Modified bitumen containing compatibilizers, compatibilizers, and their uses in asphalt, roofing, or road applications.

Abstract

This invention relates to an asphalt composition comprising modified asphalt and a hydroxyl-functionalized polymer configured to generate a thermally reversible crosslinked network in the composition, wherein the hydroxyl-functionalized polymer is selected from: hydroxyl-functionalized polyolefin thermoplastics, hydroxyl-functionalized polyolefin elastomers, and hydroxyl-functionalized polyolefin plastics.

Description

Technical Field

[0001] This invention relates to a modified bitumen, a compatibilizer for asphalt, and its use in roofing or road applications. Background Technology

[0002] Asphalt is used in a variety of applications, but its main uses are currently in road construction and roofing.

[0003] Asphalt is typically composed of a mixture containing bitumen and minerals, along with optional additives such as polymers, particularly polyolefins, to improve its properties. Indeed, over the years, researchers have demonstrated that adding, for example, 3 to approximately 8 wt% or more of certain polymers can improve asphalt properties: increasing toughness, resilience, viscosity, elasticity, impact resistance, and resistance to deformation at low and high temperatures.

[0004] In fact, asphalt becomes brittle and cracks at low temperatures. At high temperatures, it softens under the weight of heavy trucks passing by. In summer, roads can be 80-100°F hotter than in winter, and for every 100°F increase in temperature, the asphalt softens a million times. While it won't actually leave the road, it will creep into bulges and grooves, making driving dangerous. Asphalt roads need more built-in strength to hold their shape better.

[0005] Polymers function by creating a support matrix within the asphalt. An original paper by JEW et al. (J. Appl. Polym. Sci., 31. 2685-2704 (1986)) demonstrated that 8 wt% polyethylene in asphalt mixtures can increase flexural strength / modulus, elongation, and fracture energy.

[0006] These researchers concluded that the presence of polyethylene in hot-mix paving materials can extend the operating temperature range at both high and low temperatures, thereby reducing both pavement deformation (grooving) and low-temperature cracking, thus more than doubling pavement life.

[0007] These researchers also suggested using triblock copolymers to control the stability of the mixture, disperse the particle size and compatibility of the polyethylene phase.

[0008] However, this approach is not economically feasible due to the use of high weight percentages of polymers and the cost of processing asphalt-polymer blends.

[0009] However, while many thermoplastics can impart the aforementioned properties to asphalt to a surprising degree, serious problems remain that polymers typically cannot solve. This involves the difference in interfacial surface energy between the asphalt, mineral aggregates, and polymers. Aggregates are highly hydrophilic, while most polymers tend to be very hydrophobic. Poor adhesion between the two leads to material delamination, especially during freeze-thaw cycles, high temperatures, and exposure to salt, oil, gasoline, water, etc.

[0010] In addition, due to the hydrophilic / hydrophobic properties of asphalt components, it is particularly difficult to obtain good dispersion of polymers and asphalt, and it also presents cost issues for polyolefins, often requiring specialized high-energy mixing equipment.

[0011] These problems have been solved by using compatibilizers and polyolefins with both hydrophilic and hydrophobic portions (which function at the interface between the mineral components, bitumen, and polyolefin).

[0012] US 6,759,453 B2 discloses a compatibilizer: a polymer that has been functionalized to react chemically with a polyamine to form an adduct, the adduct containing at least one or more groups selected from amino, amide, imino, imide, or imidazole groups.

[0013] When blended with asphalt and polymers, this functionalized polymer provides excellent paving compositions with improved physical properties and enhanced resistance to spalling.

[0014] However, such asphalt compositions must be applied to their final use before the asphalt cools and solidifies. In fact, once cooled, such asphalt cannot be reprocessed without losing its properties. Furthermore, such asphalt compositions have the disadvantage of losing their stability during long-term storage at high temperatures. This is related to the lack of chemical and physical interactions between the nonpolar polymer and the polar asphalt components, such as asphaltene or resins, ultimately leading to system instability.

[0015] Therefore, there is a need for new compositions that can be thermally stored for extended periods and that have the ability to reprocess cooled asphalt and recycled asphalt compositions in an economical manner. Summary of the Invention

[0016] This invention achieves this goal.

[0017] In a first aspect, the present invention relates to modified asphalt comprising a randomly hydroxyl-functionalized polymer or a graft copolymer (PO-graft-SMA) containing the randomly functionalized polymer and a styrene-maleic anhydride copolymer, the graft copolymer being configured to generate a thermally reversible crosslinking network within the asphalt, wherein the randomly hydroxyl-functionalized polymer is selected from: hydroxyl-functionalized polyolefin thermoplastics or hydroxyl-functionalized polyolefin elastomers, hydroxyl-functionalized polyolefin plastics.

[0018] The thermally reversible crosslinked network in this composition allows the modified asphalt to be reheated after cooling without losing its properties. When used as a compatibilizer, this network behaves similarly to multiblock copolymers, ensuring significantly higher entanglement with the matrix and dispersed phase compared to linear block copolymers. Although forming a network, the crosslinked material is moldable at elevated temperatures due to the thermally reversible properties of the crosslinking, allowing the reprocessing of cooled asphalt and even recycled old asphalt / asphalt into new asphalt compositions.

[0019] In one embodiment, the amount of hydroxyl functional groups is 1-8 per polymer chain, and the hydroxyl functionality level is at least 0.05 mol% of the total polymer, preferably more than 0.1 mol% of the total polymer.

[0020] In one embodiment, the amount of the hydroxyl-functionalized polymer is 0.5-10 wt% based on the weight of the composition, preferably less than 5 wt%, preferably about 1-2.5 wt%, more preferably about 1 wt%, based on the weight of the composition.

[0021] In one embodiment, the hydroxyl-functionalized olefin is selected from hydroxyl-functionalized HDPE, hydroxyl-functionalized LDPE, hydroxyl-functionalized ethylene copolymer (LLDPE), hydroxyl-functionalized PP, hydroxyl-functionalized propylene copolymer, preferably poly(ethylene-copoly-5-hexen-1-ol), poly(ethylene-copoly-10-undecen-1-ol), poly(propylene-copoly-5-hexen-1-ol), poly(propylene-copoly-10-undecen-1-ol) or mixtures thereof.

[0022] In one embodiment, the hydroxyl-functionalized elastomer or plastic is based on an elastomer or plastic selected from: poly(ethylene-copoly-propylene), poly(ethylene-copoly-1-butene), poly(ethylene-copoly-1-hexene), poly(ethylene-copoly-1-octene), poly(ethylene-copoly-norbornene), atactic polypropylene, poly(propylene-copoly-1-butene), poly(propylene-copoly-1-hexene), poly(propylene-copoly-1-octene), containing additional hydroxyl-functionalized comonomers, preferably poly(ethylene-copoly-1-hexene-copoly-5-hexen-1-ol), poly(ethylene-copoly-1-hexene-copoly-10-undecen-1-ol). Poly(propylene-copoly-1-hexene-copoly-5-hexen-1-ol), poly(propylene-copoly-ethylene-copoly-5-hexen-1-ol), poly(propylene-copoly-1-hexene-copoly-10-undecen-1-ol), poly(propylene-copoly-ethylene-copoly-10-undecen-1-ol), poly(ethylene-copoly-1-octene-copoly-5-hexen-1-ol), poly(ethylene-copoly-1-octene-copoly-10-undecen-1-ol), poly(ethylene-copoly-norbornene-copoly-5-hexen-1-ol), poly(ethylene-copoly-norbornene-copoly-10-undecen-1-ol) or mixtures thereof, and T m Preferably below 150°C, and more preferably below 140°C.

[0023] In one embodiment, the hydroxyl-functionalized polymer has been reacted with styrene-maleic anhydride (SMA) to obtain polymer-grafted SMA (PO-grafted-SMA).

[0024] In one embodiment, the PO-grafted-SMA content is 1-10 wt%, preferably 1-5 wt%, more preferably 1-2.5 wt%, wherein PO represents a polyolefin thermoplastic, plasmon, or elastomer.

[0025] In one embodiment, the POE-grafted-SMA content is 1-10 wt%, preferably 1-5 wt%, more preferably 1-2.5 wt%.

[0026] In one implementation, PO-grafted-SMA is PP-grafted-SMA.

[0027] In one implementation, bitumen is refinery or cracking unit residue or reused paving material or recycled asphalt.

[0028] In one implementation, at least one, preferably two, more preferably three, and more preferably four of the following parameters are satisfied:

[0029] - Viscosity [Pas] at 180°C: <2 Pas, preferably <1 Pas

[0030] - Average softening point [°C]: >45.7

[0031] -Aging Δpenetration rate: <10, preferably <5

[0032] - Softening point after aging: <10, preferably <5

[0033] A second aspect of the present invention is a compatibilizer for asphalt comprising PO-grafted SMA, wherein the amount of PO is 60-95 wt%, preferably 70-90 wt%, more preferably above 80 wt%, and the amount of SMA is 5-40 wt%, preferably 10-30 wt%, more preferably below 20 wt%, wherein PO is a polyolefin thermoplastic, polyolefin plastic (POP) or polyolefin elastomer (POE), such as, but not limited to, HDPE, LDPE, LLDPE, VLDPE, ULDPE, EPR, aPP, iPP, sPP, propylene-α-olefin copolymer.

[0034] In one embodiment, the amount of PO compatibilizer is 60-90 wt%, preferably 65-80 wt%, preferably 70-75 wt%, and the amount of SMA is 10-40 wt%, preferably 20-35 wt%, preferably 25-30 wt%.

[0035] A third aspect of the invention is the use of asphalt compositions according to the invention or containing a compatibilizer according to the invention for roofing or road applications.

[0036] It should be noted that this invention relates to all possible combinations of the features described herein, and particularly preferred are those combinations of features present in the claims. Therefore, it will be understood that this document describes all combinations of embodiments; features related to the compositions according to the invention; all combinations of features related to the methods according to the invention; and all combinations of features related to the compositions according to the invention and the methods according to the invention.

[0037] It should be further noted that the term "comprising / including" does not exclude the presence of other elements. However, it should also be understood that a description of a product / composition comprising certain components also discloses a product / composition composed of those components. A product / composition composed of these components can be advantageous because it provides a simpler and more economical method for preparing the product / composition. Similarly, it should be understood that a description of a method including certain steps also discloses a method composed of those steps. A method composed of these steps can be advantageous because it provides a simpler and more economical method.

[0038] When the lower and upper limits of a parameter are mentioned, it is also understood that the range generated by the combination of the lower and upper limits is disclosed. Attached Figure Description

[0039] Figure 1a and 1b Fluorescence images of pure bitumen and selected polymer-modified bitumen samples, recorded after thermal storage stability testing, are shown.

[0040] Figure 2a and 2b The surface morphology and mechanical properties of pure bitumen and polymer-modified bitumen samples recorded after thermal storage stability testing are shown.

[0041] Figure 3 The image shows the AFM image (top) of an asphalt sample modified with poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol) (the amount of modifier used is equal to 2.5 wt%) (Table 2, entry 12), recorded after the thermal storage stability test.

[0042] Figure 4 The image shows the AFM image (top) of the asphalt sample modified with poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol)-grafted-SMA (the amount of modifier used is equal to 1.5 wt%) (Table 2, entry 15), recorded after the thermal storage stability test.

[0043] Figure 5 The rheological measurements of pure bitumen and polymer-modified bitumen—storage modulus (G')—are shown.

[0044] Figure 6 Rheological measurements of pure bitumen and polymer-modified bitumen – loss modulus (G”) are shown.

[0045] Figure 7 The rheological measurements of pure asphalt and polymer-modified asphalt—loss factor (tan[δ])—are shown.

[0046] Figure 8 The rheological measurements of pure asphalt and polymer-modified asphalt—groove parameters (G* / sin[δ])—are shown.

[0047] Figure 9 Rheological measurements of pure bitumen and polymer-modified bitumen – complex modulus (G*) – are shown.

[0048] Figure 10 Rheological measurements of pure bitumen and polymer-modified bitumen are shown in black graphs. Detailed Implementation

[0049] The present invention preferably relates to a novel asphalt composition that can be thermally stored for a long period of time and that can be reprocessed from cooled asphalt and recycled asphalt compositions.

[0050] To achieve these properties, a compatibilizer is added to the asphalt composition, which is a mixture of asphalt (residue from a cracking unit (non-volatile residue from a cracking unit) or reused paving material or reused asphalt) and a polymer, particularly a polyolefin (PO) such as HDPE, LDPE, LLDPE, VLDPE, ULDPE, EPR, aPP, iPP, sPP, and propylene-α-olefin copolymers. These polyolefins can be virgin or recycled polyolefins.

[0051] Such a compatibilizer must be able to generate a thermally reversible crosslinked network in the composition, which is achieved using a random hydroxyl-functionalized polymer, more preferably a hydroxyl-functionalized polyolefin thermoplastic, a hydroxyl-functionalized polyolefin elastomer, a hydroxyl-functionalized plastic, or a mixture thereof, which is optionally coupled to SMA to form a polyolefin-SMA graft copolymer, PO-graft-SMA.

[0052] To obtain such a thermally reversible crosslinked network, the amount of random hydroxyl functional groups can be 1-8 per polymer chain, with the aim of achieving a hydroxyl functionality level of at least 0.05 mol% of the total polymer, which is sufficient to produce such a network.

[0053] What is essential for this invention is to obtain a suitable crosslinking network, i.e., the hydroxyl-functionalized groups are generated randomly, in order to avoid the polymer having groups only at the head and / or end of the polymer chain, which tends to form a weak network.

[0054] Hydroxyl functionality level through 1 The determination was performed using 1H NMR spectroscopy, where the functionalized mol% was determined by... 1 ¹H NMR analysis was performed at 130 °C using deuterated tetrachloroethane (TCE-D2) as solvent and recorded on a 5 mm tube on a Varian Mercury spectrometer operating at 400 MHz. Chemical shifts are reported in ppm relative to tetramethylsilane and determined with reference to residual solvent protons. In this application, the hydroxyl functionality level includes not only the amount of OH groups within the polymer, It also includes the amount of OH groups that have reacted with SMA and are no longer present in the reaction products. .

[0055] Preferably, the randomly hydroxyl-functionalized polymer is a substantially saturated functionalized polymer in the main chain, because saturated functionalized polymers are more stable than unsaturated functionalized polymers with unsaturation in the main chain.

[0056] When using hydroxyl-functionalized polyolefins (wherein the polyolefin is a thermoplastic, plasmon, or elastomer) or graft copolymers (PO-grafted-SMA) containing functionalized polyolefins and styrene-maleic anhydride copolymers as compatibilizers in asphalt compositions, an amount of 0.5-10 wt% based on the weight of the composition, or about 1-5 wt% based on the weight of the composition, is preferred to improve product properties, more preferably about 1-2.5 wt%. Furthermore, graft copolymers (PO-grafted-SMA) prepared via solution grafting methods affect asphalt properties more effectively than those prepared via melt extrusion methods. This difference is due to the more efficient coupling of hydroxyl-functionalized polyolefins and SMA in solution compared to reactive extrusion. The reaction in solution lasts for several hours, while reactive extrusion lasts only a few minutes. Most likely, the time required for reactive extrusion is insufficient to completely complete the copolymerization, as hydroxyl-functionalized polyolefins and SMA are immiscible polymers. The hydroxyl-functionalized polyolefin may be selected from: hydroxyl-functionalized HDPE, hydroxyl-functionalized LDPE, hydroxyl-functionalized ethylene copolymer (LLDPE), hydroxyl-functionalized PP, hydroxyl-functionalized propylene copolymer, preferably poly(ethylene-copoly-5-hexen-1-ol), poly(ethylene-copoly-10-undecen-1-ol), poly(propylene-copoly-5-hexen-1-ol), poly(propylene-copoly-10-undecen-1-ol) or mixtures thereof. Hydroxyl-functionalized elastomers and plastics are based on elastomers or plastics selected from: poly(ethylene-copoly-propylene), poly(ethylene-copoly-1-butene), poly(ethylene-copoly-1-hexene), poly(ethylene-copoly-1-octene), poly(ethylene-copoly-norbornene), atactic polypropylene, poly(propylene-copoly-1-butene), poly(propylene-copoly-1-hexene), poly(propylene-copoly-1-octene), containing additional hydroxyl-functionalized comonomers, preferably poly(ethylene-copoly-1-hexene-copoly-5-hexen-1-ol), poly(ethylene-copoly-1-hexene-copoly-10-undecen-1-ol), poly(propylene-copoly-1-butene), poly(ethylene-copoly-1-hexene-copoly-10-undecen-1-ol), poly(ethylene-copoly-1-hexene-1-ol), poly(ethylene-copoly-1-hexene-1-undecen-1-ol), poly(ethylene-copoly-1-butene ... Poly(propylene-copoly-1-hexene-copoly-5-hexen-1-ol), poly(propylene-copoly-ethylene-copoly-5-hexen-1-ol), poly(propylene-copoly-1-hexene-copoly-10-undecen-1-ol), poly(propylene-copoly-ethylene-copoly-10-undecen-1-ol), poly(ethylene-copoly-1-octene-copoly-5-hexen-1-ol), poly(ethylene-copoly-1-octene-copoly-10-undecen-1-ol), poly(ethylene-copoly-norbornene-copoly-5-hexen-1-ol), poly(ethylene-copoly-norbornene-copoly-10-undecen-1-ol) or mixtures thereof, and T m Preferably below 150°C, and more preferably below 140°C.

[0057] In a preferred embodiment, the hydroxyl-functionalized polymer has been reacted with SMA to obtain the corresponding graft copolymer PO-graft-SMA, wherein the amount of polyolefin (PO) is 60-95 wt%, preferably 70-90 wt%, more preferably above 80 wt%, and the amount of SMA is 5-40 wt%, preferably 10-30 wt%, more preferably below 20 wt%, wherein PO is a polyolefin thermoplastic, polyolefin plastic (POP), or polyolefin elastomer (POE), such as, but not limited to, HDPE, LDPE, LLDPE, VLDPE, ULDPE, EPR, aPP, iPP, sPP, propylene-α-olefin copolymer.

[0058] Optimal results may be achieved when the wt% of PO-grafted-SMA is 1-5 wt% of the total composition, preferably 1-2.5 wt%.

[0059] Therefore, the asphalt according to the present invention satisfies at least one, preferably two, more preferably three, and more preferably four of the following parameters:

[0060] • Viscosity at 180°C [Pas]: <2 Pas, preferably <1 Pas

[0061] • Average softening point [°C]: >45.7

[0062] • Δ transmittance after aging: <10, preferably <5

[0063] • Softening point after aging: <10, preferably <5

[0064] The following compositions are within the scope of this invention. Therefore, the asphalt obtained by such compositions satisfies at least one, preferably two, more preferably three, and even more preferably four or five of the above parameters.

[0065] Example

[0066] A typical procedure for preparing poly(propylene-grafted-2-hydroxyethyl succinimide) (iPP-grafted-OH) via reactive extrusion.

[0067] The iPP-grafted MAH (Exxelor PO1020, 0.94 mol% MAH, 10.0 g, M) was used. n =22kg·mol -1 , The antioxidant Irganox 1010 (2500 ppm) and a nitrogen atmosphere were introduced into miniature extruder chambers with three different temperature zones: 160°C, 180°C, and 190°C. The screw speed was set to 100 rpm. After one minute, ethanolamine (0.08 g, 0.44 mmol, 3 times excess compared to the amount of MAH grafted onto iPP-grafted-MAH) was added via syringe. The mixture was processed for 60 seconds, and the miniature extruder chambers were emptied. The OH-functionalized polypropylene was then purified as follows: dissolved in xylene at 120°C, precipitated in cold acetone, and subsequently dried in a vacuum oven at 40°C for 24 hours.

[0068] A typical procedure for preparing iPP-grafted-SMA using 9 wt% SMA via reactive extrusion.

[0069] grafting iPP-with-OH(M) n = 26.9 kg·mol -1 M w =106.2 kg·mol -1 , T m =153.4℃, ΔH m =110.0 J·g -1 FG / chain ~1,910 g) was premixed with Sn(Oct)2 (5 g, 0.012 mol) dissolved in heptane (200 mL), stirred at 100 °C for 1 hour, precipitated in methanol, and then dried in an oven. Sn(Oct)2-treated PP-grafted-OH (915 g) and SMA (M n = 36.3 kg·mol -1 T g =150℃)(90g) was fed into a co-rotating twin-screw extruder at 120-170-180-190-210-210-190-175-155℃ and a screw speed of 100 rpm. The mixture was processed, then cooled and granulated. The product was insoluble in o-DCB and therefore did not pass SEC analysis. T m =154.2℃, ΔH m = 96.8 J·g -1 .

[0070] A typical procedure for preparing iPP-grafted-SMA using 11 wt% SMA via reactive extrusion.

[0071] The same procedure as above was used, with 889 g of iPP-grafted-OH and 111 g of SMA. The product was insoluble in o-DCB and therefore did not pass SEC analysis. m =153.9℃, ΔHm =88.4 J·g -1 .

[0072] A typical procedure for preparing iPP-grafted-SMA using 14 wt% SMA via reactive extrusion.

[0073] The same procedure as above was used, with 857 g of iPP-grafted-OH and 143 g of SMA. The product was insoluble in o-DCB and therefore did not pass SEC analysis. m =154.5℃, ΔH m =104.8 J·g -1 .

[0074] A typical procedure for preparing poly(ethylene-copolymer-1-octene-grafted-(2-hydroxyethyl succinimide))(POE-grafted-OH) by reactive extrusion.

[0075] The POE-graft-MAH (Engage 8407-graft-MAH[POE-graft-MAH]M) is used to graft MAH. n =18.1 kg·mol -1 M w = 65.2 kg·mol -1 , T m =109.4℃, ΔH m =114.9 J·g -1 FG / chain ~1, or Elite AT 6111-graft-MAH[POE-graft-MAH]M n = 23.7 kg·mol -1 M w =71.1 kg·mol -1 , T m =64.4℃, ΔH m =29.8 J·g -1FG / chain-1 (2000 g), antioxidant Irganox 1010 (2500 ppm), and TBPP (tris[2,3-dibromopropyl]phosphate) (2500 ppm) were introduced under a nitrogen atmosphere into a co-rotating twin-screw extruder at 120-150-180-230-230-230-230-230-230°C and a screw speed of 200 rpm. After one minute, an excess of ethanolamine three times that of the MAH grafted onto the POE-graft-MAH was added (24.3 g, 0.13 mol for Engage 8407-graft-MAH; 28.4 g, 0.16 mol for Elite AT 6111-graft-MAH). The mixture was processed, then cooled and granulated.

[0076] A typical procedure for preparing poly(ethylene-copolymer-1-octene-grafted-styrene-copolymer-maleic anhydride) (POE-grafted-SMA) using 11 wt% SMA via reactive extrusion.

[0077] POE-grafted-OH (0.89 kg; 0.1 mol MAH, POE-grafted-OH#1 (derived from Engage 8407-grafted-MAH), FG / chain ~1, POE-grafted-OH#2 (derived from Elite AT 6111-grafted-MAH), FG / chain ~1), antioxidant Irganox 1010 (2500 ppm), and titanium isopropylidene oxide (IV) (5 g, 17.6 mmol, the molar ratio of catalyst to -OH groups in this polymer is 1:5) were premixed with SMA (0.11 kg) and introduced under a nitrogen atmosphere into a co-rotating twin-screw extruder at 120-150-180-230-230-230-230-230-230°C and a screw speed of 200 rpm. The mixture was processed, then cooled and granulated.

[0078] Typical procedure for preparing isotactic poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol).

[0079] The polymerization reaction is carried out in a stirred 20L stainless steel batch feeder. The polymerization was carried out in a reactor. Prior to polymerization, the reactor was dried by vigorous stirring of a solution of TiBA (20.0 mL, 1.0 M toluene solution) in 15 L of pentamethylheptane (PMH) solvent for approximately 1 hour. After draining the cleaning solvent and drying, the reactor was refilled with PMH solvent (15 L) and heated to 50 °C. A solution of TiBA (20 mL, 1.0 M toluene solution) and MAO (5 mL, 2.25 M toluene solution) prepared in a glove box was injected into the reactor (0.5 bar N2 overpressure). Subsequently, a predetermined amount of 1-hexene (13 mL, 105 mmol) and TiBA-protected 10-undecen-1-ol (molar ratio 1:1, 25 mL, 25 mmol) prepared in the glove box were injected into the reactor (0.5 bar N2 overpressure). The reactor was then purged to 1 bar nitrogen with stirring (300 RPM). The mixture was heated to 80 °C and saturated with gaseous propylene (5 bar propylene partial pressure). In a glove box, a pre-activated solution of racemic -Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ main catalyst (0.8 μmol, 0.5 mg, dissolved in 5 mL toluene containing TiBA (1.6 wt%)) and MAO (2 mL, 2.25 M toluene solution) was prepared and transferred to the reactor under polymerization conditions. Subsequently, a DEZ solution (1.0 mL, 1.5 M toluene solution) was added, and an additional 0.5 bar N₂ overpressure was applied for each injection. The propylene pressure in the reactor was automatically maintained at 5 bar propylene partial pressure, and propylene intake was measured using a mass flow meter (Bronkhorst). At the end of the reaction, the reactor was evacuated to 1 bar, and the mixture was discharged via a bottom valve into a 20 L vessel containing acidified isopropanol (3 L, 2.5 wt% acetic acid). The polymer mixture was filtered, and the wet powder was transferred to a 5 L Erlenmeyer flask containing acidified isopropanol (1.0 L, 2.5 wt% acetic acid) and stirred (150 RPM) for at least 30 minutes. Subsequently, the mixture was filtered (using 2 μm pore size qualitative filter paper), washed with softened water, sprayed with Irganox 1010 (antioxidant), and vacuum dried in a vacuum oven at 80 °C for 48 hours.

[0080] Typical procedure for preparing poly(propylene-copolymer-1-hexene-copolymer-10-undecene-1-ol)-grafted-SMA.

[0081] Poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol) (M) n = 76.9 kg·mol -1 , T m =143.4℃, ΔH m = 95.4 J·g-1 The solution (FG / chain = 5.7; 50 g) was placed in a 2 L glass reactor equipped with a magnetic stirrer and dried in toluene (1500 mL) for 24 hours by Dean-Stark distillation. In the next step, the solution was cooled to 80 °C and the catalyst titanium isopropylidene (IV) (0.25 mL, 0.24 g, 0.8 mmol) was added. The reaction was carried out for 1 hour under a nitrogen atmosphere. Then, a styrene-maleic anhydride (SMA) random copolymer (M... n = 36.3 kg·mol -1 T g =150℃)(12.5g), reacted under a nitrogen atmosphere for 24 hours. The synthesized poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol)-graft-SMA graft copolymer was separated by precipitation in cold methanol, then filtered and dried in a vacuum oven at 40℃ for 24 hours. The product is insoluble in o-DCB, T m =140.2℃, ΔH m =78.9 J·g -1 .

[0082] A typical procedure for preparing poly(propylene-copolymer-1-hexene-copolymer-10-undecene-1-ol)-grafted-SMA via reactive extrusion.

[0083] Poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol) (M) n =72.1 kg / mol T m =148.0℃, ΔH m =108.4 J·g -1 FG / chain = 1.4; 50 g) was dissolved in toluene (500 mL) and premixed with the catalyst titanium isopropylidene (IV) (0.25 mL, 0.24 g, 0.8 mmol). The product was precipitated in cold methanol and dried. Titanium-treated poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol) and SMA (M n = 36.3 kg / mol, T g =150℃)(24, 1g) is fed into an extruder at 210-230℃ and a screw speed of 40 rpm under a nitrogen atmosphere. The mixture is processed, then cooled and granulated.

[0084] Typical procedure for preparing isotactic poly(propylene-copolymer-ethylene-copolymer-10-undecene-1-ol).

[0085] Polymerization reaction in stainless steel 2L The polymerization was carried out in a reactor. Prior to polymerization, the reactor was hot-cleaned with 1.5 L of heptane at 100°C for 1 hour. After decanting, 1 L of heptane was added to the reactor and heated to 80°C. In a glove box, a predetermined amount of 10-undecen-1-ol was introduced into a vial and injected into the reactor. The reactor was then purged to 1 bar of nitrogen pressure while stirring at 300 rpm. After purging, the mixture was saturated with propylene to a partial pressure of 5 bar. In a glove box, approximately 3 mg of racemic -Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ catalyst was dissolved in a corresponding toluene solution containing TIBA (5 mL TiBA in 300 mL toluene), by volume (approximately 3 mL). A predetermined amount of the main catalyst solution (typically 0.3 mL) was then further dissolved in approximately 5 mL of the TiBA toluene solution. A solution of DEZ at a predetermined concentration in approximately 5 mL of toluene was prepared. The main catalyst was activated by adding an appropriate amount of MAO / MMAO and transferred to the reactor. DEZ solution was then added. The reactor was then operated in flow-controlled mode, where the pressure was maintained at 5 bar by feeding a propylene and ethylene mixture (5:1 ratio) at a stable flow rate. The temperature was maintained at 80°C. After a set time, the monomer feed was stopped, and the reactor was evacuated to 1 bar, and the mixture was poured into an Erlenmeyer flask. After pouring, the post-reaction mixture was quenched with 0.1 L of acidified isopropanol (10 wt% acetic acid, 0.1 L isopropanol). The mixture was cooled to room temperature and filtered through a 5–13 μm paper filter. The resulting white powder was then washed with heptane and dried in a vacuum oven at 80°C under reduced pressure for 48 hours. For polymer characterization, see Table 1.

[0086] Typical procedure for preparing poly(propylene-copolymer-ethylene-copolymer-10-undecene-1-ol)-grafted-SMA.

[0087] Poly(propylene-co-ethylene-co-10-undecene-1-ol) (M) n = 45.2 kg·mol -1 , T m =135.3℃, ΔH m = 96.7 J·g -1 FG / chain = 1; 50 g) was placed in a 2 L glass reactor equipped with a magnetic stirrer and dried in toluene (1500 mL) for 24 hours by Dean-Stark distillation. In the next step, the solution was cooled to 80 °C and the catalyst titanium isopropylidene (IV) (0.25 mL, 0.24 g, 0.8 mmol) was added. Mixing was carried out for 1 hour under a nitrogen atmosphere. Then, styrene-maleic anhydride (SMA) random copolymer (M n = 36.3 kg·mol-1 T g =150℃)(12.5g). The synthesized graft copolymer was separated by precipitation in cold methanol followed by filtration and drying in a vacuum oven at 40℃ for 24 hours. The product is insoluble in o-DCB, so it cannot be analyzed by SEC. m =152.2℃, ΔH m =36.7 J·g -1 .

[0088]

[0089]

[0090] A typical procedure for asphalt modification.

[0091] Asphalt modification was carried out at 180°C using an Ultra-Turrax T 50 base homogenizer (IKA) operating at speeds ranging from 4000 to 6000 rpm. Typically, the hot asphalt was mixed with the modifier for 60 minutes.

[0092] Typical procedures for softening point analysis.

[0093] The softening point test was performed according to European Standard 1427 using a Ring & Ball apparatus. In this method, two metal rings filled with tar are heated in a water bath at a controlled rate of 5°C / min, while each metal ring supports a steel ball. The temperature at which the tar-coated steel ball is dropped from a height of 25 mm is determined as the softening point temperature. The reported softening point value is the average temperature measured for each ball.

[0094] A typical procedure for penetration analysis.

[0095] The penetration test was conducted according to European Standard 1426. In this method, a needle of specified size and weight is inserted into an asphalt sample at 25°C for 5 seconds under a 100g load. The penetration value is expressed as the vertical distance the needle travels into the asphalt, measured in micrometers (µm). The penetration value is the average of three separate measurements.

[0096] A typical procedure for analyzing the stability of thermal storage.

[0097] Thermal storage stability testing was conducted according to European Standard 13399. In this method, two sealed aluminum tubes filled with asphalt were vertically placed in an oven at 180°C for 72 hours. In the next step, the tubes with asphalt were cooled and frozen. The aluminum caps were then removed, and the asphalt and bitumen were separated into three sections: top, middle, and bottom. The top and bottom sections were then melted separately and used for penetration and softening point analysis.

[0098] Optical and fluorescence microscopy.

[0099] Optical and fluorescence imaging were performed directly on the asphalt samples prepared for AFM analysis at 20× magnification, without further environmental conditioning. For fluorescence microscopy imaging, an exposure time of 300 ms was used.

[0100] AFM analysis.

[0101] For AFM analysis, approximately 50 mg of bitumen sample was first deposited onto a microscope slide. The sample was then heated on a baking tray at 100°C for a few seconds to produce a thin, flat film approximately 100 μm thick. The sample was then cooled to room temperature under ambient conditions and held for at least one day before AFM analysis. AFM imaging was performed directly on the surface of the film under ambient conditions without further sample preparation. AFM imaging was performed on a Bruker Dimension FastScan AFM system using a tapping mode AFM tip (Model TESPA-V2, k: 42 N / m, f: 320 kHz) at a scan frequency of 1 Hz. Bruker's Nanoscope 9.4 software was used as the computer interface, and Bruker's Nanoscope Analysis 2.0 was used to analyze the AFM measurements. All AFM measurements were performed under ambient conditions.

[0102] AFM HA-QNM experiment.

[0103] The samples were also characterized in HA-QNM mode at a frequency of 0.5 Hz using an AFM tip under environmental conditions, with a spring constant of 5 N / m (TAP-150-30, No. 3k = 5 N / m). Using this special tip, all the tip information required for QNM mode is immediately transferred to the AFM run procedure via a click of a barcode reader. Therefore, no calibration steps for the spring constant and tip radius are required before actual measurement. QNM mode enables the quantitative measurement of the mechanical properties of nanoscale materials by generating pixel-wise force curves over the scanned area. Analysis of individual force curve data using AFM Nanoscope software provides material property maps in morphological images with the same resolution. The elastic modulus of the scanned surface was extracted from the force curves using the Derjaguin-Muller-Toropov model and presented as a modulus plot.

[0104] Dynamic shear rheometer (DSR) analysis.

[0105] Rheological testing (DSR analysis) was performed using a Discovery Hybrid Rheometer HR-3 (TA Instruments) in oscillatory shear mode. Each sample was conditioned at 20°C for at least 20 minutes prior to testing. Temperature sweep tests in oscillatory shear were conducted at a frequency of 10 rad / s, at 1% strain, using a flat plate geometry with a 25 mm diameter and 1 mm gap size, and at temperatures ranging from 20 to 120°C. As a result of the DSR tests, the obtained rheological indices were the dynamic shear modulus (G', G", G*), phase angle (δ), loss tangent (tanδ), and groove factor (G* / sinδ), which were used to evaluate the grooving resistance of the modified asphalt.

[0106] Viscosity test at 180℃

[0107] The dynamic viscosity of the obtained PMB was determined using a TermoElectron-HaakeViscotester 2Plus viscometer according to EN 13302 standard. Measurements were performed at 180°C, with the appropriate measuring head of the viscometer immersed in the PMB to the depth determined by a scale placed above the test cylinder. The dynamic viscosity value [dPa·s] was then read from the device's digital display.

[0108] Average softening point

[0109] The test was conducted according to PN-EN 1427. Immediately after homogenization, a hot sample of PMB was poured into two brass rings placed on a metal plate with circular drilled holes. The plate was pre-lubricated with an anti-stick agent (containing silicone). After at least 30 minutes, excess modified bitumen was removed with a hot blade to align the cut surface with the top edge of each ring. The next step was to place the rings on a stand and suspend them vertically in a standardized beaker (V = 600 mL) specifically designed for this test. The beaker was then filled with distilled water or glycerin to the level indicated by the line at the top of the container, based on the expected softening point of PMB. The sample in the bath was then cooled in a refrigerator at 5 ± 1 °C for at least 15 minutes. Next, the beaker was placed on the heating element of the R&B measuring apparatus (Petrotest R&B tester). A thermometer and stirrer were placed in the beaker to ensure that the heat was evenly distributed throughout the entire volume of the liquid. The final step involves placing two steel balls (each with a mass of 3.5 g) into holes in a frame located directly on the ring, and heating the system at a constant rate of 5 °C / min. The temperature is read from a thermometer when the given balls reach the bottom of the beaker (the height from the ring to this point is 25 mm). The result for a given sample is the average temperature reading of a pair of rings filled with the same PMB sample.

[0110] Average penetration and softening point after aging

[0111] The thermal oxidative aging resistance of the obtained PMB samples was determined by the Rotary Thin Film Oven Test (RTFOT) according to PN-EN 12607-1. This test was conducted in an oven equipped with a circular cavity (with eight openings for placing glass containers containing PMB samples). The glass containers used for this test should be cylindrical, with a diameter of 64 mm, a height of 140 mm, and a wall thickness not exceeding 2.3 mm. To determine the aging resistance of a single adhesive, two containers (hereinafter referred to as A and B) were filled with a type of bitumen sample. Thus, four different adhesives could be tested in a single test. The first step was to weigh the empty containers to obtain the mass mA0 i mB0. The weighed containers were then filled with 35.0 ± 0.5 g of the polymer bitumen sample to be tested, and their mass mA1 i mB1 was determined again using an analytical balance. The prepared samples were then placed in an oven preheated to 163 °C and started rotating at a speed of 15 rpm. During the test, the air flow rate through the oven cavity was set to 4 L / min according to the standard. The test duration was 75 minutes, starting when the temperature reached 163°C again. After this time, the sample was removed from the furnace and allowed to cool to room temperature. The aged sample was then weighed to obtain mass mA2 i mB2. All sample mass measurements were performed with an accuracy of 1 mg. The average mass of the two containers in each test phase was used to obtain masses m0, m1, and m2. These values ​​were then substituted into the formula contained in the standard to produce the percentage change in sample mass, which is one of the measures of the aging resistance of polymer-modified asphalt. Finally, the average residual penetration % and softening point of the residual polymer asphalt at 25°C after the RTFOT test were measured according to PN-EN 12607-1 and compared with these parameter values ​​obtained for the PMB sample before the RTFOT test.

[0112] Used to determine hydroxyl functionality levels 1 H NMR spectroscopy

[0113] Functionalizations were determined by 1H NMR analysis at 130 °C using deuterated tetrachloroethane (TCE-D2) as solvent and recorded on a 5 mm tube of a Varian Mercury spectrometer operating at 400 MHz. Chemical shifts were reported in ppm relative to tetramethylsilane and determined with reference to residual solvent protons.

[0114] In this application, the hydroxyl functionality level includes not only the amount of OH groups in the polymer, but also the amount of OH groups that have reacted with SMA and are no longer present in the reaction product.

[0115] result

[0116] Figure 1 shows a fluorescence image of one embodiment of pure bitumen (Lo-s SA, grade 70 / 100) and its comparison with selected polymer-modified bitumen samples, namely POE-grafted-MAH, POE-grafted-SMA (Table 1, entry 10), poly(propylene-copoly-ethylene-copoly-10-undecene-1-ol) (Table 1, entry 19), poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol) (Table 1, entry 12), and poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol)-grafted-SMA (30 wt%) (Table 1, entry 15). The fluorescence image of pure bitumen shows a uniform structure with no fluorescent particles on the sample surface. The introduction of the modifier into the bitumen significantly affected the morphology, as several fluorescent clusters were observed. The polymer-based modifier swells in the bitumen and likely attracts aromatic units present in the bitumen. Therefore, the dispersion of asphalt modifiers can be easily analyzed using fluorescence microscopy. As shown in Figure 1, as an asphalt modifier, introducing up to approximately 2.5 wt% POE-grafted-MAH yielded a uniform distribution of the polymer in the asphalt matrix. Further increasing the POE-grafted-MAH content in the asphalt resulted in significant phase separation between the polymer and the matrix. The uniform morphology of the asphalt sample could again be observed through copolymerization of POE and SMA. Similar results can be observed in products modified with poly(propylene-copolymer-ethylene-copolymer-10-undecene-1-ol) and poly(propylene-copolymer-1-hexene-copolymer-10-undecene-1-ol)-grafted-SMA.

[0117] Figure 2 shows the surface morphology and mechanical properties obtained through HA-QNM experiments. AFM morphology images of pure asphalt show significant phase separation of the asphalt components and the presence of a uniformly dispersed "honeybee" structure on the sample surface. The appearance of this "honeybee" microstructure is believed to be a result of the chemical properties of the binder and various external factors such as temperature history, sample preparation, and annealing / resting time. These structures have also been reported to be associated with the presence of asphaltenes (the largest polar component in asphalt). Another hypothesis is that the "honeybee" structure contains nonpolar crystalline alkane waxes (linear n-alkanes), and sometimes the lack of "honeybee" structure in asphalt involves the binding of waxes with other asphalt components. As shown in Figure 2, the introduction of POE-grafted-MAH, POE-grafted-OH, or poly(propylene-copoly-ethylene-copoly-10-undecene-1-ol) into the asphalt resulted in the disappearance of the non-uniform "honeybee" microstructure and improved the asphalt surface morphology. AFM HA-QNM experiments showed that the introduction of functionalized polyolefins reduced the modulus of the material and improved the adhesion between the tip and the asphalt surface. This clearly demonstrates that the surface is more elastic and exhibits higher wettability compared to pure bitumen.

[0118] Figure 3 and 4 AFM images of asphalt modified with poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol) and poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol)-grafted-SMA are shown. The AFM images clearly demonstrate the absence of any non-uniform "bee" microstructure in the polymer-modified asphalt, the improved morphology, and the enhanced compatibility between the compositional components.

[0119] Figure 5-10 The DSR results are displayed. Figure 5 The storage modulus changes of pure asphalt and polymer-modified asphalt samples with respect to temperature are shown. Most of the polymer-modified asphalt samples shown exhibit improved elasticity compared to pure asphalt. As an asphalt modifier, the introduction of poly(propylene-copoly-5-hexen-1-ol)-grafted-SMA (with SMA content equal to 30 wt% in the graft copolymer) obtained by reactive extrusion alone did not improve the elasticity of the final product compared to pure asphalt.

[0120] Figure 6 The change in loss modulus with respect to temperature is shown. The polymer-modified asphalt used exhibits similar properties to pure asphalt, meaning that the plasticity of the asphalt remains unchanged. Figure 7 The relationship between the loss factor (tan[δ]) and temperature of the studied compositions is shown. This value should be as close to 0 as possible, up to approximately 80-90 °C. Significant improvements in the loss factor parameter were observed for all the modifiers shown. The best results were obtained for the asphalt samples modified with polymers of POE-grafted-OH and POE-grafted-SMA (SMA content in the graft copolymer equal to 11 wt%).

[0121] Figure 8 The data for the grooving parameter (G* / sin[δ]) relative to temperature are shown. According to the SuperPave standard, grooving occurs when this parameter is below 1 kPa. Most of the modifiers shown improved the properties of the asphalt. Introducing only poly(propylene-copoly-5-hexen-1-ol)-grafted-SMA (SMA content in the graft copolymer equals 30 wt%) obtained by reactive extrusion as an asphalt modifier did not improve the grooving resistance of the asphalt. The best results were obtained with polymer-modified asphalt using poly(propylene-copoly-ethylene-copoly-10-undecene-1-ol) and its SMA graft copolymer, which produced an improvement of approximately 8 °C in the grooving temperature of the modified asphalt.

[0122] Figure 9 The data show the complex modulus of polymer-modified asphalt samples with respect to temperature. All the asphalt modifiers used provided improvements in this parameter, indicating better resistance to permanent damage in the paving material.

[0123] Figure 10 The graph displayed is a "black chart" (complex modulus versus phase shift angle), similar to a van Grup-Palmen plot. Inflection points on the curve indicate structural or morphological changes that occurred in the modified bitumen during the measurement. These changes are temperature-dependent—the higher the temperature, the lower the complex modulus of the observed sample. Figure 10 It was shown that in the low modulus region, corresponding to high temperatures, all modified asphalt samples were more elastic than pure asphalt because they exhibited a lower phase angle. Among the modifiers shown, poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol)-grafted-SMA (SMA content in the graft copolymer equals 30 wt%), poly(propylene-copoly-ethylene-copoly-10-undecene-1-ol), and POE-grafted-OH, prepared in a reactor via solution methods, showed the best rheological properties.

[0124]

[0125]

[0126]

Claims

1. A modified asphalt comprising a randomly hydroxyl-functionalized polymer or a graft copolymer of a styrene-maleic anhydride copolymer (PO-graft-SMA) containing the randomly hydroxyl-functionalized polymer and a styrene-maleic anhydride copolymer, the polymer or graft copolymer being configured to generate a thermally reversible crosslinked network in the asphalt, wherein the randomly hydroxyl-functionalized polymer is selected from: poly(ethylene-copoly-5-hexen-1-ol), poly(ethylene-copoly-10-undecen-1-ol), poly(propylene-copoly-5-hexen-1-ol), poly(propylene-copoly-10-undecen-1-ol) or mixtures thereof, or based on an elastomer or plasticity selected from: poly(ethylene-copoly-1-hexen-copoly-5-hexen-1-ol), poly(ethylene-copoly-5-hexen-1-ol), poly(ethylene-copoly-5-hexen-1-ol), poly(ethylene-copoly-5-hexen-1-ol), poly(propylene ... -1-hexene-copoly-10-undecene-1-ol), poly(propylene-copoly-1-hexene-copoly-5-hexene-1-ol), poly(propylene-copoly-ethylene-copoly-5-hexene-1-ol), poly(propylene-copoly-1-hexene-copoly-10-undecene-1-ol), poly(propylene-copoly-ethylene-copoly-10-undecene-1-ol), poly(ethylene-copoly-1-octene-copoly-5-hexene-1-ol), poly(ethylene-copoly-1-octene-copoly-10-undecene-1-ol), poly(ethylene-copoly-norbornene-copoly-5-hexene-1-ol), poly(ethylene-copoly-norbornene-copoly-10-undecene-1-ol) or mixtures thereof, and T m Below 140°C, The amount of hydroxyl functional groups is 1-8 per polymer chain, and the hydroxyl functionality level is at least 0.05 mol% of the total polymer, which is achieved through... 1 HMNR measurement.

2. The asphalt according to claim 1, wherein the hydroxyl functionality level is higher than 0.1 mol% of the total polymer, which is achieved through... 1 HMNR measurement.

3. The asphalt according to claim 1 or 2, wherein the amount of the random hydroxyl-functionalized polymer is 0.5-10 wt% based on the weight of the composition.

4. The asphalt according to claim 3, wherein the amount of the random hydroxyl-functionalized polymer is less than 5 wt% based on the weight of the composition.

5. The asphalt according to claim 3, wherein the amount of the random hydroxyl-functionalized polymer is 1-2.5 wt% based on the weight of the composition.

6. The asphalt according to claim 3, wherein the amount of the random hydroxyl-functionalized polymer is 1 wt% based on the weight of the composition.

7. The asphalt according to claim 1, wherein the PO-grafted-SMA content is 1-10 wt%, wherein PO represents a polyolefin thermoplastic, plasmon, or elastomer.

8. The asphalt according to claim 7, wherein the PO-grafted-SMA content is 1-5 wt%, wherein PO represents a polyolefin thermoplastic, plastic, or elastomer.

9. The asphalt according to claim 7, wherein the PO-grafted-SMA content is 1-2.5 wt%, wherein PO represents a polyolefin thermoplastic, plasmon, or elastomer.

10. The asphalt according to any one of claims 7-9, wherein the PO-grafted-SMA is PP-grafted-SMA.

11. The asphalt according to claim 1 or 2, wherein the asphalt is a refinery or cracking unit residue or a reused paving material.

12. The bitumen according to claim 1 or 2, wherein the bitumen is recycled asphalt.

13. The asphalt according to claim 1 or 2, wherein at least one of the following parameters is satisfied: Viscosity at 180°C in Pas: <2 Pas, measured using a TermoElectron-Haake Viscotester 2 Plus viscometer according to EN 13302 standard; Average softening point in °C: >45.7, determined according to PN-EN 1427 standard; After aging, the Δ transmittance is <10, which is determined by rotating film oven test (RTFOT) according to PN-EN 12607-1 standard. Δ softening point after aging: <10, which is determined by rotating thin film oven test (RTFOT) according to PN-EN 12607-1 standard.

14. The asphalt according to claim 13, wherein two of the parameters are satisfied.

15. The asphalt according to claim 13, wherein three of the parameters are satisfied.

16. The asphalt according to claim 13, wherein four of the parameters are satisfied.

17. The bitumen according to claim 13, wherein the viscosity at 180°C, in Pas, is <1 Pas, as determined using a TermoElectron-Haake Viscotester 2 Plus viscometer according to EN13302.

18. The asphalt according to claim 13, wherein the Δ penetration rate after aging is <5, which is determined by rotating thin film oven test (RTFOT) according to PN-EN 12607-1 standard.

19. The asphalt according to claim 13, wherein the Δ softening point after aging is <5, which is determined by rotating thin film oven test (RTFOT) according to PN-EN 12607-1 standard.

20. The asphalt according to claim 1 or 2, wherein in the PO-grafted-SMA, the amount of PO is 60-95 wt% and the amount of SMA is 5-40 wt%.

21. The asphalt according to claim 20, wherein in PO-grafted-SMA, the amount of PO is 70-90 wt%.

22. The bitumen according to claim 20, wherein in the PO-grafted-SMA, the amount of PO is higher than 80 wt%.

23. The bitumen according to claim 20, wherein in PO-grafted-SMA, the amount of SMA is 10-30 wt%.

24. The bitumen according to claim 20, wherein in PO-grafted-SMA, the amount of SMA is less than 20 wt%.

25. The asphalt according to claim 1 or 2, wherein in the PO-grafted-SMA, the amount of PO is 60-90 wt% and the amount of SMA is 10-40 wt%.

26. The bitumen according to claim 25, wherein the amount of PO in the PO-grafted-SMA is 65-80 wt%.

27. The bitumen according to claim 25, wherein the amount of PO in the PO-grafted-SMA is 70-75 wt%.

28. The bitumen according to claim 25, wherein in PO-grafted-SMA, the amount of SMA is 20-35 wt%.

29. The bitumen according to claim 25, wherein in PO-grafted-SMA, the amount of SMA is 25-30 wt%.

30. Use of the bitumen according to any one of claims 1-29, for roofing or road applications.

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