Paving and roofing composite comprising asphalt, ground tire rubber and compatibilizer

Abstract

A composite for paving and roofing applications comprising: from 5 to 20 wt%, preferably from 10 to 15 wt%, of the composite of regenerated vulcanized rubber, from 70 to 93 wt%, preferably from 80 to 90 wt%, of pure asphalt, from 2 to 10 wt%, preferably from 2.5 to 7.5 wt%, more preferably from 4 to 6 wt%, of a compatibilizer, the present invention relates to a compatibilizer comprising a hydroxyl-functionalized propylene-based copolymer, preferably having a hydroxyl-functionalized comonomer content of 0.1 to 0.6 mol%, more preferably 0.2 to 0.5 mol%, and an aluminum-containing residue comprising an elemental aluminum content in an amount of 0 to 1.5 wt% of the hydroxyl-functionalized propylene-based copolymer.

Description

Technical Field

[0001] The present invention relates to a sustainable modified bitumen composition comprising ground tyre rubber and a compatibilizer, having enhanced storage stability, and to its use in roofing or road construction applications. Background Art

[0002] When added to bitumen, rubber tends to improve the service life of bitumen compositions by enhancing its elasticity, low-temperature properties and rutting resistance. Rubberized bitumen compositions are also known in the art to have excellent sound-damping properties. By mixing rubberized bitumen compositions with mineral aggregates, so-called "quiet pavements" are constructed.

[0003] Natural raw rubber is a suitable raw material for rubberized asphalt mixes. However, in view of the growing demand for sustainability, ground tyre rubber (GTR), which can be considered as waste, is an option of interest.

[0004] Rubberized asphalt mixes are usually produced by the dry method, which consists of mixing preheated aggregates with rubber particles in a mobile mini hot mixing unit at ambient temperature and then mixing it with annealed liquefied pure bitumen.

[0005] Several disadvantages are encountered when using this method, such as: (i) short contact time between the binder and the rubber filler, which limits the efficiency of pure bitumen modification, (ii) hampered compaction of the rubberized asphalt mix, or (iii) increased emissions of volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs) at the road construction site.

[0006] Another way of producing rubberized asphalt mixes is by the wet method, which consists of premixing pure bitumen with GTR particles at high temperature (160 - 180 °C) using a high-shear mixer. The resulting rubber-modified bitumen is then transferred to a mixing unit and mixed with hot aggregates in an intermittent mixer. The advantage of this method over the dry method is the extended impregnation efficiency, which leads to improved interaction between GTR and pure bitumen and also reduces the emission of toxic fumes during the preparation of rubber-modified bitumen in a closed equipment system.

[0007] A well-known adjustment of the wet method of bitumen modification is the so-called terminal blending technique, which consists of mixing GTR with pure bitumen at a temperature above 200 °C to partially cleave the sulfur crosslinks present in the vulcanized rubber. This scheme is beneficial for maintaining relatively low dynamic viscosity values, thus improving the processability of the resulting rubberized bitumen. The partial in-situ "desulfurization" of GTR particles in pure bitumen is also used to enhance the dispersion of rubber crumbs throughout the modified bitumen matrix.

[0008] Despite the significantly enhanced properties of asphalt, when processed by wet or terminal blending methods, GTR particles tend to phase-separate from the asphalt matrix under static conditions during high-temperature storage and transportation. As a result, the rubber particles coalesce and settle to the bottom of the storage tank, which has an adverse effect on the further processing of rubberized asphalt and deteriorates the ductility of the material.

[0009] The most prevalent asphalt modifier, namely styrene - co - butadiene - co - styrene block copolymer (SBS), cannot provide sufficient storage stability when mixed with low amounts (about 5 - 10 wt%) and medium amounts (about 10 - 20 wt%) of GTR in pure asphalt by the wet method. Therefore, such compositions are not sufficient for road construction.

[0010] Therefore, a suitable wet and terminal blending method for asphalt modification is needed for producing mixtures of rubber and asphalt designed for both paving and roofing applications, which uses GTR and compatibilizers to prevent rubber particle coalescence, which typically leads to deterioration of the ductility and storage stability of the resulting material. Summary of the Invention

[0011] This object is achieved by the present invention, a composite material for paving and roofing applications, comprising:

[0012] · Vulcanized rubber, which is preferably recycled, accounts for 5 - 20 wt% of the composite material, preferably 10 - 15 wt%,

[0013] · Pure asphalt, which accounts for 70 - 93 wt% of the composite material, preferably 80 - 90 wt%,

[0014] · Compatibilizer, which accounts for 2 - 10 wt% of the composite material, preferably 2.5 - 7.5 wt%, more preferably 3 - 7 wt%, even more preferably 4 - 6 wt%, and comprises:

[0015] a. Hydroxy - functionalized propylene copolymer, whose 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, and is either atactic or syndiotactic, and preferably has a hydroxy - functionalized comonomer content of 0.1 - 0.6 mol%, more preferably 0.2 - 0.5 mol%,

[0016] b. Aluminum - containing residue, which contains a certain elemental aluminum content such as aluminum oxide and / or aluminum hydroxide and / or aluminum alkoxide or a mixture thereof, in an amount of at least 0.1 wt%, preferably 0.29 wt%, preferably and at most 1.5 wt%, preferably at most 1.2 wt% of the hydroxy - functionalized propylene copolymer.

[0017] In another embodiment, the vulcanized rubber is ground tire rubber, preferably used ground tire rubber.

[0018] In another embodiment, the hydroxy-functionalized propylene-based copolymer is a polymer comprising propylene, optionally a second olefin monomer, and a hydroxy-functionalized olefin.

[0019] In another embodiment, the hydroxy-functionalized propylene-based copolymer is amorphous or semi-crystalline.

[0020] In another embodiment, the hydroxy-functionalized propylene-based copolymer is selected from poly(propylene-co-5-hexen-1-ol), poly(propylene-co-10-undecen-1-ol), poly(propylene-co-ethylene-co-5-hexen-1-ol), poly(propylene-co-ethylene-co-10-undecen-1-ol), poly(propylene-co-1-hexene-co-5-hexen-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-10-undecen-1-ol).

[0021] In another embodiment, the compatibilizer comprises poly(propylene-co-1-hexene-co-5-hexen-1-ol) and an aluminum-containing residue, the residue comprising an elemental aluminum content in an amount of 0.8 - 1.2 wt% of the hydroxy-functionalized propylene-based copolymer.

[0022] In another embodiment, the hydroxy-functionalized propylene-based copolymer is made in a solution polymerization process.

[0023] In another embodiment, the composite material has at least all of the following properties:

[0024] · According to EN 13302, the dynamic viscosity (η 180 ) at 180 °C is not higher than 0.345 Pa·s,

[0025] · According to EN 1426, the average permeability (P 平均 ) < 54 dmm, and

[0026] · According to EN 1427, the average softening point (SP 平均 ) > 53 °C, and

[0027] · According to EN 13399, the Δ permeability (ΔP) <= 10 dmm, preferably <= 5 dmm, more preferably <= 1 dmm, and

[0028] · According to EN 13399, the Δ softening point (ΔSP) <= 10 °C, preferably <= 5 °C, more preferably <= 1 °C, and

[0029] · According to AASHTO M332-20, the performance grade plus (PG+) grade at 64 °C is V or E.

[0030] In another embodiment, the composite material has at least all of the following properties:

[0031] · The non-recoverable creep compliance J measured at 64 °C nr,3.2kPa < 1, preferably < 0.6 kPa -1 , and

[0032] · According to AASHTO M332-20, J at 64 °C nr,diff < 75%, according to AASHTO M332-20, the performance grade plus (PG+) grade at 70 °C is S, H or V, and

[0033] · According to AASHTO M332-20, R at 64 °C 3.2kPa > 21%.

[0034] In another embodiment, the composite material has at least all of the following properties:

[0035] · According to ASTM D7643, continuous PG >= 85 °C, and

[0036] · According to AASHTO M320, true PG >= 82.

[0037] Another aspect of the present invention is a method for manufacturing a composite material according to any one of the preceding claims, wherein the mixing of pure asphalt and vulcanized rubber is carried out under wet conditions at a temperature of 160 - 240 °C, preferably 160 - 200 °C, more preferably 170 - 190 °C, with constant stirring of the mixture, preferably using a high-shear mixer for 0.5 - 3 h, preferably 1 - 2 h.

[0038] In another embodiment, the mixing of pure asphalt and vulcanized rubber is carried out under a terminal blending method at a temperature of 230 - 260 °C, preferably 240 °C, with constant stirring of the mixture, preferably using a high-shear mixer for 0.5 - 3 h, preferably 1 - 2 h.

[0039] In another embodiment, a compatibilizer is added to the mixture of pure asphalt and vulcanized rubber, and the resulting rubber-modified asphalt mixture is stirred for an additional 1 - 6 h, preferably 1 - 3 h, more preferably 1 - 2 h under constant stirring, and maintained at a constant temperature of 160 - 200 °C.

[0040] In another embodiment, the method is carried out under an inert atmosphere to prevent thermal degradation of the compatibilizer.

[0041] A last aspect of the invention is the use of the composite material according to any of the preceding claims for roofing applications, and it is used for road applications only when Δ softening point (ΔSP) ≤ 5 °C. Detailed description

[0042] To meet the needs of the road construction industry, the compositions of the invention comprise compatibilizers to improve the interaction between the GTR particles and the bitumen component and to prevent phase separation of the individual components in the system.

[0043] The invention relates to new paving and roofing composite materials which promote longer service life of paving and roofing fabrics by using inexpensive, post-consumer recycled materials.

[0044] The invention can be used as a binder matrix for, for example, mineral and synthetic fillers. The products thus obtained can be used for the production of waterproofing materials such as roofing membranes, sealants and shingles. Such a matrix can further provide improved adhesion of the formed products to standard roofing substrates such as steel and concrete. In addition, the structural features of the invention (which ensure improved temperature susceptibility of the product) will limit the occurrence of undesirable, temperature-induced defects in bitumen-containing roofing materials such as leaks and thermal cracks.

[0045] In addition, the invention can also be designed for road applications, where it acts as a binder between mineral aggregates in hot and warm asphalt mixture blends applied to road construction.

[0046] The object of the invention is to introduce new paving and roofing composite materials which comprise recycled vulcanized rubber and a compatibilizer, have improved in-service performance compared to pure bitumen, and exhibit better storage stability and lower dynamic viscosity than GTR-modified bitumen compatibilized with the corresponding amount or a lower amount of SBS copolymer.

[0047] Interestingly, the inventors of the present application have found that a hydroxy-functionalized propylene copolymer (which preferably has a hydroxy-functionalized comonomer content of 0.1 - 0.6 mol%, more preferably 0.2 - 0.5 mol%) is sufficient to act as a compatibilizer between the GTR particles and most of the polar bitumen fractions (i.e., resins and asphaltenes), which improves the storage stability of the formed blend and is a good alternative to SBS-based polymer bitumen modifiers.

[0048] Thus, the new paving and roofing composite material according to the invention, which comprises recycled vulcanized rubber and has a sulfur content of 1 - 2 wt%, comprises at least:

[0049] a. pure bitumen

[0050] b. ground tire rubber

[0051] c. Compatibilizer

[0052] wherein the compatibilizer comprises a hydroxy-functionalized propenyl copolymer,

[0053] wherein the hydroxy-functionalized propenyl copolymer is a copolymer comprising propylene, optionally a second non-functionalized olefin, and a hydroxy-functionalized olefin, and

[0054] wherein the paving or roofing composite material has at least partially or preferably all of the following properties:

[0055] · According to EN 13302, the dynamic viscosity (η 180 ) at 180 °C is not higher than 0.345 Pa·s,

[0056] · According to EN 1426, the average penetration (P 平均 ) < 54 dmm,

[0057] · According to EN 1427, the average softening point (SP 平均 ) > 53 °C,

[0058] · According to EN 13399, the Δ penetration (ΔP) <= 10 dmm, preferably 9 dmm, more preferably <= 5 dmm, even more preferably <= 1 dmm,

[0059] · According to EN 13399, the Δ softening point (ΔSP) <= 10 °C, preferably <= 5 °C, more preferably <= 1 °C,

[0060] · According to AASHTO M332-20, the performance grade plus (PG+) grade at 64 °C is V or E,

[0061] · The non-recoverable creep compliance J nr,3.2kPa < 1, preferably < 0.6 kPa -1 ,

[0062] · According to AASHTO M332-20, the J nr,diff < 75% at 64 °C,

[0063] · According to AASHTO M332-20, the R 3.2kPa > 21% at 64 °C,

[0064] · According to ASTM D7643, the continuous PG >= 85 °C,

[0065] · According to AASHTO M320, the true PG >= 82.

[0066] A 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 0.1-0.6 mol%, more preferably 0.2-0.5 mol%. The copolymer is amorphous or semi-crystalline. The copolymer is atactic, isotactic, or syndiotactic.

[0067] To meet the technical requirements for paving and roofing composites, an adhesion promoter is needed to improve the affinity of asphalt for ground tire rubber with a maximum melt temperature (T m ) below 160-260 °C, as it is the temperature range used in the methods for manufacturing those composites.

[0068] Surprisingly, the inventors have found that it is necessary to meet a threshold within the melt temperature (T m ) range in order to obtain an adhesion promoter suitable for processing in paving and roofing composites and allowing good adhesion and physical (bulk) properties as listed below. Fundamentally, the hydroxy-functionalized propylene-based copolymer needs to have a T m below 100 °C in order to have a material with a viscosity compatible with the processing method.

[0069] Therefore, the hydroxy-functionalized propylene-based copolymer according to the present invention must have a melt temperature T m below 100 °C, preferably below 90 °C, more preferably below 85 °C, even more preferably below 80 °C, and above 60 °C, or be atactic, or syndiotactic.

[0070] The hydroxy-functionalized propylene-based copolymer is amorphous or semi-crystalline.

[0071] The second olefin monomer can be selected from: ethylene, 1-butene, 1-hexene, 1-octene, 1-decene.

[0072] Hydroxy-functionalized allyl copolymers can be produced in a solution process according to the method described in WO 2022 / 106689 using 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 dimethylhafnium(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 hafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dimethylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dichloride hafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dibenzylhafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dimethylhafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dichloride hafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dimethylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dichloride hafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dibenzylhafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dimethylhafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,Hafnium(IV) 4-pentanediyldichloride, 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-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldichloride(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzylhafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediyl-dimethylhafnium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediyl-dichloride(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediyl-dibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediyl-dimethylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediyl-dichloride(IV), and bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediyl-dibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)phenyl)-2-phenoxy)-1,3-propyldibenzylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)phenyl)-2-phenoxy)-1,4-butylenedimethylhafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)phenyl)-2-phenoxy)-1,4-butylenedibenzylhafnium(IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazol-9-yl)phenyl)-2-phenoxy)-1,3-propyldimethylhafnium(IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazol-9-yl)phenyl)-2-phenoxy)-1,3-Propyl dibenzyl hafnium(IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-butyl dimethyl hafnium(IV), bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-butyl dibenzyl hafnium(IV), bis((2-oxoacyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-butyl dimethyl hafnium(IV), bis((2-oxoacyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-butyl dibenzyl hafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)phenyl)-2-phenoxy)-1,2-ethyl dimethyl hafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)phenyl)-2-phenoxy)-1,2-ethyl dibenzyl hafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)phenyl)-2-phenoxy)-1,3-propyl dimethyl hafnium(IV); preferably bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dimethyl hafnium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dichloride hafnium(IV); or a zirconium complex of a polyvalent aryloxy ether selected from: bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dimethyl zirconium(IV), bis((2-oxoacyl-3-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl 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 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-(dibenz[b,f]azepin-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-Propylenedimethyldizirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propylenedichlorodizirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propylenedibenzylzirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedimethyldizirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedichlorodizirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedibenzylzirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedimethyldizirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedichlorodizirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedibenzylzirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedimethyldizirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedichlorodizirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedibenzylzirconium(IV), bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedibenzylzirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediyl-dimethyldizirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediyl-dichlorodizirconium(IV), bis((2-oxoacyl-3-(1,2,3,4,6,7,8,9-(octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-(phenoxymethyl)-methylenetrans-1,2-cyclohexanediylzirconium(IV) bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-(phenoxymethyl)-methylenetrans-1,2-cyclohexanediylzirconium(IV) dichloride, and bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-(phenoxymethyl)-methylenetrans-1,2-cyclohexanediylzirconium(IV) dibenzyl, bis((2-oxoacyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-butylzirconium(IV) dibenzyl, bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,2-ethylzirconium(IV) dibenzyl, bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propylzirconium(IV) dibenzyl, bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-butylzirconium(IV) dibenzyl, bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylzirconium(IV) dibenzyl, bis((2-oxoacyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-butylzirconium(IV) dibenzyl, 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-pentanediyldichlorozirconium(IV).

[0073] Other suitable metal catalyst precursors can also be those described in WO 9319104 or WO 9613529 for trivalent transition metals, such as [(C 5 H 4 )CH 2 CH 2 N(Me) 2 MCl 2 ,[(C 5 Me 4 )CH 2 CH 2 N(Me) 2 MCl 2 ,[(C 5 H 4 )CH 2 CH 2 N(i-Pr) 2 MCl 2 ,[(C 5 Me 4 )CH 2 CH 2 N(i-Pr) 2 MCl 2 ,[(C 5 H 4 )CH 2 CH 2 N(n-Bu) 2 MCl 2 ,[(C 5 Me 4 )CH 2 CH 2 N(n-Bu) 2 MCl 2 ,[(C 9 H 6 )CH 2 CH 2 N(Me) 2 MCl 2 ,[(C 9 H 6 )CH 2 CH 2 N(i-Pr) 2 MCl2 , [(C 5 Me 4 )C 9 H 6 N]MCl 2 , [(C 5 Me 3 (SiMe 3 ))C 9 H 6 N]MCl 2 , [(C 9 H 6 )C 9 H 6 N]MCl 2 , [(C 5 Me 4 )CH 2 C 5 H 4 N]MCl 2 or [(C 9 H 6 )CH 2 C 5 H 4 N]MCl 2 , where M is titanium or chromium. Examples of catalyst precursors are (C 5 Me 4 )CH 2 CH 2 N(Me) 2 TiCl 2 , [C 6 H 5 C(NSiMe 3 ) 2 TiCl 2 (THF) 2 and [C 6 H 5 C(NSiMe 3 )CH 2 CH 2 N(CH 3 ) 2 TiCl 2 (THF).

[0074] Other non-limiting examples of suitable metal catalyst precursors according to the present invention are: (pyrrolidinyl)ethyl-tetramethylcyclopentadienyltitanium dichloride, (N,N-dimethylamino)ethyl-fluorenyltitanium dichloride, (bis(1-methylethyl)phosphino)ethyl-tetramethylcyclopentadienyltitanium dichloride, (bis(2-methylpropyl)phosphino)ethyl-tetramethylcyclopentadienyltitanium dichloride, (diphenylphosphino)ethyl-tetramethylcyclopentadienyltitanium dichloride, (diphenylphosphino)methyldimethylsilyl-tetramethylcyclopentadienyltitanium dichloride.

[0075] According to the present invention, other suitable catalyst precursors can be, for example, {N’,N”-bis[2,6-bis(1-methylethyl)phenyl]-N,N-diethylguanidino}metal dichloride, {N’,N”-bis[2,6-bis(1-methylethyl)phenyl]-N-methyl-N-cyclohexylguanidino}metal dichloride, {N’,N”-bis[2,6-bis(1-methylethyl)phenyl]-N,N-pentamethyleneguanidino}metal dichloride, {N’,N”-bis[2,6-bis(methyl)phenyl]-sec-butyl-amidinato}metal dichloride, {N,N’-bis(trimethylsilyl)benzamidinato}metal dichloride, {N-trimethylsilyl, N’-(N”,N”-dimethylaminomethyl)benzamidinato}metal dichloride and their THF or other Lewis acid-base adducts, wherein the metal is titanium or chromium.

[0076] Other suitable metal catalyst precursors can also be hafnium, zirconium or titanium complexes supported by bis-anionic tridentate and / or tetradentate ligands, such as: hafnium dimethyl [2’-((3-(9H-carbazol-9-yl)-2-phenoxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; zirconium dimethyl [2’-((3-(9H-carbazol-9-yl)-2-phenoxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; hafnium dimethyl [2’-((3-(9H-carbazol-9-yl)-2-phenoxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(adamantan-1-yl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; zirconium dimethyl [2’-((3-(9H-carbazol-9-yl)-2-phenoxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(adamantan-1-yl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; zirconium dimethyl [2’-((3-(adamantan-1-yl)-2-phenoxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; hafnium dimethyl [2’-((3-(adamantan-1-yl)-2-phenoxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; zirconium dimethyl [2’-((3-(adamantan-1-yl)-2-phenoxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; hafnium dimethyl [2’-((3-(adamantan-1-yl)-2-phenoxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; zirconium dibenzyl [2’-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(tert-butyl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; zirconium dibenzyl [2’-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(tert-butyl)-5-methyl-[1,1’-biphenyl]-2-phenoxy]; zirconium dibenzyl [3-(tert-butyl)-2’-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1’-biphenyl]-2-phenoxy];Hafnium dibenzyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'-((3-methoxypropyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'-((3-methoxypropyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'-((2-methoxyethyl)(2-((4-methoxyphenyl)amino)-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'-((2-methoxyethyl)(2-((4-methoxyphenyl)amino)-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'-((2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'-((2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'-((2-methoxyethyl)(5-isopropyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'-((2-methoxyethyl)(5-isopropyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide];Titanium dichloride [25:3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Titanium monochloride dimethylamide [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Titanium dichloride [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dibenzyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-(dimethylamino)ethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-(dimethylamino)ethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-(dimethylamino)ethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dibenzyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dibenzyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoxide];Hafnium dibenzyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dibenzyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [2'-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylphenyl)(2-methoxyethyl)amino)-3-(9H-carbazol-9-yl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [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-phenoxide]; Zirconium dimethyl [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-phenoxide]; Hafnium dibenzyl [6,6'-(((2-methoxyethyl)imino)bis(methylene))bis(2,4-di-tert-butylphenoxide)]; Zirconium dibenzyl [6,6'-(((2-methoxyethyl)imino)bis(methylene))bis(2,4-di-tert-butylphenoxide)]; Hafnium dimethyl [2-(tert-butyl)-6-((3-methoxypropyl)(2'-(p-tolylamino)-[1,1'-biphenyl]-2-yl)amino)-4-methylphenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-phenoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methoxyphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dibenzyl [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-(trifluoromethyl)phenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide];[3-(tert-Butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-(phenylthio)propyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxy]dimethylhafnium; [3-(tert-Butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-(phenylthio)propyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxy]dimethylzirconium; [3-(tert-Butyl)-2'-((3-methoxypropyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxy]titanium dichloride; 3-(tert-Butyl)-2'-((2-methoxyethyl)(5-methyl-2-(p-tolylamino)phenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxy]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'-phenoxy]dimethylhafnium; 3-(tert-Butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(2-ethoxyethyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxy]titanium dichloride; 3-(tert-Butyl)-2'-(butyl(3-(tert-butyl)-2-hydroxy-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxy]dibenzylhafnium; 3-(tert-Butyl)-2'-(butyl(3-(tert-butyl)-2-hydroxy-5-methylphenyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxy]dibenzylzirconium; [2"-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-2,4,5',6-tetramethyl-[1,1':3',1"-terphenyl]-2'-phenoxy]dimethylzirconium; [3-(tert-Butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-(dimethylamino)propyl)amino)-[1,1'-biphenyl]-2-phenoxy]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]dimethylhafnium;Dimethylzirconium bis[N2-(3-methoxypropyl)-N2-(5-methyl-2-(p-tolylamino)phenyl)-N2'-(p-tolyl)-[1,1'-biphenyl]-2,2'-diamine]; Titanium dichloride [3-(tert-butyl)-2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-(dimethylamino)propyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; 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-phenoxide]; Hafnium dimethyl [2'-((3-((3r,5r,7r)-adamantan-1-yl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [3-(tert-butyl)-2'((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(4-methoxybutyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(4-methoxybutyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-(tert-butyl)-2'((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-ethoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Titanium dichloride [3-(tert-butyl)-2'((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-ethoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dimethyl [2''-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-2,4,5',6-tetramethyl-[1,1':3',1''-terphenyl]-2'-phenoxide]; Hafnium dimethyl [3-((1s,3s)-adamantan-1-yl)-2'((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Zirconium dimethyl [3-((1s,3s)-adamantan-1-yl)-2'((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-[1,1'-biphenyl]-2-phenoxide]; Hafnium dibenzyl [2-(tert-butyl)-6-((2'-(isopropylamino)-5'-methyl-[1,1'-biphenyl]-2-yl)(3-methoxypropyl)amino)-4-methylphenoxide];[2-(tert-Butyl)-6-((2'-(isopropylamino)-5'-methyl-[1,1'-biphenyl]-2-yl)(3-methoxypropyl)amino)-4-methylphenoxy]dibenzylzirconium; [2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-3-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-phenoxy]dimethylhafnium; [2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-3-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-phenoxy]dimethylzirconium; [2'-((3-(tert-butyl)-2-hydroxy-5-methylphenyl)(3-methoxypropyl)amino)-5-methyl-3-(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2-phenoxy]dimethylzirconium, and;

[0077] · A cocatalyst selected from: MAO, DMAO, MMAO, SMAO or an ammonium salt or trityl salt of a fluorinated tetraarylborate, preferably MAO, MMAO, and

[0078] · Optionally a scavenger selected from: trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and optionally a chain transfer agent selected from: dihydrogen, AlR 3 , BR 3 , MgR 2 or ZnR 2 , where each R is independently selected from hydrogen or a hydrocarbyl group.

[0079] Preferably, the hydroxy-functionalized propylene copolymer can be selected from: poly(propylene-co-5-hexen-1-ol), poly(propylene-co-10-undecen-1-ol), poly(propylene-co-ethylene-co-5-hexen-1-ol), poly(propylene-co-ethylene-co-10-undecen-1-ol), poly(propylene-co-1-hexene-co-5-hexen-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-10-undecen-1-ol) or mixtures 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).

[0080] Preferably, the amount of the hydroxy-functionalized alkenyl copolymer in the paving and roofing composite material is 2 wt% - 10 wt%, preferably 2 wt% - 7 wt%, more preferably 2.5 - 5 wt%.

[0081] In a preferred embodiment, the compatibilizer may further comprise components other than the hydroxy-functionalized alkenyl copolymer and 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 composite material.

[0082] The amount of elemental aluminum should not be higher than 1.5 wt% of the hydroxy-functionalized alkenyl copolymer in the asphalt composition, because its presence in the asphalt mixture composition reduces the adhesion to mineral aggregates. Preferably, the amount of elemental aluminum content is 0.1 - 0.5 wt% of the hydroxy-functionalized alkenyl copolymer, preferably 0.2 - 0.4 wt%.

[0083] The aluminum-containing residue containing a certain amount of elemental aluminum can be, for example, aluminum oxide and / or aluminum hydroxide and / or alkoxyaluminum or a mixture thereof, preferably conforming to the formula: Al(O) x (OH) y (OR) z , where x = 0 - 1.5, y = 0 - 3, z = 0 - 3, and (2x + y + z) = 3, and where R is an aliphatic hydrocarbon group, preferably C 1 -C 6 , preferably Me, Et, nPr, iPr, nBu, iBu or tBu, even more preferably isopropyl.

[0084] The introduction of the aluminum-containing residue can be achieved by incorporating an organoaluminum compound, more preferably an alkylaluminum, at the beginning stage of the copolymer synthesis. These alkylaluminums will react with the hydroxy groups of the functional comonomers. Alkylaluminum substances are known in the art, especially as functionalized comonomer passivators in WO 2022 / 106689, which prevent the poisoning or deactivation of the oxygenophilic metal centers of the catalyst during the polymerization process. The hydrolysis of the alkylaluminum-passivated hydroxy-functionalized alkenyl copolymer provides a hydroxy-functionalized alkenyl copolymer with finely dispersed aluminum-containing residues.

[0085] Preferably, after the hydrolysis of the polymer product at the end of the polymerization method, the alkylaluminum precursors (which are in the form of aluminum-containing residue nodes) that provide cross-linking of the hydroxy-functionalized comonomer segments in the alkenyl copolymer structure can be selected from: trioctylaluminum (TOA), triisobutylaluminum (TiBA), triethylaluminum (TEA), methylaluminoxane (MAO), trimethylaluminum (TMA), or a mixture thereof.

[0086] In some embodiments containing aluminum residues, the aluminum residues derived from the hydrolysis of alkylaluminum are passivators that are used to passivate the hydroxyl functional groups of the functional monomers during the synthesis of the hydroxyl-functionalized propenyl copolymer.

[0087] In a more preferred embodiment, the new paving and roofing composite material according to the present invention comprises:

[0088] a. Pure asphalt in an amount of 75 - 87.5 wt% of the composite material composition,

[0089] b. Ground tire rubber in an amount of 10 - 20 wt% of the composite material composition,

[0090] c. Hydroxyl-functionalized propenyl copolymer, 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), in an amount of 2.5 - 5.0 wt% of the composite material composition, and

[0091] d. Aluminum residue, which contains an elemental aluminum content in an amount of 0.1 - 1.5 wt% of the hydroxyl-functionalized propenyl copolymer in the composite material composition.

[0092] In an even more preferred embodiment, the new paving and roofing composite material according to the present invention comprises:

[0093] a. Pure asphalt in an amount of 85 wt% of the composite material composition,

[0094] b. Ground tire rubber in an amount of 10 wt% of the composite material composition,

[0095] c. Hydroxyl-functionalized propenyl copolymer, 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), more preferably poly(propylene - co - 1 - hexene - co - 5 - hexen - 1 - ol), in an amount of 2.5 - 5.0 wt% of the composite material, and

[0096] d. Aluminum residue, which contains an elemental aluminum content in an amount of 0.1 - 1.5 wt%, more preferably 0.5 - 1.0 wt% of the hydroxyl-functionalized propenyl copolymer.

[0097] Another aspect of the present invention is a compatibilizer, which comprises:

[0098] a. Hydroxyl-functionalized propylene-based copolymer, 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), and

[0099] b. Aluminum-containing residue, which contains an elemental aluminum content in an amount of 0.1 - 1.5 wt% of the hydroxyl-functionalized propylene-based copolymer.

[0100] In a preferred embodiment, the compatibilizer comprises:

[0101] a. Hydroxyl-functionalized propylene-based copolymer, more preferably selected from poly(propylene-co-1-hexene-co-5-hexen-1-ol),

[0102] b. Aluminum-containing residue, which contains an elemental aluminum content in an amount of 1.5 wt% of the hydroxyl-functionalized propylene-based copolymer.

[0103] In an even more preferred embodiment, the novel paving and roofing composite according to the present invention comprises:

[0104] · A compatibilizer having the following specific composition:

[0105] a. Hydroxyl-functionalized propylene-based copolymer, namely poly(propylene-co-1-hexene-co-5-hexen-1-ol),

[0106] b. Aluminum-containing residue, which contains an elemental aluminum content in an amount of 1.0 wt% of the hydroxyl-functionalized propylene-based copolymer.

[0107] A paving and roofing composite having the following specific composition within ±1 wt%:

[0108] a. Pure asphalt in an amount of 85 wt%,

[0109] b. Ground tire rubber in an amount of 10 wt%,

[0110] c. Hydroxyl-functionalized propylene-based copolymer in an amount of 5 wt%, namely poly(propylene-co-1-hexene-co-5-hexen-1-ol,

[0111] d. Aluminum-containing residue, which contains an elemental aluminum content in an amount of 0.99 wt% of the hydroxyl-functionalized propylene-based copolymer.

[0112] Examples

[0113] Typical preparation procedure of isotactic poly(propylene-co-1-hexene-co-5-hexen-1-ol).

[0114] A stainless steel tube filled with pentamethylheptane (PMH) solvent (1 L) was used. Reactor (2L), using a stirring speed of 600rpm for polymerization experiments. Catalyst and comonomer solutions were prepared in a glove box under an inert dry nitrogen atmosphere. First, the reactor was heated to 40°C, and then TEA (1.0M toluene solution, 2mL), 1-hexene (pure 10mL) and triethylaluminum (TEA)-passivated 5-hexene-1-ol (1.0M toluene solution, TEA:5-hexene-1-ol=1:1, 10mL) were added. Gaseous propylene (100g) was added to the reactor at 40°C, and the reactor was heated to the desired polymerization temperature of 130°C, which produced a propylene partial pressure of about 15 bar. Once the set temperature was reached, the catalyst precursor bis((2-oxoacyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV) [CAS 958665-18-4]; also known as [[2',2"'-[(1,3-dimethyl-1,3-propanediyl)bis(oxy-κO)]bis[3-(9H-carbazol-9-yl)-5-methyl[1,1'-biphenyl]-2-phenoloxy-κO]](2-)]dimethyl]hafnium (Hf-O4, 2 μmol) was used to initiate the polymerization reaction. The reaction was stopped by pouring the polymer solution into a volumetric 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, and then Irganox 1010 was added as an antioxidant. Poly(propylene-co-1-hexene-co-5-hexene-1-ol) was obtained as an elastic transparent material.

[0115] Deashing Procedure of Isotactic Poly(propylene-co-1-hexene-co-5-hexene-1-ol)

[0116] The copolymer obtained by the solution process can be deashed to remove traces of protective substances. To this end, the copolymer (10 g) is dispersed in a mixture of anhydrous toluene (400 mL) and concentrated (37%) HCl (10 mL, 0.13 mol, 4.74 g) and heated under reflux until the copolymer is dissolved. Once the polymer is properly 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 at 80° C. in a vacuum oven for 24 hours.

[0117] Commercially available materials used in the experiments

[0118] Paving grade asphalt 70 / 100 (PG58-22) from LOTOS Asfalt Sp.z o.o. (Poland) was used as a reference material and neat binder in the experiments, which is dedicated to the further polymer modification process by the wet method. Ground tire rubber powder (GTR, average particle size 0.0 - 0.8 mm) was purchased from Recykl Group S.A. (Poland) and was used as received as a raw material in the preparation of rubberized asphalt samples in further experiments, and a synthetic hydroxy-functionalized copolymer was incorporated as a compatibilizer between the disintegrated particles of GTR and the asphalt components. Poly(styrene-co-butadiene-co-styrene) (SBSDST L30-01) supplied by Sibur International GmbH (Austria) was used as received in the processes of asphalt modification and rubberized asphalt compatibilization to obtain reference samples.

[0119]

[0120]

[0121]

[0122]

[0123] Table 5. Selected MSCR results for the obtained samples

[0124]

[0125] J nr,3.2kPa - Non-recoverable creep compliance at 3.2 kPa load

[0126] J nr,diff - Difference in non-recoverable creep compliance values at 3.2 kPa and 1.0 kPa, respectively

[0127] R 3.2kPa - Recovery rate percentage at 3.2 kPa load

[0128] PG+ - Performance grade + published system high temperature limit according to AASHTO M332

[0129] δ - Phase shift angle

[0130] |G*| / sin(δ) - Rutting factor

[0131] Failure - According to the standard, it indicates that a given composition does not meet the requirements at the specified maximum application temperature, but can still be used at the following temperature grades. CE examples may of course fail at the test temperature points because they do not exhibit sufficient mechanical properties in the case without modifiers / compatibilizers (FPO)

[0132] Table 6. Performance Grading of Test Samples According to ASTM D7643 and AASHTO M320

[0133] Project Continuous PG [℃] True PG [-] CE1 62.7 58 CE2 72.7 70 CE3 84.9 82 CE4 90.4 88 CE5 94.4 94 CE6 87.4 82 1 87.2 82 2 91.2 88 3 87.6 82 4 91.3 88 5 85.0 82 6 89.1 88 7 88.2 88 8 92.9 88 9 85.2 82 10 89.0 88

[0134] Results

[0135] From the above, the inventors found that the hydroxy-functionalized allyl copolymer needs to have a minimum content of alumina content [%] of 1.00 and a melting temperature of 60 - 100 °C (CFPO 1 - 3) to achieve the present invention.

[0136] As can be seen from Table 4, compared with pure bitumen CE1 and GTR-modified bitumen CE2, adding a hydroxy-functionalized allyl copolymer with or without a limited amount of aluminum-containing residue (i.e., FPO 1 - 6, FPO1(d)) to the rubber-modified bitumen composition:

[0137] · Significantly increased the dynamic viscosity, which does not prevent the conventional mixing and pumping procedures of the composition added at a concentration of 2.5 wt% or 5 wt%,

[0138] · Provided sufficient thermal storage stability, given that the addition amount of the compatibilizer is higher than 2.5 wt%, more preferably higher than 3.5 wt%, which is beneficial to prevent the ground tire rubber particles from phase separating from the composition at high operating temperatures during storage and transportation.

[0139] When compared with the rubber-modified bitumen (CE3) compatibilized with SBS copolymer, even better performance was obtained in terms of basic properties and storage stability improvement when the hydroxy-functionalized allyl copolymer was added in an amount of 2.5 wt%, more preferably 5 wt%.

[0140] As can be seen from Table 5, compared with pure bitumen CE1 and GTR-modified bitumen CE2, adding a hydroxy-functionalized allyl copolymer with or without a limited amount of aluminum-containing residue to the rubber-modified bitumen composition:

[0141] · Reduced the J nr,3.2kPa value and increased the PG+ grade, which promoted the application of the composition in paving exposed to very heavy (2.5 wt% compatibilizer) and extremely high traffic loads (5 wt% compatibilizer), as long as its 7-day average maximum temperature does not exceed 64 °C,

[0142] · Provided sufficient J nr,diff value under the given temperature conditions of the MSCR test, which is beneficial to maintaining the proper shear stress resistance of the paving, except in the case where the composition contains 5 wt% of the compatibilizer.

[0143] · Increased the R 3.2kPaThe value is conducive to improving the elasticity of pure asphalt.

[0144] Compared with the rubber-modified asphalt (CE3) compatibilized with SBS copolymer, when the hydroxy-functionalized propylene copolymer is added in an amount of 2.5 wt%, the performance is comparable at two test temperatures, except that the 3.2kPa R value is slightly lower. If a higher amount of the hydroxy-functionalized propylene copolymer is introduced, the difference in elasticity decreases, which also results in a lower nr,3.2kPa J value and thus rutting resistance.

[0145] As can be seen from Table 6, compared with pure asphalt CE1 and GTR-modified asphalt CE2, adding the hydroxy-functionalized propylene copolymer with or without a limited amount of aluminum residue to the rubber-modified asphalt composition:

[0146] · Increases the continuous PG and the true PG, which enables the application of the compositions containing 2.5 wt% and 5 wt% of the compatibilizer to regions mainly with hot climate conditions in the world by extending the high-temperature PG limit of the road surface to 82 or 88 respectively.

[0147] Compared with the rubber-modified asphalt (CE3) compatibilized with SBS copolymer, when the hydroxy-functionalized propylene copolymer is added in an amount of 2.5 wt%, the performance is comparable. If a higher amount of the hydroxy-functionalized propylene copolymer is incorporated, the true PG of the sample is improved by one grade compared with CE3.

[0148] Examples 1 and 3 (Δ softening point (ΔSP) > 5 °C but <= 10 °C, 6 and 10 °C respectively) will not be suitable for road applications, but will be suitable for roofing, because achieving Δ softening point (ΔSP) <= 5 °C is a standard requirement for road applications.

[0149] Other embodiments according to the present invention meet all the requirements for road and roofing applications.

[0150] By comparing Examples 4 and 5, it can be concluded that the terminal blending (TB) method cannot achieve a continuous PG >= 85 °C. However, by using the standard wet process at 180 °C, this feature can be achieved. The inventors believe that using the TB method, which is higher than 200 °C, degrades a part of the components in the mixture. Therefore, the materials according to the present invention manufactured by the conventional wet method at 180 °C are preferably used for roofing and road applications.

[0151] Typical procedure for differential scanning calorimetry (DSC) analysis

[0152] By DSC, the thermal properties of the polymer modifier are analyzed using a DSC Q100 (TA Instruments, Newcastle, Delaware, USA, UK). The recording was carried out in N 2Thermogram of the sample heated in atmosphere during heating and cooling from -100°C to 200°C at a rate of 10°C / min. After the first heating, the sample was kept at 200°C for 3min and then cooled to ensure the same thermal history. The phase transitions during cooling and the second heating were studied. The crystallinity (χ) of the sample was calculated according to the following formula:

[0153]

[0154] Where △H m is the melting enthalpy, α and △H m 0 are the weight fraction of PP and the melting enthalpy of 100% crystalline PP, respectively, and the assumed value △H m 0 =207J / g.

[0155] Typical procedure for size exclusion chromatography (SEC) analysis

[0156] The molar mass (M) of the bitumen modifiers was determined by high temperature size exclusion chromatography (HT-SEC) at 150°C using a Polymer Char GPC-IR (Polymer Char, Valencia, Spain) built around an Agilent GC oven model 7890 equipped with an autosampler and an integrated refractive index detector IR4. n and M w ). 1,2-Dichlorobenzene (o-DCB) was used as the eluent at a flow rate of 1 mL / min.

[0157] Used for 1 H NMR ( 1 Typical Procedure for HNMR Analysis

[0158] The spectroscopy was carried out in deuterated tetrachloroethane (TCE-D2) at 130 °C using a Varian mercury spectrometer (Bruker Company, Billerica, MA, USA) operating at 400 MHz. 1 H NMR analysis. A trace amount of tetramethylsilane was used as an internal standard.

[0159] Inductively coupled plasma mass spectrometry (ICP-MS) analysis

[0160] The residual element aluminum content [%] in the functionalized polyolefin was determined by ICP-MS. Approximately 150 mg of each sample was digested by microwave-assisted acid digestion in 6 mL of concentrated nitric acid (trace metal grade) 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 sample using a multi-element calibration device from Inorganic Ventures.

[0161] Typical procedure for wet asphalt modification

[0162] For asphalt modification with GTR as a modifier, the modification was carried out at 180 °C using an Ultra-Turrax T50 basic homogenizer (IKA Company, Warsaw, Poland) equipped with an S50N-G45M dispersion tool, operating at a speed of 4000 rpm for 60 minutes. The resulting rubberized asphalt sample was then compatibilized with the disclosed polymers (SBS, FPO or FPO(d)) at 180 °C using the same device and shear rate for 120 minutes.

[0163] Typical procedure for the terminal blending method for asphalt modification

[0164] For the terminal blending method, a GTR modifier was used at 240 °C using an Ultra-Turrax T50 basic homogenizer (IKA Company, Warsaw, Poland) equipped with an S50N-G 45M dispersion tool, operating at a speed of 4000 rpm for 60 minutes. The resulting rubberized asphalt sample was then compatibilized with the disclosed compatibilizer (FPO) at 180 °C using the same device and shear rate for 120 minutes.

[0165] Typical procedure for penetration analysis

[0166] The penetration test was carried out according to EN 1426. In this method, a needle of specified size and weight was penetrated into the asphalt mixture sample at 25 °C under a 100 g load for 5 seconds. The penetration value is expressed as the vertical distance the needle penetrates into the asphalt body, in decimillimeters (dmm). The final value for a given sample was derived from the average of three individual measurements.

[0167] Typical procedure for softening point analysis

[0168] The softening point test is carried out according to EN 1427 using a Ring & Ball apparatus. In this method, two metal rings filled with the asphalt mixture are heated in a water bath at a controlled rate of 5 °C / min while each supports a standardized steel ball. The softening point is determined as the temperature at which the steel ball coated with the asphalt film drops through a height of 25 mm. The reported softening point (SP) value is the average of the temperatures determined for each ball.

[0169] Typical procedure for dynamic viscosity analysis

[0170] The dynamic viscosity test is carried out according to EN 13302 at 180 °C using a Haake Visco tester 2Plus (TermoElectron, Waltham, Massachusetts, USA). The test is performed by immersing the appropriate cylindrical measuring head of the viscometer into the asphalt body to the depth determined by the scale placed on the rotor. Finally, the dynamic viscosity value [dPa·s] is read from the electronic display of the device.

[0171] Typical procedure for thermal storage stability analysis

[0172] The thermal storage stability test is carried out according to EN 13399. In this method, two sealed aluminum tubes (200 mm × 40 mm) are filled with liquid asphalt and placed vertically in an oven at 180 °C for 72 h. In the next step, the tubes are cooled to room temperature and stored at 5 °C for at least 24 h. Subsequently, the aluminum caps are removed manually and the samples are divided into three segments: the top segment, the middle segment, and the bottom segment. The top and bottom segments are melted and used for penetration and softening point analysis, while the middle segment is discarded.

[0173] Rheological analysis using a dynamic shear rheometer (DSR)

[0174] Rheological tests (DSR analysis) are carried out on unaged binder samples in oscillatory shear mode using a simulated compact rheometer Physica MCR301 (Anton Paar). Before the test, each sample is conditioned at 20 °C for at least 20 minutes. Temperature creep tests in oscillatory shear are carried out at 30 - 120 °C with a frequency of 10 rad / s, 1% strain, using a plate geometry with a diameter of 25 mm and a gap size of 1 mm. As a result of the DSR test, the rheological indices obtained are the dynamic shear modulus and its components (G’, G”, |G*|), the phase angle (δ), the loss factor (tan(δ)), and the rutting factor (|G*| / sin(δ)). The latter parameter is introduced to evaluate the rutting resistance of the modified asphalt and to determine the high-temperature continuous performance grade (continuous PG) and the true performance grade (true PG) of the tested samples according to ASTM D7643 and AASHTO M320, respectively.

[0175] The Multiple Stress Creep Recovery (MSCR) test was conducted on asphalt samples (AASHTO T240) aged in accordance with AASHTO M350-20 in the Rolling Thin Film Oven Test (RTFOT). Test temperatures (64 °C, 70 °C) were selected in accordance with AASHTO M350-20 specifications, taking into account the main climatic conditions in the potential application areas of the modified binder. Additionally, it was decided to conduct additional tests on the reference samples (Table 4, items CE1-CE3) at 58 °C as they failed to meet the requirements of the initially specified test conditions. The essence of this method is to predict the binder's tolerance to the accumulation of permanent deformation (rutting), and to evaluate the effectiveness of asphalt modification by assessing the presence of an elastic network within the tested asphalt samples (due to the application of load values above its linear viscoelastic region (LVE)). The following mechanisms were examined during the MSCR test: the creep properties of the binder, when a stress of a specific value is applied for 1 s, followed by the elastic recovery of the material during a 9 s relaxation period after the applied stress is removed. Measurements were taken at 10 load cycles with stress values of 0.1 kPa and 3.2 kPa, respectively. For the two applied stress levels, two basic parameters were obtained, namely the non-recoverable creep compliance (J nr , kPa -1 ) and the percentage recovery rate (R, %). The J nr value (J nr,3.2kPa ) at a stress of 3.2 kPa is of crucial importance as it is a measure of the binder's resistance to deformation. A lower J nr,3.2kPa value represents a higher rutting resistance of the tested asphalt sample. On the other hand, a higher percentage recovery rate value (R 3.2kPa ) at 3.2 kPa demonstrates the effectiveness of the binder modification, which is evaluated by the presence of an elastic network within the asphalt matrix. In accordance with AASHTO standards, the percentage difference between the J nr,3.2kPa and J nr,0.1kPa values (J nr,diff , %) must not be higher than 75% for the tested binder as it can indicate high shear susceptibility of the material, and thus the determination of the high-temperature PG+ range is inaccurate for the actual conditions at the potential construction site. The MSCR test of the disclosed PMB samples can detect the high-temperature PG limits of specific compositions within the Performance Grade+ (PG+) system according to AASHTO M332 specifications.

[0176] Fluorescence and optical microscopy

[0177] Fluorescence and optical imaging were carried out directly at 20x magnification under ambient conditions on asphalt samples prepared for AFM analysis (without further treatment) using a DeltaOptical 800M microscope with a UV light source. For fluorescence microscopy imaging, an exposure time of 300 - 1000 ms was used.

[0178] AFM HA-QNM experiment

[0179] The sample was also characterized under ambient conditions by the HA-QNM mode using an AFM tip with a spring constant of 5 N / m (TAP-150-30, No. 3k = 5 N / m) at a frequency of 0.5 Hz. With this specific 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 actual measurement. The QNM mode can quantitatively measure the mechanical properties of nanoscale materials by performing pixel-by-pixel force curves in the scanning area. The analysis of individual force curve data by the AFM nano-scope software provides a depiction of the material properties in a topological image with the same resolution. Here, the elastic modulus of the scanned surface is extracted from the force curves using the Derjaguin-Muller-Toropov model and presented as a modulus mapping image.

Claims

1. A composite material for paving and roofing applications, comprising: · Vulcanized rubber, which is preferably recycled, accounting for 5 - 20 wt%, preferably 10 - 15 wt% of the composite material, · Pure bitumen, which accounts for 70 - 93 wt%, preferably 80 - 90 wt% of the composite material, · A compatibilizer, which accounts for 2 - 10 wt%, preferably 2.5 - 7.5 wt%, more preferably 3 - 7 wt%, even more preferably 4 - 6 wt% of the composite material, and comprises: a. Hydroxy-functionalized allyl copolymer, with a melting temperature T m 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, or syndiotactic, and preferably has an OH functionalization degree of 0.1 - 0.6 mol%, more preferably 0.2 - 0.5 mol%, b. An aluminum-containing residue, which comprises an elemental aluminum content in an amount of at least 0.1, preferably 0.29, preferably and at most 1.5, preferably at most 1.2 wt% of the hydroxy-functionalized propylene-based copolymer.

2. The composite material according to any one of the preceding claims, wherein the vulcanized rubber is ground tire rubber, preferably used ground tire rubber.

3. The composite material according to any one of the preceding claims, wherein the hydroxy-functionalized propylene-based copolymer is a polymer comprising propylene, optionally a second olefin monomer, and a hydroxy-functionalized olefin.

4. The composite material according to any one of the preceding claims, wherein the hydroxy-functionalized propylene-based copolymer is amorphous or semi-crystalline.

5. The composite material according to any one of the preceding claims, wherein the hydroxy-functionalized propylene-based copolymer is selected from: poly(propylene-co-5-hexen-1-ol), poly(propylene-co-10-undecen-1-ol), poly(propylene-co-ethylene-co-5-hexen-1-ol), poly(propylene-co-ethylene-co-10-undecen-1-ol), poly(propylene-co-1-hexene-co-5-hexen-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-10-undecen-1-ol).

6. The composite material according to any one of the preceding claims, wherein the compatibilizer comprises poly(propylene-co-1-hexene-co-5-hexen-1-ol) and an aluminum-containing residue, and the aluminum-containing residue comprises an elemental aluminum content in an amount of 0.8 - 1.2 wt% of the hydroxy-functionalized propylene-based copolymer.

7. The composite material according to any one of the preceding claims, wherein the hydroxy-functionalized propylene-based copolymer is manufactured in a solution polymerization process.

8. The composite material according to any one of the preceding claims, wherein the composition has at least all of the following properties: · According to EN 13302, the dynamic viscosity (η180) at 180 °C is not higher than 0.345 Pa·s, ·According to EN 1426, the average infiltration (P 均 ) < 54 dmm, and · According to EN 1427, the average softening point (SP 均 ) > 53 °C, and · According to EN 13399, Δ penetration (ΔP) <= 10 dmm, preferably <= 5 dmm, more preferably <= 1 dmm, and · According to EN 13399, Δ softening point (ΔSP) <= 10 °C, preferably <= 5 °C, more preferably <= 1 °C, and · According to AASHTO M332 - 20, the performance grade plus (PG+) grade at 64 °C is V or E.

9. The composite material according to any one of the preceding claims, wherein the composition has at least all of the following properties: · The non-recoverable creep compliance J measured at 64 °C nr,3.2kPa <1, preferably <0.6 kPa -1 , and · According to AASHTO M332-20, at 64 °C, J nr,diff < 75%, and ·According to AASHTO M332-20, at 64 °C, R 3.2kPa > 21%.

10. The composite material according to any one of the preceding claims, wherein the composition has at least all of the following properties: · According to ASTM D7643, continuous PG >= 85 °C, and · According to AASHTO M320, true PG >= 82.

11. A method for manufacturing the composite material according to any one of the preceding claims, wherein the mixing of the neat asphalt and the vulcanized rubber is carried out under wet conditions at a temperature of 160 - 240 °C, preferably 160 - 200 °C, more preferably 170 - 190 °C, with constant stirring of the mixture, preferably using a high-shear mixer for 0.5 - 3 h, preferably 1 - 2 h.

12. A method for manufacturing the composite material according to any one of the preceding claims, wherein the mixing of the neat asphalt and the vulcanized rubber is carried out under a terminal blending method at a temperature of 230 - 260 °C, preferably 240 °C, with constant stirring of the mixture, preferably using a high-shear mixer for 0.5 - 3 h, preferably 1 - 2 h.

13. The method according to claim 11 or 12, wherein the compatibilizer is added to the mixture of the neat asphalt and the vulcanized rubber, and the resulting rubber-modified asphalt mixture is stirred for an additional 1 - 6 h, preferably 1 - 3 h, more preferably 1 - 2 h under constant stirring, and maintained at a constant temperature of 160 - 200 °C.

14. The method according to any one of claims 11 - 13, wherein the method is carried out under an inert atmosphere to prevent thermal degradation of the compatibilizer.

15. Use of the composite material according to any one of the preceding claims for roofing applications, and the composite material is used for road applications only when Δ softening point (ΔSP) <= 5 °C.

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