JP6236014B2 - Recovery of recovered asphalt - Google Patents

Description

  The present invention relates to a recovered asphalt composition and its 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, oxidizes and becomes brittle and is prone to cracking, especially under stress or at 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. Therefore, the recovered pavement asphalt has characteristics different from those of unused asphalt and is difficult to process. Untreated RAP can be used only slightly; in general, asphalt mixtures containing up to 30% by weight of RAP can be used as subsurface black rock. Furthermore, due to the higher requirements on the pavement surface, the use of untreated RAP there is generally limited to 15-25%.

  The recovered asphalt can be blended with virgin asphalt, virgin binder, or both (see, eg, US Pat. No. 4,459,834). Regenerants have been developed to increase the amount of recovered asphalt that can be incorporated into both the foundation and the surface layer. The regenerant restores some of the physical properties of paving asphalt properties and bituminous binders, such as viscoelastic behavior, so that the properties of recovered asphalt are more similar to unused 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 oil or other hydrocarbon oil-based materials (see, eg, US Pat. Nos. 5,766,333 or 6,117,227). .

  A regenerant of plant origin is also described. For example, U.S. Pat. No. 7,811,372 (regenerative agents including bitumen and palm oil); U.S. Pat. No. 7,0086,070 (soy oil used for sealing or regeneration, alkyl esters derived from soybean 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). U.S. Patent Application Publication No. 2011/0015312 describes a binder composition comprising a resin of plant origin, a vegetable oil, and a polymer having an anhydride, carboxylic acid, or epoxide functional group. 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, it can be obtained as RheoFalt (registered trademark) 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, U.S. Patent Application Publication No. 2010/0170417 (CTO distillation fraction as a cutting solvent application in asphalt compositions); U.S. Patent Application Publication No. 2010/0147190 (distilled or oxidized tall oil for use in asphalt compositions). Component) and U.S. Pat. Nos. 4,479,827 and 4,373,960 (patching compositions comprising asphalt, tall oil and possibly organopolysiloxane).

  Esters made from downstream products of CTO, such as tall oil fatty acids (TOFA), tall oil rosin, tall oil pitch or monomeric acids (eg, unique products described in US Pat. No. 7,256,162), dimer acids, There is no suggestion of use as a regenerant 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 US Patent Application Publication No. 2010/0034586 US Patent Application Publication No. 2008/0041276 US Patent Application Publication No. 2011/0015312 International Publication No. 2010/077141 International Publication No. 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 an improved regenerant for recovered asphalt. In particular, the industry needs an amorphous additive for recovered asphalt that can improve cold 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 to be. Preferred regenerants would reduce the viscosity of the binder to a level comparable to virgin binder, and would reduce the glass transition temperature of the binder to allow a softer and more easily processable asphalt mixture. Ideally, the regenerant originates from renewable resources, has good thermal stability at the elevated temperatures normally used to mix and lay asphalt, and the original performance grade for the binder Can be revived.

  In one aspect, the invention relates to an asphalt composition comprising recovered asphalt and an ester functional regenerant. The recovered asphalt includes aggregate and an oxidative binder. The regenerant is present in an amount effective to reduce the glass transition onset temperature of the oxidized binder by at least 5 ° C. relative to the glass transition onset temperature of the oxidized binder without the regenerant. Our invention includes a binder composition suitable for use with recovered asphalt and a method for making the asphalt and binder composition 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 and a polyol selected from diethylene glycol, triethylene glycol, glycerol, pentaerythritol and mixtures thereof. Our invention includes a method comprising regenerating the recovered asphalt by mixing with 0.01 to 10% by weight tall oil ester, rosin ester or mixtures thereof.

  In yet another aspect, the present invention relates to an asphalt composition comprising an ester functional regenerant and recovered asphalt comprising at least 15% by weight oxidative binder. 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. The mixture of oxidative binder and regenerant forms 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 greater than 20 dmm.

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

The inventors surprisingly found that by incorporating an ester functional regenerant, the recovered bitumen oxidized bitumen binder was regenerated and physically similar to the physical properties of the original performance grade of the bitumen prior to oxidation. It has been found that regenerated bituminous binders having properties can be produced. The regenerated binder exhibits improved creep stiffness due to reduced glass transition onset temperature as well as dynamic shear viscoelasticity measurement (DSR). These results translate into improved low temperature crack resistance in recycled asphalt. DSR analysis also revealed that the regenerated binder has a reduced G ^* sin δ value, which is consistent with improved fatigue crack resistance. When regenerated binders are formed with up to 10% by weight of regenerant, such binders also have good elevated temperature performance associated with rubbing 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 regenerant is effective in reducing the temperature required to compact or mix the asphalt composition, which saves energy and reduces costs. 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 that can decompose at heated 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, the regenerant of the present invention uses higher levels of recovered asphalt 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 regenerants. In particular, it relates to the regeneration of recovered asphalt containing aggregate and oxidized asphalt binder, in particular recovered paved asphalt (RAP).

  In the literature, the term “asphalt” may be used to describe a binder and may also be used to describe a binder plus aggregate. In the description of the present invention, “asphalt” refers to a composite material comprising a bituminous binder and aggregate, commonly used for paving applications. Such asphalt is 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 dense grained asphalt, gap type asphalt, porous asphalt, and mastic asphalt. Typically, the total amount of bituminous binder in the asphalt is 1 to 10% by weight, in some cases 2.5 to 8.5% by weight, and in some cases 4 to 7.5% based on the total weight of the asphalt. % By 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.

  “Recovered pavement asphalt” (RAP) is an asphalt that has been used in the past as pavement. RAP can be obtained from asphalt that has been removed from roads or other structures and then processed by known methods including crushing, tearing, breaking, crushing, and / or granulation. Prior to use, the RAP can be inspected, classified and selected, for example, depending on the final paving 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 with asphalt can be used. Examples of suitable aggregates include granite, limestone, gravel and mixtures thereof.

  “Bitumen” refers to a viscous organic liquid or quasi-solid mixture from crude oil that is black, sticky, soluble in carbon disulfide, and consists primarily of condensed 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 can be of natural origin. This may be a crude bitumen or a purified bitumen obtained as a bottom residue from vacuum distillation, pyrolysis or hydrocracking of crude oil. Bitumen contained in recovered pavement asphalt or bitumen obtained from recovered pavement asphalt is further referred to as RAP-derived bitumen.

  “Unused bitumen” (also known as “fresh bitumen”) refers to bitumen that has never been used, eg, bitumen that has not been recovered from road pavement.

  “Binder” refers to a combination of bitumen and optionally other ingredients. Other ingredients include elastomers, non-bituminous binders, adhesion promoters, softeners, additional regenerants (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 elastomer 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. Usually, the oxidized binder is not isolated from the recovered asphalt. Oxidized binders have a higher viscosity compared to that of unused bitumen as a result of aging and exposure to outdoor weather.

  “Aged binder” refers to an unused binder that has been aged to resemble an oxidized binder using the RTFO and PAV laboratory aging test methods described herein.

  “Regenerant” refers to regenerated oxidized binder or recovered asphalt in combination with oxidized binder or recovered asphalt (or unused binder and / or a mixture of unused asphalt and this). It refers to a composition or mixture that restores some or all of the original characteristics of the asphalt used. “Ester functional” regenerants have at least one ester group and are further described below.

The bitumen in the binder may be a pavement grade bitumen, i.e. a commercially available unused bitumen such as a 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). In PEN classification, the product number refers to the bitumen penetration range as measured by ASTM D1586 method, for example, 40/60 PEN bitumen is a bitumen with a penetration in the range of 40-60 decimeters (dmm). Correspond. 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 includes recovered asphalt and an ester functional regenerant. The recovered asphalt includes aggregate and an oxidative binder.

  In another aspect, the invention relates to a binder composition suitable for use with recovered asphalt. The binder composition includes a combination of oxidative binder and ester functional regenerant. 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 regenerant. In a preferred approach, the regenerant is combined with virgin binder, recovered asphalt, and optionally virgin asphalt and mixed to obtain a regenerated asphalt product.

  The asphalt and binder composition of the present invention includes an ester functional regenerant. 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. It is present in an amount effective to reduce ° C.

Ester functional regenerant is mainly (containing a resin acid) carboxylic acid, or a _C 8 _{-C 20} fatty _acids, it is preferably derived from from a C 1 _{-C 18} alcohol. The acid moiety can be linear, branched, cyclic, aromatic, or combinations thereof; the acid moiety can be saturated, unsaturated, or combinations thereof. Resin acids include monocarboxylic acids in the form of C ₁₉ H ₂₉ COOH with three fused 6-carbon ring nuclei and contain double bonds that vary in number and position. The fatty acid can be in polymerized form, such as in a dimerized fatty acid mixture. The alcohol portion of the ester functional regenerant may be primary, secondary or tertiary; it may be a monol, diol or 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, Palmitic acid, monomeric acid (defined below), dimer acid, tall oil head, and the like, and mixtures thereof are included. Suitable _C 1 _{-C 18} alcohols, such as 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. The regenerant is preferably amorphous and preferably has a melting point or titer of preferably 30 ° C. or lower, more preferably less than 20 ° C., and most preferably less than 0 ° C. Since many resin acids are solids, resin acids can be blended with fatty acids or selected to have a relatively low softening point to provide a preferred regenerant.

In a preferred embodiment, the ester functional regenerant is derived from tall oil fatty acid (TOFA) or a TOFA 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 tall oil fatty acids and a small amount of tall oil rosin that make up the majority. 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 regenerant.

  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. More diverse and highly branched compositions of monomers result from the contacting step performed on 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 monomer products are Century® MO5 and MO6 fatty acids, products of Arizona Chemical Company. See US Pat. No. 7,256,162, the teachings of which are incorporated herein by reference for further information regarding the composition of the monomers and their conversion to various esters.

  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-Ethyl Hexyl Monomerate , Ethylene glycol dimethylate, 2-ethylhexyl dimethylate, 2-ethylhexyl trimellate, 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 regenerant can be used in combination with other regenerants 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). A combination ethylene glycol monomerate) is exemplified.

  In the asphalt and binder composition of the present invention, the regenerative agent has a glass transition start temperature of the oxidized asphalt binder of at least 5 ° C., preferably compared to the glass transition start temperature of the oxidized asphalt binder not containing 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 regenerants lower the onset temperature of the glass transition and narrow the spread. DSC has heretofore been used as a diagnostic tool for evaluating asphalt compositions; see, for example, Asphalt Science and Technology, A.D. M.M. Edited by Usnami, Marcel Dekker, Inc. NY (1997) pages 59-101. F. Turner and J.M. 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. I found. Reduction is important because it correlates with the expected improvement in cold crack resistance in paving asphalt. As suggested by the results in Tables 1 and 2 (below), the glass transition onset temperature is reduced by at least 5 ° C. when various ester derivatives are used at 2.5-10 wt% relative to the oxidized asphalt binder. It is effective to do. Many of the ester functional regenerants reduce the onset temperature of 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, high hydroxyl rosin ester (C16), terpene phenol (C18), polyterpene (C23), and phenolic rosin ester (C24), among others, can reduce the Tg onset temperature. Not valid (see “ΔStart” column). Note that Tudalen® 65, a hydrocarbon flux oil currently used to reclaim recovered paving asphalt, does not reduce the desired 5 ° C. Tg initiation at the 10% additive level. Cardanol, the active ingredient of another commercially available regenerant (RheoFalt® HP-EM, a product of Ventraco Chemie, BV), effectively reduces the Tg onset temperature, but cardanol It is a long chain unsaturated alkylate and has no ester functionality.

  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 regenerants that have this ability, including others. Although somewhat less diagnostic than lowering the Tg onset temperature, the narrower Tg broadening of the binder generally indicates greater uniformity, which reduces the fatigue crack resistance of the asphalt composition at ambient temperatures. Can be better.

  Asphalt and binder compositions can be made by combining the components in any desired order. In one convenient approach, the asphalt composition is made by combining the regenerant with virgin binder and then blending the product mixture with RAP. In another approach, the asphalt composition is made by combining a regenerant with RAP and optionally virgin asphalt.

  The asphalt composition of the present invention preferably comprises a regenerant, 5-95% by weight RAP, and at least some unused 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 of unused 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 regenerant may vary depending on the asphalt source. In general, the regenerant is preferably 0.1 to 15 wt%, more preferably 0.5 to 10 wt%, even more preferably 2 to 8 wt%, most preferably based on the amount of oxidized asphalt binder. Preferably, it is used at 3 to 6% by weight.

  Further evidence of the value of the ester functional regenerant comes from dynamic shear viscoelasticity measurement (DSR) data. Table 3 shows the improvement in low temperature performance, especially m-value and creep stiffness at -15 ° C. For example, EG monomethylate, trimethylolpropane tartrate, and glycerin monomale all work well compared to terpene phenol 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. While the benefits in low and ambient temperature performance are significant, it is too often that such benefits can only be obtained at the expense of enhanced temperature characteristics such as rutting resistance. However, as shown in Table 3, the low value of G * / sin δ measured at 70 ° C. (relative to the control) also works well at elevated temperatures for binders containing ester functional regenerants. It shows what is expected. The results of the test are used to infer the amount of rutting formation expected by the use of a specific binder. The results in Table 3 suggest that softening of the binder with the regenerant does not create rutting problems in the ultimate asphalt composition even on hot summer days.

  In one aspect, the present invention relates to a playback method. This method comprises the step of regenerating 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, Polyols such as sorbitol, neopentyl glycol and trimethylolpropane are included. Useful alcohols that are readily available include diethylene glycol, triethylene glycol and pentaerythritol.

Rosinic acids include monocarboxylic acids having the general formula C ₁₉ H ₂₉ COOH with three fused 6-carbocyclic nuclei and containing double bonds that vary in number and position. Examples of rosin acids include abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, levopimaric acid, sandaracopimaric acid, isopimaric acid and pulpstriic acid.

  The rosin acid can be used in isolated form or as part of a composition that can include multiple rosin acids. 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 rosin (eg, Sylvaros® 85, Sylvaros® 90 or Sylvaros® 95 from Arizona Chemical).

  The rosin acid can be modified prior to esterification, for example, by hydrogenation, disproportionation, oligomerization, Diels-Alder reaction, isomerization, or combinations thereof. The rosin ester can be modified to form a disproportionated rosin ester. 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 thermal reaction of rosin acid with alcohol. To proceed to completion of the esterification reaction, 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.

  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 (registered trademark) SG2, Dertoline (registered trademark) P 05, Dertoline (registered trademark) P110, Dertoline (registered trademark) P2L, Dertoline (registered trademark) PL5, Dertoline P125, Granolite SG, Granolite P, Granolite P118 and Granolite TEG; Can also be used.

  The rosin ester may contain some residual unreacted acid and alcohol. Typically, rosin esters have an acid number of less than 20 mg KOH / g, in particular less than 15 mg KOH / g. The acid value can be measured by methods known to those skilled in the art, such as the ASTM D974 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. To react with one or more of rosin, including some alcohols and glycols are suitable, 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. Specifically, 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 can be, for example, 1 to 10%, or 2.5 to 7.5%, or 3 to 6% by weight of the total amount of binder present in the recovered asphalt. Higher or lower amounts of rosin ester relative to the amount of binder present in the RAP can also be used. In general, a relative amount of less than 1% by weight, even to a lower extent, can still provide a regenerative effect. 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 such higher amounts do not significantly enhance regeneration. There is nothing.

  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, a known amount of RAP can be treated with a suitable solvent, such as dichloromethane, to extract the binder. The weight of the binder in the extract fraction can be measured, thereby determining the binder content in the RAP. The amount of binder in the RAP is usually 1 to 10% by weight, specifically 2.5 to 8.5% by weight, more specifically 4 to 7.5% by weight relative to the total weight of the 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, which is Example 64 in Table 7 below. When used as a regenerant, this product has a beneficial effect on the rheological properties including the ring and ball softening point and glass transition temperature of the binder, as well as storage and loss moduli.

  In another aspect, the invention relates to an asphalt composition comprising an ester functional regenerant and at least 15% by weight of recovered asphalt comprising an oxidized binder. The regenerant is present in an amount in the range of 1 to 10% by weight, preferably 3 to 8% by weight, more preferably 4 to 6% by weight, based on the combined amount of oxidative binder and regenerant. Furthermore, the mixture of oxidative binder and regenerant forms 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.

  Suitable ester functional regenerants have already been described. Particularly preferred regenerants are trimethylolpropane taleate, ethylene glycol monomaleate, neopentyl glycol monomaleate, 2-ethylhexyl monomaleate and glycerol monomaleate. 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 regenerant comprises a rosin ester having a ring and ball softening point according to EN 1427 of 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). The inventors have surprisingly found that regenerated binders comprising rosin esters, rosin acids, or mixtures thereof are similar regenerated binders made without rosin acids, rosin esters or mixtures thereof. It has been found that it can have a reduced temperature sensitivity compared to 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 regenerant 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 high temperatures are required to reach a viscosity of 200 mPa / s, the process consumes too much energy and can be cost-effective. Therefore, it is valuable to reduce any temperature required to reach a reasonable viscosity for mixing. In another aspect, the regenerant reduces the temperature required to consolidate with a viscosity of 3000 mPa / s or less by at least 5 ° C, preferably at least 10 ° C. If high temperatures are required to reach a viscosity of 3000 mPa / s, the process consumes too much energy and may be cost-effective. It is therefore valuable to reduce any temperature required to reach a reasonable viscosity for consolidation. As shown in Table 10, ester functional regenerants are effective in reducing the minimum temperature required for both mixing and compaction.

  In another aspect, the invention relates to a regenerative binder. The regenerative binder includes an oxidative binder and 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. 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. A suitable regenerant has 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.

Preferred regenerative binders reach a forced ductility of 1.0 J / cm ² at any temperature within the range of 15 ° C. to 25 ° C. as measured by AASHTO T-300. Also particularly preferred are regenerative binders having a ring and ball softening point of less than 60 ° C. (see Table 15 and 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 the short-term or long-term aging of asphalt compositions.

  The present invention includes the use for the asphalt composition or binder of the present invention. Asphalt compositions and binders can be used, for example, for pavement 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 paved surface comprising the asphalt or binder composition of the invention.

The following examples merely illustrate the invention; those skilled in the art will recognize many variations that are within the spirit of the invention and the 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 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 uncolored 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. The material is agitated and the resulting solvent / asphalt mix is decanted. 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 material with medium grade filter (Whatman # 4). The filtrate is charged batchwise into a 5 L flask and the solvent is stripped under vacuum while warming to 40-50 ° C. Concentration is continued until the material reaches the solids target of ˜20-25%. Put all the concentrated materials together in a single container, recover the solvent and recycle.

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

Differential Scanning Calorimetry (DSC) Analysis of Samples Differential scanning calorimetry analysis was performed under the following conditions: sample weight: 4-6 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: Metrics for Tg are applied to data from the following method log segment (23): (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 min isothermal; (6) cycle 1 end mark; (7) data storage on; (8)-45.00 (9) Data storage off; (10) Isothermal for 5.00 minutes; (11) Cycle 2 end mark; (12) Data storage on; (13) 165. (14) Data storage off; (15) Isothermal for 5.00 minutes; (16) Cycle 3 end mark; (17) Data storage on; (18) − 5.00 up to 85.00 ° C (19) Data storage off; (20) 5.00 minutes isothermal; (21) Cycle 4 end mark; (22) Data storage on; (23) 10.00 to 165.00 ° C. C / min ramp; (24) End mark of cycle 5; (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. An inflection point representing the beginning of the glass transition and the end point of the glass transition is entered, and the intermediate point is determined. “Spread” is the difference between the glass transition end point temperature and the glass transition start temperature. Thus, for samples with an onset Tg at -36 ° C and an endpoint at 10 ° C, the spread is reported as 46 ° C. The onset Δ and spread Δ (each in ° C) values for each sample are reported relative 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. . Rheofalt® distillate (cardanol), a long chain alkylated phenol, which is the main component of a commercial regenerant is provided for comparison.

  The reduction of fatigue cracks is usually inferred from an improvement in uniformity that correlates with a narrower spread of the glass transition temperature. Therefore, the improvement of fatigue cracks may result from narrowing the Tg spread by at least 5 ° C. 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 4 mm diameter parallel plate structure with a Malvern Kinexus® rotary dynamic shear viscoelasticity meter. Perform frequency sweeps 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 extracted binder without added regenerant. A stress sweep is performed before each frequency sweep to ensure a low strain level and to ensure that the test results are within the linear viscoelastic 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. Extrapolating by using Paving Technologies, 61 (1992) 67). The CA model relates the frequency dependence of the complex modulus to glass modulus (G _g ), crossover frequency (ω _c ), and rheology index (R). The form of the mathematical function is

It is.

  G (by converting the storage modulus (G ′ (ω)) using the Christensen approximation (see Christensen, RM, Theory of Viscoelasticity (1971) Academic Press, New York). t) Create a master curve.

1. Low temperature characteristics Low temperature characteristics are measured using a 4 mm plate viscoelasticity 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 creep stiffness curve at performance grade temperature plus 10 ° C. at 60 seconds. This is an indicator of the ability of asphalt to relieve stress. A minimum m-value of 0.3 is usually specified for laboratory RTFO / PAV (Rotating Thin Film Oven / Pressure Aged Bessel) aged asphalt. Creep stiffness is used to evaluate the potential for high thermal stress generation. A higher creep stiffness value indicates a higher latent thermal stress generation in the pavement and usually specifies a maximum value of 300 MPa. 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 characteristics The fatigue crack resistance of RTFO / PAV aged asphalt binders is usually evaluated using G * sinδ (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. The binder purchase standard usually requires 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 highest and lowest service temperatures. 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 rutting resistance 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 is significantly reduced 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 an improvement in material ability to mitigate and prevent the generation of thermal stress that can lead to thermal cracks. Directly related to improvement. G * sin δ provides an indicator of fatigue performance. Samples F (glycerin monomaleate) and A (EG monomaleate) stand out as the highest ranks in terms of both (m-value) and (G * sinδ) improvements. 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 ester as regenerant Preparation of rosin ester H To a 1 L flask equipped with a thermometer, overhead stirrer, nitrogen purge line, Dean-Stark trap, condenser, collection vessel and sampling port, A combination of pentaerythritol monoester and glycerol monoester of rosin (acid number: 107 mg KOH / g, total 83.5 g) 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. Triethylene glycol (16.2 g) is then added at a rate slow enough 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, that is, the monoesterified byproduct. After removal of the light oil, rosin ester H is obtained, which has a maximum viscosity of 6000 mPa.s at 40 ° C. 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. Fumaric acid (5 g) is added at a rate slow enough to ensure that the temperature does not drop above about 3 ° C. The reactor temperature is then raised to 200 ° C. and the reactor is 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 increased to 250 ° C. at a rate of 10-15 ° C. per hour. The reactor temperature is held at 250 ° C. for 4 hours. After 2 hours the temperature has dropped 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 A conventional apparatus is charged with tall oil rosin (Sylvaros® 90, 95 g). The reactor is heated to 180 ° C. until the rosin is sufficiently melted and allowed to stir. 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 rate slow enough to ensure that the temperature does not drop above 3 ° C. The reactor temperature is held at about 160 ° C. for 1 hour and then the temperature is increased at a rate of 10-15 ° C. per hour to a temperature between 270-280 ° C. 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. s.

  The acid value is measured according to ASTM D465. A known weight sample is dissolved in isopropyl alcohol. The solution is then titrated with a potassium hydroxide alcohol solution. 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 uses Brookfield equipment 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. Make the material fit into the ring, clean the ring, place a steel ball and place it on the 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. When the sphere falls completely through the ring, the temperature of the water is recorded. Temperature values are reported as ring and ball softening points.
Preparation of test sample Bitumen from RAP is prepared by washing RAP (BAM Wegen, from the Netherlands) with dichloromethane. The extracted bitumen is dried by evaporation of dichloromethane.

  The compositions of Examples 64-67 in Table 4 and Comparative Examples 70 and 71 are prepared as follows: RAP-derived bitumen (19.95 g) and unused bitumen (PEN 40/60, from Total, Netherlands, 9 g ) And heat to 100 ° C. in a 50 mL beaker. Additive (1.05 g) is then mixed thoroughly. The temperature is held 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 each bituminous composition are taken to determine the ring and ball softening point, glass transition temperature and 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. 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 asphalt in which 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,
-Pan: standard aluminum 40 μL pan 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 modulus and loss modulus of the bitumen sample are measured by Anton Paar physical rheometer MCR101. A temperature profile of −20 ° C. to 80 ° C. at a rate of 5 ° 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 viscoelastic behavior of bitumen at temperatures below 15 ° C. is an indicator of cracking tendency at low temperatures for bitumen containing bitumen. Viscoelastic behavior can be expressed in terms of storage modulus and loss modulus. The lower the storage modulus and the loss modulus, the lower the tendency to crack.

  Table 7 shows the respective additives used for the unused bitumen (Comparative Example 68), i.e. the sample with the target performance, and the mixture of unused bitumen and RAP-derived bitumen (Comparative Example 69), i.e. the sample with the 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 positive symbols, 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. Specifically, the softening point and glass transition temperature are modified for all of them. Rosin ester L (Example 64) also modifies storage modulus and loss modulus over most of the measured temperature (see Tables 5 and 6).

  Palm oil is described in US 2010/0041798 as acting as a regenerant. 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 with 15 carbon atoms in the meta position relative to the hydroxyl group is, for example, Rheofalt ™ HCP-22 (from 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 several 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. The Sylvatac® rosin esters RE5, RE25, RE40 and RE55, products of Arizona Chemical having a formula softening point, are further evaluated.

  The binders tested are oxidized binders (“RA”) recovered from recovered asphalt, or binders aged in the laboratory (“AB”).

  An aged binder is prepared in two steps. The first stage is a rotating thin film oven (RTFO) test, which is performed according to EN12607-1. 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 rotating conveyor in an air blown oven. After the test, the mass loss is recorded and the binder properties are measured.

  The second stage is a pressurized 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 survey, the basic properties of the regenerative binder are investigated. The binder's ring and ball softening point as measured by EN 1427 reflects the consistency of the hot binder. The higher the softening point, the more heat is needed to soften it or induce flow. The penetration value of the binder at 25 ° C. measured according to 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 on a daily basis. The penetration index (PI) quantifies how the consistency of asphalt varies 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 negative PI, but oxidation tends to push PI to positive values. Therefore, a negative value of PI is more desirable.

  Table 8 summarizes the results from this study. Ideally, the regenerant restores the properties of the oxidized binder so that the oxidized binder performs better than the unused 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 shown in the table, TMP tarates effectively achieve their results with only 5% by weight based on the combined amount of aging binder and TMP tartrate. Liquid or lower melting rosin esters, Sylvatac® RE5 and Sylvatac® RE25 also require somewhat higher levels (about 10% by weight) for optimal results, but the regeneration effect Have Interestingly, Sylvatac® RE55, a rosin ester with a higher softening point, is not effective in restoring the basic properties of aged binders to those found in virgin binders.

  Table 9 summarizes the results of experiments conducted to determine the amount of regenerant needed to achieve the desired softening while maintaining acceptable low penetration values. For EG monomelate and TMP tartrate, the penetration value at 25 ° C. is comparable to the penetration value of the unused binder 35/50 while the softening point reaches the desired value <60 ° C. with about 4-5 wt% regenerant. Is maintained. 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 lowest temperature at which the viscosity is suitable for consolidation (<3000 mPa · s) can be reduced by as much as 20 ° C. by combining the oxidative binder with an 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 particular, in the United States, dynamic shear viscoelasticity measurement (DSR) is used to test the expected performance at low, ambient, and elevated temperatures by evaluating the asphalt product. At low temperatures (for example, −10 ° C.), the road surface needs to have crack resistance. At ambient temperatures, stiffness and fatigue properties are important. At elevated temperatures, roads need rutting resistance if the asphalt becomes excessively soft. Criteria have been established by the asphalt industry to identify binder rheological properties that correlate with the expected paved road surface properties over three normal 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 a 30/50 grade virgin binder, the G * at −10 ° C. is ideally 2.8 × 10 ⁸ Pa or less (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) Which does not improve this parameter even at 10% by weight).

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

  Fatigue criteria are also related to ambient temperature performance. Determine the product of the complex modulus (G *) and the sine of the phase angle (δ) measured at 10 rad / s. The temperature at which the value of G * sin δ at 10 rad / s is equal to 5000 MPa should be below 20 ° C. for regenerated binders, comparable to 35/50 grade unused binders. As shown in Table 12, the fatigue criteria can be satisfied when using at least about 4% by weight of EG monomerate or TMP tartrate, but Sylvatac® RE55 is totally 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 is equal to 1000 Pa should be reduced with regenerative binder compared to aging binder. For 30/50 grade virgin binder, the temperature at which G * / sin δ at 10 rad / s is equal to 1000 Pa is about 70 ° C. (see Table 12). The high temperature standard is generally satisfied with up to about 10% by weight of 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 regenerants soften the aging binder to some extent, some more than others at the same dose. Thus, vegetable oils and fatty acid esters provide a high degree of softening, while petroleum flux oils and cardanols do so to a lesser extent. On the other hand, cyclic esters such as rosin esters do not soften very effectively.

  Moreover, oxidative and virgin binders have fatigue properties that are relatively insensitive to temperature, but most regenerants tend to make the regenerative binder more temperature sensitive. Ideally, the regenerative binder will behave more like a fresh binder, i.e. it will be preferred that the regenerative binder is 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 has been found that it has fatigue properties to withstand. However, since cyclic compounds usually lack the ability to impart sufficient softening, it is preferable to combine those cyclic compounds with other regenerants such as fatty acid esters or vegetable oils. Thus, the use of rosin esters, rosin acids or mixtures thereof in combination with other regenerants softens the binder while desirably maintaining 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 by 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 relates 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 results at a baseline energy level such as 1 J / cm ² to determine the temperature at which this forced ductility value is realized. 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 to match the target value of 17 ° C.

  Table 16 provides the results of a swirling consolidation study (according to EN12697-31). In that study, 75% by weight recovered pavement asphalt (RAP) is combined with virgin binder and aggregate with or without regenerant. TMP tartrate is used at 6% by weight relative to the amount of oxidized binder present in the RAP. The result after 10 turns shows how well the mixing was performed. The void content after 60 or 100 turns 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, the void content desirably remains low when TMP tarate is included as a regenerant. ASTM D6925 can also be used.

  Also, the water sensitivity according to EN12697-12 is evaluated for an asphalt mixture containing 75% by weight of 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, by including 6 wt% TMP tartrate, the RAP-containing mixture behaves more like the control, i.e., this TMP tartrate reduces the water sensitivity of the asphalt mixture.

  The laboratory method used to age the binder to behave more like the oxidized 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 regenerated binders before and after aging using first the RTFO test and then the PAV test. In all cases of regenerated binder, the cumulative mass loss is less than about 1% by weight, which is consistent with the results obtained using virgin binder. Thus, there is no detrimental effect on mass loss when using regenerants.

  Following the aging step, all ring and ball softening points of the test binder increase somewhat. However, the overall increase (see fairly right column, ΔR & B) is consistent with the increase seen with virgin binder. In other words, the ester functional regenerant does not appear to accelerate the short or long term aging of the binder. Similarly, the penetration value is 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]
Recovered asphalt and ester functional regenerant, the recovered asphalt includes aggregate and oxidized asphalt binder, and the regenerant is compared to the glass transition start temperature of the oxidized asphalt binder without regenerator. 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 the regenerant based on the combined amount of the oxidized asphalt binder and the regenerant.
[4]
The composition according to [1], wherein the regenerative agent is derived from C _{1 to} C ₁₈ monool, diol or triol, and C _{8 to} C ₂₀ fatty acid or dimer acid thereof.
[5]
The composition of [1], wherein the regenerant 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.
[7]
The composition according to [1], wherein the regenerant is selected from the group consisting of trimethylolpropane tartrate, ethylene glycol monomaleate, neopentyl glycol monomaleate, 2-ethylhexyl monomaleate and glycerin monomaleate.
[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 regenerative agent is derived from C _{1 to} C ₁₈ monool, diol or triol, and C _{8 to} C ₂₀ fatty acid or dimer acid thereof.
[13]
Combining the recovered asphalt with an ester functional regenerant, the recovered asphalt comprising aggregate and oxidized asphalt binder, wherein the regenerant is compared to the glass transition onset temperature of the oxidized asphalt binder without regenerator. 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 the regenerant is used with respect to the combined amount of the oxidized asphalt binder and the regenerant.
[17]
The method of [13], wherein the regenerant 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 of [13], wherein the regenerant is used in an amount effective to narrow the glass transition temperature broadening of the oxidized asphalt binder by at least 5 ° C.
[19]
[13] The method according to [13], wherein the regenerant is selected from the group consisting of trimethylolpropane tartrate, ethylene glycol monomaleate, neopentyl glycol monomaleate, 2-ethylhexyl monomaleate and glycerin monomaleate.
[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 of [26], further comprising additional aggregate and / or binder.
[28]
[26] The composition according to [26], wherein the regenerant is selected from the group consisting of trimethylolpropane tartrate, ethylene glycol monomaleate, neopentyl glycol monomaleate, 2-ethylhexyl monomaleate and glycerin monomaleate.
[29]
The composition of [26], wherein the regenerant comprises a rosin ester having a ring and ball softening point according to EN 1427 of 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 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;
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] , wherein the forced ductility is 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]
[35] A pavement surface containing the binder according to [35].

Claims (41)

  An asphalt composition comprising recovered asphalt and an ester functional regenerant, wherein the recovered asphalt includes aggregate and oxidized asphalt binder, and the regenerant combines the oxidized asphalt binder and the regenerant. The glass transition initiation temperature of the oxidized asphalt binder is reduced by at least 5 ° C. compared to the glass transition initiation temperature of the oxidized asphalt binder that is present in an amount of 0.1 to 15% by weight relative to the amount. The asphalt composition, wherein the regenerant is an ester derived from trimethylolpropane, pentaerythritol, or neopentyl glycol.   The composition of claim 1, further comprising 1-99% by weight of unused binder based on the combined amount of unused binder and oxidized asphalt binder. The regenerant is derived from a C ₈ -C ₂₀ fatty acid or dimer acid composition of claim 1.   The composition of claim 1, wherein the regenerant reduces the glass transition onset temperature of the oxidized asphalt binder by at least 10 ° C.   The composition of claim 1, wherein the regenerant reduces the glass transition temperature spread of the oxidized asphalt binder by at least 5 ° C. compared to the glass transition temperature spread when no regenerant is included.   The composition of claim 1, wherein the regenerant is selected from the group consisting of trimethylol propane tartrate and neopentyl glycol monomethylate.   The 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. Composition. A regenerative binder suitable for use with recovered asphalt,
(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,
The regenerant reduces the glass transition start temperature of the oxidized asphalt binder by at least 5 ° C. compared to the glass transition start temperature of the oxidized asphalt binder that does not contain the regenerant, and the regenerant comprises trimethylolpropane, pentaerythritol. Or the regenerated binder which is an ester derived from neopentyl glycol.   9. The binder of claim 8, further comprising 1 to 99% by weight of unused binder based on the combined amount of unused binder and oxidized asphalt binder.   9. The binder according to claim 8, comprising 0.5 to 10% by weight of the regenerant. The regenerant is derived from a C ₈ -C ₂₀ fatty acid or dimer acid, binding agent according to claim 8.   A method comprising the step of combining recovered asphalt with an ester functional regenerant, wherein the recovered asphalt comprises aggregate and oxidized asphalt binder, wherein the regenerant is a combined amount of oxidized asphalt binder and regenerant. Is used in an amount of 0.1 to 15% by weight and reduces the glass transition start temperature of the oxidized asphalt binder by at least 5 ° C. compared to the glass transition start temperature of the oxidized asphalt binder that does not contain a regenerant. The method, wherein the regenerant is an ester derived from trimethylolpropane, pentaerythritol, or neopentyl glycol.   13. The recovered asphalt, the regenerant or mixtures thereof are combined with 1 to 99% by weight of unused binder based on the combined amount of unused binder and oxidized asphalt binder. Method.   13. The recovered asphalt, the regenerant or a mixture thereof is combined with 30-70% by weight of unused binder based on the combined amount of unused binder and oxidized asphalt binder. Method.   The method of claim 12, wherein the regenerant reduces the glass transition onset temperature of the oxidized asphalt binder by at least 10 ° C.   13. The method of claim 12, wherein the regenerant narrows the glass transition temperature broadening of the oxidized asphalt binder by at least 5 ° C.   13. The method of claim 12, wherein the regenerant is selected from the group consisting of trimethylol propane tartrate and neopentyl glycol monomethylate.   A method comprising combining a binder composition comprising an oxidized asphalt binder with an ester functional regenerant, wherein the regenerant is 0.1 to 15 relative to the combined amount of the oxidized asphalt binder and the regenerant. Used in an amount of% by weight to reduce the glass transition initiation temperature of the oxidized asphalt binder by at least 5 ° C compared to the glass transition initiation temperature of the oxidized asphalt binder without regenerant, wherein the regenerant comprises trimethylol Such a process, which is an ester derived from propane, pentaerythritol, or neopentyl glycol.   An asphalt composition comprising 0.01 to 10% by weight rosin ester and at least 15% by weight recovered asphalt, wherein the rosin ester is a reaction product of tall oil rosin or tall oil and pentaerythritol. The asphalt composition.   20. A composition according to claim 19, further comprising a binder and / or aggregate.   The composition of claim 19, wherein the recovered asphalt is recovered paved asphalt. A method comprising regenerating the recovered asphalt by mixing the recovered asphalt with 0.01 to 10 wt% tall oil ester, rosin ester or a mixture thereof, wherein the tall oil ester or rosin ester is Or an ester derived from trimethylolpropane, pentaerythritol, or neopentyl glycol.   23. The method of claim 22, wherein the rosin ester is a reaction product of tall oil rosin and pentaerythritol. An asphalt composition comprising:
(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 with respect to the combined amount of the oxidizing binder and the regenerant, and the regenerant is derived from trimethylolpropane, pentaerythritol, or neopentyl glycol. An ester
The asphalt composition wherein the regenerant and the 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.   25. The composition of claim 24, further comprising additional aggregate and / or binder.   25. The composition of claim 24, wherein the regenerant is selected from the group consisting of trimethylol propane taleate and neopentyl glycol monomethylate.   25. The composition of claim 24, wherein the regenerant comprises a rosin ester having a ring and ball softening point according to EN 1427 of less than 50 <0> C.   25. The composition of claim 24, wherein the regenerant comprises a rosin ester, rosin acid or a mixture thereof.   29. The composition of claim 28, wherein the regenerant further comprises a fatty acid ester, vegetable oil, or petroleum flux oil.   29. The composition of claim 28, wherein the regenerative binder has a reduced temperature sensitivity compared to the temperature sensitivity of a similar regenerative binder made without rosin acid, rosin ester or mixtures thereof. object.   25. The composition of claim 24, wherein the regenerant reduces the temperature required to mix at a viscosity of 200 mPa · s or less by at least 5 ° C.   25. The composition of claim 24, wherein the regenerant reduces the temperature required to consolidate with a viscosity of 3000 mPa · s or less by at least 5 ° C. A regenerative binder,
(A) an oxidizing binder;
(B) an ester functional regenerant,
The regenerant is present in an amount in the range of 1 to 10% by weight with respect to the combined amount of the oxidizing binder and the regenerant, and the regenerant is derived from trimethylolpropane, pentaerythritol, or neopentyl glycol. An ester
The regenerative binder, wherein the regenerative binder has 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. 34. The binder of claim 33, 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.   34. The binder of claim 33, wherein the regenerant is selected from the group consisting of trimethylol propane tartrate and neopentyl glycol monomethylate.   34. The binder of claim 33, 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.   A paved surface comprising the asphalt composition according to claim 1.   A pavement surface comprising the binder according to claim 8.   A pavement surface comprising the asphalt composition according to claim 19.   A paved surface comprising the asphalt composition according to claim 24.   A pavement surface comprising the binder according to claim 33.