WO2024129869A1

WO2024129869A1 - Modified asphalt compositions containing vinyl acetate latexes and methods for making same

Info

Publication number: WO2024129869A1
Application number: PCT/US2023/083849
Authority: WO
Inventors: Kostas S. Avramidis; William J. Kirk
Original assignee: Basf Corporation
Priority date: 2022-12-15
Filing date: 2023-12-13
Publication date: 2024-06-20

Abstract

Disclosed herein are asphalt compositions containing a vinyl acrylic latex polymer additive. In some embodiments, the vinyl acrylic latex polymer may include a copolymer derived from: vinyl acetate; an acrylate monomer having a glass transition temperature (Tg) of 20°C or less; and water. Methods of making and using the asphalt compositions are also disclosed.

Description

MODIFIED ASPHALT COMPOSITIONS CONTAINING VINYL ACETATE LATEXES AND METHODS FOR MAKING SAME

FIELD OF THE DISCLOSURE

[0001] This disclosure relates generally to asphalt compositions, and more particularly to asphalt compositions that include a vinyl acetate 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. The properties of asphalt may be improved by the incorporation of polymer-based additives. The addition of a polymer can improve adhesion, ductility, tensile strength, durability, and cold temperature properties of the asphalt. Polymer modified asphalt compositions can be prepared by melting the asphalt and adding a polymer to the molten asphalt. However, this process is energy intensive. Alternately, polymer modified asphalt compositions can be prepared by mixing emulsions of asphalts with a latex of the polymer. While this process is less energy intensive, it increases the delay in setting times and drying times of asphalt emulsions. This delay is extremely expensive when traffic must be kept off a lane of a highway for a lengthy period of time. Another problem encountered is that the asphalt emulsion may get too fluid and can separate from the aggregate, reducing the lifetime of the pavement. There is a need for asphalt compositions with better adhesion to aggregates, setting times, and viscosity. The compositions and methods described herein address these and other needs.

SUMMARY OF THE DISCLOSURE

[0003] Disclosed herein are vinyl acetate latex modified asphalt compositions including emulsions and hot mixes.

[0004] In one form thereof, the present disclosure provides an asphalt emulsion composition comprising: asphalt; a vinyl acrylic latex polymer comprising a copolymer derived from: vinyl acetate; an acrylate monomer having a glass transition temperature (T_g) of 20°C or less; and water.

[0005] Methods of making and using the asphalt compositions are also disclosed. The method can include mixing asphalt, an aqueous dispersion, and the polymer latex. Methods of coating a surface comprising applying an asphalt composition as described herein are also disclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the disclosure and together with the description, serve to explain the principles of the disclosure.

[0007] Fig. 1 A is an image of the sweep test results for cationic styrene butadiene (SB) freeze coagglomerated + 2.1% curing agent.

[0008] Fig. IB is an image of sweep test results for cationic SB as is / styrene butadiene rubber (SBR):50/50 + 3.1% curing agent

[0009] Fig. 1C is an image of sweep test results for the vinyl acrylic latex according to the invention.

[00010] Fig.2A is an image of sweep test results for cationic SBR + 2.1% curing agent.

[00011] Fig. 2B is an image of sweep test results for cationic SB freeze agglomerated +2.1 % curing agent.

[00012] Fig. 2C is an image of sweep test results for vinyl acrylic latex according to the invention.

[00013] Fig. 3 A is an image of sweep test results for cationic commercial SBR.

[00014] Fig. 3B is an image of sweep test results for crosslinked vinyl acrylic latex according to the invention.

[00015] Fig. 4 shows a particle size distribution comparison for a polymer latex modified asphalt.

DETAILED DESCRIPTION

I, Definitions

[00016] 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.

[00017] 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.

[00018] “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.

[00019] 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.

[00020] The term “(meth)acryl ...” includes “acryl . . . ,” “methacryl . . . ,” or mixtures thereof.

[00021] The term “(co)polymer” includes homopolymers, copolymers, or mixtures thereof.

II. Vinyl Acetate Latex Polymers

[00022] Described herein are asphalt compositions comprising a vinyl acrylic latex polymer. In some examples, the compositions include a copolymer derived from: vinyl acetate; an acrylate monomer having a glass transition temperature (Tg) of 20°C or less; and water.

[00023] In some examples the copolymer may include further monomers, a carboxylic acid, a carboxylic acid anhydride, or a combination thereof; and may further include an organosilane. The copolymer may also be derived in the presence of maltodextrin.

[00024] In some examples, the copolymer can be derived from 30% or more by weight vinyl acetate, based on the total weight of the polymer latex (e.g., 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, or 85% or more). In some examples, the copolymer can be derived from 90% or less by weight vinyl acetate, based on the total weight of the polymer latex (e.g., 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, or 40% or less). The amount of vinyl acetate the copolymer is derived from can range from any of the minimum values described above to any of the maximum values described above. For example, the copolymer can be derived from 30% to 90% by weight vinyl acetate, based on the total monomer content (e.g., from 20-70% from 30% to 60%, from 60% to 90%, from 45% to 75%, from 40% to 90%, from 50% to 90%, from 70% to 90%, from 80% to 90%, or from 85% to 90%).

[00025] In some examples, the vinyl acrylic latex polymer can include poly(vinyl acetate).

[00026] As used herein, an acrylate monomer having a T_g of 20°C or less refers to an acrylate monomer that when homopolymerized forms a polymer having a measured glass transition temperature of 20°C, as measured using differential scanning calorimetry (DSC) using the mid-point temperature using the method described, for example, in ASTM 3418/82. Examples of acrylate monomers having a T_g of 20°C or less include, but are not limited to, ethyl acrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, /.w-decyl acrylate, dodecyl methacrylate, lauryl methacrylate, ethyldiglycol acrylate, heptadecyl acrylate, iso-tridecyl methacrylate, , 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, dibutyl maleate, dioctyl maleate, 2-octyl acrylate, and combinations thereof. In some examples, the acrylate monomer includes butyl acrylate, 2-ethylhexyl acrylate, or a combination thereof. In some examples, the acrylate monomer includes butyl acrylate. In some examples, the acrylate monomer consists of butyl acrylate.

[00027] The copolymer can, for example, be derived from 20% or more by weight of the acrylate monomer, based on the total monomer content (e.g., 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, or 60% or more). In some examples, the copolymer can be derived form 70% or less by weight of the acrylate monomer, based on the total weight of the polymer latex (e.g., 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, or 30% or less). The amount of the acrylate monomer the copolymer is derived from can range from any of the minimum values described above to any of the maximum values described above. For example, the copolymer can be derived from 20% to 70% by weight of the acrylate monomer, based on the total monomer content (e.g., from 20% to 45%, from 45% to 70%, from 20% to 30%, from 30% to 40%, from 40% to 50%, from 50% to 60%, from 60% to 70%, from 25% to 65%, or from 30% to 60%).

[00028] As disclosed herein, the copolymer may also be derived from a carboxylic acid, a carboxylic acid anhydride, or a combination thereof. The carboxylic acid, carboxylic acid anhydride, or a combination thereof can, for example, be derived from a monocarboxylic acid, a dicarboxylic acid, or a combination thereof. Examples of suitable carboxylic acids and carboxylic anhydrides include, but are not limited to, (meth)acrylic acid, crotonic acid, dimethacrylic acid, ethylacrylic acid, allylacetic acid, vinylacetic acid maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, methylmalonic anhydride, and combinations thereof. In some examples, the carboxylic acid, carboxylic acid anhydride, or a combination thereof can be selected from the group consisting of (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, anhydrides thereof (e.g., itaconic anhydride, maleic anhydride), and combinations thereof. In some examples, the carboxylic acid includes acrylic acid. In some examples, the carboxylic acid consists of acrylic acid.

[00029] The copolymer can, for example, be derived from greater than 0% by weight of the carboxylic acid, carboxylic acid anhydride, or a combination thereof, based on the total weight of the polymer latex (e.g., 0.1% or more, 0.25% or more, 0.5% or more, 0.75% or more, 1% or more, 1.5% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, 5% or more, 6% or more, 7% or more, or 8% or more). In some examples, the copolymer can be derived from 10% or less by weight of the carboxylic acid, carboxylic acid anhydride, or a combination thereof, based on the total weight of the polymer latex (e.g., 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, 1.5% or less, 1 % or less, 0.75% or less, or 0.5% or less). The amount of carboxylic acid, carboxylic acid anhydride, or a combination thereof the copolymer is derived from can range from any of the minimum values described above to any of the maximum values described above. For example, the copolymer can be derived from greater than 0% to 5% by weight carboxylic acid, carboxylic acid anhydride, or a combination thereof, based on the total weight of the polymer latex (e.g., from greater than 0% to 9%, from greater than 0% to 8%, from greater than 0% to 7%, from greater than 0% to 6%, from greater than 0% to 5%, from greater than 0% to 4%, from 0.1% to 3%, from 0.25% to 2.5%, or from 0.5% to 2%). [00030] 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.

[00031] The copolymer can, for example, be derived from 0.01% or more by weight of the organosilane, based on the total weight of the polymer latex (e.g., 0.1% or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, or 1.5% or more). In some examples, the copolymer can be derived from 3% or less by weight of the organosilane, based on the total monomer content (e.g., 2.9% or less, 2.8% or less, 2.7% or less, 2.6% or less, 2.5% or less, 2.4% or less, 2.3% or less, 2.2% or less, 2.1% or less, 2.0% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5% or less, 1.4% or less, 1.3% or less, 1.2% or less, 1.1% or less, 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, or 0.5% or less). The amount of organosilane the copolymer is derived form can range from any of the minimum values described above to any of the maximum values described above. For example, the copolymer can be derived from 0.01-3% by weight of the organosilane, based on the total weight of the polymer latex (e.g., from 0.05% to 1.5%, from 0.05% to 1%, from 0.05% to 0.9%, from 0.05% to 0.8%, from 0.05% to 0.7%, from 0.05% to 0.6%, or from 0.1% to 0.5%).

[00032] The copolymer can be derived from other monomers. For example, the copolymer can be derived from vinyl esters of branched mono-carboxylic 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 neo-decanoate, vinyl neo- undecanoate, vinyl neo-dodecanoate and mixtures thereof, and copolymerizable surfactant monomers (e.g., those sold under the trademark ADEKA REASOAP).

[00033] In addition to the monomers, the copolymer may be formed in the presence of and include maltodextrin. The maltodextrin can have, for example, a dextrose equivalent (DE) of 10 or more (e.g., 10.5 or more, 11 or more, 11.5 or more, 12 or more, 12.5 or more, 13 or more, 13.5 or more, 14 or more, 14.5 or more, 15 or more, 16 or more, 17 or more, 18 or more, 19 or more, 20 or more, 21 or more, 22 or more, 23 or more, 24 or more, 25 or more, 30 or more, or 35 or more). In some examples, the maltodextrin can have a DE of 50 or less (e.g., 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 24 or less, 23 or less, 22 or less, 21 or less, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14.5 or less, 14 or less, 13.5 or less, 13 or less, or 12.5 or less). The DE value of the maltodextrin can range from any of the minimum values described above to any of the maximum values described above. For example, the maltodextrin can have a DE of from 10 to 50 (e.g., from 15 to 50, from 10 to 40, from 10 to 35, from 12.5 to 25, or from 15 to 20). The DE value can be determined in accordance with the Lane and Eynon test method (International Standard ISO 5377: 1981).

[00034] The weight average molecular weight (M_w) of the maltodextrin can be, for example, 3,000 Daltons or more (e.g., 3,500 or more; 4,000 or more; 4,500 or more; 5,000 or more; 6,000 or more; 7,000 or more; 8,000 or more; 9,000 or more; 10,000 or more; 11,000 or more; 12,000 or more; 13,000 or more; 14,000 or more; 15,000 or more; 16,000 or more; or 17,000 or more). In some examples, the weight average molecular weight (M_w) of the maltodextrin can be 20,000 Daltons or less (e.g., 19,000 or less; 18,000 or less; 17,000 or less; 16,000 or less; 15,000 or less; 14,000 or less; 13,000 or less; 12,000 or less; 11,000 or less; 10,000 or less; 9,000 or less; 8,000 or less; 7,000 or less; 6,000 or less; or 5,000 or less). The weight average molecular weight (M_w) of the maltodextrin can range from any of the minimum values described above to any of the maximum values described above. For example, the weight average molecular weight (M_w) of the maltodextrin can be from 3,000 to 20,000 Daltons (e.g., from 3,000 to 19,000; from 4,000 to 19,000; from 4,500 to 18,000; from 5,000 to 17,000; or from 8,000 to 14,000). The weight average molecular weight (M_w) of the maltodextrin can be determined by size exclusion chromatography.

[00035] In some examples, the maltodextrin can be soluble in water at room temperature in an amount of greater than about 40% by weight (e.g., 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more). In some examples, the maltodextrin can be completely soluble in water at room temperature. The maltodextrin is generally degraded starches whose degradation is affected by heating with or without addition of chemicals, it being possible to recombine degradation fragments under the degradation conditions to form new bonds which were not present in this form in the original starch. Roast dextrins such as white and yellow dextrins that are prepared by heating moist-dry starch, usually in the presence of small amounts of acid, are less preferred. The maltodextrin can be prepared as described in Guinther Tegge, Starke und Starkederivate, Behr's Verlag, Hamburg 1984, p. 173 and p. 220 ff. and in EP 441 197.

[00036] The maltodextrin can be prepared from any native starches, such as cereal starches (e.g., corn, wheat, rice or barley), tuber and root starches (e.g. potatoes, tapioca roots or arrowroot) or sago starches. The maltodextrin can also have a bimodal molecular weight distribution and can have a weight average molecular weight as described above. The maltodextrin can have a nonuniformity U (defined as the ratio between the weight average weight M_w and the number average molecular weight M_n) that characterizes the molecular weight distribution in the range from 6 to 12, from 7 to 11 or from 8 to 10. The proportion by weight of maltodextrin having a molecular weight of below 1000 can be from 10% to 70% by weight, or 20 to 40% by weight.

[00037] In some examples, the maltodextrin can be chemically modified such as by etherification or esterification. The chemical modification can also be carried out in advance on a starting starch before its degradation. Esterifications are possible using both inorganic and organic acids, or anhydrides or chlorides thereof. Phosphated and acetylated degraded starches can also be used. The most common method of etherification is treatment with organohalogen compounds, epoxides or sulfates in aqueous alkaline solution. The ethers can be alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allylethers.

[00038] The copolymer can, for example, include 1% or more by weight of the maltodextrin, based on the total weight of the polymer latex (e.g., 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 15% or more, 20% or more, 25% or more, or 30% or more). In some examples, the copolymer can include 40% or less by weight of the maltodextrin (e.g., 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, or 5% or less). The amount of the maltodextrin the copolymer includes can range from any of the minimum values described above to any of the maximum values described above. For example, the copolymer can include from 1% to 40% by weight of the maltodextrin (e.g., from 1% to 30%, from 5% to 40%, from 5% to 35%, from 5% to 30%, from 5% to 25%, from 7% to 40%, from 7% to 35%, from 7% to 30%, from 7% to 25%, from 8% to 30%, from 8% to 25%, or from 8% to 20%). In further examples, hydrocolloids other than maltodextrin, such as hydroxyethyl cellulose, may also be used in the emulsion polymerization.

[00039] In some examples, the copolymer may be polymerized in the presence of a surfactant. The surfactant can include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, or a mixture thereof. In some examples, the surfactant can include a non-ionic surfactant and an anionic surfactant. In some examples, the surfactant can include a copolymerizable surfactant. In some examples, the surfactant can include oleic acid surfactants, alkyl sulfate surfactants, alkyl aryl disulfonate surfactants, sulfonic acid surfactants, or alkylbenzene sulfonic acid or sulfonate surfactants. Exemplary surfactants can include sodium vinyl sulfate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), ammonium lauryl sulfate, sodium laureth-1 sulfate, sodium laureth-2-sulfate, and the corresponding ammonium salts, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, C12 (branched) sodium diphenyl oxide disulfonate, or combinations thereof. Examples of commercially available surfactants include Calfoam® ES-303 (a sodium laureth sulfate), Calfoam SLS 30, and Calfax® DB-45 (a sodium dodecyl diphenyl oxide disulfonate), available from Pilot Chemical Company (Cincinnati, OH); Disponil SDS; Disponil FES; Disponil AFX 4030; Polystep LAS-40; Polystep B-19; Polystep B-29; Polystep A-18; Steol CS-230; Bio-Terge AS-40; Tergitol 15-S-40; Tergitol 15-S-20; Aerosol A-102;

Aerosol MA-80-I; copolymerizable surfactants (e.g., those sold under the trademark ADEKA REASOAP); or combinations thereof. In some examples, the copolymerizable surfactant includes sodium vinyl sulfonate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), or a combination thereof.

[00040] The amount of the surfactant employed can be 0.1% or more based on the total amount of the monomers to be polymerized (e.g., 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 1% or more, 1.5% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, or 4% or more). In some examples, the amount of surfactant employed can be 5% or less based on the total amount of the monomers to be polymerized (e.g., 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2% or less, 1.5% or less, 1% or less, or 0.5% or less). The amount of the surfactant employed can range from any of the minimum values described above to any of the maximum values described above. For example, the amount of the surfactant employed can be from 0.1 to 5%, based on the total amount of the monomers to be polymerized (e.g., from 0.1% to 2.5%, from 2.5% to 5%, from 0.1% to 1%, from 1% to 2%, from 2% to 3%, from 3% to 4%, from 4% to 5%, or from 0.5% to 4.5%).

[00041] As described herein, the monomers in the polymer can, in some examples, be polymerized in the presence of a chain transfer agent. A “chain transfer agent” as used herein refers to chemical compounds that are useful for controlling the molecular weights of polymers, for reducing gelation when polymerizations and copolymerizations involving diene monomers are conducted, and/or for preparing polymers and copolymers with useful chemical functionality at their chain ends. The chain transfer agent reacts with a growing polymer radical, causing the growing chain to terminate while creating a new reactive species capable of initiating polymerization. The phrase “chain transfer agent” is used interchangeably with the phrase “molecular weight regulator.”

[00042] Suitable chain transfer agents for use during polymerization of the copolymers disclosed herein can include compounds having a carbon-halogen bond, a sulfur-hydrogen bond, a silicon-hydrogen bond, or a sulfur-sulfur bond; an allyl alcohol, or an aldehyde. In some examples, the chain transfer agents contain a sulfur-hydrogen bond and are known as mercaptans. In some examples, the chain transfer agent can include C3- C20 mercaptans. Specific examples of the chain transfer agent can include octyl mercaptan such as n-octyl mercaptan and t-octyl mercaptan, decyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, dodecyl mercaptan such as n-dodecyl mercaptan and t-dodecyl mercaptan, tert-butyl mercaptan, mercaptoethanol such as P-mercaptoethanol, 3- mercaptopropanol, mercaptopropyltrimethoxysilane, tert-nonyl mercaptan, tert-dodecyl mercaptan, 6-mercaptomethyl-2-methyl-2-octanol, 4-mercapto-3-methyl-l-butanol, methyl- 3 -mercaptopropionate, butyl-3-mercaptopropionate, i-octyl-3-mercaptopropionate, i-decyl- 3 -mercaptopropionate, dodecyl -3 -mercaptopropionate, octadecyl-3 -mercaptopropionate, and 2-phenyl-l-mercapto-2-ethanol. Other suitable examples of chain transfer agents that can be used during polymerization of the copolymers include thioglycolic acid, methyl thioglycolate, n-butyl thioglycolate, i-octyl thioglycolate, dodecyl thioglycolate, octadecyl thioglycolate, ethylacrylic esters, terpinolene. In some examples, the chain transfer agent can include tert-dodecyl mercaptan.

[00043] The amount of the chain transfer agent employed can be 0.05% or more based on the total amount of the monomers to be polymerized (e.g., 0.1% or more, 0.15% or more, 0.2% or more, 0.25% or more, 0.3% or more, 0.35% or more, 0.4% or more, 0.45% or more, 0.5% or more, 0.55% or more, 0.6% or more, 0.65% or more, 0.7% or more, 0.75% or more, 0.8% or more, 0.85% or more, or 0.9% or more). In some examples, the amount of the chain transfer agent employed can be 1% or less based on the total amount of the monomers to be polymerized (e.g., 0.95% or less, 0.9% or less, 0.85% or less, 0.8% or less, 0.75% or less, 0.7% or less, 0.65% or less, 0.6% or less, 0.55% or less, 0.5% or less, 0.45% or less, 0.4% or less, 0.35% or less, 0.3% or less, 0.25% or less, 0.2% or less, 0.15% or less, or 0.1% or less). The amount of chain transfer agent employed can range from any of the minimum values described above to any of the maximum values described above. For example, the amount of the chain transfer agent employed can be from 0.05% to 1% based on the total amount of the monomers to be polymerized (e.g., from 0.05% to 0.5%, from 0.5% to 1%, from 0.05% to 0.3%, from 0.3% to 0.6%, 0.6% to 1%, or from 0.1% to 0.9%). [00044] In some examples, the monomers can be polymerized in the presence of a crosslinker, such as triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, butane diol di acrylate, diallyl maleate, diallyl fumarate, or a combination thereof. The amount of crosslinker employed can be 0.05% or more based on the total amount of the monomers to be polymerized (e.g., 0.1% or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, 1.6% or more, 1.7% or more, or 1.8% or more). In some examples, the amount of crosslinker employed can be 2% or less based on the total amount of the monomers to be polymerized (e.g., 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, 1.5% or less, 1.4% or less, 1.3% or less, 1.2% or less, 1.1% or less, 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, or 0.2% or less). The mount of crosslinker employed can range from any of the minimum values described above to any of the maximum values described above. For example, the amount of crosslinker employed can be from 0.05% to 2% based on the total amount of monomers to be polymerized (e.g., from 0.05% to 1%, from 1% to 2%, from 0.05% to 0.5%, from 0.5% to 1%, from 1% to 1.5%, from 1.5% to 2%, or from 0.1% to 1.9%).

[00045] The copolymers described herein can have a glass-transition temperature (T_g) and/or a T_g as measured by differential scanning calorimetry (DSC) using the mid-point temperature using the method described, for example, in ASTM 3418/82. The theoretical glass transition temperature or “theoretical T_g” of the copolymer refers to the estimated T_g calculated using the Fox equation. The Fox equation can be used to estimate the glass transition temperature of a polymer or copolymer as described, for example, in L. H. Sperling, "Introduction to Physical Polymer Science", 2^nd Edition, John Wiley & Sons, New York, p. 357 (1992) and T. G. Fox, Bull. Am. Phys. Soc, 1, 123 (1956), both of which are incorporated herein by reference. For example, the theoretical glass transition temperature of a copolymer derived from monomers rz, Z>, . . . , and i can be calculated according to the equation below

[00046] where w_a is the weight fraction of monomer a in the copolymer, T_ga is the glass transition temperature of a homopolymer of monomer rz, Wb is the weight fraction of monomer b in the copolymer, T_gb is the glass transition temperature of a homopolymer of monomer Z>, Wi is the weight fraction of monomer z in the copolymer, T_gi is the glass transition temperature of a homopolymer of monomer z, and T_g is the theoretical glass transition temperature of the copolymer derived from monomers rz, Z>, . . . , and z.

[00047] In some examples, the copolymers described herein can have a measured T_g of -35°C or more, as measured by differential scanning calorimetry (DSC) using the midpoint temperature (e.g., -25°C or more, -20°C or more, -15°C or more, -10°C or more, -5°C or more, 0°C or more, 5°C or more, 10°C or more, 15°C or more, 20°C or more, or 25°C or more). In some examples, the copolymers described herein can have a measured T_g of 30°C or less, as measured by differential scanning calorimetry (DSC) using the mid-point temperature (e.g., 25°C or less, 20°C or less, 15°C or less, 10°C or less, 5°C or less, 0°C or less, -5°C or less, -10°C or less, -15°C or less, -20°C or less, or -25°C or less). The measured T_g of the copolymer can range from any of the minimum values described above to any of the maximum values described above. For example, the copolymers described herein can have a measured T_g of from -35 °C to 30°C, as measured by differential scanning calorimetry (DSC) using the mid-point temperature (e.g., from -35°C to 0°C, from 0°C to 30°C, from -35°C to -20°C, from -20°C to -5°C, from -5°C to 10°C, from 10°C to 30°C, or from -25°C to 30°C).

[00048] In some embodiments, the copolymer can be in the form of a latex composition. The latex composition can be an aqueous dispersion including particles of the polymer dispersed in water. In some embodiments, the latex composition can be prepared with a total solids content of from 5% to 90% by weight, for example, 10% to 80% by weight, 20% to 70% by weight, 25% to 65% by weight, 35% to 60% by weight, or 45% to 60% by weight, based on the weight of the latex composition. In some embodiments, the latex composition can have a total solids content of 40% or greater or 50% or greater by weight, based on the weight of the latex composition. In some embodiments, the latex composition can have a total solids content of 90% or less, 80% or less, or 70% or less by weight, based on the weight of the latex composition. The polymer particles in the latex composition can have an average particle size of from 1 nm to 500 nm, such as from 1 nm to 400 nm, from 20 nm to 400 nm, from 30 nm to 300 nm, from 50 nm to 250 nm or from 1 nm to 200 nm. The particle size of the polymer particles can be measured using dynamic light scattering measurements, for example using a Nicomp Model 380 available from Particle Sizing Systems, Santa Barbara, CA.

[00049] The vinyl acrylic latex polymer may have a molecular weight of as low as 1000 g/mol, 2000 g/mol, 5000 g/mol, 10,000 g/mol, 20,000 g/mol, 30,000 g/mol, 50,000 g/mol, 75,000 g/mol, or as high as 100,000 g/mol, 150,000 g/mol, 175,000 g/mol, 200,000 g/mol, 225,000 g/mol, 250,000 g/mol, 275,000 g/mol, 300,000 g/mol, or within any range encompassed by any two of the foregoing values as endpoints. For example, the vinyl acrylic polymer may have a molecular weight of from 5,000-250,000 g/mol [00050] The latex composition can be cationic, anionic, or non-ionic. In some embodiments, the latex composition can be cationic. For example, the latex composition can include a cationic surfactant such as an amine-containing surfactant at a suitable pH (e.g., below the pKa of the amine group in the cationic surfactant). In some embodiments, the latex composition can be anionic. For example, the latex composition can include a carboxylated polymer, such as a carboxylated styrene butadiene (SB) copolymer. In some embodiments, the latex composition can be non-ionic. Preferably, the latex composition may be non-ionic. In some embodiments, the latex composition (including the cationic, anionic, or non-ionic latex composition) can have a pH of 7 or less. For example, the latex composition can have a pH of 6.5 or less, 6 or less, 5.5 or less, 5 or less, 4.5 or less, 4 or less, or 3.5 or less. In some examples, the latex composition can have a pH of 2 or greater, 2.5 or greater, 3 or greater, 3.5 or greater, 4 or greater, 4.5 or greater, 5 or greater, 5.5 or greater, 6 or greater, 6.5 or greater, or 7 or greater. In some embodiments, the latex composition can have a pH of from 2 to 7, from 2 to 6.5, from 2 to 6, from 3 to 7, from 3 to 6.5, from 3 to 6, from 4 to 7, from 4 to 6.5, or from 4 to 6.

[00051] The latex composition can include one or more surfactants (emulsifiers) such as nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, or a mixture thereof. In some embodiments, the latex compositions include an amine derived surfactant. Suitable surfactants include polyamines, fatty amines, fatty amido-amines, ethoxylated amines, diamines, imidazolines, quaternary ammonium salts, and mixtures thereof. Examples of commercially available surfactants that can be used in the latex composition include those available from Akzo Nobel under the REDICOTE® trademark (such as REDICOTE® 4819, REDICOTE® E-64R, REDICOTE® E-5, REDICOTE® E-9, REDICOTE® E9A, REDICOTE® E-l 1, REDICOTE® E-16, REDICOTE® E-44, REDICOTE® E-120, REDICOTE® E-250, REDICOTE® E-2199, REDICOTE® E-4868, REDICOTE® C-346, REDICOTE® C-404, REDICOTE® C-450, and REDICOTE® C- 471), surfactants available from MeadWestvaco under the INDULIN® and AROSURF® trademarks (such as INDULIN® 814, INDULIN® AMS, INDULIN® DF-30, INDULIN® DF-40, INDULIN® DF-42, INDULIN® DF-60, INDULIN® DF-80, INDULIN® EX, INDULIN® FRC, INDULIN® MQK, INDULIN® MQK-1M, INDULIN® MQ3, INDULIN® QTS, INDULIN® R-20, INDULIN® SBT, INDULIN® W-l, and INDULIN® W-5), ASFIER® N480 available from Kao Specialties Americas, CYPRO™ 514 available from Cytec Industries, polyethyleneimines such as those available from BASF under the POLYMIN® trademark (such as POLYMIN® SK, POLYMIN® SKA, POLYMIN® 131, POLYMIN® 151, POLYMIN® 8209, POLYMIN® P, and POLYMIN® PL), and polyvinylamines such as those available from BASF under the CATIOFAST® trademark (such as CATIOFAST® CS, CATIOFAST® FP, CATIOFAST® GM, and CATIOFAST® PL). [00052] The latex composition can include an antioxidant to prevent oxidation of, for example, the double bonds of the vinyl acrylic polymer. Suitable antioxidants can include substituted phenols or secondary aromatic amines. The composition can include antiozonants to prevent ozone present in the atmosphere from, for example, cracking the styrene butadiene polymer, by cleaving the double bonds of the styrene butadiene polymer. The latex composition can include prevulcanization inhibitors to prevent premature vulcanization or scorching of the polymer. Suitable antioxidants, antiozonants, and prevulcanization inhibitors are disclosed in U.S. Patent No. 8,952,092. The antioxidants, antiozonants, and/or prevulcanization inhibitors can be provided in an amount from 1% to 5% by weight, based on the weight of the solids in the latex composition.

[00053] The latex compositions described herein can include an inorganic acid. In some embodiments, the latex compositions can include an inorganic acid selected from hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, C1-C14 organic acids such as acetic acid, formic acid, citric acid, tartaric acid, and mixtures thereof. In some embodiments, the inorganic acid can be present in an amount of from 0.3% to 3% by weight, based on the total weight of the latex composition. For example, the latex composition can include 0.3% or greater, 0.5% or greater, 1% or greater, 1.5% or greater, 2% or greater, or 2.5% or greater by weight of the latex composition, of the inorganic acid. In some embodiments, the latex composition can include 3% or less, 2.5% or less, 2.0% or less, 1.5% or less, 1.0% or less, or 0.5% or less by weight of the latex composition, of the inorganic acid. In some embodiments, the latex composition can include from 0.3% to 3%, 0.5% to 3%, or 1% to 3% by weight of the latex composition, of the inorganic acid. In some embodiments, the inorganic acid can be in an amount such that the pH of the latex composition or asphalt compositions thereof, can be from 1 to 6, such as from 2 to 4 or from 3 to 5. The inorganic acid can be present in an amount of from 0.005% to 0.1% by weight, based on the total weight of the asphalt composition.

[00054] In some embodiments, the latex composition can include phosphoric acid. In some embodiments, the latex compositions can include phosphoric acid and polyphosphoric acid. The amount of phosphoric acid in the latex composition can be 0.1% by weight or greater, based on the total weight of the latex composition. For example, the latex composition can include 0.2% or greater, 0.3% or greater, 0.5% or greater, 0.6% or greater, 0.7% or greater, 0.8% or greater, 0.9% or greater, 1% or greater, 1.5% or greater, 2% or greater, 2.5% or greater, or 3% or greater by weight of the latex composition, of phosphoric acid. In some embodiments, the latex composition can include 3% or less, 2.5% or less, 2% or less, 1.5% or less, or 1% or less by weight of the latex composition, of phosphoric acid. In some embodiments, the latex composition can include from 0.3% to 3%, 0.5% to 3%, or 1% to 3% by weight of the latex composition, of phosphoric acid.

[00055] The amount of phosphoric acid in the asphalt composition can be 0.005% by weight or greater, based on the total weight of the asphalt composition. For example, the asphalt composition can include 0.01% or greater, 0.02% or greater, 0.03% or greater, 0.04% or greater, 0.05% or greater, 0.06% or greater, 0.07% or greater, 0.08% or greater, 0.09% or greater, or 0.1% or greater by weight of the asphalt composition, of phosphoric acid. In some embodiments, the asphalt composition can include 0.1% or less, 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, 0.04% or less, 0.03% or less, 0.02% or less, 0.01% or less, 0.009% or less, 0.008% or less, 0.007% or less, or 0.005% or less by weight of the asphalt composition, of phosphoric acid. In some embodiments, the asphalt composition can include from 0.005 to 0.1%, or 0.01% to 0.1% by weight of the asphalt composition, of phosphoric acid.

[00056] In some embodiments, the latex composition can further include other latexes including but not limited to anionic styrene-butadiene latex, cationic styrenebutadiene latex, carboxylated styrene-butadiene latex, and combinations of the foregoing. These further latexes can present with the vinyl acrylic latex polymer as a blend. Any of the further latexes may be present in the range of from 80/20 to 20/80 based on ratio of weights of the vinyl acrylic latex polymer/further latex. For example, the ratio between the vinyl acrylic latex polymer/further latex may be 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, or 20/80.

III. Asphalt Emulsion Compositions [00057] The vinyl acrylic latex polymers described in Section II above may be used in asphalt emulsion compositions to improve their characteristics.

[00058] 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 compositions can include 50% or greater by weight of the asphalt compositions, of asphalt. In some embodiments, the asphalt compositions can include 55% or greater, 60% or greater, 65% or greater, 70% or greater, 75% or greater, 80% or greater, 85% or greater, 90% or greater, 95% or greater, or 99% or greater by weight of the asphalt compositions, of asphalt. In some embodiments, the asphalt compositions can include 99.9% or less, 99% or less, 95% or less, 90% or less, 87% or less, 85% or less, 83% or less, or 80% or less by weight of the asphalt compositions, of asphalt. In some embodiments, the asphalt compositions can include 50% to 99.9%, 50% to 99%, 50% to 95%, 50% to 90%, 50% to 85%, 50% to 80%, 60% to 95%, 60% to 90%, or 60% to 80% by weight of the asphalt compositions, of asphalt.

[00059] The vinyl acrylic latex polymer as described in Section II above may be incorporated into asphalt compositions in an amount of 0.01% or greater by weight, based on the weight of the asphalt composition. In some embodiments, the asphalt composition can include the polymer in an amount of 0.01% or greater, 0.1 w% or greater, 0.25% or greater, 0.5% or greater, 0.75% or greater, 1% or greater, 1.5% or greater, 2% or greater, 2.5% or greater, 3% or greater, 3.5% or greater, 4% or greater, 4.5% or greater, 5% or greater, 6% or greater, 7% or greater, 8% or greater, or 9% or greater by weight, based on the weight of the asphalt composition. In some embodiments, the asphalt composition can include the polymer in an amount of 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less by weight, based on the weight of the asphalt composition. In some embodiments, the asphalt composition can include the polymer in an amount of 0.01%-10%, 0.5% to 8%, 0.5% to 6%, 0.75% to 5%, or 0.75% to 4% by weight, based on the weight of the asphalt composition.

[00060] The amount of latex composition used to produce the asphalt composition can be in an amount of 0.5% or greater by weight, based on the weight of the asphalt emulsion. In some embodiments, the asphalt composition can include the latex composition in an amount of 1% or greater, 1.5% or greater, 2% or greater, 2.5% or greater, 3% or greater, 3.5% or greater, 4% or greater, 4.5% or greater, 5% or greater, 6% or greater, 7% or greater, 8% or greater, 9% or greater, 10% or greater, 11% or greater, 12% or greater, 13% or greater, or 14% or greater by weight, based on the weight of the asphalt emulsion. In some embodiments, the asphalt composition can include the latex composition in an amount of 15% or less, 12% or less, 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less by weight, based on the weight of the asphalt emulsion. In some embodiments, the asphalt composition can include the latex composition in an amount of 0.5% to 15%, 0.5% to 12%, 0.5% to 10%, 1% to 15%, or 1% to 10% by weight, based on the weight of the asphalt emulsion. [00061] The amount of vinyl acrylic latex polymer solids may be in the range of 20% or greater, 25% or greater, 30% or greater, 40% or greater, 45% or greater, 50% or greater, 55% or less, 60% or less, 65% or less, 70% or less 75% or less, or 80% or less based on the total weight of the asphalt emulsion.

[00062] The asphalt compositions described herein can be vulcanized or cured to crosslink the polymer included in the asphalt composition, thereby increasing the tensile strength and elongation of the polymer. In some embodiments, the asphalt compositions can include vulcanizing (curing) agents, vulcanization accelerators, antireversion agents, or a combination thereof. In some embodiments, the vulcanizing (curing) agents, vulcanization accelerators, antireversion agents, or a combination thereof can be included in the latex composition. In some embodiments, the vulcanizing agents, vulcanization accelerators, and/or antireversion agents can be included in the asphalt composition. Exemplary vulcanizing agents are sulfur curing agents and 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. The vulcanizing agent can be present from 0.01 to 1% or from 0.01 to 0.6% by weight, based on the weight of the asphalt composition. In some embodiments, the asphalt compositions can include a sulfur containing curing agent such as sulfur dispersions or sulfur donors.

[00063] Exemplary vulcanization accelerators include sulfenamide-type vulcanization accelerators such as 7V-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, /f'-di isopropyl -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, di ethylenethiourea, dibutylthiourea and trimethylthiourea; thiazole-type vulcanization accelerators such as 2-mercaptobenzothiazole, dib enzothi azyl 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 in an amount of from 0.01 to 1% or from 0.01 to 0.6% by weight, based on the weight of the asphalt compositions.

[00064] Antireversion agents can also be included 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 bissuccinimide polysulfides (e.g., N, A'-xylenedicitraconamides). The antireversion agent can be present in an amount of from 0.01 to 1% or from 0.01 to 0.6% by weight, based on the weight of the asphalt composition.

[00065] The asphalt compositions can include a solvent such as water to disperse or emulsify the polymer and/or the asphalt. The asphalt compositions can include water in an amount of 1% to 35%, 5% to 30%, or 5% to 25% by weight, based on the weight of the asphalt compositions.

[00066] 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 emulsifiability, 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.

[00067] 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. [00068] In some embodiments, the asphalt compositions can have a pH of 7 or less. For example, the asphalt composition can have a pH of 6.5 or less, 6 or less, 5.5 or less, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, or 2.5 or less. In some examples, the asphalt composition can have a pH of 1.5 or greater, 2 or greater, 2.5 or greater, 3 or greater, 3.5 or greater, 4 or greater, 4.5 or greater, 5 or greater, 5.5 or greater, 6 or greater, 6.5 or greater, or 7 or greater. In some embodiments, the asphalt composition can have a pH of from 1.5 to 7, from 2 to 6.5, from 1.5 to 6, from 2 to 6, from 3 to 7, from 3 to 6.5, from 3 to 6, from 4 to 7, from 4 to 6.5, or from 4 to 6.

IV. Methods for Preparing Asphalt Emulsion Compositions

[00069] Methods for preparing the asphalt emulsion compositions described herein are also provided. In some embodiments, the method can include preparing a latex from the copolymer derived from vinyl acetate and an acrylate monomer having a glass transition temperature (T_g) of 20°C or less.

[00070] The vinyl acrylic latex polymer composition can be prepared by polymerizing monomers in an aqueous emulsion polymerization reaction at a suitable temperature. The polymerization can be carried out at temperatures such as from 40°C or greater, 50°C or greater, or 60°C or greater. In some embodiments, the polymerization temperature can be from 40°C to 100°C, 40°C to 95°C, or 50°C to 90°C.

[00071] The polymerized polymer can be produced using either a continuous, semibatch (semi -continuous) or batch process. In some examples, the polymer can be produced using a continuous method by continuously feeding one or more monomer streams, a surfactant stream, and an initiator stream to one or more reactors. The surfactant stream includes a surfactant and water and can, in some embodiments, be combined with the initiator stream.

[00072] The polymerization reaction can be conducted in the presence of molecular weight regulators to reduce the molecular weight of the copolymer of other additives such as dispersants, stabilizers, chain transfer agents, buffering agents, salts, preservatives, fire retardants, wetting agents, protective colloids, biocides, crosslinking promoters, antioxidants, antiozonants, prevulcanization inhibitors, and lubricants. In some embodiments, the additives can be added to the latex composition after the polymerization reaction. The latex composition can be agglomerated, e.g., using chemical, freeze or pressure agglomeration, and water removed to produce the desired solids content. In some embodiments, the solids content is 55% or greater, 60% or greater, or 65% or greater. [00073] In some embodiments, the latex composition can have an overall anionic charge, non-ionic, or cationic charge. One of ordinary skill in the art understands that the overall charge of the latex composition can be influenced by the surfactant used, the particular monomers used to form the polymer in the latex composition, and the pH of the latex composition.

[001] In some embodiments, the vinyl acrylic latex polymer composition may be substantially free of a charged flipping surfactant. Examples of these cationic flipping surfactants include REDICOTE.RTM. E-5 (Akzo Nobel, Chicago, Ill ), REDICOTE.RTM. E-l l (Akzo Nobel, Chicago, Ill.), REDICOTE.RTM. E-53 (Akzo Nobel, Chicago, Ill.), REDICOTE.RTM. E-606 (Akzo Nobel, Chicago, Ill ), REDICOTE.RTM. E-5127 (Akzo Nobel, Chicago, Ill.), ADOGEN.RTM. 477HG (Chemtura Corp., Greenwich, Conn.), INDULIN.RTM. W-l (MeadWestvaco, Charleston, S.C.), INDULIN.RTM. W-5 (MeadWestvaco, Charleston, S.C.), INDULIN.RTM. SBT (MeadWestvaco, Charleston, S.C.), and INDULIN.RTM. MQK (MeadWestvaco, Charleston, S.C.), TETRONIC.TM. and PLURONIC.TM. (BASF Corporation), nonyl phenol ethoxylates, octylphenol ethoxylates, dodecyl phenol ethoxylates, linear alcohol ethoxylates, branched alcohol ethoxylates such as tridecyl alcohol ethoxylates, alcohol ethoxylates, block copolymers, PEG esters and castor oil ethoxylates. The vinyl acrylic latex polymer may contain less than 10 wt.%, less than 9 wt.%, less than 8 wt.%, less than 7 wt.%, less than 6 wt.%, 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, less than 1 wt.%, less than 0.1 wt.%, less than 0.01 wt.% or 0 wt.% of these flipping surfactants

[00074] The method of preparing the asphalt emulsions can include contacting a vinyl acrylic latex, asphalt, and an optional cationic, anionic, or non-ionic surfactant solution to form an asphalt emulsion. The method can further include contacting the asphalt with a basic salt, such as aluminum sulfate. The particular components, including the asphalt, the latex composition, the surfactant, and the basic salt in the asphalt emulsions can be mixed together by any means known in the art. The particular components can be mixed together in any order.

[00075] The particular components, including the asphalt, the latex composition, the optional anionic, cationic, or non-ionic surfactant, and the asphalt can be fed into a colloid high shear mill at a temperature of less than 100°C (e.g., 60°C to 95°C) where high shear mixing produces an asphalt emulsion having asphalt droplets dispersed in the water. The basic salt can be added simultaneously or the basic salt post-added to the asphalt emulsion (comprising the latex composition and asphalt). In some embodiments, the latex composition and the basic salt, if present, are mixed with the asphalt simultaneously. For example, the latex composition can include the basic salt such that the polymer, inorganic acid (if present), and the basic salt are simultaneously mixed with the asphalt. In some embodiments, the basic salt can be combined directly with the asphalt prior to mixing with the other ingredients. In some embodiments, the vinyl acrylic latex can be post-added to a cationic asphalt emulsion. In some embodiments, the vinyl acrylic latex can be post-added to an anionic asphalt emulsion. In some embodiments, the vinyl acrylic latex can be postadded to a non-ionic asphalt emulsion.

[00076] The droplets in the asphalt emulsion can have a narrow particle size distribution. In some embodiments, the droplets in the asphalt emulsion can have a median particle size of 15 pm or less, 14 pm or less, 13 pm or less, 12 pm or less, 11 pm or less, 10 pm or less, 9 pm or less, 8 pm or less, 7 pm or less, 6 pm or less, or 5 pm or less and/or of 5 pm or greater, 6 pm or greater, 7 pm or greater, 8 pm or greater, 9 pm or greater, or 10 pm or greater. In some embodiments, the droplets in the asphalt emulsion can have a mean particle size of 15 pm or less, 14 pm or less, 13 pm or less, 12 pm or less, 11 pm or less, 10 pm or less, 9 pm or less, 8 pm or less, 7 pm or less, 6 pm or less, or 5 pm or less and/or of 5 pm or greater, 6 pm or greater, 7 pm or greater, 8 pm or greater, 9 pm or greater, or 10 pm or greater. In some embodiments, the droplets in the asphalt emulsion can have a median particle size of from 3 to 15 pm. In some embodiments, the droplets in the asphalt emulsion can have a median distribution of droplet particles having a standard deviation of less than 30%, less than 25%, less than 20%, less than 15%, or less than 10%. In some embodiments, the droplets in the asphalt emulsions comprising the phosphoric acid flipped cationic latex composition and/or aluminum sulfate can have a narrower particle size distribution than an asphalt emulsion that does not include the phosphoric acid flipped cationic latex composition and/or aluminum sulfate.

[00077] The asphalt emulsions can have a viscosity of 100 cp or greater, when the asphalt is present in an amount of 65% by weight, based on the asphalt emulsion, in the absence of a thickener. In the event the asphalt content is less than or greater than 65% by weight, the asphalt content can be adjusted by adding or removing water. In some embodiments, the asphalt emulsions can have a viscosity of 150 cp or greater, 200 cp or greater, 250 cp or greater, 300 cp or greater, 350 cp or greater, 400 cp or greater, 450 cp or greater, 500 cp or greater, 600 cp or greater, 700 cp or greater, 800 cp or greater, 900 cp or greater, 1000 cp or greater, 1500 cp or greater, 2000 cp or greater, or 2500 cp or greater, when the asphalt is present in an amount of 65% by weight, based on the asphalt emulsion. In some embodiments, the asphalt emulsions can have a viscosity of 2500 cp or less, 2000 cp or less, 1500 cp or less, 1250 cp or less, 1000 cp or less, 950 cp or less, 900 cp or less, 850 cp or less, 800 cp or less, 750 cp or less, 700 cp or less, 650 cp or less, 600 cp or less, 550 cp or less, 500 cp or less, 400 cp or less, 250 cp or greater, 300 cp or less, or 200 cp or less, when the asphalt is present in an amount of 65% by weight, based on the asphalt emulsion. In some embodiments, the viscosity of the asphalt emulsions can be from 100 cp to 2500 cp, for example, 100 cp to 1500 cp, 100 cp to 1000 cp, 100 cp to 800 cp, 100 cp to 600 cp, 100 cp to 500 cp, 200 cp to 1500 cp, 200 cp to 1000 cp, 200 cp to 800 cp, 200 cp to 600 cp, 200 cp to 500 cp, 100 cp to 500 cp, 100 cp to 450 cp, or 150 cp to 500 cp, when the asphalt is present in an amount of 65% by weight, based on the asphalt emulsion. In some embodiments, the addition of the phosphoric acid flipped cationic latex composition and/or aluminum sulfate to the asphalt emulsions can result in an increase in viscosity of 1 time or greater, 2 times or greater, 3 times or greater, 4 times or greater, 5 times or greater, 6 times or greater, or up to 10 times or greater, compared to an asphalt emulsion without the phosphoric acid flipped cationic latex composition and/or aluminum sulfate.

[00078] In some embodiments, the polymer-modified asphalt emulsion has a softening point that is 5°C or greater, 10°C or greater, or 15°C or greater than the softening point of the same asphalt emulsion without the phosphoric acid and polyphosphoric acid. In some embodiments, the (polymer-modified) asphalt emulsion has a softening point that is 5°C or greater, 10°C or greater, or 15°C or greater than the softening point of the same asphalt emulsion without the aluminum sulfate and polyphosphoric acid. In some embodiments, the (polymer-modified) asphalt emulsion has a softening point that is 5°C or greater, 10°C or greater, or 15°C or greater than the softening point of the same asphalt emulsion without the phosphoric acid, the polyphosphoric acid and the aluminum sulfate. In some embodiments, the asphalt emulsion using a PG 58-28 base asphalt can have a softening point of 65°C or greater (for example, 70°C or greater, 75°C or greater, or 80°C or greater). In some embodiments, the asphalt emulsion using a PG 58-28 base asphalt can have a softening point of 85°C or less (for example, 80°C or less, 75°C or less, or 70°C or less). In some embodiments, the asphalt emulsion using a PG 58-28 base asphalt can have a softening point of from 65°C to 85°C or from 70°C to 80°C. The Ring and Ball Softening Point test, such as those described in ASTM D36 and/or AASHTO T53, can be used to measure the temperature at which an asphalt composition becomes soft and flowable.

[00079] The asphalt emulsions described herein can adhere to the standards of ASTM D977, ASTM D2397, AASHTO M140, and AASHTO M208.

[00080] The latex composition can be used to prepare polymer modified hot mix asphalt compositions. A hot mix asphalt can be prepared, for example, by blending asphalt, a latex composition as described herein, and optionally a basic salt at a blending temperature exceeding the boiling point of water. In some embodiments, the latex composition can have a pH of 7 or less as described herein. In some embodiments, the latex composition can be anionic. For example, the latex composition can include a carboxylated polymer. In some embodiments, the latex composition can be nonionic. In some embodiments, the latex composition can be cationic, for example, by including a cationic surfactant. The blending temperature of the hot mix asphalt can be 150°C or greater or 160°C or greater and 200°C or less. The hot mix asphalt composition can have, for example, a viscosity of 3000 cp or less, 2500 cp or less, 2000 cp or less, 1500 cp or less, lOOOcp or less. 750 cp or less, 500 cp or less, 250 cp or less 100 cp or less or 50 cp or less at 135°C. In some embodiments, the hot-mix asphalt composition can have a viscosity of 1000 cp or greater, 1250 cp or greater, 1500 cp or greater, 2000 cp or greater, or 2500 cp or greater. In some embodiments, the viscosity of the hot-mix asphalt composition can be from 250 cp to 1000 cp, for example 500-1000 cp. The latex composition can be in the amounts described above when added to the hot mix asphalt, but the resulting hot mix asphalt will include less of the latex composition because the water is evaporated leaving the latex polymer and any other non-volatile additives. For example, the latex polymer can be present in a hot mix asphalt composition in an amount of as low as 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, or as high as 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, or within any range encompassed by any two of the foregoing values as endpoints.

[00081] In some embodiments, the hot mix asphalt composition has a pH of 7 or less, or 6 or less (e.g., 1.5 to 6), as described herein.

[00082] In some embodiments, the hot mix asphalt composition has a softening point that is 5°C or greater, 10°C or greater, or 15°C or greater than the softening point of the same hot mix asphalt composition without the phosphoric acid and polyphosphoric acid. In some embodiments, the (polymer-modified) hot mix asphalt composition has a softening point that is 5°C or greater, 10°C or greater, or 15°C or greater than the softening point of the same hot mix asphalt composition without the aluminum sulfate and polyphosphoric acid. In some embodiments, the (polymer-modified) hot mix asphalt composition has a softening point that is 5°C or greater, 10°C or greater, or 15°C or greater than the softening point of the same hot mix asphalt composition without the phosphoric acid the polyphosphoric acid and the aluminum sulfate. In some embodiments, the hot mix asphalt compositions can have a softening point of 75°C or greater or 80°C or greater using a PG 58-28 base asphalt.

[00083] In some embodiments, the hot mix asphalt composition comprising the vinyl acrylic latex polymer may provide a 1 performance grade (IPG) or 2 performance grade bump (2PG) to the asphalt.

[00084] Methods of using the asphalt compositions described herein are disclosed. The asphalt compositions can be applied to a surface to be treated, restored, or sealed. Prior to application of the asphalt composition, the surface to be treated is usually cleaned to remove excess surface dirt, weeds, and contaminants by, for example, brushing the surface, blasting the surface with compressed air, or washing the surface. The asphalt compositions can be applied using any suitable method for applying a liquid to a porous surface, such as brushing, wiping and drawing, or spraying.

[00085] In some embodiments, the asphalt compositions, once applied, wet the surface thereby forming a layer on at least a portion and typically at least a substantial portion (e.g., more than 50%) of the surface. In some embodiments, when asphalt emulsions are applied to a surface, water loss occurs in the emulsion, primarily due to adsorption of the water. The water also delivers the asphalt and the cationic latex composition to the surface. In some embodiments, the asphalt emulsion penetrates and adheres to the surface it is applied to, cures in a reasonably rapid time, and provides a water-tight and air-tight barrier on the surface. The asphalt emulsion layer also promotes adhesion between the older surface and the later applied surface treatment layer. It is desirable for the asphalt compositions to be easily applied and have an adequate shelf life.

[00086] An aggregate can be blended into the asphalt compositions before application to a surface. In some embodiments, the aggregate can be applied to the asphalt compositions after it is applied to a surface. For example, sand can be applied to the asphalt compositions after it is applied to a surface, for example, if the composition is to be used as a tack coat, to reduce the tackiness of the surface. The asphalt compositions and optionally the aggregate can be compacted after application to the surface as would be understood by those of skill in the art.

[00087] The asphalt compositions can be applied for use in a pavement or paved surface. A pavement surface or a paved surface is a hard surface that can bear pedestrian or vehicular travel can include surfaces such as motorways/roads, parking lots, bridges/overpasses, runways, driveways, vehicular paths, running paths, walkways, and the like. The asphalt compositions can be applied directly to an existing paved surface or can be applied to an unpaved surface. In some embodiments, the asphalt compositions can be applied to an existing paved layer as a tie layer, and a new layer comprising asphalt such as a hot mix layer is applied to the tie layer. The asphalt compositions can be applied to a surface “cold,” i.e., at a temperature below 40°C, or can be applied to at an elevated temperature, for example, from 50°C to 120°C, from 55°C to 100°C, or from 60°C to 80°C. [00088] 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 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 as mentioned herein.

[00089] As described herein, 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, hours to days after the emulsion is applied to the substrate. In some embodiments, the applied composition can cure in 15 minutes to 45 minutes and may cure as rapidly as less than 1 minute to 15 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.

[00090] In some embodiments, the asphalt compositions can also be used as a fog seal. A fog seal is a surface treatment that applies a light application of the composition to an existing paved surface such as a parking lot to provide an enriched pavement surface that looks fresh and black. In some embodiments, the fog seal would include a filler such as carbon black to blacken the composition. As would be understood by those skilled in the art, the fog seal might not include aggregate. The fog seal compositions, like the bond coat compositions, have also been shown to be to be low-tracking or “trackless” coatings.

[00091] In some embodiments, the asphalt compositions can be used as a chip seal composition. Chip seals are the most common surface treatment for low-volume roads. The chip seal composition can be applied to a surface followed by the application of aggregate. In some embodiments, the asphalt compositions can be used in a microsurfacing application. Microsurfacing is designed for quick traffic return with the capacity of handling high traffic volume roadways. For the microsurfacing composition, aggregate can be mixed in with the cationic asphalt composition before application to a surface.

[00092] In some embodiments, the asphalt compositions can be used in paints, coatings, paper coating or binding compositions, carpet compositions (e.g., carpet backing), foams, or adhesives.

[00093] 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.

[00094] By way of non-limiting illustration, examples of certain embodiments of the present disclosure are given below. EXAMPLES

[00095] 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.

Example 1 : Sweep Testing of Asphalt Emulsions

[00096] The ASTM D-7000 Standard Test Method for Sweep Test of Bituminous Emulsion Surface Treatment Samples was used to evaluate the emulsions prepared according to the methods described above. This test method measures the curing performance characteristics of bituminous emulsion and aggregates by simulating the brooming of a surface treatment in the laboratory. Specifically, curing performance is reflected in the sweep test which measures the aggregate mass loss by the aforementioned ASTM D-7000 Standard test method. The lower the aggregate mass loss, the better the pavement performance or equivalently the shorter the time before the road can be to reopened to traffic.

TABLE 1

Sweep testing asphalt emulsions with according to ASTM D7000, 2 hours curing.

[00097] Table 1 demonstrates acceptable sweep performance for the asphalt emulsions, modified by either a crosslinked or non-crosslinked vinyl acrylic latex of the invention. Acceptable sweep performance means aggregate loss of less than 20 wt.% in the sweep test outlined in the ASTM D-7000 Standard test method. In addition, the vinyl acrylic polymer modified emulsions have sweep performance comparable to the cationic styrene-butadiene rubber (SBR) modified asphalt emulsions and to the cationic styrenebutadiene (SB) latex modified asphalt emulsion controls. The cationic styrene-butadiene rubber (SBR) latex and the cationic styrene-butadiene (SB) latex, and their 50/50 blend, contain a curing agent at levels of either 2.1% or 3.1%. The curing agent includes a vulcanizing agent and accelerator as it is customarily used in the industry. It was surprisingly found that the curing performance characteristics, reflected in the aggregate mass loss, of the asphalt emulsion modified with the vinyl acrylic latex of the invention were comparable to those of cationic SBR latex modified asphalt emulsions, and in the absence of both the curing agent and of the cationic charge typically utilized in SBR latex modified asphalt emulsions. The same comparison applies to SB modified latex asphalt emulsions. The absence of the raw materials and process equipment to impart cationic charge and the absence of the curing agent in the vinyl acrylic latexes of the invention result in significant economic benefits and advantages.

Example 2: Viscosity of Asphalt Modified with 3% Latex Polymer [00098] The viscosity of asphalts based on NuStar 64-22 asphalt and modified with 3% latex polymer was measured. The results are summarized in Table 2 below. The vinyl acrylic latexes with different vinyl acetate-to-butyl acrylate (VA/BA) ratios impart significantly less viscosity to the modified asphalt than SBR latexes. Accordingly, the viscosity of asphalt modified with 3 wt% vinyl acrylic latex polymer of the invention is less than 800 cp at 135°C compared to 2155 cp for the same asphalt modified with 3 % SBR latex polymer, and to 650 cp for the unmodified asphalt. The viscosity of the asphalt modified with the vinyl acrylic latexes amounts to an increase of 1.2 times over the viscosity of the neat asphalt, compared to 3.3 times for SBR, which has significant advantages, such as workability, let-down and compaction of the asphalt mix on the pavement under construction. In addition, a Strategic Highway Research Program (SHRP) evaluation of the asphalt modified with 3% vinyl acrylic latex of the invention results in 1 performance grade (PG) increase above that of the un-modified asphalt and the texture of the modified asphalt is almost smooth compared to the grainy texture for the vulcanized SBR latex. TABLE 2

Viscosity of Asphalt Modified with 3% Vinyl Acrylic Latexes of the Invention with Different VA/BA ratios in Comparison to Neat Asphalt and to SBR Modified Asphalt

Example 3: Determination of Particle Sizes

[00099] The distribution of particle size 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 aqueous polymer dispersion was diluted and the dilution was 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 3 are the z-average of the cumulant evaluation of the measured of the measured autocorrelation function.

[000100] A plot of particle diameter vs volume % is provided in FIG. 4.

TABLE 3

Average particle size of asphalt emulsion modified with Commercial Cationic SBR latex and Vinyl acrylic latex of the Invention

[000101] Table 3 demonstrates the emulsion droplet size for the cationic SBR latex modified emulsion is equal to the particle size of the asphalt emulsion modified with the vinyl acrylic latex of the invention. The larger standard deviation suggests an emulsion with lower viscosity when the polymer modification is made by the vinyl acrylic latex compared to the cationic SBR latex. A lower viscosity for the emulsions modified with vinyl acrylic latexes of the invention suggests that emulsions with higher asphalt content can be achieved using the vinyl acrylic latex polymers of the invention.

[000102] 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 emulsion composition comprising: asphalt; a vinyl acrylic latex polymer comprising a copolymer derived from: vinyl acetate; an acrylate monomer having a glass transition temperature (T_g) of 20°C or less; and water.

2. The asphalt emulsion of claim 1, wherein the vinyl acrylic latex polymer is present in an amount of from about 0.01 wt.% to 10 wt.% based on the weight of the asphalt emulsion.

3. The asphalt emulsion of claim 1 or claim 2, wherein the vinyl acrylic latex polymer has a molecular weight of from 5,000-250,000 g/mol.

4. The asphalt emulsion of any one of claims 1-3, wherein the vinyl acrylic latex polymer is derived from about 30-90 wt.% vinyl acetate based on the total weight of the polymer latex.

5. The asphalt emulsion of any one of claims 1-4, wherein the vinyl acrylic latex polymer is derived from about 20-70 wt.% of the acrylate monomer, based on the total weight of the polymer latex.

6. The asphalt emulsion of any one of claim 1-5, wherein the vinyl acrylic latex polymer comprises poly (vinyl acetate).

7. The asphalt emulsion of any one of claims 1-6, wherein the acrylate monomer is selected from the group consisting of ethyl acrylate, methyl acrylate, butyl acrylate, 2- ethylhexyl acrylate, methyl methacrylate, lauryl methacrylate, 2-octyl acrylate or a combination thereof.

8. The asphalt emulsion of any one of claims 1-7, wherein the vinyl acrylic latex polymer comprises from about 0-5 wt.% carboxylic acid, carboxylic acid anhydride, or combination thereof, based on the total weight of the polymer latex.

9. The asphalt emulsion of any one of claims 1-8, wherein the carboxylic acid, carboxylic acid anhydride, or combination thereof is selected from the group consisting of (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, anhydrides thereof, and combinations thereof.

10. The asphalt emulsion of any one of claims 1-9, wherein the vinyl acrylic latex polymer further comprises an organosilane.

11. The asphalt emulsion of claim 10, wherein the vinyl acrylic latex polymer comprises from about 0.01-3 wt.% of the organosilane, based on the total weight of the polymer latex.

12. The asphalt emulsion of claim 10 or claim 11, wherein the organosilane comprises vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2-methoxyethoxysilane), vinyl triisopropoxysilane, gamma-methacryloxypropyltrimethoxy silane, or combinations thereof.

13. The asphalt emulsion of any one of claims 1-12, wherein the vinyl acrylic latex polymer further comprises maltodextrin.

14. The asphalt emulsion of claim 13, wherein the molecular weight of the maltodextrin is from about 3000-20,000 Daltons.

15. The asphalt emulsion of claim 13 or claim 14, wherein the maltodextrin has a dextrose equivalent (DE) of about 10-50.

16. The asphalt emulsion of any one of claims 1-15, wherein the vinyl acrylic latex polymer is polymerized in the presence of a surfactant.

17. The asphalt emulsion of claim 16, wherein the surfactant comprises sodium vinyl sulfonate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), or a combination thereof.

18. The asphalt emulsion of any one of claims 1-17, wherein the vinyl acrylic latex polymer is polymerized in the presence of a chain transfer agent.

19. The asphalt emulsion of any one of claims 1-18, wherein the vinyl acrylic latex polymer is polymerized in the presence of a crosslinker.

20. The asphalt emulsion of claim 19, wherein the crosslinker comprises triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, butane diol di acrylate, diallyl maleate, diallyl fumarate, or a combination thereof.

21. The asphalt emulsion of any one of claims 1-20, wherein the vinyl acrylic latex polymer composition comprises less than 1 wt.% of flipping surfactant, based on the total weight of the polymer latex.

22. The asphalt emulsion of any one of claims 1-21, further comprising a further latex selected from the group consisting of anionic styrene-butadiene latex, cationic styrenebutadiene latex, and carboxylated styrene-butadiene latex.

23. The asphalt emulsion of claim 22, wherein a blend ratio of the vinyl acrylic latex polymer to the further latex is in a range of from 80/20 to 20/80 based on weight.

24. The asphalt emulsion of any one of claims 1-23, wherein vinyl acrylic latex polymer solids are in the range of 30 to 75 wt.% based on the total weight of the asphalt emulsion.

25. The asphalt emulsion of any of claims 1-24, wherein the asphalt is present in an amount of from 50% to 99.9% by weight based on the weight of the asphalt emulsion.

26. A tack coat comprising the asphalt emulsion composition of any one of claims 1-25.

27. A fog seal comprising the asphalt emulsion composition of any one of claims 1-25.

28. A chip seal comprising the asphalt emulsion composition of any one of claims 1-25.

29. A method of forming the asphalt emulsion of any one of claims 1-25 comprising contacting a vinyl acrylic latex, asphalt, and a cationic surfactant solution to form an asphalt emulsion.

30. The method of claim 29, wherein the vinyl acrylic latex, asphalt, and a cationic surfactant solution are co-milled in a colloid high shear mill to form a cationic asphalt emulsion.

31. The method of claim 29 or claim 30, wherein the vinyl acrylic latex is post-added to a cationic asphalt emulsion.

32. A method of forming the asphalt emulsion of any one of claims 1-25 comprising contacting a vinyl acrylic latex, asphalt, and an anionic surfactant solution to form an asphalt emulsion.

33. The method of claim 32, wherein the vinyl acrylic latex, asphalt, and an anionic surfactant solution are co-milled in a colloid high shear mill to form an anionic asphalt emulsion.

34. The method of claim 32 or claim 33, wherein the vinyl acrylic latex is post-added to an anionic asphalt emulsion

35. A method of forming the asphalt emulsion of any one of claims 1-25, comprising, contacting a vinyl acrylic latex, asphalt, and a non-ionic surfactant solution to form an asphalt emulsion.

36. The method of claim 35, wherein the vinyl acrylic latex, asphalt, and a non-ionic surfactant solution are co-milled in a colloid high shear mill to form a non-ionic asphalt emulsion.

37. The method of claim 35 or claim 36, wherein the vinyl acrylic latex is post-added to a non-ionic asphalt emulsion

38. A hot mix asphalt composition comprising a vinyl acrylic latex made by emulsion polymerization.

39. The hot mix asphalt composition of claim 38, wherein the particle size of the vinyl acrylic latex is from 1 nm to 200 nm.

40. The hot mix asphalt composition of claim 38 or 39, wherein the composition comprises 3 wt.% of the vinyl acrylic latex based on the total weight of the composition.

41. The hot mix asphalt composition of claim 40, wherein the viscosity of the composition is lower than 1000 cP at 135°C.

42. The hot mix asphalt composition of claim 40, wherein the viscosity of the composition is lower than 500 cP at 135°C.

43. The hot mix asphalt composition of claim 40, wherein the viscosity of the composition is lower than 250 cP at 135°C.

44. The hot mix asphalt composition of any of claims 40-43, wherein the asphalt composition provides a 1 performance grade (IPG) increase to the asphalt.