • 2.5% by weight of the polymerized oil of Example #3.

[00052] The modifier was blended into the asphalt after the binder had been annealed at 150"C for i hour.

[00053] The modified asphalt was used as the oil phase in a latex modified anionic rapid set emulsion. The oil phase was 67% by total weight of the emulskm. A rapid setting anionic aqueous phase. typically used for RS2-P type emulsions was utilized. The emulsion can be used in rapid setting applications such as chip seals, fog seals, and sand seals. The content of Polymerized Oil wiH vary depending on the grade of the base oil and the final desired propeities.

Example 5: Cationic, Emulsion ofSulforized Soybean Oil Blend f{.l.

[00054] An oil in water cationic emulsion was made using the polymerized oil of Exam pie# l as the "oil phase. "The oil phase was 50% by total weight of the emulsion, The aqueous phase consisted of the following components: • 0.5% by weight of emulsion of a cationic rapid set emulsifier (AA-89, manufactured by MeadWest Vac.o). • HCJ in sufficient content to achieve a pH of2,0~2.2

[00055] This formulation is suitable for rejuvenating surface applications used for pavernent maintenance and preservation, especiaHy rejuvenating fog seals and sand seals.

Furthermore, the emulsified solution enables use in low unheated paving applications (known as "Cold Mixeii') such a.."! cold in place recycling, cold patch, and cold mix pavement layers. Use of rapid-setting surfactant formulations, such as that used in this example, enable rapid buildup of aggregate retention and traffic resistance.

Example 6: Cationic Emulsion ofSulfurized Soybean Oil Blend #2

[00056] This example demonstrntes the use of a quick setting emulsifier in place of a rapid setting emulsifier, for solutions that may be used in applications simila1· to that described in Example #5.

[00057] An oil in water cationic emulsion was made using the following polymerized oil as the "oil phase": • 59.0% by weight of a sulfurized soybean oil reacted with 7.0% by weight of elemental sulfur at 160°C for 19 hrs under a Nitrogen sparge. This resulted in a modifier with 70.8% oligomer • 41. 0% by weight of straight soybean oil • Blend of the sulfud1..ed oil and the soybean oil had about 45.6% oligomer content and a PDl ofapprnximateiy 3,95.

[00058] The oil phase was 50% by total weight ofthe emulsion. The aque-0us phase consisted of the following components: • 0.5°/.; by weight of emulsion of a cationic quick set imidazoline emulsifier (Anova 1620 manufactured by Cargill) • HCI in sufficient content to achieve a pH of 2.0-2.2 11 Examnle 7: Cationic Emulsion of Sulfurized Soybean_ Oil Blend #3

[00059] This example demonstrates the use of another polymerized oil, for solutions that may be used in applications similar to that described in Example #5.

[00060] An oil in water cationic emulsion was made using the following polymerized oil as the "oil phase": • 14.S-io by weight of a sulfurir..ed soybean oil reacted with 7.0% by weight of elemental su !fur at 160°C for 19 hrs under a Nitrogen sparge. This resulted in a modifier with 70.8% oiigomers • 85.5% by weight of straight soybean oil • Blend of the sulfurized oil and the straight soybean oil had about 17% oligomer content

[00061] The oil phase was 50% by total weight of the emulsion. The aqueous phase consisted of the following components: • 0.5% by weight of emulsion of a cationic quick set imidazoline emulsifier (Anova 1620 manufactured by Cargill) • HCl in sufficient content to achieve a pH of 2.0-2.2 •1~~~m,:it~fi,·•·L:~.nF~lli,~ .. •~~~~9n •hit··s.u11~.ti•~g1~~1111:~ilibiadll@.rnwr:fsb~iQmJQUSt4leud: #l ,·~'.'~

[00062] This example demonstrates the use of another polymerized oil, for solutions that may be used in applications similar to that described in Example #5. (00063] An oil in water cationic emulsion was made using the following polymerized oil as the "oil phase": • 59.0% by weight of a sulfurized soybean oil reacted with 7.0% by weight of elemental sulfur at l60°C for 19 hrs under a Nitrngen sparge. This resulted in a modifier with 70.8% oligomer • 41.0% by weight of recovered com oil • Blend of the sulfurized oil and the recovered com oil had about 46.31 % oligomer content and a PD l of approximately 4 AO. (00064] The oiJ phase was 50% by total weight of the emulsion. The aqueous phase consisted of the following components: 12 • 0.5% by weight of emulsion of a cationic quick set imidazoline emulsifier (Anova 1620 manufactured by Cargill) • HCl in sufficient content to achieve a pH of2.0-2.2 f~tulltllej!;J~~~l);t~nfoJ.&l!wl:!iirutgilli!i!fkti:l:t~L~flMMl!!~;.!l.tb1faiJi1$~Q~ii1-ed , l"!$lrti•·Oi•l·•B·te.11d.• #2

[00065] This example demonstrates the use of another polymerized oil, for solutions that may be used in applications similar to that described in Example #5.

[00066] An oil in water cationic emulsion was made using the following polymerized oil as the "oil phase": • 14.5% by weight of a sulfurized soybean oil reacted with 7.0% by weight of elemental sulfur at 160°C for 19 hrs under a Nitrogen sparge. This resulted in a modifier with 70.~% oligomer • 85.5% by weight of recovered corn oil • Blend of the sulforized oil and the recovered com oil had about 16.03% oligomer content and a PDI or approximately 3.28.

[00067] The oil phase was 50% by total weight of the emulsion. The surfactant phase consisted of the following components: • 0.5% by weight of emulsion of a cationic quick set imidazoline emulsifier. • HCl in sufficient content to achieve a pH of 2.0-2.2. •hl~.ittti}cl~JJ?,L,¥E;%!!1L~~;f.;Ji~.tll#<t1H}f8t1lfli~iztt~.s~~e"i(1f{iJ:l •. i.1tid,&~$:~~t~:~l\~~m}~tt,,Ill~JJa, . . ~.t

[00068] This example demonstrates the use ofa triethylamine (TEA) as an emulsifier, utilizing the acid functionality of tbe recovered com oil (AV of approximately 30 mg KOH/g) to produce a surfactant. The resulting product may be used in applications similar to that described in Example #5.

[00069] An oil in water cationic emulsion was made using the following polymerized oil as the "oil phase". The oil phase was 50% by total weight of the emulsion. • 59.m•'o by weight of a sulfurized soybean oil reacted with 7.0% by weight of elemental sulfor at 160°C for 19 hrs under a Nitrogen sparge. This resulted in a modifier with 70.8% oligomer • 41.0% by weight of re.covered com oil 13 • Blend of the sulfuri:r..ed oil and the recovered corn oil had about 46.31% oligomer content and a PDI of approximately 4.40. • TEA was added at 0. 75% by weight of the polymerized oil and blended into the oil phase ·fuwnn·ie•.1 .• 1· .. :·(~tlth~ltk~tt''s:ult\t:&'i?,~~~l:Rt,yl){.t<,1,tl.·()•1f.Hfon.dJ1sli1;f.~MethvJ'·.•nsfar

[00070] A "cutback" formulation was made using Soy Methyl Ester and a polymerized oil. This product is suitabki for use in low temperature and unheated paving applications (known as "Cold Mixes") such as cold in place recycling, cold patch, and cold mix pavement layers.

[00071] The cutback contained the following material, blended. at 60°C: • 59.0% by weight of a sulfurized soybean oil reacted with 7.0t% by weight of elemental sulfor at 160"'C for 19 hrs under a Nitrogen sparge. This resulted in a modifier with 70.8% oligomer • 8.5'H, by weight of straight soybean oil • 32.3 % by weight of Soy Methyl Ester [00072] 111e resulting cutback blend of the sulfuifaed oil had the following properties: • Oligomer content of about 50. l % • PDI of apprnximately 4.12 • Density at 25"C of 0.934 g!ml • Viscosity at 40°C of 90.4 cSt • Visc,osity at 25C of 150 cSt 14

Claims (29)

1. CLAIMS 1. A rejuvenating composition for asphalt applications, the composition comprising: a polymerized oil comprising a starting oil crosslinked with elemental sulfur, the polymerized oil having a polymeric distribution ranging from about 2 wt% to about 80 wt% oligomer content, wherein the oligomer is defined as a polymer having a number average molecular weight (Mn) larger than 1000, and a Hildebrand solubility ranging from about 6 to about 12.
2. 2. The composition according to claim 1, wherein the polymerized oil has a flash point of about 100°C to about 400°C.
3. 3. The composition according to claim 1 or 2, further comprising asphalt.
4. 4. The composition according to any one of claims 1 to 3, further comprising recycled asphalt.
5. 5. The composition according to any one of claims 1 to 4, further comprising a biorenewable oil or petroleum based oil.
6. 6. The composition according to any one of claims 1 to 5, further comprising a modified oil.
7. 7. The composition according to any one of claims 1 to 6, wherein the starting oil is a biorenewable oil or petroleum based oil.
8. 8. The composition according to any one of claims 1 to 7, further comprising thermoplastic elastomeric polymers, thermoplastic plastomeric polymers, polyphosphoric acid, anti-stripping additives, warm mix additives, emulsifiers and/or fibers.
9. 9. The composition according to any one of claims 1 to 8, wherein the crosslinking comprises heating to about 130°C to about 250°C.
10. 10. The composition according to any one of claims 1 to 8, wherein the crosslinking comprises heating to about 130°C to about 220°C. 16
11. 11. The composition according to any one of claims 1 to 8, wherein the crosslinking comprises heating to about 160°C to about 200°C.
12. 12. The composition according to any one of claims 1 to 11, wherein the polymerized oil has a sulfur content of about 0.01 wt % to about 8 wt %.
13. 13. The composition according to any one of claims 1 to 12, wherein the composition is an emulsion.
14. 14. A method comprising applying the composition according to any one of claims 1 to 13 to an existing pavement surface.
15. 15. A method comprising applying the composition according to any one of claims 1 to 13 to treat recycled asphalt shingles (RAS) or reclaimed asphalt pavement (RAP) and further mixing the treated RAS or RAP with virgin asphalt thereby obtaining a rejuvenated asphalt blend.
16. 16. Use of the composition according to claim 13 as part of a cold patching material, a high performance cold patch or a cold mix application each of which contains recycled asphalt.
17. 17. Use of the composition according to claim 13 for cold-in-place recycling of milled asphalt pavements.
18. 18. Use of the composition according to claim 13 for hot-in-place recycling of milled asphalt pavements.
19. 19. A rejuvenating composition for asphalt applications, the composition comprising: a modified oil crosslinked using sulfurization to achieve polymerization, the polymerized modified oil having a polymeric distribution ranging from about 2 wt% to about 80 wt% oligomer content, the oligomer being a polymer having a number average molecular weight (Mn) larger than 1000, the polymerized modified oil having a Hildebrand solubility ranging from about 6 to about 12 and a flash point ranging from about 100°C to about 400°C. 17
20. 20. The composition according to claim 19, wherein the modified oil is modified utilizing maleic anhydride, acrylic acid, hydrogen, dicyclopentadiene, a conjugation via reaction with iodine, or interesterification.
21. 21. The composition according to claim 19 or 20, further comprising asphalt.
22. 22. The composition according to any one of claims 19 to 21 further comprising recycled asphalt.
23. 23. The composition according to any one of claims 19 to 22, further comprising thermoplastic elastomeric polymers, thermoplastic plastomeric polymers, polyphosphoric acid, anti-stripping additives, warm mix additives, emulsifiers and/or fibers.
24. 24. The composition according to any one of claims 19 to 23, wherein the composition is an emulsion.
25. 25. A method comprising applying the composition according to any one of claims 19 to 24 to an existing pavement surface.
26. 26. A method comprising applying the composition according to any one of claims 19 to 24 to treat recycled asphalt shingles (RAS) or reclaimed asphalt pavement (RAP) and further mixing the treated RAS or RAP with virgin asphalt thereby obtaining a rejuvenated asphalt blend.
27. 27. Use of the composition according to claim 24 as part of a cold patching material, a high performance cold patch or cold mix application each of which contains recycled asphalt.
28. 28. Use of the composition according to claim 24 for cold-in-place recycling of milled asphalt pavements.
29. 29. Use of the composition according to claim 24 for hot-in-place recycling of milled asphalt pavements.