WO2025117784A1 - Latexes for fog and scrub seal asphalt emulsions - Google Patents

Abstract

Disclosed herein are latex polymer-modified fog and scrub seal asphalt emulsions for rejuvenating or repairing deteriorated asphalt pavements. Methods of forming and applying the fog and scrub seal asphalt emulsion compositions are also disclosed.

Description

LATEXES FOR FOG AND SCRUB SEAL ASPHALT EMULSIONS

FIELD OF THE DISCLOSURE

[0001] This disclosure relates generally to asphalt compositions for fog and scrub seal applications, and more particularly to fog and scrub seal asphalt compositions that include polymer latex, and to methods of making and using the polymer-modified asphalt compositions.

BACKGROUND OF THE DISCLOSURE

[0002] Asphalt compositions have a wide number of applications, including but not limited to the production of aggregate pavement. Asphalt pavement is a composite material that include mineral aggregate and an asphalt (bitumen) binder which hardens to form a robust surface.

[0003] Over time, asphalt pavement deteriorates from oxidation of the asphalt binder, heavy loads, and weathering. These conditions can result in issues such as cracking, potholes, rutting, and surface deterioration. One method for fixing deteriorated asphalt pavement is to simply excavate, remove, and replace old pavement with newly prepared or recycled pavement. These repaving procedures, however, can be expensive, timeconsuming, and wasteful.

[0004] An alternative to asphalt replacement is asphalt rejuvenation. Asphalt rejuvenation procedures aim to restore and extend the life of deteriorating asphalt pavements. This provides several advantages such as extending the life of existing pavement and minimization of disruption of traffic flow and business operations.

SUMMARY OF THE DISCLOSURE

[0005] Disclosed herein are polymer latexes for modification of fog, scrub seal and tack coat asphalt emulsions. These asphalt emulsion compositions can be used to rejuvenate a deteriorating asphalt surface. The asphalt emulsions can also be used as trackless tack coats.

[0006] In one form thereof, the present disclosure provides an asphalt rejuvenating emulsion composition comprising: (i) asphalt; (ii) a latex composition comprising an styrene-modified polymer; (iii) a rejuvenating agent; (iv) one or more emulsifying agents; and (v) water. [0007] In another form thereof, the present disclosure provides a method for rejuvenating asphalt comprising: (i) providing an asphalt rejuvenating emulsion composition comprising: asphalt; a latex composition comprising a styrene-modified polymer; a rejuvenating agent; one or more emulsifying agents; water; and (ii) applying the asphalt rejuvenating emulsion composition to a deteriorated asphalt pavement surface.

DETAILED DESCRIPTION

I. Definitions

[0008] The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of’ and “consisting of’ can be used in place of “comprising” and “including” to provide for more specific embodiments and are also disclosed. As used in this disclosure and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise. The disclosure of percentage ranges and other ranges herein includes the disclosure of the endpoints of the range and any integers provided in the range.

[0009] As used in the description and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a composition” includes mixtures of two or more such compositions, reference to “an agent” includes mixtures of two or more such agents, reference to “the component” includes mixtures of two or more such components, and the like.

[00010] “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[00011] It is understood that throughout this specification the identifiers “first” and “second” are used solely to aid in distinguishing the various components and steps of the disclosed subject matter. The identifiers “first” and “second” are not intended to imply any particular order, amount, preference, or importance to the components or steps modified by these terms.

[00012] The term “(meth)acryl. includes “acryl. “methacryl. . or mixtures thereof. [00013] The term “copolymer” includes homopolymers, copolymers, or mixtures thereof.

[00014] The terms “surfactant”, “emulsifier”, and “dispersant” are all used interchangeably and refer to substances or compounds that alter the surface tension of a system, stabilize emulsions, or facilitate mixing and dispersion of immiscible substances.

[00015] As used herein, the term “substantially free” means that the composition as a whole contains no more than about 1 % by weight of the species in question. For example, if a product composition is substantially free of water, it contains no more than about 1 wt.% of water.

[00016] As used herein, the phrase “within any range encompassing any two of these values as endpoints” literally means that any range may be selected from any two of the values listed prior to such phrase regardless of whether the values are in the lower part of the listing or in the higher part of the listing. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.

II. Latex Polymer Compositions for Asphalt Modification

[00017] Described herein are latex polymer compositions for use in asphalt modification. Advantageously, the incorporation of the latex polymers of the present disclosure into asphalt emulsions improves their adhesion, ductility, tensile strength, durability, and makes the polymer-modified asphalt emulsions suitable for rejuvenation applications such as scrub seals and fog seals.

[00018] In some embodiments, the latex comprises a styrene-modified polymer. In one preferred embodiment, the latex comprises a terpolymer of styrene, butadiene, and acrylate monomers. In another preferred embodiment, the latex comprises a quadripolymer of styrene, butadiene, acrylate, and acrylonitrile monomers.

[00019] The acrylate monomers in the polymer latex may, for example, be based on (meth)acrylic acid, esters of (meth)acrylic acid, (meth)acrylamide, (meth)acrylonitrile and derivatives of these acrylate monomers. Exemplary esters of (meth)acrylic acids include, but are not limited to, alkyl and hydroxyalkyl esters, e.g., methyl (meth)acrylates, ethyl (meth)acrylates, butyl (meth) acrylates, hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, and longer chain alkyl (meth) acrylates such as ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, and stearyl (meth)acrylate. Derivatives of (meth)acrylamide include, but are not limited to, alkyl substituted (meth) acrylamides, e.g., N,N-dimethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, t-butyl (meth)acrylamide, N-octyl (meth) acrylamide, and longer chain alkyl (meth)acrylamides such as N-lauryl (meth)acrylamide and N-stearyl (meth)acrylamide. The acrylic polymers also include polymers commonly known as acrylics, acrylate polymers, poly acrylates or acrylic elastomers. Acrylate polymers belong to a group of polymers which could be referred to generally as plastics while acrylic elastomer is a general term for a type of synthetic rubber whose main component is an acrylic acid alkyl ester (for example, an ethyl or butyl ester). [00020] As described above, the latex copolymers of the present invention can be derived from styrene along with other monomers such as acrylates, methacrylates, butadiene, acrylonitrile and acrylamide. The copolymer can be derived from other monomers. For example, the copolymer can be derived from vinyl esters of branched monocarboxylic acids having a total of 8 to 12 carbon atoms in the acid residue moiety and 10 to 14 total carbon atoms such as, vinyl 2-ethylhexanoate, vinyl neo-nonanoate, vinyl neodecanoate, vinyl neo-undecanoate, vinyl neo-dodecanoate and mixtures thereof, and copolymerizable surfactant monomers (e.g., those sold under the trademark ADEKA REASOAP). The copolymer can also include at least one additional vinyl aromatic monomer such as alpha. -methylstyrene or o-chlorostyrene. Other suitable monomers include acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide. In some embodiments, the one or more additional monomers can include at least one (meth)acrylic acid ester. For example, methyl, ethyl, n-butyl, isobutyl and 2-ethylhexyl acrylates and methacrylates can be used.

[00021] As disclosed herein, the copolymer may also be derived from or further include an organosilane. The organosilane can be represented by the formula (R¹) — (Si) — (OR²)₃, wherein R¹ is a Ci-Cs substituted or unsubstituted alkyl or a Ci-Cs substituted or unsubstituted alkene and R², which are the same or different, each is a Ci-Cs substituted or unsubstituted alkyl group. In some examples, the organosilane includes a vinyl silane. Exemplary organosilanes can include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2-methoxyethoxysilane), vinyl triisopropoxysilane, (meth)acryloyloxypropyltrimethoxysilane, gamma-(meth)acryloxypropyltrimethoxysilane, gamma-(meth)acryloxypropyltriethoxysilane, or a mixture thereof. In some examples, the organosilane includes vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2- methoxyethoxysilane), vinyl triisopropoxysilane, gamma-methacryloxypropyltrimethoxy silane, or combinations thereof. In some examples, the organosilane includes vinyltriethoxysilane. In some examples, the organosilane consists of vinylethoxysilane. [00022] Any of the foregoing monomers may be present in the latex in an amount as low as 1 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, or as high as 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, 99 wt.%, or within any range encompassed by any two of the foregoing values as endpoints. For example, the latex may comprise styrene monomers in an amount of from 20 wt.% to 70 wt.%, or from 30 wt.% to 60 wt.%.

[00023] The latex compositions disclosed herein can be prepared by any polymerization method known in the art. In some embodiments, the compositions disclosed herein are prepared by a dispersion, a mini-emulsion, or an emulsion polymerization. The compositions disclosed herein can be prepared, for instance, by polymerizing the styrene, butadiene, and optionally other monomers using free -radical emulsion polymerization. In some embodiments, the polymerization medium is an aqueous medium. Solvents other than water can be used in the emulsion. The emulsion polymerization can be carried out either as a batch, semi-batch, or continuous process. In some embodiments, a portion of the monomers can be heated to the polymerization temperature and partially polymerized, and the remainder of the polymerization batch can be subsequently fed to the polymerization zone continuously, in steps or with superposition of a concentration gradient. The process can use a single reactor, or a series of reactors as would be readily understood by those skilled in the art.

[00024] The polymer dispersion can be prepared by first charging a reactor with a seed latex, water, the monomers, and optionally at least one nonionic surfactant. The seed latex, although optional, helps initiate polymerization and helps produce a polymer having a consistent particle size. Any seed latex appropriate for the specific monomer reaction can be used such as a polystyrene seed. The initial charge can also include a chelating or complexing agent such as ethylenediamine tetraacetic acid (EDTA). Other compounds such as buffers can be added to the reactor to provide the desired pH for the emulsion polymerization reaction. For example, bases or basic salts such as KOH or tetrasodium pyrophosphate can be used to increase the pH whereas acids or acidic salts can be used to decrease the pH. The initial charge can then be heated to a temperature at or near the reaction temperature. The reaction temperature can be, for example, from 5°C to 100°C (e.g., from 40°C to 90°C, from 50°C to 85°C, or from 55°C to 80°C). [00025] After the initial charge, the monomers that are to be used in the polymerization can be continuously fed to the reactor in one or more monomer feed streams. The monomers can be supplied as a pre-emulsion in an aqueous medium, particularly if acrylate monomers are used in the polymerization. An initiator feed stream can be also continuously added to the reactor at the time the monomer feed stream is added although it may also be desirable to include at least a portion of the initiator solution to the reactor before adding a monomer pre-emulsion if one is used in the process. The monomer and initiator feed streams are typically continuously added to the reactor over a predetermined period of time (e.g., 1.5-15 hours) to cause polymerization of the monomers and to thereby produce the polymer dispersion. A nonionic or anionic surfactant, or any combination of non-ionic and anionic, surfactants can be added at this time as part of either the monomer stream or the initiator feed stream although they can be provided in a separate feed stream. Furthermore, one or more buffers can be included in either the monomer or initiator feed streams or provided in a separate feed stream to modify or maintain the pH of the reactor.

[00026] The monomers can be fed in one or more feed streams with each stream including one or more of the monomers being used in the polymerization process. For example, styrene and butadiene (when used) can be provided in separate monomer feed streams or can be added as a pre-emulsion. It can also be advantageous to delay the feed of certain monomers to provide certain polymer properties or to provide a layered or multiphase structure (e.g., a core/shell structure).

[00027] The molecular weight of the copolymers can be adjusted by adding a small amount of molecular weight regulators, for example, 0.01 to 4% by weight, based on the monomers being polymerized. Particular regulators which can be used include organic thio compounds (e.g., Zert-dodecylmercaptan), terpinolene, allyl alcohols and aldehydes. [00028] The initiator feed stream can include at least one initiator or initiator system that is used to cause the polymerization of the monomers in the monomer feed stream. The initiator stream can also include water and other desired components appropriate for the monomer reaction to be initiated. The initiator can be any initiator known in the art for use in emulsion polymerization such as azo initiators; ammonium, potassium or sodium persulfate; or a redox system that typically includes an oxidant and a reducing agent. Exemplary initiators include azo initiators and aqueous solutions of sodium persulfate. The initiator stream can optionally include one or more buffers or pH regulators. [00029] In addition to the monomers and initiator, an anionic, or nonionic surfactant (i.e. , emulsifier) or any combination of non-ionic and anionic surfactants such as those described herein can be fed to the reactor. The surfactant can be provided in the initial charge of the reactor, provided in the monomer feed stream, provided in an aqueous feed stream, provided in a pre -emulsion, provided in the initiator stream, or a combination thereof. The surfactant can also be provided as a separate continuous stream to the reactor. The surfactant can be provided in an amount of l%-5% by weight, based on the total weight of monomer and surfactant. In some embodiments, the surfactant is provided in an amount less than 2% by weight.

[00030] Once polymerization is completed, the polymer dispersion can be chemically stripped thereby decreasing its residual monomer content. This stripping process can include a chemical stripping step and/or a physical stripping step. In some embodiments, the polymer dispersion is chemically stripped by continuously adding an oxidant such as a peroxide (e.g., t-butylhydroperoxide) and a reducing agent (e.g., sodium acetone bisulfite), or another redox pair to the reactor at an elevated temperature and for a predetermined period of time (e.g., 0.5 hours). Suitable redox pairs are described by A.S. Sarac in Progress in Polymer Science 24, 1149-1204 (1999). An optional defoamer can also be added if needed before or during the stripping step. In a physical stripping step, a water or steam flush can be used to further eliminate the non-polymerized monomers in the dispersion. Once the stripping step is completed, the pH of the polymer dispersion can be adjusted and a biocide or other additives can be added. Cationic, anionic, and/or amphoteric surfactants or polyelectrolytes may optionally be added after the stripping step or at a later time if desired in the end product to provide a cationic or anionic polymer dispersion.

[00031] Once the polymerization reaction is complete, and the stripping step is completed, the temperature of the reactor can be reduced.

[00032] At a polymerization temperature of 70°C or greater, a thermal initiator can be used in the reactor such as ammonium persulfate, potassium persulfate, or sodium persulfate. At temperatures of less than 70°C, the thermal initiator can be combined with or replaced by a redox initiator comprising a free radical generator, a reducing agent and an activator (e.g., a water-soluble metal salt).

[00033] Suitable free radical generators include organic peroxygen compounds such as benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,4- dichlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, a-pinene hydroperoxide, t-butyl hydroperoxide, acetyl acetone peroxide, methyl ethyl ketone peroxide, succinic acid peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxymaleic acid, t- butyl peroxybenzoate, and the like; and alkyl perketals, such as 2,2-bis-(t- butylperoxy)butane, ethyl 3,3-bis(t-butylperoxy)butyrate, or l,l-di-(t- butylperoxy)cyclohexane. In some embodiments, the free radical generator includes diisopropylbenzene hydroperoxide or p-methane hydroperoxide. The free radical generator is typically present in an amount between 0.01 and 1% by weight based on total monomer weight.

[00034] Suitable reducing agents for use in the initiator stream include sulfur dioxide; alkali metal disulfites; alkali metal and ammonium hydrogen sulfites; thiosulfate, dithionite and formaldehyde sulfoxylates; hydroxylamine hydrochloride; hydrazine sulfate; glucose and ascorbic acid. For example, the reducing agent can include sodium formaldehyde sulfoxylate dihydrate (SFS), sodium metabisulfite, or a mixture thereof. The reducing agent can be present in an amount between 0.01 and 1% by weight based on total monomer weight. In addition, the weight ratio of reducing agent to free radical generator can be between 0.2:1 and 1:1.

[00035] The water-soluble metal salt can be aniron, copper, cobalt, nickel, tin, titanium, vanadium, manganese, chromium or silver salt and can be chosen from a wide variety of water-soluble metal salts. Suitable water-soluble metal salts include copper (II) amine nitrate, copper (II) metaborate, copper (II) bromate, copper (II) bromide, copper perchlorate, copper (II) dichromate, copper (II) nitrate hexahydrate, iron (II) acetate, iron (III) bromide, iron (III) bromide hexahydrate, iron (II) perchlorate, iron (III) dichromate, iron (III) formate, iron (III) lactate, iron (III) malate, iron (III) nitrate, iron (III) oxalate, iron (II) sulfate pentahydrate, cobalt (II) acetate, cobalt (II) benzoate, cobalt (II) bromide hexahydrate, cobalt (III) chloride, cobalt (II) fluoride tetrahydride, nickel hypophosphite, nickel octanoate, tin tartrate, titanium oxalate, vanadium tribromide, silver nitrate, and silver fluosilicate. The metal can also be complexed with a compound, such as ethylenediaminetetraacetic acid (EDTA) to increase its solubility in water. For example, iron/EDTA complexes or cobalt/EDTA complexes can be used. The water-soluble metal salt can be present in an amount less than 0.01% by weight based on total monomer weight. [00036] The polymerization reaction can be conducted in the presence of molecular weight regulators to reduce the molecular weight of the copolymer. Suitable molecular weight regulators include Cs to C12 mercaptans, such as octyl, nonyl, decyl or dodecyl mercaptans. In some embodiments, tert-dodecyl mercaptan is used as a molecular weight regulator. In some embodiments, terpinolene is used as a molecular weight regulator. In some embodiments, a blend of tert-dodecyl mercaptan and terpinolene is used as a molecular weight regulator.

[00037] Terpinenes are a group of isomeric hydrocarbons that are classified as monoterpenes. Each compound has the same molecular formula and carbon framework but differs in the position of carbon-carbon double bonds. a-Terpinene can be isolated from cardamom and marjoram oils, and from other natural sources. [3-Terpinene has no known natural source but can been prepared from sabinene. y-Terpinene and 5-terpinene (also known as terpinolene, Formula (I)) may be isolated from a variety of plant sources. These compounds are all colorless liquids with a turpentine-like odor. In the context of present disclosure, terpinolene is used as a chain transfer agent and does not enter into the total monomer weight. Formula (I) below is 4-isopropylidene- 1 -methylcyclohexene.

[00038] The amount of tert-dodecyl mercaptan used will depend upon the molecular weight that is desired for the copolymer. In some embodiments, the amount of molecular weight regulator is from 0.01 and 4% by weight (e.g., 0.1 to 1% by weight) based on total monomer weight.

[00039] The one or more monomer feeds, surfactant feed and initiator feed can be separately fed to a reactor where polymerization of the styrene and butadiene monomers occurs. The polymer content of the latex compositions of the present invention can be in the 30% to 75% range. The latex solids may also be in the range of 30 wt.% to 75 wt.%, based on the total weight of the composition.

[00040] As mentioned above, latex polymers of the present disclosure can also be produced using a batch process. In the batch process, the monomers, the surfactant, the free radical generator and water are all added to a reactor and agitated. After reaching the desired polymerization temperature, an activator solution if desired, that includes the reducing agent and the water-soluble metal salt if desired can be added to initiate polymerization.

[00041] If a semi-batch process is used, the monomers, the surfactant in an aqueous solution, and the free radical generator in an aqueous solution are all fed to a reactor over a period of time, usually from 3 to 20 hours. If desired, an activator solution that includes a reducing agent and/or a water-soluble metal salt can also be added in the reactor prior to commencing the other feeds or can be fed over a time interval to the reactor. The high temperature polymerized styrene-butadiene copolymer is preferably allowed to complete monomer conversion, i.e., greater than 99%.

[00042] After the polymerization is completed, non-ionic emulsifiers such as those typically used for the manufacture of asphalt emulsions may be directly added or post-added to the latex composition.

[00043] Suitable nonionic surfactants include, but are not limited to, REDICOTE® E-47, polyoxyalkylene alkyl ethers and polyoxyalkylene alkylphenyl ethers (e.g., diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene nonylphenyl ether); oxy ethyleneoxypropylene block copolymers; sorbitan fatty acid esters (e.g., sorbitan monolaurate available as SPAN® 20 from Merck Schuchardt OHG, sorbitan monooleate available as SPAN® 80 from Merck Schuchardt OHG, and sorbitan trioleate available as SPAN® 85 from Merck Schuchardt OHG); polyoxyethylene sorbitan fatty acid esters (e.g., polyoxyethylene sorbitan monolaurate available as TWEEN® 20 and TWEEN® 21 from Uniqema, polyoxyethylene sorbitan monopalmitate available as TWEEN® 40 from Uniqema, polyoxyethylene sorbitan monostearate available as TWEEN® 60, TWEEN® 60K, and TWEEN® 61 from Uniqema, polyoxyethylene sorbitan monooleate available as TWEEN® 80, TWEEN® 80K, and TWEEN® 81 from Uniqema, and polyoxyethylene sorbitan trioleate available as TWEEN® 85 from Uniqema); polyoxyethylene sorbitol fatty acid esters (e.g., tetraoleic acid polyoxyethylene sorbitol); glycerin fatty acid esters (e.g., glycerol monooleate); polyoxyethylene glycerin fatty acid esters (e.g., monostearic acid polyoxyethylene glycerin and monooleic acid polyoxyethylene glycerin); polyoxyethylene fatty acid esters (e.g., polyethylene glycol monolaurate and polyethylene glycol monooleate); polyoxyethylene alkylamine; and acetylene glycols. In some embodiments, the nonionic surfactant can have a HLB (hydrophilic lipophilic balance) at room temperature such that 8 < HLB < 15. In some embodiments, the HLB is 14 or less. In some embodiments, the nonionic surfactant includes an ethylene oxide (EO)_m and/or propylene oxide (PO)_n adduct of an alkyl, alkylbenzene or dialkylbenzene alcohol wherein (m+n) < 14, (m+n) < 12, or (m+n) < 10 (e.g., 6 < (m+n) < 10), such as those available from BASF under the LUTENSOL™ trademark.

[00044] The non-ionic surfactant may be present in the latex composition in an amount of from 0.01 wt.% to 30 wt.%, based on the total weight of the latex. For example, the non-ionic emulsifier may comprise 0.01 wt.% to 3 wt.%, 0.01 wt.% to 5 wt.%, 0.01 wt.% to 10 wt.%, 0.01 wt.% to 15 wt.%, 0.01 wt.% to 20 wt.%, 0.01 wt.% to 25 wt.%, or 0.01 wt.% to 30 wt.% of the latex polymer.

[00045] Once polymerization is terminated (in either the continuous, semi-batch or batch process), the unreacted monomers can be removed from the latex dispersion. For example, butadiene monomers can be removed by flash distillation at atmospheric pressure and then at reduced pressure. The styrene monomers can be removed by steam stripping in a column.

[00046] An antioxidant can be added latex composition to prevent oxidation of the double bonds of the polymer and can either be added before or after vulcanization of the latex. The antioxidants can be substituted phenols or secondary aromatic amines.

[00047] Exemplary substituted phenols include 2,6-di-t-butyl-p-cresol (DBT); 4,4'- thiobis(6-t-butyl-m-cresol); 3-t-butyl-4-hydroxyanisole (3-BHT); 2-t-butyl-4- hydroxyanisole (2-BHT); 2,2-methylenebis(4-methyl-6-t-butylphenol) (MBMBP); 2,2- methylenebis(4-ethyl-6-t-butylphenol) (MB EBP); 4,4'-butylidenebis(3-methyl-6-t- butylphenol) (SBMBP); 2,2-ethylidenebis(4,6-di-t-butylphenol); 2,6-di-t-butyl-4-sec- butylphenol; styrenated phenol; styrenated-p-cresol; l,l,3-tris(2-methyl-4-hydroxy-5-t- butylphenol)butane; tetrakis[methylene-3-(3,5-di-t-butyl-4- hydroxyphenol)propionate] methane; n-octadecyl-3-(4-hydroxy-3,5-di-t- butylphenyl)propionate; triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxy- phenyl)propionate]; l,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene; 2,2'- dihydroxy-3,3'-di(.alpha.-methylcyclohexyl)-5,5’-dimethyldiphenyl methane; 4,4- methylenebis(2,6-di-t-butylphenol); tris(3,5-di-t-butyl-4-hydroxyphenol); tris(3,5-di-t-butyl- 4-hydroxyphenyl) isocyanurate; 1,3,5 tris(3',5'-di-t-butyl-4-hydroxybenzoyl)isocyanurate; bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; l-oxy-3- methylisopropylbenzene; 2,5-dibutylhydroquinone; 2,2'-methylenebis(4-methyl-6- nonylphenol); alkylated bisphenol; 2,5-di-t-amylhydroquinone; polybutylated bisphenol-A; bisphenol- A; 2,6-di-t-butyl-p-ethylphenol; 2,6-bis(2'-hydroxy-3-t-butyl-5'-methylbenzyl)-4- methylphenol; l,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; terephthaloyl-di(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl sulfide); 2,6-t-butylphenol; 2,6-di- t-butyl-2-dimethylamino-p-cresol; 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); hexamethylene glycol bis(3,5-t-butyl-4-hydroxyphenyl)propionate; (4-hydroxy-3,5-di-t- butylanilino)-2,6-bis(octylthio)-l,3,5-triazine; 2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate]; N,N’-hexamethylene(3,5-di-t-butyl-4-hydroxycinnamide); 3,5- di-t-butyl-4-hydroxybenzylphosphoric acid diethyl ester; 2,4-dimethyl-6-t-butylphenol; 4,4'- methylenebis(2,6-di-t-butylphenol); 4,4'-thiobis(2-methyl-6-t-butylphenol); tris[2-(3,5-di-t- butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate; 2,4,6-tributylphenol; bis[3,3- bis(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester; 4-hydroxymethyl-2,6-di-t- butylphenol; and bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide. Exemplary secondary aromatic amines include N-phenyl-N'-isopropyl-p-phenylenediamine; N-phenyl N'-(l,3- dimethylbutyl)-p-phenylenediamine; N,N'-diphenyl-p-phenylenediamine; dioctyl- diphenylamine; dibetanaphthyl-p-phenylenediamine; 2,2,4-trimethyl- 1 ,2-dihydroquinoline polymer and diaryl-p-phenylenediamine. In addition, sulfur containing antioxidants such as dilauryl thiodipropionate, distearyl thiodipropionate and 2-mercapto-benzimidazole; phosphorus containing antioxidants such as distearylpentaerythritol diphosphite; nickel containing antioxidants such as nickel diisobutyldithiocarbamate, nickel dimethyldithiocarbamate and nickel di-n-butyldithiocarbamate; 2-mercaptotoluimidazole; zinc 2-mercaptotoluimidazole; and 1,1 l-(3,6,9-trioxaundecyl)bis-3-(dodecylthio)propionate can be used. The antioxidant can be provided in an amount from 0.1 to 5.0 percent or from 0.5 to 2.0 percent by weight based on the weight of the copolymer.

[00048] The SBR dispersion can be vulcanized or cured to crosslink the SBR polymer thereby increasing the tensile strength and elongation of the rubber by heating the SBR, typically in the presence of vulcanizing agents, vulcanization accelerators, antireversion agents, and optionally crosslinking agents. Exemplary vulcanizing agents include various kinds of sulfur such as sulfur powder, precipitated sulfur, colloidal sulfur, insoluble sulfur and high-dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; sulfur donors such as 4,4’-dithiodimorpholine; selenium; tellurium; organic peroxides such as dicumyl peroxide and di-tert-butyl peroxide; quinone dioximes such as p- quinone dioxime and p,p'-dibenzoylquinone dioxime; organic polyamine compounds such as triethylenetetramine, hexamethylenediamine carbamate, 4,4'- methylenebis(cyclohexylamine) carbamate and 4,4'-methylenebis-o-chloroaniline; alkylphenol resins having a methylol group; and mixtures thereof. In some examples, the vulcanizing agents include sulfur dispersions or sulfur donors. The vulcanizing agent can be present from 0.1 to 15%, from 0.3 to 10%, or from 0.5 to 5%, by weight based on the weight of the SBR polymer.

[00049] Prevulcanization inhibitors can also be added to the latex composition to prevent premature vulcanization or scorching of the polymer. For example, N- cyclohexylthio-phthalimide; phthalic anhydride; N-cyclohexyl-thiophthalimide; N-phenyl- N-(trichloromethyl sulfenyl)-benzene sulfonamide; bis-(sulfonamido)-sulfides or polysulfides (e.g., bis-(N-methyl-p-toluenesulfonamido)-disulfide); substituted thiophosphoramides (e.g., N-cyclohexylthio-N-phenyldiethylphosphoramide); N-(sulfenyl) methacrylamides; thio-substituted-l,3,5-triazine, -diamine or -triamines; 2-(thioamino)-4,6- diamino-l,3,5-triazines; N,N’-substituted bis-(2,4-diamino-s-triazin-6-yl)-oligosulfides; and substituted thioformamidines can be used as prevulcanization inhibitors. In some embodiments, the prevulcanization inhibitor is N-cyclohexylthio-phthalimide (SANTOGARD™ PVI commercially available from Flexsys) or N-phenyl-N- (trichloromethyl sulfenyl)benzene sulfonamide (VULKALENT™ E commercially available from Bayer). The prevulcanization inhibitor is typically provided in an amount from 1 and 5 percent or from 1.5 to 3 percent by weight based on the weight of the latex polymer.

[00050] Exemplary vulcanization accelerators include sulfenamide-type vulcanization accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide, N-t-butyl-2- benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N-oxydiethylene- 2-benzothiazole sulfenamide, N-oxydiethylene-thiocarbamyl-N-oxydiethylene sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide and N,N'-diisopropyl-2-benzothiazole sulfenamide; guanidine-type vulcanization accelerators such as diphenylguanidine, di-o- tolylguanidine and di-o-tolylbiguanidine; thiourea-type vulcanization accelerators such as thiocarboanilide, di-o-tolylthiourea, ethylenethiourea, diethylenethiourea, dibutylthiourea and trimethylthiourea; thiazole-type vulcanization accelerators such as 2- mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, 2- mercaptobenzothiazole sodium salt, 2-mercaptobenzothiazole cyclohexylamine salt, 4- morpholinyl-2-benzothiazole disulfide and 2-(2,4-dinitrophenylthio)benzothiazole; thiadiazine-type vulcanization accelerators such as activated thiadiazine; thiuram-type vulcanization accelerators such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide and dipentamethylenethiuram tetrasulfide; dithiocarbamic acid-type vulcanization accelerators such as sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n- butyldithiocarbamate, lead dimethyldithiocarbamate, lead diamyldithiocarbamate, zinc diamyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di- n-butyldithiocarbamate, zinc pentamethylene dithiocarbamate, zinc ethylphenyldithiocarbamate, tellurium diethyldithiocarbamate, bismuth dimethyldithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, cadmium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, diethylamine diethyldithiocarbamate, piperidinium pentamethylene dithiocarbamate and pipecoline pentamethylene dithiocarbamate; xanthogenic acid-type vulcanization accelerators such as sodium isopropylxanthogenate, zinc isopropylxanthogenate and zinc butylxanthogenate; isophthalate-type vulcanization accelerators such as dimethylammonium hydrogen isophthalate; aldehyde amine-type vulcanization accelerators such as butyraldehyde-amine condensation products and butyraldehyde-monobutylamine condensation products; and mixtures thereof. The vulcanization accelerator can be present within a range of from 0. 1 to 15%, from 0.3 to 10%, or from 0.5 to 5%, by weight based on the weight of the latex polymer.

[00051] Antireversion agents can also be included in the vulcanization system to prevent reversion, i.e., an undesirable decrease in crosslink density. Suitable antireversion agents include zinc salts of aliphatic carboxylic acids, zinc salts of monocyclic aromatic acids, bismaleimides, biscitraconimides, bisitaconimides, aryl bis-citraconamic acids, bissuccinimides, and polymeric bis succinimide polysulfides (e.g., N,N'- xylenedicitraconamides). The antireversion agent can be present in a range of from 0 to 5%, from 0.1 to 3%, or from 0.1 to 2% by weight based on the weight of the latex polymer.

[00052] The above additives (antioxidants, antiozonants, prevulcanization inhibitors, vulcanizing agents, vulcanization accelerators and antireversion agents) can be mixed with the latex dispersion before it is used to modify an asphalt composition. Crosslinking agents can also be included in the vulcanization system in small amounts to facilitate crosslinking of the polymer chains and are typically organic peroxides. The latex dispersion can be vulcanized at an elevated temperature and pressure and the vulcanization process is well understood by those skilled in the art. III. Asphalt Emulsion Compositions

[00053] The latex polymers described in Section II above may be used in asphalt rejuvenation emulsion compositions to improve their characteristics. When the latex polymers are mixed with asphalt and other optional additives, the resulting composition may be used as a rejuvenator, scrub seal, fog seal, sand seal, chip seal, tack coat, bond coat, or crack filler asphalt composition.

[00054] In one embodiment, the asphalt rejuvenating emulsion composition comprises:

(i) asphalt;

(ii) a latex composition comprising a styrene-modified polymer;

(iii) a rejuvenating agent;

(iv)one or more emulsifying agents; and

(v) water.

[00055] The term “asphalt” as used herein, includes the alternative term “bitumen.” Thus, the asphalt compositions can be termed bitumen compositions. “Asphalt composition” as used herein, include asphalt emulsions and hot-mix asphalt compositions. The asphalt can be molten asphalt. The asphalt rejuvenating emulsion compositions may comprise asphalt in an amount as low as 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, or as high as 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, 99 wt.%, or within any range encompassed by any two of the foregoing values as endpoints. For example, the asphalt rejuvenating emulsion may comprise from 60 wt.% to 99 wt.% of asphalt, based on the total weight of the asphalt emulsion composition.

[00056] The latex composition comprising styrene-modified polymers as described in Section II above may be present in asphalt compositions in an amount of as low as 0.01%, 0.1 wt.%, 1 wt.%, 5 wt.%, or as high as 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the asphalt emulsion composition. For example, the latex composition comprising the styrene-modified polymer may be present in an amount of from 1 wt.% to 20 wt.%.

[00057] The asphalt compositions may also comprise a rejuvenating agent. Rejuvenating agents are sometimes referred to as recycling agents, may be petroleum- or bio-based. Rejuvenating agents are designed to replenish the essential components of the asphalt binder such as oils and resins, which may have been lost over time due to weathering or oxidation. Suitable rejuvenating agents include maltenes which are the nonasphaltene fraction of asphalt, referred to as deasphalted or deasphaltened oil. Rejuvenating agents which are classified into types such as RA-1, RA-5, RA-25, and RA-75 as defined by ASTM D4552 may also be used. Exemplary rejuvenating agents are available from Holly Frontier under their HYDROLENE™ brand asphalt oils, from American Refining Group, Inc. under their KENDEX™ brand or from Tricor Refining, LLC under their Golden Bear Preservation products RECLAMITE™ brand. Asphalt oils meeting ASTM standard D4552, and classified as RA-1 are suitable for harder asphalts, such as PG 64 asphalts. RA-5, RA- 25 and RA-75 oils may also be used with lower viscosity asphalts, such as PG 52 asphalts. The rejuvenating agent used in the present invention can be a biobased rejuvenating agent or it can be a blend of a petroleum- and a bio-based rejuvenating agents. Biobased rejuvenating agents may be bio-renewable oils or esters that include oils isolated from plants and animals. An example of a suitable plant based rejuvenation agent is RHEOPHALT marketed by BASF. Non-limiting examples of plant-based oils include soybean oil, linseed oil, canola oil, cottonseed oil, sunflower oil, palm oil, peanut oil and blends thereof and non-limiting examples of animal-based oils may include animal fat such as lard and tallow, and lecithin and blends thereof as listed in WO2016/138384 which is incorporated herein by reference. In addition, non-limited examples of biobased rejuvenating agents may include oils or esters from natural or biological sources as listed in W02017/011747 which is incorporated herein by reference.

[00058] The asphalt compositions may also optionally comprise water. If present, the water may be present in an amount of as low as 0.01%, 0.1 wt.%, 1 wt.%, 5 wt.%, 10 wt.%, or as high as 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the asphalt emulsion composition. For example, the water may be present in an amount of from 1 wt.% to 20 wt.%.

[00059] The asphalt compositions may also further comprise an emulsifying agent to aid the dispersion and suspension of the asphalt binder. The emulsifying agent may be cationic, anionic, or non-ionic or a blend of emulsifying agents such as a blend of cationic and non-ionic or a blend of anionic and non-ionic emulsifying agents.

[00060] Exemplary cationic emulsifying agents include polyamines, fatty amines, fatty amido-amines, ethoxylated amines, diamines, imidazolines, quaternary ammonium salts, and mixtures thereof. Commercial cationic emulsifying agents include, for example, those available from Nouryon Surface Chemistry under the REDICOTE™ brand (including REDICOTE 4819, REDICOTE E-64R, REDICOTE E16, REDICOTE E-9, REDICOTE EM-44, REDICOTE C-346, REDICOTE E-7000 and REDICOTE E-70), and from Ingevity under the INDULIN™ brand (including INDULIN F-80, INDULIN DF-60, INDULIN DF- 40, INDULIN DF-42, INDULIN DF-30, INDULIN R-20, INDULIN AA 56, INDULIN AA 57), and the AROSURF™ brand (including AROSURF AA-54, AROSURF AA-71, AROSURF AA-78, AROSURF AA-83, AROSURFAA-86 and AROSURF AA-89).

[00061] Exemplary anionic emulsifying agents include alkali metal or ammonium salts of fatty acids, alkali metal polyalkoxycarboxylates, alkali metal N-acylsarcosinates, alkali metal hydrocarbylsulphonates, for example, sodium alkylsulphonates, sodium arylsulphonates, sodium alkylarylsulphonates, sodium alkylarenesulphonates, sodium lignosulphonates, sodium dialkylsulphosuccinates and sodium alkyl sulphates, long chain carboxylic and sulphonic acids, their salts and mixtures thereof.

[00062] Exemplary non-ionic emulsifying agents include ethoxylated compounds and esters, for example ethoxylated fatty alcohols, ethoxylated fatty acids, sorbitan esters, ethoxylated sorbitan esters, ethoxylated alkylphenols, ethoxylated fatty amides, glycerine fatty acid esters, alcohols, alkyl phenols, and mixtures thereof.

[00063] Any of the foregoing emulsifying agents may be present in the asphalt emulsion composition in an amount as low as 0.01%, 0.1 wt.%, 1 wt.%, 5 wt.%, 10 wt.%, or as high as 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the asphalt emulsion composition. For example, the emulsifying agent may be present in an amount of from 1 wt.% to 20 wt.%.

[00064] The asphalt compositions can further include one or more additional additives. Suitable additional additives include chloride salts, thickeners, and fillers.

Chloride salts can be added, for example to improve emulsifyability, in an amount of up to 1 part by weight. Suitable chloride salts include sodium chloride, potassium chloride, calcium chloride, aluminum chloride, or mixtures thereof. Thickeners can be added in an amount of 0.5 parts by weight or greater and can include associative thickeners, polyurethanes, alkali swellable latex thickeners, cellulose, cellulose derivatives, modified cellulose products, plant and vegetable gums, starches, alkyl amines, polyacrylic resins, carboxyvinyl resins, polyethylene maleic anhydrides, polysaccharides, acrylic copolymers, hydrated lime (such as cationic and/or nonionic lime), or mixtures thereof. In some embodiments, the asphalt compositions described herein do not include a thickener. Mineral fillers and/or pigments can include calcium carbonate (precipitated or ground), kaolin, clay, talc, diatomaceous earth, mica, barium sulfate, magnesium carbonate, vermiculite, graphite, carbon black, alumina, silicas (fumed or precipitated in powders or dispersions), colloidal silica, silica gel, titanium oxides (e.g., titanium dioxide), aluminum hydroxide, aluminum trihydrate, satine white, magnesium oxide, hydrated lime, limestone dust, Portland cement, silica, alum, fly ash, or mixtures thereof. Fillers such as mineral fillers and carbon black can be included in an amount of up to 5 parts by weight or up to 2 parts by weight.

[00065] The asphalt compositions can also include an aggregate. The aggregate can be of varying sizes as would be understood by those of skill in the art. Any aggregate that is traditionally employed in the production of bituminous paving compositions can be used, including dense-graded aggregate, gap-graded aggregate, open-graded aggregate, reclaimed asphalt pavement, and mixtures thereof. In some embodiments, the asphalt compositions can include an aggregate in an amount of 1 % to 90% by weight, based on the weight of the asphalt composition. In some embodiments, the asphalt compositions can include an aggregate in an amount of 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, or 45% or less by weight, based on the weight of the asphalt composition. In some embodiments, the asphalt compositions can include an aggregate in an amount of 5% or greater, 10% or greater, 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 40% or greater, 45% or greater, or 50% or greater by weight, based on the weight of the asphalt composition.

[00066] The latex compositions can also be used in asphalt tack coats and the asphalt tack compositions using the polymers of the invention can have a tack-free time of 20 minutes or less.

IV. Methods for Applying Asphalt Rejuvenating Emulsions

[00067] The present disclosure also provides a method for rejuvenating asphalt using the polymer latex compositions and asphalt compositions described herein.

[00068] In one embodiment, the method comprises:

(i) providing an asphalt rejuvenating emulsion composition comprising:

• asphalt;

• a latex composition comprising a styrene-modified polymer; a rejuvenating agent; one or more emulsifying agents; and water; and

(ii) applying the asphalt rejuvenating emulsion composition to a deteriorated asphalt pavement surface.

[00069] The asphalt rejuvenating emulsion may be applied by hand spreading, conventional spreading, spraying, or other techniques. A recommended application rate may be, for example, about 0.045 to about 2.7 liters/sq. meter (about 0.01 to about 0.60 gal/sq. yd.) or about 0.14 to about 2.0 liters/sq. meter (about 0.03 to about 0.45 gal/sq. yd.). The emulsion can be applied in multiple passes over the substrate layers at lower rates to achieve a comparable product, where the total application rate is equal to the sum of the multiple passes and is from about 0.045 liters/sq. meter to about 2.7 liters/sq. meter (about 0.01 to about 0.60 gal/sq. yd.). For example, an emulsion may be applied in three passes over the substrate layer at application rates of 0.04 liters/sq. meter (about 0.01 gal/sq. yd.) each, or a total application rate of about 0.12 liters/sq. meter (0.03 gal/sq. yd.). The emulsion application rate may also vary depending on the specified application conditions, emulsion composition, the surface to which it is applied, and the nature of the permanent materials or base (viz., the pavement structure), and other similar factors.

[00070] The emulsion temperature during application may, for example, be from about 4° C. (40° F.) to about 99° C. (210° F.), from about 49° C. (120° F.) to about 77° C. (170° F.), or from about 38° C. (100° F.) to about 71° C. (160° F.). Alternatively, the emulsion may be at ambient temperature (e.g. about 20° C. to 25° C. (68° F. to 77° F.), but if so applied may require a longer curing time. The emulsion typically is placed on top of a deteriorated surface and is allowed to cure before traffic passes over the coated surface or additional pavement layer(s) are applied to the coated surface.

[00071] The present composition also encompasses a tack coat asphalt composition as described herein. Methods for applying tack coats comprising the asphalt compositions are also disclosed. The method can include applying the tack coat to a surface, wherein the tack coat is at a temperature of from ambient temperature to 130°C, such as from 20°C to 130°C, from 60°C to 130°C, or from ambient temperature to 100°C. The applying step can be carried out using a brush, a squeegee, or a spray equipment. The surface can be selected from dirt, gravel, slurry seal pavement, chip seal pavement, hot mix asphalt, warm mix asphalt, microsurfaced pavements, and concrete pavements. The methods disclosed herein can further include applying an asphalt composition to the tack coat once the tack coat has become trackless.

[00072] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative materials and method steps disclosed herein are specifically described, other combinations of the materials and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

[00073] By way of non-limiting illustration, examples of certain embodiments of the present disclosure are given below.

EXAMPLES

[00074] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compositions and/or methods claimed herein are made and evaluated and are intended to be purely exemplary and are not intended to limit the scope of the disclosure. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.

Preparation of a Non-Carboxylated Styrene-Butadiene-Acrylate Latex [00075] A non-carhoxylated styrene-butadiene-hutyl acrylate latex was prepared as follows. A copolymer derived from 43.41 parts by weight styrene, 4.88 parts by weight acrylamide, 46.83 parts of n-butyl acrylate, and 4.88 parts by weight butadiene was produced. A styrene feed, an acrylamide feed, an n-butyl acrylate feed, and an initiator feed comprising an aqueous solution of sodium persulfate initiator (1.15 parts by weight of the total monomers) and /e/y -dodecyl mercaptan (0.75 parts by weight of the total monomers) were added over 4 hours to a pre-heated reactor (85 °C) containing water, a polystyrene seed latex (0.63 parts by weight of the total monomers), and TRILON BX (0.02 parts by weight of the total monomers), an ethylenediaminetetraacetic acid commercially available from BASF Corporation (Florham Park, NJ). The stabilization of the latex particles during polymerization was accomplished by feeding an aqueous solution of a 10-mole ethylene oxide adduct of tridecyl alcohol surfactant (2.0 parts by weight of the total monomers) over the course of the polymerization. Two hours into the monomer feed, a butadiene feed was started. In addition, 0.12 parts of tetrasodium pyrophosphate were fed into the reactor over the course of the polymerization. The temperature was maintained at 85 °C throughout the polymerization reaction. Following the polymerization process, the latex dispersion was stripped of the residual monomers to provide an aqueous dispersion with residual styrene levels of less than 400 ppm and acrylonitrile levels of less than 100 ppm, if used. Following the same general procedure as above, the following examples were prepared. Sodium hydroxide was used to adjust pH as needed.

Table 1

Mass Balance for Examples 1-3

[00076] Example 4 is a commercial aqueous styrene-acrylate copolymer dispersion: 48.0 solids content by weight, pH = 7.0, viscosity at 23 °C (Brookfield RV, Spindle #5, at 50 rpm) 100 - 500 cps, Tg by DSC = 12°C. [00077] Example 5 is Showa Denko Chloroprene 115 which is a copolymer of chloroprene and methacrylic acid, stabilized with polyvinyl alcohol, 47% solids by weight, pH = 7.0, viscosity at 23°C (Brookfield RV, Spindle #1, at 30 rpm) 350 - 500 cps, Tg by DSC = -37°C.

Table 2

Mass Balance for Examples 6-9

ND = not determined

Table 3

Mass Balance for Examples 10-12

Table 4

Mass balance for Examples 13-15

Swelling Resistance to Asphalt Rejuvenators

The rejuvenating agent swelling resistance of the various latexes from the Instant Examples were tested by soaking polymer films made from the latex compositions in an asphalt rejuvenator. According to ASTM D487, 1” x 1” polymer films were cut in triplicate, weighed, and placed in aluminum tins. Reclamite Base asphalt rejuvenator was added to each of the tins to a level so as to completely submerge the polymer films. The sealed tins were placed in an oven at 50 °C for 48 hrs. After cooling to room temperature, the films were removed from the asphalt rejuvenator and lightly rinsed with acetone and blotted dry before being reweighed. The results are summarized in Table 5 below: Table 5

Mass Change after Immersion in Reclamite Base for 48 hours at 50°C

Scrub Seal Emulsions Modified with the Instant Polymers

[00078] The emulsifier solution, latex polymer, and molten asphalt performance grade (PG) 64-22 PG or 58-28 PG from a Midwestern refinery with a range of hydrocarbon rejuvenator contents were pumped into a colloid mill where high shear mixing produced a scrub seal emulsion with a 69 wt.% residue. Table 6

Scrub Seal Emulsions

Determination of Particle Sizes

[00079] The particle size distribution of the asphalt emulsions was determined by quasi-elastic light scattering (QELS), also known as dynamic light scattering (DLS) according to ISO 13321: 1996 standard. The determination was carried out using High- Performance Particle Sizer (Malvern) at 22°C and a wavelength of 633 nm. For this purpose, a sample of the asphalt emulsion was diluted, and the dilution is analyzed. In the context of DLS, the aqueous dilution may have a polymer concentration in the range from 0.001 to 0.5% by weight, depending on the particle size. For most purposes, a proper concentration will be 0.01% by weight. The reported particle size values in Table 7 are the z-average of the cumulant evaluation of the measured of the measured autocorrelation function.

Table 7

Scrub Seal Emulsion Particle Size

Example 16: Percent Recovery Testing

[00080] The percent recovery of the latexes of the invention across a variety of temperatures was measured using Multiple Stress Creep Recovery test according to AASHTO T-350 or ASTM D7405.

Table 8

Percent Recovery at 100 Pa

Table 9

Percent Recovery at 3200 Pa

[00081] The results from Tables 8 and 9 suggest that the asphalt scrub seal emulsion comprising the copolymer composition comprising acrylonitrile has the highest percent recovery at 100 Pa and at 3200 Pa.

[00082] In some embodiments, the asphalt compositions can be used as a tack coat or coating. The tack coat is a very light spray application of diluted asphalt emulsion that can be used to promote a bond between an existing surface and the new asphalt application. The tack coat acts to provide a degree of adhesion or bonding between asphalt layers, and in some instances, can fuse the layers together. The tack coat also acts to reduce slippage and sliding of the layers relative to other layers in the pavement structure during use or due to wear and weathering of the pavement structure. In some embodiments, the asphalt compositions of the present invention can be applied to an existing paved layer (such as a hot-mix layer) as a tack coat, and a new layer comprising asphalt such as a hot-mix layer can be applied to the tack coat. As would be understood by those skilled in the art, the tack coat typically does not include aggregate, although sand may be applied to the tack coat after application.

[00083] The tack coat compositions of the present invention have been shown to be low-tracking or “trackless” coatings and meet an ASTM-D-977 standard. In particular, the asphalt compositions cure/dry quickly. For example, where the asphalt compositions are used as a tack coating, the coating cures quickly such that a pavement layer may be applied to the coating, soon after the asphalt composition of the present invention is applied to the substrate. In some embodiments, the applied asphalt composition can become trackless (tack-free) in less than 20 minutes, such as less than 19 minutes, less than 18 minutes, less than 17 minutes, less than 16 minutes, less than 15 minutes, or less than 10 minutes. In some embodiments, the applied asphalt composition can cure in 15 minutes to 30 minutes, and may cure as rapidly as less than 10 minute to 20 minutes after the composition is applied to the exposed surface. The cure rate will depend on the application rate, the dilution ratios used, the base course conditions, the weather, and other similar considerations. If the prepared pavement surface or base course contains excess moisture, the curing time of the asphalt compositions may be increased.

[00084] Methods for applying tack coats comprising the asphalt compositions of the present invention can include applying the tack coat to a surface, wherein the tack coat is at a temperature of from ambient temperature to 130°C, such as from 20°C to 130°C, from 60°C to 130°C, or from ambient temperature to 100°C. The applying step can be carried out using a brush, a squeegee, or spray equipment. The surface can be selected from dirt, gravel, slurry seal pavement, chip seal pavement, hot mix asphalt, warm mix asphalt, microsurfaced pavements, and concrete pavements. The methods disclosed herein can further include applying an asphalt composition to the tack coat once the tack coat has become trackless. [00085] The asphalt emulsion compositions were applied to a substrate at a film thickness of 15 mils and at ambient temperature and the time for the asphalt composition to become trackless was determined. The results are summarized in Table 10. Addition of the polymers of the invention showed improvement in tracking as reflected by the shorter drying times compared to the unmodified tack coat asphalt emulsion.

Table 10

Trackless tack coat asphalt emulsion compositions.

⁺Time (min) - refers to the time for the coatings to become trackless.

Example 17: Swelling Resistance of Terpolymer Samples in Kerosene

[00086] In order to test the swelling resistance of the inventive terpolymer further, samples were immersed in kerosene for 48 hours at 50°C. The results are included in Table 11 below.

Table 11

Mass Change after Immersion in Kerosene, wt%

Example 18: Swelling Resistance of Terpolymer Samples in Diesel Fuel [00087] In order to test the swelling resistance of the inventive terpolymer further, samples were immersed in diesel fuel for 48 hours at 50°C. The results are included in Table 12 below.

Table 12

Mass Change after Immersion in Diesel Fuel, wt%

Example 19: Tensile and Elongation of Terpolymer Samples

[00088] The inventive terpolymers were tested for tensile strength and elongation at break. The results of that testing is included in the Table 13 below.

Table 13

Tensile and Elongation

Example 20: Water Absorption of Polymer Modified Asphalt Performance [00089] Water Absorption was tested in a polymer modified asphalt to determine the effect of the inventive terpolymer on water absorption of the asphalt. The results are contained in Table 14 below.

Table 14

Water Absorption of Polymer Modified Asphalt Performance

[00090] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of’ and “consisting of” can be used in place of “comprising” and “including” to provide for more specific embodiments of the invention and are also disclosed. Other than in the examples, or where otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood at the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be construed in light of the number of significant digits and ordinary rounding approaches.

Claims

CLAIMS What is claimed is:

1. An asphalt rejuvenating emulsion composition comprising:

(i) asphalt;

(ii) a latex composition comprising a styrene-modified polymer;

(iii) a rejuvenating agent;

(iv) one or more emulsifying agents; and

(v) water.

2. The asphalt emulsion composition of claim 1 , wherein the styrene-modified polymer is a styrene-butadiene-acrylate terpolymer.

3. The asphalt emulsion composition of claim 1, wherein the styrene-modified polymer is a styrene-acrylate copolymer.

4. The asphalt emulsion composition of claim 1, wherein the styrene-modified polymer is a styrene-acrylate-acrylonitrile terpolymer.

5. The asphalt emulsion composition of claim 1, wherein the styrene-modified polymer is a styrene-butadiene-acrylate-acrylonitrile copolymer.

6. The asphalt emulsion composition of claim 1 , wherein the latex composition is present in an amount of from 1 wt.% to 20 wt.%, based on the total weight of the asphalt emulsion composition.

7. The asphalt emulsion composition of claim 1 wherein the asphalt is an asphalt binder for scrub-seal applications.

8. The asphalt emulsion composition of claim 1, wherein the asphalt is present in an amount of from 60 wt.% to 99 wt.%, based on the total weight of the asphalt emulsion composition.

9. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is present in an amount of from 1 wt.% to 99 wt.%, based on the total weight of the asphalt emulsion composition.

10. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is present in an amount of from 1 wt.% to 40 wt.%, based on the total weight of the asphalt emulsion composition.

11. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is hydrocarbon-based rejuvenating agent.

12. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is selected from the group consisting of RA-1, RA-5, RA-25, or RA-75 rejuvenating agents.

13. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is a bio-based rejuvenating agent.

14. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is a blend of a hydrocarbon-based and a bio-based rejuvenating agents.

15. The asphalt emulsion composition of claim 1, wherein the asphalt is recycled asphalt.

16. The asphalt emulsion composition of claim 1, wherein the asphalt is a blend of virgin and recycled asphalt.

17. The asphalt emulsion composition of claim 1 wherein the composition is substantially free of emulsifying agents and water.

18. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is present in an amount of 0 wt.% to 95 wt.%, based on the total weight of the asphalt.

19. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is a bio-based rejuvenating agent.

20. The asphalt emulsion composition of claim 1, wherein the rejuvenating agent is a blend of a hydrocarbon-based and a bio-based rejuvenating agents.

21. A rejuvenated asphalt pavement comprising the asphalt rejuvenating emulsion composition of claim 1.

22. A trackless tack coat comprising the composition of claim 1.

23. The composition of claim 22 wherein the trackless tack coat is cationic.

24. The composition of claim 22wherein the trackless tack coat is anionic.

25. The composition of claim 22 wherein the trackless tack coat is non-ionic.

26. The composition of any one of claims 21-25, wherein the asphalt composition has a tack-free time of 20 minutes or less.

27. A scrub seal comprising the composition of claim 1.

28. A fog seal comprising the composition of claim 1.

29. A chip seal comprising the composition of claim 1.

30. A paving asphalt comprising the composition of claim 1.

31. The composition of claim 30 wherein the paving asphalt composition is fuel resistant.

32. A hot-mix asphalt composition comprising the latex composition of claim 1.

33. A microsurfacing asphalt composition comprising the composition of claim 1.

34. A waterproofing composition comprising the composition of claim 1.

35. The composition of claim 1 where the latex Tg is in the range of -60 °C to + 60°C.

36. The composition of claim, 47 wherein the latex Tg is in the range of -25 °C to + 45°C.

37. The composition of claim, 47 wherein the latex Tg is in the range of -15°C to + 30°C.

38. A method for rejuvenating asphalt comprising:

(i) providing an asphalt rejuvenating emulsion composition comprising: asphalt; a latex composition comprising a styrene-modified polymer; a rejuvenating agent; one or more emulsifying agents; water; and

(ii) applying the asphalt rejuvenating emulsion composition to a deteriorated asphalt pavement surface.

39. The method of claim 38, wherein the styrene-modified polymer is a styrene- butadiene-acrylate terpolymer.

40. The method of claim 38, wherein the styrene-modified polymer is a styrene-acrylate copolymer.

41. The method of claim 38, wherein the styrene-modified polymer is a styrene- acrylate-acrylonitrile terpolymer.

42. The method of claim 38, wherein the asphalt rejuvenating emulsion composition further comprises a terpinolene chain transfer agent.

43. The method of claim 38, wherein the styrene-acrylic polymer is a styrene-butadiene- acry late- acrylonitrile copolymer.

44. The method of claim 38, wherein the latex composition is present in an amount of from 1 wt.% to 20 wt.%, based on the total weight of the asphalt emulsion composition.

45. The method of claim 38, wherein the asphalt is present in an amount of from 60 wt.% to 99 wt.%, based on the total weight of the asphalt emulsion composition.

46. The method of claim 38, wherein the rejuvenating agent is present in an amount of from 1 wt.% to 40 wt.%, based on the total weight of the asphalt emulsion composition.

47. The method of claim 38, wherein the rejuvenating agent is selected from the group consisting of RA-1, RA-5, RA-25, or RA-75 rejuvenating agents.

48. The method of claim 38, wherein the emulsifying agent is present in an amount of 0. 1 wt.% to 5 wt.%, based on the total weight of the asphalt emulsion composition.