Asphalt mixture composition with improved service life

Abstract

The present invention relates to a mineral adhesion promoter composition for bitumen, comprising at least a hydroxyl-functionalized propylene-based copolymer, preferably having a hydroxyl-functionalized olefin comonomer content of 0.1 to 0.6 mol%, more preferably 0.2 to 0.5 mol%, and an aluminum-containing residue, and the aluminum-containing residue comprises an aluminum content in an amount of 0.05 to 1.5 wt% of the hydroxyl-functionalized propylene-based copolymer; relates to a modified asphalt composition comprising at least: a mineral adhesion promoter composition according to the invention and pure asphalt; finally, an asphalt mixture composition comprising the modified asphalt composition according to the invention and some minerals.

Description

Technical Field

[0001] The present invention relates to an asphalt composition having an improved service life, a mineral adhesion promoter, and the use thereof in an asphalt composition. Background Art

[0002] Asphalt mixtures are usually composed of a mixture containing bitumen and minerals and optionally additives such as amines, which act as adhesion promoters to improve the affinity of the bitumen to the mineral. By improving the affinity of the bitumen to the mineral, the asphalt mixture composition can have a longer service life.

[0003] However, those amines are generally considered to be toxic components and can leak into the environment.

[0004] Therefore, there is a need for a non-toxic adhesion promoter which does not degrade the mechanical properties of asphalt below the standards such as its permeability, softening point, wheel track slope, indirect tensile strength ratio, binder coverage after 6h, etc. and ultimately is able to improve some of those parameters. Summary of the invention

[0005] This object is achieved by the present invention.

[0006] In a first aspect, the present invention relates to a mineral adhesion promoter composition for asphalt comprising:

[0007] At least a hydroxyl-functionalized propylene-based copolymer, preferably T m Below 100°C, preferably below 90°C, more preferably below 85°C, even more preferably below 80°C, or is atactic, and the hydroxyl-functionalized olefin comonomer content is 0.1-0.6 mol%, more preferably 0.2-0.5 mol%,

[0008] - Aluminium-containing residue comprising elemental aluminium in an amount of 0.05 to 1.5 wt% of the hydroxy-functionalised propylene-based copolymer.

[0009] In some embodiments, the hydroxy-functionalized propylene-based copolymer is a polymer comprising propylene, optionally a second olefin monomer, and a hydroxy-functionalized olefin monomer.

[0010] In some embodiments, the hydroxyl-functionalized propylene-based copolymer is selected from 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) or poly(propylene-co-1-octene-co-5-hexen-1-ol).

[0011] In a second aspect, the present invention relates to a modified asphalt composition comprising at least:

[0012] Pure asphalt, and

[0013] • Mineral adhesion promoters according to the invention.

[0014] In some embodiments, the modified asphalt composition has at least the following properties:

[0015] Average penetration < 80 dmm according to European Standard 1426, and

[0016] Average softening temperature > 46°C according to European Standard 1427, and

[0017] · Δ penetration < 9 and / or Δ softening point < 5 according to European Standard 13399,

[0018] Adhesion force>40nN according to SABIC Internal QNM-AFM method,

[0019] According to SABIC Internal QNM-AFM method, DMT modulus>1.75GPa,

[0020] According to PN-84 / B-06714 / 22, the adhesive coverage on the granite [%] is >= 80, preferably >= 90,

[0021] Binder coverage [%] on limestone according to PN-84 / B-06714 / 22 >= 60, preferably >= 70, more preferably >= 80.

[0022] In a third aspect, the present invention relates to an asphalt mixture composition comprising:

[0023] The modified asphalt composition according to the present invention, the amount of which is 1.0-10 wt% of the asphalt mixture composition, and

[0024] Minerals in an amount of 90-99.0 wt% of the asphalt mixture composition, and

[0025] The asphalt mixture composition has at least the following properties:

[0026] According to EN 12697-11 (method A), the aggregate surface coverage [%] on the granite is higher than 50, preferably >= 60 or higher, more preferably >= 80,

[0027] Aggregate surface coverage [%] on limestone according to EN 12697-11 (Method A) higher than 70, preferably >= 80,

[0028] According to EN 12697-12A, the indirect tensile strength ratio ITSR [%] is >= 85, preferably >= 90, and

[0029] According to EN 12697-22, 10 3 The wheel track slope WTS after cycles AIR [mm / 10 3 cycles]<0.10.

[0030] In another aspect, the present invention relates to the use of a mineral adhesion promoter composition according to the invention as a mineral adhesion promoter in a modified bitumen composition or in an asphalt mixture composition.

[0031] In another aspect, the present invention relates to the use of a modified bitumen composition according to the present invention in an asphalt mixture composition or in roofing applications.

[0032] In a last aspect, the present invention relates to the use of the asphalt mixture composition according to the invention for road applications or construction applications. DETAILED DESCRIPTION

[0033] The present invention relates to a new asphalt mixture composition which achieves a longer service life by improving the affinity of the bitumen present in the asphalt mixture composition with minerals.

[0034] In order to obtain such properties, mineral adhesion promoter additives, which have the function of adhesion promoter, are added to the composition.

[0035] Commonly used mineral adhesion promoters are aliphatic amines, such as the Teramin family of products from ICSOChemical Production. Such promoters enhance adhesion to mineral aggregates, especially acidic aggregates (granodiorite, granite, quartzite, porphyry).

[0036] However, those amine-based accelerators are generally considered to be toxic components due to the amines within their compositions and can leak into the environment when the asphalt mixture deteriorates.

[0037] Therefore, the object of the present invention is to propose a new amine-free composition having better properties than pure bitumen and having similar or improved properties than bitumens comprising amine-based mineral adhesion promoters in their composition.

[0038] Surprisingly, the inventors of the present application have found that hydroxyl-functionalized propylene-based copolymers, preferably having a hydroxyl-functionalized comonomer content (or degree of OH functionalization content) of 0.1-0.6 mol%, preferably 0.1-0.5 mol%, more preferably 0.1-0.4 mol%, more preferably 0.2-0.5 mol%, even more preferably 0.2-0.4 mol%, even more preferably 0.2-0.3 mol%, are suitable for acting as mineral adhesion promoters and are good alternatives to amine-based mineral adhesion promoters.

[0039] Therefore, the new "amine-free" asphalt mixture composition according to the present invention comprises at least:

[0040] a. Asphalt,

[0041] b. Minerals,

[0042] c. an additive package comprising at least one mineral adhesion promoter,

[0043] wherein the mineral adhesion promoter comprises a hydroxyl-functionalized propylene-based copolymer and an aluminum-containing residue,

[0044] wherein the aluminum-containing residue comprises an elemental aluminum content, for example aluminum oxide and / or aluminum hydroxide and / or aluminum alkoxide,

[0045] Wherein the hydroxy-functionalized propylene-based copolymer is a copolymer of propylene, a second non-functionalized olefin and a hydroxy-functionalized olefin.

[0046] Preferably, the asphalt mixture composition has at least the following properties:

[0047] Average penetration <80dmm according to EN 1426, and

[0048] Average softening temperature > 46°C according to EN 1427, and

[0049] Δ Penetration (ΔP) < 5 and / or Δ Softening Point (ΔSP) < 5 according to EN 13399, and

[0050] According to PN-84 / B-06714 / 22, the aggregate surface coverage on the granite is higher than 70%, preferably 80%, and

[0051] According to EN 12697-12A, indirect tensile strength ratio ITSR [%]> 90, and

[0052] Adhesive coverage [%] > 80 after 6h according to EN 12697-11, and

[0053] According to EN 12697-22, wheel track slope WTS after 10,000 cycles AIR[mm / 10 3 cycles]<0.10.

[0054] The hydroxy-functionalized propylene-based copolymer is a polymer comprising propylene, optionally a second olefin monomer, and a hydroxy-functionalized olefin, preferably having a hydroxy-functionalized olefin comonomer content of 0.1 to 0.6 mol%, more preferably 0.2 to 0.5 mol%.

[0055] The common prior art for obtaining asphalt mixtures / bituminous compositions requires the use of adhesion promoters to improve the affinity of bitumen with minerals, the maximum melting temperature (T m ) is 135°C, which is an application in the method of manufacturing asphalt mixture / asphalt.

[0056] Surprisingly, the inventors have found that the melting temperature (T m ) range, the adhesion promoter is suitable for processing in asphalt mixtures / bitumen compositions and is able to obtain good adhesion and the physical (bulk) properties listed below.

[0057] Therefore, the hydroxyl-functionalized propylene-based copolymer according to the present invention must have a T value lower than 100°C, preferably lower than 90°C, more preferably lower than 85°C, even more preferably lower than 80°C and higher than 60°C. m , or it is atactic or syndiotactic.

[0058] The hydroxy-functionalized propylene-based copolymers are amorphous or semi-crystalline.

[0059] The second optional olefin monomer may be selected from: ethylene, 1-butene, 1-hexene, 1-octene, 1-decene.

[0060] The hydroxyl-functionalized propylene copolymer can be produced in a solution process according to the method described in WO2022 / 106689 using one of the following catalyst precursors: bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl hafnium(IV) dimethyl, bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl hafnium(IV) dichloride, bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl hafnium(IV) dichloride )-2-phenoxy)-1,3-propanediyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldimethyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldichlorohafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-( bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethyl hafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldibenzyl hafnium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethyl hafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethyl hafnium(IV), Hafnium(IV)dichloride, bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldibenzyl hafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethyl hafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-Pentanediylhafnium(IV)dichloride, bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldichloride, bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)- Bis((2-oxyacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl hafnium(IV) dimethyl, bis((2-oxyacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl hafnium(IV) dichloride, bis((2-oxyacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2 -cyclohexanediyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldimethyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldichlorohafnium (IV), and bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldichlorohafnium (IV). -yl)phenyl)-2-phenoxy)-1,3-propyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyldimethyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propyldimethyl hafnium (IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzyl hafnium (IV),3-propyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldimethyl hafnium (IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzyl hafnium (IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldimethyl hafnium (IV), bis((2-oxoacyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldimethyl hafnium (IV), bis((2-oxoacyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldimethyl bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,2-ethyldibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,2-ethyldibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propyldimethylhafnium(IV); preferably bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2, 4-pentanediyl dimethyl hafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dichlorohafnium (IV); or a zirconium complex selected from the following polyvalent aryloxy ethers: bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dimethyl zirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dichlorozirconium (IV), bis((2-oxoacyl-3-(1,2,3,4,6,7 ,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dimethyl zirconium (IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dichloride zirconium (IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dibenzyl zirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-Propanediylzirconium(IV)dimethyl, bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium(IV)dichloride, bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldibenzylzirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium(IV)dimethyl, bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl) Bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium dichloride, bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldibenzylzirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethylzirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethylzirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldichloride 1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldibenzylzirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylzirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzylzirconium(IV) dichloride, bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzylzirconium( IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dibenzylzirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dimethylzirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dichloride zirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dichloride9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dibenzylzirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dimethylzirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dichloride zirconium (IV), and bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl) bis((2-oxoacyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldimethylzirconium(IV), bis((2-oxoacyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylzirconium(IV), bis((2-oxoacyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylzirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,2-ethyldimethylzirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl )-2-phenoxy)-1,2-ethyldibenzylzirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propyldimethylzirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propyldibenzylzirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyldimethylzirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylzirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylzirconium (IV), ((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propyldimethylzirconium (IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propyldibenzylzirconium (IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldimethylzirconium (IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylzirconium (IV); preferably bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylzirconium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium dichloride (IV); more preferably bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium (IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldichloride hafnium (IV). ,

[0061] Other suitable metal catalyst precursors may also be trivalent transition metals such as those described in WO 9319104 or 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]MCl2 or [(C9H6)CH2C5H4N]MCl2, wherein M is titanium or chromium. Examples of catalyst precursors are (C5Me4)CH2CH2N(Me)2]TiCl2, [C6H5C(NSiMe3)2]TiCl2(THF)2 and [C6H5C(NSiMe3)CH2CH2N(CH3)2]TiCl2(THF).

[0062] Other non-limiting examples of suitable metal catalyst precursors 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.

[0063] According to the present invention, other suitable catalyst precursors may be, for example, {N',N"-bis[2,6-di(1-methylethyl)phenyl]-N,N-diethylguanidinyl} metal dichloride, {N',N"-bis[2,6-di(1-methylethyl)phenyl]-N-methyl-N-cyclohexylguanidinyl} metal dichloride, {N',N"-bis[2,6-di(1-methylethyl)phenyl]-N,N-pentamethyleneguanidinyl} metal dichloride, {N',N"-bis[2,6-di(methyl)phenyl]-sec-butyl-amidinyl} metal dichloride, {N,N'-bis(trimethylsilyl)benzamidinyl} metal dichloride, {N-trimethylsilyl, N'-(N",N"-dimethylaminomethyl)benzamidinyl} metal dichloride and their THF or other Lewis acid-base adducts, wherein the metal is titanium or chromium.

[0064] Other suitable metal catalyst precursors may also be hafnium or zirconium or titanium complexes supported by dianionic tridentate and / or tetradentate ligands, for example: 2'-((3-(9H-carbazole-9-yl)-2-phenoloxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazole-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl hafnium; 2'-((3-(9H-carbazole-9-yl)-2-phenoloxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazole-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl zirconium; [2'-((3-(9H-carbazole-9-yl)-2-phenoloxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazole-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl zirconium; [2'-((3-(9H-carbazole-9-yl)-2-phenoloxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium; [2'-((3-(adamantan-1-yl)-2-phenoloxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium; [2'-((3-(adamantan-1-yl)-2-phenoloxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazole-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium; [2'-((3-(adamantan-1-yl)-2-phenoloxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazole-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium; [2'-((3-(adamantan-1-yl)-2-phenoloxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl hafnium; [2'-((3-(adamantan-1-yl)-2-phenoloxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium; [2'-((3-(adamantan-1-yl)-2-phenoloxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] 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-phenoloxy]dibenzylzirconium; [2'-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dibenzylzirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dibenzylzirconium;[3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dibenzyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] [3-(tert-butyl)-2'-((3-methoxypropyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl zirconium; [3-(tert-butyl)-2'-((2-methoxyethyl)(2-((4-methoxyphenyl)amino)-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl hafnium; [3-(tert-butyl)-2'-((2-methoxyethyl)(2-((4-methoxyphenyl)amino)-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl hafnium; [3-(tert-butyl)-2'-((2-methoxyethyl)(2-((4-methoxyphenyl)amino) [3-(tert-butyl)-2'-((2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] zirconium dimethyl; [3-(tert-butyl)-2'-((2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] zirconium dimethyl; [3-(tert-butyl)-2'-((2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] zirconium dimethyl; [3-(tert-butyl)-2'-((2-methoxyethyl)(5-isopropyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1, [1'-biphenyl]-2-phenoloxy] dimethyl hafnium; [3-(tert-butyl)-2'-((2-methoxyethyl)(5-isopropyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium;[3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] titanium dichloride; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] monochlorodimethylamidotitanium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] titanium dichloride; [3-(tert-butyl)- 2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethylzirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethylhafnium; [2'-((3-(9H-carbazole-9-yl)-2-hydroxy-5-methylphenyl)(2-(dimethylamino)ethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dibenzylhafnium; [2'-((3-(9H-carbazole-9-yl)-2-hydroxy-5-methylphenyl)(2-(dimethylamino)ethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-(dimethylamino)ethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]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-phenoloxy]dimethyl zirconium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dibenzyl hafnium; [2' -((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl hafnium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dibenzylzirconium; [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethylzirconium;[2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]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-phenoloxy]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-phenoloxy]dimethyl hafnium [2'-((3-(9H-carbazole-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazole-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethylzirconium; [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-phenoloxy]dimethylhafnium; [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-phenoloxy]dimethylzirconium; [6,6'-(((2-methoxyethyl)azadiyl)bis(methylene))bis(2,4-di-tert-butylphenoloxy)dibenzylhafnium; [6,6'-(((2-methoxyethyl)azadiyl)bis(methylene))bis(2,4-di-tert-butylphenoloxy)dibenzylzirconium; [2-(tert-butyl)-6-((3-methoxypropyl)(2'-(p-tolylamino)-[1,1'-biphenyl]-2-yl)amino)-4-methylphenol [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-phenoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethylhafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methoxyphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethylzirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-(trifluoromethyl)phenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dibenzylzirconium;[3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-(phenylthio)propyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl hafnium; → [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-(phenylthio)propyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium; [3-(tert-butyl)-2'-((3-methoxypropyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dichlorotitanium; 3-(tert-butyl)-2'-(( 2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] titanium dichloride; [3",5"-di-tert-butyl-2-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5'-methyl-[1,1':3',1"-terphenyl]-2'-phenoloxy] hafnium dimethyl; 3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-ethoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] titanium dichloride; 3-(tert-butyl)-2'-(butyl(3-(tert-butyl)-2 3-(tert-butyl)-2'-(butyl(3-(tert-butyl)-2-hydroxy-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dibenzyl zirconium; [2"-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-2,4,5',6-tetramethyl-[1,1':3',1"-terphenyl]-2'-phenoloxy]dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-(dimethylamino)propyl)amino)- [1,1'-biphenyl]-2-phenoloxy] dibenzylzirconium; [N2-(3-methoxypropyl)-N2-(5-methyl-2-(p-tolylamino)phenyl)-N2'-(p-tolyl)-[1,1'-biphenyl]-2,2'-diamino] hafnium dichloride; [N2-(3-methoxypropyl)-N2-(5-methyl-2-(p-tolylamino)phenyl)-N2'-(p-tolyl)-[1,1'-biphenyl]-2,2'-diamino] zirconium dichloride; [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]zirconium dimethyl; 3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-(dimethylamino)propyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] titanium dichloride; [2'-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dichloride 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-phenoloxy]dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(4-methoxybutyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl hafnium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(4-methoxybutyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]dimethyl Zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-ethoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] dimethyl zirconium; [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-ethoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy] titanium dichloride; [2"-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-2,4,5',6-tetramethyl-[1,1':3',1"-terphenyl]-2'-phenoloxy] dimethyl hafnium; [3-(( [3-((1s,3s)-adamantan-1-yl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoloxy]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-phenoloxy]dimethyl zirconium; [2-(tert-butyl)-6-((2'-(isopropylamino)-5'-methyl-[1,1'-biphenyl]-2-yl)(3-methoxypropyl)amino)-4-methylphenoloxy]dibenzyl hafnium;[2-(tert-butyl)-6-((2'-(isopropylamino)-5'-methyl-[1,1'-biphenyl]-2-yl)(3-methoxypropyl)amino)-4-methylphenoloxy]dibenzylzirconium; [2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-3-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-phenoloxy]dimethylhafnium; [2'- ((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-3-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-phenoloxy]zirconium dimethyl; [2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-3-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-phenoloxy]zirconium dimethyl. ;

[0065] Other non-limiting examples of suitable metal catalyst precursors according to the present invention are hafnium or zirconium complexes supported by tridentate ligands containing dianionic phenoloxy groups bridged by neutral N-heterocyclic groups, such as: -(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)pyridinium dimethyl hafnium, 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) -((1r,3r)-adamantan-2-yl)-2'-methoxy-5'-methyl-[1,1'-biphenyl]-2-yl)zirconium dimethyl pyridine, 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-dimethyl hafnium, 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) 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)-hafnium pyridine dimethyl, 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)zirconium dimethyl pyridine, 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)hafnium dimethyl pyridine, 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)zirconium pyridine dimethyl, 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'- 2,6-bis(2'-methoxy-5'-methyl-3'-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-yl)zirconium pyridine methyl, 2,6-bis(2'-methoxy-5'-methyl-3'-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-yl)zirconium pyridine methyl, 2,6-bis(2'-methoxy-4,5'-dimethyl-3'-(2-phenylpropan-2-yl)-[1,1'-biphenyl]- 2-yl) pyridine dimethyl hafnium, 2,6-bis(2'-methoxy-4,5'-dimethyl-3'-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-yl) pyridine dimethyl hafnium, 2,6-bis(3'-(9H-carbazol-9-yl)-2'-methoxy-5'-methyl-[1,1'-biphenyl]-2-yl) pyridine dimethyl hafnium, 2,6-bis(3'-(9H-carbazol-9-yl)-2'-methoxy-5'-methyl-[1,1'-biphenyl]-2-yl) pyridine dimethyl zirconium, ,6-bis(3'-(9H-carbazole-9-yl)-2'-methoxy-4,5'-dimethyl-[1,1'-biphenyl]-2-yl)pyridine dimethyl hafnium, 2,6-bis(2",6"-di-tert-butyl-2'-methoxy-4,5'-dimethyl-[1,1':3',1"-terphenyl]-2-yl)pyridine dimethyl hafnium, 2,6-bis(2",6"-di-tert-butyl-2'-methoxy-4,5'-dimethyl-[1,1':3',1"-terphenyl]-2-yl)pyridine dimethyl zirconium. ,

[0066] Other non-limiting examples of suitable metal catalyst precursors according to the present invention are rac-dimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride, dimethylsilylbis(1,3-dimethyl-inden-2-yl)(2,4-diphenyl-inden-1-yl)hafnium dimethyl, dimethylsilyl(1,3-dimethyl-inden-2-yl)(2-phenyl-cyclopenta[a]naphthalen-3-yl)zirconium dichloride.

[0067] In addition to one of the above catalyst precursors, the method of producing a hydroxyl-functionalized propylene-based copolymer may further include:

[0068] A cocatalyst selected from the group consisting of: MAO, DMAO, MMAO, SMAO or ammonium or trityl salts of fluorinated tetraarylborates, preferably MAO, MMAO, and

[0069] Optionally, a scavenger selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and

[0070] Optionally, a chain transfer agent selected from: dihydrogen or AlR 10 3. BR 10 3 or MgR 10 2 or ZnR 10 2, where each R 10 Independently selected from hydrogen or hydrocarbon, preferably C1-C 10 Hydrocarbon.

[0071] Preferably, the hydroxyl-functionalized propylene-based copolymer may be selected from the group consisting of: poly(propylene-co-5-hexen-1-ol), poly(propylene-co-10-undecene-1-ol), poly(propylene-co-ethylene-co-5-hexen-1-ol), poly(propylene-co-ethylene-co-10-undecene-1-ol), poly(propylene-co-1-hexene-co-5-hexen-1-ol), poly(propylene-co-1-hexene-co-10-undecene-1-ol). The present invention relates to poly(propylene-co-5-hexen-1-ol), poly(propylene-co-ethylene-co-5-hexen-1-ol), poly(propylene-co-1-octene-co-5-hexen-1-ol), poly(propylene-co-1-octene-co-5-hexen-1-ol), poly(propylene-co-1-octene-co-10-undecene-1-ol) or a mixture thereof, more preferably selected from 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).

[0072] Preferably, the amount of the hydroxyl-functionalized propylene-based copolymer in the modified asphalt composition is 1.25-5 wt%, preferably 1.25-2.5 wt%, preferably 2-3 wt%, preferably 2.3-2.7 wt%.

[0073] In a preferred embodiment, the mineral adhesion promoter may further comprise components other than the hydroxyl functionalized propylene copolymer, the aluminum-containing residue. The inventors have surprisingly found that the interaction of the aluminum-containing residue with the copolymer structure can increase the stiffness, compatibility and softening point of the polymer modified asphalt.

[0074] The amount of aluminum-containing residues comprising an elemental aluminum content should not be higher than 1.5 wt% of the hydroxyl-functionalized propylene-based copolymer in the asphalt mixture composition, because it will reduce the bonding to the mineral aggregate when present in the asphalt mixture composition. Preferably, the amount of aluminum-containing residues comprising an elemental aluminum content is 0.05-1.5 wt%, more preferably 0.05-1.2 wt%, even more preferably 0.1-1.0 wt%, even more preferably 0.8-1.0 wt%, even more preferably 0.2-0.4 wt%, even more preferably 0.20-0.35 wt%, even more preferably 0.26-0.32 wt%, or preferably 0.05-0.3 wt% of the hydroxyl-functionalized propylene-based copolymer.

[0075] The aluminum-containing residue containing a certain elemental aluminum content can be, for example, aluminum oxide and / or aluminum hydroxide and / or aluminum alkoxide or mixtures thereof, preferably conforming to the formula: Al(O) x (OH) y (OR) z , wherein x=0-1.5, y=0-3, z=0-3, and (2x+y+z)=3, and wherein R is an aliphatic hydrocarbon group, preferably C1-C6, preferably Me, Et, nPr, iPr, nBu, iBu or tBu, even more preferably isopropyl.

[0076] The introduction of aluminum-containing residues can be achieved by incorporating an organoaluminum compound, more preferably an aluminum alkyl, at the beginning of the copolymer synthesis. These aluminum alkyls react with the hydroxyl functionality of the functional comonomer. Alkyl aluminum materials are known in the art, in particular in WO 2022 / 106689 as functional comonomer deactivators that prevent the oxophilic metal centers of the catalyst from being poisoned or deactivated during the polymerization process. Hydrolysis of the alkylaluminum-deactivated hydroxy-functionalized propylene copolymer provides a hydroxy-functionalized propylene copolymer having finely dispersed aluminum-containing residues.

[0077] Preferably, after hydrolysis, the cross-linked alkylaluminum precursor (which is in the form of aluminum-containing residual nodes) that provides hydroxyl-functionalized comonomer segments within the propylene-based copolymer structure can be selected from: triisobutylaluminum (TiBA), triethylaluminum (TEA), methylaluminoxane (MAO), trimethylaluminum (TMA), trihexylaluminum, trioctylaluminum, or mixtures thereof.

[0078] In some embodiments, the aluminum-containing residue is the residue of a deactivating agent used to deactivate the hydroxyl functional group of one of the monomers during the synthesis of the hydroxyl-functionalized propylene-based copolymer, obtained after reaction with water and / or alcohol.

[0079] In a more preferred embodiment, the "amine-free" asphalt mixture composition according to the present invention comprises:

[0080] a. mineral aggregate in an amount of 95-99wt% of the asphalt mixture composition,

[0081] b. A modified asphalt composition in an amount of 1.0-10wt% of the asphalt mixture composition, the modified asphalt composition comprising:

[0082] i. pure asphalt in an amount of 95-98.75 wt% of the modified asphalt composition, and

[0083] ii. a hydroxyl-functionalized propylene-based copolymer, preferably selected from poly(propylene-co-5-hexene-1-ol), poly(propylene-co-ethylene-co-5-hexene-1-ol), poly(propylene-co-1-hexene-co-5-hexene-1-ol), poly(propylene-co-1-octene-co-5-hexene-1-ol), in an amount of 1.25-5.0 wt% of the modified asphalt composition, and preferably having a hydroxyl-functionalized olefin comonomer content of 0.1-0.6 mol%, more preferably 0.2-0.5 mol%, and

[0084] iii. an aluminum-containing residue containing a certain elemental aluminum content in an amount of 0.05-1.5wt% of the hydroxyl-functionalized propylene-based copolymer in the modified asphalt composition,

[0085] In an even more preferred embodiment, the "amine-free" asphalt mixture composition according to the present invention comprises:

[0086] a. mineral aggregate, in an amount of 93-95wt% of the asphalt mixture composition,

[0087] b. a modified asphalt composition in an amount of 5.0-7.0wt% of the asphalt mixture composition, i. pure asphalt in an amount of 97.5-98.75wt% of the modified asphalt composition, and

[0088] ii. a hydroxyl-functionalized propylene-based copolymer, more preferably poly(propylene-co-1-hexene-co-5-hexene-1-ol), in an amount of 1.25-2.5 wt%, more preferably 2.3-2.5 wt%, of the modified asphalt composition, and preferably having a hydroxyl-functionalized olefin comonomer content of 0.1-0.6 mol%, more preferably 0.2-0.5 mol%, and

[0089] iii. an aluminum-containing residue comprising an elemental aluminum content in an amount of 0.05-1.5 wt %, preferably 0.8-1.0 wt %, of the hydroxyl-functionalized propylene-based copolymer in the asphalt mixture composition.

[0090] One embodiment of the present invention is an asphalt mixture composition having the following specific composition:

[0091] Mineral aggregate, in an amount of 93-95 wt % of the asphalt mixture composition, preferably 93.5-94.5 wt %,

[0092] · Modified asphalt composition, the amount of which is 5-7wt% of the asphalt mixture composition, preferably 5.5-6.5wt%,

[0093] a. Pure asphalt, in an amount of 97-98wt% of the modified asphalt, preferably 97.3-97.7wt%,

[0094] b. A hydroxyl-functionalized propylene-based copolymer, poly(propylene-co-1-hexene-co-5-hexene-1-ol, preferably having a hydroxyl-functionalized olefin comonomer content of 0.1-0.4, preferably 0.2-0.3 mol%, in an amount of 2-3 wt%, preferably 2.3-2.7 wt%, of the modified asphalt, and comprising: an aluminum-containing residue containing a certain elemental aluminum content, preferably in an amount of 0.20-0.35 wt%, preferably 0.26-0.32 wt%, of the total amount of the hydroxyl-functionalized propylene-based copolymer.

[0095] One embodiment of the present invention is a modified asphalt having the following specific composition: pure asphalt, in an amount of 97-98wt%, preferably 97.3-97.7wt% of the modified asphalt, a hydroxyl-functionalized propylene-based copolymer, poly(propylene-co-1-hexene-co-5-hexene-1-ol, preferably having a hydroxyl-functionalized olefin comonomer content of 0.1-0.4mol%, preferably 0.2-0.3mol%, in an amount of 2-3wt%, preferably 2.3-2.7wt% of the modified asphalt, and it includes: an aluminum-containing residue containing a certain elemental aluminum content, preferably in an amount of 0.20-0.35wt%, preferably 0.26-0.32wt% of the total amount of the hydroxyl-functionalized propylene-based copolymer.

[0096] Another aspect of the invention is a mineral adhesion promoter comprising:

[0097] a. a hydroxyl-functionalized propylene-based copolymer, preferably selected from poly(propylene-co-5-hexene-1-ol), poly(propylene-co-ethylene-co-5-hexene-1-ol), poly(propylene-co-1-hexene-co-5-hexene-1-ol), poly(propylene-co-1-octene-co-5-hexene-1-ol), and preferably having a hydroxyl-functionalized olefin comonomer content of 0.1 to 0.6 mol%, more preferably 0.2 to 0.5 mol%,

[0098] b. an aluminum-containing residue comprising an elemental aluminum content in an amount of 0.05 to 1.5 wt % of the hydroxy-functionalized propylene-based copolymer.

[0099] In one embodiment, the mineral adhesion promoter comprises:

[0100] a. a hydroxyl-functionalized propylene-based copolymer, more preferably poly(propylene-co-1-hexene-co-5-hexene-1-ol), and preferably having a hydroxyl-functionalized olefin comonomer content of 0.1 to 0.6 mol%, more preferably 0.2 to 0.5 mol%,

[0101] b. an aluminum-containing residue comprising an elemental aluminum content in an amount of 0.05-0.3 wt % of the hydroxyl-functionalized propylene-based copolymer in the asphalt mixture composition.

[0102] Another embodiment of the present invention is an accelerator having the following specific composition:

[0103] a. a hydroxyl-functionalized propylene-based copolymer, poly(propylene-co-1-hexene-co-5-hexene-1-ol), preferably having a hydroxyl-functionalized olefin comonomer content of 0.2 to 0.3 mol%,

[0104] b. an aluminum-containing residue comprising an elemental aluminum content in an amount of 0.20-0.35 wt %, preferably 0.26-0.32 wt %, of the hydroxy-functionalized propylene-based copolymer.

[0105] Example

[0106] Typical preparation procedure of isotactic poly(propylene-co-1-hexene) (Table 1, PO):

[0107] A stainless steel tube filled with pentamethylheptane (PMH) solvent (1 L) was used. Reactor (2L), using a stirring speed of 600rpm for the experiment. First, the reactor was heated to 40°C, followed by the addition of TiBA (2mL, 1.0M toluene solution, 2mmol). The reactor was charged with gaseous propylene (100g) and 1-hexene (30mL, pure, 240mmol) at 40°C, and heated to the desired polymerization temperature of 130°C, which formed a propylene partial pressure of about 15 bar. Once the set temperature was reached, the polymerization reaction was initiated by injecting the preactivated catalyst precursor bis((2-oxyacyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV) [CAS958665-18-4] (Hf-O4, 0.25mg, 0.25μmol) in MAO (2.5mL, 30wt% toluene solution, 11.3mmol) in toluene (5mL). The reaction was stopped by pouring the polymer solution into an Erlenmeyer flask containing water and isopropanol (50% v / v, 500 mL) and Irganox 1010 (5 mL, 1.0 M solution in acetone, 0.5 mmol). The resulting suspension was stirred for 4 h, filtered, washed with demineralized water and iPrOH solution (50% v / v, 2×500 mL), and dried in a vacuum oven at 80° C., followed by the addition of Irganox 1010 (5 mL, 1.0 M solution in acetone, 0.5 mmol) as an antioxidant. Poly(propylene-co-1-hexene) was obtained as an elastic, transparent material.

[0108] Typical preparation procedure of isotactic poly(propylene-co-1-hexene-co-5-hexene-1-ol) (Table 1, FPO1-3):

[0109] Use stainless steel Reactor (2L), using the stirring speed of 600rpm to carry out polymerization experiment.Catalyst and comonomer solution were prepared in a glove box under an inert dry nitrogen atmosphere.First, heptane solvent (1L) was filled into the reactor, and heated to 40°C, followed by addition of TEA (2mL, 1.0M toluene solution, 2mmol), 1-hexene (30mL, pure, 240mmol) and triethylaluminum (TEA)-passivated 5-hexene-1-alcohol (1.0M toluene solution, TEA:5-hexene-1-alcohol (mol ratio)=1,10mL). Reactor was pressurized with gaseous propylene (100g) at 40°C, and the reactor was heated to the desired polymerization temperature of 130°C, which formed a propylene partial pressure of about 15 bar. Once the set temperature was reached, the polymerization reaction was initiated by injecting the preactivated catalyst precursor bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV) [CAS 958665-18-4] (Hf-O4, 2 mg, 2 μmol) in MAO (2.5 mL, 30 wt% solution in toluene, 11.2 mmol). The reaction was stopped by pouring the polymer solution into a flask containing demineralized water and iPrOH solution (50% v / v, 1 L) and Irganox 1010 (2 mL, 1.0 M solution in acetone, 2 mmol). The resulting suspension was filtered and dried in a vacuum oven at 60°C, and then Irganox 1010 (5 mL, 1.0 M solution in acetone, 0.5 mmol) was added as an antioxidant. Poly(propylene-co-1-hexene-co-5-hexene-1-ol) was obtained as an elastic and transparent material.

[0110] Deashing procedure of isotactic poly(propylene-co-1-hexene-co-5-hexene-1-ol) (Table 1, FPO1(d), FPO2(d):

[0111] The copolymer obtained by the solution process can be deashed to remove the aluminum-containing residues present as residues from the above-mentioned polymerization / precipitation method. The terpolymer (10 g) is dispersed in a mixture of toluene (400 mL) and concentrated HCl (10 mL, 37 wt % aqueous solution, 0.12 mol), and heated under reflux until the copolymer dissolves. Once the polymer is completely dissolved, methanol (250 ml) is added to the hot mixture, and the mixture is heated at 70-80 ° C for another hour under stirring. The polymer is then precipitated in cold methanol, filtered and washed twice with methanol. The formed polymer is dried in a vacuum oven at 80 ° C for 24 hours.

[0112] Typical preparation procedure of atactic poly(propylene-co-1-hexene-co-5-hexen-1-ol) (Table 1, FPO4):

[0113] The polymerization of propylene and 5-hexene-1-ol was carried out in a stainless steel autoclave with an internal volume of 2.2 L. The reactor equipped with a mechanical stirrer interMIG was operated at 900 rpm. The reactor was first flushed with propylene for at least 30 minutes. Heptane diluent (300 mL), TEA solution (4 mL, 1.0 M toluene solution, 4 mmol) and TiBA-passivated 5-hexene-1-ol comonomer solution (10 mL, 1.0 M toluene solution, 10 mmol, TEA:5-hexene-1-ol (molar ratio) = 1) were added, followed by 1-hexene (30 mL, pure, 240 mmol). Heptane was added to bring the total volume to 1 L. The reactor was then heated to 40 ° C and the pressure was brought to 9 bar with propylene. Simultaneously preactivated [C5Me4CH2CH2NMe2]TiCl2 catalyst solution was prepared in a glove box by dissolving 5 mg of solid precatalyst in 5 mL of toluene (~16 μmol) and MAO solution (4 mL, 30 wt% toluene solution, 18 mmol), the mixture was injected into the reactor, and an overpressure of nitrogen was applied. The reactor temperature was maintained at 40 ± 3 ° C by cooling with an oil LAUDA system. At the end of the reaction, the mixture was collected via the bottom discharge valve of a beaker containing demineralized water and iPrOH (50% v / v, 1 L) and Irganox 1010 (2 mL, 1.0 M acetone solution, 2 mmol). The formed suspension was dried in a vacuum oven at 60 ° C, and then Irganox 1010 was added as an antioxidant. Atactic poly (propylene-co-1-hexene-co-5-hexene-1-ol) was obtained as a rubbery transparent material.

[0114] Typical preparation procedure of isotactic poly(propylene-co-ethylene-co-5-hexen-1-ol) (Table 1, FPO5):

[0115] The polymerization of propylene, ethylene and TiBA-passivated 5-hexene-1-ol was carried out in a stainless steel autoclave (2.2 L). The mechanical stirrer of the reactor was operated at 900 rpm. The reactor was first flushed with a mixture of ethylene and propylene at a set flow rate for about 30 minutes. Pentamethylheptane diluent (300 mL), TEA solution (4 mL, 1.0 M toluene solution, 4.0 mmol), TEA-passivated 5-hexene-1-ol (10 mL, 1.0 M toluene solution, 10 mmol, TiBA:5-hexene-1-ol (molar ratio) = 1) and MAO (0.8 mL, 30 wt% toluene solution, 3.6 mmol) were added. Pentamethylheptane was added to make the total volume reach 1 L. The reactor was then heated to 80° C. and the overall pressure was brought to 9 bar with a propylene / ethylene mixture (feed rate wt% = 70 / 30), and maintained at this pressure using set ethylene and propylene flows and a vent valve set at 9 bar. A solution of racemic-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst precursor, prepared by dissolving 2 mg of solid precatalyst in 5 mL of toluene (~3.2 μmol) in a glove box, was injected into the reactor and an overpressure of nitrogen was applied. The reactor temperature was maintained at 80±3°C by cooling with an oil LAUDA system. At the end of the reaction, the mixture was collected via the bottom discharge valve of a beaker containing demineralized water and a solution of iPrOH (50% v / v, 1 L) and Irganox 1010 (2 mL, 1.0 M in acetone, 2 mmol). The resulting suspension was dried at 60°C in a vacuum oven and then Irganox 1010 was added as an antioxidant. Isotactic poly(propylene-co-ethylene-co-5-hexene-1-ol) was obtained as a rubbery transparent material.

[0116] Typical preparation procedure of isotactic poly(propylene-co-1-octene-co-5-hexen-1-ol) (Table 1, FPO6):

[0117] Use stainless steel Reactor (2L), use the stirring speed of 600rpm to carry out polymerization experiment.Catalyst and comonomer solution are prepared in glove box under inert dry nitrogen atmosphere.First fill heptane solvent (1L) in reactor and be heated to 40 ℃, then add TEA (1.0M toluene solution, 2mL), 1-octene (pure, 20mL, 128mM) and triethylaluminum (TEA)-passivated 5-hexene-1-alcohol (1.0M toluene solution, TEA:5-hexene-1-alcohol (molar ratio)=1,10mL). Reactor is pressurized with gaseous propylene (100g) at 40 ℃, and is heated to the desired polymerization temperature of 130 ℃, which forms a propylene partial pressure of about 15 bar. Once the set temperature was reached, the polymerization reaction was initiated by injecting the preactivated catalyst precursor bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV) [CAS 958665-18-4] (Hf-O4, 1 μmol) in MAO (10 wt% solution in toluene, 6 mmol). The reaction was stopped by pouring the polymer solution into a flask containing demineralized water / iPrOH (50 wt%, 1 L) and Irganox 1010 (1.0 M, 2 mmol). The resulting suspension was filtered and dried in a vacuum oven at 60°C, and then Irganox 1010 was added as an antioxidant. Poly(propylene-co-1-octene-co-5-hexene-1-ol) was obtained as an elastic transparent material.

[0118] Commercially available materials used in the experiments:

[0119] Reference samples for asphalt mixture testing: PMB 45 / 80-55 MODBIT was provided by LOTOS Asphalt Mixtures and used as received. Fatty amine adhesion promoter Teramin 14 (ICSO Chemical Production) was purchased and used as received.

[0120]

[0121]

[0122]

[0123] result

[0124] From Table 2, all experiments can be processed into asphalt mixture. However, Example 5 has m Above 100°C the requirement of a delta softening point (ΔSP) < 5 according to EN 13399 is not met.

[0125] Furthermore, it can be seen from Table 3 that when the hydroxyl-functionalized propylene-based copolymer having a limited amount of aluminum-containing residues is added to the asphalt mixture composition, compared to the neat asphalt CE1:

[0126] The binder coverage and ITSR value on the granite increased after 6h testing, which helps to improve the peeling and moisture resistance of the mixture, prevent raveling and low temperature cracking, and improve the service life of the pavement.

[0127] · In 10 3 WTS after cycles AIR The value decreases, which is beneficial to improving the road surface's resistance to permanent deformation.

[0128] When compared to modified bitumen with Teramin CE2, the performance is comparable but without the toxicity to the environment.

[0129] Typical procedures for asphalt modification

[0130] Bitumen modification was performed using an Ultra-Turaxx T50 basic homogenizer (IKA Company) equipped with a S50N-G45G dispersing tool (IKA Company) operating at a speed of 4000-6000 rpm at 180° C. The hot bitumen was typically mixed with the polymer modifier for 120 minutes.

[0131] Typical Procedure for Permeation Analysis

[0132] The penetration test is carried out according to European Standard 1426. In this method, a needle of specified size and weight is penetrated into the asphalt mixture sample under a load of 100 g at 25°C for 5 seconds. The penetration value is expressed as the vertical distance the needle penetrates into the asphalt mixture in decimeters (dmm). The penetration value is the average of three individual measurements.

[0133] Typical procedure for softening point analysis

[0134] The softening point test was carried out with the Ring & Ball apparatus according to European Standard 1427. In this method, two metal rings filled with bituminous mixture are heated in a water bath at a controlled rate of 5°C / min, while each supports a steel ball. The softening point temperature is determined as the temperature at which the bituminous mixture coated steel ball falls through a height of 25 mm. The softening point value reported is the average of the temperatures determined for each ball.

[0135] Typical Procedure for Thermal Storage Stability Analysis

[0136] The hot storage stability test was performed according to European Standard 13399. In this method, two sealed aluminum tubes filled with asphalt mixture are placed vertically in an oven at 180°C for 72 hours. In the next step, the tubes with asphalt mixture are cooled and frozen. The aluminum covering is then removed, and the asphalt mixture and asphalt are separated into 3 sections: top section, middle section and bottom section. The top section and bottom section are then melted separately and used for penetration and softening point analysis.

[0137] AFM HA-QNM experiments

[0138] The samples were also characterized at ambient conditions using an AFM tip with a 5 N / m spring constant (TAP-150-30, No.3k=5 N / m) in HA-QNM mode at a frequency of 0.5 Hz. Using this particular tip, all the information of the tip required for the QNM mode can be immediately transferred to the AFM operating program by clicking with a barcode reader. Therefore, no calibration steps for the spring constant and tip radius are required before the actual measurement. The QNM mode enables quantitative measurement of the mechanical properties of nano-sized materials by performing pixel-by-pixel force curves in the scanned area. The single force curve data are analyzed by the AFM nano-range software to provide a depiction of the material properties with a topological image of the same resolution. Here the elastic modulus of the scanned surface is extracted from the force curve using the Derjaguin-Muller-Toropov model and presented as a modulus plot image.

[0139] Typical Procedure for Preparation of Hot Mix Asphalt (HMA)

[0140] Liquid polymer modified asphalt samples were mixed with hot aggregates in a laboratory mixer at 160°C. Continuously, samples of asphalt mixtures were prepared for further mechanical tests by obtaining HMA from the mixing process. Stone Mash Asphalt (SMA) fines were used as a formulation for HMA design, which is specifically used for the abrasion process of pavements in most European countries.

[0141] Typical Procedure for Indirect Tensile Strength (ITS) Testing

[0142] The variation of the indirect tensile strength (ITS) after water storage is carried out according to EN 12697-12A. In this method, the durability and resistance of mix sheets of compacted cylindrical asphalt mixtures before and after exposure to water are examined by means of the ITS test. The ITS variation is tested on 3 dry samples and on 3 samples that have been immersed in water at 60°C for 24h. Freeze-thaw cycles are also included as part of the conditioning of the wet samples: 1 cycle for 16h at -18°C. During the ITS test, the sample is connected between two load bars and radially loaded at a speed of 50mm / min, and the maximum load at rupture is measured. The relationship between the strength values ​​before and after water storage / freeze-thaw cycles is determined and is called the Indirect Tensile Strength Ratio (ITSR).

[0143] Typical procedure for wheel track testing

[0144] The rutting measurements are carried out according to EN 12697-22 on a small wheel tracking machine. The machine is equipped with a solid load wheel with an outer diameter of 200-205 mm. On the circumference of the wheel, there is a ribbed cast rubber with a rectangular cross section of 50 mm width and 20 ± 2 mm thickness. The wheel of the machine applies a load of 700 ± 10 N to the sample surface. The device ensures the movement of the wheel or the sample under the wheel, which reciprocates for 60 s on a cross section of 230 ± 5 mm with a frequency of 26.5 load cycles (a load cycle corresponds to 2 wheel passes: forward and backward). During the test, the following are recorded: the test temperature with an accuracy of 1 ° C, the number of wheel passes and the rutting depth, i.e. the wheel depression measured by the LVDT inductive sensor. The test is carried out until the rutting depth reaches 20 mm or 10,000 wheel travel cycles are reached. As a result of the test carried out in dry conditions (ambient temperature, "in air"), two indices are obtained, namely the proportional rutting depth (PRD AIR ) and wheel track slope (WTS AIR ).

[0145] Typical procedure for quantifying the bonding of asphalt mixtures to mineral aggregates (bottle roll test)

[0146] The affinity between the binder and the mineral aggregate and the susceptibility of the mixture to stripping were evaluated using the rolling bottle test method according to PN-EN 12697-11 (method A). Two different mineral materials, i.e. (acidic-high SiO2 content) and limestone (alkaline-low SiO2 content) were used to compare the adhesive properties of the tested binders. Before the test, the aggregates were washed several times and finally dried to avoid any dust or contamination. In this method, 170g of a given aggregate was heated at 105±5°C overnight and coated with the liquefied tested binder (5.7g) by manual stirring at 120±5°C. The mixed aggregate-binder system was then placed to cool to room temperature and stored for 12-24h before the rolling bottle test. Subsequently, the glass test bottles were filled to half of their volume with demineralized water, and 150g of the binder-coated aggregates of a specific source were added. The assembly thus obtained was then placed on a 60rpm rolling bottle machine for 6h. At the end of the test time, the water is removed from the bottle and the mineral material is transferred to a glass container, which is continuously filled with portions of demineralized water above the top side of the aggregate sample, to optimize the visual assessment of the coverage [%] of the binder on a given portion of the mineral by two different observers.

[0147] Typical procedure for quantifying the bond of a binder to a mineral aggregate (boiling water test)

[0148] The effect of water on asphalt coated aggregates was measured according to PN-84 / B-06714 / 22 using the boiling water method, which was included in the test set for determining the bonding of asphalt and polymer modified asphalt samples to mineral aggregates, namely granite (acidic - high SiO2 content) and limestone (alkaline - low SiO2 content). Before the test, the aggregates were washed several times and finally dried to avoid the presence of any dust or contamination. In this method, 100 g of a given aggregate portion 6.3 / 10 [mm] was heated at 150°C for 1 h and completely coated with the tested binder (2.7 g, heated at 150°C for 10 minutes) by manual stirring at the same temperature. Continuously, the coated aggregate was placed in a beaker and filled with 135 g of distilled water. The beaker containing the aggregate and water was then heated using a hot plate until the boiling point of the water was reached. Boiling continued for 3 minutes, while the excess floating binder was removed using strips of paper towels. At the end of the test, the water was removed and the aggregate was transferred to a white cloth. Independent visual evaluations were performed by two observers and the percentage of binder-coated aggregate was established as the final result of the test.

[0149] Inductively coupled plasma mass spectrometry (ICP-MS)

[0150] The residual aluminum content in the samples listed in Table 1 was determined by ICP-MS. Approximately 150 mg of each sample was digested in 6 mL of concentrated nitric acid (trace metal grade) by microwave-assisted acid digestion using an Anton Paar Multiwave PRO equipped with a closed high-pressure quartz digestion vessel. After the microwave digestion run, the acid analysis was transferred to a pre-cleaned plastic centrifuge tube containing 1 mL of an internal standard solution and diluted to the 50 mL mark with MilliQ water. An Agilent 8900 ICP-MS system was used to quantify the elements in the samples using a multi-element calibration device from Inorganic Ventures.

[0151] Differential Scanning Calorimetry (DSC)

[0152] On a TA Instruments DSC Q100, the -1 The thermal analysis was performed with a heating rate of 1.1 Å. The first and second runs were recorded after cooling to about -40 °C.

[0153] Nuclear Magnetic Resonance (NMR)

[0154] The functionalization percentage was determined by using deuterated tetrachloroethane (TCE-D2) as solvent at 130 °C. 1 Chemical shifts are reported in ppm relative to tetramethylsilane and are determined with reference to residual solvent protons.

Claims

1. A mineral adhesion promoter composition for asphalt, comprising: At least hydroxyl-functionalized propylene-based terpolymer having a melting temperature (T m ) is below 100°C, preferably below 90°C, more preferably below 85°C, even more preferably below 80°C, and above 60°C, or is atactic, and preferably has a hydroxy-functional olefin comonomer content of 0.1 to 0.6 mol%, more preferably 0.2 to 0.5 mol%, and - Aluminium-containing residues comprising elemental aluminium in an amount of up to 1.5 wt%, preferably 0.05-1.5 wt%, more preferably 0.1-1.2 wt% of the hydroxy-functionalised propylene-based terpolymer.

2. The mineral adhesion promoter for bitumen in asphalt mixture compositions according to claim 1, wherein the aluminum-containing residue containing a certain content of elemental aluminum is aluminum oxide and / or aluminum hydroxide and / or aluminum alkoxide or a mixture thereof.

3. A mineral adhesion promoter for bitumen in an asphalt mixture composition according to any one of the preceding claims, wherein the hydroxyl-functionalized propylene-based copolymer is a polymer comprising propylene, optionally a second olefin monomer and a hydroxyl-functionalized olefin.

4. A mineral adhesion promoter for asphalt in an asphalt mixture composition according to any one of the preceding claims, wherein the hydroxyl-functionalized propylene-based copolymer is selected from poly(propylene-co-5-hexene-1-ol), poly(propylene-co-ethylene-co-5-hexene-1-ol), poly(propylene-co-1-hexene-co-5-hexene-1-ol) or poly(propylene-co-1-octene-co-5-hexene-1-ol).

5. A modified asphalt composition comprising at least: a. Pure asphalt, and b. A mineral adhesion promoter according to any one of the preceding claims.

6. The modified bitumen composition according to the preceding claims, wherein it has at least the following properties: Average penetration < 80 dmm according to European Standard 1426, and Average softening temperature > 46°C according to European Standard 1427, and · Δ penetration < 9 and / or Δ softening point < 5 according to European Standard 13399, Adhesion force>40nN according to SABIC Internal QNM-AFM method, According to SABIC Internal QNM-AFM method, DMT modulus>1.35GPa, According to PN-84 / B-06714 / 22, the adhesive coverage on the granite [%]>=80, preferably>=90, According to PN-84 / B-06714 / 22, the binder coverage [%] on the limestone is >=60, preferably >=70, more preferably >=80.

7. An asphalt mixture composition comprising: The modified asphalt composition according to claim 5 or 6, wherein the amount thereof is 1.0-10 wt% of the asphalt mixture composition, and Minerals in an amount of 90-99.0 wt% of the asphalt mixture composition, and The asphalt mixture composition has at least the following properties: According to EN 12697-11 (method A), the aggregate surface coverage [%] on the granite is higher than 50, preferably >= 60 or higher, more preferably >= 80, Aggregate surface coverage [%] on limestone according to EN 12697-11 (Method A) higher than 70, preferably >= 80, According to EN 12697-12A, the indirect tensile strength ratio ITSR [%] is >= 85, preferably >= 90, and According to EN 12697-22, 10 3 The wheel track slope WTS after cycles AIR [mm / 10 3 cycles]<0.

10.

8. Use of the mineral adhesion promoter composition according to claims 1 to 4 as a mineral adhesion promoter in a modified asphalt composition or in an asphalt mixture composition.

9. Use of the modified bitumen composition according to claim 5 or 6 in an asphalt mixture composition or in a roofing application.

10. Use of the asphalt mixture composition according to claim 7 in road applications or construction applications.

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