Micronized asphalt modifiers, methods of modifying asphalt, asphalt compositions and methods of making

Abstract

An asphalt additive comprising a primary rheology modifying component and a secondary rheology modifying component, and asphalt compositions and products having such additive incorporated therein. The primary rheology modifying component is generally a polymer, and the secondary rheology modifying component may comprise a petroleum micro-wax.

Claims

1. An asphalt comprising: a first component comprising a low asphaltine petroleum asphalt having an asphaltene content in the range of about 3 to 5 wt %; and, a second component comprising particles of polypropylene resin; wherein the resin particles have a diameter less than about 420 microns.

2. The asphalt of claim 1, further comprising glycidyl functional terpolymers, a wax, and ground tire rubber.

3. The asphalt of claim 1, further comprising a wax, ground tire rubber and at least one of reactive elastomeric terpolymers, polymers having glycidyl functionality, polymers having glycidyl acrylate functionality, and polymers having epoxide functionality.

4. The asphalt of claim 2, wherein the resin particles have a diameter less than about 297 microns.

5. The asphalt of claim 1, wherein the resin particles have a diameter less than about 250 microns.

6. The asphalt of claim 3, wherein the resin particles have a diameter less than about 177 microns.

7. The asphalt of claim 1, wherein resin particles have a diameter less than about 149 microns.

8. A method of treating a petroleum asphalt having an asphaltene content, the method comprising: contacting a petroleum asphalt with particles of resin component, wherein the resin is polypropylene and the aspahaltene content is in the range of about 3 to 5 wt %, and the resin particles have a diameter less than about 420 microns.

9. The method of claim 8, wherein the resin particles have a diameter less than about 177 microns.

10. The method of claim 8, wherein the resin particles have a diameter less than about 250 microns.

11. The method of claim 8, wherein the resin particles have a diameter less than about 297 microns.

12. The method of claim 8, wherein the resin particles have a diameter less than about 37 microns.

13. An asphalt comprising: a first component comprising a petroleum asphalt having an asphaltene content; a second component dispersed in the asphalt comprising resin particles; and, a third component dispersed in the asphalt selected from the group consisting of ground tire rubber and polymers of styrene and butadiene, wherein the resin is polypropylene and the aspahaltene content is in the range of about 3 to 5 wt %, and the resin particles have a diameter less than about 420 microns.

14. The asphalt of claim 13, wherein the resin particles have a diameter less than about 297 microns.

15. The asphalt of claim 13, wherein the resin particles have a diameter less than about 177 microns.

16. The asphalt of claim 13, further comprising glycidyl functional terpolymers, and a wax.

17. The asphalt of claim 13, wherein the asphalt when tested according to ASTM D 7173 has a temperature differential of less than or equal to a 10 C. (18 F.) temperature differential using ASTM D 7173.

18. The asphalt of claim 13, wherein the asphalt when tested according to ASTM D 7173 has a temperature differential of less than or equal to a 6 C. (10.8 F.) temperature differential using ASTM D 7173.

19. The asphalt of claim 13, wherein the asphalt when tested according to ASTM D 7173 has a temperature differential of less than or equal to a 4 C. (7.2 F.) temperature differential using ASTM D 7173.

20. The asphalt of claim 13, wherein the asphalt when tested according to ASTM D 7173 has a temperature differential of less than or equal to a 2 C. (3.6 F.) temperature differential using ASTM D 7173.

21. A method of modifying a petroleum asphalt having an asphaltene content, the method comprising: forming a composition comprising the petroleum asphalt, a first component, a second component, a third component and a fourth component to form a modified asphalt, wherein the first component comprises polypropylene resin particles; the second component comprises wax, and the third component is a glycidyl functional polymer, and the fourth component is selected from the group consisting of ground tire rubber and polymers of styrene and butadiene, wherein the aspahaltene content is in the range of about 3 to 5 wt %, and the resin particles have a diameter less than about 420 microns.

22. The method of claim 21, wherein the resin particles have a diameter less than about 250 microns.

23. The method of claim 21, wherein the resin comprises glycidyl methacrylate functionality.

24. The method of claim 21, wherein the resin particles have a diameter less than about 297 microns.

25. The method of claim 21, wherein the resin comprises an ethylene-butyl acrylate-glycidyl methacrylate polymer.

26. The method of claim 21, wherein the resin particles have a diameter less than about 250 microns.

27. The method of claim 21, wherein the modified asphalt when tested according to ASTM D 7173 has a temperature differential of less than or equal to a 10 C. (18 F.) temperature differential using ASTM D 7173 and the resin particles have a diameter less than about 250 microns.

28. The method of claim 21, wherein the modified asphalt when tested according to ASTM D 7173 has a temperature differential of less than or equal to a 6 C. (10.8 F.) temperature differential using ASTM D 7173.

29. The method of claim 21, wherein the modified asphalt when tested according to ASTM D 7173 has a temperature differential of less than or equal to a 4 C. (7.2 F.) temperature differential using ASTM D 7173.

30. The method of claim 21, wherein the modified asphalt when tested according to ASTM D 7173 has a temperature differential of less than or equal to a 2 C. (3.6 F.) temperature differential using ASTM D 7173.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

(2) FIG. 1 is TABLE 7, Separation Test Results for Test Highway using Rheopave 10XP.

(3) FIG. 2 is TABLE 9, PG67-22 Base Asphalt Upgraded to PG76-22 GTR with MSCR Specification.

(4) FIG. 3 is TABLE 11 for PG (ARB)-22 Test Sections.

(5) FIGS. 4A and 4B are TABLE 12, Part 1 and TABLE 12, Part 2, respectively, showing certification for the Rheopave modified asphalt.

(6) FIGS. 5A and 5B are TABLE 13, Part 1 and TABLE 13, Part 2, respectively, showing certification for the Rheopave modified asphalt.

(7) FIG. 6 is TABLE 5 showing the results of a 10% GTR FORMULATION IN 67-22, subjected to various testing.

(8) FIG. 7 is TABLE 6 showing a comparison of PG64-22 TO PG76-22TR RHEOPAVE XP10 VS. VESTENAMER 8021 (a cyclo octene polymer), with both subjected to various testing.

DETAILED DESCRIPTION OF THE INVENTION

(9) This invention describes an additive used as an asphalt binder modifier that in some embodiments includes a polymer component that is the primary rheology modifying component, and a secondary rheology modifying component. In some non-limiting embodiments of the present invention, the primary rheology modifying component and the secondary rheology modifying component are melted together into a single liquid phase before being formed into a solid asphalt additive. In other non-limiting embodiments, the additive comprises only the primary rheology modifying component(s). This invention may find applicability with any type of asphalt including straight asphalt and blown asphalt. As a more particular non-limiting example, this invention finds applicability in paving applications with straight asphalt. As non-limiting examples, the additive may be in some sort of solid form, non-limiting examples of which include a one pack additive in pastille, bead, pill or granule form. In some non-limiting embodiments, the additive provides for Pavement and Roofing applications that meet the target Performance Grading (PG) in terms of binder stiffness (as measured by the Dynamic Shear Rheometer or Softening Point) and Low Temperature flexibility (as measured by Bending Beam Rheometer or Fraas Breaking point or Mandrel Bending Test). Further, this invention may be formulated by specific design to produce the desired binder within the Warm Mix Asphalt concept for Paving applications as well as reduced temperature and enhanced application speeds for Roofing applications. In other non-limiting embodiments, the additive of the present invention functions to stabilize ground tire rubber in asphalt as measured by the cigar tube test.

(10) Some embodiments of the present invention may also find use in providing roofing and paving materials having improved UV resistance.

(11) Some non-limiting methods of the present invention may obviate the need for grinding of polymers at the point of mixing with bitumen.

(12) Some non-limiting embodiments of the present invention may facilitate the addition of crumb rubber to asphalt.

(13) Some non-limiting embodiments of the present invention may prevent or reduce phasing of crumb rubber in asphalt formulations.

(14) In some embodiments, the combined effect of the additive package may be to reduce the asphalt aggregate mixing, transportation, lay down and/or compaction temperatures, by between 10 C. (50 F.) to 32 C. (90 F.) as a non-limiting example. Further, in certain embodiments, this invention may provide the benefit of enhancing the useful temperature range of the modified asphalt binder. This additive may be used to modify the asphalt binder first and then add to the aggregate mix or it may be added directly to the aggregate mixing drum whether a continuous drum mixer or a batch mixer. Some embodiments provide ease of transportation, storage and handling.

(15) The present invention utilizes one or more polymers as the primary rheology modifying component. In some non-limiting embodiments, this primary rheology modifying component may be a polyolefin homo-polymer or copolymer resins. In some non-limiting embodiments, the polyolefin homopolymer or copolymer is a poly -olefin (PAO), which may be formed from polymerizing same (in the case homopolymer) or 2 or more different (in the case of copolymer) C2 to C36 -olefins (i.e. -olefins having from 2 to 36 carbon atoms). The PAO copolymers may be formed by mixing 2 or more already formed PAO's, by copolymerizing 2 or more different PAO's, by copolymerizing 2 or more different -olefins, or any combination of the foregoing. In non-limiting examples, these polyolefin resins may include polyethylene (PE) homopolymers, polypropylene (PP) homo-polymer and polypropylene/polyethylene (PP/PE) co-polymer resins and by-product waxes in asphalt modification. Since these resins have a substantially higher melting point (above 140 C.) than the base asphalt binder (approximately 60 C.), the use of such resins has been excluded since the asphalt binder would degrade and become a fume emission hazard at such high temperatures. The technology described herein is novel in producing a compound of certain polymers, as a non-limiting example the PE homo-polymer, PP Homo-polymer and/or PP plus PE co-polymer, such that the compound is uniquely dispersible in asphalt binder at the safe and usual operating temperatures. In some non-limiting embodiments, the resin is combined with a binder (in some embodiments melted together). Without being limited by theory, applicants believe that when the particles of polyolefin resin/binder (or in general the primary rheology modifying component) are heated to the melt point of the binder (or in general the secondary rheology modifying component), the binder materials quickly melt and physically partition the resin molecules such that the resin will fall apart in the hot/warm asphalt base and disperse quickly and homogenously. In this way the additive value in certain embodiments may be realized to bump the high temperature PG to the desired level whilst at the same time taking the Low temperature PG value to the desired grade i.e. the unique ability to stretch the PG box or escalate the useful performance temperature range of the asphalt binder.

(16) A non-limiting example of suitable polyolefin materials include polyethylene (PE) homo-polymer or polypropylene (PP) homo-polymer having a molecular weight in the range of about 20,000 to about 200,000. A non-limiting example of suitable PP plus polyethylene (PE) co-polymer includes those having a molecular weight in the range of about 20,000 to about 200,000.

(17) A second aspect of this novel invention is that the systems described herein meets the requirements of Warm Mix Asphalt Paving.

(18) This invention describes an asphalt/bitumen additive formulation that may be used in combination with modified or unmodified asphalt binder and aggregates to produce an aggregate paving mixture used to pave roads/pavements. In some non-limiting embodiments, the primary rheology modifying component comprises a polyolefin homo-polymer and/or copolymer in any ratio. Some non-limiting embodiments employ PE homo-polymer resin, PP Homo-polymer resin or PP plus PE co-polymer resin or combinations of these in any ratio. As a non-limiting example, the resins described herein have a melting point range of 266 F. (130 C.) to 482 F. (250 C.) and above.

(19) While the primary rheology modifying component (i.e., resin component) is mostly described herein in terms of polyolefins, the primary rheology component should not be considered so limited, as there are other polymers that are believed to also be useful as the primary rheology modifying component in the present invention, including, but not limited to ethylene vinyl acetate; polystyrene; styrene butadiene block copolymer (SB); styrene ethylene butylene styrene (SEBS); natural rubber, synthetic rubber (most commonly styrene-butadiene rubbers (SBR) derived from the copolymerization of styrene and 1,3-butadiene; but may also include synthetic rubbers are prepared from isoprene (2-methyl-1,3butadiene), chloroprene (2-chloro-1,3-butadiene), and isobutylene (methylpropene) with a small percentage of isoprene for cross-linking); reactive elastomeric terpolymers (RET) a non-limiting example of which includes alkylene-alky acrylate-glycidyl acrylate terpolymers; polymers having glycidyl or glycidyl acrylate functionality a non-limiting example of which includes alkylene-alkylacrylate-glycidyl acrylate terpolymers, and polymers having an epoxide functionality. A non-limiting example of a suitable alkylene-alklyacrylate-glycidyl acrylate terpolymers includes ethylene-butyl acrylate-glycidyl methacrylate terpolymers, a commercial example of which are Elvaloy terpolymers.

(20) In some embodiments, the primary rheology modifying component will comprise at least one PAO selected from the group consisting of homopolymers and copolymers formed from -olefins having 2 or more carbon atoms.

(21) In some embodiments, the primary rheology modifying component will comprise at least one selected from the group consisting of polyethylene homopolymer, homopolymers formed from -olefins having more then 3 carbon atoms, and copolymers formed from 2 or more different -olefins having 2 or more carbon atoms.

(22) As a non-limiting example, certain embodiments of the present invention utilize as the primary rheology modifying component, a reactive elastomeric terpolymer which in some embodiments may be in combination with polystyrene, styrene butadiene block copolymer (SB), styrene ethylene butylene styrene (SEBS), and styrene-butadiene rubbers (SBR).

(23) As another non-limiting example, certain embodiments of the present invention utilize as the primary rheology modifying component polymers having glycidyl methacrylate functionality which in some embodiments may be in combination with polystyrene, styrene butadiene block copolymer (SB), styrene ethylene butylene styrene (SEBS), and styrene-butadiene rubbers (SBR).

(24) Polymers with epoxide functionality, include those derived from bisphenols, non-limiting examples of which include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z.

(25) Some embodiments of the present invention provide the use of a secondary rheology modifying component having a lower melting point than the primary rheology modifying component, that when the additive is subjected to the hot/warm asphalt base, the secondary rheology modifying component(s) quickly melts and physically partitions the primary rheology modifying component(s) such that the primary rheology modifying component(s) will fall apart in the hot/warm asphalt base and disperse quickly and homogenously. The main requirement of the secondary rheology modifying component is that it have a lower melting point that the primary rheology modifying component, and will quickly melt when the additive is introduced to the hot/warm asphalt. The quicker that the secondary rheology modifying component can melt than the primary rheology modifying component when the additive is exposed to the hot/warm asphalt base, the better. It is believed that a wide range of polymers may function as the secondary rheology modifying component.

(26) As non-limiting examples, some embodiments may employ a secondary rheology modifying component which may comprise a petroleum micro-wax obtained from conventional crude refining. This secondary rheology modifying component, or binder for the primary rheology modifying component, may act as a partitioning/dispersion agent for the primary rheology modifying component, and can be any one of waxes, vegetable oils and most hydrocarbons in the melt point range of 70 C to 135 C.

(27) This secondary rheology modifying component may be referred to herein as a binder, dispersant, or binding, dispersing or partitioning agent. As a non-limiting example, a suitable wax may have a melting point range between 140 F. (60 C.) to 239 F. (115 C.). In some non-limiting embodiments, it may be at times be desired to use a blend of two or more separate micro-waxes in the above melt range to achieve the desired rheology properties. The dispersing effect may also be achieved through the use of an additional component that is either Crude Tall Oil (CTO) or an oxidized Tall Oil Pitch. Non-limiting examples of other secondary rheology modifiers that may be used alone or in any combination may be Low Molecular Weight PE Waxes, Fischer-Tropsch Waxes, Petroleum Paraffin Waxes, Montan Wax, SBS, SBR, Natural and Synthetic Latex, Trinidad Lake Asphalt, Gilsonite and other natural asphalts, Crumbed Tire Rubber, etc. As a non-limiting example a polyethylene (PE) wax having a molecular weight in the range of about 650-2500, although a PE wax having a molecular weight greater or less than that range may also be suitable. As another non-limiting example, a Fischer-Tropsch wax having a molecular weight in the range of about 450-1200, although a Fischer-Tropsche wax having a molecular weight greater or less than that range may also be suitable. Another non-limiting example of suitable secondary rheology modifying components includes reactive elastomeric terpolymers (RET) a non-limiting example of which includes alkylene-alky acrylate-glycidyl acrylate terpolymers; polymers having glycidyl or glycidyl acrylate functionality a non-limiting example of which includes alkylene-alkylacrylate-glycidyl acrylate terpolymers, and polymers having an epoxide functionality. A non-limiting example of a suitable alkylene-alklyacrylate-glycidyl acrylate terpolymers includes ethylene-butyl acrylate-glycidyl methacrylate terpolymers, a commercial example of which are Elvaloy terpolymers.

(28) The additive package described above may contribute to the Warm Mix in the following manner:

(29) (a) In some non-limiting embodiments, the reduction in viscosity of the asphalt binder may be achieved through the combination of rheology/viscosity modifiers described above, that in turn reduces the viscosity of the aggregate mix making it possible to compact the mix at the lower temperatures in the Warm Mix range.

(30) (b) In some non-limiting embodiments, the CTO and or oxidized tall oil pitch acts as a dispersing agent for the primary rheology modifying component, (as a non-limiting example, polyolefin homo-polymer and co-polymer resins), and may further reduce the viscosity of the additive package thereby contributing to further improvements in compaction and increasing the useful paving window.

(31) (c) In some non-limiting embodiments, the combination of the primary rheology modifying component (as a non-limiting example polyolefin homo-polymer and co-polymer resins) may contribute to the binder stiffness at the pavement performance temperature producing the effect of a performance grading grade bump.

(32) (d) In some non-limiting embodiments, the combination of micro-waxes provides the effect of viscosity reduction at the paving temperatures while contributing to the binder and pavement flexibility at Low Temperatures during winter periods. In this way the stiffness of the binder may be offset at Low Temperature Performance.

(33) (e) In some non-limiting embodiments, the CTO and oxidized CTO may perform as adhesive agents linking the asphalt binder to the aggregate surfaces.

(34) Different combinations of the secondary rheology modification component may be used to achieve the specific desired specification/property such that several grades of the additive may be commercially produced.

(35) The additive invention described above can easily be used in any conventional Hot Mix asphalt to reduce the asphalt mix production, transportation, paving and compaction temperatures. As a non-limiting examples, to reduce temperatures by between 10 C. (50 F.) to 32 C. (90 F.). The additive package may be first added to the asphalt binder and the so modified binder may be added to the aggregate mix in a continuous drum mixer or batch mixer. Also, the additive package may be added directly to the aggregate mix in a continuous drum mixer or a batch mixer immediately after the binder comes into contact with the aggregate.

(36) The additive package may also be used for surface dressings such as hot applied chip seals, slurry seals and such surface dressings as a viscosity reducer and to eliminate the use of volatile cut back solvents and associated fume emissions. Such Warm Mix applications may also include coatings and sealants for moisture protection as well as solvent and chemical resistance mixtures.

(37) The additive package described herein may also be used in Roofing applications as follows:

(38) (1) In a non-limiting example for the manufacture of roofing shingles, the asphalt binder may be modified with the described additive package to meet the target specifications (Softening Point, Penetration, Flash Point, Ductility, Tensile Strength, and/or UV resistance, etc.) and may then be coated onto the non-woven substrate (usually glass fiber).

(39) (2) In a non-limiting example for the manufacture of Built Up Roofing (BUR) grades or Mopping Grades, the additive package described herein may be used to modify the asphalt binder to achieve the desired specifications (Softening Point, Penetration, Flash point, Ductility, Tensile Strength, etc.) and then used for Hot Applied or Emulsion Applied coatings.

(40) (3) In a non-limiting example, the additive package may be used to manufacture adhesive coatings for roofing applications.

(41) (4) In a non-limiting example, the additive package described herein may be used in asphalt feed stocks prior to blowing to harden the binder through oxidation. As a non-limiting example the additive package will be present in the at 0.5% up to 10% range by weight, although more than 10% and less than 0.5% are also believed to be beneficial. The benefits of this additive are reduced batch cycle times for example by 20% to 35%, less aging of the blown binder, lower viscosity and workability of the blown binder and easier achievement of target specifications. Also, this technology may enable the blowing methods to operate on a wider available pool of asphalts including fluxes and paving grades to achieve the same target specifications. In some embodiments in which the blowing operation can actually be operated at lower blowing temperatures, a wider pool of asphalts may become available for blowing.

(42) The polyolefin homo-polymer and copolymer utilized herein may be obtained by any suitable method and means, using any suitable catalyst as is well known in the polyolefin art. As a non-limiting example, suitable polyolefin may be derived from olefins having from about 2 to about 36 carbon atoms, or may comprise blends of two or more of such polyolefins, or may comprises copolymers of two or more such olefins. As a non-limiting example, PP homo-polymer and PP plus PE co-polymer may be derived from the manufacture of PP resins either as a by-product stream(s) or as intermediate grades during the changeover form one grade to the next. These streams may be collected from the process and segregated into several qualities and which may be combined again to yield product that is suitable for specific asphalt applications either as such or in combination with the secondary rheology modifying agent described herein.

(43) As a non-limiting embodiment, when manufactured as a compound, the resin or by-product wax content of the additive package may comprise in the range of 5% to 95% and preferably in the range of 50% to 85%. The Melting Point of the resin or by-product wax component is in the range of 120 C (248 F) to 200 C (392 F) and preferably in the range of 130 C (266 F) to 175 C (347 F).

(44) In some non-limiting embodiment, the resin component may comprise a Needle Penetration at 77 F. in the range of 0 to 10 (units being 0.1 mm).

(45) The resin component or primary rheology portion serves as a one component of the rheology/viscosity modifier and may also contribute to the overall binder stiffness at the pavement performance temperature as measured by the Dynamic Shear Rheometer.

(46) Any suitable petroleum wax may be utilized in the present invention as desired. As a non-limiting example, the petroleum micro-wax may be derived from crude oil refining processes. One non-limiting example of a suitable petroleum was has a melting point in the range of 150 F. (66 C.) to 220 F. (104 C.). A combination of two or more separate micro-wax streams may also be used at times to achieve the desired effect. In some embodiments, the micro-wax may serve a dual purpose of viscosity modifier as well as to impart Low Temperature Performance flexibility to the asphalt binder and pavement mix.

(47) The content of micro-wax in the additive package can be in the range of from 2, 5, 10, 15, 20, 30, 40, 50 60, 70 80 wt % to 50, 60, 70, 80, 90, 95, and 99 wt %. As non-limiting examples in the range of about 2 to 50 wt %, and in the range of 10 to 20 wt %.

(48) In general, microcrystalline waxes are a type of wax produced by de-oiling petrolatum, as part of the petroleum refining process. In contrast to the more familiar paraffin wax which contains mostly unbranched alkanes, microcrystalline wax contains a higher percentage of isoparaffinic (branched) hydrocarbons and naphthenic hydrocarbons. It is characterized by the fineness of its crystals in contrast to the larger crystal of paraffin wax. It consists of high molecular weight saturated aliphatic hydrocarbons. It is generally darker, more viscous, denser, tackier and more elastic than paraffin waxes, and has a higher molecular weight and melting point. The elastic and adhesive characteristics of microcrystalline waxes are related to the non-straight chain components which they contain. Typical microcrystalline wax crystal structure is small and thin, making them more flexible than paraffin wax.

(49) Microcrystalline waxes when produced by wax refiners are typically produced to meet a number of ASTM specifications. These include congeal point (ASTM D938), needle penetration (D1321), color (ASTM D6045), and viscosity (ASTM D445). Microcrystalline waxes can generally be put into two categories: laminating grades and hardening grades. The laminating grades typically have a melt point of 140-175 F and needle penetration of 25 or above. The hardening grades will range from about 175-200 F, and have a needle penetration of 25 or below. Color in both grades can range from brown to white, depending on the degree of processing done at the refinery level.

(50) Microcrystalline waxes are derived from the refining of the heavy distillates from lubricant oil production. This by product then must be de-oiled at a wax refinery. The product then may have its odor removed and color removed (which typically starts as a brown or dark yellow). This is usually done by means of a filtration method or by hydro-treating the wax material.

(51) A non-limiting example of a suitable crude oil derived micro-wax may have the following properties: Drop Melt Point (ASTM D 127) in the range of 150 F. (66 C.) to 220 F. (104 C.); and Kinematic Viscosity (ASTM D445) at 212 F. (100 C.) in the range 10 to 320 centi-stokes.

(52) Any suitable Crude Tall Oil and Oxidized Tall Oil Pitch Component may be utilized in the present invention. As a non-limiting example, the crude tall oil and oxidized tall oil pitch component can be in the range of 2% to 20% of the formulation and preferably in the range of 2% to 10% of the formulation. The function of the oxidized tall oil pitch is as a dispersant for the resins so that it is evenly distributed in the final asphalt mixture to impart a consistent stiffness modulus to the asphalt binder as well as to the asphalt mix.

(53) As used herein, including the claims, tall oil materials includes man made and naturally occurring tall oil, tall oil pitch, tall oil blends, and similar tall oil products. Tall oil is a liquid resinous material that may be obtained in the digestion of wood pulp from paper manufacture. Commercial tall oils comprise a complex of fatty acids, resin acids, sterols, higher alcohols, waxes and hydrocarbons. The acid components also may be present as the esters thereof.

(54) A common source of tall oil that may be used in the practice of the present invention is from pine trees. Besides cellulose, tall oil contains fatty acids, esters, rosin acids, sterols, terpenes, carbohydrates and lignin. These may be separated when wood is converted to paper pulp by the sulfide or Kraft process. The acids may then be neutralized in an alkaline digestion liquor. The mixture of rosin and fatty acid soap may be recovered by subsequent acidification that releases free rosin and fatty acids, the major constituents of tall oil.

(55) A non-limiting example of a suitable oxidized tall oil pitch may have the following properties: Softening Point in the range of 125 F. (52 C.) to 220 F. (104 C.); and Needle Penetration value at 25 C. in the range of 2 to 40 and preferably in the range of 5 to 20.

(56) Some embodiments of the additive package of the present invention described herein may provide one or more of the following advantages over other Warm Mix products:

(57) (a) Some non-limiting embodiments may be in the form of a one pack product that can be easily transported globally and handled to be added either to the asphalt binder and then to the aggregate mix as modified binder or it may be added directly to the aggregate mixing drum.

(58) (b) In some non-limiting embodiments, the aggregate particles may be evenly coated with binder due to the lower surface tension imparted by the additive package to the binder. Also, the aggregate coated binder is not as sticky as conventionally mixed aggregate and this influences the workability of the aggregate mix and makes to less sticky onto transportation and paving equipment. Also, the compacted pavement may support traffic quickly without having any issues of stickiness onto traffic wheels.

(59) (c) In some non-limiting embodiments, the high temperature PG (ie. the stiffness modulus) of the additive modified binder may be improved without or with little degrading of the Low Temperature PG.

(60) (d) In some non-limiting embodiments, the additive may be detected and quantified in binder samples or aggregate mix samples or field core samples at any time during the life of the pavement and this is unlike most Warm Mix technologies that merely dissipate and can no longer be detected with passage of time.

(61) Some embodiments of the present invention may incorporate one or more other Rheology Modifying Components. Non-limiting examples of such components may be as follows.

(62) 1. Polyethylene By-Product Waxes (polyethylene waxes or PE waxes) in the melt Point range of 100 C to 160 C. The content of the by-product PE wax can be in the range of 5% to 50% and preferably 5% to 20%. The purpose of the by-product PE wax is as a dispersant for the resin component as well as viscosity modifier.

(63) 2. Fischer-Tropsch Hard Wax in the melting point range of 70 C to 115 C in the same content as described in (1) above.

(64) 3. SBS (styrene butadiene styrene), SB (styrene butadiene), SEBS (styrene ethylene butadiene styrene), SBR (stryrene butadiene rubber), Natural and Synthetic Latex, Crumb Tire Rubber and a polymer having glycidyl acrylate functionality, as a non-limiting example, Elvaloy Terpolymer, in the same content as described in (1) above. Elvaloy terpolymer is a commercially available ethylene-butyl acrylate (BA)-glycidyl methacrylate (GMA) terpolymer from DuPont, and may have compositions such as 28 wt % BA and 5.3 wt % GMA or 20 wt % BA and 9 wt % GMA (the balance being ethylene in both).

(65) 4. Trinidad Lake Asphalt (TLA), Gilsonite, Montan Waxes and natural Rubber in the same content as described in (1) above.

(66) 5. Petroleum micro waxes as described above.

(67) A non-limiting example of the present invention includes first contacting the polymeric primary rheology modifying component and the dispersant secondary rheology modifying component together prior to adding either to the asphalt. As a non-limiting example, the polymer and the dispersant may both be melted and then thoroughly mixed together before being reformed into particles which may then be added to the asphalt. The melting may be accomplished separately with the melted materials then added together, or may be accomplished separately but simultaneously with the melted materials then added together, or may be accomplished simultaneously with the unmelted materials contacted together and then melted, or may be accomplished sequentially with the melted materials then added together, or may be accomplished by first melting one than contacting it with the unmelted one and then further melting of both. As another non-limiting example, polymer particles may be mixed into the melted dispersant with this mixture then formed into particles which may then be added to the asphalt. As even another non-limiting example, a dry mix of polymer particles and dispersant particles may first be formed, and this mix added directly to the asphalt, or the dry mix may then be melted and formed into particles which may then be added to the asphalt. As a further non-limiting example, the invention may also include use of a cross-linking pre-cursor is incorporated into the mixture to initiate active sites on the PP molecule chain and create a network structure in asphalt to give unique stiffness modulus properties, separation, stability and UV light protection. In the practice of the present invention, selected additives are chosen that are effective dispersing agents that partition between the PP molecules and thereby cause the PP to fall apart and disperse in asphalt binders. The polymer and dispersant may be formed into particles utilizing any suitable method/apparatus, including extrusion and subsequent cutting, pelletizing and the like. As a non-limiting embodiment, pellets may be formed from a mixture of a polyolefin and a wax (or in general from the primary rheology modifying component(s) and secondary rheology modifying component(s)). A melted mixture may be formed by melting the polyolefin and wax together in any desired order (i.e., sequentially melting one and then melting the other and then mixing, sequentially melting one and then mixing with the other unmelted and then melting the mixture, simultaneously apart and then mixing, simultaneously together, or any other suitable order/arrangement). A solid form of the additive, non-limiting examples of which include particles, pellets, pills, powder, pastilles, beads, granules, or the like may be formed by any suitable method with any suitable apparatus including extrusion, pelletizing, cutting, chopping and the like.

(68) In even another non-limiting embodiment pellets may be formed from a mixture of a polyethylene homopolymer, polypropylene homopolymer or polypropylene/polyethylene copolymer and a wax (or in general from the primary rheology modifying component(s) and secondary rheology modifying component(s)). A melted mixture may be formed by melting the polymer and wax together in any desired order (i.e., sequentially melting one and then melting the other and then mixing, sequentially melting one and then mixing with the other unmelted and then melting the mixture, simultaneously apart and then mixing, simultaneously together, or any other suitable order/arrangement). Particles, pellets, pills, powder, pastilles, beads, granules or the like may be formed by any suitable method with any suitable apparatus including extrusion, pelletizing, cutting, chopping and the like.

(69) In still another non-limiting embodiment pellets may be formed from a mixture of a polypropylene homopolymer or polypropylene/polyethylene copolymer, and a polyethylene wax or a petroleum micro wax (or in general from the primary rheology modifying component(s) and secondary rheology modifying component(s)). A melted mixture may be formed by melting the polymer and wax together in any desired order (i.e., sequentially melting one and then melting the other and then mixing, sequentially melting one and then mixing with the other unmelted and then melting the mixture, simultaneously apart and then mixing, simultaneously together, or any other suitable order/arrangement). Particles, pellets, pills, powder, pastilles, beads, granules or the like may be formed by any suitable method with any suitable apparatus including extrusion, pelletizing, cutting, chopping and the like. In some non-limiting embodiments the binder may comprise a polyethylene wax. In some non-limiting embodiments the binder may comprise a petroleum micro wax.

(70) It is believed that any known asphalt composition or product may be made using the additives of the present invention to replace part or all of the petroleum based asphalt binder therein. Non-limiting examples include blown asphalt and straight asphalt. As a non-limiting example, a paving application may be formed utilizing a straight asphalt. The known equipment and methods of making the known asphalt compositions and products are believed to be sufficient for making the asphalt compositions and products of the present invention in which part or all of the petroleum based asphalt has been partially or wholly replaced by modified asphalt of the present invention.

(71) In addition to the above embodiments, the present invention may also include the following non-limiting embodiments.

(72) Non-limiting embodiments of the present invention include a one product additive package formulation for asphalt modification which comprises PP homo-polymer (or in general any of the primary rheology modifying component(s)) plus PE by-product wax and/or petroleum micro-wax and/or CTO and/or Oxidized Tall Oil Pitch and/or any of the Other Rheology Modifying Agents above. In some embodiments, the additive may increase the useful performance temperature range of the asphalt binder which may already be modified or not.

(73) Non-limiting embodiments of the present invention include the additive package described above which may be used as the Warm Mix Asphalt Paving concept.

(74) Non-limiting embodiments of the present invention include the additive package described above and which may be used in roofing applications.

(75) Non-limiting embodiments of the present invention include the PE Wax described above that is derived as a byproduct wax from polyethylene manufacture in the Softening Point range of 215 F. (102 C.) to 275 F. (135 C.), Needle penetration value at 25 C. in the range of 2 to 10 and Brookfield Viscosity at 300 F. in the range of 15 to 300 cps.

(76) Non-limiting embodiments of the present invention include the Petroleum Micro-Wax described in the invention above that is derived from crude oil refining and has a Drop Melt Point (ASTM D127) in the range of 150 F. (66 C.) to 220 F. (104 C.) and Kinematic Viscosity (ASTM D445) at 212 F. (100 C.) in the range of 10 to 320 Centi-Stokes.

(77) Non-limiting embodiments of the present invention include the oxidized tall oil pitch described above with a Softening Point in the range of 125 F. (52 C.) to 220 F. (104 C.).

(78) Non-limiting embodiments of the present invention include the additive package described above used with neat asphalt binder or with polymer modified binder (including modified asphalt that has been modified with any of Styrene Butadiene Styrene, Styrene Butadiene Rubber, Natural Latex Rubber, Synthetic Latex Rubber, Crumbed Tire Rubber, Ethylene Vinyl Acetate, Terpolymers, and Atactic Polypropylene).

(79) Non-limiting embodiments of the present invention include the additive package above used in roofing applications (including shingles, rolls, mop on grades, adhesives and sealants) to reduce working temperatures and enhance workability.

(80) Non-limiting embodiments of the present invention include the additive package described above used in hot applied surface dressings including chip seals, slurry seals, joint sealants, crack sealants, etc.

(81) Non-limiting embodiments of the present invention include a Warm Mix asphalt mix formulation for the pavement of road surfaces where the formulation comprises of a mixture of bitumen and aggregates and between 0.2 to 30% by weight of the additive package based on weight of the asphalt binder content.

(82) Non-limiting embodiments of the present invention include the formulation of above wherein the temperature of compaction of the aggregate mix is 10 F. to 90 F. below conventional Hot Mix asphalt.

(83) Non-limiting embodiments of the present invention include the asphalt formulation above where the additive package may be added to the drum mixer or batch mixer directly or added to the asphalt binder and then introduced into the drum mixer or batch mixer as additive modified binder.

(84) Non-limiting embodiments of the present invention include the Warm Mix asphalt of above wherein the additive package is added to produce a Warm Mix aggregate, and also include embodiments wherein the individual components of the additive package are added to produce the Warm Mix aggregate.

(85) Non-limiting embodiments of the present invention include the additive package described above for use in co-extrusion with polymers and wax additives to render these more easily dispersible in asphalt binders. These co-extrusion components may be any of the primary and/or secondary rheology modifying components mentioned above.

(86) Non-limiting embodiments of the present invention include the use of the any of the present invention for asphalt modification for Pavement and Roofing applications.

(87) The additives of the present invention may be formed by a wide variety of methods utilizing a wide variety of apparatus. All of the additives herein may be utilized in combination with ground tire rubber (GTR) or any recycled rubber material. In some embodiments, it is necessary to stabilize the GTR in asphalt, which may be accomplished by the addition of the above described reactive elastomeric terpolymer, and/or with the above described polymers having a glycidyl or glycidyl acrylate functionality, a non-limiting example of such functionality includes glycidyl methacrylate functionality, and a non-limiting example of such a polymer includes ethylene-butyl acrylate-glycidyl methacrylate terpolymer (a commercial example of which is Elvaloy terpolymer available from DuPont). Further, it is believed that any of the polymers mentioned herein as suitable as the primary rheology modifying component may be functionalized with glycidyl or glycidyl acrylate (including glycidyl methacryalate, and glycidyl ethacrylate functionality). In some embodiments, the secondary rheology modifying component is not necessary to stabilize ground tire rubber in asphalt.

(88) As explained above, the stability of GTR in asphalt is generally determined by the Separation test (cigar tube test) ASTM D 7173; Determining Separation Tendency of Polymer from Polymer Modified Asphalt. The closer the temperature between the top and the bottom of the cigar tube, the higher the stability. SBS is regarded as the gold standard benchmark for modifying asphalt, with SBS modified asphalt having a cigar test of 2 C. (3.6 F.) difference. In sharp contrast, GTR modified asphalt will have a 30 F. (16.7 C.) difference or worse. Various embodiments of the present invention provide for stabilizing GTR modified asphalt with the additives of the present invention so that the cigar test temperature difference for the GTR modified asphalt is greatly improved

(89) When the additives of the present invention are utilized in making GTR modified asphalt, or otherwise incorporated into GTR modified asphalt, the cigar test results are a lot better than 30 F. (16.7 C.) difference, specifically less than or equal to 14 C. (25.2 F.), 12 C. (21.6 F.), 10 C. (18 F.), 8 C. (14.4 F.), 6 C. (10.8 F.), 4 C. (7.2 F.), 2 C. (3.6 F.), 1 C. (1.8 F.), or 0.5 C. (0.9 F.) temperature difference using ASTM D 7173. In other words, the additives of the present invention stabilize GTR in asphalt so that the GTR modified asphalt now meets the SBS gold standard regarding the cigar test of 2 C. (3.6 F.). In some embodiments, the additive may not require the secondary rheology modifying component to stabilize the ground tire rubber in asphalt.

(90) As one non-limiting embodiment, the primary rheology modifying component(s) and the secondary rheology modifying component(s) may be melted together into a molten liquid phase, mixed, and then formed into solid form which is now useful as an asphalt additive. As a specific non-limiting example of this embodiment, melt wax, polymers, and Elvaloy terpolymer, mix and form solid additive. As another specific non-limiting example of this embodiment, melt wax and Elvaloy terpolymer, mix and form solid additive.

(91) As a more specific non-limiting embodiment of the above embodiment, the primary rheology modifying component(s) and the secondary rheology modifying component(s) may be melt mixed via extrusion, with the extrudate made into solid form which is now useful as an asphalt additive. As a specific non-limiting example of this embodiment, melt mix via extrusion the polymers, wax and Elvaloy terpolymer, next form the extrudate into the solid additive.

(92) As another non-limiting embodiment, the primary rheology modifying component(s) and the secondary rheology modifying component(s) may be melted together into a molten liquid phase, mixed, and then formed into solid form. This additive in solid form may be combined with additional primary rheology modifying component(s) and/or secondary rheology modifying component(s) and utilized as an asphalt additive. It should be appreciated the formed solid additive and additional rheology modifying component(s) may be combined prior to contacting with asphalt, added to asphalt simultaneously, or added to asphalt consecutively. As a specific non-limiting example of this embodiment, melt wax and polymers mix and form into pellets, then combine these pellets with Elvaloy pellets in the asphalt blend tank.

(93) Some embodiments of the present invention will melt the primary and secondary rheology modifying components together at the same time. Other embodiments will first melt the primary rheology modifying component(s), and then introduce the secondary rheology modifying component(s) to the melted primary rheology modifying component(s). The secondary rheology modifying component(s) may or may not be melted at the time of the introduction. As a non-limiting example, utilizing a twin screw extruder, the primary rheology modifying component(s) (as a non-limiting example a PAO and an Elvaloy terpolymer) are introduced at the front end of the extruder. The secondary rheology modifying component may be introduced at the front end of the extruder along with the primary rheology modifying component(s) (as a non-limiting example a wax) or may be introduced after the front end of the extruder (generally at the end of the first screw/beginning of the second screw) to join the already melted primary rheology modifying component(s).

(94) As a more specific non-limiting embodiment of the above embodiment, the primary rheology modifying component(s) and the secondary rheology modifying component(s) may be melt mixed via extrusion, with the extrudate then formed into solid form. This additive in solid form may then be combined with additional primary rheology modifying component(s) and/or secondary rheology modifying component(s) and utilized as an asphalt additive. It should be appreciated the formed solid additive and additional rheology modifying component(s) may be combined prior to contacting with asphalt, added to asphalt simultaneously, or added to asphalt consecutively. As a specific non-limiting example of this embodiment, melt mix the polymers and wax via extrusion, then pelletize the extrudate, then combine these pellets with Elvaloy terpolymer in the asphalt blend tank.

(95) As even another non-limiting embodiment, the primary rheology modifying component(s) and the secondary rheology modifying component(s) may be micronized via high shear grinding to form the asphalt additive. As a specific non-limiting example of this embodiment micronize via high shear grinding polymer, wax and Elvaloy to form the asphalt additive. The components may be combined before the high shear grinding and subjected to the grinding together, or may be subjected to the grinding separately and combined afterwards.

(96) As even another non-limiting embodiment, the asphalt additive may be formed by micronizing the primary rheology modifying component(s) via high shear grinding, without the need for the secondary rheology modifying component(s). It is believed that the micronized primary rheology modifying component(s) will sufficiently disperse in asphalt without the need for the secondary rheology modifying component. As a specific non-limiting example of this embodiment, would include micronizing Elvaloy terpolymer and adding to the asphalt blend tank.

(97) Should more than one primary rheology modifying component and/or secondary rheology modifying component be micronized, the components may be combined before micronizing and subjected to micronizing together, or may be subjected to micronizing separately and combined afterwards, or added simultaneously or sequentially to the asphalt after micronizing.

(98) Any suitable micronizing method and apparatus may be utilized to form the micronized additive of the present invention. Common traditional micronization techniques are based on friction to reduce particle size, and such methods include milling, bashing and grinding. A typical industrial mill is composed of a cylindrical metallic drum that usually contains steel spheres. As the drum rotates the spheres inside collide with the particles of the solid, thus crushing them towards smaller diameters. In the case of grinding, the solid particles are formed when the grinding units of the device rub against each other while particles of the solid are trapped in between. Methods like crushing and cutting are also used for reducing particle diameter, but produce more rough particles compared to the two previous techniques (and are therefore the early stages of the micronization process). Crushing employs hammer-like tools to break the solid into smaller particles by means of impact. Cutting uses sharp blades to cut the rough solid pieces into smaller ones. There are also cryogenic techniques for micronizing. For example, some methods use supercritical fluids in the micronization process. The most widely applied techniques of this category include the RESS process (Rapid Expansion of Supercritical Solutions), the SAS method (Supercritical Anti-Solvent) and the PGSS method (Particles from Gas Saturated Solutions).

(99) Another embodiment of the present invention provides for the dispersion of the primary rheology modifying component(s) by first micronizing those components which allows for dispersion of those components into asphalt without the need for the secondary rheology modifying component(s). In general additive particles of the present invention will be dispersible in asphalt if an effective amount of the particles to modify the asphalt have a diameter less than about 590, 420, 297, 250, 177, 149, 74, 37, or 15 m (microns), or will pass through a mesh size of 30, 40, 50, 60, 80, 100, 200, 400, or 800 mesh.

(100) Some embodiments of the present invention favor utilizing additive with glycidyl functionality, glycidyl acrylate functionality, or epoxide functionality for modifying asphalts with higher asphaltene content, while other embodiments favor utilizing additive with polyolefin(s) (PAO's) for modifying asphalts with lower asphaltene content. Generally, low asphaltene asphalts will have in the range of about 3 to 5 wt % asphaltene content (or less) whereas high asphaltene asphalts will have in the range of about 12 to 15 wt % asphaltene content (or more). The should be considered a continuum, with those asphalts with asphaltene content in the middle (i.e, between 5 and 12 wt %), utilizing an additive having a mixture.

(101) Some non-limiting embodiments of the present invention provide for methods of modifying a petroleum asphalt, the method comprising: combining the petroleum asphalt with an additive to form a modified asphalt, wherein the additive comprises ground tire rubber and resin, wherein the resin is selected from the group consisting of reactive elastomeric terpolymers, polymers having glycidyl functionality, polymers having glycidyl acrylate functionality, and polymers having epoxide functionality.

EXAMPLES

(102) For the Examples Rheopave 10XP (also referred to as Rheopave XP 10) is a melt blended mixture of a wax, polypropylene homopolymer and a functionalized polymer containing glycidyl methacrylate functionality (Elvaloy terpolymer) in solid form. Rheopave 100 is a melt blended mixture of a wax and polypropylene homopolymer in solid form.

(103) For the Examples, production of Rheopave products involve melt blending via extrusion for complete dispersion of the components which are wax, PP homopolymer and Elvaloy 4170 for Rheopave 10XP (no Elvaloy in Rheopave 100). The resulting Rheopave product is in the physical form of pellets. The Rheopave pellets are added to hot asphalt base in a stirred vessel at 375 DEG F. and stirred for one hour after addition. The resultant modified asphalt is then cooled and the various standardized laboratory tests are performed according to standard procedures. Rheopave 10XP is generally PP with MFR 20 (35 wt %), Elvaloy 1117 (50 wt %), and CWP 500 PE Wax (15 wt %). Rheopave 100 is generally PP (70 wt %) and wax (30 wt %).

Example 1

(104) Supporting data for asphalt modifier patent based on polypropylene homo-polymer and polypropylene plus polyethylene co-polymer as primary rheology agents and specified secondary rheology modifying agents.

(105) TABLE-US-00001 TABLE 1 Base Base Asphalt Asphalt plus 4% plus 4% Base Additive Additive Method Asphalt A B Continuous PG Grade 68.4- 78.9- 75.3- 24.2 23.03 23.69 Rotational Visco. at 270 F., cps TP 48 Rotational Visco. at 300 F., cps TP 48 Rotational Voisc. at 135 C., cps TP 48 0.56 1280.00 1030 Dynamic Shear Rheometer: T315 Temperature Pass, C. 67.00 76.00 70.00 Phase Angle 68.10 82.00 G* at 10 rad/sec, kPa. 1.62 1.76 G*/sin delta at 10 rad/sec., kPa. 1.27 1.74 1.77 Temperarure Fail, C. 69.00 82.00 76.00 Phase Angle 64.80 83.80 G* at 10 rad/sec, kPa. 1.00 0.93 G*/sin delta at 10 rad/sec., kPa. 1.10 0.94 Pass/Fail, Temp. C. 83.10 75.30 RTFO Residue Tests: Mass Loss, % T240 0.06 0.27 0.26 Dynamic Shear Rheometer T315 2.62 Temperature Pass, C. 68.40 76.00 70.00 Phase Angle 73.30 76.80 G* at 10 rad/sec, kPa. 2.83 4.76 G*/sin delta at 10 rad/sec., kPa. 2.95 4.83 Tempersture Fail, C. 82.00 76.00 Phase Angle 74.00 79.20 G* at 10 rad/sec, kPa. 1.55 2.35 G*/sin delta at 10 rad/sec., kPa. 1.60 2.39 Temperature Pass/Fail, C. 78.90 76.70 PAV Residue Tests: Dynamic Shear Rheometer T315 Temperature, C. 25.00 28.00 28.00 Phase Angle 43.00 41.90 G* at 10 rad/sec, kPa. 2590.00 3860.00 G*/sin delta at 10 rad/sec., kPa. 1770.00 2580.00 Bending Beam Rheometer T313 Temperature Pass, C. 12.00 12.00 12.00 Stiffness, 60 s, Mpa 104.00 142.00 147.00 M-value, 60 s 0.35 0.31 0.31 Temperature Fail, C. 18.00 18.00 Stiffness, 60 s, Mpa 283.00 300.00 M-value, 60 s 0.27 0.27 Additional Dynamic Shear Rheometer (DSR) Data Demonstrating Effectiveness of PP Compounds in High Temperature Performance Grading Phase Test Composition, Angle Temperature, Sample Reference % m/m of Additive G* G*/Sind Degrees C. Base Valero PG 67-22 1.00 1.01 84.2 67 3% SB2in V67-22 85% PP 0.73 0.75 75.8 82 (stream 1)plus 15% PE Wax 4% SB2 in V67-22 85% PP 1.28 1.31 76.5 76 (stream 1)plus 1.42 1.49 72.0 82 15% PE Wax 6% SB2 in V67-22 85% PP 1.14 1.26 64.5 88 (stream 1)plus 15% PE Wax 3% SB3 in V67-22 85% PP 0.84 0.85 82.5 76 (stream 2) plus 15% PE Wax 3% SB4 in V67-22 85% PP 1.64 1.66 81.3 70 (stream 2) plus 0.81 0.82 84.4 76 PE Wax 3% SB5 in V67-22 100% PP 1.66 1.67 83.0 70 (Stream 2) 0.87 0.88 84.0 76 3% SB6 in V67-22 42.5% PP Wax 1.76 1.78 82.6 70 Stream 1) plus 0.97 0.98 82.5 76 42.5% PP Wax 1.95 1.97 81.4 70 (stream 2) plus 15% PE Wax Notes: 1. Additive A = 85% Resin plus 15% PE By-Product Wax and Continuous PG grade escalated from PG 68.4-24.2 to PG 78.9-23.03. This represents binder PG improvement of 2 full grades. 2. Additive B = 80% Resin plus 20% Micro-Wax and Continuous PG grade escalated from PG 68.4-24.2 to PG 75.3-23.9. This represents a full one PG improvement in binder grade. A marginal incresae in Additive B will meet the PG 76-22 Grade. 3. Unlike Fischer-Tropsch Waxes and other Plastomeric additives, the Low temperature grading is not negatively impacted. 4. The Rotational Viscosity of the modified Asphalt blends are less than 50% of the specified maximum viscosity of 3,000 cps at 135 C. This substantial lower viscosity will reduce the viscosity of the aggregate mix in a corresponding manner and will result in Warm Mix Asphalt benefits.

Example 2

(106) The follow data shows PP compound (Rheopave 100) improving the separation stability in Crumbed Rubber Asphalt formulations

(107) TABLE-US-00002 TABLE 2 CIGAR CIGAR ORIGINAL TUBE TUBE DSR @ RV @ BLEND TOP BOTTOM 76 C. 300 F. 10% GTR 139.4 F. 163.5 F. MESH 80 IN V67-22 10% GTR 151.5 F. 153.5 F. MESH 80 RETEST: RESTES: IN V67-22 + 1% 150.7 F. 152.9 F. RHEOPAVE 100 10% GTR 135.1 F. 161.6 F. MESH 40 IN V67-22 10% GTR 145.7 F. 160.0 F. G*Sin() = 1740 cps MESH 40 2.33 KPa IN V67-22 + Phase Angle = 1% SBS 75.6 10% GTR 150.1 F. 149.5 F. G*Sin() = 1550 cps MESH 40 2.07 KPa IN V67-22 + 1% Phase Angle = RHEOPAVE 100 77.4 10% GTR 140.0 F. 163.2 F. G*Sin() = 1445 cps MESH 40 1.91 KPa IN V67-22 + 0.5% Phase Angle = RHEOPAVE 100 79.0 10% GTR 149.4 F. 150.3 F. G*Sin() = 1630 cps MESH 40 2.39 KPa IN V67-22 + 0.5% Phase Angle = SBS + 0.5% 76.3 RHEOPAVE 100 SFMC ARB-5 126.0 F. 145.0 F. 550 cps SFMC ARB-5 + 130.1 F. 145.5 F. 0.5% RHEOPAVE 100 SFMC ARB-5 + 136.0 F. 138.8 F. 795 cps 1% RHEOPAVE 100

Example 3

(108) TABLE-US-00003 TABLE 3 Hamburg Wheel Rut Depth @ Total Passes to 20,000 Passes, mm 12.5 mm Rut Depth Mix Sample Sample Sample Sample Type 1 2 Average 1 2 Average PG 76-22 6.392 5.549 5.971 95,130 173,593 134,362 GTR 8.792 9.727 9.260 54,328 49,580 51,954

(109) Based upon the Hamburg testing criteria set forth by the Texas Department of Transportation, shown in Table 4, both samples meet the Hamburg criteria for a PG 76 and above high temperature grade. Stripping inflection points were not observed for either mixture.

(110) TABLE-US-00004 TABLE 4 Minimum # of Passes @ High Temperature 12.5 mm Rut Depth, Binder Grade Tested @ 122 F. PG 64 or Lower 10,000 PG 70 15,000 PG 76 or Higher 20,000

Example 4

Example 5

Example 6

(111) Referring now to FIG. 1, there is provided TABLE 7, Separation Test Results for Test Highway using Rheopave 10XP. The evaluating state DOT noted the workability and compaction of the Rheopave mix and which was superior to usual Asphalt Rubber Binder Mixes.

Example 7

(112) Table 8 provides various test results for 82-22 ARB binder.

(113) TABLE-US-00005 TABLE 8 82-22 ARB BINDER. LTRC Results Physical Properties Sample Sample Sample (Tests) #1 #2 #3 AVG Rotational Viscosity @ 135 C. 3.16 (Pa .Math. s) Original DSR @ 82 C. (G*/Sin) 1.74 1.78 1.76 Original DSR-Phase Angle @ 82 C. 76.5 76.2 76.4 RTFO DSR @ 82 C. (G*/Sin) 3.88 3.83 3.86 RTFO DSR-Phase Angle @ 82 C. 67.0 67.3 67.2 % Elastic Recovery @ 25 C., 64.0 64.0 64.0 10 cm elongation MSCR % R.sub.3.2 @ 64 C. 59.250 59.218 59.234 MSCR J.sub.nr,3.2 @ 64 C. 0.105 0.109 0.107 MSCR % R.sub.3.2 @ 67 C. 52.017 51.719 51.868 MSCR J.sub.nr,3.2 @ 67 C. 0.173 0.181 0.177 PAV DSR @ 25 C. (G*Sin) 2470 2570 2520 PAV DSR-Phase Angle @ 25 C. 41.4 41.0 41.2 BBR Creep Stiffness, S, 109 112 103 108 Mpa @ 12 C. BBR Creep Slope, 0.311 0.313 0.310 0.311 m Value @ 12 C.

Example 8

(114) Referring now to FIG. 2, there is provided TABLE 9, showing various test results for PG67-22 Base Asphalt Upgraded to PG76-22 GTR with MSCR Specification.

Example 9

(115) TABLE 10 provides various test results for PG67-22 Base Asphalt Upgraded to PG 76-22 GTR with MSCR Specification.

(116) TABLE-US-00006 TABLE 10 PG67-22 Base Asphalt Upgraded to PG 76-22 GTR with MSCR Specification 9% GTR Formula Property with Rheopave 10XP Target RV at 135 C. (cP) 2850 3000 Max Original DSR at 76 C. Phase Angle ( Deg) 71.6 <75 G*/Sin (kPa) 1.97 Min 1.0 RTFO DSR at 76 C. Phase Angle (Deg) 63.5 G*Sin (kPa) 4.83 Min 2.2 Fail Temp (Deg C.) 85.1 Min 76 PAV DSR at 76 C. Phase Angle 44.1 MSCR at 64 C. Jnr/% Rec 0.208/62.98% % Rec > 50% BBR at 12 Deg C. Tm Value (Mpa) 0.334 Min 0.30 Stiffness (Mpa) 152 Max 300 BBR at 18Deg C. m-Value (Mpa) 0.283 Min 0.30 Stiffness (Mpa) 273 Max 300 Continuous PG: 83.4-26.0 76-22 PG Grade: 82-22 76-22

Example 10

(117) Referring now to FIG. 3 there is provided TABLE 11 showing testing date for the PG (ARB)-22 TEST SECTION completed for a state DOT, and also to FIGS. 4A and 4B providing Table 12 (Parts 1 and 2), and to FIGS. 5A and 5B (Providing Table 13 (Parts 1 and 2), showing certification for the Rheopave modified asphalt. The evaluating state DOT noted the workability and compaction of the Rheopave mix and which was superior to usual Asphalt Rubber Binder Mixes.

(118) The present disclosure is to be taken as illustrative rather than as limiting the scope or nature of the claims below. Numerous modifications and variations will become apparent to those skilled in the art after studying the disclosure, including use of equivalent functional and/or structural substitutes for elements described herein, use of equivalent functional couplings for couplings described herein, and/or use of equivalent functional actions for actions described herein. Any insubstantial variations are to be considered within the scope of the claims below.