Rejuvenating agents for asphalt regeneration

Abstract

The present invention relates to an adhesive composition comprising an asphalt adhesive and at least one rejuvenating agent. The present invention also relates to a method for evaluating the efficacy of a rejuvenating agent in an adhesive composition.

Description

[0001] The present invention relates to a binder composition comprising a bituminous binder and at least one rejuvenating agent. In addition, the present invention relates to an asphalt composition comprising the binder composition of the present invention. The present invention also relates to a method for evaluating the efficacy of a rejuvenating agent in a binder composition.

[0002] Recycled asphalt binders from road pavements as well as other sources (e.g. recycled asphalt pavement, RAP, or asphalt shingles, RAS, from roofs) are important and valuable waste materials and are increasingly being reused in asphalt manufacturing. According to the European Asphalt Pavement Association (EAPA, Asphalt Chart 2018), about 50 million tonnes of recycled asphalt were reused in Europe in 2018 - out of a total of 298 million tonnes of asphalt produced in 2018, this represents about 17% of asphalt produced with recycled asphalt. The amount of recycled asphalt reused in asphalt production will increase further in the coming years and could reach 50% in Europe by 2035. The situation is similar in other parts of the world, forming a global trend and making asphalt one of the most important materials for recycling in the world.

[0003] However, asphalt in paving or any other application shows degradation over time, resulting in higher viscosity and increased brittleness at high temperatures, and is therefore more susceptible to cracking, particularly at lower temperatures. These aging effects are attributed to the binder phase of asphalt, i.e., soil asphalt. In order to reuse the recovered asphalt without sacrificing the performance of the asphalt, it is necessary to restore the performance curve of the soil asphalt to be as close as possible to the original soil asphalt (virgen bitumen) curve. The regeneration of the aged soil asphalt in this so-called recovered asphalt is carried out using chemical substances (so-called regeneration agents), which are added to the asphalt manufacturing process in an appropriate manner. Although many such regeneration agents have been documented in the literature, and some of them are also commercially available, they are still rarely used. The main concerns expressed by asphalt manufacturers in this regard are usually the expected lack of performance, particularly the uncertainty of its long-term performance, particularly in high-value applications (such as surface layers), and safety concerns, because many existing benchmarks (benchmarks) are aromatic oils, known to have safety hazards such as their toxicological characteristics.

[0004] Regenerants can be classified according to their chemical structure and composition:

[0005] - Supplementation of the earth bitumen phase by adding soft bitumen (e.g. Konink BAM Groep NV, WO2014168478; or RECYCLED ASPHALT SHINGLE TECHNOLOGY LLC, WO2013075088) remains the most frequently applied method, since it allows the aged earth bitumen to be adjusted very close to the original earth bitumen curve. However, this method fails with increasing share of recycled bitumen for reuse, since the necessary amount of soft bitumen required exceeds the total amount of earth bitumen to obtain the desired bituminous composition.

[0006] - Modification with low viscosity products (mainly aromatics) obtained from crude oil distillation or any other hydrocarbon-based process. These products, also called "flux oils", are also well established for use in bitumen manufacturing, but have significant disadvantages in terms of recovery of the rheological profile, lack of long-term performance and unacceptable safety profiles.

[0007] - Oils from renewable resources, in particular plant-based oils (triglycerides), such as soybean oil or rapeseed oil, which have similar behavior and disadvantages to "fluxing oils" (eg M. Freisthler, US 7008670).

[0008] - Modified triglycerides: In order to overcome the described disadvantages of triglycerides, several examples can be found in the literature of modifications thereof in a suitable manner and also of the same being offered as commercial products (e.g. Cargill is using oligomeric triglycerides containing unsaturated fatty acids, e.g. WO 2018191501; Sasol claims a combination of “fluxing oils” with hydrocarbon waxes, e.g. EP 2052056; synergistic aggregates combining triglycerides with curing agents such as salicylic acid (e.g. WO2015070180)).

[0009] - Aromatic oils from renewable resources, such as cashew nut shell liquid (CNSL) (Ventraco, EP 3208288)

[0010] - tall oil fatty acid and esters including rosin esters (eg claimed by ARIZONACHEM in WO 2013163463).

[0011] - Bio-based oils plus polymers (triglycerides and tallow esters) (e.g. Kraton, WO 2017117127)

[0012] - Plant-based oligoterpenes and sterols (e.g., as claimed by ARIZONA CHEM in WO 2016102314 and Ergon in WO 2018031540)

[0013] - reactive regenerating agents (e.g., as claimed by the University of Huelva in ES 22375125)

[0014] - (non-ionic) or (cationic) surfactants (e.g. CECA as claimed in WO 2013053882)

[0015] All products or product mixtures described in the literature show a (more or less) positive influence on the soil bitumen property curve and / or on the properties of bitumen, but the property curves of all these products are only partially described, always using different test methods, which does not allow a full assessment of their regeneration potential by following the published information and is ultimately not completely convincing.

[0016] Chemicals preferably derived from renewable resources have resulted in some commercially available products that allow very reasonable regeneration of recycled bitumen for some candidates, but for many of these candidates have a negative impact on the recycled binder. The industry needs more flexible concepts that allow processing of even larger quantities of recycled bitumen and reusing bitumen even in surface layers. In addition, there is a need for acceptable safety profiles and performance-oriented rejuvenators - which have a real impact on the microstructure of the native bitumen (e.g., asphaltene micelles) rather than simply diluting it - as well as easily applicable test methods, for example allowing easy adaptation of the recycled material to the actual properties of the usable binder from recycled bitumen.

[0017] In summary, there is a continuing need for a comprehensive concept to improve the utilization of recycled asphalt, especially recycled asphalt in the surface layer. This concept includes:

[0018] Rejuvenators, allowing almost complete or complete restoration of the performance curve of the soil-bituminous phase, including showing acceptable aging behavior,

[0019] Analytical testing procedures which allow the application of the rejuvenating agent to be adapted to the specific recycled bitumen and the desired use of the bitumen to be manufactured,

[0020] An acceptable safety curve, and

[0021] Functional regeneration, based on tailor-made synthetic protocols.

[0022] In this context, an object of the present invention is to provide a flexible product solution that allows processing of any type of recycled asphalt with as few restrictions as possible. In this regard, an object of the present invention is to provide an adhesive composition comprising a rejuvenating agent. In particular, an object of the present invention is to provide an adhesive composition, wherein the rejuvenating agent allows almost complete or complete recovery of the performance curve of the soil asphalt phase, including showing an acceptable aging behavior. A particular object is to provide an adhesive composition having well-balanced properties in terms of softening, viscosity and elasticity. In this regard, an object of the present invention is to provide an adhesive composition that contains a particularly high content of recycled asphalt and / or allows it to be reused in asphalt layers that require higher performance, such as top layers. In particular, an object of the present invention is to provide an adhesive composition with an acceptable safety curve. In addition, an object of the present invention is to provide an asphalt composition comprising a large amount of recycled asphalt. In addition, an object of the present invention is to provide an analytical testing procedure that allows the rejuvenating agent to be adapted to the desired use of a specific recycled asphalt and the asphalt to be produced.

[0023] It has surprisingly been found that at least one of these objects can be achieved by the claimed binder composition. It has been found that the binder composition as given below provides improved regeneration performance. It has also been found that the method for evaluating the efficacy of the claimed rejuvenating agent is suitable for determining the microstructure of soil asphalt, by which method the advantages of the herein claimed rejuvenating agent over the prior art can be clearly distinguished.

[0024] Therefore, in a first aspect, the present invention relates to an adhesive composition comprising

[0025] (a) asphalt binder; and

[0026] (b) 0.05 to 20% by weight of a rejuvenating agent, based on the total amount of the adhesive composition,

[0027] Wherein, the regeneration agent at least comprises an asphaltene dispersant, which is selected from alkoxylates, N,N-dialkylamides of aliphatic carboxylic acids, N-alkyllactams and poly(alkylamines); an asphaltene reactivator, which is selected from monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols, and mixtures thereof with catalysts; a maltenereactivator, which is a plasticizer; or a mixture thereof.

[0028] In the following, preferred embodiments of the components of the adhesive composition are described in further detail. It should be understood that each preferred embodiment is suitable both on its own and in combination with other preferred embodiments.

[0029] In a preferred embodiment A1 of the first aspect, the rejuvenating agent causes microstructural changes in the asphalt micelle structure, preferably, wherein the loss tangent of the adhesive composition is increased compared to the loss tangent of the asphalt binder, and / or wherein the amount of mobile components and / or their respective fluidities of the adhesive composition according to TD NMR are increased compared to the amount of mobile components and / or their respective fluidities of the asphalt binder.

[0030] In a preferred embodiment A2 of the first aspect, the regeneration agent comprises:

[0031] (i) 1 to 100 wt % of an asphaltene dispersant, based on the total amount of the rejuvenating agent;

[0032] (ii) 1 to 100 wt % of an asphaltene reactivating agent, based on the total amount of the reactivating agent;

[0033] (iii) 1 to 100 wt. % of a soft asphalt reactivator, based on the total amount of the reactivator; or

[0034] (iv) 1 to 100% by weight of a mixture consisting of at least two components selected from components (i) to (iii), based on the total amount of the regeneration agent.

[0035] In a preferred embodiment A3 of the first aspect, the earth asphalt binder comprises recycled asphalt pavement binder, recycled asphalt shingle binder, virgin earth asphalt having a hardness of at least 50 / 70, or a mixture thereof, optionally in combination with a virgin binder.

[0036] In a preferred embodiment A4 of the first aspect, the adhesive composition comprises:

[0037] Asphaltene dispersant, which is selected from alkoxylates having the structure of formula (1)

[0038]

[0039] The parts thereof are as hereinafter defined;

[0040] N,N-dialkylamide of aliphatic carboxylic acid having the structure of formula (2),

[0041]

[0042] The parts thereof are as hereinafter defined;

[0043] An N-alkyl lactam having the structure of formula (3),

[0044]

[0045] each of which is as hereinafter defined; or

[0046] A poly(alkylamine) having the structure of formula (4),

[0047]

[0048] The parts are defined as follows:

[0049] These poly(alkylamines) may further have C 1 -C 4 - alkyl, fatty acid or alkoxylated;

[0050] and / or an asphaltene reactivator selected from monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols, and mixtures thereof with catalysts such as N,N-dimethylbenzylamine, wherein the monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols have the structures of formula (5a), (5b), (5c) and (5d):

[0051]

[0052] Wherein, the components of formula (5a) to (5d) are as defined below;

[0053] and / or a soft asphalt reactivator, which is a plasticizer of formula (7a), (7b), (7c), (7d) or (7e),

[0054]

[0055]

[0056] Wherein, the various parts of formulae (7a) to 7(e) are as defined below.

[0057] In preferred embodiment A5 of the first aspect, the asphaltene dispersant is present and is selected from alkoxylates having the structure of formula (1):

[0058]

[0059] in

[0060] Where R is H, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, phenyl or alkylphenyl, preferably H or C 1 -C 22-alkyl, more preferably H or C 1 -C 18 -alkyl,

[0061] n is 0 to 20, preferably 0 to 15, more preferably 0 to 10,

[0062] m is 0 to 20, preferably 0 to 15, more preferably 0 to 10, wherein

[0063] n+m≥1, preferably n+m≥5;

[0064] In particular, the alkoxide has the structure of formula (1), wherein

[0065] R is C 10 -alkyl or C 13 -alkyl, preferably 2-propylheptyl or isotridecyl,

[0066] n is 0 to 6,

[0067] m is 0 to 8, and wherein

[0068] n+m≥5;

[0069] N,N-dialkylamide of an aliphatic carboxylic acid having the structure of formula (2),

[0070]

[0071] in

[0072] n is 3 to 16, wherein at least one "CH 2 The carbon atoms in the "part" may be further replaced by at least one C 1 -C 5 -alkyl, and at least two adjacent "CH 2 The two carbon atoms of the " part may form a double bond, preferably 6 to 14, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 5 - alkyl substituted,

[0073] R 1 C 1 -C 4 - alkyl, preferably methyl or ethyl, and

[0074] R 2 C 1 -C 4 - alkyl, preferably methyl or ethyl;

[0075] In particular, the N,N-dialkylamide of the aliphatic carboxylic acid has the structure of formula (2), wherein

[0076] n is 8 to 12,

[0077] R 1 is methyl or ethyl, and

[0078] R 2 is methyl or ethyl;

[0079] N-alkyl lactam having the structure of formula (3)

[0080]

[0081] in

[0082] n is 3 to 11, wherein at least one "CH 2 The carbon atoms in the "part" may be further replaced by at least one C 1 -C 3 - alkyl substituted, preferably 3 (pyrrolidone), 5 (caprolactam) or 11 (laurolactam), and

[0083] R is C 1 -C 22 -alkyl or C 2 -C 22 -alkenyl, preferably C 4 -C 18 -alkyl;

[0084] In particular, the N-alkyl lactam has the structure of formula (3), wherein

[0085] n is 3 (pyrrolidone), and

[0086] R is C 8 -C 12 -alkyl; or

[0087] Poly(alkylamine) having the structure of formula (4)

[0088]

[0089] in

[0090] n is 1 to 6, preferably 2 to 3, wherein at least two adjacent "CH 2 The carbon atoms in the " part can form double bonds,

[0091] m is 1 to 6, preferably 2 to 3, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0092] x is 4 to 50, and

[0093] R 1 C 1 -C 4 -alkyl, preferably C1 -C 2 -alkyl,

[0094] These poly(alkylamines) may be further derivatized with C 1 -C 4 - alkyl, fatty acid or alkoxylated;

[0095] In particular, the poly(alkylamine) is selected from oligo-N,N-bis-(3-aminopropyl)methylamine and poly-N,N-bis-(3-aminopropyl)methylamine.

[0096] In preferred embodiment A6 of the first aspect, the asphaltene reactivator is present and is selected from monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols, and mixtures thereof with catalysts such as N,N-dimethylbenzylamine, wherein the monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols have the structures of Formula 5(a), 5(b), 5(c) and 5(d).

[0097]

[0098] in

[0099] For formula 5(a)

[0100] R is C 1 -C 20 -alkoxy, C 2 -C 20 -Alkenyloxy, phenoxy or C 1 -C 20 -carboxyalkyl, wherein the phenoxy group may be further substituted with at least one C 1 -C 15 -alkyl substituted, preferably C 4 -C 16 -alkoxy, preferably 2-ethylhexanol, n-butanol, tert-butanol, C 12 -C 15 - alkoxy, nonylphenol, allyl alcohol or neodecanoic acid;

[0101] For formula (5b)

[0102] R is a straight chain C 5 -C 20 -alkylene, which may be further substituted with at least one C 1 -C 5 -alkyl or C 1 -C 4 -alkylene substituted, the C 1 -C 5 -alkyl or C1 -C 4 -Alkylene is further substituted with at least one C 1 -C 10 -alkyl and / or at least one phenyl substitution, preferably a straight chain C 5 -C 15 -alkylene, which is further substituted by at least one C 1 -C 4 -alkyl or C 1 -C 3 -alkylene substituted, which is further substituted with at least one C 1 -C 5 - alkyl and / or at least one phenyl substitution;

[0103] For formula (5c)

[0104] R is C 1 -C 5 -alkylene, preferably C 3 - alkylene; and

[0105] For formula (5d)

[0106] R n Formula (6a), (6b) or (6c)

[0107] (-CH 2 CH 2 O-) n (6a),

[0108] Where n is 3 to 20,

[0109] (-CH 2 CH(CH 3 )O-) n (6b),

[0110] wherein n is 3 to 18, preferably 3 to 15, or

[0111] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0112] wherein n is 3 to 18, preferably 3 to 15;

[0113] Preferably, the asphaltene reactivating agent is selected from polyethylene glycol bis(glycidyl) ether, polypropylene glycol bis(glycidyl) ether, neopentyl glycol bisglycidyl ether, 2-methyl-2-phenyl-1,3-propanediol bisglycidyl ether, 2-ethylhexyl glycidyl ether, and a mixture of these compounds with a catalyst such as N,N-dimethylbenzylamine; more preferably, the asphaltene reactivating agent is polypropylene glycol bis(glycidyl) ether.

[0114] In a preferred embodiment A7 of the first aspect, the soft asphalt reactivator is present and is a plasticizer having formula (7a), (7b), (7c), (7d) or (7e),

[0115]

[0116]

[0117] in

[0118] For formula (7a)

[0119] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0120] For formula (7b)

[0121] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0122] For formula (7c)

[0123] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0124] For formula (7d)

[0125] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0126] For formula (7e)

[0127] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl, and

[0128] n is 4 to 10, wherein at least two adjacent "CH 2 The two carbon atoms of the " portion may form a double bond, preferably wherein the plasticizer has formula (7a), (7c) or (d), wherein

[0129] For formula (7a)

[0130] R is C 8 -C 12 -alkyl or C 7 -C 12 -alkenyl, preferably C 8 -C 11 -alkyl;

[0131] For formula (7c)

[0132] R is C 8 -C 12 -alkyl or C 7 -C 12 -alkenyl, preferably C 8 -C 11 -alkyl;

[0133] For formula (7d)

[0134] R is C 8 -C 12 -alkyl or C 7 -C 12 -alkenyl, preferably C 8 -C 11 -alkyl, and

[0135] n is 4 to 8, wherein at least two adjacent "CH 2 The two carbon atoms of the " part can form a double bond, more preferably, the soft asphalt reactivator is selected from diisononyl phthalate or cyclohexane-1,2-dicarboxylate diisononyl ester, more preferably, the soft asphalt reactivator is cyclohexane-1,2-dicarboxylate diisononyl ester.

[0136] In a preferred embodiment A8 of the first aspect, the soil asphalt binder comprises 10 to 100 wt % of recycled asphalt pavement and / or recycled asphalt shingle binder, based on the total weight of the soil asphalt binder.

[0137] In a preferred embodiment A9 of the first aspect, the asphalt binder comprises other additives, preferably wherein the other additives are selected from polymers, waxes, fibers or mixtures thereof.

[0138] In a second aspect, the present invention relates to an asphalt composition comprising aggregate and the claimed binder composition.

[0139] In a third aspect, the present invention relates to a paved road surface, road subsurface, runway, driveway, parking lot, shoulder, bridge, abutment, roof, bank revetment or unpaved road comprising the claimed bituminous composition.

[0140] In a fourth aspect, the present invention relates to a method for evaluating the efficacy of a rejuvenating agent in an adhesive composition, wherein the efficacy of the rejuvenating agent is demonstrated by:

[0141] (i) the loss tangent before or after aging, obtained at a given temperature from a dynamic shear rheometer (DSR) frequency sweep, wherein the frequency sweep is measured at a temperature between 0 and 90°C, and wherein the effective regenerant satisfies inequality (a)

[0142] Loss tangent [bc]>1.3×loss tangent [bb], (a)

[0143] wherein loss tangent [bc] represents the loss tangent of the adhesive composition and loss tangent [bb] represents an asphalt adhesive, and wherein loss tangent [bc] and loss tangent [bb] are evaluated at a frequency of 0.01 to 10 rad / s, or

[0144] (ii) TD NMR relaxation experiments on asphalt samples at temperatures ranging from -50 to 200 °C, where the effective regenerant satisfies inequality (aa1)

[0145] T2e1[bc]>1.3×T2e1[bb] (aa1)

[0146] wherein T2e1[bc] represents the relaxation time corresponding to the individual components of the binder composition, and T2e1[bb] represents the relaxation time corresponding to the individual components of the asphalt binder.

[0147] In a fifth aspect, the present invention relates to the use of a rejuvenating agent for recycling recovered asphalt pavement (RAP) and / or asphalt shingles from roofs (RAS), the rejuvenating agent comprising at least one asphaltene dispersant selected from alkoxylates, N,N-dialkylamides of aliphatic carboxylic acids, N-alkyllactams and poly(alkylamines); an asphaltene reactivating agent selected from monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols, and mixtures thereof with catalysts; a soft asphalt reactivating agent, which is a plasticizer; or mixtures thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0148] Figure 1 The regenerant of the present invention is disclosed to increase the loss tangent.

[0149] Figure 2 Discloses the use of 5% of some of the herein claimed regenerants or benchmarks Tan δ of HP-AM regenerated soil asphalt 20 / 30 after 3×RTFOT aging.

[0150] Figure 3 Discloses the use of 5% of some of the herein claimed regenerants or benchmarks Tan δ of HP-AM regenerated RTFOT+PAV aged dirt asphalt 50 / 70 (BP).

[0151] Figure 4 Discloses the use of 5% of some of the herein claimed regenerants or benchmarks Tan δ of HP-AM regenerated RTFOT+PAV aged dirt asphalt 50 / 70 (Schwedt).

[0152] Figure 5 Discloses the use of 5% of some of the herein claimed regenerants or benchmarks Tan δ of RAP soil asphalt regenerated by HP-AM.

[0153] Figure 6 Discloses the use of 5% of some of the herein claimed regenerants or benchmarks Tan delta of Olexobit 45 regenerated by HP-AM.

[0154] Figure 7 Discloses the use of 5% of some of the herein claimed regenerants or benchmarks Tan δ of HP-AM regenerated Olexobit 45 after 3×RTFOT. DETAILED DESCRIPTION

[0155] Before describing exemplary embodiments of the present invention in detail, definitions important for understanding the present invention are given.

[0156] As used in this specification and the appended claims, the singular forms "a" and "an" also include the corresponding plural forms unless the context clearly indicates otherwise. In the context of the present invention, the terms "about" and "approximately" represent an interval of precision that a person skilled in the art will understand will still ensure the technical effect of the features mentioned. The term generally indicates a deviation of ±20%, preferably ±15%, more preferably ±10%, and even more preferably ±5% from the numerical value shown. It should be understood that the term "comprising" is not restrictive. For the purposes of the present invention, the term "consists of" is considered to be a preferred embodiment of the term "comprising". If a group is defined below as comprising at least a certain number of embodiments, this means that a group that is preferably only composed of these embodiments is also included. In addition, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" and the like in this specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequence or time order. It should be understood that the terms so used are interchangeable where appropriate, and that the embodiments of the invention described herein may be operated in a sequence other than that described or illustrated herein. In the case where the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)", "i", "ii", etc. relate to steps of a method or use or test, there is no continuity of time or time interval between the steps, i.e., the steps may be performed simultaneously, or there may be a time interval of a few seconds, minutes, hours, days, weeks, months or even years between the steps, unless otherwise expressly indicated above or below in this application. It should be understood that the present invention is not limited to the particular methods, protocols, reagents, etc. described herein, as these may vary. It should be understood that the terms used herein are only for the purpose of describing specific embodiments, and are not intended to limit the scope of the invention, which will be limited only by the appended claims. . Unless otherwise defined, all technical and scientific terms used herein have the same meanings as understood by those of ordinary skill in the art.

[0157] When referring to weight percentages of compositions and ingredients contained therein, it is to be understood that the total amount of ingredients according to the present invention does not exceed 100% (± 1% due to rounding).

[0158] As used herein, the term "alkyl" each refers to a straight chain or branched chain alkyl group, which generally has 1 to 25 carbon atoms, preferably 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and even more preferably 1 to 15 carbon atoms.

[0159] As used herein, the term "alkenyl" refers to an unsaturated straight or branched hydrocarbon group, which generally has 2 to 25, preferably 2 to 22 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 2 to 15 carbon atoms, which contains at least one carbon-carbon double bond in any position. If geometric isomers about the double bond are possible, the present invention relates to E- and Z-isomers.

[0160] As used herein, the term "alkoxy" each refers to a straight-chain or branched alkyl group, which is bonded through an oxygen atom and generally has 1 to 25 carbon atoms.

[0161] As used herein, the term "alkenyloxy" each refers to a straight-chain or branched alkenyl group, which is bonded through an oxygen atom and generally has from 2 to 25 carbon atoms.

[0162] As used herein, the term "carboxyalkyl" each refers to a straight-chain or branched alkyl group which is bonded through the oxygen atom of a carboxyl group and generally has 1 to 25 carbon atoms.

[0163] As used herein, the term "alkylene" refers to a linked straight or branched chain alkyl group typically having 1 to 15 carbon atoms. The alkylene group bridges certain groups of the molecule. According to the present invention, an alkylene group can bridge two or three groups of the molecule. A person skilled in the art will understand that if, for example, CH 2 , a tetravalent carbon atom has two remaining valences for attachment (-CH 2 -). Similarly, when referring to CH 2 CH 2 Each carbon atom has a valence remaining to form a bridge (-CH 2 CH 2 -), or by (-C 2 H 4 -)express.

[0164] As used herein, the term "alkylphenyl" refers to a phenyl group which may be substituted with at least one alkyl group.

[0165] As used herein, the term "phenoxy" or "phenylhydroxy" refers to the corresponding group (ie, phenyl) bonded to the rest of the molecule through an oxygen atom.

[0166] As used herein, the term “ n -C m -alkyl)" each refers to a linking moiety wherein the moiety to which it is linked is attached to a terminal carbon.

[0167] As used herein, the term "bitumen" refers to a composite material comprising "aggregate" and "earth bitumen" and used, for example, for road paving or roofing. The most common application of bitumen is for paving applications. Different asphalt grades are defined for these paving applications - mainly with a very clearly specified aggregate composition, which forms a much larger portion of 92.5-96 weight %. Typically, the amount of earth bitumen is 4-7.5 weight %. However, even a smaller portion of the composition, the performance curve of the earth bitumen will have a huge impact on the performance curve of the bitumen.

[0168] As used herein, the term "recycled asphalt" refers to any kind of asphalt that is recovered after use. In particular, mention should be made of "recycled asphalt pavement (RAP)" and "recycled asphalt shingles (RAP)" obtained from pavement removed from roads or any other asphalt containing material from roofing applications.

[0169] As used herein, the term "earth bitumen" refers to a viscous, black, highly viscous liquid or semisolid material obtained as a residue in petrochemical refineries or found in natural deposits.

[0170] As used herein, the term "fresh earth asphalt" refers to earth asphalt that originates from a refinery and, before that, has not been used for road paving, roofing, or any other application. In this regard, it is understood that fresh earth asphalt has not yet aged.

[0171] As used herein, the term "virgin binder" refers to "fresh earth asphalt" that does not contain a rejuvenating agent (and thus has not been rejuvenated) and refers to "fresh earth asphalt" that contains at least one rejuvenating agent. In this regard, it is understood that the virgin binder has not aged. The virgin binder may also contain at least one additive selected from polymers, waxes, fibers, or anti-stripping agents.

[0172] As used herein, the term "aged soil asphalt" refers to soil asphalt present in or extracted from recycled asphalt. Due to the aging process, the aged soil asphalt exhibits, for example, a higher viscosity and a higher softening point than the corresponding fresh soil asphalt that has been used to make asphalt. Typically, the aged soil asphalt is not separated from the recycled asphalt. The chemical composition of the aged soil asphalt, characterized by SARA analysis, shows a significant increase in asphaltene content, which is the main influence on the deterioration of soil asphalt. Aged binders are generally not separated from the recycled asphalt used to produce new asphalt using RAP. Instead, the recycled asphalt is mixed with the regeneration agent in an appropriate manner at the asphalt mixing plant, with or without fresh soil asphalt (forming a binder composition), and with or without aggregate. Only at a laboratory scale, the aged binder is separated from the recycled asphalt (usually by solvent extraction) to study the function of the regeneration agent and determine the optimal composition and dosage of the regeneration agent.

[0173] As used herein, the term "aggregate" is defined as coarse materials spanning medium to fine-grained materials used in construction, such as sand, gravel, crushed stone, or slag, and based on, for example, limestone, granite, basalt, or quartzite.

[0174] As used herein, the term "binder composition" refers to a mixture of fresh and / or aged earth asphalt (i.e., earth asphalt binder) and optionally other components, such as polymers, adhesion promoters, rejuvenators or other suitable additives. According to the present invention, the binder composition also includes at least one rejuvenator.

[0175] As used herein, the term "rejuvenating agent" refers to a composition or chemical complex mixed with aged earth asphalt in a suitable manner, which allows restoring the performance curve of the aged earth asphalt to a level close to that of fresh earth asphalt.

[0176] Analytical methods

[0177] As used herein, the term "SARA analysis" refers to the description of the chemical composition of soil asphalt. Usually, soil asphalt is described by its physical properties, especially viscoelastic behavior. It is very complicated to describe with its chemical composition because it is composed of a large number of chemical individuals, and their composition depends on the source of soil asphalt to a great extent. However, in order to describe the chemical composition of soil asphalt, SARA analysis has been established in the soil asphalt industry. SARA reflects four groups of chemicals found in each soil asphalt: saturated compounds (non-polar, aliphatic and cycloaliphatic hydrocarbons), aromatic compounds (less polar, aromatic hydrocarbons), resins (polar, condensed cycloaliphatic, aromatic and heteroaromatic compounds--soluble in normal heptane) and asphaltenes (polar, condensed cycloaliphatic, aromatic and heteroaromatic compounds--insoluble in normal heptane). For the performance curve of soil asphalt, the very good equilibrium ratio between these SARA components is very important, and asphaltenes play a very important role.

[0178] "Rheology" studies "the deformation and flow of matter, especially the non-Newtonian flow of liquids and the plastic flow of solids". For rheological properties in the medium and high temperature range, DSR rheological measurements are often used, but not limited to, to characterize the rheology of adhesives. The following rheological parameters are usually analyzed:

[0179] • The "softness" of a binder is an indication of its softness in a given temperature range. Experimentally, for earth bitumen, this is usually obtained from the "softening point ring & ball" (DIN EN 1427) or the needle penetration test (DIN EN 1426).

[0180] "Viscosity" is an indication of the fluidity of the binder. Viscosity is particularly important in the preparation of clay bitumen and during the preparation of bitumen. For clay bitumen, the viscosity depends to a large extent on the temperature at which the measurement is made. The viscosity of clay bitumen is most often determined using a DSR rheometer measurement with plate / plate geometry, most often at 135°C, but also at other temperatures such as 60°C (DIN EN 12595, DIN EN 12596).

[0181] "Loss tangent" (also called "loss factor" (tan δ)") is the ratio between the viscous contribution G" and the elastic contribution G' of a viscoelastic adhesive. The loss tangent can be obtained, for example but not limited to, by a frequency sweep of the adhesive at a specific temperature. Since the loss tangent is the ratio between G" / G', it is a direct indication of the molecular mobility within the adhesive (G" itself is a viscous contribution, defined only by the fluidity of the adhesive), particularly but not limited to at low frequencies, when the rheological measurement itself has little effect on the adhesive system, thereby directly studying the intrinsic fluidity of the adhesive.

[0182] "Elasticity" is the elastic recovery obtained from the MSCR test or conventional elastic recovery (DIN EN 13398). The Multiple Stress Creep Recovery ("MSCR") test (DIN EN 16659) gives an indication of the elastic recovery strength of an adhesive. After stress is applied to the adhesive confined in a board / board geometry, the test measures the ability of the adhesive to recover to its original state before distortion. The higher the recovery percentage, the more elastic the system is.

[0183] • "Ductility" is a measure of the plastic deformation and cohesion of an asphalt and is usually measured by a force ductility test (DIN EN 13589) using an extensometer.

[0184] · Although the latest studies suggest that the "cold behavior" of soil bitumen can be approximated using DSR measurements at low temperatures, it is generally believed that the most reliable low-temperature test to this day is still the bending beam rheometer (BBR) test (DIN EN14771). In this article, two values ​​are determined - the bending creep stiffness S and the m-value (value describing the relaxation capacity of the system = the slope of the logarithm of the stiffness versus the logarithm of the time curve at a given time).

[0185] "Aging behavior": The rejuvenating agent must withstand new cycles of asphalt aging, and it is important to determine the influence of the rejuvenating agent on the aging behavior of the asphalt. The aging of the rejuvenating agent can be tested by subjecting the adhesive composition to the RTFOT aging test (DIN EN 12607) and determining the change in viscosity at 135°C and / or the change in loss tangent due to aging. Aging can be characterized by an aging index (AI), which is defined as the viscosity after aging divided by the viscosity before aging. In order to obtain more accurate results about the aging behavior of the rejuvenating agent, we usually perform an extended RTFOT aging test (at 163°C, 3×RTFOT), which is known in the scientific community to be able to approximate the long-term stability of the adhesive. Another test known to approximate the long-term stability of the adhesive is the so-called Pressure Ageing Vessel (PAV, DIN EN 14769), in which the adhesive is aged for an extended time (usually 20 hours) at elevated temperatures (at 85 to 110°C) under pressure (about 2.1 MPa).

[0186] Preferred embodiments of the adhesive composition and its use are described in detail below. It should be understood that the preferred embodiments of the present invention are preferred individually or in combination with each other.

[0187] As described above, in one embodiment, the present invention relates to an adhesive composition comprising

[0188] (a) asphalt binder; and

[0189] (b) 0.05 to 20% by weight of a rejuvenating agent, based on the total amount of the adhesive composition,

[0190] The regeneration agent at least comprises an asphaltene dispersant, an asphaltene reactivator, a soft asphalt reactivator, or a mixture thereof.

[0191] Without wishing to be bound by any theory, it is considered that the soil bitumen of the present invention is a dispersion of polar micelles in a continuous hydrocarbon medium (= "soft bitumen" or "soft bitumen phase"). In this model, "soft bitumen" includes "saturates" and "aromatics", which are based on, for example, aliphatic, alicyclic and aromatic hydrocarbons, usually with small amounts of heteroatom functional groups (such as alcohols, carboxylic acids, thiols or amines); and "resins" (= less condensed aromatic or aromatic cycloaliphatic systems with lower molecular weight than asphaltenes, with a certain degree of polarity), etc. The micelles are based on "asphaltenes" (= condensed aromatic systems with higher molecular weight and higher polarity resulting from the higher number of heteroatom functional groups), surrounded by "resins". These resins play an important role in the stabilization of the colloidal system and therefore also in any regeneration process.

[0192] After vacuum distillation, only very small quantities of crude oils (more than about 100 out of 1500) provide a residue suitable for earth bitumen applications, especially for asphalt manufacturing. This is believed to be related to the minimum content of "asphaltenes" and a well-balanced ratio between "soft bitumen" and "asphaltenes", which is specific to each crude oil source and produces the desired rheological profile of earth bitumen. This balance is disturbed by aging processes, especially chemical oxidation, chain loss or polycondensation, which shift the rheological profile towards higher viscosities and ultimately increase the brittleness of the material at lower temperatures, making the binder no longer suitable for, for example, asphalt paving applications.

[0193] Although sometimes claimed, rejuvenators are not believed to restore the exact original soil asphalt composition. However, the rejuvenators of the present invention can create a new balance between "saturates", "aromatics", "resins" and "asphaltenes" to produce a performance curve close to that of the original soil asphalt.

[0194] As the amount of recycled asphalt utilized increases and as recycled asphalt is recycled multiple times, the need to restore the properties of the soil asphalt phase will increase to ensure the desired asphalt properties in the future.

[0195] The asphaltene dispersant of the present invention is a chemical substance or a composition comprising said chemical substance, which improves the dispersibility of asphaltene with micelles. In particular, the asphaltene dispersant either decomposes the asphaltene stack to reduce the asphaltene aggregates or improves the dispersion of the asphaltene stack in the soft asphalt phase. In this regard, alkoxylates, N,N-dialkylamines of aliphatic carboxylic acids, N-alkyllactams and poly(alkylamines) should be mentioned. Asphaltene dispersants without toxicological identification are preferred.

[0196] In one embodiment of the present invention, the alkoxylate has the structure of formula (1).

[0197]

[0198] in

[0199] Where R is H, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, phenyl or alkylphenyl,

[0200] n is 0 to 20,

[0201] m is 0 to 20, and wherein

[0202] n+m≥1.

[0203] In a preferred embodiment of the present invention, the alkoxylate has the structure of formula (1), wherein

[0204] R is H or C 1 -C 22 -alkyl, preferably H or C 1 -C 18 -alkyl, more preferably H or C 4 -C 13 -alkyl,

[0205] n is 0 to 20, preferably 0 to 15, more preferably 0 to 10,

[0206] m is 0 to 20, preferably 0 to 15, more preferably 0 to 10, and wherein

[0207] n+m≥1, preferably n+m≥5.

[0208] In a particular embodiment of the present invention, the alkoxylate has the structure of formula (1), wherein

[0209] R is C 10 -alkyl or C 13 -alkyl, preferably 2-propylheptyl or isotridecyl,

[0210] n is 0 to 6,

[0211] m is 0 to 8, and wherein

[0212] n+m≥5.

[0213] In one embodiment of the present invention, the N,N-dialkanoic acid amide of the aliphatic carboxylic acid has the structure of formula (2)

[0214]

[0215] in

[0216] n is 3 to 16, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 5 -alkyl, and at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0217] R 1 C 1 -C 4 -alkyl, and

[0218] R 2 C 1 -C 4 -alkyl.

[0219] In a preferred embodiment of the present invention, the N,N-dialkylamide of an aliphatic carboxylic acid has the structure of formula (2), wherein

[0220] n is 6 to 14, preferably 6 to 12, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 5 - alkyl substituted,

[0221] R 1 C 1 -C 4 - alkyl, preferably methyl or ethyl, and

[0222] R 2 C 1 -C 4 - alkyl, preferably methyl or ethyl.

[0223] In a particular embodiment of the present invention, the N,N-dialkylamide of an aliphatic carboxylic acid has the structure of formula (2), wherein

[0224] n is 8 to 12,

[0225] R 1 is methyl or ethyl, and

[0226] R 2 It is methyl or ethyl.

[0227] In one embodiment of the present invention, the N-alkyl lactam has the structure of formula (3)

[0228]

[0229] in

[0230] n is 3 to 11, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 3 -alkyl substituted, and

[0231] R is C 1 -C 22 -alkyl or C 2 -C 22 -alkenyl.

[0232] In a preferred embodiment of the present invention, the N-alkyl lactam has the structure of formula (3), wherein

[0233] n is 3 (pyrrolidone), 5 (caprolactam) or 11 (laurolactam), and

[0234] R is C 1 -C 22 -alkyl, preferably C 4 -C18 -alkyl, more preferably C 8 -C 12 -alkyl.

[0235] In a particular embodiment of the present invention, the N-alkyl lactam has the structure of formula (3), wherein

[0236] n is 3 (pyrrolidone), and

[0237] R is C 8 -C 12 -alkyl.

[0238] In one embodiment of the present invention, the poly(alkylamine) has the structure of formula (4)

[0239]

[0240] in

[0241] n is 1 to 6, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0242] m is 1 to 6, wherein at least two adjacent "CH 2 The two carbon atoms in the " part may form a double bond,

[0243] x is 4 to 50, and

[0244] R 1 C 1 -C 4 -alkyl,

[0245] These poly(alkylamines) may be further derivatized with C 1 -C 4 - alkyl, fatty acid or alkoxylated.

[0246] In a preferred embodiment of the present invention, the poly(alkylamine) has the structure of formula (4), wherein

[0247] n is 1 to 6, preferably 2 to 3,

[0248] m is 1 to 6, preferably 2 to 3,

[0249] X is 4 to 50, and

[0250] R 1 C 1 -C 2 -alkyl,

[0251] These poly(alkylamines) may further be derivatized with fatty acids or alkoxylated at the terminal amine moiety.

[0252] In a particular embodiment of the present invention, the poly(alkylamine) is selected from oligo-N,N-bis(3-aminopropyl)methylamine and poly-N,N-bis(3-aminopropyl)methylamine (hereinafter also referred to as poly(bisaminopropylamine) or polyBAPMA).

[0253] As described above, according to the present invention, the poly(alkylamine) having formula (4) may be further derivatized with a fatty acid at the terminal amine moiety.

[0254] In one embodiment of the invention, the poly(alkylamine) has the structure of formula (4a)

[0255]

[0256] in

[0257] n is 1 to 6, preferably 2 to 3, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0258] m is 1 to 6, preferably 2 to 3, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0259] x is 4 to 50,

[0260] R 1 C 1 -C 4 -alkyl, preferably C 1 -C 2 -alkyl, and

[0261] y is 10 to 20.

[0262] As described above, according to the present invention, the poly(alkylamine) having formula (4) may be further derivatized at the terminal amine moiety by alkoxylation.

[0263] In one embodiment of the invention, the poly(alkylamine) has the structure of formula (4b)

[0264]

[0265] in

[0266] n is 1 to 6, preferably 2 to 3, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0267] m is 1 to 6, preferably 2 to 3, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0268] x is 4 to 50,

[0269] R 1 C 1 -C 4 -alkyl, preferably C 1 -C 2 -alkyl, and

[0270] a+b≥1≤10.

[0271] Examples of suitable asphaltene dispersants are TO 8, TO 3, TO 15, FEP 3830PA, XL 60, XP 70, AMD 12, TO 5, TO A 500PE, polyBAPMA with partially varying MW, and their possible fatty acid amide derivatives after reaction with, for example, stearic acid, N-dodecylpyrrolidone and N,N-dimethyldodecanoic acid amide.

[0272] In a preferred embodiment of the present invention, the asphaltene dispersant is an alkoxide having the structure of formula (1):

[0273]

[0274] in

[0275] R is H, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, phenyl or alkylphenyl,

[0276] n is 0 to 20,

[0277] m is 0 to 20, and wherein

[0278] n+m≥1,

[0279] Poly(bisaminopropylamine) (polyBAPMA), or N-dodecylpyrrolidone.

[0280] The asphaltene reactivator of the present invention is a chemical substance or a composition comprising the chemical substance, which increases the solubility of asphaltene in soft bitumen by chemical connection with asphaltene through organic chains (e.g. olefin chains) after losing solubility due to the aging process of the binder. The mode of action of the asphaltene reactivator is a chemical reaction with the functional groups of the asphaltene, and thereby counteracts the agglomeration of the asphaltene. Preferred asphaltene reactivators have no toxicological identification. In this regard, monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols, and mixtures thereof with catalysts such as N, N-dimethylbenzylamine should be mentioned.

[0281] In one embodiment of the present invention, the monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols have the structures of formula (5a), (5b), (5c) and (5d).

[0282]

[0283] in

[0284] For formula (5a)

[0285] R is C 1 -C 20 -alkoxy, C 2 -C 20 -Alkenyloxy, phenoxy or C 1 -C 20 -carboxyalkyl, wherein the phenoxy group may be further substituted with at least one C 1 -C 15 - alkyl substitution;

[0286] For formula (5b)

[0287] R is a straight chain C 5 -C 20 -alkylene, which may be further substituted with at least one C 1 -C 5 -alkyl or C 1 -C 4 -alkylene substituted, the C 1 -C 5 -alkyl or C 1 -C 4 -Alkylene is further substituted with at least one C 1 -C 10 - alkyl and / or at least one phenyl substitution;

[0288] For formula (5c)

[0289] R is C 1 -C 5 - alkylene; and

[0290] For formula (5d)

[0291] R n Having formula (6a), (6b) or (6c)

[0292] (-CH 2 CH 2 O-) n (6a),

[0293] Where n is 3 to 20,

[0294] (-CH 2 CH(CH 3 )O-) n (6b),

[0295] where n is 3 to 18, or

[0296] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0297] Wherein n is 3 to 18.

[0298] In a preferred embodiment of the present invention, monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols have the structures of Formula 5(a), 5(b), 5(c) and 5(d):

[0299] in

[0300] For equation 5(a)

[0301] R is C 4 -C 16 -alkoxy, preferably 2-ethylhexanol, n-butanol, tert-butanol, C 12 -C 15 - an alkoxy group, a nonylphenol group, an allyl alcohol group or a neodecanoic acid carboxylic acid group,

[0302] For formula (5b)

[0303] R is a straight chain C 5 -C 15 -alkylene, which may be further substituted with at least one C 1 -C 4 -alkyl or C 1 -C 3 -alkylene substituted, which is further substituted with at least one C 1 -C 5 -alkyl and / or at least one phenyl group, preferably (-C6 H 12 -)、(-CH 2 C(CH 3 ) 2 CH 2 -) and (-CH 2 C(CH 3 )(C 6 H 6 )CH 2 -);

[0304] For formula (5c)

[0305] R is C 3 -alkyl, preferably (-C 3 H 6 -);and

[0306] For formula (5d)

[0307] R n Having formula (6a), (6b) or (6c)

[0308] (-CH 2 CH 2 O-) n (6a),

[0309] Where n is 3 to 20,

[0310] (-CH 2 CH(CH 3 )O-) n (6b),

[0311] Where n is 3 to 15, or

[0312] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0313] wherein n is 3 to 15.

[0314] In another preferred embodiment of the present invention, the monoglycidyl ether, diglycidyl ether and triglycidyl ether, diglycidyl ether of polymeric alcohol has the structure of Formula 5(b), 5(c) and 5(d).

[0315] in

[0316] For formula (5b)

[0317] R is (-C 6 H 12 -)、(-CH 2 C(CH3 ) 2 CH 2 -) and (-CH 2 C(CH 3 )(C 6 H 6 )CH 2 -);

[0318] For formula (5c)

[0319] R is (-C 3 H 6 -);and

[0320] For formula (5d)

[0321] Rn has the formula (6a), (6b) or (6c)

[0322] (-CH 2 CH 2 O-) n (6a),

[0323] Where n is 3 to 20,

[0324] (-CH 2 CH(CH 3 )O-) n (6b),

[0325] Where n is 3 to 15, or

[0326] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0327] wherein n is 3 to 15.

[0328] In a preferred embodiment of the present invention, the glycidyl ether has a structure of formula 5(d), wherein R is a compound of formula (6a), (6b) or (6c)

[0329] (-CH 2 CH 2 O-) n (6a),

[0330] Where n is 3 to 20,

[0331] (-CH 2 CH(CH 3 )O-) n (6b),

[0332] Where n is 3 to 15, or

[0333] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0334] wherein n is 3 to 15.

[0335] In a particular embodiment of the present invention, the glycidyl ether has the structure of Formula 5(d), wherein

[0336] R is the formula (6b) or (6c)

[0337] (-CH 2 CH(CH 3 )O-) n (6b),

[0338] Where n is 3 to 15, or

[0339] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0340] wherein n is 3 to 15.

[0341] Most preferably, the glycidyl ether has the structure of formula (5d), wherein R is of formula (6b)

[0342] (-CH 2 CH(CH 3 )O-) n (6b),

[0343] Where n is 3 to 12.

[0344] Suitable examples of asphaltene reactivators are bis(glycidyl) ethers such as polyethylene glycol bis(glycidyl) ether and polypropylene glycol bis(glycidyl) ether, 2-ethylhexyl glycidyl ether, 2-methyl-2phenyl-1,3-propanediol bisglycidyl ether (MPPD-DGE), neopentyl glycol diglycidyl ether (also known as neopentyl glycol bisglycidyl ether), and mixtures of these compounds with catalysts such as N,N-dimethylbenzylamine.

[0345] In one embodiment of the present invention, the asphaltene reactivating agent is selected from polyethylene glycol bis(glycidyl) ether, polypropylene glycol bis(glycidyl) ether, neopentyl glycol bisglycidyl ether, 2-methyl-2-phenyl-1,3-propanediol bisglycidyl ether, 2-ethylhexyl glycidyl ether, and a mixture of these compounds and a catalyst, preferably wherein the asphaltene reactivating agent is polypropylene glycol bis(glycidyl) ether.

[0346] The soft asphalt reactivator of the present invention is a chemical substance or a composition comprising the chemical substance, which can not only replenish the soft asphalt phase but also (re)build the colloidal stability in the binder through a combination of π-π interactions, polar interactions and van der Waals interactions. According to the present invention, the soft asphalt reactivator is a plasticizer. Preferred soft asphalt reactivators have no toxicological identification. Examples of suitable soft asphalt reactivators are DINP or DINCH.

[0347] In one embodiment of the present invention, the plasticizer is of formula (7a), (7b), (7c), (7d), or (7e)

[0348]

[0349] in

[0350] For formula (7a)

[0351] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0352] For formula (7b)

[0353] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0354] For formula (7c)

[0355] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0356] For formula (7d)

[0357] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0358] For formula (7e)

[0359] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl, and

[0360] n is 4 to 10, wherein at least two adjacent "CH 2 The two carbon atoms in the " portion can form a double bond.

[0361] In a preferred embodiment of the present invention, the plasticizer is of formula (7a), (7c) or (d), wherein

[0362] For formula (7a)

[0363] R is C 8 -C 12 -alkyl or C 7 -C 12 -alkenyl, preferably C 8 -C 11 -alkyl;

[0364] For formula (7c)

[0365] R is C 8 -C 12 -alkyl or C 7 -C 12 -alkenyl, preferably C 8 -C 11 -alkyl;

[0366] For formula (7d)

[0367] R is C 8 -C 12 -alkyl or C 7 -C 12 -alkenyl, preferably C 8 -C 11 -alkyl, and

[0368] n is 4 to 8, wherein at least two adjacent "CH 2 The two carbon atoms in the " portion can form a double bond.

[0369] In a more preferred embodiment of the present invention, the plasticizer is of formula (7a), (7c) or (d), wherein

[0370] For formula (7a)

[0371] R is C 9 -C 10 -alkyl, preferably 2-propylheptyl or isononyl;

[0372] For formula (7c)

[0373] R is C 9 -C 10 -alkyl, preferably 2-propylheptyl or isononyl;

[0374] For formula (7d)

[0375] R is C 9 -C 10 -alkyl, preferably 2-propylheptyl or isononyl, and

[0376] n is 4 to 6, preferably 4.

[0377] In a particular embodiment of the present invention, the plasticizer is of formula (7c), wherein

[0378] For formula (7c)

[0379] R is C 9 -C 10 -alkyl, preferably 2-propylheptyl or isononyl, more preferably isononyl.

[0380] According to the present invention, the preferred soft asphalt reactivating agent is selected from diisononyl phthalate or diisononyl cyclohexane-1,2-dicarboxylate, more preferably diisononyl cyclohexane-1,2-dicarboxylate.

[0381] In one embodiment of the present invention, the adhesive composition comprises

[0382] An asphaltene dispersant selected from alkoxylates, N,N-dialkylamides of aliphatic carboxylic acids, N-alkyllactams and poly(alkylamines), preferably, wherein the asphaltene dispersant is selected from alkoxylates having a structure of formula (1)

[0383]

[0384] in

[0385] R is H, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, phenyl or alkylphenyl,

[0386] n is 0 to 20,

[0387] m is 0 to 20, and wherein

[0388] n+m≥1;

[0389] N,N-dialkylamide of aliphatic carboxylic acid having the structure of formula (2)

[0390]

[0391] in

[0392] n is 3 to 16, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 5 -alkyl, and at least two adjacent "CH 2 The two carbon atoms in the "part can form a double bond,

[0393] R 1 C 1 -C 4 -alkyl, and

[0394] R 2 C 1 -C 4 -alkyl;

[0395] N-alkyl lactam having the structure of formula (3)

[0396]

[0397] in

[0398] n is 3 to 11, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 3 -alkyl substituted, and

[0399] R is C 1 -C 22 -alkyl or C 2 -C 22 -alkenyl; or

[0400] Poly(alkylamine) having the structure of formula (4)

[0401]

[0402] in

[0403] n is 1 to 6, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0404] m is 1 to 6, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0405] x is 4 to 50, and

[0406] R 1 C 1 -C4 -alkyl,

[0407] These poly(alkylamines) may be further derivatized with C 1 -C 4 - alkyl, fatty acid or alkoxylated;

[0408] and / or an asphaltene reactivator selected from monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols, and mixtures thereof with catalysts such as N,N-dimethylbenzylamine, preferably wherein the monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols have the structures of formula (5a), (5b), (5c) and (5d)

[0409]

[0410] in

[0411] For formula (5a)

[0412] R is C 1 -C 20 -alkoxy, C 2 -C 20 -Alkenyloxy, phenoxy or C 1 -C 20 -carboxyalkyl, wherein the phenoxy group may be further substituted with at least one C 1 -C 15 - alkyl substitution;

[0413] For formula (5b)

[0414] R is a straight chain C 5 -C 20 -alkylene, which may be further substituted with at least one C 1 -C 5 -alkyl or C 1 -C 4 -alkylene substituted, the C 1 -C 5 -alkyl or C 1 -C 4 -Alkylene is further substituted with at least one C 1 -C 10 - alkyl and / or at least one phenyl substitution;

[0415] For formula (5c)

[0416] R is C 1 -C 5 - alkylene; and

[0417] For formula (5d)

[0418] R n Having formula (6a), (6b) or (6c)

[0419] (-CH 2 CH 2 O-) n (6a),

[0420] Where n is 3 to 20,

[0421] (-CH 2 CH(CH 3 )O-) n (6b),

[0422] where n is 3 to 18, or

[0423] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0424] Where n is 3 to 18;

[0425] and / or a soft asphalt reactivator, which is a plasticizer, preferably having formula (7a), (7b), (7c), (7d) or (7e)

[0426]

[0427]

[0428] in

[0429] For formula (7a)

[0430] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0431] For formula (7b)

[0432] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0433] For formula (7c)

[0434] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0435] For formula (7d)

[0436] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0437] For formula (7e)

[0438] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl, and

[0439] n is 4 to 10, wherein at least two adjacent "CH 2 The two carbon atoms in the " portion can form a double bond.

[0440] In a particular embodiment of the present invention, the regeneration agent is selected from alkoxylates having the structure of formula (1):

[0441]

[0442] in

[0443] R is C 10 -alkyl or C 13 -alkyl, preferably 2-propylheptyl or isotridecyl,

[0444] n is 0 to 6,

[0445] m is 0 to 8, and wherein

[0446] n+m≥5, poly(bisaminopropylamine), N-dialkylpyrrolidone, polypropylene glycol bis(glycidyl) ether and cyclohexane-1,2-dimethyldicarboxylic acid diisononyl ester.

[0447] The rejuvenating agent of the invention is active at the microstructural level of the soil asphalt binder compared to the predominantly known benchmarks for diluting soil asphalt binders. In a preferred embodiment of the invention, the rejuvenating agent improves the properties of the soil asphalt binder in all temperature ranges and / or has no negative effect or even a positive effect on the aging of the recycled soil asphalt binder. In a particularly preferred embodiment of the invention, the rejuvenating agent is toxicologically safe.

[0448] In a preferred embodiment of the present invention, the rejuvenating agent causes microstructural changes in the micellar structure of the soil asphalt. It should be understood that the microstructural changes are accompanied by improvements in the processability (especially viscosity) of the soil asphalt binder after adding the rejuvenating agent.

[0449] In one embodiment of the invention, the microstructural changes in the earth asphalt micellar structure are detected by loss tangent. Therefore, in a preferred embodiment of the invention, the loss tangent of the adhesive composition is increased compared to the loss tangent of the earth asphalt binder. In this regard, it is understood that the adhesive composition of the present invention is a regenerated adhesive composition (because it contains the regeneration agent of the present invention), and the earth asphalt binder is not a regenerated earth asphalt binder. It is understood that the loss tangent is determined according to the present invention.

[0450] In a preferred embodiment of the present invention, the microstructural changes of the asphalt micelle structure can be expressed by satisfying inequality (a)

[0451] Loss tangent [bc]>1.3×loss tangent [bb] (a),

[0452] More preferably, by satisfying inequality (b)

[0453] Loss tangent [bc]>1.5×loss tangent [bb], (b),

[0454] In particular, by satisfying inequality (c)

[0455] Loss tangent [bc]>2×loss tangent [bb], (c)

[0456] wherein loss tangent [bc] represents the loss tangent of the adhesive composition and loss tangent [bb] represents the asphalt adhesive, and wherein loss tangent [bc] and loss tangent [bb] are evaluated at a frequency of 0.01 to 10 rad / s, preferably at a frequency of 0.01 to 1 rad / s.

[0457] In one embodiment of the present invention, the microstructural changes in the micellar structure of the asphalt are alternatively or additionally detected by TD NMR. The microstructural changes in the micellar structure of the asphalt increase the amount of mobile components and / or its / their fluidity. Therefore, in a preferred embodiment of the present invention, the amount of mobile components and / or their respective fluidity of the adhesive composition according to TD NMR is increased compared to the amount of mobile components and / or their respective fluidity of the asphalt binder. In another preferred embodiment of the present invention, the amount of solid components of the adhesive composition according to TD NMR is reduced compared to the amount of solid components of the asphalt binder. In a further preferred embodiment of the present invention, the amount of mobile components and / or their respective fluidity of the adhesive composition according to TDNMR is increased compared to the amount of mobile components and / or their respective fluidity of the asphalt binder, and the amount of solid components of the adhesive composition according to TDNMR is reduced compared to the amount of solid components of the asphalt binder.

[0458] In a preferred embodiment of the present invention, the microstructural change of the asphalt micelle structure can be expressed by satisfying the inequality (aa1):

[0459] T2e1[bc]>1.3×T2e1[bb] (aa1),

[0460] More preferably, by satisfying inequality (bb1)

[0461] T2e1[bc]>1.5×T2e1[bb] (bb1)

[0462] wherein T2e1[bc] represents the relaxation time corresponding to the individual components of the binder composition and T2e1[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 30°C.

[0463] In a preferred embodiment of the present invention, the microstructural change of the asphalt micelle structure can be expressed by satisfying the inequality (aa2):

[0464] pe1[bc]>1.05×pe1[bb] (aa2),

[0465] More preferably, by satisfying inequality (bb2)

[0466] pe1[bc]>1.1×pe1[bb] (bb2),

[0467] wherein pe1[bc] represents the signal fraction of the individual components of the binder composition graded in the range 0 to 1, and pe1[bb] represents the signal fraction of the individual components of the asphalt binder graded in the range 0 to 1, each measured at 30°C.

[0468] In a preferred embodiment of the present invention, the microstructural change of the asphalt micelle structure can be expressed by satisfying inequality (aa3):

[0469] T2g2[bc]>1.05×T2g2[bb] (aa3),

[0470] More preferably, by satisfying inequality (bb3)

[0471] T2g2[bc]>1.1×T2g2[bb] (bb3),

[0472] wherein T2g2[bc] represents the relaxation time corresponding to the individual components of the binder composition and T2g2[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 30°C.

[0473] In a preferred embodiment of the present invention, the microstructural change of the asphalt micelle structure can be expressed by satisfying inequality (aa4):

[0474] pe1[bc]>1.05×pe1[bb] (aa4),

[0475] More preferably, by satisfying inequality (bb4)

[0476] pe1[bc]>1.1×pe1[bb](bb4),

[0477] Wherein pe1[bc] represents the signal fraction of the individual components of the adhesive composition graded in the range 0 to 1, and pe1[bb] represents the signal fraction of the individual components of the asphalt adhesive graded in the range 0 to 1, each measured at 80°C.

[0478] In a preferred embodiment of the present invention, the microstructural change of the asphalt micelle structure can be expressed by satisfying inequality (aa5):

[0479] T2e2[bc]>1.2×T2e2[bb] (aa5),

[0480] More preferably, by satisfying inequality (bb5)

[0481] T2e2[bc]>1.3×T2e2[bb] (bb5),,

[0482] wherein T2e2[bc] represents the relaxation time corresponding to the individual components of the binder composition and T2e2[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 80°C.

[0483] In a preferred embodiment of the present invention, the microstructural change of the asphalt micelle structure can be expressed by satisfying inequality (aa6):

[0484] T2e2[bc]>1.2×T2e2[bb] (aa6),

[0485] More preferably, by satisfying inequality (bb6)

[0486] T2e2[bc]>1.3×T2e2[bb] (bb6),,

[0487] wherein T2e2[bc] represents the relaxation time corresponding to the individual components of the binder composition and T2e2[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 140°C.

[0488] In a preferred embodiment of the present invention, the microstructural change of the asphalt micelle structure can be expressed by satisfying inequality (aa7):

[0489] T2e3[bc]>1.15×T2e3[bb] (aa7),

[0490] More preferably, by satisfying inequality (bb7)

[0491] T2e3[bc]>1.25×T2e3[bb] (bb7),

[0492] wherein T2e7[bc] represents the relaxation time corresponding to the individual components of the binder composition and T2e3[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 140°C.

[0493] In one embodiment, the adhesive composition comprises 0.05 to 20 wt % of the rejuvenating agent, preferably 0.1 to 18 wt %, more preferably 0.5 to 15 wt %, even more preferably 1 to 13 wt %, still more preferably 2 to 10 wt %, and in particular 3 to 7 wt %, based on the total amount of the adhesive composition.

[0494] In one embodiment, the binder composition comprises 80 to 99.95 wt % of asphalt binder, preferably 82 to 99.9 wt %, more preferably 85 to 99.5 wt %, even more preferably 87 to 99 wt %, still more preferably 90 to 98 wt %, and in particular 93 to 97 wt %, based on the total amount of the binder composition.

[0495] In one embodiment of the present invention, the regeneration agent comprises

[0496] (i) 1 to 100 wt % of an asphaltene dispersant, preferably 20 to 100 wt %, more preferably 40 to 100 wt %, still more preferably 60 to 100 wt %, and in particular 80 to 100 wt %, based on the total amount of the regeneration agent;

[0497] (ii) 1 to 100 wt % of an asphaltene reactivating agent, preferably 20 to 100 wt %, more preferably 40 to 100 wt %, still more preferably 60 to 100 wt %, and in particular 80 to 100 wt %, based on the total amount of the reactivating agent;

[0498] (iii) 1 to 100% by weight of a soft bitumen reactivating agent, preferably 20 to 100% by weight, more preferably 40 to 100% by weight, still more preferably 60 to 100% by weight, and in particular 80 to 100% by weight, based on the total amount of the reactivating agent; or

[0499] (iv) 1 to 100 weight %, based on the total amount of the regeneration agent, of a mixture consisting of at least two components selected from components (i) to (iii), preferably 20 to 100 weight %, more preferably 40 to 100 weight %, still more preferably 60 to 100 weight %, and in particular 80 to 100 weight %, based on the total amount of the regeneration agent.

[0500] The rejuvenating agent may also include at least two different asphaltene dispersants.

[0501] The rejuvenating agent may also comprise at least two different asphaltene reactivating agents.

[0502] The rejuvenating agent may also comprise at least two different soft asphalt reactivating agents.

[0503] The rejuvenating agent may comprise a mixture of an asphaltene dispersant and an asphaltene reactivating agent.

[0504] The rejuvenating agent may comprise a mixture of an asphaltene dispersant and a soft asphalt reactivating agent.

[0505] The rejuvenating agent may comprise a mixture of an asphaltene reactivating agent and a soft bitumen reactivating agent.

[0506] The rejuvenating agent may include a mixture of an asphaltene dispersant, an asphaltene reactivator, and a soft asphalt reactivator.

[0507] By adding the above-mentioned amount of rejuvenating agent, the rejuvenated asphalt composition (i.e., the binder composition of the present invention) has improved performance in one or more parameters selected from the following: softening, viscosity, MSCR, loss tangent, elasticity, low temperature behavior and aging behavior compared to the untreated (i.e., non-rejuvenated) asphalt composition and / or the asphalt composition rejuvenated using the benchmark commonly used in the industry.

[0508] In a preferred embodiment of the present invention, the rejuvenating agent is non-toxic. In another preferred embodiment of the present invention, the rejuvenating agent is durable, meaning that it is not lost during the asphalt manufacturing process as is possible with conventional aromatic based rejuvenating agents.

[0509] In a particular embodiment of the present invention, the rejuvenating agent is non-toxic and durable, meaning that it is not lost during the asphalt manufacturing process as is possible with conventional aromatic based rejuvenating agents.

[0510] According to the invention, the earth asphalt binder may include recycled asphalt containing an aged binder containing modifiers such as polymers. In these cases, the chemical balance (between "saturates", "aromatics", "resins" and "asphaltenes") is already challenged in the original earth asphalt and becomes even more challenging after aging. However, this becomes increasingly important, especially since most recycled asphalt will be obtained from surface processes that preferably contain these modifiers.

[0511] The asphalt binder to be regenerated in the present invention may be an asphalt binder derived from various sources, such as original asphalt, natural asphalt, and different types of aged asphalt binders that need to be regenerated. For example, the asphalt binder to be regenerated is selected from original asphalt, natural asphalt, expanded asphalt composition, polymer-containing asphalt composition, metallocene-containing asphalt composition, and synthetic wax-containing asphalt composition. The polymer-containing asphalt composition may be an asphalt binder that has been modified with a polymer, such as styrene-butadiene-styrene (SBS) or ethylene vinyl acetate (EVA).

[0512] In one embodiment of the present invention, the asphalt binder comprises recycled asphalt.

[0513] The soil asphalt binder to be reclaimed according to the present invention suitably comprises asphaltenes in an amount ranging from 1 to 40% by weight.

[0514] In a preferred embodiment of the present invention, the soil asphalt binder comprises a recycled asphalt pavement binder, a recycled asphalt shingle binder, virgin soil asphalt having a hardness of at least 50 / 70, or a mixture thereof. Optionally, the soil asphalt binder of the present invention may comprise a recycled asphalt pavement binder, a recycled asphalt shingle binder, virgin soil asphalt having a hardness of at least 50 / 70, or a mixture thereof in combination with a virgin binder. In this regard, it should be understood that the softening degree of the soil asphalt binder comprising virgin soil asphalt having a hardness of at least 50 / 70 can be fully adjusted using the rejuvenating agents outlined in the present invention, if desired. In a particularly preferred embodiment of the present invention, the soil asphalt binder comprises a recycled asphalt pavement binder, a recycled asphalt shingle binder, or a mixture thereof, optionally in combination with a virgin binder.

[0515] In another embodiment of the present invention, the soil asphalt binder includes 10 to 100 wt % of recycled asphalt pavement binder, based on the total amount of the soil asphalt binder.

[0516] In one embodiment of the present invention, the earth asphalt binder includes 10 to 100 weight percent of recycled asphalt shingle binder, based on the total amount of earth asphalt binder.

[0517] In another embodiment of the present invention, the soil asphalt binder includes a mixture of 10 to 100 weight percent of recycled asphalt pavement binder and recycled asphalt shingle binder, based on the total amount of soil asphalt binder.

[0518] In one embodiment of the invention, the asphalt binder comprises further additives, preferably wherein the additives are selected from polymers, waxes, fibers or mixtures thereof.

[0519] In this regard, mention may be made of suitable polymers such as styrene-butadiene-styrene (SBS), styrene-butadiene rubber, ethylene vinyl acetate (EVA) and rubber.

[0520] Suitable waxes may be mentioned, for example, polyethylene waxes.

[0521] Suitable fibers may be mentioned, for example, cellulose.

[0522] If the addition of the rejuvenating agent of the present invention brings the measured value of the relevant property close to the ideal value or range of ideal values ​​of the property, or brings the measured value within the ideal range of the property, then the adhesive composition of the present invention has improved at least one property compared to the corresponding adhesive composition to which no rejuvenating agent is added or to which a baseline rejuvenating agent is added. The ideal values ​​are as follows:

[0523] Softness, viscosity, MSCR, elasticity, low temperature behavior, BBR S value and aging behavior

[0524] (AI): As low as possible;

[0525] Loss tangent, low temperature behavior BBR m value: as high as possible.

[0526] The rejuvenators of the present invention generally can reduce at least one property selected from the group consisting of softening, viscosity, MSCR elastic recovery, aging index and BBR S value compared to conventional benchmark rejuvenators. This is true not only in systems representing aged earth asphalt (e.g., Earth Asphalt 20 / 30), but also in actual laboratory aged earth asphalt samples and in earth asphalt extracted from, for example, RAP or RAS.

[0527] In the following, other aspects of the present invention will be summarized. It should be understood that all the above embodiments, especially with respect to the binder composition, the asphalt binder and the rejuvenating agent, should also apply to the following aspects unless otherwise stated.

[0528] As mentioned above, the present invention also relates in one embodiment to an asphalt composition comprising aggregate and a binder composition as defined above. In one embodiment, the asphalt composition is an emulsion.

[0529] The bituminous composition of the present invention may comprise 2 to 15 wt. % of the binder composition as defined above, preferably 3 to 10 wt. %, more preferably 4 to 7.5 wt. %, based on the total weight of the bituminous composition.

[0530] The bituminous composition of the present invention may comprise 85 to 98 wt. % of aggregate, preferably 90 to 97 wt. %, more preferably 92.5 to 96 wt. %, based on the total weight of the bituminous composition.

[0531] In a preferred embodiment of the present invention, the asphalt composition comprises at least one rejuvenating agent selected from alkoxylates; N,N-dialkyllactams of aliphatic carboxylic acids; N-alkyllactams; poly(alkylamines); monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols, and mixtures thereof with catalysts; and plasticizers.

[0532] As stated above, the present invention also relates in one embodiment to a paved road surface, road subsurface, runway, driveway, parking lot, shoulder, bridge, abutment, roof, revetment or unpaved road comprising the bituminous composition defined above.

[0533] In one embodiment, the present invention relates to a paved road surface, road subsurface, runway, driveway, parking lot, shoulder, bridge, abutment, roof, revetment or unpaved road comprising the asphalt composition defined above, wherein the earth asphalt binder comprises recycled asphalt pavement (RAP) and / or asphalt shingles from roofs (RAS).

[0534] As mentioned above, the present invention also describes two novel analytical methods for analyzing the microstructure of soil asphalt, through which the advantages of the regeneration agent to be protected herein relative to the prior art in the field are clearly distinguished. In addition, these two new analytical methods are easy to implement.

[0535] Thus, one embodiment of the present invention is directed to a method of evaluating the efficacy of a rejuvenating agent in an adhesive composition, wherein the efficacy of the rejuvenating agent is demonstrated by:

[0536] (i) the loss tangent before or after aging, obtained from a dynamic shear rheometer (DSR) frequency sweep at a given temperature, wherein the frequency sweep is measured from 0 to 90°C, and wherein the effective regenerant satisfies inequality (a)

[0537] Loss tangent [bc]>1.3×loss tangent [bb], (a)

[0538] wherein the loss tangent [bc] represents the loss tangent of the adhesive composition and the loss tangent [bb] represents the asphalt adhesive, and wherein the loss tangent [bc] and the loss tangent [bb] are evaluated at a frequency of 0.01 to 10 rad / s, preferably at a frequency of 0.01 to 1 rad / s, or

[0539] (ii) TDNMR relaxation experiments on asphalt samples at temperatures between -50 and 200 °C, where the effective regenerant satisfies inequality (aa1)

[0540] T2e1[bc]>1.3×T2e1[bb] (aa1)

[0541] wherein T2e1[bc] represents the relaxation time corresponding to the individual components of the binder composition, and T2e1[bb] represents the relaxation time corresponding to the individual components of the asphalt binder.

[0542] It is understood that an effective rejuvenating agent improves the processability (especially viscosity) of the asphalt binder after addition of the rejuvenating agent. The rejuvenating agent is particularly considered effective when the loss tangent and / or the flow component determined by TDNMR increase after addition of the rejuvenating agent compared to the corresponding values ​​of the untreated asphalt binder (especially aged asphalt binder). It is further preferred that the negative impact of the rejuvenating agent on the rejuvenated asphalt binder is as small as possible.

[0543] Using the loss tangent, it can be demonstrated that the regenerants of the present invention have a different mode of action than conventional benchmark regenerants. The effect of the regenerants of the present invention on the loss tangent is completely different. Here, a much stronger increase in the loss tangent after regeneration using the regenerants of the present invention can be seen compared to the conventional benchmark. This means that the regenerants of the present invention have an effect on the microstructure of the asphalt, for example by dissolving the asphaltene aggregates or reorganizing the micelles, rather than simply diluting the binder phase as most benchmarks do.

[0544] The assessment methods of the invention provide an indication of mechanism of action.

[0545] When using the loss tangent (tan δ) analysis, the frequency sweep is monitored. The loss tangent is the ratio between G" (viscous contribution) and G' (elastic contribution). The higher the ratio, the greater the viscous contribution to the rheological properties and thus the higher the mobility of the molecules in the asphalt phase. Especially at low frequencies, when the measurement itself has little influence on the system, information about the mobility of the asphalt components can be extracted.

[0546] Typically, the frequency sweep can be measured at a temperature of 0 to 200° C., preferably at 20 to 100° C. According to the present invention, the frequency sweep is measured at a temperature of 0 to 90° C., preferably at 20 to 90° C., more preferably at 30 to 90° C., even more preferably at 40 to 80° C., still more preferably at 50 to 70° C., and in particular at 55 to 65° C.

[0547] Preferably, the frequency sweep is measured at 0.5% shear strain γ from 0.01 to 100 rad / s at 60° C. Tan δ is preferably evaluated at frequencies of 0.01 to 10 rad / s, more preferably 0.01 to 1 rad / s, especially at the lowest frequencies.

[0548] In a preferred embodiment, inequality (b) is satisfied

[0549] Loss tangent [bc]>1.5×loss tangent [bb], (b)

[0550] wherein loss tangent [bc] represents the loss tangent of the adhesive composition and loss tangent [bb] represents the earth asphalt adhesive, and wherein loss tangent [bc] and loss tangent [bb] are evaluated at a frequency of 0.01 to 10 rad / s.

[0551] In a more preferred embodiment, inequality (c) is satisfied

[0552] Loss tangent [bc]>2×loss tangent [bb], (c)

[0553] wherein loss tangent [bc] represents the loss tangent of the adhesive composition and loss tangent [bb] represents the earth asphalt adhesive, and wherein loss tangent [bc] and loss tangent [bb] are evaluated at a frequency of 0.01 to 10 rad / s.

[0554] Using TDNMR analysis, it can be demonstrated that the regenerant of the present invention has an increased effect on the fluidity of the binder compared to the conventional benchmark regenerant. The effect of the regenerant of the present invention on the number and type of mobile components is different. The binder that has been regenerated by the regenerant of the present invention has more mobile components and components with higher fluidity compared to the conventional benchmark. This means that the regenerant of the present invention has a different effect on the microstructure of the soil asphalt.

[0555] When using TDNMR analysis, signal fractions of individual components with different mobility and their relaxation times are detected. The higher the amount of mobile or partially mobile components, the higher their mobility (which means the corresponding relaxation time of the individual mobile components is longer), the greater the contribution of viscosity to the rheological properties and therefore the higher the mobility of the molecules in the asphalt phase.

[0556] Typically, TDNMR can be measured at a temperature of -100 to 200° C. According to the present invention, TDNMR is measured at a temperature of -50 to 200° C., preferably 0 to 180° C., more preferably 20 to 150° C.

[0557] In a preferred embodiment, the effective regenerant satisfies inequality (bb1)

[0558] T2e1[bc]>1.5×T2e1[bb] (bb1)

[0559] wherein T2e1[bc] represents the relaxation time corresponding to the individual components of the binder composition and t2e1[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 30°C.

[0560] In a preferred embodiment, the effective regenerant satisfies inequality (aa2)

[0561] pe1[bc]>1.05×pe1[bb] (aa2),

[0562] More preferably, the inequality (bb2) is satisfied

[0563] pe1[bc]>1.1×pe1[bb] (bb2),

[0564] wherein pe1[bc] represents the signal fraction of the individual components of the binder composition graded in the range 0 to 1, and pe1[bb] represents the signal fraction of the individual components of the asphalt binder graded in the range 0 to 1, each measured at 30°C.

[0565] In a preferred embodiment, the effective regenerant satisfies inequality (aa3)

[0566] T2g2[bc]>1.05×T2g2[bb] (aa3),

[0567] Preferably satisfying inequality (bb3)

[0568] T2g2[bc]>1.1×T2g2t2g2[bb](bb3),

[0569] wherein T2g2[bc] represents the relaxation time corresponding to the individual components of the binder composition, and T2g2[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 30°C.

[0570] In a preferred embodiment, the effective regenerant satisfies inequality (aa4)

[0571] pe1[bc]>1.05×pe1[bb] (aa4),

[0572] Preferably satisfying inequality (bb4)

[0573] pe1[bc]>1.1×pe1[bb] (bb4),

[0574] Wherein pe1[bc] represents the signal fraction of the individual components of the adhesive composition graded in the range 0 to 1, and pe1[bb] represents the signal fraction of the individual components of the asphalt adhesive graded in the range 0 to 1, each measured at 80°C.

[0575] In a preferred embodiment, the effective regenerant satisfies inequality (aa5)

[0576] T2e2[bc]>1.2×T2e2[bb] (aa5),

[0577] Preferably satisfying inequality (bb5)

[0578] T2e2[bc]>1.3×T2e2[bb] (bb5),

[0579] wherein T2e2[bc] represents the relaxation time corresponding to the individual components of the binder composition, and T2e2[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 80°C.

[0580] In a preferred embodiment, the effective regenerant satisfies inequality (aa6)

[0581] T2e2[bc]>1.2×T2e2[bb] (aa6),

[0582] Preferably satisfying inequality (bb6)

[0583] T2e2[bc]>1.3×T2e2[bb] (bb6),,

[0584] wherein T2e2[bc] represents the relaxation time corresponding to the individual components of the binder composition, and T2e2[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 140°C.

[0585] In a preferred embodiment, the effective regenerant satisfies inequality (aa7)

[0586] T2e3[bc]>1.15×T2e3[bb] (aa7),

[0587] Preferably satisfying inequality (bb7)

[0588] T2e3[bc]>1.25×T2e3[bb] (bb7),,

[0589] wherein T2e7[bc] represents the relaxation time corresponding to the individual components of the binder composition, and T2e3[bb] represents the relaxation time corresponding to the individual components of the asphalt binder, each measured at 140°C.

[0590] Preferably, the effective regeneration agent satisfies at least two, more preferably at least three, still more preferably at least four, and in particular at least five inequalities selected from (aa1), (aa2), (aa3), (aa3), (aa4), (aa4), (aa5), (aa6) and (aa7).

[0591] Preferably, the effective regeneration agent satisfies at least two, more preferably at least three, still more preferably at least four, and in particular at least five inequalities selected from (bb1), (bb2), (bb3), (bb4), (bb5), (bb6) and (bb7).

[0592] For more details on the TDNMR technique, please refer to the Experimental section below.

[0593] As mentioned above, the present invention, in one embodiment, also relates to the use of a rejuvenating agent for recycling recovered asphalt pavement (RAP) and / or asphalt shingles from roofs (RAS), wherein the rejuvenating agent includes at least one asphaltene dispersant, asphaltene reactivator, soft asphalt reactivator or a mixture thereof.

[0594] In a preferred embodiment of the present invention, the regenerating agent is selected from alkoxylates; N,N-dimethylamides of aliphatic carboxylic acids; N-alkyllactams; poly(alkylamines); monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols and mixtures thereof with catalysts; and plasticizers.

[0595] In a preferred embodiment of the present invention, the regeneration agent is selected from alkoxylates having the structure of formula (1):

[0596]

[0597] in

[0598] R is for C 10 -alkyl or C 13 -alkyl, preferably 2-propylheptyl or isotridecyl,

[0599] n is 0 to 6,

[0600] m is 0 to 8, where

[0601] n+m≥5, poly(bisaminopropylamine), N-dodecylpyrrolidone, polypropylene glycol bis(glycidyl) ether and cyclohexane-1,2-dimethyldicarboxylic acid diisononyl ester.

[0602] The present invention also relates to the following items:

[0603] 1. An adhesive composition comprising

[0604] (a) asphalt binder; and

[0605] (b) 0.05 to 20% by weight of a rejuvenating agent, based on the total amount of the adhesive composition,

[0606] Wherein, the regeneration agent comprises at least one asphaltene dispersant, asphaltene reactivator, soft asphalt reactivator or a mixture thereof.

[0607] 2. The adhesive composition according to item 1, wherein the rejuvenating agent causes microstructural changes in the earth bitumen micellar structure, preferably wherein the loss tangent of the adhesive composition is increased compared to the loss tangent of the earth bitumen adhesive, and / or

[0608] Therein, the amount of mobile components of the binder composition and / or their respective flowability is increased compared to the amount of mobile components of the asphalt binder and / or their respective flowability according to TDNMR.

[0609] 3. The adhesive composition according to item 1 or 2,

[0610] The regeneration agent comprises:

[0611] (i) 1 to 100 wt % of an asphaltene dispersant, based on the total amount of the rejuvenating agent;

[0612] (ii) 1 to 100 wt % of an asphaltene reactivating agent, based on the total amount of the reactivating agent;

[0613] (iii) 1 to 100 wt. % of a soft asphalt reactivator, based on the total amount of the reactivator; or

[0614] (iv) 1 to 100% by weight of a mixture consisting of at least two components selected from components (i) to (iii), based on the total amount of the regeneration agent.

[0615] 4. The adhesive composition according to any one of items 1 to 3, wherein the earth asphalt adhesive comprises recycled asphalt pavement adhesive, recycled asphalt shingle adhesive, or a mixture thereof, optionally in combination with a virgin adhesive.

[0616] 5. The adhesive composition according to any one of items 1 to 4, wherein the adhesive composition comprises:

[0617] An asphaltene dispersant selected from alkoxylates, N,N-dialkylamides of aliphatic carboxylic acids, N-alkyllactams and poly(alkylamines), preferably wherein the asphaltene dispersant is selected from alkoxylates having the structure of formula (1),

[0618]

[0619] in

[0620] R is H, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, phenyl or alkylphenyl,

[0621] n is 0 to 20,

[0622] m is 0 to 20, and wherein

[0623] n+m≥1;

[0624] N,N-dialkylamide of aliphatic carboxylic acid having the structure of formula (2)

[0625]

[0626] Where n is 3 to 16, and at least one of the "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 5 -alkyl, and at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0627] R 1 C 1 -C 4 -alkyl, and

[0628] R 2 C 1 -C 4 -alkyl;

[0629] N-alkyl lactam having the structure of formula (3)

[0630]

[0631] in

[0632] n is 3 to 11, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 3 -alkyl substituted, and

[0633] R is C 1-C 22 -alkyl or C 2 -C 22 -alkenyl; or

[0634] Poly(alkylamine) having the structure of formula (4)

[0635]

[0636] in

[0637] n is 1 to 6, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0638] m is 1 to 6, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0639] x is 4 to 50, and

[0640] R 1 C 1 -C 4 -alkyl,

[0641] These poly(alkylamines) may be further derivatized with C 1 -C 4 Alkyl, fatty acid or alkoxylated;

[0642] and / or an asphaltene reactivator selected from monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols and mixtures thereof with catalysts such as N,N-dimethylbenzylamine; preferably, monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols have the structures of formula (5a), (5b), (5c) and (5d):

[0643]

[0644] in

[0645] For formula (5a)

[0646] R is C 1 -C 20 -alkoxy, C 2 -C 20 -Alkenyloxy, phenoxy or C 1 -C 20 -carboxyalkyl, wherein the phenoxy group may be further substituted with at least one C 1 -C 15 - alkyl substitution;

[0647] For formula (5b)

[0648] R is a straight chain C 5 -C 20 -alkylene, which may be further substituted with at least one C 1 -C 5 -alkyl or C 1 -C 4 -alkylene substituted, the C 1 -C 5 -alkyl or C 1 -C 4 The -alkylene group may be further substituted with at least one C 1 -C 10 - alkyl and / or at least one phenyl substitution;

[0649] For formula (5c)

[0650] R is C 1 -C 5 - alkylene; and

[0651] For formula (5d)

[0652] R n Having formula (6a), (6b) or (6c)

[0653] (-CH 2 CH 2 O-) n (6a),

[0654] Where n is 3 to 20,

[0655] (-CH 2 CH(CH 3 )O-) n (6b),

[0656] where n is 3 to 18, or

[0657] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0658] Where n is 3 to 18;

[0659] and / or a soft asphalt reactivator, which is a plasticizer, preferably having formula (7a), (7b), (7c), (7d) or (7e)

[0660]

[0661]

[0662] in

[0663] For formula (7a)

[0664] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0665] For formula (7b)

[0666] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0667] For formula (7c)

[0668] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0669] For formula (7d)

[0670] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0671] For formula (7e)

[0672] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl, and

[0673] n is 4 to 10, wherein at least two adjacent "CH 2 The two carbon atoms in the " portion can form a double bond.

[0674] 6. The adhesive composition according to any one of items 1 to 5, wherein the asphaltene dispersant is selected from alkoxylates, N,N-dialkylamides of aliphatic carboxylic acids, N-alkyllactams and poly(alkylamines), preferably wherein the asphaltene dispersant is selected from alkoxylates having the structure of formula (1):

[0675]

[0676] in

[0677] R is H, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, phenyl or alkylphenyl,

[0678] n is 0 to 20,

[0679] m is 0 to 20, and wherein

[0680] n+m≥1;

[0681] N,N-dialkylamide of aliphatic carboxylic acid having the structure of formula (2)

[0682]

[0683] in

[0684] n is 3 to 16, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 5 -alkyl, and at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0685] R 1 C 1 -C 4 -alkyl, and

[0686] R 2 C 1 -C 4 -alkyl;

[0687] N-alkyl lactam having the structure of formula (3)

[0688]

[0689] in

[0690] n is 3 to 11, wherein at least one "CH 2 The carbon atoms in the " portion may be further replaced by at least one C 1 -C 3 -alkyl substituted, and

[0691] R is C 1 -C 22 -alkyl or C 2 -C 22 -alkenyl; or

[0692] Poly(alkylamine) having the structure of formula (4)

[0693]

[0694] in

[0695] n is 1 to 6, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0696] m is 1 to 6, wherein at least two adjacent "CH 2 The two carbon atoms in the " part can form a double bond,

[0697] x is 4 to 50, and

[0698] R 1 C 1 -C 4 -alkyl,

[0699] These poly(alkylamines) may be further derivatized with C 1 -C 4 - alkyl, fatty acid or alkoxylated.

[0700] 7. The adhesive composition according to any one of items 1 to 6, wherein the asphaltene reactivating agent is selected from monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols, and mixtures thereof with catalysts; preferably wherein the monoglycidyl ethers and monoglycidyl esters, diglycidyl ethers and triglycidyl ethers, diglycidyl ethers of polymeric alcohols have the structures of Formula 5(a), 5(b), 5(c) and 5(d)

[0701]

[0702] in

[0703] For equation 5(a)

[0704] R is C 1 -C 20 -alkoxy, C 2 -C 20 -Alkenyloxy, phenoxy or C 1 -C 20 -carboxyalkyl, wherein the phenoxy group may be further substituted by at least one C 1 -C 15 - alkyl substitution;

[0705] For formula (5b)

[0706] R is a straight chain C 5 -C 20 -alkylene, which may be further substituted with at least one C 1 -C 5 -alkyl or C 1 -C 4 -alkylene substituted, the C 1 -C 5 -alkyl or C 1 -C 4 -Alkylene is further substituted with at least one C 1 -C10 - alkyl and / or at least one phenyl substitution;

[0707] For formula (5c)

[0708] R is C 1 -C 5 - alkylene; and

[0709] For formula (5d)

[0710] R n Having formula (6a), (6b) or (6c)

[0711] (-CH 2 CH 2 O-) n (6a),

[0712] Where n is 3 to 20,

[0713] (-CH 2 CH(CH 3 )O-) n (6b),

[0714] where n is 3 to 18, or

[0715] (-CH 2 CH 2 CH 2 CH 2 O-) n (6c)

[0716] Where n is 3 to 18;

[0717] More preferably, the asphaltene reactivating agent is selected from polyethylene glycol bis(glycidyl) ether, polypropylene glycol bis(glycidyl) ether, neopentyl glycol bisglycidyl ether, 2-methyl-2phenyl-1,3-propanediol bisglycidyl ether, 2-ethylhexyl glycidyl ether, and a mixture of these compounds and a catalyst; even more preferably, the asphaltene reactivating agent is polypropylene glycol bis(glycidyl) ether.

[0718] 8. The adhesive composition according to any one of items 1 to 7, wherein the soft asphalt reactivating agent is a plasticizer, preferably wherein the plasticizer has formula (7a), (7b), (7c), (7d) or (7e),

[0719]

[0720] in

[0721] For formula (7a)

[0722] R is C 4 -C14 -alkyl or C 4 -C 14 -alkenyl;

[0723] For formula (7b)

[0724] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0725] For formula (7C)

[0726] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0727] For formula (7D)

[0728] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl;

[0729] For formula (7E)

[0730] R is C 4 -C 14 -alkyl or C 4 -C 14 -alkenyl, and

[0731] n is 4 to 10, wherein at least two adjacent "CH 2 The two carbon atoms of the " part can form a double bond, and more preferably the soft asphalt reactivator is selected from diisononyl phthalate or diisononyl cyclohexane-1,2-dicarboxylate, and more preferably the soft asphalt reactivator is diisononyl cyclohexane-1,2-dicarboxylate.

[0732] 9. The adhesive composition according to any one of items 1 to 8, wherein the soil asphalt adhesive comprises 10 to 100 weight percent of recycled asphalt pavement and / or recycled asphalt shingle adhesive, based on the total weight of the soil asphalt adhesive.

[0733] 10. The binder composition according to any one of items 1 to 9, wherein the asphalt binder comprises other additives, preferably wherein the other additives are selected from polymers, waxes, fibers or mixtures thereof.

[0734] 11. An asphalt composition comprising aggregate and the binder composition according to any one of items 1 to 10.

[0735] 12. A paved road surface, road subsurface, runway, driveway, parking lot, shoulder, bridge, abutment, roof, revetment or unpaved road comprising the bituminous composition according to item 11.

[0736] 13. A method for evaluating the efficacy of a rejuvenating agent in an adhesive composition, wherein the efficacy of the rejuvenating agent is demonstrated by:

[0737] (i) the loss tangent before or after aging, obtained from a dynamic shear rheometer (DSR) frequency sweep at a given temperature, or

[0738] (ii) TD NMR relaxation experiment on a soil asphalt sample at a defined temperature.

[0739] 14. Use of a rejuvenating agent for recycling recovered asphalt pavement (RAP) and / or asphalt shingles from roofs (RAS), the rejuvenating agent comprising at least one asphaltene dispersant, asphaltene reactivator, soft asphalt reactivator or mixtures thereof.

[0740] The present invention will now be further illustrated by the following examples, which are not intended to limit the present invention in any way.

[0741] Example

[0742] Example 1: Softness and viscoelasticity of recycled soil asphalt 20 / 30

[0743] The capabilities of various chemically different structures of regenerated earth asphalt 20 / 30, a type of earth asphalt known to be largely similar to aged earth asphalt (e.g. asphaltene content, rheological behavior), were evaluated. The selected test substances are listed in Table 1. In order to test the different substances, 100 g of earth asphalt 20 / 30 was regenerated at 180°C for 30 minutes with 5% of the corresponding compound under stirring. The softening point (SP), viscosity at 135°C and percentage of elastic recovery in the MSCR test of the regenerated earth asphalt (i.e., adhesive composition) samples were subsequently analyzed. All test samples were compared with pure 20 / 30 earth asphalt, which was stirred at 180°C for 30 minutes, but without any additives.

[0744] If the softening point, viscosity and elastic recovery increase, do not change or only slightly decrease, the test substance is judged to be not regenerated or only slightly regenerated. If the softening point decreases strongly (by about 10° C.), the viscosity decreases to below 1000 mPas and the MSCR elastic response decreases to, for example, below 10% for 0.1 kPa, or if at least most of these criteria are met, the test substance has a very good ability to regenerate soil bitumen 20 / 30.

[0745] As can be seen from Table 1, not all tested samples can regenerate the soil asphalt 20 / 30. The sample of 2300 (Example 1.2) itself is too sticky or too elastic to achieve the desired effect of earth asphalt 20 / 30. Soft (Example 1.3) and (Example 1.5) samples, it is believed that due to their high molecular weight, no regeneration phenomenon could be observed. Dodecylbenzenesulfonic acid (Example 1.8) hardened the earth bitumen, most likely due to its high polarity.

[0746] However, many of the tested samples were able to regenerate the dirt bitumen 20 / 30. DINP or Dinch softens dirt asphalt 20 / 30 very well and without being bound by any theory, it is believed that this is due to their successful replenishment of the soft asphalt phase due to their similar chemical properties to the soft asphalt.

[0747] In another example, N-dodecylpyrrolidone (which is thought to disrupt the asphaltene stack) or poly(bisaminopropylamine) (which is thought to better disperse the asphaltene stack in the soft asphalt) work well. A large class of surfactants ( TO3, TO8, TO15, XP70, XL60, TO5, Agnique Triton TM X-100) were very effective and are considered here to successfully disrupt the asphaltene pile. Not all tested surfactants were able to regenerate the dirt bitumen 20 / 30 in all tested parameters, e.g. PE6400, 90R4 or FEP3830PA, this may be due to their higher polarity or too high molecular weight.

[0748] Another class of compounds (dodecenyl succinic anhydride, polypropylene glycol bisglycidyl ether, neopentyl glycol bisglycidyl ether, 2-methyl-2-phenyl-1,3-propanediol bisglycidyl ether) was also found to regenerate well, where it is believed that they can react with polar functional groups (e.g., COOH or OH groups) of the asphaltenes and / or resins, thereby reintroducing solubility of the asphaltenes previously lost during aging. Only polyethylene glycol bisglycidyl ether only slightly regenerated the system, which may be due to its higher polarity and / or hardness compared to polypropylene glycol bisglycidyl ether.

[0749] Particularly preferred rejuvenating agents are determined to have an (eco)toxicological profile which should not be toxic or harmful to human health (e.g. inhalation toxicity) under the conditions of the asphalt mixing process. As a result, the following samples were determined from the presented examples to be the most preferred candidates (hereinafter also referred to as preferred candidates): DINCH (Example 1.7), poly(bisaminopropylamine) (Example 1.11), XL60 (Example 1.17), N-dodecylpyrrolidone (Example 1.9) and polypropylene glycol bisglycidyl ether (Example 1.24). These compounds were found to regenerate well and can preferably be used as regeneration agents in asphalt mixing plants.

[0750] Table 1. The following abbreviations are used: Suppl. - supplier; SP - softening point; Rec. - response; tox - toxicology / ecotoxicology

[0751]

[0752]

[0753]

[0754] Comparative Example (Comparative Example)

[0755] In order to be able to evaluate the selected candidates in the context of an existing benchmark, a benchmark study was performed in a manner similar to that performed in Example 1. The results of the benchmark study can be seen in Table 2. Product 1 was able to reduce the softening point, with large differences between the different products. None of the products was able to reduce the softening point to 50°C or below as the preferred candidates claimed herein. All samples were able to reduce the viscosity at 135°C, again with significant differences between the different benchmarks, and only three of them were able to reduce the viscosity to 1,000 mPas or below. All products except Product 1 were able to reduce the elastic recovery during the MSCR test. In particular, Products HP-AM (commercially available from Ventraco, comparative example 1.3) can reduce elastic recovery the most, which is why, combined with its ability to reduce softening point and viscosity, it is considered the best performing benchmark under the tested samples. However, it also does not perform well compared to the preferred candidate (from example 1).

[0756] Table 2. The following abbreviations are used: SP-softening point; Rec.-recovery;

[0757]

[0758] Example 2: Softness and viscoelasticity of regenerated aged soil asphalt

[0759] Since the earth asphalt 20 / 30 used in Example 1 is only a model system and not actual aged earth asphalt, it is critical to verify the performance of the selected candidates in actual aged earth asphalt. Therefore, the preferred candidates were tested in three different aged earth asphalt samples: two 50 / 70 earth asphalt types from two different refineries that were laboratory aged (RTFOT+PAV), and one recycled asphalt pavement sample consisting of extracted earth asphalt from a road.

[0760] Three different samples of earth bitumen were regenerated and analyzed in the same manner as performed in Example 1. The preferred candidates were each targeted at the product HP-AM (Comparative Example 1.3) was used as a benchmark and also on unregenerated clay asphalt. The results can be seen in Table 3. It can be seen that regardless of the type of clay asphalt used, whether it is 20 / 30 or these three aged samples, the preferred candidates performed very well. This is very important because different clay asphalt plants use very different clay asphalt qualities and a well-functioning rejuvenator must work across a wide spectrum of different clay asphalt compositions.

[0761] Table 3. The following abbreviations are used: Suppl. - supplier; SP - softening point; Rec. - recovery; * Earth bitumen extracted from RAP using trichloroethylene extraction according to DIN EN 12697-1.

[0762]

[0763]

[0764] Example 3: Low temperature performance (BBR)

[0765] Examples 1-2 illustrate the performance of different rejuvenators in the medium or high temperature range. However, it is known that aged earth asphalt has sharply reduced low temperature properties, such as increased brittleness. Therefore, an excellent rejuvenator must also improve the low temperature properties of earth asphalt.

[0766] Different samples of clay bitumen were regenerated as in Example 1 and the BBR values ​​S (bending creep stiffness) and m (creep recovery) were evaluated at -16°C. The results were compared with clay bitumen samples without regeneration agent and with the benchmark The soil asphalt regenerated by HP-AM (Comparative Example 1.3) was compared.

[0767] In general, all tested samples have a strong ability to reduce the stiffness of the earth bitumen samples at -16 °C. It is sufficient that all tested additives make the samples more flexible compared to earth bitumen 50 / 70. It can be seen that from the samples tested in earth bitumen 20 / 30, the base HP-AM (Comparative Example 1.3) had the lowest performance, indicating that the preferred candidate of the present invention has a stronger impact.

[0768] Table 4

[0769]

[0770] Example 4: Loss tangent tanδ of regenerated soil asphalt sample

[0771] Examples 1 to 3 demonstrate well the ability of the rejuvenating agents according to the invention and in particular the preferred candidates according to the invention to regenerate earth bitumen, independently of the type of earth bitumen. Furthermore, it can be shown that for low, medium and high temperature ranges the additives according to the invention perform better most of the time than conventional benchmarks according to standard testing techniques. What cannot be extracted from these measurements, however, is an indication of the working mechanism. For this purpose, an analysis of the loss tangent (tan δ), for example by frequency scanning, is more suitable. The loss tangent is the ratio between G" (viscous contribution) and G' (elastic contribution). The higher the ratio, the greater the contribution of viscosity to the rheological properties and therefore the higher the mobility of the molecules in the earth bitumen phase. Especially at low frequencies, when the measurement itself has very little influence on the system, this means that choosing the measurement conditions so as to characterize the earth bitumen within the linear viscoelastic region (LVE) allows information to be extracted about the mobility of the earth bitumen components.

[0772] Different soil asphalt types were regenerated using the preferred candidates of Example 1. Then, a frequency sweep was measured from 0.01 to 100 rad / s at 60°C at a shear deformation γ of 5%. This temperature was chosen because it is a temperature at which the viscous contribution is not yet too high and the elastic contribution is still strong, in order to determine the rheological response. The tanδ of each sample was then evaluated at the lowest frequency (see Table 5). It can be seen that the preferred candidates of the present invention strongly increase the loss tangent, which means that they strongly increase the fluidity within the soil asphalt phase, thereby changing the microstructure of the soil asphalt. This effect was observed to be independent of the soil asphalt type. As can be seen from Example 4.7, on the other hand, HP-AM (Comparative Example 1.3) did not have the same effect, which means that it mainly works based on dilution rather than on changing the asphaltene packing and / or their dispersion. Figure 1 It can be seen that this effect is also the same for the other benchmarks tested in Earth Bitumen 20 / 30 (see Comparative Examples 1.4, 1.7 and 1.8), indicating that this effect is inherent to the preferred candidates of the present invention. Figure 1 It can also be seen in FIG. 1 that this effect is observed not only at low frequencies but even over the entire frequency range, meaning that it is a very significant effect.

[0773] Table 5. The following abbreviations are used: Suppl. - supplier; * Earth bitumen extracted from RAP using trichloroethylene extraction according to DIN EN 12697-1.

[0774]

[0775]

[0776] Example 5: Aging behavior after 3×RTFOT, monitored by loss tangent tanδ

[0777] In the following, it will be shown that the positive effect of the regenerants claimed herein on the fluidity of the molecules persists even after aging. Thus, according to Example 4, different soil asphalt types were regenerated using some of the regenerants claimed herein, but then by repeated RTFOT aging before the frequency sweep test (RTFOT aging 3 cycles). As can be seen from all the figures shown below, the positive effect of the regenerants claimed herein on the fluidity of the binder molecules persists and is also observed over the entire frequency range, meaning that their effect on the molecular structure is a significant one. All figures also show the values ​​of fresh soil asphalt (50 / 70) for reference, and it can also be seen that the regenerants claimed herein are partially or at some times even completely able to restore the properties of fresh soil asphalt, an effect never observed for any benchmark.

[0778] First, we tested some of the claimed rejuvenators in Earth Asphalt 20 / 30, a system very similar to aged Earth Asphalt as described above. In order to be able to evaluate the effectiveness of the claimed rejuvenators ( Figure 2 ), we compared the results with Earth Asphalt 20 / 30 (purchased from TOTAL Chimie) (using It can be seen that the regenerator claimed herein achieves a higher loss tangent than the benchmark over the entire frequency range, which demonstrates the improved impact of the regenerator claimed herein over the prior art, which is believed to have only a limited impact on the asphalt microstructure.

[0779] To demonstrate that this effect is independent of the binder used, the same rejuvenating agent of the invention was tested in different types of aged earth asphalt. Those different earth asphalt types were two 50 / 70 binders (BP, Figure 3 and Schwedt, Figure 4 )—which was aged by RTFOT and PAV before regeneration, and binders extracted from asphalt pavement (RAP, Figure 5 ). Similarly, HP-AM was used as a benchmark in these tests. From the results, it can be seen that the rejuvenants claimed herein always perform better than the benchmark, meaning that after 3x RTFOT aging, they always have a higher loss tangent than pure earth asphalt as well as earth asphalt rejuvenated with the benchmark. Of the two earth asphalt types, only the rejuvenant poly-BAPMA shows a lower loss tangent, which may indicate that the aging of this additive is more binder-dependent than the other rejuvenants.

[0780] Example 6: Regeneration Agent Performance on Polymer Modified Bitumen (PmB)

[0781] It will be demonstrated here that the positive influence of the protected regenerants claimed herein can also be applied to PmB, thus in this case Olexobit 45 was regenerated according to the process of Example 1. As can be seen from Table 6, the protected regenerants claimed herein are able to regenerate Olexobit 45 and their effect is stronger than the test benchmark. Figure 6 It can be seen that the molecular mobility is also changed for Olexobit 45 in a similar manner as for unmodified clay asphalt. Figure 7 It can be seen from Table 6 that this effect still exists after 3×RTFOT aging. In addition, from the aging index (AI) in Table 6, it can be seen that the aging of Olexobit is unchanged or improved after regeneration.

[0782] Table 6. The following abbreviations are used: SP - softening point; Rec. - recovery; AI - aging index

[0783]

[0784]

[0785] Example 7: Regenerant performance evaluated by TD NMR relaxation time measurements

[0786] In order to demonstrate that the observed effects of the rejuvenating agents claimed herein on the asphalt microstructure are not merely the effects of the DSR frequency scans used in Examples 4 and 5, the effects on the microstructure were also probed using physicochemical analysis of the asphalt samples, in this specific case using time domain NMR (TD NMR).

[0787] TD NMR, also known as NMR relaxometry, is a known NMR technique that relies on measuring the relaxation time of a nuclear spin system rather than frequency domain spectroscopy. Recording these parameters can be achieved with much lower, less uniform magnetic fields, so TD NMR spectrometers are relatively compact and rugged instruments with permanent magnets that do not require cooling. Likewise, sample preparation is much simpler, as there is no need to worry about sample homogeneity and no solvents are required.

[0788] TD NMR is well suited for the purpose of evaluating the impact on the microstructure of soil asphalt, since protons with different local molecular mobilities in a chemical environment exhibit different and characteristic relaxation times. Like that, a clear distinction can be made with good precision between protons in the solid, amorphous and liquid components. Therefore, if a regeneration agent affects the microstructure of soil asphalt, it will reduce the amount of solid components and increase the amount of liquid components. Likewise, the more effective the regeneration agent, the higher the mobility of the liquid component.

[0789] The soil bitumen 20 / 30 was regenerated using the regeneration agent according to Example 1 as claimed herein. Then, pure soil bitumen 20 / 30 as well as regenerated soil bitumen 20 / 30 samples were analyzed by TD NMR. For this purpose, all samples were heated to a maximum of 80°C in order to fill the samples into the NMR tube. Subsequently, TD NMR measurements were performed at 30°C, 80°C and 140°C using the SE-CMPG sequence. This sequence consists of a solid echo and is combined with a so-called CPMG (Carr-Purcell-Meiboom-Gill) series of subsequent spin echoes and is able to record the coherence decay of the transverse nuclear magnetization within about 5 orders of magnitude in time. The experimental data were then fitted to a semi-empirically selected multicomponent model, which includes several Gaussian components and exponential components, depending on the measured temperature:

[0790] To evaluate the effect of temperature on the mobility of soil bitumen molecules, tests were conducted at temperatures of 30 °C, 80 °C, and 140 °C, and the following model was demonstrated to provide an adequate fit to the corresponding normalized signal decay curves:

[0791] Two Gaussian components and one exponential component at 30°C

[0792] Two Gaussian components and two exponential components at 80°C

[0793] Three exponential components at 140°C

[0794] Different values ​​can be obtained from the fit:

[0795] p-values ​​(pg1, pg2, pe1, pe2, and pe3), indicating the fraction of the signal of a single component with a modulation level ranging from 0 to 1

[0796] T2 values ​​(T2g1, T2g2, T2e1, T2e2, and T2e3), which represent the relaxation time corresponding to each of the individual components. The longer the relaxation time, the higher the molecular mobility of the corresponding component

[0797] In addition to the values ​​T2e1, T2e2, and T2e3, for temperatures where more than one mobile component is present (80 and 140°C), we also calculated the average relaxation time of the mobile components, 1 / <1 / T2e>. 1 / <1 / t2e> is calculated as the harmonic mean of the relaxation times involved:

[0798]

[0799] Component type, which is:

[0800] -g1: hard component

[0801] -g2: Partial flow components

[0802] -e1, e2 and e3: mobile components with gradually increasing local molecular mobility

[0803] The hard component g1 is considered to be directly related to the amount of bituminous aggregates. On the other hand, the mobile component can be attributed to the soft bituminous phase. Both the p value (the amount of the individual components) and the T2 value (relaxation time and therefore the mobility of the components) are important values ​​to consider in interpreting TD NMR data.

[0804] In general, all regenerants (including the benchmark) were found to cause a shift towards longer relaxation times (and higher molecular mobility) at all temperatures studied. All regenerants reduced the solids content pg1 at 30 and 80°C, and at 140°C the solids content was no longer present, even in the non-regenerated samples. The performance of the different effectiveness of the regenerants was found to decrease relatively with increasing temperature. However, this is due to the temperature-dependent melting of the earth bitumen as a dominant effect at higher temperatures, rather than a lower effectiveness of the regenerants at higher temperatures. As a constant trend, the regenerants claimed in this article were found to perform better on average than the benchmark. The ranking of the various shifts of the regenerants claimed in this article at different temperatures is different, but it can be said that XL60 and N-dodecylpyrrolidone have the greatest effect on the fluidity of the clay asphalt phase. Detailed results for the individual temperatures are described below.

[0805] 30℃:

[0806] At 30 °C, the signal fraction of the hard solid component pg1 was found to decrease for all regenerated samples. Among the tested samples, the baseline had the lowest impact on pg1, indicating that the regenerants claimed herein had a greater impact. The relaxation time T2g1 of the solid component pg1 was almost similar for all samples, meaning that although they were reduced in quantity, the type of structure did not change. Similarly, all regenerants increased the amount of mobile component pe1 and its fluidity t2e1, with the regenerants claimed herein having the greatest effect. The impact on the weakly mobile Gaussian pg2 was less significant but followed a similar trend.

[0807] Table 7. Multicomponent fitting results at 30 °C.

[0808]

[0809] 80℃:

[0810] At 80°C, due to the melting of the clay bitumen, the signal fraction of the hard solid component pg1 is greatly reduced compared to 30°C. For all regenerated samples, it is also strongly reduced compared to the unregenerated clay bitumen 20 / 30. Likewise, all the regeneration agents claimed herein are HP-AM reduces pg1 more. For 30 °C, the relaxation time T2g1 of the solid component pg1 is similar for all samples. Note that the relaxation time of the exponential component is more significantly different than that of the weak flow Gaussian pg2. From the relaxation times T2e1 and T2e2 and from 1 / <1 / T2e>, it can be seen that Hp-Am has minimal effect on the flowability of mobile components.

[0811] Table 8. Multicomponent fitting results at 80 °C.

[0812]

[0813] 140℃:

[0814] At 140°C, the hard solid component pg1 is no longer present in any sample, which means that all samples are liquid. At this temperature, since the soil bitumen is already liquid when not regenerated, the differences between the component patterns are less obvious than at lower temperatures. However, it can be clearly seen that the signal fractions of the components with higher fluidity (pe2 and pe3) of the regenerant claimed in this article are higher, while the signal fraction of the component with the lowest fluidity of the benchmark (pe1) is the highest. For the samples with added regenerants, the relaxation times of all components are systematically longer. It can be seen from the average relaxation time 1 / <1 / T2e> that HP-AM had the shortest relaxation time, meaning it produced the lowest mobility among all regenerant samples.

[0815] Table 9. Multicomponent fitting results at 140 °C.

[0816]

[0817]

Claims

1. An adhesive composition comprising: (a) asphalt binder; and (b) 3 to 7% by weight of a rejuvenating agent, based on the total amount of the adhesive composition, in, The rejuvenating agent comprises at least one asphaltene dispersant, asphaltene reactivator, soft asphalt reactivator, or a mixture thereof, wherein The asphaltene dispersant is selected from alkoxylates having a structure of formula (1), in R is C 10 -alkyl or C 13 -alkyl, n is 0 to 6, m is 0 to 8, and wherein n+m≥5; N,N-dialkylamide of aliphatic carboxylic acid having the structure of formula (2) in n is 8 to 12, R 1 is methyl or ethyl, and R 2 is methyl or ethyl; N-alkyl lactam having the structure of formula (3) in n is 3, and R is C8-C 12 -alkyl; or Poly(alkylamine) having the structure of formula (4) in The poly(alkylamine) is selected from oligo-N,N-bis-(3-aminopropyl)methylamine and poly-N,N-bis-(3-aminopropyl)methylamine, The asphaltene reactivating agent is selected from compounds having the structure of formula (5b), in R is a straight chain C5-C 15 - alkylene, which may be further substituted by at least one C1-C4-alkyl or C1-C3-alkylene, which is further substituted by at least one C1-C5-alkyl and / or at least one phenyl; or A compound having the structure of formula (5d), in R n With formula (6b), (-CH2CH(CH3)O-) n (6b), wherein n is 3 to 15, The soft asphalt reactivator is a plasticizer having formula (7a), in R is C8-C 11 -alkyl, or a plasticizer having formula (7c), in R is C8-C 11 -alkyl.

2. The adhesive composition of claim 1, wherein the rejuvenating agent causes a microstructural change in the micellar structure of the earth asphalt, wherein the loss tangent of the adhesive composition increases compared to the loss tangent of the earth asphalt adhesive, and / or Wherein the amount of mobile components and / or their respective flowability of the binder composition according to TD NMR is increased compared to the amount of mobile components and / or their respective flowability of the asphalt binder.

3. The adhesive composition according to claim 1 or 2, The regeneration agent comprises: (i) 1 to 100 wt % of an asphaltene dispersant, based on the total amount of the rejuvenating agent; (ii) 1 to 100 wt % of an asphaltene reactivating agent, based on the total amount of the reactivating agent; (iii) 1 to 100 wt. % of a soft asphalt reactivator, based on the total amount of the reactivator; or (iv) 1 to 100% by weight of a mixture consisting of at least two components selected from (i) to (iii), Based on the total amount of regenerant.

4. The binder composition of claim 1 or 2, wherein the earth asphalt binder comprises recycled asphalt pavement binder, recycled asphalt shingle binder, virgin earth asphalt having a hardness of at least 50 / 70, or a mixture thereof, optionally in combination with a virgin binder.

5. The adhesive composition according to claim 1 or 2, wherein the asphaltene reactivating agent is selected from the group consisting of polyethylene glycol bis(glycidyl) ether, polypropylene glycol bis(glycidyl) ether, neopentyl glycol bisglycidyl ether, 2-methyl-2-phenyl-1,3-propanediol bisglycidyl ether, 2-ethylhexyl glycidyl ether, and mixtures of these compounds with catalysts.

6. The adhesive composition according to claim 5, wherein the asphaltene reactivating agent is polypropylene glycol bis(glycidyl) ether.

7. The adhesive composition according to claim 1 or 2, wherein the soft asphalt reactivating agent is selected from diisononyl phthalate or diisononyl cyclohexane-1,2-dicarboxylate. 8 . The adhesive composition according to claim 7 , wherein the soft asphalt reactivating agent is diisononyl cyclohexane-1,2-dicarboxylate.

9. The adhesive composition of claim 1 or 2, wherein the soil asphalt adhesive comprises 10 to 100 weight percent of recycled asphalt pavement and / or recycled asphalt shingle adhesive, based on the total weight of the soil asphalt adhesive.

10. The adhesive composition according to claim 1 or 2, wherein the asphalt adhesive comprises other additives.

11. The adhesive composition according to claim 10, wherein the other additives are selected from polymers, waxes, fibers or mixtures thereof.

12. An asphalt composition comprising aggregate and a binder composition according to any one of claims 1 to 11.

13. A paved road surface, road subsurface, runway, driveway, parking lot, shoulder, bridge, abutment, roof, revetment or unpaved road comprising the asphalt composition according to claim 12.

14. A method for evaluating the efficacy of a rejuvenating agent in an adhesive composition according to any one of claims 1 to 11, wherein the efficacy of the rejuvenating agent is demonstrated by: (i) the loss tangent before or after aging, obtained at a given temperature from a dynamic shear rheometer (DSR) frequency sweep, wherein the frequency sweep is measured at a temperature between 0 and 90°C, and wherein the effective regenerant satisfies inequality (a) Loss tangent [bc]>1.3×loss tangent [bb], (a) wherein the loss tangent [bc] represents the loss tangent of the adhesive composition and the loss tangent [bb] represents the asphalt adhesive, and wherein the loss tangent [bc] and the loss tangent [bb] are evaluated at a frequency of 0.01 to 10 rad / s, or (ii) TD NMR relaxation experiments were performed on asphalt samples at temperatures ranging from -50 to 200 °C, where the effective regeneration agent satisfied inequality (aa1) T2e1[bc]>1.3×T2e1[bb](aa1) wherein T2e1[bc] represents the relaxation time corresponding to the individual components of the binder composition, and T2e1[bb] represents the relaxation time corresponding to the individual components of the asphalt binder.

15. Use of a rejuvenating agent for recycling recovered asphalt pavement (RAP) and / or asphalt shingles from roofs (RAS), in, The rejuvenating agent comprises at least one asphaltene dispersant, asphaltene reactivator, soft asphalt reactivator, or a mixture thereof, wherein The asphaltene dispersant is selected from alkoxylates having a structure of formula (1), in R is C 10 -alkyl or C 13 -alkyl, n is 0 to 6, m is 0 to 8, and wherein n+m≥5; N,N-dialkylamide of aliphatic carboxylic acid having the structure of formula (2) in n is 8 to 12, R 1 is methyl or ethyl, and R 2 is methyl or ethyl; N-alkyl lactam having the structure of formula (3) in n is 3, and R is C8-C 12 -alkyl; or Poly(alkylamine) having the structure of formula (4) in The poly(alkylamine) is selected from oligo-N,N-bis-(3-aminopropyl)methylamine and poly-N,N-bis-(3-aminopropyl)methylamine, The asphaltene reactivating agent is selected from compounds having the structure of formula (5b), in R is a straight chain C5-C 15 - alkylene, which may be further substituted by at least one C1-C4-alkyl or C1-C3-alkylene, which is further substituted by at least one C1-C5-alkyl and / or at least one phenyl; or A compound having the structure of formula (5d), in R n With formula (6b), (-CH2CH(CH3)O-) n (6b), wherein n is 3 to 15, The soft asphalt reactivator is a plasticizer having formula (7a), in R is C8-C 11 -alkyl, or a plasticizer having formula (7c), Where R is C8-C 11 -alkyl.

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