Asphalt composition with an improved life span

Abstract

The invention is related to an amine-free mineral adhesion promoter composition for bitumen comprising at least of a non-functionalized polyolefin, a hydroxyl-functionalized propylene-based co- or terpolymer having degree of OH-functionalization between 0.1 and 0.6 mol%, more preferably 0.2 to 0.4 mol%, and an aluminum oxide hydroxide having an elemental metal content from a quantity up to 1.5 wt% of the hydroxyl-functionalized propylene-based co- or terpolymer; to a modified bitumen composition comprising at least: an amine-free mineral adhesion promoter composition according to the invention and neat bitumen; and finally to an asphalt composition comprising the modified bitumen composition according to the invention and some mineral aggregates.

Description

23POLY0046-WO-PCT ASPHALT COMPOSITION WITH AN IMPROVED LIFE SPAN TECHNICAL FIELD OF THE INVENTION

[0001] The present invention relates to an asphalt composition with an improved life span, an amine-free mineral adhesion promoter and its use in asphalt composition. TECHNOLOGICAL BACKGROUND OF THE INVENTION

[0002] Asphalt is generally constituted from a mixture comprising bitumen and mineral aggregates and optionally additives as amines, which are used as adhesion promoter to improve the affinity of the bitumen to the mineral aggregates. By improving the affinity of bitumen to the mineral aggregates, the asphalt composition is able to have a longer span life.

[0003] However, those amines are commonly considered as toxic component and could leak into the environment.

[0004] WO2022 / 101132 disclose the use of hydroxyl-functionalized polyolefins to enhance the mechanical performance of bitumen.

[0005] However, hydroxyl-functionalized polyolefins are expensive materials, and therefore, it is difficult to justify their usage inroad or roofing application when large quantities are required.

[0006] Therefore, there is a need for a cheaper non-toxic adhesion promoter, which will not deteriorate the mechanical property of the bitumen below the standard such as its penetration, softening point, wheel tracking slope, Indirect tensile strength ratio, degree of binder coverage upon 6h etc., and could eventually improve some of those parameters. SUMMARY

[0007] This object is achieved by the present invention.

[0008] In a first aspect the present invention relates to an amine-free mineral adhesion promoter composition for bitumen comprising at least a blend of: ^ A non-functionalized polyolefin having a Tmbelow 120 °C according to the DSC measurement within the description or being amorphous (meaning no melting temperature (Tm) ),23POLY0046-WO-PCT ^ A hydroxyl-functionalized propylene-based co- or terpolymer having a Tmbelow 100 °C according to the DSC measurement within the description or be amorphous (meaning no melting temperature (Tm) )and having degree of OH-functionalization between 0.1 and 0.6 mol%, more preferably 0.2 to 0.4 mol%.

[0009] In some embodiments, it further comprises an aluminum oxide hydroxide having an elemental metal content from a quantity up to 1.5 wt%, preferably 0.02 to 1.5 wt%, more preferably 0.05 to 1.0 wt%, more preferably 0.1 to 0.7 wt%, more preferably 0.2 to 0.6 wt% of the blend of non- functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer.

[0010] In some embodiments, the blend of non-functionalized polyolefin and hydroxyl- functionalized propylene-based co- or terpolymer consists of up to 90 wt% of the non-functionalized polyolefin is co- or terpolymer.

[0011] Preferably, the hydroxyl-functionalized propylene-based co- or terpolymer forms at least 0.5 wt% of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer, more preferably at least 1 wt%, more preferably at least 5 wt%, more preferably at least 10 wt%, even more preferably at least 30 wt%, and / or at most 90 wt%, preferably at most 80 wt% more preferably at most 70 wt% more preferably at most 60 wt% more preferably at most 50 wt% more preferably at most 40 wt%. In some embodiment the range of hydroxyl-functionalized propylene-based co- or terpolymer within the blend of non-functionalized polyolefin and hydroxyl- functionalized propylene-based co- or terpolymer could be selected from the following list 0.5 to 90; 0.5 to 80; 0.5 to 70; 0.5 to 60; 0.5 to 50; 0.5 to 40; 0.5 to 30; 0.5 to 20; 0.5 to 10; 0.5 to 5; 1 to 90; 1 to 80; 1 to 70; 1 to 60; 1 to 50; 1 to 40; 1 to 30; 1 to 20; 1 to 10; 1 to 5; 5 to 90; 5 to 80; 5 to 70; 5 to 60; 5 to 50; 5 to 40; 5 to 30; 5 to 20; 5 to 10; 10 to 90; 10 to 80; 10 to 70; 10 to 60; 10 to 50; 10 to 40; 10 to 30; 10 to 20; 20 to 90; 20 to 80; 20 to 70; 20 to 60; 20 to 50; 20 to 40; 20 to 30; 30 to 90; 30 to 80; 30 to 70; 30 to 60; 30 to 50; 30 to 40 wt% of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer.

[0012] In some embodiments, the non-functionalized polyolefin is selected from the list comprising: polyethylene, poly(ethylene–co–propylene), poly(ethylene–co–1-butene), poly(ethylene–co–1-hexene), poly(ethylene–co–1-octene), polypropylene, poly(propylene–co– ethylene), poly(propylene–co–1-butene), poly(propylene–co–1-hexene), poly(propylene–co–1- octene).23POLY0046-WO-PCT

[0013] In some embodiment, the hydroxyl-functionalized propylene-based co- or terpolymer is selected from the list comprising poly(propylene–co–5-hexen-1-ol), poly(propylene–co–7-octen- 1-ol), poly(propylene––co–10-undecen-1-ol), poly(propylene–co–ethylene–co–5-hexen-1-ol), poly(propylene–co–ethylene–co–7-octen-1-ol), poly(propylene–co–ethylene–co–10-undecen-1-ol), poly(propylene–co–1-butene–co–5-hexen-1-ol), poly(propylene–co–1-butene–co–7-octen-1-ol), poly(propylene–co–1-butene–co–10-undecen-1-ol), poly(propylene–co–1-hexene–co–5-hexen-1- ol), poly(propylene–co–1-hexene–co–7-octen-1-ol), poly(propylene–co–1-hexene–co–10- undecen-1-ol), poly(propylene–co–1-octene–co–5-hexen-1-ol), poly(propylene–co–1-octene–co– 7-octen-1-ol), poly(propylene–co–1-octene–co–10-undecen-1-ol).

[0014] In some embodiments, the amine-free mineral adhesion promoter composition further comprise one of the following compounds: poly(styrene–block–butadiene), star–poly(styrene– block–butadiene), poly(styrene–block–[ethylene–co–butylene–graft–(maleic anhydride)]–block– styrene).

[0015] In some embodiments, the further compound: poly(styrene–block–butadiene), star– poly(styrene–block–butadiene), or poly(styrene–block–[ethylene–co–butylene–graft–(maleic anhydride)]–block–styrene) is added in an quantity of 0.25:1 to 4:1 ratio in regard of the hydroxyl- functionalized propylene-based co- or terpolymer, preferably 1:1 ratio.

[0016] In some embodiment, the blend of non-functionalized polyolefin and hydroxyl- functionalized propylene-based co- or terpolymer consists of up to 50 wt% of the non-functionalized polyolefin co- or terpolymer.

[0017] In a second aspect, the present invention relates to a modified bitumen composition comprising at least: ^ Neat bitumen and ^ Amine-free mineral adhesion promoter according to the invention.

[0018] In some embodiments, the modified bitumen composition has at least the followings: ^ Avg. penetration < 80 dmm according to European Standard 1426, and ^ Avg. softening > 46 °C according to European Standard 1427, and ^ Δ softening point < 5 according to European Standard 13399 ^ Adhesion force > 40 nN according to SABIC Internal QNM-AFM method23POLY0046-WO-PCT ^ DMT modulus > 1.75 GPa according to SABIC Internal QNM-AFM method ^ Degree of binder coverage on Granite [%] >= 80, preferably >= 90 according to PN-84 / B- 06714 / 22, ^ Degree of binder coverage on Limestone [%] >= 60, preferably >= 70, more preferably >= 80 according to PN-84 / B-06714 / 22,

[0019] In a third aspect, the present invention relates to an asphalt composition comprising ^ Modified bitumen composition according to the invention in which the amine-free mineral adhesion promoter comprises up to 50 wt% of non-functionalized polyolefin in regard of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer, in a quantity of 1.0 to 10 wt% of the asphalt composition, and ^ Mineral aggregates in a quantity of 90 to 99.0 wt% of the asphalt composition.

[0020] In another aspect, the present invention relates to use of an amine-free mineral adhesion promoter composition according to the invention, in modified bitumen composition.

[0021] In another aspect, the present invention relates to use of a modified bitumen composition, according to the invention, in roofing application.

[0022] In a final aspect, the present invention relates to the use of an asphalt composition, according to the invention, in a road application. DETAILED DESCRIPTION

[0023] The present invention relates to an amine-free mineral adhesion promoter for bitumen, a modified bitumen usable in an asphalt composition and a new asphalt composition having a longer life span, by improving the affinity of bitumen to the mineral aggregates present within the composition of the asphalt.

[0024] In order for the asphalt to obtain such properties, an amine-free mineral adhesion promoter additive, which has the role of adhesion promoter, is added to the composition comprising bitumen and mineral aggregates.23POLY0046-WO-PCT

[0025] In some embodiments, the amine-free mineral adhesion promoter can be added in a preliminary step to the bitumen composition before that the newly modified bitumen composition is blended with the mineral aggregates.

[0026] In alternative embodiments, the amine-free mineral adhesion promoter can be added during the blend of bitumen (neat) and mineral aggregates in order to form the asphalt composition.

[0027] The commonly used amine-free mineral adhesion promoters are fatty aliphatic amines, such as the Teramin family of product from ICSO Chemical Production. This promoter enhances the adhesion to mineral aggregates, in particular acidic aggregates (granodiorite, granite, quartzite, porphyry).

[0028] However, due to the amine within their composition, those amine-based promoters are commonly considered as toxic components and could leak into the environment when the asphalt deteriorates.

[0029] Therefore, the goal of this invention is to present a new amine-free composition, which has better property as compared to neat bitumen and having similar or improved properties as bitumen comprising an amine-based amine-free mineral adhesion promoter in their composition. “Amine-free” asphalt composition according to the invention

[0030] Accordingly, the new “amine-free” asphalt composition according to the invention comprises at least: a. Neat bitumen, b. Mineral aggregates, preferably in a quantity of 90 to 99 wt%, preferably from 93 to 95 wt% of the asphalt composition, c. An additive package, which comprises at least an amine-free mineral adhesion promoter according to the invention, or alternately at least: a. Modified bitumen according to the invention, preferably in a quantity from 1 to 10 wt%, preferably 5 to 7 wt% of the asphalt composition, b. Mineral aggregates, in a quantity from 90 to 99 wt%, preferably from 93 to 95 wt% of the asphalt composition.23POLY0046-WO-PCT

[0031] In an embodiment, the “amine-free” asphalt composition according to the invention comprises: a. Mineral aggregates in a quantity from 90 to 99 wt.% of the asphalt composition b. A modified bitumen composition in a quantity from 1.0 to 10 wt.% of the asphalt composition which comprises i. Neat bitumen in a quantity from 90 to 99 wt.% of the modified bitumen composition, ii. A non-functionalized polyolefin having a Tmbelow 120 °C, preferably below 100 °C and preferably selected from the list comprising: polyethylene, poly(ethylene–co–propylene), poly(ethylene–co–1-butene), poly(ethylene– co–1-hexene), poly(ethylene–co–1-octene), polypropylene, poly(propylene– co–ethylene), poly(propylene–co–1-butene), poly(propylene–co–1-hexene), poly(propylene–co–1-octene), iii. A hydroxyl-functionalized propylene-based co- or terpolymer having a Tmbelow 100 °C, preferably below 90 °C, and preferably selected from the list comprising: poly(propylene–co–5-hexen-1-ol), poly(propylene–co–7-octen- 1-ol), poly(propylene––co–10-undecen-1-ol), poly(propylene–co–ethylene– co–5-hexen-1-ol), poly(propylene–co–ethylene–co–7-octen-1-ol), poly(propylene–co–ethylene–co–10-undecen-1-ol), poly(propylene–co–1- butene–co–5-hexen-1-ol), poly(propylene–co–1-butene–co–7-octen-1-ol), poly(propylene–co–1-butene–co–10-undecen-1-ol), poly(propylene–co–1- hexene–co–5-hexen-1-ol), poly(propylene–co–1-hexene–co–7-octen-1-ol), poly(propylene–co–1-hexene–co–10-undecen-1-ol), poly(propylene–co–1- octene–co–5-hexen-1-ol), poly(propylene–co–1-octene–co–7-octen-1-ol), poly(propylene–co–1-octene–co–10-undecen-1-ol), preferably from the list comprising poly(propylene–co–5-hexen-1-ol), poly(propylene–co–ethylene– co–5-hexen-1-ol), poly(propylene–co–1-hexene–co–5-hexen-1-ol), poly(propylene–co–1-octene–co–5-hexen-1-ol) and having a degree of OH- functionalization between 0.1 and 0.6 mol%, more preferably 0.2 to 0.5 mol%, iv. Optionally an aluminum oxide hydroxide having an elemental metal content in a quantity up to 1.5 wt% of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer, v. Optionally a styrene-based copolymer, preferably selected from poly(styrene–block–butadiene), star–poly(styrene–block–butadiene),23POLY0046-WO-PCT poly(styrene–block–[ethylene–co–butylene–graft–(maleic anhydride)]– block–styrene), or mixtures thereof, in a quantity from 1.25 to 5.0 wt% of the amine-free mineral adhesion promoter, wherein preferably the ratio between non-functionalized polyolefin and hydroxyl- functionalized propylene-based co- or terpolymer between 90 wt% / 10 wt% to 10 wt% / 90 wt%, preferably 50 wt% / 50 wt%.

[0032] In another embodiment, the “amine-free” asphalt composition according to the invention comprises: a. Mineral aggregates in a quantity from 93 to 95 wt% of the asphalt composition, b. A modified bitumen composition in a quantity from 5.0 to 7.0 wt% of the asphalt composition, which comprises i. A neat bitumen in a quantity from 97.5 to 98.75 wt% of the modified bitumen composition, ii. A non-functionalized polyolefin having a Tmbelow 120 °C, preferably below 100 °C and preferably selected from the list comprising: polyethylene, poly(ethylene–co– propylene), poly(ethylene–co–1-butene), poly(ethylene–co–1-hexene), poly(ethylene– co–1-octene), polypropylene, poly(propylene–co–ethylene), poly(propylene–co–1- butene), poly(propylene–co–1-hexene), poly(propylene–co–1-octene), preferably poly(propylene–co–1-hexene), iii. A hydroxyl-functionalized propylene-based co- or terpolymer having a Tmbelow 100 °C, preferably below 90 °C preferably selected from the list comprising: poly(propylene–co–5-hexen-1-ol), poly(propylene–co–7-octen-1-ol), poly(propylene–– co–10-undecen-1-ol), poly(propylene–co–ethylene–co–5-hexen-1-ol), poly(propylene–co–ethylene–co–7-octen-1-ol), poly(propylene–co–ethylene–co–10- undecen-1-ol), poly(propylene–co–1-butene–co–5-hexen-1-ol), poly(propylene–co– 1-butene–co–7-octen-1-ol), poly(propylene–co–1-butene–co–10-undecen-1-ol), poly(propylene–co–1-hexene–co–5-hexen-1-ol), poly(propylene–co–1-hexene–co–7- octen-1-ol), poly(propylene–co–1-hexene–co–10-undecen-1-ol), poly(propylene–co– 1-octene–co–5-hexen-1-ol), poly(propylene–co–1-octene–co–7-octen-1-ol), poly(propylene–co–1-octene–co–10-undecen-1-ol), preferably poly(propylene–co–1- hexene–co–5-hexen-1-ol), having a degree of OH-functionalization between 0.1 to 0.4 mol%, preferably between 0.2 to 0.3 mol%, in a quantity of 2 to 3 wt%, preferably 2.3 to 2.7 wt% of the modified bitumen composition,23POLY0046-WO-PCT iv. An aluminum oxide hydroxide having an elemental metal content from a quantity of 0 to 1.5 wt%, preferably from 0.2 to 0.6 wt% of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer within the asphalt composition, wherein the part of non-functionalized polyolefin and hydroxyl-functionalized propylene- based co- or terpolymer is between 2 to 3 wt%, preferably 2.3 to 2.7 wt% of the modified bitumen composition and wherein the ratio between non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer is between 90 wt% / 10 wt% to 10 wt% / 90 wt%, preferably 50 wt% / 50 wt%.

[0033] In another embodiment, the “amine-free” asphalt composition according to the invention comprises: ^ Mineral aggregates in a quantity of 93 to 95 wt%, preferably 93.5 to 94.5 wt.% of the asphalt composition, ^ A modified bitumen composition in a quantity of 5 to 7 wt%, preferably 5.5 to 6.5 wt.% of the asphalt composition, which comprises: a. Neat bitumen in a quantity of 97 to 98 wt%, preferably 97.3 to 97.7 wt% modified bitumen b. A non-functionalized polyolefin having a Tmbelow 120 °C, preferably below 100 °C and preferably selected from the list comprising: polyethylene, poly(ethylene–co– propylene), poly(ethylene–co–1-butene), poly(ethylene–co–1-hexene), poly(ethylene–co–1-octene), polypropylene, poly(propylene–co–ethylene), poly(propylene–co–1-butene), poly(propylene–co–1-hexene), poly(propylene–co–1- octene), preferably poly(propylene–co–1-hexene), c. A hydroxyl-functionalized propylene-based co- or terpolymer having a Tmbelow 100 °C, preferably below 90 °C preferably selected from the list comprising: poly(propylene–co–5-hexen-1-ol), poly(propylene–co–7-octen-1-ol), poly(propylene––co–10-undecen-1-ol), poly(propylene–co–ethylene–co–5-hexen-1- ol), poly(propylene–co–ethylene–co–7-octen-1-ol), poly(propylene–co–ethylene– co–10-undecen-1-ol), poly(propylene–co–1-butene–co–5-hexen-1-ol), poly(propylene–co–1-butene–co–7-octen-1-ol), poly(propylene–co–1-butene–co– 10-undecen-1-ol), poly(propylene–co–1-hexene–co–5-hexen-1-ol), poly(propylene– co–1-hexene–co–7-octen-1-ol), poly(propylene–co–1-hexene–co–10-undecen-1-23POLY0046-WO-PCT ol), poly(propylene–co–1-octene–co–5-hexen-1-ol), poly(propylene–co–1-octene– co–7-octen-1-ol), poly(propylene–co–1-octene–co–10-undecen-1-ol), having a degree of OH-functionalization between 0.1 to 0.4 mol%, preferably between 0.2 to 0.3 mol%, in a quantity of 2 to 3 wt%, preferably 2.3 to 2.7 wt% of modified bitumen composition, d. An aluminum oxide hydroxide having an elemental metal content, preferably in a quantity of 0.1 to 0.7 wt%, preferably 0.2 to 0.6 wt% of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer, wherein the part of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer is between 2 to 3 wt%, preferably 2.3 to 2.7 wt% of the modified bitumen composition and wherein the ratio between non-functionalized polyolefin and hydroxyl-functionalized propylene- based co- or terpolymer between 90 wt% / 10 wt% to 10 wt% / 90 wt%, preferably 50 wt% / 50 wt%. Modified Bitumen according to the invention

[0034] Accordingly, the modified bitumen according to the invention comprise: ^ Neat bitumen ^ Amine-free mineral adhesion promoter according to the invention

[0035] In some embodiments, the amount of the amine-free mineral adhesion promoter according to the invention within the modified bitumen composition is from 1 wt% to 7 wt%, preferably from 1.25 wt% to 5 wt%, more preferably from 2 wt% to 3 wt%.

[0036] In some embodiments, the bitumen having the amine-free mineral adhesion promoter according the invention in its composition, has at least the followings: ^ Avg. penetration < 80 dmm according to EN 1426, and ^ Avg. softening > 46 °C according to EN 1427, and ^ Δ penetration < 5 and / or Δ softening point < 5 according to EN 13399, and ^ Adhesion force > 37 nN according to SABIC Internal QNM-AFM method ^ DMT modulus > 1.75 GPa according to SABIC Internal QNM-AFM method ^ Degree of binder coverage on Granite [%] >= 70, preferably >= 80 preferably >= 90 according to PN-84 / B-06714 / 22,23POLY0046-WO-PCT ^ Degree of binder coverage on Limestone [%] >= 60, preferably >= 70, more preferably >= 80 according to PN-84 / B-06714 / 22

[0037] An embodiment of the invention is a modified bitumen having this following composition: a. A neat bitumen in a quantity of 97 to 98 wt%, preferably 97.3 to 97.7 wt% modified bitumen composition, b. A non-functionalized polyolefin having a Tmbelow 120 °C, preferably below 100 °C and preferably selected from the list comprising: polyethylene, poly(ethylene–co– propylene), poly(ethylene–co–1-butene), poly(ethylene–co–1-hexene), poly(ethylene–co–1-octene), polypropylene, poly(propylene–co–ethylene), poly(propylene–co–1-butene), poly(propylene–co–1-hexene), poly(propylene–co–1- octene), preferably poly(propylene–co–1-hexene), c. A hydroxyl-functionalized propylene-based co- or terpolymer having a Tmbelow 100 °C, preferably below 90 °C preferably selected from the list comprising: poly(propylene–co–5-hexen-1-ol), poly(propylene–co–7-octen-1-ol), poly(propylene––co–10-undecen-1-ol), poly(propylene–co–ethylene–co–5-hexen-1- ol), poly(propylene–co–ethylene–co–7-octen-1-ol), poly(propylene–co–ethylene– co–10-undecen-1-ol), poly(propylene–co–1-butene–co–5-hexen-1-ol), poly(propylene–co–1-butene–co–7-octen-1-ol), poly(propylene–co–1-butene–co– 10-undecen-1-ol), poly(propylene–co–1-hexene–co–5-hexen-1-ol), poly(propylene– co–1-hexene–co–7-octen-1-ol), poly(propylene–co–1-hexene–co–10-undecen-1- ol), poly(propylene–co–1-octene–co–5-hexen-1-ol), poly(propylene–co–1-octene– co–7-octen-1-ol), poly(propylene–co–1-octene–co–10-undecen-1-ol), having a degree of OH-functionalization between 0.1 to 0.4 mol%, preferably between 0.2 to 0.3 mol%, in a quantity of 2 to 3 wt%, preferably 2.3 to 2.7 wt% of modified bitumen composition d. An aluminum oxide hydroxide having an elemental metal content, preferably in a quantity of 0.10 to 0.7 wt%, preferably 0.2 to 0.6 wt% of the blend of non- functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer, wherein the part of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer is between 2 to 3 wt%, preferably 2.3 to 2.7 wt% of the modified bitumen composition and23POLY0046-WO-PCT wherein the ratio between non-functionalized polyolefin and hydroxyl-functionalized propylene- based co- or terpolymer between 90 wt% / 10 wt% to 10 wt% / 90 wt%, preferably 50 wt% / 50 wt%. Amine-free mineral adhesion promoter according to the invention

[0038] Surprisingly, the inventors of the present application found that a blend of a non- functionalized olefin with hydroxyl-functionalized propylene-based co- or terpolymers having a melting temperature (Tm) below 100 °C or being atactic, is suitable to act as amine-free mineral adhesion promoter and is a good alternative to amine-based mineral adhesion promoters.

[0039] In some embodiments, the quantity of non-functionalized polyolefin is up to 90 wt% of the blend.

[0040] In some embodiments, the quantity of non-functionalized polyolefin it at most 50 wt% of the blend.

[0041] The inventors found that this non-functionalized polyolefin maximum limit (at most 50 wt%) allows to obtain modified bitumen suitable to be used for road application. However, with a quantity of non-functionalized polyolefin up to 90 wt% of the blend, the modified bitumen is still suitable to be used for roofing application.

[0042] In some embodiments, the amine-free mineral adhesion promoter could further comprise in addition to the hydroxyl-functionalized propylene-based co- or terpolymer, an aluminum oxide hydroxide. As inventors surprisingly discovered, the interaction of aluminum oxide hydroxide with the co- or terpolymers structure can increase softening point, stiffness, compatibility and hence, storage stability of the polymer modified bitumen.

[0043] The amount of aluminum oxide hydroxide shall not be above an elemental metal content of 1.5 wt% of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer within the asphalt composition, as its presence within the asphalt composition decreases the adhesion to mineral aggregates. Preferably, the amount of aluminum oxide hydroxide is between having an elemental metal content of 0.02 and 1.5 wt%, preferably 0.05 and 1.0 wt%, more preferably 0.1 and 0.7 wt%, more preferably 0.2 and 0.6 wt% of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer.23POLY0046-WO-PCT

[0044] Preferably, the total amount of the aluminum content with the blend shall have an elemental metal content between 0.2 to 0.6 wt%.

[0045] The introduction of aluminum oxide hydroxide can be achieved by incorporation of organoaluminum compounds, more preferably aluminum alkyls, at the commencement stage of the synthesis of the non-functionalized polyolefin and / or the hydroxyl-functionalized propylene-based co- or terpolymer. These aluminum alkyls can react with the hydroxyl functionality of the functional comonomer. Aluminum alkyl species are known in the art, in particular in WO2022 / 106689 as functional comonomer passivating agents, which prevent poisoning and deactivation of the catalyst’s oxophilic metal center during the polymerization. Hydrolysis of the aluminum alkyl- passivated hydroxyl-functionalized propylene-based co- or terpolymers affords hydroxyl- functionalized propylene-based co- or terpolymers having finely dispersed aluminum oxide hydroxide residues.

[0046] Preferably, aluminum alkyl precursors providing, after hydrolysis, crosslinking of hydroxyl-functionalized comonomer segments within propylene-based co- or terpolymers architecture in the form of aluminum oxide hydroxide nodes can be selected from the group comprising: triisobutylaluminum (TiBA), triethylaluminum (TEA), methylaluminumoxane (MAO), trimethyl aluminum (TMA) or a mixture thereof.

[0047] In some embodiment, which contains aluminum oxide hydroxide, the aluminum oxide hydroxide is the hydrolysis product of the passivating agent residue used to passivate the hydroxyl functional groups of one of the monomers during the synthesis of the hydroxyl functionalized propylene-based co- or terpolymer.

[0048] In some embodiment, the blend of a non-functionalized olefin with the hydroxyl- functionalized propylene-based co- or terpolymers according to the invention is produced by mixing the non-functionalized polyolefin and the hydroxyl-functionalized propylene-based co- or terpolymers in the melt, using for example an extruder, or by dissolving the polymers in a common solvent followed by precipitation the polymer blend in a non-solvent or by flashing off the solvent in a devolatizer unit.

[0049] In another embodiment, the blend of a non-functionalized olefin with hydroxyl- functionalized propylene-based co- or terpolymers, according to the invention, is produced by a23POLY0046-WO-PCT cascade solution polymerization process using two or more reactors in series where the non- functionalized polyolefin is being produced in one reactor and the hydroxyl-functionalized propylene-based co- or terpolymers is produced in the other reactor, followed by flashing off the solvent in a devolatizer unit. This solution process is preferred as it affords blend of the functionalized polymer within the non-functionalized polymer mixed at a molecular level, which is better than the melt extrusion process cannot achieve.

[0050] In some embodiment, the amine-free mineral adhesion promoter comprises: a. A non-functionalized polyolefin having a Tmbelow 120 °C, preferably below 100 °C and preferably selected from the list comprising: polyethylene, poly(ethylene–co– propylene), poly(ethylene–co–1-butene), poly(ethylene–co–1-hexene), poly(ethylene–co–1-octene), polypropylene, poly(propylene–co–ethylene), poly(propylene–co–1-butene), poly(propylene–co–1-hexene), poly(propylene–co–1- octene), b. A hydroxyl-functionalized propylene-based co- or terpolymer having a Tmbelow 100 °C, preferably below 90 °C, and preferably selected from the list comprising: poly(propylene–co–5-hexen-1-ol), poly(propylene–co–7-octen-1-ol), poly(propylene––co–10-undecen-1-ol), poly(propylene–co–ethylene–co–5-hexen-1- ol), poly(propylene–co–ethylene–co–7-octen-1-ol), poly(propylene–co–ethylene– co–10-undecen-1-ol), poly(propylene–co–1-butene–co–5-hexen-1-ol), poly(propylene–co–1-butene–co–7-octen-1-ol), poly(propylene–co–1-butene–co– 10-undecen-1-ol), poly(propylene–co–1-hexene–co–5-hexen-1-ol), poly(propylene– co–1-hexene–co–7-octen-1-ol), poly(propylene–co–1-hexene–co–10-undecen-1- ol), poly(propylene–co–1-octene–co–5-hexen-1-ol), poly(propylene–co–1-octene– co–7-octen-1-ol), poly(propylene–co–1-octene–co–10-undecen-1-ol), preferably from the list comprising poly(propylene–co–5-hexen-1-ol), poly(propylene–co– ethylene–co–5-hexen-1-ol), poly(propylene–co–1-hexene–co–5-hexen-1-ol), poly(propylene–co–1-octene–co–5-hexen-1-ol) and preferably having a degree of OH-functionalization between 0.1 and 0.6 mol%, more preferably 0.2 to 0.5 mol%, c. Optionally, an aluminum oxide hydroxide having an elemental metal content from a quantity up to 1.5 wt% of the blend of non-functionalized polyolefin and hydroxyl- functionalized propylene-based co- or terpolymer, d. Optionally a styrene-based copolymer, preferably selected from poly(styrene–block– butadiene), star–poly(styrene–block–butadiene), poly(styrene–block–[ethylene–co–23POLY0046-WO-PCT butylene–graft–(maleic anhydride)]–block–styrene), or mixtures thereof, in a quantity from 1.25 to 5.0 wt% of the amine-free mineral adhesion promoter. wherein preferably the ratio between non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer between 90 wt% / 10 wt% to 10 wt% / 90 wt%, preferably 50 wt% / 50 wt%.

[0051] In an embodiment, the amine-free mineral adhesion promoter composition comprises: a. Poly(propylene–co–1-hexene) having a Tmbelow 120 °C, preferably below 100 °C b. Poly(propylene–co–1-hexene–co–5-hexen-1-ol) having a Tmbelow 100 °C, preferably below 90 °C, having degree of OH-functionalization between 0.2 or 0.4 mol%, c. An aluminum oxide hydroxide having an elemental metal content in a quantity of 0.2 to 0.6 wt% of the amine-free mineral adhesion promoter composition, wherein the content of poly(propylene–co–1-hexene) is from 10 to 90 wt% of the amine-free mineral adhesion promoter composition. Non-functionalized olefin according to the invention

[0052] The non-functionalized polyolefin according to the invention suitable to be integrated in to the blend of the amine-free mineral adhesion promoter according to the invention is formula (1): whereinx is at least 50 mol%, preferably at least 80 mol%, y is 0 or 100-(x) mol%, R1is H or CH3, R2is selected from the list comprising: hydrocarbyl group having 0 to 10 carbon atoms, preferentially 1 to 6 and more preferentially 1 or 6 when R1= H, and preferably 0, 2, 4 or 6 and more preferentially 0 or 4 when R1= CH3.23POLY0046-WO-PCT

[0053] Preferably, the non-functionalized polyolefin is either amorphous or semi-crystalline with a Tmbelow 120 °C, preferably below 100 °C, and is atactic, isotactic or syndiotactic.

[0054] In some embodiment, the non-functionalized polyolefin is selected from the list comprising: polyethylene, poly(ethylene–co–propylene), poly(ethylene–co–1-butene), poly(ethylene–co–1-hexene), poly(ethylene–co–1-octene), polypropylene, poly(propylene–co– ethylene), poly(propylene–co–1-butene), poly(propylene–co–1-hexene), poly(propylene–co–1- octene).

[0055] In some embodiment, the non-functionalized polyolefin is having: ^ Number average molecular weight (Mn) between 4 to 200 kg / mol, preferably between 10 to 150 kg / mol, measured by the method described in the section “Size exclusion chromatography (SEC)” of the Measurement and Methods section of the present disclosure, ^ Polydispersity index (Đ) ranging from 1.5 to 12, preferably from 2 to 8, more preferably from 2.5 to 5, measured by the method described in the section “Size exclusion chromatography (SEC)” of the Measurement and Methods section of the present disclosure, ^ Crystallinity (Xc) content between 0 and 30 %, preferably 8 and 25 %, more preferably between 10 and 15 %, measured by the method described in the section “Differential scanning calorimetry (DSC)” of the Measurement methods section of the present disclosure, ^ Melting temperature (Tm) for a semi-crystalline polymer between 40 and 120 °C, preferably between 60 and 110 °C, more preferably between 70 and 100 °C, or no melting temperature for an amorphous polymer, measured by the method described in the section “Differential scanning calorimetry (DSC)” of the Measurement methods section of the present disclosure, Hydroxyl-functionalized propylene-based co- or terpolymer according to the invention

[0056] The hydroxyl-functionalized propylene-based co- or terpolymer according to the invention is a polymer comprising propylene, optionally a second olefin monomer and a hydroxyl functionalized olefin and having a melting temperature (Tm) below 100 °C, preferably below 90 °C to be able to be processed in an asphalt / bitumen composition.

[0057] Preferably, the co- or terpolymer is either amorphous or semi-crystalline, and atactic, isotactic or syndiotactic.23POLY0046-WO-PCT

[0058] Preferably, the hydroxyl-functionalized propylene-based co- or terpolymer according to formula (2) consists of at least propylene, optionally a second olefin and a hydroxyl-functionalized C2to C12, preferably C4to C12, more preferably C4to C10olefin monomer: wherein^ x is at least 80 mol%, ^ z is 0.1 to 1 mol%, preferably 0.1 to 0.6 mol%, more preferably 0.2 to 0.5 mol%. ^ y is 100-(x+z) mol%, ^ R3is selected from the list comprising: hydrocarbyl group having 0 to 10 carbon atoms, preferentially 0 to 6 and more preferentially 1 or 4, ^ R4is an hydrocarbyl group having 2 to 10 carbon atoms, preferentially 2 to 8, preferentially 4 to 8, more preferentially 4 or 6

[0059] In some embodiment, the second olefin monomer can be selected from the group comprising: ethylene, 1-butene, 1-hexene, 1-octene, 1-decene.

[0060] In some embodiment, the hydroxyl-functionalized olefin can be selected from the group comprising: 5-hexen-1-ol, 7-octen-1-ol 10-undecen-1-ol.

[0061] Preferably, the hydroxyl-functionalized propylene-based co- or terpolymer can be selected from the group comprising: poly(propylene–co–5-hexen-1-ol), poly(propylene–co–7-octen- 1-ol), poly(propylene––co–10-undecen-1-ol), poly(propylene–co–ethylene–co–5-hexen-1-ol), poly(propylene–co–ethylene–co–7-octen-1-ol), poly(propylene–co–ethylene–co–10-undecen-1-ol), poly(propylene–co–1-butene–co–5-hexen-1-ol), poly(propylene–co–1-butene–co–7-octen-1-ol), poly(propylene–co–1-butene–co–10-undecen-1-ol), poly(propylene–co–1-hexene–co–5-hexen-1- ol), poly(propylene–co–1-hexene–co–7-octen-1-ol), poly(propylene–co–1-hexene–co–10- undecen-1-ol), poly(propylene–co–1-octene–co–5-hexen-1-ol), poly(propylene–co–1-octene–co– 7-octen-1-ol), poly(propylene–co–1-octene–co–10-undecen-1-ol), or a mixture of them, and having23POLY0046-WO-PCT a hydroxyl-functionalized olefin comonomer content between 0.1 and 0.6 mol%, more preferably 0.2 to 0.5 mol%.

[0062] In some embodiment, the hydroxyl-functionalized propylene-based co- or terpolymer is having: ^ Number average molecular weight (Mn) ranging from 2 to 150 kg / mol, preferably from 4 to 150 kg / mol, preferably from 2 to 9 kg / mol, preferably 10 to 50 kg / mol, preferably 55 to 150 kg / mol, more preferably from 100 to 150 kg / mol, more preferably 4 to 30 kg / mol, measured by the method described in the section “Size exclusion chromatography (SEC)” of the Measurement methods section of the present disclosure, ^ Polydispersity index (Đ) from 1.5 to 8, preferably from 2 to 7, preferably from 1.5 to 6, preferably from 3 to 7, more preferably 2, to 6, measured by the method described in the section “Size exclusion chromatography (SEC)” of the Measurement methods section of the present disclosure, ^ Crystallinity (Xc) content below 30 %, preferably below 15 %, more preferably below 10 %, or 0 % for a fully amorphous polymer, measured by the method described in the section “Differential scanning calorimetry (DSC)” of the Measurement methods section of the present disclosure, ^ Melting temperature (Tm) for a semi-crystalline polymer between 40 and 100 °C, preferably between 60 °C and 90 °C, more preferably between 70 °C and 90 °C, or no melting temperature for a fully amorphous polymer, measured by the method described in the section “Differential scanning calorimetry (DSC)” of the Measurement methods section of the present disclosure.

[0063] The hydroxyl-functionalized propylene-based co- or terpolymer can be produced in a solution process according to the process described in WO2022 / 106689 using the one of the following catalyst precursors: bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5- (methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV) dimethyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9- octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3- propanediylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2- phenoxy)-1,3-propanediylhafnium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5- (methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1H- pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV) dibenzyl, bis((2-oxoyl-3-23POLY0046-WO-PCT (1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4- butanediylhafnium (IV) dimethyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5- (methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV) dichloride, bis((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4- butanediylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2- phenoxymethyl)-1,4-butanediylhafnium (IV)dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5- (methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV) dibenzyl, bis((2- oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4- pentanediylhafnium (IV) dimethyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5- (methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9- octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4- pentanediylhafnium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2- phenoxy)-2,4-pentanediylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9- octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans- 1,2- cyclohexanediylhafnium (IV) dimethyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5- (methyl)phenyl)-2-phenoxymethyl)-methylenetrans- 1,2-cyclohexanediylhafnium (IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)- methylenetrans- 1,2-cyclohexanediylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1- yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2- cyclohexanediylhafnium (IV) dichloride, and bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5- (methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV) dimethyl, bis((2-oxoyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3- propylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2- phenoxy)-1,4-n-butylhafnium (IV) dimethyl, bis((2-oxoyl-3-(3,6-bis(1,1-dimethylethyl)-9H- carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(4-methoxy-3,5- bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV) dimethyl, bis((2-oxoyl-3-23POLY0046-WO-PCT (4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV) dimethyl, bis((2- oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV) dibenzyl, bis((2-oxoyl- 3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV) dimethyl; preferably bis((2- oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4- pentanediylhafnium (IV) dichloride; or a zirconium complex of a polyvalent aryloxyether selected from the group: bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4- pentanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2- phenoxy)-2,4- pentanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9- octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5- (methyl)phenyl)-2-phenoxy)-1,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H- pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3- (dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2- phenoxymethyl)-1,4-butanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9- octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4- butanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2- phenoxymethyl)-1,4- butanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5- (methyl)phenyl)-2-phenoxymethyl)-1,4- butanediylzirconium (IV)dimethyl, bis((2-oxoyl-3-(dibenzo- 1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4- butanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4- butanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5- (methyl)phenyl)-2-phenoxy)-2,4- pentanediylzirconium (IV) dimethyl, bis((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4- pentanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2- phenoxy)-2,4- pentanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5- (methyl)phenyl)-2-phenoxy)-2,4- pentanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3- (1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans- 1,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5- yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans- 1,2- cyclohexanediylzirconium (IV)23POLY0046-WO-PCT dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2- phenoxymethyl)-methylenetrans- 1,2- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3- (dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5- (methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2- cyclohexanediylzirconium (IV) dichloride, and bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans- 1,2- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(4-methoxy-3,5-bis(1,1- dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV) dimethyl, bis((2-oxoyl-3-(4- methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,2-ethylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,2-ethylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3- propylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2- phenoxy)-1,4-n-butylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,6-bis(1,1-dimethylethyl)-9H- carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV) dibenzyl; preferably bis((2-oxoyl-3- (dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium (IV) dichloride;

[0064] Other suitable metal catalyst precursors can also be the trivalent transition metal as those described in WO 9319104 or in WO 9613529, for example [(C5H4)CH2CH2N(Me)2]MCl2, [(C5Me4)CH2CH2N(Me)2]MCl2, [(C5H4)CH2CH2N(i-Pr)2]MCl2, [(C5Me4)CH2CH2N(i-Pr)2]MCl2, [(C5H4)CH2CH2N(n-Bu)2]MCl2, [(C5Me4)CH2CH2N(n-Bu)2]MCl2, [(C9H6)CH2CH2N(Me)2]MCl2, [(C9H6)CH2CH2N(i-Pr)2]MCl2, [(C5Me4)C9H6N]MCl2, [(C5Me3(SiMe3))C9H6N]MCl2, [(C9H6)C9H6N]MCl2, [(C5Me4)CH2C5H4N]MCl2or [(C9H6)CH2C5H4N]MCl2, where M is titanium or chromium. Examples of catalyst precursors are (C5Me4)CH2CH2N(Me)2]TiCl2, [C6H5C(NSiMe3)2]TiCl2(THF)2and [C6H5C(NSiMe3)CH2CH2N(CH3)2]TiCl2(THF).23POLY0046-WO-PCT

[0065] Other non-limiting examples of metal catalyst precursors that would be suitable according to the present invention are: (pyrrolidinyl)ethyl-tetramethylcyclopentadienyl titanium dichloride, (N,N-dimethylamino)ethyl-fluorenyl titanium dichloride, (bis(1-methyl- ethyl)phosphino)ethyl-tetramethylcyclopentadienyl titanium dichloride, (bis(2-methyl- propyl)phosphino)ethyl-tetramethylcyclopentadienyl titanium dichloride, (diphenylphosphino)ethyl- tetramethylcyclopentadienyl titanium dichloride, (diphenylphosphino)methyldimethylsilyl- tetramethylcyclopentadienyl titanium dichloride.

[0066] According to the invention, other suitable catalyst precursors can be for example {N',N"-bis[2,6-di(1-methylethyl)phenyl]-N,N-diethylguanidinato} metal dichloride, {N',N"bis[2,6-di(1- methylethyl)phenyl]-N-methyl-N-cyclohexylguanidinato} metal dichloride, {N',N"-bis[2,6-di(1- methylethyl)phenyl]-N,N-pentamethyleneguanidinato} metal dichloride, {N',N"-bis[2,6- di(methyl)phenyl]-sec-butyl-aminidinato} metal dichloride, {N,N’-bis(trimethylsilyl)benzamidinato} metal dichloride, {N-trimethylsilyl,N’-(N”,N”-dimethylaminomethyl)benzamidinato} metal dichloride and their THF or other Lewis base adducts, where metal is titanium or chromium.

[0067] Other suitable metal catalyst precursors can also be hafnium or zirconium or titanium complex supported by a dianionic tri-and / or tetra-dentate ligand, for example: 2'-((3-(9H-carbazol- 9-yl)-2-olato-5- methylphenyl)(3- methoxypropyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'- biphenyl]-2-olato] dimethyl hafnium; 2'-((3-(9H-carbazol-9-yl)-2-olato-5- methylphenyl)(3- methoxypropyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [2'-((3-(9H-carbazol-9-yl)-2-olato-5- methylphenyl)(3- methoxypropyl)amino)-3-(adamantan-1-yl)-5- methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [2'-((3-(9H-carbazol-9-yl)-2-olato-5- methylphenyl)(3- methoxypropyl)amino)-3-(adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [2'-((3-(adamantan-1-yl)-2-olato-5- methylphenyl)(3- methoxypropyl)amino)-3- (9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [2'-((3-(adamantan-1-yl)-2- olato-5- methylphenyl)(3- methoxypropyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2- olato] dimethyl hafnium; [2'-((3-(adamantan-1-yl)-2-olato-5- methylphenyl)(2-methoxyethyl)amino)- 3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [2'-((3-(adamantan-1-yl)- 2-olato-5- methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2- olato] dimethyl hafnium; [2'-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5-methylphenyl)(3- methoxypropyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-olato] dibenzyl zirconium; [2'-((3- ((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(tert-butyl)-5- methyl-[1,1'-biphenyl]-2-olato] dibenzyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-23POLY0046-WO-PCT methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dibenzyl zirconium; [3- (tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'- biphenyl]-2-olato] dibenzyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3- methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert- butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((3-methoxypropyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5- methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3-(tert-butyl)-2'-((3-methoxypropyl)(5-methyl-2- (p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-(tert-butyl)-2'- ((2-methoxyethyl)(2-((4-methoxyphenyl)amino)-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2- olato] dimethyl hafnium; [3-(tert-butyl)-2'-((2-methoxyethyl)(2-((4-methoxyphenyl)amino)-5- methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((2- methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3-(tert-butyl)-2'-((2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'- biphenyl]-2-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((2-methoxyethyl)(5-isopropyl-2-(p- tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3-(tert-butyl)-2'-((2- methoxyethyl)(5-isopropyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5- methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5- methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [25: 3- (tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'- biphenyl]-2-olato] dichloro titanium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2- methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] monochloro dimethylamido titanium; [3-(tert- butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'- biphenyl]-2-olato] dichloro titanium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2- methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert- butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-(dimethylamino)ethyl)amino)-3- (tert-butyl)-5-methyl-[1,1'-biphenyl]-2-olato] dibenzyl hafnium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy- 5-methylphenyl)(2-(dimethylamino)ethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2- (dimethylamino)ethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [2'- ((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl- [1,1'-biphenyl]-2-olato] dibenzyl hafnium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2- methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [2'-((3-(9H-23POLY0046-WO-PCT carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'- biphenyl]-2-olato] dibenzyl zirconium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2- methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [2'-((3-(9H- carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl- [1,1'-biphenyl]-2-olato] dibenzyl hafnium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2- methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [2'- ((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5- methyl-[1,1'-biphenyl]-2-olato] dibenzyl zirconium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5- methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-((1s,3s)-adamantan-1-yl)-2'-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5- methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3- ((1s,3s)-adamantan-1-yl)-2'-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5-methylphenyl)(2- methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [6,6'-(((2- methoxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenolato) dibenzyl hafnium; [6,6'-(((2- methoxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenolato) dibenzyl zirconium; [2-(tert- butyl)-6-((3-methoxypropyl)(2'-(p-tolylamino)-[1,1'-biphenyl]-2-yl)amino)-4-methylphenolato] dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3- phenoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert- butyl)-2-hydroxy-5-methoxyphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-(trifluoromethyl)phenyl)(3- methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dibenzyl zirconium; [3-(tert-butyl)-2'-((3- (tert-butyl)-2-hydroxy-5-methylphenyl)(3-(phenylthio)propyl)amino)-5-methyl-[1,1'-biphenyl]-2- olato] dimethyl hafnium; →[3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3- (phenylthio)propyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((3- methoxypropyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dichloro titanium; 3-(tert-butyl)-2'-((2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'- biphenyl]-2-olato] dichloro titanium; [3'',5''-di-tert-butyl-2-((3-(tert-butyl)-2-hydroxy-5- methylphenyl)(3-methoxypropyl)amino)-5'-methyl-[1,1':3',1''-terphenyl]-2'-olato] dimethyl hafnium; 3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-ethoxyethyl)amino)-5-methyl-[1,1'- biphenyl]-2-olato] dichloro titanium; 3-(tert-butyl)-2'-(butyl(3-(tert-butyl)-2-hydroxy-5- methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dibenzyl hafnium; 3-(tert-butyl)-2'-(butyl(3- (tert-butyl)-2-hydroxy-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dibenzyl zirconium; [2''-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-2,4,5',6-tetramethyl- [1,1':3',1''-terphenyl]-2'-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-23POLY0046-WO-PCT methylphenyl)(3-(dimethylamino)propyl)amino)-[1,1'-biphenyl]-2-olato] dibenzyl zirconium; [N2-(3- methoxypropyl)-N2-(5-methyl-2-(p-tolylamino)phenyl)-N2'-(p-tolyl)-[1,1'-biphenyl]-2,2'-diamino] dichloro hafnium; [N2-(3-methoxypropyl)-N2-(5-methyl-2-(p-tolylamino)phenyl)-N2'-(p-tolyl)-[1,1'- biphenyl]-2,2'-diamino] dichloro zirconium; [N2-(3-methoxypropyl)-N2-(5-methyl-2-(p- tolylamino)phenyl)-N2'-(p-tolyl)-[1,1'-biphenyl]-2,2'-diamino] dimethyl hafnium; [N2-(3- methoxypropyl)-N2-(5-methyl-2-(p-tolylamino)phenyl)-N2'-(p-tolyl)-[1,1'-biphenyl]-2,2'-diamino] dimethyl zirconium; 3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3- (dimethylamino)propyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dichloro titanium; [2'-((3-((3r,5r,7r)- adamantan-1-yl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(tert-butyl)-5-methyl-[1,1'- biphenyl]-2-olato] dichloro titanium; [2'-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5- methylphenyl)(3-methoxypropyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(4-methoxybutyl)amino)-5- methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5- methylphenyl)(4-methoxybutyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [3-(tert- butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-ethoxypropyl)amino)-5-methyl-[1,1'-biphenyl]- 2-olato] dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3- ethoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dichloro titanium; [2''-((3-(tert-butyl)-2- hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-2,4,5',6-tetramethyl-[1,1':3',1''-terphenyl]-2'- olato] dimethyl hafnium; [3-((1S,3s)-adamantan-1-yl)-2'-((3-(tert-butyl)-2-hydroxy-5- methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [3- ((1S,3s)-adamantan-1-yl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5- methyl-[1,1'-biphenyl]-2-olato] dimethyl zirconium; [2-(tert-butyl)-6-((2'-(isopropylamino)-5'-methyl- [1,1'-biphenyl]-2-yl)(3-methoxypropyl)amino)-4-methylphenolato] dibenzyl hafnium; [2-(tert-butyl)- 6-((2'-(isopropylamino)-5'-methyl-[1,1'-biphenyl]-2-yl)(3-methoxypropyl)amino)-4-methylphenolato] dibenzyl zirconium; [2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5- methyl-3-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-olato] dimethyl hafnium; [2'-((3-(tert-butyl)-2- hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-3-(2-phenylpropan-2-yl)-[1,1'- biphenyl]-2-olato] dimethyl zirconium; [2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3- methoxypropyl)amino)-5-methyl-3-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-olato] dimethyl zirconium,

[0068] Other non-limiting examples of metal catalyst precursors that would be suitable according to the present invention are hafnium or zirconium complexes supported by a tridentate ligand containing dianionic phenolate groups bridged by a neutral N-heterocyclic group, for example: -(3'-23POLY0046-WO-PCT ((3r,5r,7r)-adamantan-1-yl)-2'-methoxy-5'-methyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2- yl)-2'-methoxy-5'-methyl-[1,1'-biphenyl]-2-yl)pyridine dimethylhafnium, 2-(3'-((3r,5r,7r)-adamantan- 1-yl)-2'-methoxy-5'-methyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2-yl)-2'-methoxy-5'- methyl-[1,1'-biphenyl]-2-yl)pyridine dimethylzirconium, 2-(3'-((3r,5r,7r)-adamantan-1-yl)-2'- methoxy-4,5'-dimethyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2-yl)-2'-methoxy-4,5'-dimethyl- [1,1'-biphenyl]-2-yl)pyridine-dimethylhafnium, 2-(3'-((3r,5r,7r)-adamantan-1-yl)-2'-methoxy-4,5'- dimethyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2-yl)-2'-methoxy-4,5'-dimethyl-[1,1'- biphenyl]-2-yl)pyridine dimethylzirconium, 2-(3'-((3r,5r,7r)-adamantan-1-yl)-5'-(tert-butyl)-2'- methoxy-4-methyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2-yl)-5'-(tert-butyl)-2'-methoxy-4- methyl-[1,1'-biphenyl]-2-yl)pyridine dimethylhafnium, 2-(3'-((3r,5r,7r)-adamantan-1-yl)-5'-(tert- butyl)-2'-methoxy-4-methyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2-yl)-5'-(tert-butyl)-2'- methoxy-4-methyl-[1,1'-biphenyl]-2-yl)pyridine dimethylzirconium, 2-(3'-((3r,5r,7r)-adamantan-1-yl)- 5'-isopropyl-2'-methoxy-4-methyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2-yl)-5'-isopropyl-2'- methoxy-4-methyl-[1,1'-biphenyl]-2-yl)pyridine dimethylhafnium, 2-(3'-((3r,5r,7r)-adamantan-1-yl)- 5'-isopropyl-2'-methoxy-4-methyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2-yl)-5'-isopropyl-2'- methoxy-4-methyl-[1,1'-biphenyl]-2-yl)pyridine dimethylzirconium, 2-(3'-((3r,5r,7r)-adamantan-1-yl)- 2'-methoxy-4,5'-dimethyl-[1,1'-biphenyl]-2-yl)-6-(3'-((1r,3r)-adamantan-2-yl)-2'-methoxy-4,5'- dimethyl-[1,1'-biphenyl]-2-yl)-4-(trifluoromethyl)pyridine dimethylhafnium, 2,6-bis(2'-methoxy-5'- methyl-3'-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-yl)pyridine dimethylhafnium, 2,6-bis(2'-methoxy- 5'-methyl-3'-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-yl)pyridine methylzirconium, 2,6-bis(2'- methoxy-4,5'-dimethyl-3'-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-yl)pyridine dimethylhafnium, 2,6- bis(2'-methoxy-4,5'-dimethyl-3'-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-yl)pyridine dimethylhafnium, 2,6-bis(3'-(9H-carbazol-9-yl)-2'-methoxy-5'-methyl-[1,1'-biphenyl]-2-yl)pyridine dimethylhafnium, 2,6-bis(3'-(9H-carbazol-9-yl)-2'-methoxy-5'-methyl-[1,1'-biphenyl]-2-yl)pyridine dimethylzirconium, 2,6-bis(3'-(9H-carbazol-9-yl)-2'-methoxy-4,5'-dimethyl-[1,1'-biphenyl]-2- yl)pyridine dimethylhafnium, 2,6-bis(2'',6''-di-tert-butyl-2'-methoxy-4,5'-dimethyl-[1,1':3',1''- terphenyl]-2-yl)pyridine dimethylhafnium, 2,6-bis(2'',6''-di-tert-butyl-2'-methoxy-4,5'-dimethyl- [1,1':3',1''-terphenyl]-2-yl)pyridine dimethylzirconium.

[0069] In addition of one of the above catalyst precursors, the polymerization process to produce the hydroxyl-functionalized propylene-based co- or terpolymer may further include: ^ a co-catalyst selected from the group: MAO, DMAO, MMAO, SMAO or ammonium salts or trityl salts of fluorinated tetraarylborates, preferably MAO, MMAO, and23POLY0046-WO-PCT ^ optionally, a scavenger selected from the group: trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum and ^ optionally, a chain transfer agent selected from the group: dihydrogen or AlR53, BR53or MgR52or ZnR52, where each R5is independently selected from hydrogen or hydrocarbyl. Further additives

[0070] In another embodiment, asphalt, modified bitumen or the amine-free mineral adhesion promoter according to the invention could further comprise in addition to the blend of non- functionalized olefin and hydroxyl-functionalized propylene-based co- or terpolymer, at least one styrene-based copolymer. As inventors surprisingly noted, a styrene-based copolymer can increase even more the adhesion to the mineral aggregates, in particular acidic aggregates, such as granite, and improve the Proportional Rut Depth, when applied in quantity above 1.25 wt% of the weight of the total asphalt composition. However, the styrene-based copolymer shall not be added in a quantity above 5.0 wt% of the weight of the total asphalt composition, as it decreases the storage stability and anti-stripping properties of the obtained compositions.

[0071] Preferably, the styrene-based copolymer can be selected from the group comprising: poly(styrene–block–butadiene), star–poly(styrene–block–butadiene), poly(styrene–block– butadiene–block–styrene), poly(styrene–block–ethylene–co–butylene), poly(styrene–block– ethylene–co–butylene–block–styrene), poly(styrene–block–[ethylene–co–butylene–graft–(maleic anhydride)]–block–styrene), poly(styrene–block–isoprene), poly(styrene–block–isoprene–block– styrene), poly(styrene–block–ethylene–co–propylene), poly(styrene–block–ethylene–co– propylene–block–styrene), or mixtures thereof.

[0072] In a preferred embodiment, the amine-free mineral adhesion promoter comprises he blend of non-functionalized olefin and hydroxyl-functionalized propylene-based co- or terpolymer, an aluminum oxide hydroxide and at least one of the following compounds: poly(styrene–block– butadiene), star–poly(styrene–block–butadiene) or poly(styrene–block–[ethylene–co–butylene– graft–(maleic anhydride)]–block–styrene), in their quantity respectively disclosed above. Examples Typical preparation procedure of isotactic poly(propylene–co–1-hexene) (poly(C3-co-C6)) (Table 1, PO):23POLY0046-WO-PCT

[0073] The polymerization experiment was carried out using a stainless steel BÜCHI reactor (2 L) filled with pentamethylheptane (PMH) solvent (1 L) using a stirring speed of 600 rpm. Catalyst and comonomer solutions were prepared in a glove box under an inert dry nitrogen atmosphere.

[0074] The reactor was first heated to 40 °C followed by the addition of TiBA (1.0 M solution in toluene, 2 mL) and 1-hexene (neat 30 mL). The reactor was charged at 40 °C with gaseous propylene (100 g) and the reactor was heated up to the desired polymerization temperature of 130 °C resulting in a partial propylene pressure of about 15 bar. Once the set temperature was reached, the polymerization reaction was initiated by the injection of the pre-activated catalyst precursor bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV) dimethyl [CAS 958665-18-4]; other name hafnium [[2',2'''-[(1,3-dimethyl-1,3- propanediyl)bis(oxy-κO)]bis[3-(9H-carbazol-9-yl)-5-methyl[1,1'-biphenyl]-2-olato-κO]](2-)]dimethyl] (Hf-O4, 1.5 µmol) in MAO (30 wt % solution in toluene, 11.2 mmol). The reaction was stopped by pouring the polymer solution into a container flask containing demineralized water / iPrOH (50 wt%, 1 L) and Irganox 1010 (1.0 M, 2 mmol). The resulting suspension was filtered and dried at 80 °C in a vacuum oven, prior the addition of Irganox 1010 as an antioxidant. The poly(propylene-co-hexene) (29.5 g) was obtained as a powder. Typical preparation procedure of isotactic poly(propylene–co–1-hexene–co–5-hexen-1-ol) (poly(C3-co-C6-co-C6OH)) (Table 1, FPO):

[0075] The polymerization experiment was carried out using a stainless steel BÜCHI reactor (2 L) filled with pentamethylheptane (PMH) solvent (1 L) using a stirring speed of 600 rpm. Catalyst and comonomer solutions were prepared in a glove box under an inert dry nitrogen atmosphere. The reactor was first heated to 40 °C followed by the addition of TiBA (1.0 M solution in toluene, 2 mL), 1-hexene (neat 10 mL), and triethyl aluminum (TEA)-pacified 5-hexen-1-ol (1.0 M solution in toluene, TEA:5-hexen-1-ol (mol ratio) = 1, 10 mL). The reactor was charged at 40 °C with gaseous propylene (100 g) and the reactor was heated up to the desired polymerization temperature of 130 °C, resulting in a partial propylene pressure of about 15 bar. Once the set temperature was reached, the polymerization reaction was initiated by the injection of the pre-activated catalyst precursor bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV) dimethyl [CAS 958665-18-4]; other name hafnium [[2',2'''-[(1,3-dimethyl-1,3- propanediyl)bis(oxy-κO)]bis[3-(9H-carbazol-9-yl)-5-methyl[1,1'-biphenyl]-2-olato-κO]](2-)]dimethyl] (Hf-O4, 2 µmol) in MAO (30 wt % solution in toluene, 11.2 mmol). The reaction was stopped by pouring the polymer solution into a container flask containing demineralized water / iPrOH (50 wt%, 1 L) and Irganox 1010 (1.0 M, 2 mmol). The resulting suspension was filtered and dried at 80 °C in23POLY0046-WO-PCT a vacuum oven, prior the addition of Irganox 1010 as an antioxidant. The poly(propylene-co-1- hexene-co-5-hexen-1-ol) (25.6 g) was obtained as a powder. Preparation of blend comprising 70%wt poly(propylene-co-1-hexene-co-5-hexen-1-ol) (poly(C3-co-C6-co-C6OH)) and 30%wt poly(propylene–co–1-hexene) (poly(C3-co-C6))

[0076] Solid hydroxyl functionalized propylene-based co- or terpolymer poly(C3-co-C6-co-C6OH) (7 g, FPO) and unfunctionalized polyolefin poly(C3-co-C6) (3 g, PO) were dispersed in toluene (400 mL) and the mixture was heated under nitrogen at 100 °C and stirred at 500 rpm until the polymers dissolved. Then the polymer was precipitated in cold methanol (500 mL), filtered and washed 2 x with methanol. Table 1. Molecular characterization and thermal properties of copolymers utilized in the bitumen modification process. Al MnMwÐ Tm^Hm Tc^cOH Entry Structure content [kg / mol] [kg / mol] [-] [°C] [J / g] [°C] [%] [%mol] [wt%] PO C3-co-C630.5 94.5 3.1 83.5 37.5 50.5 18.1 0.0 n.a. C3-co-C6-co- FPO 31.2 133.1 4.3 82.0 26.8 40.9 12.9 0.2 0.29 C6OHaused as a diluter for the blends preparationbsample applied as a binder’s modifier for further asphalt mixture productionc^ was calculated assuming the heat of fusion of 100%-crystalline iPP of 207 J / g Table 2. Molecular characterization and thermal properties of the blends utilized in the bitumen modification process.23POLY0046-WO-PCT n w m ^Hm Tc ^cAl M M Ð T OH Entry Composition content [kg / mol] [kg / mol] [-] [°C] [J / g] [°C] [%] [%mol] [wt%] 1% PO EX1 32.2 137.4 4.3 85.3 23.2 55.4 11.2 0.2 0.29 99% FPO 3% PO 32.0 139.7 4.4 85.0 24.7 55.0 11.9 0.2 0.29 EX2 97% FPO 5% PO EX3 31.8 152.8 4.8 84.6 25.5 54.8 12.3 0.2 0.28 95% FPO 10% PO 31.5 159.2 5.1 84.2 27.2 54.0 13.1 0.18 0.27 EX4 90% FPO 30% PO EX5 31.0 188.2 6.1 84.0 29.0 53.5 14.0 0.15 0.24 70% FPO 50% PO EX6 30.8 205.5 6.7 84.0 33.1 52.7 16.0 0.1 0.21 50% FPO 70% PO EX7 30.7 155.3 5.1 83.7 35.5 52.2 17.1 0.07 0.17 30% FPO 90% PO EX8 30.7 120.7 3.9 83.7 36.5 51.2 17.6 0.03 0.14 10% FPO 95% PO EX9 30.6 115.5 3.8 83.6 36.9 50.9 17.8 0.02 0.12 5% FPO 97% PO EX10 30.5 106.5 3.5 83.5 37.1 50.7 17.9 0.02 0.12 3% FPO 99% PO EX11 30.5 97.8 3.2 83.5 37.3 50.6 18.0 0.01 0.11 1% FPO Table 3. Properties of a neat bitumen and Polymer Modified Bitumen (PMB) samples. CE1 is Neat bitumen with penetration grade of 70 / 100 CE2 is a blend of Neat bitumen (99.70%) with Teramin 14 (0.3%) CE3 is a blend of Neat bitumen (97.50%) with PO (2.5%) from Table 1 CE4 is a blend of Neat bitumen (97.50%) with FPO (2.5%) from table 1 TEX1 is a blend of Neat bitumen (97.50%) with EX1 (2.5%) TEX2 is a blend of Neat bitumen (97.50%) with EX2 (2.5%) TEX3 is a blend of Neat bitumen (97.50%) with EX4 (2.5%)23POLY0046-WO-PCT TEX4 is a blend of Neat bitumen (97.50%) (2.5%) TEX5 is a blend of Neat bitumen (97,50%) with EX5 (2.5%) TEX6 is a blend of Neat bitumen (97.50%) with EX6 (2.5%) TEX7 is a blend of Neat bitumen (97.50%) with EX7 (2.5%) TEX8 is a blend of Neat bitumen (97.50%) with EX8 (2.5%) TEX9 is a blend of Neat bitumen (97.50%) with EX9 (2.5%) TEX10 is a blend of Neat bitumen (97.50%) with EX10 (2.5%) TEX11 is a blend of Neat bitumen (97.50%) with EX11 (2.5%) Boiling water test Basic properties Hot-storage stability test results QNM-AFM results results PN-84 / B-06714 / 22 Entry Aggregates ^DMTAdhesion 180 P SP Ptop Pbot Δ P SPtop SP.bot ∆SPsurface coverage modulus force granite limestone [Pa∙s] [dmm] [°C] [dmm] [dmm] [dmm] [°C] [°C] [°C] [GPa] [nN] [%] CE1 0.040 90 44.2 82 82 0 46.1 46.0 0.1 2.5 35 60 45 CE2 0.035 91 44.0 83 83 0 46.3 46.2 0.1 2.3 55 95 60 CE3 0.040 60 51.5 45 75 30 65.3 48.3 16.5 2.2 37 60 45 CE4 0.056 78 46.8 66 75 9 47.4 48.8 1.4 1.75 57 95 85 TEX1 0.056 78 46.8 66 75 9 48.8 47.3 1.4 1.75 57 95 85 TEX2 0.054 78 46.9 65 74 9 49.0 47.3 1.7 1.75 57 95 85 TEX3 0.050 75 47.5 62 71 9 49.3 47.5 1.8 1.80 56 95 85 TEX4 0.047 70 48.5 61 70 9 50.1 47.5 2.6 1.85 55 95 85 TEX5 0.045 67 49.9 59 69 10 51.5 48.0 3.5 1.95 53 90 80 TEX6 0.044 65 50.2 55 64 9 53.5 48.8 4.7 2.0 50 90 80 TEX7 0.042 62 50.8 52 63 11 56.0 49.0 7.0 2.1 46 80 70 TEX8 0.040 60 51.0 50 70 20 60.2 48.4 11.8 2.2 40 70 60 TEX9 0.040 60 51.2 48 72 24 62.2 48.8 13.4 2.2 40 70 6023POLY0046-WO-PCT TEX10 0.040 60 51.4 47 74 63.0 49.0 14.0 2.2 39 70 60 TEX11 0.040 60 51.5 45 75 30 65.3 49.5 15.8 2.2 39 70 60aapplied as a binder for asphalt mixture production ^180- dynamic viscosity at 180 ^C P - average penetration value ΔP – average penetration value after storage stability test and the corresponding difference, respectively S – average softening point S, Stop / bot, ΔS - average softening point after storage stability test and the corresponding difference, respectively Results It can be seen from Table 3 that samples TEX1 to TEX6, which comprise a blend of non- functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer up to 50 / 50 allow to obtain modified bitumen suitable to be incorporated in an asphalt composition with enhanced mechanical and adhesive performances suitable for road application. Sample TEX7 to TEX11, which comprise less than 50 wt% of hydroxyl-functionalized propylene- based co- or terpolymer allow to obtain modified bitumen suitable for roofing application. Surprisingly with a dilution of 50 wt% of the hydroxyl-functionalized propylene-based co- or terpolymer, 85% of the mechanical and adhesive performances are maintained compare to the use a of pure hydroxyl-functionalized propylene-based co- or terpolymer as an adhesion promoter. Furthermore, surprisingly when the dilution is up to 99 wt%, 69.9% of the mechanical and adhesive performances are maintained. Typical procedure for bitumen modification.

[0077] The modification of bitumen was carried out at 180 °C using Ultra-Turaxx T50 basic homogenizer (IKA Company) equipped with S50N – G45G dispersing tool (IKA Company), working at the speed range 4000 – 6000 rpm. Usually the hot bitumen was mixed with the polymer modifier for 120 minutes. Typical procedure for penetration analysis.

[0078] Penetration tests were performed according to the European Standard 1426. In this method, a needle with specified dimension and weight is penetrating the asphalt sample, under a23POLY0046-WO-PCT 100 g load for 5 seconds at 25 °C. The penetration value was expressed in decimillimeters as a vertical distance penetrated by needle into asphalt. The penetration value is the average from three individual measurements. Typical procedure for softening point analysis.

[0079] Softening point tests were performed with Ring & Ball apparatus according to European Standard 1427. In this method two metal rings filled with asphalt were heated at a controlled rate 5 °C / min in a water bath while each supports a steel ball. The softening point temperature was determined as a temperature at which steel balls coated with asphalt fall through a height of 25 mm. The reported softening point value was an average of the temperatures determined for each ball. Typical procedure for the dynamic viscosity analysis. The dynamic viscosity test was performed at 180 °C using a Haake Viscotester 2 Plus (TermoElectron, Waltham, MA, USA) according to EN 13302 standard. The test was performed by immersing the appropriate cylindrical measuring head of the viscometer in the bitumen’s bulk to a depth determined by the scale placed above the spindle. Eventually, the dynamic viscosity value [dPa∙s] was read from the digital display of the apparatus. Typical procedure for hot storage stability analysis.

[0080] Hot storage stability tests were performed according to the European Standard 13399. In this method, two sealed aluminum tubes filled with asphalt were vertically placed in the oven at 180 °C for 72 h. In the next step, the tubes with asphalt were cooled down and frozen. Then the aluminum cover was removed and asphalt and bitumen are divided into 3 sections: top, middle and bottom, respectively. Then the top and bottom sections were molten separately and used for penetration and softening point analysis. AFM HA-QNM experimental. Samples were also characterized by HA-QNM mode with a frequency of 0.5 Hz using an AFM tip with a spring constant of 5 N / m (TAP-150-30, No. 3 k = 5 N / m) at ambient conditions. With this special tip all the information of the tip needed for the QNM mode can be transferred immediately to the AFM operation program by a click with a bar-reader. Therefore, no calibration steps for spring constant and tip radius are needed before real measurements. QNM mode enables the quantitative measurements of nano-scale material mechanical properties by performing pixelwise force curves23POLY0046-WO-PCT in the scanned area. Analysis of the individual force curve data by the AFM Nano-scope software provides a map of material properties with the same resolution of topography image. Here the elastic modulus of the scanned surface was extracted from the force curve using the Derjaguin-Muller- Toropov model and presented in the modulus mapping images. Typical procedure for quantifying the adhesion of a binder to the mineral aggregates (Boiling Water Test).

[0081] Effect of water on bitumen-coated aggregate using boiling water method acc. PN-84 / B- 06714 / 22 was included in the test set to determine the adhesion of bitumen and polymer modified bitumen samples to mineral aggregates viz. granite (acidic – high SiO2content) and limestone (basic - low SiO2content). Prior to testing, the aggregates were multiply washed and eventually dried to avoid the presence of any dust or contamination. In this method, the 100 g of the given aggregates of fraction 6.3 / 10 [mm] is heated at 150oC for 1 h and fully coated by tested binder (2.7 g, heated at 150oC for 10 minutes) by manual stirring at the same temperature. Successively, the coated aggregates were put into the beaker and filled with 135 g of distilled water. The beaker containing aggregates and water was then warmed up using heating plate until boiling point of water was reached. The boiling was continued for 3 minutes, whilst excess of a floating binder was removed using paper towel strips. At the end of the test, water was removed and aggregates were transferred into a white cloth. Visual assessment was performed independently by two observers and percent of aggregates coated with a binder was established, as final result of the test. Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Residual aluminum content in the functionalized polyolefins was established by ICP-MS. Approximately 150 mg of each sample was digested in 6 mL concentrated nitric acid (trace metal grade) by microwave assisted acid digestion using an Anton Paar Multiwave PRO equipped with closed high pressure Quartz digestion vessels. After the microwave digestion run, the acid was analytically transferred into a pre-cleaned plastic centrifuge tube containing 1 mL of internal standard solution and is diluted with MilliQ water up to the 50 mL mark. The elements in the sample are quantified using a multi-element calibration set from Inorganic Ventures using an Agilent 8900 ICP-MS system. Size exclusion chromatography (SEC).

[0082] SEC measurements were performed at 150 °C on a Polymer Char GPC-IR® built around an Agilent GC oven model 7890, equipped with an autosampler and the Integrated Detector23POLY0046-WO-PCT IR4.1,2-Dichlorobenzene (o-DCB) was used as an eluent at a flow rate of 1 mL / min. The data were processed using Calculations Software GPC One®. The molecular weights were calculated with respect to polyethylene or polystyrene standards. Liquid-state 1H NMR.

[0083] 1H NMR and 13C NMR spectra were recorded at room temperature or at 80 °C using a Varian Mercury Vx spectrometer operating at Larmor frequencies of 400 MHz and 100.62 MHz for 1H and 13C NMR, respectively. For 1H NMR experiments, the spectral width was 6402.0 Hz, acquisition time 1.998 s and the number of recorded scans equal to 64. 13C NMR spectra were recorded with a spectral width of 24154.6 Hz, an acquisition time of 1.3 s, and 256 scans. Differential scanning calorimetry (DSC).

[0084] Melting temperatures (Tm) as well as melting enthalpies ( ^H [J / g]) were measured using a Differential Scanning Calorimeter Q100 from TA Instruments. The measurements were carried out at a heating and cooling rate of 10 °C / min from −40 °C to 240 °C. The melting temperatures were deducted from the second heating and cooling curves.

Claims

POLY0046-WO-PCT CLAIMS 1. Amine-free mineral adhesion promoter composition for bitumen having a melting temperature (Tm) below 100 °C or not having no melting temperature (Tm) according to the DSC measurement within the description , comprising at least a blend of ^ a non-functionalized polyolefin having a Tmbelow 120 °C, ^ a hydroxyl-functionalized propylene-based co- or terpolymer having a Tmbelow 100°C or no melting temperature (Tm) ) according to the DSC measurement within the description and having a degree of OH-functionalization between 0.1 and 0.6 mol%, more preferably 0.2 to 0.4 mol%.

2. Amine-free mineral adhesion promoter composition according to claim 1, wherein it further comprise an aluminum oxide hydroxide having an elemental metal content from a quantity up to 1.5 wt%, preferably 0.02 to 1.5 wt%, more preferably 0.05 to 1.0 wt%, more preferably 0.1 to 0.7 wt%, more preferably 0.2 to 0.6 wt% of the blend of non-functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer.

3. Amine-free mineral adhesion promoter composition according to one of the preceding claims, wherein the non-functionalized polyolefin is up to 90 wt% of the blend of non- functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer.

4. Amine-free mineral adhesion promoter according to one of the preceding claims wherein the non-functionalized polyolefin is selected from the list comprising: polyethylene, poly(ethylene–co–propylene), poly(ethylene–co–1-butene), poly(ethylene–co–1-hexene), poly(ethylene–co–1-octene), polypropylene, poly(propylene–co–ethylene), poly(propylene– co–1-butene), poly(propylene–co–1-hexene), poly(propylene–co–1-octene).

5. Amine-free mineral adhesion promoter composition according to one of the preceding claims, wherein the hydroxyl-functionalized propylene-based co- or terpolymer is selected from the list comprising poly(propylene–co–5-hexen-1-ol), poly(propylene–co–7-octen-1-ol), poly(propylene––co–10-undecen-1-ol), poly(propylene–co–ethylene–co–5-hexen-1-ol), poly(propylene–co–ethylene–co–7-octen-1-ol), poly(propylene–co–ethylene–co–10- undecen-1-ol), poly(propylene–co–1-butene–co–5-hexen-1-ol), poly(propylene–co–1- butene–co–7-octen-1-ol), poly(propylene–co–1-butene–co–10-undecen-1-ol),POLY0046-WO-PCT poly(propylene–co–1-hexene–co–5-hexen-1-ol), poly(propylene–co–1-hexene–co–7- octen-1-ol), poly(propylene–co–1-hexene–co–10-undecen-1-ol), poly(propylene–co–1- octene–co–5-hexen-1-ol), poly(propylene–co–1-octene–co–7-octen-1-ol), poly(propylene– co–1-octene–co–10-undecen-1-ol) or mixtures thereof,.

6. Amine-free mineral adhesion promoter composition according to one of the preceding claims, wherein it further comprise one of the following compounds: poly(styrene–block– butadiene), star–poly(styrene–block–butadiene), poly(styrene–block–[ethylene–co– butylene–graft–(maleic anhydride)]–block–styrene).

7. Amine-free mineral adhesion promoter composition according to the preceding claim, wherein the compound: poly(styrene–block–butadiene), star–poly(styrene–block– butadiene), or poly(styrene–block–[ethylene–co–butylene–graft–(maleic anhydride)]– block–styrene) is added in an quantity of 0.25:1 to 4:1 ratio in regard of the hydroxyl- functionalized propylene-based co- or terpolymer , preferably 1:1 ratio.

8. Amine-free mineral adhesion promoter composition according to one of the preceding claims, wherein the non-functionalized polyolefin is up to 50 wt% of the blend of non- functionalized polyolefin and hydroxyl-functionalized propylene-based co- or terpolymer 9. Modified bitumen composition comprising at least: a. Neat bitumen and b. Amine-free mineral adhesion promoter according to one of the preceding claims.

10. Amine-free modified bitumen composition according to the preceding claim wherein it have at least the followings: ^ Avg. penetration < 80 dmm according to European Standard 1426, and ^ Avg. softening > 46 °C according to European Standard 1427, and ^ Δ softening point < 5 according to European Standard 13399 ^ Adhesion force > 37 nN according to SABIC Internal QNM-AFM method ^ DMT modulus > 1.75 GPa according to SABIC Internal QNM-AFM method ^ Degree of binder coverage on Granite [%] >= 80, preferably >= 90 according to PN- 84 / B-06714 / 22,POLY0046-WO-PCT ^ Degree of binder coverage on Limestone [%] >= 60, preferably >= 70, more preferably >= 80 according to PN-84 / B-06714 / 22, 11. Asphalt composition comprising ^ Modified bitumen composition according to claim 9 or 10 which comprises an amine- free mineral adhesion promoter according to claim 8, in a quantity of 1.0 to 10 wt% of the asphalt composition, and ^ Mineral aggregates in a quantity of 90 to 99 wt% of the asphalt composition.

12. Use of an amine-free mineral adhesion promoter composition according to the claims 1 to 7, in modified bitumen composition.

13. Use of Modified Bitumen composition according to the claims 9 or 10, in roofing application.

14. Use of Modified Bitumen composition according to claim 9 or 10 which comprises an amine- free mineral adhesion promoter according to claim 8 in an asphalt composition.

15. Use of an asphalt composition according to the claim 11, in a road application.

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