JP6554147B2 - Recovery of recovered asphalt - Google Patents

Description

  The present invention relates to recovered asphalt compositions and their regeneration.

  Recovered asphalt includes, among other sources, recovered pavement asphalt (RAP), recovered asphalt gravel (RAS), asphalt recovered from factory waste, and asphalt recovered from roof felt.

  Paved asphalt is one of the most recycled materials in the world, as a gravel substitute on unpaved roads and as a substitute for unused aggregates and binders on paved asphalt on paved surfaces and abutment shoulders. It is used. However, recycled pavement asphalt is usually limited to use as a “black rock” below the surface, or to a limited amount of use in asphalt foundations and surface layers. The usefulness of recycled materials in critical surface layers is limited. The reason is that asphalt degrades with time, loses flexibility, is prone to oxidation and embrittlement, and in particular cracks at stress or low temperatures. This result is due to the aging of the organic component of asphalt, i.e. the bitumen-containing binder, especially on exposure to the weather. Oxidative binders are also very viscous. Thus, recovered paving asphalt has different properties than virgin asphalt and is difficult to process. Untreated RAP can only be used in small quantities; in general, asphalt mixtures containing up to 30% by weight RAP can be used as black rock below the surface. Furthermore, the use of untreated RAP there is generally limited to 15-25%, as the requirements for pavement surfaces are more sophisticated.

  The recovered asphalt can be blended with virgin asphalt, virgin binder, or both (see, eg, US Pat. No. 4,549,834). Regeneration agents have been developed to increase the amount of recovered asphalt that can be incorporated into both the base and surface layers. Because the rejuvenating agent restores some of the asphalt properties of the pavement and physical properties of the bituminous binder, such as its visco-elastic behavior, the properties of the recovered asphalt are more similar to virgin asphalt. By improving the properties of recycled asphalt, particularly the properties of bituminous binders in RAP, it is possible to increase the amount of RAP used in the asphalt mixture without degrading the properties and life of the final pavement.

  Commonly used regenerants for RAP include low viscosity products obtained by distillation of crude oils or other hydrocarbon oil based materials (see, eg, US Pat. Nos. 5,766,333 or 6,117,227). .

  Regeneration agents of plant origin are also described. For example, U.S. Pat. No. 7,811,372 (rejuvenating agents including bitumen and palm oil); U.S. Pat. No. 7,0086,670 (soybean oil used for sealing or rejuvenating, alkyl esters derived from soya oil, and terpenes); 2010/0034586 (regenerant based on soybean, sunflower, rapeseed or other plant-derived oils) and US 2008/0041276 (recycled asphalt, which can be vegetable oils or alkyl esters made from vegetable oils) See plasticizers). US Patent Application Publication No. 2011/015312 describes a binder composition comprising a resin of vegetable origin, a vegetable oil, and a polymer having an anhydride, a carboxylic acid, or an epoxide functional group, wherein the binder is Specifically, it is not taught for reproduction.

Cashew nut shell oil-derived regenerants have recently been introduced, which mainly contain cardanol, ie, a phenolic compound having a C ₁₅ unsaturated chain (eg, PCT International Publication Nos. WO 2010/077141 and WO No. 1). 2010/110651). Such products are described in Ventraco Chemie, B.C. V. For example as RheoFalt® HP-EM.

  Various fractions isolated from the distillation of crude tall oil (CTO) are used in asphalt compositions. However, they are not specifically taught for reproduction. For example, US Patent Application Publication No. 2010/0170417 (CTO distilled fraction as cutting solvent application in asphalt composition); US Patent Application Publication No. 2010/0147190 (distilled or oxidized tall oil for use in asphalt composition) Component) and U.S. Pat. Nos. 4,479,827 and 4,373,960 (patching compositions comprising asphalt, tall oil and possibly organopolysiloxane).

  Tall oil fatty acids (TOFA), tall oil rosins, tall oil pitch or esters made from downstream products of CTO such as monomeric acids (eg unique products as described in US Pat. No. 7,256,162), dimer acids etc. It is not suggested for use as a rejuvenating agent for recovered asphalt.

U.S. Pat. No. 4,549,834 US Pat. No. 5,766,333 US Pat. No. 6,117,227 U.S. Pat. No. 7,811,372 US Patent No. 70008670 U.S. Patent Application Publication No. 2010/0034586 U.S. Patent Application Publication No. 2008/0041276 U.S. Patent Application Publication No. 2011/015312 International Publication No. 2010/077141 WO 2010/110651 US Patent Application Publication No. 2010/0170417 US Patent Application Publication No. 2010/0147190 U.S. Pat. No. 4,479,827 U.S. Pat. No. 4,373,960 U.S. Pat. No. 7,256,162

  There is a need for improved rejuvenating agents for recovered asphalt. In particular, the industry needs non-crystalline additives for recovered asphalt that can improve low temperature crack resistance and fatigue crack resistance while maintaining good rutting resistance. Better regenerative agents reduce road construction costs by allowing greater use of RAP in new pavements and reducing reliance on unused and non-renewable binders and aggregate materials It seems that. The preferred rejuvenating agents are believed to reduce the viscosity of the binder to a level comparable to virgin binder and also to lower the glass transition temperature of the binder to allow for a softer, more easily processable asphalt mixture. Ideally, the rejuvenating agent is derived from renewable resources and has good thermal stability at elevated temperatures commonly used to mix and lay asphalt, with the initial performance grade of the binder It seems that you can revive.

  In one aspect, the present invention relates to an asphalt composition comprising recovered asphalt and an ester functional rejuvenating agent. The recovered asphalt contains aggregate and an oxidation binder. The rejuvenating agent is present in an amount effective to reduce the glass transition onset temperature of the oxidative binder by at least 5 ° C. as compared to the glass transition onset temperature of the oxidative binder without regenerant. Our invention includes binder compositions suitable for use with recovered asphalt and methods for making the asphalt and binder compositions of the present invention.

  In another aspect, our invention relates to an asphalt composition comprising 0.01 to 10 wt% rosin ester and at least 15 wt% recovered asphalt. The rosin ester is the reaction product of tall oil rosin or tall oil with a polyol selected from diethylene glycol, triethylene glycol, glycerol, pentaerythritol and mixtures thereof. Our invention includes a process comprising the step of regenerating recovered asphalt by mixing with 0.01 to 10% by weight of tall oil ester, rosin ester or mixtures thereof.

  In yet another aspect, the invention relates to an asphalt composition comprising an ester functional rejuvenating agent and a recovered asphalt comprising at least 15% by weight of an oxidative binder. The rejuvenating agent is present in an amount ranging from 1 to 10% by weight based on the combined amount of the oxidizing binder and the rejuvenating agent. The mixture of oxidative binder and rejuvenating agent forms a regenerative binder having a ring and ball softening point according to EN 1427 below 60 ° C. and a penetration value according to EN 1426 above 20 dmm.

  Our invention also includes a paving surface comprising the binder of the present invention and an asphalt composition.

We have surprisingly found that the incorporation of an ester functional rejuvenating agent regenerates the oxidized bituminous binder of the recovered asphalt and the physical properties are similar to the physical properties of the original performance grade of bitumen prior to oxidation. It has been found that it is possible to produce regenerated bituminous binders having properties. Regenerative binders exhibit reduced glass transition onset temperature, as well as improved creep stiffness by dynamic shear visco-elastic measurement (DSR). These results translate into improved low temperature crack resistance in recycled asphalt. The DSR analysis also shows that the regenerated binder has a reduced value of G ^* sin δ, which is consistent with the improved fatigue crack resistance. If up to 10% by weight of the rejuvenating agent forms a regenerated binder, such binders also have good elevated temperature performance associated with rut resistance. Rutting is a common failure mode on asphalt road surfaces, especially on asphalt road surfaces with heavy traffic or heavy traffic.

  The inventors have also found that certain regenerants restore the desired softening at low additions while maintaining acceptable penetration values. The rejuvenating agent is effective to reduce the temperature required to consolidate or mix the asphalt composition, which saves energy and reduces cost. Some of our regenerants improve the temperature sensitivity of the regenerative binder and so can be used in a heated mixed asphalt process. Reduced temperature sensitivity is an advantage over conventional additives, such as vegetable oils, which may decompose at heating mixing temperatures above 150 ° C. The binders of the present invention have good ductility, lose very little properties upon aging and are similar to unused binders.

  In summary, for the rejuvenating agents of the present invention, higher levels of recovered asphalt are used in asphalt mixtures by reducing the glass transition temperature (Tg) of the binder and thereby improving the processability of the recovered asphalt It becomes possible to do. Incorporating more recovered asphalt on the road reduces the cost of both the binder and aggregate and helps reduce the road construction industry's dependence on unused and non-renewable materials.

  The present invention relates to the regeneration of asphalt compositions with ester functional rejuvenating agents. In particular, it relates to the regeneration of recovered asphalt comprising aggregate and oxidized asphalt binder, in particular recovered paved asphalt (RAP).

  In the literature, the term "asphalt" may be used to describe binders and may also be used to describe binders plus aggregate. In the context of the present invention, "asphalt" refers to a composite material comprising bituminous binder and aggregate, which is generally used for paving applications. Such asphalts are also known as "asphalt concrete". Asphalt is usually a grade that is qualified for paving applications. Examples of asphalt grades used in paving applications include fine particle size asphalt, gap type asphalt, porous asphalt, and mastic asphalt. Typically, the total amount of bituminous binder in asphalt is 1 to 10% by weight, in some cases 2.5 to 8.5% by weight, in some cases 4 to 7.5%, based on the total weight of the asphalt It is weight%.

  “Recovered asphalt” includes recovered pavement asphalt (RAP), recovered asphalt gravel (RAS), recovered asphalt from factory waste, recovered asphalt from roof felt, and asphalt from other applications.

  “Reclaimed pavement asphalt” (RAP) is asphalt that has been used as pavement in the past. RAP can be obtained from asphalt which has been removed from roads or other structures and then treated by known methods including grinding, tearing, breaking, crushing and / or granulation. Prior to use, RAP can, for example, be inspected, classified and selected depending on the final pavement application.

  “Aggregate” (or “construction aggregate”) is a particulate mineral material suitable for use in asphalt. This generally includes sand, gravel, crushed stone, and slag. Any conventional aggregate suitable for use on asphalt can be used. Examples of suitable aggregates include granite, limestone, gravel and mixtures thereof.

  "Bitumen" refers to a viscous, organic liquid or semi-solid mixture from a crude oil that is black, sticky, soluble in carbon disulfide, and consists primarily of fused polycyclic aromatic hydrocarbons. Alternatively, bitumen may refer to a mixture of marten and asphaltenes. The bitumen may be any conventional bitumen known to those skilled in the art. Bitumen may be of natural origin. This may be crude bitumen, or it may be refined bitumen obtained as bottom residue from vacuum distillation, pyrolysis or hydrogenolysis of crude oil. Bitumen obtained from bituminous or recovered paving asphalt contained in recovered paving asphalt is further referred to as RAP-originated bitumen.

  "Unused bitumen" (also known as "fresh bitumen") refers to bitumen that has not been used, eg, bitumen that has not been recovered from road pavements.

"Binder" refers to a combination of bitumen and optionally other ingredients. Other ingredients may include elastomers, non bituminous binders, adhesion promoters, softeners, additional rejuvenating agents (other than the present invention), or other suitable additives. Useful elastomers include, for example, ethylene-vinyl acetate copolymer, polybutadiene, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, butadiene-styrene block copolymer, styrene-butadiene-styrene (SBS) block terpolymer, isoprene-styrene. And block copolymers and styrene-isoprene-styrene (SIS) block terpolymers. The aged elastomeric additive can comprise a ground tire rubber material.
An “unused binder” is a binder that has not been used so far for road pavement.

  "Oxidized binder" refers to a binder present in, or recovered from, recovered asphalt. In general, oxidative binders are not isolated from recovered asphalt. Oxidized binders have a higher viscosity compared to that of unused bitumen as a result of aging and exposure to outdoor weather.

  "Aging binder" refers to virgin binder that has been aged to be similar to an oxidative binder, using the RTFO and PAV laboratory aging test methods described herein.

  A "rejuvenating agent" is a combination of an oxidation binder or recovered asphalt (or a virgin binder and / or a mixture of virgin asphalt and / or unused asphalt) to regenerate the oxidized binder or recovered asphalt, a virgin binder or virgin A composition or mixture that restores some or all of the original properties of the asphalt used. An "ester functional" rejuvenating agent has at least one ester group and is further described below.

The bitumen in the binder may be paving grade bitumen, i.e. commercially unused bitumen such as bitumen suitable for paving applications. Examples of commercially available pavement grade bitumen include, for example, bitumen called PEN 35/50, 40/60 and 70/100 in the penetration grade (PEN) classification system, or PG64-22, 58- in the performance grade (PG) classification system. And bitumen called 22, 70-22 and 64-28. Such bitumen is available, for example, from Shell, Total, and British Petroleum (BP). The PEN classification, product number refers to penetration range of bitumen as measured by ASTM D1586 method, for example, 40 / 60PEN bitumen, bitumen having a penetration in the range of 40 to 60 decimeter millimeters (dmm) Corresponds to In the PG classification (AASHTO MP 1 standard), the first value of the product number refers to high temperature performance as measured by a method known in the art as the Superpave ^SM system, and the second value refers to low temperature performance. .

  In one aspect, the invention relates to an asphalt composition. The asphalt composition comprises recovered asphalt and an ester functional rejuvenating agent. The recovered asphalt contains aggregate and an oxidation binder.

  In another aspect, the invention relates to a binder composition suitable for use with recovered asphalt. The binder composition comprises a combination of an oxidative binder and an ester functional rejuvenating agent. Suitable oxidative binders for use in the compositions of the present invention are present in or recovered from the recovered asphalt, which can be RAP. The binder can be recovered from the RAP by conventional means such as solvent extraction. Preferably, the oxidative binder is not isolated from the recovered asphalt. Instead, the recovered asphalt is simply combined with the desired amount of rejuvenating agent. In a preferred approach, the rejuvenating agent is combined with virgin binder, reclaimed asphalt, and optionally virgin asphalt and mixed to obtain reclaimed asphalt product.

  The asphalt and binder compositions of the present invention comprise an ester functional rejuvenating agent. The binder composition contains 0.1 to 15% by weight, preferably 0.5 to 10% by weight of the regenerant based on the combined amount of the oxidized binder and the regenerant. In both the asphalt composition of the present invention and the binder composition of the present invention, the regenerant has a glass transition onset temperature of the oxidized binder of at least 5 compared to the glass transition onset temperature of the oxidized binder that does not include the regenerant. Present in an amount effective to reduce temperature.

Preferably, the ester functional rejuvenating agent is derived primarily from carboxylic acids (including resin acids) or C ₈ -C ₂₀ fatty acids and C ₁ -C ₁₈ alcohols. The acid moiety can be linear, branched, cyclic, aromatic or a combination thereof; the acid moiety can be saturated, unsaturated or a combination thereof. Resin acids include monocarboxylic acids in the form of C ₁₉ H ₂₉ COOH with a nucleus of three fused 6 carbon rings, including double bonds of varying numbers and positions. The fatty acids can be in polymerized form, as in dimerized fatty acid mixtures. The alcohol moiety of the ester functional regenerant may be primary, secondary or tertiary; it may be a monool, a diol or a polyol. The alcohol may also be derived from a polyether such as triethylene glycol or polyethylene glycol. Phenolate esters are also suitable.

Thus, suitable carboxylic resin acids include abietin, neoabietin, dehydroabieticin, pimar, levopimal, sandaracopimal, isopimar, and pastric acid. Suitable _C 8 _{-C 20} fatty acids, for example, benzoic acid, caprylic acid, azelaic acid, ricinoleic acid, 12-hydroxystearic acid, stearic acid, isostearic acid, tall oil fatty acids, oleic acid, linoleic acid, linolenic acid, Included are palmitic acid, monomeric acids (as defined below), dimer acids, tall oil heads and the like, and mixtures thereof. Suitable C ₁ -C ₁₈ alcohols include, for example, methanol, ethanol, 1-propanol, isobutyl alcohol, 2-ethylhexanol, octanol, isodecyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol monobutyl ether, ethylene glycol, propylene glycol , Diethylene glycol, triethylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose and the like and mixtures thereof.

  It is preferred that the ester functional regenerant has a flash point above 200 ° C, more preferably above 220 ° C, and most preferably above 250 ° C. Preferably, the rejuvenating agent is non-crystalline, preferably having a melting point or titer of 30 ° C. or less, more preferably less than 20 ° C. and most preferably less than 0 ° C. Because many resin acids are solid, they can be blended with fatty acids or selected to have a relatively low softening point to provide a preferred rejuvenating agent.

In a preferred aspect, the ester functional regenerating agent is derived from tall oil fatty acid (TOFA) or a TAFA derivative (eg, TOFA dimer acid). Tall oil fatty acids are isolated from crude tall oil (CTO) by distillation. CTO is a byproduct of the craft wood pulp process. CTO distillation results in a more volatile and highly saturated fraction of long chain fatty acids (mostly palmitic acid) called “tall oil head” in addition to tall oil fatty acids. Tall oil fatty acids are the following fractions, which are mostly C ₁₈ and C ₂₀ fatty acids with varying degrees of unsaturation (eg, oleic acid, linoleic acid, linolenic acid, and a variety of these Isomers). Another fraction, called distilled tall oil or "DTO", is a mixture of mostly tall oil fatty acid and a small amount of tall oil rosin. Then tall oil rosin isolated ( "TOR") _is mainly composed of C 19 _{-C 20} tricyclic monocarboxylic acids. The bottom fraction of the distillation is called "tall oil pitch" or simply "pitch". In general, any fraction containing at least some tall oil fatty acid is preferred for use in making the ester functional rejuvenating agent.

As already mentioned, polymerized fatty acids can be used to make ester functional regenerants. Because of its high unsaturated fatty acid content, TOFA is usually polymerized using an acid clay catalyst. In this high temperature process, the unsaturated fatty acid forms a polymerized fatty acid by performing an intermolecular addition reaction by, for example, an “ene reaction”. The mechanism is complex and not well understood. However, the product contains mostly dimerized fatty acids and a unique mixture of monomeric fatty acids. Distillation results in a fraction enriched in highly dimerized fatty acids, usually called “dimer acid”. Such dimer acids are suitable for use in making ester functional regenerants.

Distillation of polymerized TOFA is also very rich in monomeric fatty acids, resulting in a fraction called “monomer” (with uppercase “M”) or “monomer acid”. Monomers that are unique compositions are preferred starting materials for making ester functional regenerants. Naturally derived TOFA consists mostly of linear C ₁₈ unsaturated carboxylic acids, mainly olein and linoleic acid, but the monomers contain relatively small amounts of olein and linoleic acid, instead of saturated and unsaturated equivalents. Quantities of branched and cyclic _C18 acids, and elaidic acid. A more diverse and substantially branched composition of monomers results from the contacting step being performed on the TOFA during polymerization. It is recognized in the art that monomers react with alcohols to make “monomelate” esters, resulting in unique derivatives that differ from the corresponding TOFA-based esters. The monomer was designated as CAS Registry Number 68955-98-6. Examples of monomeric products are Century® MO5 and MO6 fatty acids, products of Arizona Chemical Company. For further information on the composition of the monomers and their conversion to the various esters, reference is made to US Pat. No. 7,256,162, the teaching of which is incorporated herein by reference.

  Suitable regenerants include, for example, ethylene glycol tartrate (ie ethylene glycol ester of tall oil fatty acid), propylene glycol tartrate, trimethylolpropane tartrate, neopentyl glycol tartrate, methyl tartrate, ethyl tartrate, glycerin tartrate, oleyl tartrate, octyl Talate, Benzyl Talate, 2-Ethylhexyl Talate, Polyethylene Glycol Talate, Tall Oil Pitch Ester, Ethylene Glycol Monomerate, Glycerol Monomerate, Trimethylol Propane Monomerate, Neopentyl Glycol Monomerate, 2-Ethylhexyl Monomerate , Ethylene glycol dimerate, 2-ethylhexyl dimerate, 2-ethylhexyl trimerate, trimethylo Le propane isostearate, benzyl 12-hydroxy stearate, benzyl ricinoleate, octyl dicaprylate, octyl azelate, and the like octyl benzoate is. Particularly preferred regenerants are tartrates and monomaleates, especially trimethylolpropane taleate, ethylene glycol monomaleate, and glycerin monomaleate.

  The ester functional rejuvenating agent can be used in combination with other rejuvenating agents or adjuvants. For example, ester functional regenerants can be used in combination with tall oil rosin esters, terpene phenols, polyterpenes, alkylated phenols, and the like. The examples below show a combination of tall oil fatty acid ester and rosin ester (Example 38, trimethylolpropane ester from a mixture of rosin acid and TOFA) or terpene phenol combination (Example 47, Sylvares® TP96). (Combined ethylene glycol monomers).

In the asphalt and binder compositions of the present invention, the rejuvenating agent preferably has a glass transition onset temperature of the oxidized asphalt binder at least 5 ° C., preferably, compared to the glass transition onset temperature of the oxidized asphalt binder without the regenerant. Present in an amount effective to reduce by at least 10 ° C. The glass transition onset temperature can be measured by any desired method, but is conveniently measured by differential scanning calorimetry (DSC). The course of the DSC curve is recorded as the sample is circulated by the temperature rise and / or fall program. In the heat flow (W / g) versus temperature plot, the inflection points indicate the beginning and end of the glass transition. The temperature range between the start temperature and the end point is “spread”. Desirable rejuvenating agents lower the onset temperature of the glass transition and also narrow the spread. DSC has so far been used as a diagnostic tool to evaluate asphalt compositions; see, for example, Asphalt Science and Technology, A.A. M. Edited by Usnami, Marcel Dekker, Inc. NY (1997) pages 59-101. F. Turner and J.A. F. See Branthaven, “DSC Studios of Asphalts and Asphalt Components”.

  Surprisingly, we have found that when introduced at low to medium levels, ester functional regenerants can be effective in reducing the glass transition onset temperature of oxidized asphalt binders by at least 5 ° C. Found out. The reduction is important as it correlates with the expected improvement in cold crack resistance in paving asphalt. As the results in Tables 1 and 2 (below) suggest, a variety of ester derivatives reduce the glass transition onset temperature by at least 5 ° C when used at 2.5 to 10 wt% relative to the oxidized asphalt binder It is effective to do. Many of the ester functional regenerants reduce the onset temperature of the glass transition by at least 10 ° C, and some can reduce that temperature by as much as 20 ° C. On the other hand, other tested compositions are not effective in reducing the Tg onset temperature by at least 5 ° C. at the 10 wt% level. For example, as shown in Table 1, among others, high hydroxyl rosin esters (C16), terpene phenols (C18), polyterpenes (C23), and phenolic rosin esters (C24) reduce the Tg onset temperature. Not valid (see “ΔStart” column). Note that Tudalen® 65, a hydrocarbon flux oil currently used to regenerate recovered pavement asphalt, does not reduce the desired 5 ° C. Tg onset at the 10% additive level. Cardanol, the active ingredient of another commercially available rejuvenating agent (Ventraco Chemie, RheoFalt® HP-EM, a product of B.V.), effectively reduces the Tg onset temperature, but cardanol is a phenolic It is a long chain unsaturated alkylate and has no ester functional group.

  In preferred asphalt and binder compositions of the present invention, the ester functional regenerant is present in an amount effective to reduce the glass transition temperature broadening (or melting range) by at least 5 ° C, preferably at least 10 ° C. . As shown in Tables 1 and 2 (see “Δ Spread” column), for example, trimethylolpropane tartrate, ethylene glycol monomaleate, glycerin monomaleate, oleyl tartrate, neopentyl glycol monomaleate, and There are numerous examples of ester functional rejuvenating agents with this ability, including others. Although somewhat less diagnostic than the reduction of the Tg onset temperature, narrower Tg spread of the binder generally indicates greater uniformity, which results in fatigue crack resistance of the asphalt composition at ambient temperature. It can be better.

  Asphalt and binder compositions can be made by combining the components in any desired order. In one convenient approach, asphalt compositions are made by combining the rejuvenating agent with virgin binder and then blending the resulting mixture with RAP. In another approach, asphalt compositions are made by combining the rejuvenating agent with RAP and optionally virgin asphalt.

  The asphalt composition of the present invention preferably comprises a rejuvenating agent, 5-95% by weight RAP and at least some virgin binder. More preferred asphalt compositions comprise 10-90% by weight RAP, most preferably 30-70% by weight RAP. Other preferred compositions comprise 1 to 99% by weight, preferably 10 to 90% by weight, more preferably 30 to 70% by weight virgin binder.

Depending on the source, age, history, optional pretreatment, and other factors, the RAP typically contains 2-8 wt%, more usually 3-6 wt% of an oxidized asphalt binder. Thus, the effective amount of rejuvenating agent may vary with the asphalt source. In general, the rejuvenating agent is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, even more preferably 2 to 8% by weight, based on the amount of oxidized asphalt binder Preferably, it is used at 3 to 6% by weight.

  Further evidence of the value of ester functional regenerant is obtained from dynamic shear visco-elastic measurement (DSR) data. Table 3 shows the improvement of the low temperature performance, in particular the m-value and the creep stiffness at -15 ° C. For example, EG monomer, trimethylol propane tallate, and glycerine monomerate all work well compared to terpene phenols and other neutral additives. At ambient temperatures, ester functional regenerants provide a clear reduction in the RAP binder G * sinδ, which is an indicator of improved fatigue crack properties in the ultimate asphalt composition. The benefits in low and ambient temperature performance are significant, but such benefits too often occur only at the expense of elevated temperature properties such as rutting resistance. However, as shown in Table 3, low values of G * / sin δ (relative to the control) measured at 70 ° C. work well at elevated temperatures with binders containing ester functional regenerant as well It shows what is expected. The results of the test are used to estimate the amount of rut formation expected by the use of a specific binder. The results in Table 3 suggest that binder softening by the rejuvenating agent does not create rutting problems in the ultimate asphalt composition, even on hot summer days.

  In one aspect, the invention relates to a method of regeneration. This method regenerates the recovered asphalt by mixing the recovered asphalt with 0.01 to 10 wt%, preferably 0.025 to 5 wt%, more preferably 0.05 to 2 wt% rosin ester including. Suitable rosin esters are made by esterifying at least one rosin acid with at least one alcohol.

The alcohols suitable for esterification, methanol, ethanol, butanol, C ₁ -C ₁₈ monoalcohols, such as iso-alcohols (such as isodecyl alcohol and 2-ethylhexanol), and diethylene glycol, triethylene glycol, glycerol, pentaerythritol, Included are polyols such as sorbitol, neopentyl glycol and trimethylolpropane. Useful alcohols that are easily obtained include diethylene glycol, triethylene glycol and pentaerythritol.

Rosin acids include monocarboxylic acids having the general formula C ₁₉ H ₂₉ COOH, which have three fused six-carbon rings and contain double bonds of varying numbers and positions. Examples of rosin acids include abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, levopimaric acid, sandaracopimaric acid, isopimaric acid and palustric acid.

  The rosin acid can be used in isolated form or as part of a composition that can include more than one rosin acid. In particular, rosin can be used as a source of rosin acid. Rosin is a hydrocarbon secretion of many plants, especially conifers such as Pinus palustris and Pinus caribaera. Natural rosin typically consists of a mixture of 7 or 8 rosin acids, and other minor components. Rosin is commercially available and can be obtained from pine trees by distillation of oleoresin (distillation residue gum rosin), by extraction of pine stumps (wood rosin), or by tall oil fractionation (tall oil rosin) . Any type of rosin can be used, including tall oil rosin, gum rosin and wood rosin. Tall oil rosin is commonly used because of its availability. Examples of suitable commercially available rosins include tall oil rosins (e.g. Sylvaros (R) 85, Sylvaros (R) 90 or Sylvaros (R) 95 from Arizona Chemical).

  The rosin acid can be modified prior to esterification, for example, by hydrogenation, disproportionation, oligomerization, Diels-Alder reaction, isomerization or a combination thereof. Rosin esters can be modified to form disproportionated rosin esters. For example, dehydroabietic acid may be useful.

  Rosin esters can be obtained from rosin acids and alcohols by methods known in the art (see, eg, US Pat. No. 5,504,152, the teachings of which are incorporated herein by reference). In general, rosin can be esterified by the thermal reaction of rosin acids with alcohols. The water can be removed from the reactor by methods such as distillation, application of vacuum and other methods known to those skilled in the art to drive the esterification reaction to completion.

  Commercially available rosin esters such as Sylvatac® RE103, Sylvatac® RE55, Sylvatac® RE85, Sylvatac® RE12 and Sylvatac® RE5, all from Arizona Chemical; all from Eastman Eastman (R) ester Gum 15D-M, Permalyn (R) 3100, Permalyn (R) 5110-C and Staybelite (R) ester 3-E; all from DRT (Dertores Resiniques & Terpeniques) ) G2L, Dertoline (R) SG2, Dertoline (R) P 05, Dertoline® P110, Dertoline® P2L, Dertoline® PL5, Dertopoline P125, Granolite SG, Granolite P, Granolite P118 and Granolite TEG; and NovaRes® 1100 from Georgia Pacific etc. Can also be used.

  The rosin ester may contain some residual unreacted acid and alcohol. Typically, the rosin ester has an acid number of less than 20 mg KOH / g, in particular less than 15 mg KOH / g. The acid number can be measured by methods known to those skilled in the art, such as ASTM D 974 standard method using color indicator titration.

Suitable rosin esters are liquid rosin esters or may be solid rosin esters having a softening point between 30-120 ° C, 30-80 ° C, or 40-60 ° C. The softening point can be measured by methods known to those skilled in the art, for example, the ASTM 28-99 standard method using a method known as the “ring and ball” method. Suitable rosin esters include tall oil rosin esters, gum rosin esters and wood rosin esters. Several alcohols and glycols are suitable for reacting with one or more rosins, including C ₈ -C ₁₁ alkyl and isoalkyl alcohols and glycols, pentaerythritol, glycerol, triethylene glycol, diethylene glycol. The result Suitable rosin esters obtained, for example, pentaerythritol rosin esters, glycerol rosin esters, triethylene glycol, diethylene glycol rosin esters, at least one C ₈ -C ₁₁ isoalkyl rosin esters, and mixtures thereof. In particular, the rosin ester can be a mixture of diethylene glycol rosin ester, triethylene glycol rosin ester and pentaerythritol rosin ester.

The amount of rosin ester in the asphalt composition can be adjusted relative to the amount of binder present in the recovered asphalt. The amount of rosin ester is, for example, 1 to 10% by weight, or 2.5 to 7.5% by weight, or 3 to 6% by weight of the total amount of binder present in the recovered asphalt
It can be done. Higher or lower amounts of rosin ester relative to the amount of binder present in the RAP can also be used. In general, relative amounts of less than 1% by weight can still bring about a regenerative effect, even to a lower extent. On the other hand, the use of relative amounts above 10% by weight has a negative effect on the performance of the final RAP-containing asphalt composition, even though the use of such higher amounts does not significantly enhance regeneration. There is nothing to do.

  The amount of binder in the recovered asphalt composition is generally known from the supplier, but can also be determined by methods known to those skilled in the art. For example, known amounts of RAP can be treated with a suitable solvent such as dichloromethane to extract the binding agent. The weight of binder in the extract fraction can be measured, thereby determining the binder content in RAP. The amount of binder in RAP is usually 1 to 10% by weight, specifically 2.5 to 8.5% by weight, more specifically 4 to 7.5% by weight, based on the total weight of RAP. It may be a range.

  In one aspect, the invention relates to an asphalt composition comprising 0.01 to 10 wt%, preferably 0.025 to 5 wt% rosin ester and at least 15 wt% recovered asphalt. The rosin ester is the reaction product of tall oil rosin and a polyol selected from the group consisting of diethylene glycol, triethylene glycol, glycerol, pentaerythritol and mixtures thereof. The asphalt composition preferably further comprises additional binders and / or aggregates. The recovered asphalt is preferably RAP. The inventors have found that rosin esters made from tall oil rosin and a combination of polyols have an advantageous overall property balance. In particular, see Rosin Ester L, Example 64 in Table 7 below. When used as a rejuvenating agent, this product has a beneficial effect on the ring and ball softening point and glass transition temperature of the binder as well as on the rheological properties including storage modulus and loss modulus.

  In another aspect, the invention relates to an asphalt composition comprising an ester functional rejuvenating agent and at least 15% by weight of recovered asphalt comprising an oxidation binder. The rejuvenating agent is present in an amount ranging from 1 to 10% by weight, preferably 3 to 8% by weight, more preferably 4 to 6% by weight, based on the combined amount of the oxidizing binder and the regenerating agent. Furthermore, the mixture of oxidative binder and rejuvenating agent forms a regenerative binder having a ring and ball softening point according to EN 1427 below 60 ° C. and a penetration value according to EN 1426 over 20 dmm.

  Suitable ester functional rejuvenating agents have already been described. Particularly preferred rejuvenating agents are trimethylolpropane tartrate, ethylene glycol monomelate, neopentyl glycol monomelate, 2-ethylhexyl monomelate and glycerol monomelate. Ethylene glycol monomethylate and trimethylolpropane (TMP) tartrate are particularly preferred (see Tables 8-18 below).

  Certain rosin esters, rosin acids, or mixtures thereof are also suitable. In one aspect, the rejuvenating agent comprises a rosin ester having a ring and ball softening point according to EN 1427 less than 50 ° C. In another embodiment, the regenerant comprises a fatty acid ester, vegetable oil, or petroleum flux oil in addition to rosin ester, rosin acid or mixtures thereof (see Tables 13-14 below). We have surprisingly found that a regenerated binder comprising rosin ester, rosin acid, or a mixture thereof is similar to that of a regenerated binder produced without rosin acid, rosin ester or a mixture thereof. It has been found that it may have a reduced temperature sensitivity as compared to the temperature sensitivity (see Table 14).

Inclusion of the regenerant in the recovered asphalt can facilitate handling of the asphalt composition in one or more factory operations. Thus, in one aspect, the rejuvenating agent reduces the temperature required to mix at a viscosity of 200 mPa / s or less by at least 5 ° C., preferably at least 10 ° C. If a high temperature is required to reach a viscosity of 200 mPa / s, the process can be cost effective because it consumes too much energy. Therefore, it is valuable to reduce any temperature required to reach a reasonable viscosity for mixing. In another aspect, the rejuvenating agent reduces the temperature necessary to consolidate at a viscosity of 3000 mPa / s or less by at least 5 ° C, preferably at least 10 ° C. If a high temperature is required to reach a viscosity of 3000 mPa / s, the process can be cost inefficient as it consumes too much energy. Therefore, it is valuable to reduce any temperature needed to reach a reasonable viscosity for consolidation. As shown in Table 10, ester functional rejuvenating agents are effective to reduce the minimum temperature required for both mixing and consolidation.

  In another aspect, the invention relates to a regenerative binder. The regenerative binder comprises an oxidative binder and an ester functional regenerative agent. The rejuvenating agent is present in an amount ranging from 1 to 10% by weight based on the combined amount of the oxidizing binder and the rejuvenating agent. The regenerative binder has a ring and ball softening point with EN 1427 of less than 60 ° C. and a penetration value with EN 1426 of more than 20 dmm. Suitable regenerating agents have already been described. Particularly preferred regenerants are trimethylolpropane taleate, ethylene glycol monomaleate, neopentyl glycol monomaleate, 2-ethylhexyl monomaleate and glycerin monomaleate, especially ethylene glycol monomaleate and trimethylolpropane (TMP) tartrate. It is.

The preferred regenerative binder achieves a 1.0 J / cm ² forced ductility at any temperature within the range of 15 ° C. to 25 ° C. as measured by AASHTO T-300. Also particularly preferred are regenerated binders having a ring and ball softening point less than 60 ° C. (see Table 15 and the further discussion below).

  Preferred binders actually demonstrate stability when subjected to short-term aging by the rotating thin film oven (RTFO) test according to EN 12607-1 and long-term aging by the pressurized aging vessel (PAV) test according to EN 14769. Show. As shown in Table 18, the regenerated binder of the present invention is stable when exposed to laboratory conditions designed to simulate short or long-term aging of asphalt compositions.

  The present invention comprises the use for the asphalt composition or binder of the present invention. Asphalt compositions and binders can be used, for example, for paved surfaces, road surfaces and lower surfaces, shoulders, bridges, abutments, gravel substitutes for unpaved roads, and the like. In one aspect, the invention relates to a pavement comprising the asphalt or binder composition of the invention.

The following examples merely illustrate the invention; those skilled in the art will recognize numerous variations that are within the spirit of the invention and scope of the claims.
Part 1: Evaluation of ester functional regenerant in recovered pavement asphalt: Reducing Tg onset temperature in oxidized binders Method for preparing RAP binder using regenerant RAP in 18.1 kg (40 lb) bag receive. Remove material from bag and air dry until no visible moisture remains. Divide the materials into different sizes: large, medium and fine using a sieve bed with multiple wire gauges.

The material classified as "large" is placed in a large frit column equipped with glass wool used as primary filtration. Toluene / ethanol (85:15) is poured onto the RAP and allowed to stand until gravity filtration is complete. This process is repeated several times until the solvent blend is almost colorless and clear. After the “medium” and “fine” materials are placed in a large Erlenmeyer flask, the same solvent blend is added to a certain level. Stir ingredients and decant the resulting solvent / asphalt mix. This process is again repeated to the same goal.

  The combined extract is placed in a 18.9 l (5 gallon) container and allowed to settle for 24 hours to settle mud / rock fines. Carefully decant the material with a medium grade filter (Whatman # 4). The filtrate is charged batchwise to a 5 L flask and the solvent is stripped under vacuum while warming to 40-50 ° C. Continue to concentrate until the material reaches the target of -20-25% solids. Combine all the concentrated material into a single container, recover the solvent and recycle.

  Charge the concentrated material to a 50 mL round bottom flask at a target of 2 g using solid content as a guideline. The additive to be evaluated is diluted with toluene to a minimum of 50% and a total addition of 0.2 g is charged to the same round bottom. The solution is then stripped under vacuum for 0.5 hours using a 150 ° C. oil bath. The concentrated product is kept under nitrogen purge until cooling.

Differential Scanning Calorimetry (DSC) Analysis of the Sample Differential Scanning Calorimetric Analysis, under the following conditions: sample weight: 4 to 6 mg RAP; sample container: TA Inc. Standard aluminum pans and lids (TA Inc. part numbers 900786.901 and 900779.901); Purge instrument: Thermal Analysis Inc. using nitrogen, 50 mL / min. Performed on model Q2000 equipment.

  Temperature program: The metric for Tg is applied to the data from segment (23) of the following method log: (1) sampling interval 0.60 sec / pt; (2) zero heat flow at 0.0 ° C .; (3) Equilibrate at 165.00 ° C; (4) Data storage off; (5) 5.00 minutes isothermal; (6) Cycle 1 end mark; (7) Data storage on; (8)-45.00 (9) Data storage off; (10) 5.00 minutes isothermal; (11) Cycle 2 end mark; (12) Data storage on; (13) 165. (14) Data storage off; (15) 5.00 minutes isothermal; (16) Cycle 3 end mark; (17) Data storage on; (18)- Up to 85.00 ° C 5.00 (19) Data storage off; (20) 5.00 minutes isothermal; (21) Cycle 4 end mark; (22) Data storage on; (23) 15.00 to 15.00 ° C ° C / min slope; (24) cycle 5 end mark; (25) end of method.

  Curves are generated by plotting heat flow (W / g) as a function of temperature (° C) over the range -80 ° C to 80 ° C. The inflection point representing the onset of glass transition and the end point of glass transition is entered, and the midpoint is determined. "Spread" is the difference between the temperature at the end of the glass transition and the onset temperature of the glass transition. Thus, for samples with an onset Tg at -36 ° C and an end point at 10 ° C, the spread is reported as 46 ° C. The starting Δ and spread Δ (each at ° C.) values for each sample are reported as compared to the average values obtained for multiple runs of the oxidized asphalt binder control sample. Test samples contain 90% by weight oxidized asphalt binder and 10% by weight potential regenerant additive unless otherwise indicated in Tables 1 and 2.

  If the onset of glass transition can be reduced by at least 5 ° C., a fairly significant effect on the low temperature properties of RAP is expected, and Examples 1-12 (Table 1) and Examples 27-63 (Table 2) each meet this requirement. . The main component of commercial regenerant, Rheofalt® distillate (cardanol), ie long chain alkylated phenol, is provided for comparison.

The reduction in fatigue cracking is usually inferred from the improvement in uniformity that correlates with the narrower spread of the glass transition temperature. Thus, improvement in fatigue cracking may result from narrowing the Tg spread by at least 5 ° C. as compared to the control sample. The large number of samples reported in Tables 1 and 2 still satisfy this test and are considered more preferred.

Evaluation of low, medium and high temperature performance of RAP binder regenerant by dynamic shear viscoelasticity measurement (DSR) A sample of RAP binder containing 10 wt% of regenerants A-G prepared as described above, Submitted to an independent laboratory to evaluate low, medium, and high temperature performance using dynamic shear viscoelasticity measurement (DSR). Each sample, except sample E, is found to be significantly softened by the regenerant. Rheological properties are used to evaluate the regenerated product for use on RAP rich hot and warm mixed asphalts.

  The dynamic shear modulus is measured using a parallel plate structure 4 mm in diameter with a Malvern Kinexus® rotary dynamic shear viscoelasticity tester. Perform a frequency sweep at 15 ° C intervals over a temperature range of -30 ° C to 60 ° C and an angular frequency range of 0.1 to 100 radians / sec (in some cases using 0.1 to 50 radians / sec) .

  The control sample is an extracted binder without added regenerant. A stress sweep is performed before each frequency sweep to ensure low strain levels and to ensure that the test results are within the linear visco-elastic range.

Master curves for high temperature (70 ° C.) and in some cases low temperature (−15 ° C.) performance parameters, such as G * / sin δ, are described in Christensen Anderson (CA) model (D.W. Christensen et al., J. Assoc. Asphalt. Paving
Technologies, 61 (1992) 67) are extrapolated. The CA model relates the frequency dependence of complex modulus to the glass modulus (G _g ), the crossover frequency (ω _c ) and the rheological index (R). The form of the mathematical function is

It is.

Christensen approximation (Christensen, RM, Theory)
of Viscoelasticity (1971) Academic Press, New York) is used to create a G (t) master curve by interconverting storage modulus (G ′ (ω)).

1. Low temperature properties Low temperature properties are measured using a 4 mm plate visco-elasticity measurement method. Correlation developed by Sui et al. ("A New Low-Performance Methodology using 4-mm Parallel Plates on a DSR") by m-value and creep stiffness (S (t)) measured by a bending beam viscoelasticity meter (BBR) , Transportation Research Record 2207 (2011) 43-48.).

  The m-value is the slope of the performance grade temperature at 60 seconds plus the creep stiffness curve at 10 ° C. This is an indicator of the asphalt's ability to relieve stress. A minimum m-value of 0.3 is usually specified for laboratory RTFO / PAV (rotary thin-film oven / pressure aged vessel) aged asphalt. The creep stiffness is used to assess the potential for high thermal stress development. A higher creep stiffness value indicates a higher latent thermal stress generation in the pavement and usually specifies a maximum value of 300 MPa. The creep stiffness is measured as m-value at the same time and temperature. The results of test samples A to G are in Table 3.

2. Medium Temperature Properties The fatigue crack resistance of RTFO / PAV aged asphalt binders is usually evaluated using G * sin δ (fatigue factor). G * represents the complex shear modulus of the binder and δ represents the phase angle. G * approximates the stiffness and δ approximates the viscoelastic response of the binder. Binder purchase specifications generally require that the factor be less than 5 MPa. The factor is considered to be a measure of energy dissipation related to fatigue damage. The critical temperature range for fatigue damage is close to an intermediate temperature between the maximum service temperature and the minimum service temperature. A test temperature of 25 ° C. is used. The results of test samples A to G are in Table 3.

3. High temperature properties High temperature mechanical properties are evaluated by the parameter G * / sinδ. This factor is an indicator of the rutability of the binder. Binder purchase specifications usually require this factor to be greater than 2.2 kPa for RTFO aged asphalt. In all of the test samples, G * / sin δ decreases significantly with the addition of the regenerant.

  As shown in Table 3, Samples A, B, C, and F show the greatest improvement in m-value, which is the ability of the material to mitigate and prevent thermal stress generation that may lead to thermal cracking. Directly related to improvement. G * sin δ provides an indicator of fatigue performance. Samples F (glycerine monomelate) and A (EG monomelate) dominate as the highest ranks in terms of both (m-value) and (G * sin δ) improvement. Samples B, C and D are somewhat effective. Comparative examples G (return neutral from sterols) and E (terpene phenol) are ranked at the bottom, with E being particularly ineffective.

Part 2: Evaluation of Rosin Esters as Regeneration Preparation of Rosin Ester H A 1 L flask fitted with a thermometer, overhead stirrer, nitrogen purge line, Dean-Stark trap, cooler, collection vessel and sampling port, rosin A combination of pentaerythritol monoester and glycerol monoester of rosin (acid number: 107 mg KOH / g, 83.5 g in total) is charged. The two monoesters are heated to 200 ° C. 4,4′-thiobis (2-tert-butyl-5-methylphenol) (0.1 g) and magnesium acetate (0.2 g) sufficient to ensure that the temperature does not drop above about 3 ° C. Add at a slow rate. Then triethylene glycol (16.2 g) is added at a slow enough rate to ensure that the temperature does not drop above about 3 ° C. The temperature is increased at a rate of 10-15 ° C. per hour to a temperature between 270-280 ° C. The acid value is checked as a control measurement. The reaction is continued until an acid number specification of 20 mg KOH / g is met. A vacuum is applied to remove the light oil, ie the monoesterified by-product. After removal of the light oil, rosin ester H is obtained, which has a maximum viscosity of 6000 mPa.s at 40 ° C. have s.
Preparation of Rosin Ester J The above-mentioned apparatus is charged with tall oil rosin (Sylvaros® 90 from Arizona Chemical, softening point 66 ° C., acid number 171 mg KOH / g, 11.3 g). The rosin is heated to 160 ° C. and stirred once the rosin has melted enough for the stirrer to rotate. Add fumaric acid (5 g) at a slow enough rate to ensure that the temperature does not drop above about 3 ° C. The reactor temperature is then raised to 200 ° C. and held at this temperature for 3 hours. Cool the reactor to 160 ° C. Add iodine (0.38 g) at a rate to ensure that the temperature does not drop above 3 ° C. Hold the temperature at 160 ° C. for 1 hour. Pentaerythritol (5 g) is added and the temperature is raised at a rate of 10-15 ° C. per hour to 250 ° C. The reactor temperature is held at 250 ° C. for 4 hours. After 2 hours, the temperature drops to 220 ° C. and triethanolamine (1.22 g) is added. Hold the temperature at 220 ° C. for 1 hour. The reaction is continued until the product rosin ester J has an acid value of 120 mg KOH / g and a softening point of 53 ° C.
Preparation of Rosin Ester K To a conventional apparatus is charged tall oil rosin (Sylvaros® 90, 95 g). The reactor is heated to 180 ° C. and heated until the rosin is fully melted and stirring is possible. 4,4′-thiobis (2-tert-butyl-5-methylphenol) (0.1 g) and magnesium acetate (0.13 g) sufficient to ensure that the temperature does not drop above 3 ° C. Add at a slow rate. Triethylene glycol (12.8 g) and diethylene glycol (13.7 g) are added at a slow rate sufficient to ensure that the temperature does not drop above 3 ° C. The reactor temperature is held at about 160 ° C. for 1 hour, then raised to a temperature between 270-280 ° C. at a rate of 10-15 ° C. per hour. The product, rosin ester K, has an acid number <25 mg KOH / g and a maximum viscosity of 2000 mPa.s at 60 ° C. The reaction is continued until it has s.
Preparation of Rosin Ester L A conventional apparatus is charged with rosin ester J (10.5 g), rosin ester K (8.4 g), and triethylene glycol dibenzoate (2.1 g). The mixture is stirred and heated to 160 ° C. When the temperature is reached, the mixture is held for 2 hours and then cooled. The final rosin ester blend, rosin ester L, has an acid value of 70 mg KOH / g and a viscosity at 60 ° C. of 2500 mPa.s. have s.

  The acid number is measured by ASTM D465. A sample of known weight is dissolved in isopropyl alcohol. The solution is then titrated with an alcohol solution of potassium hydroxide. The acid number corresponds to the amount of potassium hydroxide used to neutralize the measured amount of sample (generally expressed in milligrams of potassium hydroxide per gram of sample: mg KOH / g).

  Viscosity is measured according to ASTM D2196 and a Brookfield apparatus is used to provide rotational viscosity measurements.

The softening point is measured by the ring and ball method (ASTM E28-99). A sample of the product is poured into the metal ring while still warm and then cooled. Clean the ring in such a way as to fit the material into the ring, place a steel ball and place it on top of the ring. The rings and spheres are submerged in a beaker containing water and the water is heated at 5 ° C. per minute with stirring. The water temperature is recorded as the ball is completely dropped through the ring. Temperature values are reported as ring and ball softening points.
Preparation of test samples: Bitumen from RAP is prepared by washing RAP (from BAM Wegen, The Netherlands) with dichloromethane. The extracted bitumen is dried by evaporation of dichloromethane.

  The compositions of Examples 64-67 of Table 4 and Comparative Examples 70 and 71 are prepared as follows: bitumen (19.95 g) from RAP and virgin bitumen (PEN 40/60, Total, 9 g from The Netherlands) ) And heat to 100 ° C. in a 50 mL beaker. The additives (1.05 g) are then combined thoroughly. The temperature is maintained at 100 ° C. for 30 minutes and then the mixture is cooled.

Control compositions without additives were similarly prepared from PEN 40/60 (30 g) for Comparative Example 68 and from a mixture of RAP-derived bitumen (21 g) and PEN 40/60 (9 g) for Comparative Example 69. Is done.
Measurements and Results Samples of the respective bituminous compositions are taken to determine the ring and ball softening point, the glass transition temperature and the rheological profile (Tables 4, 5 and 6).

  The ring and ball softening point is measured in water by the ring and ball method (ASTM E28-99) described above for rosin esters. The temperature values are reported in Table 4 as ring and ball softening points. The bitumen ring and ball softening point is an indicator of the stiffness of the asphalt in which the bitumen is used.

The glass transition temperature (Tg) is measured with a differential scanning calorimetry (DSC) instrument from Mettler with the following parameters:
-Gas: nitrogen 65 mL / min,
-Dish: Standard aluminum 40 μL dish with small holes on the lid,
Temperature: 25.0 ° C. to −60.0 ° C. at a rate of 10 ° C. per minute, and −60.0 ° C. to 25.0 ° C. at a rate of 10 ° C. per minute.

  The glass transition temperature of bitumen is an indicator of the brittleness of asphalt in which bitumen is used.

The storage and loss moduli of the bitumen sample are measured by the Anton Paar physical rheometer MCR101. A temperature profile of -20 DEG C. to 80 DEG C. at a rate of 5 DEG C. per minute is used. The distortion is set to 0.1% by the frequency 1.592 s ⁻¹ . The spindle used is PP25mm with 1mm gap and Peltier plate. The normal force is set to 0N.

  The visco-elastic behavior of bitumen at temperatures below 15 ° C. is an indicator of the cracking tendency of asphalt containing bitumen at low temperatures. Viscoelastic behavior can be expressed in terms of storage modulus and loss modulus. The lower the storage and loss moduli, the lower the tendency to crack.

  Table 7 shows the respective additives used for virgin bitumen (comparative example 68), ie a sample having target performance, and a mixture of virgin bitumen and RAP derived bitumen (comparative example 69), ie a sample having performance before improvement Is a summary of the performance of A negative sign (-) indicates no improvement or no significant improvement with respect to Comparative Example 69, and a positive sign (+) indicates an improvement. The greater the number of plus signs, the greater the improvement. N. a. Indicates that the corresponding data is not available.

As can be seen from the results provided in Tables 4-7, the rosin ester (Examples 64-67) acts as a regenerant that restores at least some of the properties lost during the aging process. In particular, the softening point and the glass transition temperature are modified for all of them. Rosin ester L (Example 64) also modifies the storage and loss moduli at most of the measured temperatures (see Tables 5 and 6).

  Palm oil is described in US 2010/0041798 to act as a regenerating agent. However, no significant modification was observed for the composition containing palm oil as an additive (Comparative Example 70).

Alkyl-substituted phenols are described in WO 2010/077141 as acting as regenerants. The C ₁₅ -alkyl m-substituted phenol of Comparative Example 71, ie a phenol having an alkyl group having 15 carbon atoms in the meta-position to the hydroxyl group, is obtained, for example, from Rheofalt® HCP-22 (Ventraco, The Netherlands) ), Which provides improved softening point and glass transition temperature. This additive is also seen to improve loss modulus and storage modulus for some test temperatures.

Part 3: Additional evaluation of ester functional regenerants Several ester functional regenerants, in particular ethylene glycol (EG) monomethylate, trimethylolpropane (TMP) tartrate, and ring balls at about 5, 25, 40 and 55 ° C., respectively. Further evaluate Sylvatac® rosin esters RE5, RE25, RE40 and RE55, which are products of Arizona Chemical having a formula softening point.

  The binders tested are oxidized binders ("RA") recovered from recovered asphalt or laboratory aged binders ("AB").

An aged binder is prepared in two steps. The first step is the rotary thin film oven (RTFO) test, which is performed according to EN 12607-1. This reflects the short-term aging normally performed during asphalt manufacturing, transportation, and laying. The RTFO test requires heating the binder at 163 ° C. for 50 minutes in a glass cylinder on a rotary conveyor in an air-blowing oven. After the test, the mass loss is recorded and the binder properties are measured.

  The second stage is the pressure aging vessel (PAV) test according to EN 14769. In the PAV test, the binder sample is heated in an oven at 90-110 ° C. for 20 hours under a pressure of 2.07 MPa.

  In one study, the basic properties of the regenerative binder are investigated. The ring and ball softening point of the binder measured by EN 1427 reflects the consistency of the high temperature binder. The higher the softening point, the more heat required to soften or induce flow. The penetration value at 25 ° C. of the binder measured by EN 1426 reflects the consistency of the binder at ambient temperature. Higher values correspond to softer binders. The viscosities at 90, 135, 150 and 180 ° C. are measured according to EN 13302. The results show the ease of storing, pumping, mixing, compacting, laying or handling asphalt in daily operation. Penetration Index (PI) quantifies how asphalt consistency changes with temperature. this is,

Where Pen is the penetration value at 25 ° C. and T is the ring and ball softening temperature (in ° C.). Unused binders usually have a negative PI, but oxidation tends to push PI to a positive value. Therefore, negative values of PI are more desirable.

  Table 8 summarizes the results from this study. Ideally, the rejuvenating agent restores the properties of the oxidative binder so that the oxidative binder performs more like a virgin binder. Therefore, the softening point of the regenerant should be less than 60 ° C. and the penetration value of the regenerant at 25 ° C. should be at least 20 dmm. As indicated in the table, TMP Talate effectively achieves these results with only 5% by weight based on the combined amount of aged binder and TMP Talate. Liquid or lower melting rosin esters, Sylvatac® RE 5 and Sylvatac® RE 25, also require somewhat higher levels (about 10% by weight) to obtain optimum results, but the regeneration effect Have. Interestingly, Sylvatac® RE 55, a rosin ester with a higher softening point, is not effective in restoring the basic properties of aging binders to those found in virgin binders.

  Table 9 summarizes the results of experiments conducted to determine the amount of rejuvenating agent needed to achieve the desired softening while maintaining an acceptably low penetration value. For EG Monomerate and TMP Talate, Penetration value at 25 ° C comparable to that of virgin binder 35/50, while the softening point reaches the desired value <60 ° C with about 4 to 5% by weight of regenerant Maintain. In contrast, Sylvatac® RE55 does not restore these properties of oxidized binders even with 10 wt% additive.

  The viscosity curve for the regenerative binder helps to identify the ability of the regenerant to facilitate asphalt compaction, mixing, and other handling characteristics. Table 10 shows that the minimum temperature at which the viscosity is suitable for compaction (<3000 mPa · s) can be reduced as much as 20 ° C. by combining the oxidative binder with the ester functional regenerant. Furthermore, the minimum temperature at which the viscosity is suitable for mixing (<200 mPa · s) can also be reduced by 20 ° C.

  In the United States in particular, dynamic shear visco-elastic measurements (DSR) are used to assess the asphalt product at low, ambient, and elevated temperatures to test expected performance. At low temperatures (e.g. -10 <0> C), the road surface needs to be crack resistant. Under ambient temperature, stiffness and fatigue properties are important. At elevated temperatures, the road should be ruth-proof if the asphalt becomes too soft. Standards were established by the asphalt industry to identify binder rheological properties that correlate with the expected pavement surface properties over three common sets of temperature conditions.

Therefore, at low temperatures, the complex modulus (G *) of the regenerated binder measured at −10 ° C. should be less than or equal to the value for the unused binder. For 30/50 grade virgin binders, G * at -10 ° C. is ideally less than or equal to 2.8 × 10 ⁸ Pa (see Table 11). Oxidized binders are not dramatically different in this property from virgin binders, and the low temperature criterion is met with 1% by weight of EG monomerate or TMP tartrate (but results with Sylvatac® RE55) See, this does not improve this parameter even at 10 wt%).

At ambient temperature, the complex modulus of the regenerated binder should be less than or equal to the value for the unused binder. For 30/50 grade virgin binder, G * at 20 ° C. is ideally less than or equal to 6.0 × 10 ⁶ Pa. This stiffness criterion can be met with about 4% by weight of EG monomer or TMP tarate (Table 11). Again, Sylvatac® RE55 does not improve this parameter even at 10% by weight.

  Fatigue criteria are also associated with ambient temperature performance. The product of the complex modulus (G *) and the sine of the phase angle (δ) measured at 10 rad / s is determined. The temperature at which the value of G * sin δ at 10 rad / s is equal to 5000 MPa should be below 20 ° C. comparable to the 35/50 grade virgin binder in the regenerated binder. As shown in Table 12, fatigue criteria can be satisfied when using at least about 4% by weight EG Monomerate or TMP Talate, but Sylvatac® RE 55 is totally against oxidation binders. Does not bring about improvement.

  At high temperatures, the quotient G * / sin δ is important. The temperature at which G * / sin δ at 10 rad / s equals 1000 Pa should be reduced with the regenerated binder as compared to the aged binder. For a 30/50 grade virgin binder, the temperature at which G * / sin δ at 10 rad / s equals 1000 Pa is approximately 70 ° C. (see Table 12). High temperature standards are generally satisfied with up to about 10% by weight ester functional regenerant.

In another rheological test, we generated a master curve for G ^* that occurred at 20 ° C. from an isothermal frequency sweep (Table 13). When we compare results from test binders regenerated with petroleum flux oil, vegetable oil, fatty acid ester, cardanol and rosin ester, especially when analyzing data comparing high temperature and fatigue criteria, the present invention They noticed some interesting behaviors.

  All of these rejuvenating agents soften the aging binder to some extent, some at the same dose than others at the same dose. Thus, vegetable oils and fatty acid esters provide a high degree of softening while petroleum flux oils and cardanol do so to a lesser extent. In contrast, cyclic esters such as rosin esters do not soften very effectively.

  Moreover, while oxidative and virgin binders have fatigue properties that are relatively insensitive to temperature, most rejuvenating agents tend to make regenerated binders more temperature sensitive. Ideally, the regenerative binder will behave more like the virgin binder, ie it will be preferable that the regenerative binder be less sensitive to temperature.

  Surprisingly, we have found that regenerative binders containing cyclic compounds such as rosin esters, rosin acids or mixtures thereof are relatively resistant to temperature changes, similar to oxidized or unused binders. It was found to have acceptable fatigue properties. However, it is preferred to combine those cyclic compounds with other regenerants such as fatty acid esters or vegetable oils, as cyclic compounds usually lack the ability to impart sufficient softening. Thus, the use of rosin esters, rosin acids or mixtures thereof in combination with other rejuvenating agents, while softening the binder, desirably maintains low temperature sensitivity. See Table 14.

Table 15 summarizes the results of the ductility study. In general, forced ductility is related to the energy required to stretch a binder sample 200 or 400 mm at a given temperature and is a measure of strength and flexibility. Lower energy corresponds to a larger flexible sample. Ductility is related to stretching at break at a given temperature, usually 5 ° C. (for softer binders) or 15 ° C. Larger stretches are better than usual. In these experiments, TMP tarate, Sylvatac® RE5 (liquid) and Sylvatac® RE40 (softening point about 40 ° C.) are compared. Forced ductility is measured at three temperatures for each sample. The test method used is AASHTO T-300.

In general, regenerants restore at least some of the ductility that unused binders lose during aging. Comparing the results in Table 15, TMP tarate (5 wt%) and Sylvatac® RE5 (10 wt%) are better than Sylvatac® RE40 (5 wt%) Sylvatac® Works better than RE5 (5 wt%). It is useful to compare the results at baseline energy levels such as 1 J / cm ² to determine the temperature at which this forced ductility value is achieved. As shown in the table, this value is 28 ° C. for the aging binder and 17 ° C. for the unused binder. The regenerant helps the binder compare to the target value of 17 ° C.

  Table 16 provides the results of the turn consolidation survey (according to EN 12697-31). In that study, 75% by weight recovered paving asphalt (RAP) is combined with virgin binder and aggregate with or without rejuvenating agent. The use of TMP tartrate at 6% by weight with respect to the amount of oxidation binder present in RAP. The results after 10 turns show how well the mixing was done. The void content after 60 or 100 revolutions is also important. The consolidation survey ends after 200 turns. In general, the inventors have found that using RAP makes it easier to achieve a low void content compared to a control mixture without RAP. In addition, when TMP Talate is included as a rejuvenating agent, the void content desirably remains low. ASTM D6925 can also be used.

  Also, the water sensitivity according to EN 12697-12 is evaluated for asphalt mixtures containing 75% by weight RAP. The results are in Table 17. Compared to the control mixture, the wet to dry ratio of indirect tensile strength (wet ITS / dry ITS) decreases with RAP, which indicates that the water sensitivity is significant. However, the inclusion of 6% by weight of TMP Talate makes the RAP-containing mixture behave more like the control, ie it reduces the water sensitivity of the asphalt mixture.

  The laboratory method used to age the binder to behave more like the oxidative binder found in recovered asphalt has already been discussed. As described, the RTFO test, or rotating thin film oven test, is used to assess short-term aging effects, and the PAV (Pressure Aging Bessel) test assesses long-term aging.

Table 18 compares the basic properties of the regenerated binder before and after aging using RTFO test followed by PAV test first. In all cases of the regenerative binder, the cumulative mass loss is about 1% by weight
The following is consistent with the results obtained using virgin binder. Thus, there is no detrimental effect on mass loss when using a regenerant.

  Following the aging step, all ring and ball softening points of the test binders are increased somewhat. However, the overall increase (see fairly right column, ΔR & B) is consistent with the increase seen with virgin binder. In other words, ester functional rejuvenating agents do not appear to accelerate short or long term aging of the binder. Likewise, penetration values are not adversely affected by aging. Rather, a greater percentage of the binder's original penetration value is maintained when regenerant is present when compared to the unused binder (compare Ret.Pen.% Values on the far right of Table 18). I want to be

The previous examples are for illustrative purposes only; the following claims define the scope of the present invention.
Specific embodiments of the present invention are as follows.
[1]
Recovery asphalt and ester functional regenerating agent, wherein the recovery asphalt includes aggregate and oxidized asphalt binder, wherein the regenerating agent is compared to the glass transition onset temperature of the oxidized asphalt binder without regeneration agent An asphalt composition present in an amount effective to reduce the glass transition onset temperature of the oxidized asphalt binder by at least 5 ° C.
[2]
The composition according to [1], further comprising 1 to 99% by weight of an unused binder based on the combined amount of the unused binder and the oxidized asphalt binder.
[3]
The composition according to [1], comprising 0.1 to 15% by weight of regenerant based on the combined amount of the oxidized asphalt binder and the regenerant.
[4]
The composition according to [1], wherein the regenerating agent is derived from a C _{1 to} C ₁₈ monool, diol or triol, and a C _{8 to} C ₂₀ fatty acid or a dimer acid thereof.
[5]
The composition according to [1], wherein the rejuvenating agent is present in an amount effective to reduce the glass transition onset temperature of the oxidized asphalt binder by at least 10 ° C.
[6]
[1] The regenerant is present in an amount effective to narrow the glass transition temperature broadening of the oxidized asphalt binder by at least 5 ° C. compared to the glass transition temperature broadening without the regenerant. Composition of
[7]
The composition according to [1], wherein the rejuvenating agent is selected from the group consisting of trimethylol propanetalate, ethylene glycol monomelate, neopentyl glycol monomelate, 2-ethylhexyl monomelate and glycerin monomelate.
[8]
The regenerating agent is an ester derived from tall oil fatty acid, monomeric acid, dimer acid, stearic acid, isostearic acid, 12-hydroxystearic acid, ricinoleic acid, azelaic acid, caprylic acid or benzoic acid, according to [1]. Composition.
[9]
(A) an oxidized asphalt binder;
(B) 0.1 to 15% by weight of an ester functional regenerant based on the combined amount of the oxidized asphalt binder and the regenerant,
Along with the recovered asphalt, the regenerant is present in an amount effective to reduce the glass transition onset temperature of the oxidized asphalt binder by at least 5 ° C compared to the glass transition onset temperature of the oxidized asphalt binder without regenerant. Regenerative binder suitable for use in.
[10]
The binder according to [9], further comprising 1 to 99% by weight of an unused binder based on the combined amount of the unused binder and the oxidized asphalt binder.
[11]
The binder according to [9], comprising 0.5 to 10% by weight of a regenerant.
[12]
The binder according to [9], wherein the regenerating agent is derived from a C _{1 to} C ₁₈ monool, diol or triol and a C _{8 to} C ₂₀ fatty acid or a dimer acid thereof.
[13]
Combining the recovered asphalt with the ester functional rejuvenating agent, wherein the recovered asphalt comprises aggregate and oxidized asphalt binder, wherein the rejuvenating agent is compared to the glass transition onset temperature of the oxidized asphalt binder without the regenerated agent. A process used in an amount effective to reduce the glass transition onset temperature of the oxidized asphalt binder by at least 5 ° C.
[14]
The method according to [13], wherein the recovered asphalt, the regenerant or a mixture thereof is combined with 1 to 99% by weight of the unused binder with respect to the combined amount of the unused binder and the oxidized asphalt binder.
[15]
The method of [13], wherein the recovered asphalt, regenerant or mixture thereof is combined with 30 to 70% by weight of unused binder, based on the combined amount of unused binder and oxidized asphalt binder.
[16]
The method according to [13], wherein 0.1 to 15% by weight of regenerant is used, based on the combined amount of oxidized asphalt binder and regenerant.
[17]
The method according to [13], wherein the rejuvenating agent is used in an amount effective to reduce the glass transition onset temperature of the oxidized asphalt binder by at least 10 ° C.
[18]
The method according to [13], wherein the rejuvenating agent is used in an amount effective to narrow the spread of the glass transition temperature of the oxidized asphalt binder by at least 5 ° C.
[19]
The method according to [13], wherein the rejuvenating agent is selected from the group consisting of trimethylol propanetalate, ethylene glycol monomelate, neopentyl glycol monomelate, 2-ethylhexyl monomelate and glycerin monomelate.
[20]
Combining a binder composition comprising an oxidized asphalt binder with an ester functional regenerant, wherein the regenerant is compared to the glass transition onset temperature of the oxidized asphalt binder without the regenerant. A method used in an amount effective to reduce the transition onset temperature by at least 5 ° C.
[21]
An asphalt composition comprising 0.01 to 10 wt% rosin ester and at least 15 wt% recovered asphalt, wherein the rosin ester is tall oil rosin or tall oil and diethylene glycol, triethylene glycol, glycerol, pentaerythritol and An asphalt composition that is a reaction product with a polyol selected from the group consisting of mixtures thereof.
[22]
The composition according to [21], further comprising a binder and / or aggregate.
[23]
The composition according to [21], wherein the recovered asphalt is recovered pavement asphalt.
[24]
A method comprising regenerating the recovered asphalt by mixing with 0.01 to 10 wt% tall oil ester, rosin ester or mixtures thereof.
[25]
The method according to [24], wherein the rosin ester is a reaction product of tall oil rosin and a polyol selected from the group consisting of diethylene glycol, triethylene glycol, glycerol, pentaerythritol and mixtures thereof.
[26]
(A) at least 15% by weight of recovered asphalt containing an oxidizing binder;
(B) an ester functional regenerant,
The regenerant is present in an amount in the range of 1 to 10% by weight relative to the combined amount of the oxidizing binder and the regenerant
An asphalt composition wherein the regenerant and oxidative binder form a regenerative binder having a ring and ball softening point according to EN 1427 of less than 60 ° C. and a penetration value according to EN 1426 of greater than 20 dmm.
[27]
The composition according to [26], further comprising an additional aggregate and / or a binder.
[28]
The composition according to [26], wherein the rejuvenating agent is selected from the group consisting of trimethylol propanetalate, ethylene glycol monomelate, neopentyl glycol monomelate, 2-ethylhexyl monomelate and glycerin monomelate.
[29]
The composition according to [26], wherein the rejuvenating agent comprises a rosin ester having a ring and ball softening point according to EN 1427 less than 50 ° C.
[30]
The composition according to [26], wherein the regenerant comprises a rosin ester, rosin acid or a mixture thereof.
[31]
The composition according to [30], wherein the regenerant further comprises a fatty acid ester, a vegetable oil, or a petroleum flux oil.
[32]
The composition according to [30], wherein the regenerated binder has a reduced temperature sensitivity compared to the temperature sensitivity of similar regenerated binders made without rosin acid, rosin ester or mixtures thereof. .
[33]
The composition according to [26], wherein the regenerant reduces the temperature required for mixing at a viscosity of 200 mPa · s or less by at least 5 ° C.
[34]
[26] The composition according to [26], wherein the regenerant reduces the temperature necessary for consolidation at a viscosity of 3000 mPa · s or less by at least 5 ° C.
[35]
(A) an oxidation binder,
(B) an ester functional regenerant,
The regenerant is present in an amount in the range of 1 to 10% by weight relative to the combined amount of the oxidizing binder and the regenerant
A regenerative binder having a ring and ball softening point with EN 1427 of less than 60 ° C. and a penetration value with EN 1426 of more than 20 dmm.
[36]
The binder according to [35], which has a forced ductility of 1.0 J / cm ² at a temperature in the range of 15 ° C. to 25 ° C., as measured by AASHTO T-300.
[37]
The binder according to [35], wherein the regenerant is selected from the group consisting of trimethylolpropane tartrate, ethylene glycol monomaleate, neopentyl glycol monomaleate, 2-ethylhexyl monomaleate and glycerin monomaleate.
[38]
The binder according to [35], which actually exhibits stability when subjected to short-term aging by a rotating thin film oven test according to EN 12607-1 and long-term aging by a pressure aging vessel test according to EN 14769.
[39]
A paved surface comprising the asphalt composition according to [1].
[40]
A pavement surface containing the binder according to [9].
[41]
A pavement surface comprising the asphalt composition according to [21].
[42]
A pavement surface comprising the asphalt composition according to [26].
[43]
A pavement surface comprising the binder as described in [35].

Claims (24)

An asphalt composition comprising recovered asphalt and an ester functional regenerator, the recovered asphalt comprising aggregate and an oxidized asphalt binder, wherein the ester functional regenerant comprises the oxidized asphalt binder and the oxide asphalt binder. Present in an amount of 0.1 to 15% by weight relative to the combined amount of ester functional regenerant and compared to the glass transition onset temperature of the oxidized asphalt binder without the ester functional regenerator. Reducing the glass transition onset temperature of the oxidized asphalt binder by at least 5 ° C., the ester functional regenerating agent being an ester derived from an alcohol selected from the group consisting of diols and triols,
The asphalt composition. The ester functional regenerant are derived from C ₈ -C ₂₀ fatty acid or dimer acid, the asphalt composition of claim 1.   The asphalt composition of claim 1, wherein the ester functional regenerant reduces the glass transition onset temperature of the oxidized asphalt binder by at least 10 ° C.   The ester functional regenerant is an ester derived from tall oil fatty acid, monomeric acid, dimer acid, stearic acid, isostearic acid, 12-hydroxystearic acid, ricinoleic acid, azelaic acid, caprylic acid or benzoic acid. The asphalt composition as described in 1. A regenerated binder suitable for use with recovered asphalt,
(A) an oxidized asphalt binder;
(B) the amount of the ester functional regenerator, wherein the amount of the ester functional regenerant is 0.1 to 15% by weight based on the combined amount of the oxidized asphalt binder and the ester functional regenerator. Including
The ester functional regenerator reduces the glass transition onset temperature of the oxidized asphalt binder by at least 5 ° C compared to the glass transition onset temperature of the oxidized asphalt binder that does not include the ester functional regenerator; The functional rejuvenating agent is an ester derived from an alcohol selected from the group consisting of diols and triols,
Said regenerated binder.   6. A regenerated binder as claimed in claim 5, comprising 0.5 to 10% by weight of the ester functional regenerating agent. The ester functional regenerant are derived from C ₈ -C ₂₀ fatty acid or dimer acid, regenerated binding agent according to claim 5. Combining the recovered asphalt with an ester functional rejuvenating agent, the recovered asphalt comprising aggregate and an oxidized asphalt binder, the ester functional rejuvenating agent comprising the oxidized asphalt binder and the ester Used in an amount of 0.1 to 15% by weight relative to the combined amount of functional regenerant, and the oxidation compared to the glass transition onset temperature of the oxidized asphalt binder without the ester functional regenerator. Reducing the glass transition onset temperature of the asphalt binder by at least 5 ° C., the ester functional regenerating agent being an ester derived from an alcohol selected from the group consisting of diols and triols,
Said method.   9. The method of claim 8, wherein the ester functional regenerant reduces the glass transition onset temperature of the oxidized asphalt binder by at least 10 <0> C. A method comprising combining a binder composition comprising an oxidized asphalt binder with an ester functional regenerant, wherein the ester functional regenerator is a combined amount of the oxidized asphalt binder and the ester functional regenerator. Glass transition initiation temperature of the oxidized asphalt binder compared to the glass transition initiation temperature of the oxidized asphalt binder that is used in an amount of 0.1 to 15% by weight relative to the ester functional regenerant. Is reduced by at least 5 ° C., and the ester functional regenerating agent is an ester derived from an alcohol selected from the group consisting of diols and triols,
Said method. A method comprising the step of regenerating the recovered asphalt by mixing the recovered asphalt with 0.01 to 10 wt% tall oil ester, rosin ester or mixtures thereof, wherein the tall oil ester or rosin ester comprises An ester derived from an alcohol selected from the group consisting of: diols and triols,
Said method. An asphalt composition comprising:
(A) at least 15% by weight recovered asphalt comprising an oxidation binder,
(B) an ester functional regenerant,
The ester functional regenerant is present in an amount in the range of 1 to 10% by weight relative to the combined amount of the oxidative binder and the ester functional regenerator, the ester functional regenerant comprising a diol and An ester derived from an alcohol selected from the group consisting of triols;
The ester functional regenerant and the oxidative binder form a regenerated binder having a ring and ball softening point with EN 1427 of less than 60 ° C. and a penetration value with EN 1426 of greater than 20 dmm;
Said asphalt composition.   The asphalt composition according to claim 12, further comprising an additional aggregate and / or an additional binder.   The asphalt composition according to claim 12, wherein the ester functional rejuvenating agent comprises a rosin ester having a ring and ball softening point according to EN 1427 less than 50C.   The asphalt composition of claim 12, wherein the ester functional regenerant comprises a rosin ester, rosin acid or mixtures thereof.   16. The asphalt composition of claim 15, wherein the ester functional regenerant further comprises a fatty acid ester, vegetable oil, or petroleum flux oil.   The asphalt composition according to claim 12, wherein the ester functional rejuvenating agent reduces the temperature required to mix at a viscosity of 200 mPa · s or less by at least 5 ° C.   The asphalt composition according to claim 12, wherein the ester functional rejuvenating agent reduces the temperature required to consolidate at a viscosity of 3000 mPa · s or less by at least 5 ° C. A regenerated binder,
(A) an oxidizing binder;
(B) an ester functional regenerant,
The ester functional regenerant is present in an amount in the range of 1 to 10% by weight relative to the combined amount of the oxidative binder and the ester functional regenerator, the ester functional regenerant comprising a diol and An ester derived from an alcohol selected from the group consisting of triols;
The regenerated binder has a ring and ball softening point according to EN 1427 less than 60 ° C. and a penetration value according to EN 1426 more than 20 dmm,
The regenerated binder. 20. The regenerated binder of claim 19, wherein the forced ductility is 1.0 J / cm < ² > at a temperature in the range of 15 [deg.] C to 25 [deg.] C as measured by AASHTO T-300.   A pavement surface comprising the asphalt composition according to claim 1.   A paved surface comprising the regenerated binder according to claim 5.   A pavement surface comprising the asphalt composition according to claim 12.   A pavement surface comprising the regenerated binder according to claim 19.