Latex for asphalt emulsion modification

Abstract

This document discloses latexes for use in asphalt emulsion modification and asphalt emulsions containing said latexes. A method for forming a composition of latex and asphalt emulsion is also disclosed.

Description

Technical Field

[0001] This disclosure relates generally to asphalt compositions, and more specifically to asphalt compositions comprising polymer latex, and to methods for preparing and using polymer-modified asphalt compositions. Background Technology

[0002] Asphalt compositions have a wide range of applications, including but not limited to the production of aggregate pavements. The properties of asphalt can be improved by incorporating polymer-based additives such as polymeric latex. These latexes are water-based dispersions of polymers, typically synthetic rubbers or thermoplastic elastomers. The addition of polymeric latex can improve the adhesion, ductility, tensile strength, durability, and low-temperature properties of asphalt.

[0003] Polymer latexes typically possess a surface charge due to the presence of charged groups on their polymer chains. Depending on these groups, the surface charge can be positive (cationic) or negative (anionic). The charge of the latex significantly affects its interactions with asphalt binders, aggregates, and other additives used in the modification process.

[0004] In some cases, it may be desirable to alter or reverse the charge of the latex by incorporating cationic or anionic surfactants. Such modification aims to achieve improved compatibility between the latex, aggregates, and asphalt binder, prevent coagulation, and ensure proper dispersion and adhesion.

[0005] However, charge reversal can be challenging because surfactants can introduce complexities, such as changes in the rheological properties of the latex. In some cases, achieving complete charge reversal is impossible, and partial charge reversal can lead to impaired asphalt properties. Cationic surfactants, in particular, are more hazardous than other surfactants and therefore require safe handling with specialized protective equipment. Consequently, cationic latexes have a higher hazard level. This disclosure provides polymeric latexes that overcome the aforementioned challenges. Summary of the Invention

[0006] This document discloses compositions comprising styrene-butadiene latex. In some embodiments, the polymer comprises styrene and butadiene and is a styrene-butadiene copolymer, such as a non-carboxylated styrene-butadiene copolymer. The composition may be an aqueous dispersion or an emulsion. The composition comprises a styrene-butadiene latex polymerizable at high temperatures (e.g., greater than 40°C) or a blend of a styrene-butadiene latex polymerizable at high temperatures (e.g., greater than 40°C) and a styrene-butadiene latex polymerizable at low temperatures (less than 40°C, e.g., -5°C to 40°C). The composition may have a butadiene / styrene monomer weight ratio of 75 / 25. When used in polymer-modified cationic pitch emulsions, the styrene-butadiene latex does not require charge reversal. Therefore, the styrene-butadiene latex disclosed herein is significantly more economical than cationic styrene-butadiene rubber (SBR) latex that requires cationic surfactants to manufacture cationic pitch emulsions.

[0007] This document also discloses compositions comprising bitumen and styrene-butadiene latex. The compositions may further comprise water and are in the form of a dispersion or emulsion comprising bitumen and styrene-butadiene latex.

[0008] This document also discloses paints, coatings, paper adhesives or coatings, foams, binders, powders, carpet compositions, adhesive layers, and bitumen compositions comprising the compositions disclosed herein. In some embodiments, the bitumen compositions disclosed herein exhibit significantly higher glass transition temperatures compared to styrene-butadiene rubber latex used in cationic bitumen emulsions.

[0009] This document also discloses methods for preparing the compositions disclosed herein. Details of one or more embodiments are set forth in the following description. Other features, objects, and advantages will become apparent from the specification, drawings, and claims.

[0010] In one form, this disclosure provides an asphalt emulsion composition comprising: (i) asphalt; (ii) a non-carboxylated latex containing 0.01 to 20% by weight of a nonionic surfactant based on the total weight of the latex; (iii) one or more emulsifiers; and (v) water.

[0011] In another form, this disclosure provides a method for forming an asphalt emulsion composition, the method comprising: (i) polymerizing monomers to form a non-carboxylated latex; (ii) subsequently adding a nonionic emulsifier to the non-carboxylated latex; and (iii) contacting the latex, asphalt, one or more emulsifiers and water to form an asphalt emulsion.

[0012] A method for forming an asphalt emulsion composition, the method comprising: (i) polymerizing monomers to form a carboxylated latex; (ii) subsequently adding a nonionic emulsifier to the carboxylated latex; and (iii) contacting the latex, asphalt, one or more emulsifiers and water to form an asphalt emulsion. Detailed Implementation

[0013] I. Definition

[0014] As used herein, the term "comprising" and its variations are used synonymously with the term "including" and its variations, and are open, non-limiting terms. While the terms "comprising" and "including" have been used herein to describe various embodiments, the terms "substantially consisting of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific embodiments and are also disclosed. The singular forms "an" and "described" as used in this disclosure and the appended claims include plural indicators unless the context clearly indicates otherwise. Percentage ranges and other ranges disclosed herein include the endpoints of the disclosed ranges and any integers provided within the range.

[0015] Unless the context clearly indicates otherwise, the singular forms “a” and “the” as used in this specification and the appended claims include plural indicators. Thus, for example, reference to “a composition” includes a mixture of two or more such compositions, reference to “an agent” includes a mixture of two or more such agents, reference to “the component” includes a mixture of two or more such components, and so on.

[0016] "Optional" or "optionally" means that the event or situation described below may or may not occur, and the description includes instances where the event or situation occurs as well as instances where the event or situation does not occur.

[0017] It should be understood that throughout this specification, the identifiers “first” and “second” are used only to help distinguish the various components and steps of the disclosed subject matter. The identifiers “first” and “second” are not intended to imply any particular order, quantity, preference, or importance of the components or steps modified by these terms.

[0018] The term “(meth)acryl…” includes “acryl…”, “methacryl…”, or a mixture thereof.

[0019] The term "copolymer" includes homopolymers, copolymers, or mixtures thereof.

[0020] The terms “surfactant,” “emulsifier,” and “dispersant” are used interchangeably and refer to substances or compounds that alter the surface tension of a system, stabilize emulsions, or promote the mixing and dispersion of immiscible substances.

[0021] As used herein, the term "substantially free of" means that the composition as a whole contains no more than about 1% by weight of the substance under discussion. For example, if the product composition is substantially free of water, it contains no more than about 1% by weight of water.

[0022] As used in this article, the phrase “any range encompassed by any two such values ​​as endpoints” literally means that any range can be selected from any two values ​​listed before the phrase, regardless of whether those values ​​are at the bottom or top of the list. For example, a pair of values ​​can be selected from two lower values, two higher values, or one lower value and one higher value.

[0023] II. Latex polymer compositions for asphalt modification

[0024] This document discloses bitumen emulsion compositions comprising styrene-butadiene latex. In some embodiments, the polymeric styrene-butadiene latex is derived from 90% to 10% by weight (e.g., 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 45% or more, 40% or more, 35% or more, 30% or more, 25% or more, 20% or more, 15% or more, 10% or more, or any range covered by these endpoints) of styrene. In some embodiments, the polymer may be derived from 10% to 90% by weight (e.g., 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 55% or less, 60% or less, 65% or less, 70% or less, 75% or less, 80% or less, 85% or less, 90% or less, or any range covered by these end values).

[0025] The latex copolymer is non-carboxylated and does not contain acid monomer units. The copolymer may be derived solely from styrene and butadiene monomers or from other monomers, i.e., containing other monomer units. In some embodiments, the copolymer contains 10% by weight or less of other monomer units. For example, the copolymer may contain at least one additional conjugated diene monomer (e.g., isoprene) or natural rubber. The copolymer may also contain at least one additional vinyl aromatic monomer, such as α-methylstyrene or o-chlorostyrene. Other suitable monomers include acrylonitrile, methacrylonitrile, acrylamide and methacrylamide, N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide. In some embodiments, one or more additional monomers may include at least one (meth)acrylate. For example, methyl, ethyl, n-butyl, isobutyl, and ethylhexyl 2-acrylate and methacrylate can be used.

[0026] Because the copolymer is non-carboxylated and contains no acidic monomer units, commonly used cationic reverse surfactants for charge modification of the copolymer dispersion to cationic form are not necessary. Examples of such cationic reverse surfactants include REDICOTE.RTM.E-5 (Nouryon, Chicago, Illinois), REDICOTE.RTM.E-11 (Nouryon, Chicago, Illinois), REDICOTE.RTM.E-53 (Nouryon, Chicago, Illinois), REDICOTE.RTM.E-606 (Nouryon, Chicago, Illinois), REDICOTE.RTM.E-5127 (Nouryon, Chicago, Illinois), and ADOGEN.RTM.477HG (Chemtura Corp., Greenwich, Connecticut). Conn.), INDULIN.RTM.W-1 (Ingevity, Charleston, South Carolina), INDULIN.RTM.W-5 (Ingevity, Charleston, South Carolina), INDULIN.RTM.SBT (Ingevity, Charleston, South Carolina), and INDULIN.RTM.MQK (Ingevity, Charleston, South Carolina), in some embodiments, the non-carboxylated latex is substantially free of cationic reverse surfactants. In some embodiments, the non-carboxylated latex may comprise a blend of nonionic and cationic reverse surfactants.

[0027] The compositions disclosed herein can be prepared by any polymerization process known in the art. In some embodiments, the compositions disclosed herein are prepared by dispersion, microemulsion, or emulsion polymerization. The compositions disclosed herein can be prepared, for example, by polymerizing styrene, butadiene, and optionally other monomers using free radical emulsion polymerization. In some embodiments, the polymerization reaction medium is an aqueous medium. Solvents other than water may also be used in the emulsion. Emulsion polymerization can be carried out in a batch, semi-batch, or continuous manner. In some embodiments, a portion of the monomer can be heated to the polymerization temperature and partially polymerized, and then the remainder of the polymerization batch can be fed continuously, stepwise, or in a concentration gradient into the polymerization zone. As will be readily understood by those skilled in the art, the method can use a single reactor or a series of reactors. For example, a review of multiphase polymerization techniques is provided in M. Antonelli and K. Tauer, *Polymer Chemistry and Physics* (Macromol. Chem. Phys. 2003, Vol. 204, pp. 207-19).

[0028] The polymer dispersion can be prepared by first charging a reactor with a seed latex, water, monomers, and optionally at least one nonionic surfactant. The seed latex (although optional) helps initiate polymerization and contributes to the production of a polymer with a consistent particle size. Any seed latex suitable for the specific monomer reaction can be used, such as polystyrene seeds. The initial charge may also include a chelating or complexing agent, such as ethylenediaminetetraacetic acid (EDTA). Other compounds, such as buffer solutions, can be added to the reactor to provide the desired pH for the emulsion polymerization reaction. For example, a base or basic salt (such as KOH or tetrasodium pyrophosphate) can be used to raise the pH, while an acid or acidic salt can be used to lower 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., 40°C to 90°C, 50°C to 85°C, or 55°C to 80°C).

[0029] Following the initial charge, monomers to be used for polymerization can be continuously fed into the reactor as 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 also be continuously added to the reactor along with the monomer feed stream; however, if a monomer pre-emulsion is used in the process, it may also be desirable to include at least a portion of the initiator solution in the reactor before adding the monomer pre-emulsion. The monomer and initiator feed streams are typically added continuously to the reactor over a predetermined time period (e.g., 1.5 to 15 hours) to induce polymerization of the monomers and thereby produce a polymer dispersion. Nonionic and / or anionic surfactants can be added as part of the monomer or initiator feed stream, but these surfactants can also be provided in separate feed streams. Furthermore, one or more buffer solutions can be included in the monomer or initiator feed stream, or provided in separate feed streams, to alter or maintain the pH of the reactor.

[0030] Monomers can be fed in one or more feed streams, each containing one or more monomers used in the polymerization process. For example, styrene and butadiene (when used) can be provided in separate monomer feed streams or added as a pre-emulsion. It may also be advantageous to delay the feeding of certain monomers to provide certain polymer properties or to provide layered or multiphase structures (e.g., core / shell structures).

[0031] The molecular weight of the copolymer can be adjusted by adding small amounts of molecular weight regulators, for example, from 0.01% to 4% by weight based on the monomers being polymerized. Specific regulators that can be used include organothioides (e.g., tert-dodecyl mercaptan), terpinene, allyl alcohols and aldehydes, and rosin acids.

[0032] The initiator feed stream may contain at least one initiator or initiator system for initiating polymerization of monomers in the monomer feed stream. The initiator stream may also contain water and other desired components suitable for the monomer reaction to be initiated. The initiator may be any initiator known in the art for emulsion polymerization, such as azo initiators; ammonium persulfate, potassium persulfate, or sodium persulfate; or redox systems that typically contain an oxidizing agent and a reducing agent. Commonly used redox initiation systems are described, for example, by ASSArac in Advances in Polymer Science 24, 1149–1204 (1999). An exemplary initiator comprises an aqueous solution of an azo initiator and sodium persulfate. The initiator stream may optionally contain one or more buffer solutions or pH adjusters.

[0033] In addition to monomers and initiators, anionic or nonionic surfactants (i.e., emulsifiers), such as the anionic or nonionic surfactants described herein, can be fed into the reactor. The surfactant can be provided in the initial charge of the reactor, in the monomer feed stream, in the aqueous feed stream, in the pre-emulsion, in the initiator stream, or a combination thereof. The surfactant can also be provided to the reactor as a separate, continuous stream. Based on the total weight of the monomers and surfactant, the surfactant can be provided in an amount from 1% to 5% by weight. In some embodiments, the surfactant is provided in an amount of less than 2% by weight.

[0034] Once polymerization is complete, the polymer dispersion can be chemically stripped, thereby reducing its residual monomer content. This stripping process can comprise chemical stripping and / or physical stripping steps. In some embodiments, the polymer dispersion is chemically stripped by continuously adding an oxidant, such as a peroxide (e.g., tert-butyl hydroperoxide), and a reducing agent (e.g., sodium acetone bisulfite) or another redox pair to the reactor at high temperatures for a predetermined period of time (e.g., 0.5 hours). Suitable redox pairs are described by ASSArac in Advances in Polymer Science 24, 1149–1204 (1999). Optional defoamers may also be added before or during the stripping step if desired. In the physical stripping step, water or steam rinsing can be used to further remove unpolymerized monomers from the dispersion. Once the stripping step is complete, the pH of the polymer dispersion can be adjusted, and biocides or other additives can be added. Cationic, anionic, and / or amphoteric surfactants or polyelectrolytes may optionally be added after the stripping step or, if desired, later in the final product to provide a cationic or anionic polymer dispersion. In some embodiments, the latex polymer may contain plasticizers such as mineral oil, liquid polybutene, liquid polyacrylate, lanolin, and combinations thereof.

[0035] Once the polymerization reaction is complete and the stripping step is finished, the reactor temperature can be reduced.

[0036] The styrene-butadiene compositions of the present invention may include additional styrene-butadiene copolymers polymerized at low temperatures (e.g., less than 40°C, such as between -5°C and 40°C). The additional styrene-butadiene copolymers may have a styrene-butadiene monomer weight ratio such as that described above for the high-temperature styrene-butadiene copolymers described herein, or may have a styrene-butadiene monomer weight ratio such as that of SBR latex. Other styrene-butadiene copolymers polymerized at low temperatures (e.g., less than 40°C, such as between -5°C and 40°C) may be the sole copolymers of the styrene-butadiene compositions of the present invention. The additional styrene-butadiene copolymers may also contain additional monomers, such as those described above for the high-temperature styrene-butadiene copolymers described herein. The additional styrene-butadiene copolymers may also contain acid monomer units, although low-temperature SBRs typically do not contain acid monomer units. In some examples, the additional styrene-butadiene copolymers may be crosslinked or cured using a sulfur curing agent. The additional styrene-butadiene copolymer may contain less than 20% cis-1,4-butadiene units and more than 60% trans-1,4-butadiene units, representing the total number of butadiene units in the copolymer. The additional styrene-butadiene copolymer may have a higher gel content (e.g., greater than 25%) and may have a soluble fraction having a weight-average molecular weight of greater than 400,000 g / mol, greater than 450,000 g / mol, or greater than 500,000 g / mol, as measured by gel permeation chromatography (GPC).

[0037] High-temperature polymerized styrene-butadiene copolymers can be prepared by polymerizing styrene monomers and butadiene monomers in an aqueous emulsion polymerization reaction at temperatures greater than 40°C, 50°C, or 60°C, or at temperatures less than 100°C, 90°C, or 80°C. For example, high-temperature polymerization can be carried out at temperatures between 40°C and 100°C. High-temperature polymerized styrene-butadiene copolymers can be prepared using continuous, semi-batch (semi-continuous), or batch methods. In some examples, a continuous method is used to prepare high-temperature polymerized styrene-butadiene copolymers by continuously feeding one or more monomer streams, surfactant streams, and initiator streams into one or more reactors. The monomers in the one or more monomer streams can be fed in a desired butadiene-to-styrene weight ratio. Seed latex can also be initially loaded into the reactor. In some embodiments, the polymerization method using high-temperature polymerized styrene-butadiene copolymers can be prepared using single-stage polymerization (e.g., by using a single reactor). Furthermore, homogeneous copolymer particles (instead of block copolymers) can be prepared.

[0038] In some embodiments, the non-carboxylated latex may comprise styrene-butadiene latex, which is a blend of styrene-butadiene latex polymerized at temperatures ranging from 40°C to 100°C and styrene-butadiene latex polymerized at temperatures ranging from -5°C to 40°C.

[0039] The surfactant stream contains surfactant and water, and in some embodiments may be mixed with an initiator stream. The surfactant in the emulsion stream can be a synthetic or natural surfactant. For example, the surfactant can be a natural surfactant such as sodium oleate or potassium oleate or a sodium or potassium salt of rosin acid. Based on the total weight of the monomers, the surfactant may be present in the reactor in an amount from 0.5% to 5% by weight.

[0040] At polymerization temperatures of 70°C or higher, thermal initiators such as ammonium persulfate, potassium persulfate, or sodium persulfate can be used in the reactor. At temperatures below 70°C, the thermal initiator can be mixed with or replaced by a redox initiator that comprises a free radical generator, a reducing agent, and an activator (e.g., a water-soluble metal salt).

[0041] Suitable free radical generators include organic peroxides such as benzoyl peroxide, hydrogen peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, dicumyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, α-pinene hydroperoxide, tert-butyl hydroperoxide, acetylacetone peroxide, methyl ethyl ketone peroxide, succinic acid peroxide, di(hexadecyl)dicarbonate peroxide, tert-butyl peracetate, tert-butyl permaleate, tert-butyl perbenzoate, etc.; and alkyl perketals such as 2,2-bis(tert-butyl peroxide)butane, ethyl 3,3-bis-(tert-butyl peroxide)butyrate, or 1,1-bis(tert-butylperoxy)cyclohexane. In some embodiments, the free radical generator includes dicumyl hydroperoxide or p-methane hydroperoxide. Based on the total weight of the monomers, free radical generators are typically present in amounts between 0.01% and 1% by weight.

[0042] Suitable reducing agents for initiating the flow of the agent include sulfur dioxide; alkali metal disulfites; alkali metal and ammonium bisulfite; thiosulfates, dithionites, and formaldehyde hyposulfite; hydroxylamine hydrochloride; hydrazine sulfate; glucose; and ascorbic acid. For example, reducing agents may include sodium formaldehyde hyposulfite dihydrate (SFS), sodium metabisulfite, or mixtures thereof. The reducing agent may be present in an amount between 0.01% by weight and 1% by weight, based on the total weight of the monomers. Furthermore, the weight ratio of the reducing agent to the free radical generator may be between 0.2:1 and 1:1.

[0043] Water-soluble metal salts can be iron, copper, cobalt, nickel, tin, titanium, vanadium, manganese, chromium, or silver salts, and can be selected from a 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(II) perchlorate, copper(II) dichromate, copper(II) nitrate hexahydrate, ferric acetate(II), ferric bromide(III), ferric bromide(III) hexahydrate, ferric perchlorate(II), ferric dichromate(III), ferric formate(III), ferric lactate(III), ferric malate(III), ferric nitrate(III), ferric oxalate(III), ferric sulfate(II) pentahydrate, cobalt(II) acetate, cobalt(II) benzoate, cobalt(II) bromide hexahydrate, cobalt(III) chloride, cobalt(II) tetrahydrofluoride, nickel hypophosphite, nickel octoate, tin tartrate, titanium oxalate, vanadium tribromide, silver nitrate, and silver fluorosilicate. Metals can also be complexed with compounds such as ethylenediaminetetraacetic acid (EDTA) to increase their solubility in water. For example, iron / EDTA complexes or cobalt / EDTA complexes can be used. Based on the total weight of the monomers, water-soluble metal salts can be present in amounts less than 0.01% by weight.

[0044] Polymerization can be carried out in the presence of molecular weight regulators to reduce the molecular weight of the copolymer. Suitable molecular weight regulators include C8-C. 12 Thiols, such as octyl, nonyl, decyl, or dodecyl mercaptan and terpinene. In some embodiments, tert-dodecyl mercaptan is used as a molecular weight regulator. The amount of tert-dodecyl mercaptan used will depend on the desired molecular weight of the copolymer. In some embodiments, terpinene is used as a molecular weight regulator. In some embodiments, a blend of tert-dodecyl mercaptan and terpinene is used as a molecular weight regulator. In some embodiments, the amount of molecular weight regulator is from 0.01% to 4% by weight (e.g., 0.1% to 1% by weight) based on the total monomer weight.

[0045] One or more monomer feeds, surfactant feeds, and initiator feeds can be separately fed into the reactor, where the polymerization of styrene monomer and butadiene monomer occurs. The polymer content of the styrene-butadiene composition of the present invention can be in the range of 30% to 75%. Based on the total weight of the latex composition, the latex solids can also be in the range of 30% to 75% by weight.

[0046] Once the desired conversion level is reached, the polymerization reaction can be terminated by adding a quick-stopping agent to the reactor. The quick-stopping agent reacts rapidly with free radicals and oxidants, thereby destroying all remaining initiators and polymer free radicals and preventing the formation of new free radicals. Exemplary quick-stopping agents include organic compounds having a quinone-type structure (e.g., quinone) and organic compounds that can be oxidized to a quinone-type structure (e.g., hydroquinone), optionally mixed with: water-soluble sulfides (such as hydrogen sulfide, ammonium sulfide, or alkali metal or alkaline earth metal sulfides or hydrosulfides); N-substituted dithiocarbamates; reaction products of alkylene polyamines with sulfur, presumably containing sulfides, disulfides, polysulfides, and / or mixtures of these and other compounds; dialkylhydroxylamines; N,N'-dialkyl-N,N'-methylenebishydroxylamine; dinitrochlorobenzene; dihydroxydiphenyl sulfide; dinitrophenylbenzothiazole sulfide; and mixtures thereof. In some embodiments, the accelerator is hydroquinone or potassium dimethyl dithiocarbamate. The accelerator can be added in amounts between 0.01% and 0.1% by weight, based on the total monomer weight. However, high-temperature polymerization can be allowed to continue until complete monomer conversion, i.e., greater than 99%, in which case the accelerator may not be used.

[0047] As described above, styrene-butadiene copolymers polymerized at high temperatures can also be prepared using a batch process. In the batch process, the monomer, surfactant, free radical generator, and water are all added to the reactor and stirred. After reaching the desired polymerization temperature, an activator solution containing a reducing agent and, if desired, a water-soluble metal salt (if applicable) can be added to initiate the polymerization.

[0048] If a semi-batch method is used, the monomer, surfactant in the aqueous solution, and free radical generator in the aqueous solution are all fed into the reactor over a period of time (typically 3 to 20 hours). If necessary, an activator solution containing a reducing agent and / or water-soluble metal salt can be added to the reactor before starting other feeds, or it can be fed into the reactor at intervals. Preferably, the styrene-butadiene copolymer is allowed to complete monomer conversion at high temperatures, i.e., greater than 99%, in which case a quick-stop agent is not required. However, if necessary, and if the desired conversion is less than 99%, a quick-stop agent can be added to terminate the polymerization.

[0049] Once polymerization terminates (in continuous, semi-gap, or batch methods), unreacted monomers can be removed from the latex dispersion. For example, butadiene monomers can be removed by flash evaporation under atmospheric pressure and then under reduced pressure. Styrene monomers can be removed by steam stripping in a column.

[0050] The additional styrene-butadiene latex can be an SBR copolymer dispersion, which can be agglomerated, for example, using chemical agglomeration, freeze agglomeration, or pressure agglomeration, and water can be removed to produce a solids content greater than 50% to 75%. In some embodiments, the solids content is 55% or greater, 60% or greater, or 65% or greater. As described above, the high-temperature styrene-butadiene copolymer dispersion can be blended with the additional SBR copolymer dispersion prior to agglomeration. Agglomerated particles result in a polymer dispersion with larger particles having a wider particle size distribution. The agglomerated particles described herein have a particle size of 100 nm to 5 nm. For example, the particle size can be in the range of 100 nm to 2 nm or 200 nm to 1 nm.

[0051] Even when concentrated, coagulated dispersions can have a viscosity that allows them to flow easily (i.e., they do not gel). For example, an aqueous dispersion with a solids content greater than 60% can have a viscosity of less than 1000 cp at 20°C.

[0052] This document describes latex polymer compositions for asphalt modification. In some embodiments, the latex polymer composition includes a surfactant that eliminates the need to reverse the charge of the latex particles before incorporating them into the asphalt emulsion.

[0053] In one embodiment, the latex polymer is a non-carboxylated latex containing 0.01 to 20% by weight of a nonionic surfactant based on the total weight of the latex;

[0054] Latex copolymers are non-carboxylated and do not contain acid monomer units. Copolymers may be derived solely from styrene and butadiene monomers, or from other monomers, namely acrylonitrile, acrylamide, acrylates, methacrylates, and N-hydroxymethylacrylamide or N-hydroxymethylmethacrylamide.

[0055] In some embodiments, the copolymer contains 10% by weight or less of other monomer units. For example, the copolymer may contain at least one additional conjugated diene monomer (e.g., isoprene) or natural latex rubber. The copolymer may also contain at least one additional vinyl aromatic monomer, such as α-methylstyrene or o-chlorostyrene. Other suitable monomers include acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide. In some embodiments, one or more additional monomers may include at least one (meth)acrylate. For example, methyl, ethyl, n-butyl, isobutyl, and ethylhexyl 2-acrylate and methacrylate may be used.

[0056] As disclosed herein, copolymers may also be derived from or further contain organosilanes. Organosilanes may be derived from formula (R... 1 )—(Si)—(OR 2 )3 indicates that R 1The alkyl group is C1-C8 substituted or unsubstituted, or the olefin is C1-C8 substituted or unsubstituted, and the R is the same or different. 2 Each is a C1-C8 substituted or unsubstituted alkyl group. In some examples, the organosilane includes vinylsilane. Exemplary organosilanes may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxysilane), vinyltriisopropoxysilane, (meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, or mixtures thereof. In some examples, the organosilane includes vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxysilane), vinyltriisopropoxysilane, γ-methacryloyloxypropyltrimethoxysilane, or combinations thereof. In some examples, the organosilane includes vinyltriethoxysilane. In some examples, the organosilane is composed of vinylethoxysilane.

[0057] Copolymers can be derived from other monomers. For example, copolymers can be derived from vinyl esters of branched monocarboxylic acids having a total of 8 to 12 carbon atoms and a total of 10 to 14 carbon atoms in the acid residue moiety (such as vinyl 2-ethylhexanoate, vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate, vinyl neododecanoate, and mixtures thereof), as well as copolymerizable surfactant monomers (e.g., those sold under the trademark ADEKA REASOAP).

[0058] Latex may contain copolymers or terpolymers of any of the monomer units previously discussed. For example, non-carboxylated latex may contain styrene-butadiene copolymers, styrene-acrylic polymers, ethylene-acrylic polymers, or natural latex polymers, as well as blends thereof.

[0059] In some embodiments, the latex may contain styrene-butadiene-(meth)acrylate, styrene-butadiene-acrylonitrile, or styrene-butadiene-(meth)acrylate-acrylonitrile copolymer.

[0060] Any of the aforementioned monomers may be present in the non-carboxylated latex in amounts 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 in any range covered by any two of the aforementioned values ​​as endpoints. For example, the latex may contain 20 wt% to 70 wt%, or 30 wt% to 60 wt% of styrene monomer.

[0061] In some embodiments of the non-carboxylated latex containing a styrene-butadiene copolymer, the styrene to butadiene ratio can be from 80 / 20 to 20 / 80 by weight. For example, the styrene to butadiene ratio can be 70 / 30, 75 / 25, or 50 / 50.

[0062] In some embodiments, the non-carboxylated latex is substantially free of cationic or anionic reverse surfactants. In some embodiments, based on the total weight of the latex composition, the non-carboxylated latex may contain 10% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, or 0.1% or less of cationic or anionic reverse surfactants.

[0063] After polymerization is complete, nonionic emulsifiers (such as those commonly used in the manufacture of asphalt emulsions) can be added directly or later to the latex composition.

[0064] Suitable nonionic surfactants include, but are not limited to, redoote ® E-47 NPF and its ethoxylated variants, as well as any ETHYLAN surfactants (Nouryon, Bridgewater, NJ), INDULIN XD-70 (Ingevity, Charleston, South Carolina), polyoxyalkylene ethers and polyoxyalkylene phenyl ethers (e.g., diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene nonylphenyl ether); ethylene oxide-propylene oxide block copolymers; sorbitan fatty acid esters (e.g., under the trade name SPAN) ® 20g of dehydrated sorbitan monolaurate purchased from Merck Schuchardt OHG, marketed under the trade name SPAN ® 80g of dehydrated sorbitan monooleate purchased from Merck Schuchat OHG and SPAN (trade name) ® 85 sorbitan trioleate purchased from Merck Schuchat OHG; polyoxyethylene sorbitan fatty acid esters (e.g., under the trade name TWEEN) ® 20 and TWEEN ® 21. Polyoxyethylene dehydrated sorbitan monolaurate purchased from Uniqema; marketed under the trade name TWEEN ® 40g of polyoxyethylene dehydrated sorbitan monopalmitate purchased from Lilykama; marketed under the trade name TWEEN ® 60. TWEEN ® 60K and TWEEN ® 61. Polyoxyethylene dehydrated sorbitan monostearate purchased from Lilykama; sold under the trade name TWEEN ®80. TWEEN ® 80K and TWEEN ® 81. Polyoxyethylene dehydrated sorbitan monooleate purchased from Likima; and TWEEN (trade name) ® 85. Polyoxyethylene sorbitan trioleate purchased from Lirkema; ​​ethoxylated tallow amine, ethoxylated coconut amine, polyoxyethylene sorbitan fatty acid esters (e.g., tetraoleic polyoxyethylene sorbitan); glycerol fatty acid esters (e.g., glyceryl oleate); polyoxyethylene glycerol fatty acid esters (e.g., polyoxyethylene glycerol monostearate and polyoxyethylene glycerol monooleate); oleylamine ethoxylate, tallow alkyl diamine ethoxylate, polyoxyethylene fatty acid esters (e.g., polyethylene glycol monolaurate and polyethylene glycol monooleate); blends of ethoxylated fatty amines / ethoxylated fatty alcohols (Demelan VPC, BASF), polyoxyethylene alkyl amines; acetylenic diol; TETRONIC ™ (1301, 150, 701, 901, 904 and 908, BASF), PLURONIC ™ (L62 LF, L64, L81, L92, L44NH, N3, P103, P104, P105, P123, P65, and P84, BASF), Disponil AFX (BASF), nonylphenol ethoxylate, octylphenol ethoxylate, dodecylphenol ethoxylate, straight-chain alcohol ethoxylates, branched-chain alcohol ethoxylates such as tridecyl alcohol ethoxylate, fatty alcohol ethoxylates, block copolymers, PEG esters, and castor oil ethoxylates. In some embodiments, the nonionic surfactant may have an HLB (hydrophilic-lipophilic balance) at room temperature, such that 8 < HLB < 18. In some embodiments, the HLB is 14 or less. In some embodiments, the nonionic surfactant comprises ethylene oxide (EO) of alkyl, alkylbenzene, or dialkylbenzene alcohols. m And / or propylene oxide (PO) n Adducts, wherein (m+n)≤14, (m+n)≤12, or (m+n)≤10 (e.g., 6≤(m+n)≤10), such as LUTENSOL ™ Those trademarks were purchased from BASF. In some embodiments, the nonionic surfactant comprises ethylene oxide (EO) of alkyl, alkylbenzene, or dialkylbenzene alcohols. m And / or propylene oxide (PO) n Adducts, wherein (m+n)≤80, (m+n)≤60, or (m+n)≤40, (m+n)≤30.

[0065] In some implementations, the nonionic surfactant is based on the following formula (I):

[0066]

[0067] In equation (I), G can be hydrogen or C1-C 18 Alkyl groups, or C1-C groups substituted with one or more OH groups. 18 Alkyl, C1-C 18 Alkoxy, C5-C 12 Cycloalkoxy, allyloxy, halogen, =O, -COOH, -COOG8, -CONH2, -CONHG9, -CON(G9)(G 10 ), -NH2, -NHG9, =NG9, -N(G9)(G 10 ), -NHCOG 11 -CN, -OCOG 11 , phenoxy; or G is a C3-C that is separated by -O- and can be substituted by OH. 100 Alkyl; or G is C3-C6 alkenyl; glycidyl, C5-C 12 Cycloalkyl groups, C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkyl, -OCOG 11 C7-C that is unsubstituted or substituted with OH 11 Phenylalkyl, C1-C 18 Alkoxy, C1-C 18 Alkyl, -CO-G 12 or -SO2-G 13 G8 is C1-C 18 Alkyl, C3-C 18 Alkenyl groups, C3-C segments spaced by O, NH, NG9, or S, or substituted with OH 50 Alkyl, -P(O)(OG 14 )2、-N(G9)(G 10 ) or -OCOG 11 C1-C4 alkyl groups, glycidyl groups, or C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkylcyclohexyl, phenyl, C7-C 14 Alkylphenyl, C6-C 15 Bicycloalkyl, C6-C 15 Bicycloalkenyl, C6-C 15 Tricycloalkyl, C6-C 15 Dicycloalkyl alkyl or C7-C 11 Phenylalkyl; G9 and G 10 C1-C are independent of each other. 12 Alkyl, C3-C 12 Alkoxyalkyl, C2-C 18 Alkyl group, C4-C 16 Dialkylaminoalkyl or C5-C 12cycloalkyl, or G9 and G 10 Together they are C3-C9 alkylene or oxaalkylene or azaalkylene; G 11 It is C1-C 18 Alkyl, C1-C 18 Alkoxy, C2-C 18 It is alkenyl, C7-C 11 Phenylalkyl, C7-C 11 Phenylalkoxy, C6-C 12 cycloalkyl, C6-C 12 Cycloalkoxy, phenoxy, or phenyl; or C3-C separated by -O- and potentially substituted with OH. 50 Alkyl; G 12 It is C1-C 18 It is alkenyl, C2-C 18 alkenyl, phenyl, C1-C 18 Alkoxy group; C3-C 18 Alkenyl groups, C3-C atoms spaced by O, NH, NG9 or S, or substituted with OH 50 Alkoxy, cyclohexyloxy, phenoxy, C7-C 14 Alkylphenoxy, C7-C 11 Phenylalkoxy, C1-C 12 Alkylamino, phenylamino, tolylamino, or naphthylamino; G 13 It is C1-C 12 Alkyl, phenyl, naphthyl or C7-C 14 Alkylphenyl; G 14 It is C1-C 12 alkyl, methylphenyl or phenyl

[0068] In a preferred embodiment, G can be hydrogen or C1-C. 18 Alkyl groups, or C1-C groups substituted with OH. 18 Alkyl, C1-C 18 Alkoxy, C5-C 12 Cycloalkoxy, =O, -COOH, -COOG8, -CONHG9, -NH2, -NHG9, -N(G9)(G 10 ), -NHCOG 11 C1-C 18 Alkyl-, C1-C 18 alkoxy group; or G is a C3-C group separated by -O- and substituted with OH. 100 Alkyl; or G is C5-C 12 Cycloalkyl groups, C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkyl, -OCOG 11 G8 is C1-C 18Alkyl groups, C3-C atoms spaced by O, NH, NG9, or S, or substituted with OH 50 Alkyl, -P(O)(OG 14 )2、-N(G9)(G 10 ) or -OCOG 11 C1-C4 alkyl groups, glycidyl groups, or C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkylcyclohexyl, phenyl, C7-C 14 Alkylphenyl, C6-C 15 Bicycloalkyl, C6-C 15 Bicycloalkenyl, C6-C 15 Tricycloalkyl or C6-C 15 Bicycloalkylalkyl; G9 and G 10 C1-C are independent of each other. 12 Alkyl, C2-C 18 Alkyl group; or C5-C 12 cycloalkyl, or G9 and G 10 Together they are C3-C9 alkylene or oxaalkylene or azaalkylene; G 11 It is C1-C 18 Alkyl, C1-C 18 Alkoxy, C6-C 12 cycloalkyl, C6-C 12 Cycloalkoxy groups; or C3-C groups separated by -O- and potentially substituted with OH. 50 Alkyl; G 12 It is C1-C 18 It is an alkyl group, C1-C 18 Alkoxy group; C3-C 18 Alkenyl group; C3-C substituted with O, NH, NG9 or S, or OH. 50 Alkyloxy; cyclohexyloxy, phenoxy, C7-C 14 Alkylphenoxy; C7-C 11 Phenylacetoxy; C1-C 12 Alkylamino; G 13 It is C1-C 12 Alkyl; G 14 It is C1-C 12 alkyl.

[0069] In a more preferred embodiment, G may be hydrogen or C1-C 18 Alkyl groups, or C1-C groups substituted with OH. 18 Alkyl; or G is a C3-C molecule separated by -O- and potentially substituted with OH. 100 alkyl.

[0070] In the most preferred embodiment, G can be hydrogen.

[0071] In formula (I), n is preferably 1-200, more preferably 1-100, and most preferably 25-75.

[0072] In equation (I), R can be C1-C 18 Alkyl, phenyl, C1-C 18 Alkyl-substituted phenyl groups, or C1-C substituted with one or more OH groups. 18 Alkyl, C1-C 18 Alkoxy, C5-C 12 Cycloalkoxy, allyloxy, halogen, =O, -COOH, -COOG8, -CONH2, -CONHG9, -CON(G9)(G 10 ), -NH2, -NHG9, =NG9, -N(G9)(G 10 ), -NHCOG 11 -CN, -OCOG 11 , phenoxy; or R is a C3-C that is separated by -O- and can be substituted by OH. 100 Alkyl, or R is C3-C6 alkenyl, glycidyl, C5-C 12 Cycloalkyl groups, C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkyl, -OCOG 11 Unsubstituted or replaced by OH, Cl, Cl-C 18 Alkoxy or C1-C 18 Alkyl-substituted C7-C 11 Phenylalkyl, -CO-G 12 or -SO2-G 13 .

[0073] In a preferred embodiment, R can be C1-C 18 Alkyl, phenyl, C1-C 18 Alkyl-substituted phenyl or C1-C substituted with one or more OH groups 18 Alkyl groups, or C3-C groups separated by -O-. 50 alkyl.

[0074] In a more preferred embodiment, R can be C1-C 18 Alkyl, phenyl, C6-C 18 Alkyl-substituted phenyl or C1-C substituted with one or more OH groups 18 alkyl.

[0075] In the most preferred embodiment, R can be C1-C 18 Alkyl or C6-C 12 Alkyl-substituted phenyl groups.

[0076] The molecular weight of the nonionic surfactant can be from 200 g / mol to 15000 g / mol, preferably from 300 g / mol to 10000 g / mol, more preferably from 500 g / mol to 8000 g / mol, even more preferably from 1000 g / mol to 6000 g / mol, and most preferably from 1500 g / mol to 3000 g / mol.

[0077] Based on the total weight of the latex, the nonionic surfactant may be present in the latex composition in an amount from 0.01 wt% to 30 wt%. For example, the nonionic surfactant 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.

[0078] Once polymerization terminates (in continuous, semi-gap, or batch methods), unreacted monomers can be removed from the latex dispersion. For example, butadiene monomers can be removed by flash evaporation at atmospheric pressure and then under reduced pressure. Styrene monomers can be removed by steam stripping in a column.

[0079] Suitable anionic emulsifiers include, but are not limited to, fatty acids, alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonic acids, alkyl phosphates or their salts, sucrose esters, and mixtures thereof. Anionic polyelectrolytes such as tartrates, borates, oxalates, and phosphates may also be used in the composition. Other suitable anionic surfactants and polyelectrolytes include, but are not limited to, M28B and INDULIN. ® Other anionic surfactants (such as INDULIN) purchased from Medveswick are trademarked. ® AMS, INDULIN ® SA-L, INDULIN ® ISE, INDULIN ® 201, INDULIN ® 202 and INDULIN ® 206); with REDICOTE ® Trademarked anionic surfactants (such as REDICOTE) purchased from Nouryon ® E-15 and REDICOTE ® E-62C); and lignin sulfonates, such as MARASPERSE ™ Those trademarks that are available (such as MARASPERSE) ™ CBOS-3 and MARASPERSE ™(N22). In some embodiments, the emulsifier includes anionic fatty acid-based emulsifiers.

[0080] Cationic emulsifiers can be classified as cationic rapid setting (CRS) emulsifiers, cationic quick setting (CQS) emulsifiers, cationic medium setting (CMS) emulsifiers, or cationic slow setting (CSS) emulsifiers, and these classifications are known in the art and can be readily measured in emulsions as described in ASTM D977 and D2397. In some embodiments, a cationic polyelectrolyte may be provided in the composition. Suitable cationic emulsifiers and polyelectrolytes include alkylamine salts, quaternary ammonium salts, and REDICOTE... ® The trademark is purchased from Nouryon for cationic surfactants (such as REDICOTE). ® 4819, REDICOTE ® E-64R, REDICOTE ® E-5, REDICOTE ® E-9, REDICOTE ® E9A, REDICOTE ® E-11, 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), with INDULIN ® and AROSURF ® The trademark is purchased from Ingevity for cationic surfactants (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-1 and INDULIN ® W-5), ASFIER purchased from Kao Specialties Americas ® N480, CYPRO purchased from Cytec Industries ™ 514. Polyethyleneimine, such as POLYMIN ® Those trademarks purchased from BASF (such as POLYMIN) ® SK, POLYMIN ® SKA, POLYMIN ® 131. POLYMIN ® 151. POLYMIN ® 8209, POLYMIN ® P and Polymin ® PL) and polyethyleneimine such as CATIOFAST ® Those trademarks purchased from BASF (such as CATIOFAST) ® CS, CATIOFAST ® FP, CATIOFAST ® GM and CATIOFAST ® (PL). Other suitable cationic polyelectrolytes and surfactants include, for example, those listed in U.S. Patent Nos. 5,096,495, 5,160,453, and 5,443,632. In some embodiments, the cationic emulsifier includes an amine-based emulsifier.

[0081] Suitable amphoteric surfactants include, but are not limited to, acetate betaine, amide betaine, sulfobetaine, imidazoline betaine, and amine oxides. An exemplary amphoteric surfactant is REDICOTE. ®The surfactant E-7000 was purchased from Nouryon. Suitable anionic emulsifiers include fatty acids, alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonic acids, alkyl phosphates or their salts, sucrose esters, and mixtures thereof. Anionic polyelectrolytes such as tartrates, borates, oxalates, and phosphates may also be used in the composition. Other suitable anionic surfactants and polyelectrolytes include, but are not limited to, M28B and INDULIN. ® Other anionic surfactants (such as INDULIN) purchased from Medveswick are trademarked. ® AMS, INDULIN ® SA-L, INDULIN ® ISE, INDULIN ® 201, INDULIN ® 202 and INDULIN ® 206); with REDICOTE ® Trademarked anionic surfactants (such as REDICOTE) purchased from Nouryon ® E-15 and REDICOTE ® E-62C); and lignin sulfonates, such as MARASPERSE ™ Those trademarks that are available (such as MARASPERSE) ™ CBOS-3 and MARASPERSE ™ (N22). In some embodiments, the emulsifier includes anionic fatty acid-based emulsifiers.

[0082] In some embodiments, the non-carboxylated latex comprises a blend of nonionic and cationic reverse surfactants, or a blend of nonionic and anionic reverse surfactants.

[0083] Some formulations used in the applications disclosed herein contain solvents such as water to disperse or emulsify polymers and / or bitumen. Some compositions disclosed herein contain water. In some embodiments, the composition contains bitumen and the bitumen contains water and is an aqueous emulsion. In some embodiments, the composition contains a polymer and the polymer contains water and is an aqueous dispersion. In some embodiments, the bitumen and / or polymer contains water, and one or both are aqueous dispersions or emulsions. Some formulations for the applications disclosed herein do not contain water but include non-aqueous solvents. Some compositions disclosed herein do not contain water. In some embodiments, the polymer and / or bitumen may be in the form of non-aqueous dispersions or emulsions.

[0084] The composition may also contain aggregates. As those skilled in the art will understand, aggregates can have different sizes. Any aggregates conventionally used to produce asphalt paving compositions can be used, including dense-graded aggregates, gap-graded aggregates, open-graded aggregates, recycled asphalt pavements, and mixtures thereof. Dense-graded aggregates exhibit the largest mineral surface area (per unit aggregate). Open-graded aggregates consist primarily of single, large-sized (e.g., about 0.375 inches to 1.0 inch) stones with a very low level (e.g., less than about two percent of the total aggregate) of fine powder (e.g., material smaller than 0.25 inches) or filler (e.g., mineral material smaller than 0.075 mm). Gap-graded aggregates fall between dense-graded and open-graded aggregates. Recycled asphalt pavement (RAP) materials typically reflect the gradation of the pavement from which the recycled material was obtained. If the original pavement was a dense-graded mix, the RAP will also be dense-graded, but filler content is typically observed to be below the design limits of the original aggregate specifications. The aggregate can be applied in amounts ranging from 100 parts by weight to 2000 parts by weight.

[0085] In some embodiments, the composition comprising aggregate may also contain air gaps. The air gaps may be present in an amount of 2 vol% to 30 vol% (e.g., greater than 2 vol% to 10 vol%).

[0086] Asphalt compositions can be prepared by mixing asphalt, any aromatic recycling agent or non-asphalt rosin material, an ionic crosslinking agent, an emulsifier, an acid or alkali, water, and any additives and optionally a polymer derived from styrene-butadiene rubber latex. In some embodiments, the polymer is not crosslinked by an ionic crosslinking agent and can be added to the asphalt composition separately from the ionic crosslinking agent, and once the water has substantially evaporated, the polymer and asphalt can be crosslinked by the ionic crosslinking agent in the asphalt composition. For example, the asphalt composition may contain an ionic crosslinking agent, and additional components may be added to or included in the composition. For example, the asphalt composition may be an emulsion containing asphalt and an ionic crosslinking agent. In some embodiments, compositions containing asphalt and an ionic crosslinking agent can be provided, in which a polymer (e.g., as an aqueous dispersion) can be mixed with the composition, and once the water has substantially evaporated, the polymer and asphalt can be crosslinked by the ionic crosslinking agent, thereby producing an asphalt-based composition containing a crosslinked polymer.

[0087] Specific components can be mixed together using methods known in the art. As previously mentioned, specific components can be mixed together in any order. In some embodiments, a polymer derived from styrene-butadiene rubber latex is premixed with an anionic or cationic emulsifier to produce a charged polymer before the asphalt and acid or alkali are mixed with the emulsifier and polymer. In some embodiments, the polymer derived from styrene-butadiene rubber latex is not premixed with any anionic or cationic emulsifier to produce a charged latex polymer before the asphalt, acid, or alkali are mixed with the emulsifier in the soap tank for the emulsion manufacturing system. If aggregates are blended into the asphalt composition, they can be added, for example, after blending other components. In some embodiments, the asphalt composition is prepared at elevated temperatures, such as 160°C to 200°C (hot-mixed asphalt), 120°C to 160°C (warm-mixed asphalt), or at temperatures below 120°C (e.g., 5°C to 60°C or 5°C to 90°C). In some embodiments, the asphalt composition can be prepared at ambient temperature.

[0088] The asphalt composition can be used on pavement or paved surfaces. Pavement or paved surfaces are hard surfaces capable of supporting pedestrian or vehicular traffic, and can include surfaces such as highways / roads, parking lots, bridges / flyovers, runways, driveways, vehicle paths, running paths, walkways, etc. The asphalt composition can be applied directly to existing paved surfaces or to unpaved surfaces. In some embodiments, the composition is applied as a tie layer to an existing paved layer, and a new layer comprising asphalt (such as a hot-mix layer) is applied to the tie layer. The asphalt composition can be applied to "cold" surfaces, i.e., surfaces with temperatures below 40°C, or to high-temperature surfaces (e.g., 50°C to 120°C, 55°C to 100°C, or 60°C to 80°C).

[0089] In some embodiments, the aggregate is blended into the asphalt composition before being applied to the surface. In some embodiments, the aggregate is applied to the composition after being applied to the surface. In some embodiments, sand may be applied to the composition after sand is applied to the surface, for example if the composition is intended to be used as an adhesion layer to reduce the tackiness of the surface. As those skilled in the art will understand, the composition and optionally the aggregate may be compacted after being applied to the surface.

[0090] In some embodiments, the composition is used as an adhesive layer or coating. An adhesive layer is a very light spray application of a diluted asphalt emulsion that can be used to promote adhesion between an existing surface and a new asphalt application. The adhesive layer serves to provide a degree of adhesion or bonding between asphalt layers and, in some cases, can fuse the layers together. The adhesive layer also serves to reduce slippage and sliding of the layer relative to other layers in the pavement structure during use or due to wear and weathering of the pavement structure. As described above, the composition can be applied as a bonding layer to existing paving layers (such as hot-mixed layers) as an adhesive layer, and new layers comprising asphalt (such as hot-mixed layers) can be applied to the adhesive layer. As those skilled in the art will understand, the adhesive layer typically does not contain aggregate, but sand can be applied to the adhesive layer after the application described above. The composition described herein has unexpectedly been found to be a low-tracking or “trackless” coating, such that after the adhesive coating has cured, paved vehicles or other vehicles can be allowed to traverse the coating, allowing vehicle tires or treads to adhere to the coating in a limited amount (low-track) or not at all (trackless). For example, at higher pavement temperatures (50°C to 60°C) and / or with low or medium bitumen thicknesses greater than 40 dmm, the compositions described herein have been unexpectedly found to be low-track or “trackless.” The adhesive layer is viscous and capable of bonding pavement structure layers together under the environmental conditions used for pavement construction or at elevated temperatures (e.g., up to 140°C as discussed above). In fact, the adhesive layer provides sufficiently flexible bitumen at low temperatures, while maintaining sufficient adhesive strength to bond adjacent bitumen layers. The adhesive layer cures rapidly, allowing the pavement layer to be applied to the coating several hours to several days after the emulsion is applied to the substrate. The applied composition can cure within 15 to 45 minutes and can cure rapidly within 5 to 15 minutes after application to an exposed surface. The curing rate will depend on the application rate, the dilution rate used, the base course conditions, weather, and other similar considerations. Excessive moisture in the prepared pavement surface or base course may increase the curing time of the emulsion.

[0091] In some embodiments, the composition can also be used as a fog seal. A fog seal is a surface treatment that applies the light application of the composition to existing paved surfaces such as parking lots to provide a new-looking, black, enriched pavement surface. In some embodiments, the fog seal will contain fillers such as carbon black to darken the composition. As those skilled in the art will understand, the fog seal may not contain aggregates. Fog seal compositions, like adhesive coating compositions, have also been shown as low-track or "trackless" coatings.

[0092] In some embodiments for the adhesion layer and fog seal layer, the asphalt may be present in an amount of 58 to 62 parts by weight, the polymer comprising styrene-butadiene rubber latex may be present in an amount of 0 to 6 parts by weight, the emulsifier may be present in an amount of 0.75 to 3 parts by weight, the acid or alkali may be present in an amount of 0.75 to 3 parts by weight, any optional additives may be provided in an amount of up to 5 parts by weight, and water may be present in an amount of 30 to 40 parts by weight. In some embodiments, the composition may be further diluted with water. The composition may be in a concentration of 0.05 gallons / yd. 2 Up to 0.10 gallons / yd 2 Apply at a certain rate.

[0093] In some embodiments, the composition can be used as a chip seal composition. Chip seal is the most common surface treatment for low-traffic roads. The chip seal composition can be applied to the surface, followed by the application of aggregate. In some embodiments for chip seal, asphalt may be present in an amount of 64 to 67 parts by weight, a polymer comprising styrene-butadiene rubber latex may be present in an amount of 0 to 3.5 parts by weight, an emulsifier may be present in an amount of 0.15 to 0.35 parts by weight, an acid or alkali may be present in an amount of 0.15 to 0.35 parts by weight, any optional additives may be provided in an amount of up to 5 parts by weight, and water may be present in an amount of 30 to 40 parts by weight. Aggregate may be provided in an amount of 200 to 1000 parts by weight.

[0094] In some embodiments, the composition can be used as a microsurfacing application. Microsurfacing is designed for rapid traffic recovery and is capable of handling high-traffic roads. For the microsurfacing composition, aggregate can be mixed with asphalt, optionally a polymer containing styrene-butadiene rubber latex, an emulsifier, and an acid or alkali before being applied to the surface. In some embodiments for the microsurfacing, asphalt may be present in an amount of 60 to 62 parts by weight, the polymer containing styrene-butadiene rubber latex may be present in an amount of 0 to 4.5 parts by weight, the emulsifier may be present in an amount of 0.5 to 2.5 parts by weight, the acid or alkali may be present in an amount of 0.5 to 2.5 parts by weight, any optional additives may be provided in an amount of up to 5 parts by weight (e.g., 0.25 to 2 parts by weight of one or more inorganic salts or up to 5 parts by weight of mineral fillers), and water may be present in an amount of 30 to 40 parts by weight. Aggregate may be provided in an amount of 500 to 2000 parts by weight.

[0095] The paving surface layer obtained using this composition, once dried, also contains the components provided in the composition, except for water. Therefore, the paving surface layer may contain 40 to 70 parts by weight of asphalt, 0 to 10 parts by weight of a polymer comprising styrene-butadiene rubber latex, 0.1 to 4 parts by weight of an emulsifier, and 0.1 to 4 parts by weight of an acid or alkali. Regarding the adhesive layer, the paving surface may include: a first layer comprising asphalt; a bonding layer disposed on the first layer and comprising 40 to 70 parts by weight of asphalt, 0 to 10 parts by weight of a polymer comprising styrene-butadiene rubber latex, 0.1 to 4 parts by weight of an emulsifier, and 0.1 to 4 parts by weight of an acid or alkali; and a second layer comprising asphalt and disposed on the bonding layer.

[0096] Although parts by weight are used for the compositions described herein, weight percentages may be used interchangeably with parts by weight, for example, where the composition comprises asphalt, an optional polymer comprising styrene-butadiene rubber latex, an emulsifier, an acid or alkali, water, and any additives other than aggregates. For example, the composition may be described as comprising: (a) 40% to 70% by weight of asphalt; (b) 0% to 10% by weight of a polymer comprising styrene-butadiene rubber latex; (c) 0.1% to 4% by weight of an emulsifier; (d) 0.1% to 4% by weight of an acid or alkali; and (e) 25% to 60% by weight of water.

[0097] The compositions can be used in a variety of applications (e.g., warm-mixed asphalt applications at 120°C to 140°C) to provide sufficient crosslinking at a variety of temperatures. For example, the compositions can be blended with asphalt compositions at temperatures of 160°C or lower, 140°C or lower, or 120°C or lower. Depending on the degree of network formed by the crosslinking reaction between the polymer and / or asphalt and the crosslinking agent, the compositions and methods disclosed herein can also provide greater control over, for example, polymer-modified asphalt. Furthermore, the compositions and methods disclosed herein do not require the use of sulfur, thus reducing hydrogen sulfide (H2S) emissions. For example, in some embodiments, the asphalt compositions are substantially free of sulfur or sulfur-based crosslinking agents. In other words, asphalt compositions can be prepared without the use of sulfur-based crosslinking agents.

[0098] In some embodiments, the compositions disclosed herein can be used in paints, coatings, paper coatings or adhesive compositions, carpet compositions (e.g., carpet backing), foams or adhesives. In some embodiments, one or more thickeners (rheology modifiers) may be added to increase the viscosity of the composition. Suitable thickeners may include, but are not limited to, acrylic copolymer dispersions, hydroxyethyl cellulose, guar gum, jaguar, carrageenan, xanthan gum, acetylglucan, konjac, mannan, xylooligosaccharide, carbamates, and mixtures thereof sold under the trademarks STEROCOLL and LATEKOLL from BASF (Florham Park, NJ). Thickeners may be added to the composition formulation as aqueous dispersions or emulsions, or as solid powders.

[0099] The compositions described herein may include, for example, additives such as dispersants, initiators, stabilizers, chain transfer agents, buffers, salts, preservatives, flame retardants, wetting agents, protective colloids, biocides, corrosion inhibitors, crosslinking promoters, and lubricants. Exemplary dispersants may include sodium polyacrylate in an aqueous solution, such as those sold under the trademark DARVAN by RT Vanderbilt Co., Norwalk, CT, Newwart, Connecticut.

[0100] Paint and coating compositions may, for example, contain one or more pigments or dyes. Exemplary composition pigments include titanium dioxide composition pigments, MIRAGLOSS 91 (a kaolin composition pigment commercially available from BASF), LOPAQUE M (a kaolin composition pigment commercially available from Thiele Kaolin Company), and HYDROCARB 90 (a calcium carbonate composition pigment commercially available from Omya Paper). In some embodiments, the composition may contain one or more dyes or colored pigments. Exemplary dyes may include basic dyes, acid dyes, anionic direct dyes, and cationic direct dyes. Exemplary colored pigments include organic and inorganic pigments in the form of anionic and cationic pigment dispersions.

[0101] By way of non-limiting description, some embodiments of the present disclosure are given below.

[0102] Antioxidants can be added to latex compositions to prevent the oxidation of double bonds in the polymer, and can be added before or after polymer vulcanization. The antioxidants can be substituted phenols or secondary aromatic amines.

[0103] Exemplary substituted phenols include 2,6-di-tert-butyl-p-cresol (DBT); 4,4'-thiobis(6-tert-butyl-m-cresol); 3-tert-butyl-4-hydroxyanisole (3-BHT); 2-tert-butyl-4-hydroxyanisole (2-BHT); 2,2-methylenebis(4-methyl-6-tert-butylphenol) (MBMBP); 2,2-methylenebis(4-ethyl-6-tert-butylphenol) (MBEBP); 4,4-butylidenebis(3-methyl-6-tert-butylphenol) (SBMBP); 2,2-ethylidenebis(4,6-di-tert-butylphenol); 2,6-di-tert-butyl-4-sec-butylphenol; styrenated phenol; styrenated p-cresol; 1,1,3-tris(2-methyl-4-hydroxy-5- -tert-butylphenol)butane; tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenol)propionate]methane; n-octadecyl-3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate; triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate]; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; 2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane; 4,4-methylenebis(2,6-di-tert-butylphenol); tris(3,5-di-tert-butyl-4-hydroxyphenol); tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate; 1,3,5-tris(3 ',5'-Di-tert-butyl-4-hydroxybenzoyl) isocyanurate; bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-tert-butylphenyl]sulfide; 1-oxo-3-methylisopropylbenzene; 2,5-dibutylhydroquinone; 2,2'-methylenebis(4-methyl-6-nonylphenol); alkylated bisphenol; 2,5-di-tert-pentylhydroquinone; polybutenyl bisphenol-A; bisphenol-A; 2,6-di-tert-butyl-p-ethylphenol; 2,6-bis(2'-hydroxy-3-tert-butyl-5'-methylbenzyl)-4-methylphenol; 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate; terephthaloyl-di(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) 2,6-tert-butylphenol; 2,6-di-tert-butyl-2-dimethylamino-p-cresol; 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); hexamethylenediol bis(3,5-tert-butyl-4-hydroxyphenyl)propionate; (4-hydroxy-3,5-di-tert-butylaniline)-2,6-bis(octylthio)-1,3,5-triazine; 2,2-thio[diethyl-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; N,N'-hexamethylene(3,5-di-tert-butyl-4-hydroxycinnamate); 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester; 2,4-dimethyl-6-tert-butylphenol; 4,4'-methylenebis(2,6-di-tert-butylphenol);4,4'-Thiobis(2-methyl-6-tert-butylphenol); tris[2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate; 2,4,6-tributylphenol; bis[3,3-bis(4'-hydroxy-3'-tert-butylphenyl)butyrate]diol ester; 4-hydroxymethyl-2,6-di-tert-butylphenol; and bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide. Exemplary secondary aromatic amines include N-phenyl-N'-isopropyl-p-phenylenediamine; N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine; N,N'-diphenyl-p-phenylenediamine; dioctyl-diphenylamine; di(β-naphthyl)-p-phenylenediamine; 2,2,4-trimethyl-1,2-dihydroquinoline polymer and diaryl-p-phenylenediamine. In addition, sulfur-containing antioxidants such as dilaurate thiodipropionate, distearate thiodipropionate, and 2-mercapto-benzimidazole can be used; phosphorus-containing antioxidants such as pentaerythritol distearate diphosphite; nickel-containing antioxidants such as nickel diisobutyldithiocarbamate, nickel dimethyldithiocarbamate, and nickel di-n-butyldithiocarbamate; 2-mercaptobenzimidazole; zinc 2-mercaptobenzimidazole; and 1,11-(3,6,9-trioxaundecyl)bis-3-(dodecylthio)propionate can be provided in amounts from 0.1% to 5.0% by weight or from 0.5% to 2.0% by weight, based on the weight of the copolymer.

[0104] Antiozone inhibitors can also be added to copolymer dispersions to prevent atmospheric ozone from breaking down the polymer's double bonds. Typical antiozone inhibitors include waxes (e.g., VANWAX, commercially available from RT Vanderbilt Co.). ™ H) and N,N'-alkylaryl, N,N'-dialkyl and N,N'-diaryl derivatives of p-phenylenediamine, such as N,N'-di(2-octyl)-p-phenylenediamine, N,N'-di-3(5-methylheptyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (e.g., ANTOZITE, commercially available from RT Vanderbilt). ™ 67P), N-isopropyl-N'-phenyl-p-phenylenediamine and N-cyclohexyl-N'-phenyl-p-phenylenediamine. Based on the weight of the latex polymer, the antiozone agent may be provided in amounts of 0.5% to 10% by weight, 1% to 5% by weight or 1.5% to 3% by weight.

[0105] Pre-vulcanization inhibitors can also be added to latex compositions to prevent premature vulcanization or charring of the polymer. For example, N-cyclohexylthiophthalimide; phthalic anhydride; N-cyclohexylthiophthalimide; N-phenyl-N-(trichloromethylsulfinyl)-benzenesulfonamide; bis-(sulfonylamino)-sulfides or polysulfides (e.g., bis-(N-methyl-p-toluenesulfonylamino)-disulfide); substituted thiophosphoramides (e.g., N-cyclohexylthio-N-phenyldiethylphosphoramide); N-(sulfinyl)methacrylamide; thiosubstituted -1,3,5-triazine, -diamine or -triamine; 2-(thioamino)-4,6-diamino-1,3,5-triazine; N,N'-substituted bis-(2,4-diamino-s-triazine-6-yl)-low-sulfurides; and substituted thioformamidin can be used as pre-sulfurization inhibitors. In some implementations, the pre-vulcanization inhibitor is N-cyclohexylthiophthalimide (SANTOGARD, commercially available from Flexsys). ™ PVI) or N-phenyl-N-(trichloromethylsulfinyl)benzenesulfonamide (available commercially from Bayer) VULKALENT ™ E). Based on the weight of the latex polymer, pre-vulcanization inhibitors are typically provided in amounts of 1% to 5% by weight or 1.5% to 3% by weight.

[0106] Exemplary vulcanization accelerators include sulfenamide vulcanization accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N-oxodiethylene-2-benzothiazole sulfenamide, N-oxodiethylenethiocarbamoyl-N-oxodiethylene sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, and N,N'-diisopropyl-2-benzothiazole sulfenamide; guanidine vulcanization accelerators such as diphenylguanidine, di-o-tolylguanidine, and di-o-tolylbiguanidine; and thiourea vulcanization accelerators such as sulfur carbonate. Aniline, di-o-toluenethiourea, ethylenethiourea, diethylenethiourea, dibutylthiourea, trimethylthiourea, etc.; thiazole vulcanization accelerators, such as 2-mercaptobenzothiazole, dibenzothiazole disulfide, zinc salt of 2-mercaptobenzothiazole, sodium salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 4-morpholino-2-dibenzothiazole and 2-(2,4-dinitrophenylthio)benzothiazole; thiadiazine vulcanization accelerators, such as activated thiadiazine; thiuram vulcanization accelerators, such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethyl ... Butylated thiuram and tetrasulfide bis(pentamethylene)thiuram; dithiocarbamate vulcanization accelerators, such as sodium dimethyl dithiocarbamate, sodium diethyl dithiocarbamate, sodium di-n-butyl dithiocarbamate, lead dimethyl dithiocarbamate, lead dipentyl dithiocarbamate, zinc dipentyl dithiocarbamate, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc di-n-butyl dithiocarbamate, zinc pentamethylene dithiocarbamate, zinc ethylphenyl dithiocarbamate, tellurium diethyl dithiocarbamate, bismuth dimethyl dithiocarbamate, dimethyl dithiocarbamate Selenium dimethylcarbamate, selenium diethyldithiocarbamate, cadmium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, diethylamine diethyldithiocarbamate, piperidinium pentamethyldithiocarbamate, and piperidinium pentamethyldithiocarbamate; xanthate vulcanization accelerators, such as sodium isopropyl xanthate, zinc isopropyl xanthate, and zinc butyl xanthate; isophthalic acid ester vulcanization accelerators, such as dimethylammonium hydrogen isophthalate; aldehyde-amine vulcanization accelerators, such as butyraldehyde-amine condensation products and butyraldehyde-monobutylamine condensation products; and mixtures thereof. Based on the weight of the latex polymer, the vulcanization accelerator may be present in the range of 0.1% to 15% by weight, 0.3% to 10% by weight, or 0.5% to 5% by weight.

[0107] Anti-reversion agents can also be included in the vulcanization system to prevent reversion, i.e., an undesirable decrease in crosslink density. Suitable anti-reversion agents include zinc salts of aliphatic carboxylic acids, zinc salts of monocyclic aromatic acids, bismaleimides, citrconimides, bisciconimides, aryl citrconamides, bissuccinimides, and polymeric bissuccinimide polysulfides (e.g., N,N'-xylenebicycloamide). Based on the weight of the latex polymer, the anti-reversion agent may be present in the range of 0% to 5% by weight, 0.1% to 3% by weight, or 0.1% to 2% by weight.

[0108] The aforementioned additives (antioxidants, anti-ozone agents, pre-vulcanization inhibitors, vulcanizing agents, vulcanization accelerators, and anti-reversion agents) can be mixed with the latex dispersion before being used to modify the asphalt composition. Crosslinking agents, typically organic peroxides, may also be included in small amounts in the vulcanization system to promote crosslinking of the polymer chains. The latex dispersion can be vulcanized at elevated temperatures and pressures, and the vulcanization process is well known to those skilled in the art.

[0109] III. Asphalt Emulsion Composition

[0110] The latex polymers described in Part II above can be used in asphalt emulsion compositions to improve their properties.

[0111] In one embodiment, the asphalt emulsion composition comprises:

[0112] (i) Asphalt;

[0113] (ii) a non-carboxylated latex comprising 0.01 to 20% by weight of a nonionic surfactant based on the total weight of the latex; and

[0114] (iii)Optional, water.

[0115] As used herein, the term "asphalt" includes the alternative term "bitumen." Therefore, an asphalt composition may be referred to as a bitumen composition. As used herein, "asphalt composition" includes asphalt emulsions and hot-mixed asphalt compositions. The asphalt may be molten asphalt. The asphalt composition may contain 50% or more asphalt by weight. In some embodiments, the asphalt composition may contain 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 99% or more asphalt by weight. In some embodiments, the asphalt composition may contain 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 asphalt by weight. In some embodiments, the bitumen composition may contain 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% of bitumen by weight of the bitumen composition.

[0116] The vinyl acrylic latex polymer described in Part II above may be incorporated into the asphalt composition in an amount of 0.01% by weight or more based on the weight of the asphalt composition. In some embodiments, the amount of polymer that may be included in the asphalt composition is 0.01% by weight or more, 0.1% by weight or more, 0.25% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1% by weight or more, 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, 3% by weight or more, 3.5% by weight or more, 4% by weight or more, 4.5% by weight or more, 5% by weight or more, 6% by weight or more, 7% by weight or more, 8% by weight or more, or 9% by weight or more based on the weight of the asphalt composition. In some embodiments, the amount of polymer that may be included in the asphalt composition is 10% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less based on the weight of the asphalt composition. In some embodiments, the amount of polymer that the asphalt composition may contain is 0.01 wt% to 10 wt%, 0.5 wt% to 8 wt%, 0.5 wt% to 6 wt%, 0.75 wt% to 5 wt%, or 0.75 wt% to 4 wt% based on the weight of the asphalt composition.

[0117] The amount of latex composition used in the production of the asphalt composition may be 0.5% by weight or more, based on the weight of the asphalt emulsion. In some embodiments, the amount of latex composition that the asphalt composition may contain, based on the weight of the asphalt emulsion, is 1% by weight or more, 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, 3% by weight or more, 3.5% by weight or more, 4% by weight or more, 4.5% by weight or more, 5% by weight or more, 6% by weight or more, 7% by weight or more, 8% by weight or more, 9% by weight or more, 10% by weight or more, 11% by weight or more, 12% by weight or more, 13% by weight or more, or 14% by weight or more. In some embodiments, the amount of latex composition that the asphalt composition may contain, based on the weight of the asphalt emulsion, is 15% by weight or less, 12% by weight or less, 10% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less. In some embodiments, the amount of latex composition that the asphalt composition may contain, based on the weight of the asphalt emulsion, is 0.5% to 15% by weight, 0.5% to 12% by weight, 0.5% to 10% by weight, 1% to 15% by weight, or 1% to 10% by weight.

[0118] The amount of vinyl acrylic latex polymer solids, based on the total weight of the asphalt emulsion, can be in the range of 20% or more, 25% or more, 30% or more, 40% or more, 45% or more, 50% or more, 55% or less, 60% or less, 65% or less, 70% or less, 75% or less, or 80% or less.

[0119] The asphalt compositions described herein can be vulcanized or cured to crosslink the polymers contained in the asphalt compositions, thereby increasing the tensile strength and elongation of the polymers. In some embodiments, the asphalt compositions may contain vulcanizing (curing) agents, vulcanization accelerators, anti-reversion agents, or combinations thereof. In some embodiments, vulcanizing (curing) agents, vulcanization accelerators, anti-reversion agents, or combinations thereof may be contained in the latex compositions. In some embodiments, vulcanizing agents, vulcanization accelerators, and / or anti-reversion agents may be contained in the asphalt compositions. Exemplary vulcanizing agents are sulfur curing agents and include various types of sulfur, such as sulfur powder, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersed 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 hydroxymethyl groups; and mixtures thereof. The vulcanizing agent may be present in amounts from 0.01% to 1% by weight or from 0.01% to 0.6% by weight based on the weight of the asphalt composition. In some embodiments, the asphalt composition may contain a sulfur-containing curing agent, such as a sulfur dispersion or a sulfur donor.

[0120] The asphalt composition may contain a solvent (such as water) to disperse or emulsify the polymer and / or asphalt. The amount of water that the asphalt composition may contain is 1% to 35% by weight, 5% to 30% by weight, or 5% to 25% by weight, based on the weight of the asphalt composition.

[0121] The asphalt composition may also contain one or more additional additives. Suitable additional additives include chloride salts, thickeners, and fillers. Up to 1 part by weight of a chloride salt may be added, for example, to improve emulsification. Suitable chloride salts include sodium chloride, potassium chloride, calcium chloride, aluminum chloride, or mixtures thereof. 0.5 parts by weight or more of a thickener may be added, and said thickener may contain associative thickeners, polyurethanes, alkali-swellable latex thickeners, cellulose, cellulose derivatives, modified cellulose products, plant and plant gums, starch, alkylamines, polyacrylic acid resins, carboxyvinyl resins, polyethylene maleic anhydride, polysaccharides, acrylic copolymers, quicklime (such as cationic and / or nonionic lime), or mixtures thereof. In some embodiments, the asphalt composition described herein does not contain a thickener. Mineral fillers and / or pigments may comprise calcium carbonate (precipitated or ground), kaolin, clay, talc, diatomaceous earth, mica, barium sulfate, magnesium carbonate, vermiculite, graphite, carbon black, alumina, silica (in powder or dispersion form, fumed or precipitated), colloidal silica, silica gel, titanium dioxide (e.g., titanium dioxide), aluminum hydroxide, aluminum trihydrate, satin white, magnesium oxide, quicklime, limestone dust, Portland cement, silica, alum, fly ash, or mixtures thereof. The amount of fillers (such as mineral fillers and carbon black) may be up to 5 parts by weight or up to 2 parts by weight.

[0122] The asphalt composition may also contain aggregates. As those skilled in the art will understand, the aggregates may have different sizes. Any aggregates conventionally used in the production of asphalt paving compositions may be used, including dense-graded aggregates, gap-graded aggregates, open-graded aggregates, recycled asphalt pavements, and mixtures thereof. In some embodiments, the amount of aggregates that the asphalt composition may contain is from 1% to 90% by weight based on the weight of the asphalt composition. In some embodiments, the amount of aggregates that the asphalt composition may contain is 90% or less by weight, 85% or less by weight, 80% or less by weight, 75% or less by weight, 70% or less by weight, 65% or less by weight, 60% or less by weight, 55% or less by weight, 50% or less by weight, or 45% or less by weight based on the weight of the asphalt composition. In some embodiments, the amount of aggregate that the asphalt composition may contain, based on the weight of the asphalt composition, is 5% or more by weight, 10% or more by weight, 15% or more by weight, 20% or more by weight, 25% or more by weight, 30% or more by weight, 35% or more by weight, 40% or more by weight, 45% or more by weight, or 50% or more by weight.

[0123] In some embodiments, the asphalt composition may have a pH of 7 or lower. For example, the asphalt composition may have a pH of 6.5 or lower, 6 or lower, 5.5 or lower, 5 or lower, 4.5 or lower, 4 or lower, 3.5 or lower, 3 or lower, or 2.5 or lower. In some examples, the asphalt composition may have a pH of 1.5 or higher, 2 or higher, 2.5 or higher, 3 or higher, 3.5 or higher, 4 or higher, 4.5 or higher, 5 or higher, 5.5 or higher, 6 or higher, 6.5 or higher, or 7 or higher. In some embodiments, the asphalt composition may have a pH of 1.5 to 7, 2 to 6.5, 1.5 to 6, 2 to 6, 3 to 7, 3 to 6.5, 3 to 6, 4 to 7, 4 to 6.5, or 4 to 6.

[0124] Alternatively, the bitumen composition may have a pH of 9 or higher. For example, the bitumen composition may have a pH of 10 to 12, 10 to 11, or 10 to 10.5.

[0125] IV. Methods for preparing asphalt emulsion compositions

[0126] A method for preparing the asphalt emulsion composition described herein is also provided. In some embodiments, the method includes:

[0127] (i) Polymerize monomers to form non-carboxylated latex;

[0128] (ii) Adding the nonionic emulsifier to the noncarboxylated latex; and

[0129] (iii) Contact latex, asphalt, one or more emulsifiers and water to form an asphalt emulsion.

[0130] In some embodiments, the method includes:

[0131] (i) Polymerize monomers to form carboxylated latex;

[0132] (ii) Adding the nonionic emulsifier to the noncarboxylated latex; and

[0133] (iii) Contact latex, asphalt, one or more emulsifiers and water to form an asphalt emulsion.

[0134] Carboxylated or non-carboxylated latexes can be prepared by polymerizing monomers in an aqueous emulsion polymerization reaction at a suitable temperature. Polymerization can be carried out at temperatures such as 40°C or higher, 50°C or higher, or 60°C or higher. In some embodiments, the polymerization temperature can be 40°C to 100°C, 40°C to 95°C, or 50°C to 90°C.

[0135] Polymers can be prepared using continuous, semi-batch (semi-continuous), or batch methods. In some examples, a continuous method can be used to prepare polymers by continuously feeding one or more monomer streams, surfactant streams, and initiator streams into one or more reactors. The surfactant stream contains surfactant and water, and in some embodiments may be mixed with the initiator stream. Details of polymerization methods for non-carboxylated latexes are provided in Part II above.

[0136] Methods for preparing asphalt emulsions may include contacting the latex of the present invention, asphalt, and optionally a cationic, anionic, or nonionic surfactant solution to form an asphalt emulsion. Specific components of the asphalt emulsion (including asphalt, a latex composition containing the nonionic surfactant of the present invention, one or more emulsifiers, and water) may be mixed together by any means known in the art. The specific components may be mixed together in any order. In some embodiments, contact between the latex containing the nonionic emulsifier, the asphalt, and optionally a cationic, anionic, or nonionic emulsifier does not produce coagulation.

[0137] Specific components (including bitumen, a latex composition containing a nonionic emulsifier, optional anionic, cationic or nonionic surfactants and bitumen) can be fed into a colloid high-shear mill at temperatures below 100°C (e.g., 60°C to 95°C), wherein high-shear mixing produces a bitumen emulsion having bitumen droplets dispersed in water.

[0138] In some embodiments, the latex of the present invention containing a nonionic emulsifier can be subsequently added to a cationic bitumen emulsion. In some embodiments, the latex of the present invention containing a nonionic emulsifier can be subsequently added to an anionic bitumen emulsion. In some embodiments, the latex of the present invention containing a nonionic emulsifier can be subsequently added to a nonionic bitumen emulsion.

[0139] The droplets in the asphalt emulsion may have a narrow particle size distribution. In some embodiments, the droplets in the asphalt emulsion may have a median particle size of 15 μm or less, 14 μm or less, 13 μm or less, 12 μm or less, 11 μm or less, 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, or 5 μm or less and / or 5 μm or greater, 6 μm or greater, 7 μm or greater, 8 μm or greater, 9 μm or greater, or 10 μm or greater. In some embodiments, the droplets in the asphalt emulsion may have an average particle size of 15 μm or less, 14 μm or less, 13 μm or less, 12 μm or less, 11 μm or less, 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, or 5 μm or less and / or 5 μm or greater, 6 μm or greater, 7 μm or greater, 8 μm or greater, 9 μm or greater, or 10 μm or greater. In some embodiments, the droplets in the asphalt emulsion may have a median particle size of 3 μm to 15 μm. In some embodiments, the droplets in the asphalt emulsion may have a median distribution of droplet particles with a standard deviation of less than 30%, less than 25%, less than 20%, less than 15%, or less than 10%. In some embodiments, droplets in asphalt emulsions containing a cationic latex composition with reverse phosphate and / or aluminum sulfate may have a narrower particle size distribution than asphalt emulsions without a cationic latex composition with reverse phosphate and / or aluminum sulfate.

[0140] In the absence of a thickener, when the asphalt-based emulsion is present at 65% by weight, the asphalt emulsion may have a viscosity of 100 centipoise (cp) or greater. When 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, when the asphalt-based emulsion is present at 65% by weight, the asphalt emulsion may 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. In some implementations, when the asphalt is present in an amount of 65% by weight based on the asphalt emulsion, the asphalt emulsion may 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 more, 300 cp or less, or 200 cp or less. In some embodiments, when the asphalt is present in an amount of 65% by weight based on the asphalt emulsion, the viscosity of the asphalt emulsion 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. In some embodiments, the asphalt emulsion using PG 58-28 base asphalt can have a softening point of 55°C to 85°C or 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 softens and becomes flowable.

[0141] The bitumen emulsion described in this article complies with ASTM D977, ASTM D2397, AASHTO M140, and AASHTO M208 standards.

[0142] Latex compositions can be used to prepare polymer-modified hot-mix asphalt compositions. Hot-mix asphalt can be prepared, for example, by blending asphalt, the latex composition described herein, and optionally an alkaline salt at a blending temperature above the boiling point of water. In some embodiments, as described herein, the pH of the latex composition can be 7 or lower. In some embodiments, as described herein, the pH of the latex composition can be 7 or higher. In some embodiments, as described herein, the pH of the latex composition can be 8 or higher. In some embodiments, as described herein, the pH of the latex composition can be 9 or higher. In some embodiments, as described herein, the pH of the latex composition can be 10 or higher. In some embodiments, as described herein, the pH of the latex composition can be 11 or higher. In some embodiments, as described herein, the pH of the latex composition can be 11.5 or higher. In some embodiments, the latex composition can be anionic. For example, the latex composition may include a carboxylated polymer. In some embodiments, the latex composition can be nonionic. In some embodiments, the latex composition may be cationic, for example, by comprising a cationic surfactant. The blending temperature of the hot-mix asphalt can be 150°C or higher, 160°C or higher, or 200°C or lower. The hot-mix asphalt composition can have a viscosity at 135°C of, for example, 3000 cp or less, 2500 cp or less, 2000 cp or less, 1500 cp or less, 1000 cp or less, 750 cp or less, 500 cp or less, 250 cp or less, 100 cp or less, or 50 cp or less. 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 cp to 1000 cp. When added to hot-mix asphalt, the latex composition can be in the amounts described above, but the resulting hot-mix asphalt will contain less latex composition because the water evaporates, leaving latex polymers and any other non-volatile additives. For example, the latex polymers can be 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 in any range within any two of the aforementioned values ​​as endpoints, present in the hot-mix asphalt composition.

[0143] In some embodiments, the hot-mixed bitumen composition has a pH of 7 or less or 6 or less (e.g., 1.5 to 6), as described herein.

[0144] In some embodiments, the hot-mixed asphalt composition containing the latex polymer of the present invention can improve the performance grade of the asphalt by one grade (1PG) or two grades (2PG).

[0145] In some embodiments, the asphalt emulsion composition has residual solids as low as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or as high as 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or any range covered by any two of the aforementioned values ​​as endpoints. For example, the asphalt emulsion composition may have residual solids in the range of 30 wt% to 75 wt%.

[0146] Methods for using the bitumen compositions described herein are disclosed. The bitumen composition can be applied to a surface to be treated, restored, or sealed. Prior to applying the bitumen composition, the surface to be treated is typically cleaned to remove excess surface dirt, weeds, and contaminants by, for example, brushing, sandblasting with compressed air, or washing. The bitumen composition can be applied using any suitable method for applying liquids to porous surfaces, such as brushing, wiping and stenciling, or spraying.

[0147] In some embodiments, once the asphalt composition is applied, the surface is wetted, thereby forming a layer on at least a portion of the surface and typically on at least a majority (e.g., greater than 50%). In some embodiments, water loss occurs in the asphalt emulsion when it is applied to the surface, primarily due to water adsorption. Water also delivers the asphalt and cationic latex composition to the surface. In some embodiments, the asphalt emulsion penetrates and adheres to the surface to which it is applied, cures in a fairly rapid time, and provides a watertight and airtight barrier on the surface. The asphalt emulsion layer also promotes adhesion between older surfaces and later applied surface treatment layers. It is desirable that the asphalt composition be easy to apply and have a sufficient shelf life.

[0148] Aggregates can be blended into the asphalt composition before being applied to the surface. In some embodiments, the aggregates can be applied to the asphalt composition after they have been applied to the surface. For example, sand can be applied to the asphalt composition after sand has been applied to the surface, for instance, if the composition will be used as an adhesive layer to reduce the tackiness of the surface. As those skilled in the art will understand, the asphalt composition and optionally the aggregates can be compacted after being applied to the surface.

[0149] The asphalt composition can be used on pavement or paved surfaces. A pavement or paved surface is a hard surface capable of supporting pedestrian or vehicular traffic, and can include surfaces such as highways / roads, parking lots, bridges / flyovers, runways, driveways, vehicle paths, running paths, walkways, etc. The asphalt composition can be applied directly to existing paved surfaces or to unpaved surfaces. In some embodiments, the asphalt composition can be applied as a bonding layer to an existing paved layer, and a new layer comprising asphalt (such as a hot-mix layer) can be applied to the bonding layer. The asphalt composition can be applied to "cold" surfaces, i.e., surfaces with a temperature below 40°C, or to high-temperature surfaces (e.g., 50°C to 120°C, 55°C to 100°C, or 60°C to 80°C).

[0150] In some embodiments, the asphalt composition can be used as an adhesive layer or coating. An adhesive layer is a very light spray application of a diluted asphalt emulsion that can be used to promote adhesion between an existing surface and a new asphalt application. The adhesive layer serves to provide a degree of adhesion or bonding between asphalt layers and, in some cases, can fuse the layers together. The adhesive layer also serves 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 composition can be applied to an existing paving layer (such as a hot-mix layer) as an adhesive layer, and a new layer comprising asphalt (such as a hot-mix layer) can be applied to the adhesive layer. As those skilled in the art will understand, the adhesive layer typically does not contain aggregate, but sand can be applied to the adhesive layer after the application as described herein.

[0151] As described herein, the asphalt composition cures / dries rapidly. For example, when the asphalt composition is used as an adhesive coating, the coating cures rapidly, allowing the pavement layer to be applied to the coating hours to days after the emulsion is applied to the substrate. In some embodiments, the applied composition can cure within 15 to 45 minutes, and can cure rapidly within less than 1 to 15 minutes after the composition is applied to an exposed surface. The curing rate will depend on the application rate, the dilution rate used, the base condition, weather, and other similar considerations. If the prepared pavement surface or base contains excessive moisture, the curing time of the asphalt composition may be increased.

[0152] In some embodiments, the asphalt composition can also be used as a fog seal. A fog seal is a surface treatment that applies the light application of the composition to existing paved surfaces such as parking lots to provide a new-looking, black, enriched pavement surface. In some embodiments, the fog seal will contain fillers such as carbon black to darken the composition. As those skilled in the art will understand, the fog seal may not contain aggregates. Fog seal compositions, like adhesive coating compositions, have also been shown as low-track or "trackless" coatings.

[0153] In some embodiments, the asphalt composition can be used as a chip seal composition. Chip seal is the most common surface treatment for low-traffic roads. The chip seal composition can be applied to the surface, followed by the application of aggregate. In some embodiments, the asphalt composition can be used for microsurfacing applications. Microsurfacing is designed to achieve rapid traffic restoration and is capable of handling high-traffic roads. For microsurfacing compositions, the aggregate can be mixed with the cationic asphalt composition before being applied to the surface.

[0154] In some embodiments, the bitumen composition can be used in paints, coatings, paper coatings or adhesive compositions, carpet compositions (e.g., carpet backing), foams, waterproof compositions, fiber bonding compositions or adhesives.

[0155] The scope of the compositions and methods in the appended claims is not limited to the specific compositions and methods described herein, which are intended to illustrate several aspects of the claims, and any functionally equivalent compositions and methods are intended to fall within the scope of the claims. Various modifications to the methods other than those shown and described herein are intended to fall within the scope of the appended claims. Furthermore, although only certain representative materials and method steps disclosed herein are specifically described, other combinations of these materials and method steps are also intended to fall within the scope of the appended claims, even if not specifically stated. Therefore, combinations of steps, elements, components, or ingredients may be expressly referred to herein; however, other combinations of steps, elements, components, and ingredients are included, even if not expressly stated.

[0156] By way of non-limiting description, some embodiments of the present disclosure are given below.

[0157] Example

[0158] The following examples are provided to provide a complete disclosure and description to those skilled in the art of how to prepare and evaluate the compositions and / or methods claimed herein, and are intended to be purely exemplary and not to limit the scope of this disclosure. Unless otherwise indicated, parts are parts by weight, temperature is in °C or ambient temperature, and pressure is atmospheric pressure or near atmospheric pressure.

[0159] Example 1: Preparation of non-carboxylated styrene-butadiene latex

[0160] Uncarboxylated styrene-butadiene latex was prepared as follows. A copolymer derived from 41.5 parts by weight of styrene, 2.5 parts by weight of acrylamide, and 56 parts by weight of butadiene was prepared. Styrene feed, butadiene feed, an initiator feed containing an aqueous solution of sodium persulfate initiator (1.15 parts by weight of all monomers), and tert-dodecyl mercaptan (0.75 parts by weight of all monomers) were added to a preheated reactor (92°C) containing water, polystyrene seed latex (0.63 parts by weight of all monomers), and TRILONBX (0.02 parts by weight of all monomers) (ethylenediaminetetraacetic acid, commercially available from BASF (Florum Park, NJ)). Latex particle stabilization during polymerization was achieved by feeding a 10-molar aqueous solution of a tridecyl alcohol surfactant adduct (2.0 parts by weight of all monomers) during the polymerization process. A cationic emulsifier was also fed into the reactor. In addition, 0.12 parts of tetrasodium pyrophosphate are fed into the reactor during polymerization. The temperature is maintained at 92°C throughout the polymerization process. After polymerization, the latex dispersion is vaporized from the residual monomer to provide an aqueous dispersion with a residual styrene content of less than 400 ppm. The technical data are as follows: solids content = 70% as measured according to EN ISO 3251; pH value = 10.4 as measured according to EN ISO 976; dynamic viscosity (23°C, 100 1 / s) = 1000-2000 mPa s as measured according to EN ISO 3219; and Tg = -53°C as measured by DSC.

[0161] Example 2: Incorporating nonionic emulsifiers and latex into an asphalt composition.

[0162] A modified styrene-butadiene latex composition was prepared by mixing an aqueous solution of the nonionic emulsifier of the present invention into a cold-polymerized styrene-butadiene dispersion (asphalt emulsion 2 of the present invention) and into the latex composition of Example 1 (asphalt emulsion 4 of the present invention). The pH of the latex was raised to 10.5 using a 12.5% ​​by weight KOH aqueous solution, and then the nonionic emulsifier was added and blended with the latex composition. The emulsifier solution, the latex composition, and the molten asphalt were pumped into a colloid mill, where high-shear mixing produced an asphalt emulsion having droplets dispersed in water.

[0163] Table 1

[0164] Mass balance of asphalt emulsion compositions 1-4

[0165]

[0166] *The target residue for asphalt emulsions 1 and 2 is 72%, while the target residue for asphalt emulsions 3 and 4 is 69%.

[0167] Commercially available water-based high-solids-content cold-polymerized cationic styrene-butadiene dispersion for use in modified cationic bitumen emulsions.

[0168] ***Water-based high-solids-content cold-polymerized styrene-butadiene dispersion.

[0169] Nonionic surfactant A: According to formula (I): R = branched alkyl chain; n = 50; G = hydrogen.

[0170] PG 58-28 asphalt, or paving asphalt PG 58-28, is a performance grade (PG) asphalt derived from specially selected crude oil through a rigorously controlled refining process. The first digit of the PG designation specifies the maximum design temperature; the second digit specifies the minimum design temperature. For example, PG 58-28 asphalt meets a maximum pavement design temperature of 58°C over 7 days and a minimum design temperature of -28°C.

[0171] Particle size determination

[0172] Particle size distribution was determined by quasi-elastic light scattering (QELS), also known as dynamic light scattering (DLS), according to ISO 13321:1996. The determination was performed using a high-performance particle size classifier (Malvern) at 22°C and a wavelength of 633 nm. For this purpose, samples of the asphalt emulsion were diluted, and the dilution was analyzed. In the case of DLS, the aqueous dilution can have a polymer concentration ranging from 0.001 wt% to 0.5 wt%, depending on the particle size. In most cases, a suitable concentration is 0.01 wt%. The particle size values ​​reported in Table 2 are the z-mean of the cumulative evaluation of the measured values ​​of the autocorrelation function.

[0173] Table 2

[0174] Emulsion particle size comparison

[0175]

[0176] Scanning test of asphalt emulsion

[0177] The emulsions prepared according to the above method were evaluated using ASTM D-7000, "Standard Test Method for Sweep Test of Bituminous Emulsion Surface Treatment Samples." This test method measures the curing properties of the bituminous emulsion and aggregates by simulating the sweeping of the surface treatment in the laboratory.

[0178] Table 3

[0179] Scanning test of asphalt emulsion

[0180]

[0181] Table 4

[0182] Elastic recovery rate, softening point, permeability and buoyancy of asphalt emulsions

[0183]

[0184] The results in Tables 2 to 4 show that the performance of the asphalt emulsion using the latex polymer of the present invention is comparable to or better than that of the comparative asphalt emulsion.

[0185] Example 3: Incorporating nonionic surfactants and latex into an asphalt composition.

[0186] The following asphalt emulsion composition was prepared according to the procedure outlined in Example 2.

[0187] Table 5

[0188] Mass balance of asphalt emulsion composition 5-8

[0189]

[0190] The target residue of asphalt emulsion is 65-70%.

[0191] Latex polymer 1 —Waterborne high-solids-content cold-polymerized anionic styrene-butadiene dispersion; Technical data: - Solids content as measured by EN ISO 3251 = 70%; pH value as measured by EN ISO 976 = 10.4; Viscosity (Brookfield RVT, rotor No. 3, 20 rpm) = 1000-2000 mPa s; and Tg as measured by DSC = -53℃.

[0192] Latex polymer 2 It is an aqueous, high-solids-content, cold-polymerized anionic styrene-butadiene dispersion; technical data: - Solids content measured according to EN ISO 3251 = 70-72%; pH value measured according to EN ISO 976 = 10.0-11.0; viscosity (Brookfield RVT, rotor No. 3, 20 rpm) = 1000-1500 mPa s; and Tg measured by DSC = -53℃.

[0193] Nonionic surfactant B is polyoxyethylene (15) coconut oil alkylamine, which is a tertiary amine ethoxylate based on primary coconut oil amine.

[0194] Example 4: Incorporating nonionic surfactants and latex into an asphalt composition

[0195] The following asphalt emulsion composition was prepared according to the procedure outlined in Example 2.

[0196] Table 6

[0197] Mass balance of asphalt emulsion composition 9-14

[0198]

[0199] *The target residue of the asphalt emulsion is 65-70%. **Disperse at pH 4-7 before incorporating into the asphalt emulsion.

[0200] The float point is a measure of the flowability of bitumen residues at 60°C. Typically, the float test is used for anionic emulsions in cooler climates. The float point is evaluated according to ASTM D139-16—Standard Test Method for Float Testing of Bituminous Materials.

[0201] Latex polymer 1 —Waterborne high-solids-content cold-polymerized cationic and anionic styrene-butadiene dispersion; Technical data: - Solids content as measured by EN ISO 3251 = 64%-70%; pH value as measured by EN ISO 976 = 5.4-10.4; Viscosity (Brookfield RVT, rotor No. 3, 20 rpm) = 250-1000-2000 mPa s; and Tg as measured by DSC = -53℃.

[0202] Nonionic surfactant C is an alkyl polyalkoxy ether / polyethylene glycol ethoxylate.

[0203] Nonionic surfactant D is ethoxylated coconut oil amine.

[0204] The scope of the compositions and methods in the appended claims is not limited to the specific compositions and methods described herein, which are intended to illustrate several aspects of the claims, and any functionally equivalent compositions and methods are intended to fall within the scope of the claims. Various modifications to the methods other than those shown and described herein are intended to fall within the scope of the appended claims. Furthermore, although only certain representative compositions and method steps disclosed herein are specifically described, other combinations of these compositions and method steps are also intended to fall within the scope of the appended claims, even if not specifically stated. Therefore, combinations of steps, elements, components, or ingredients may be explicitly or less explicitly referred to herein; however, other combinations of steps, elements, components, and ingredients are included, even if not explicitly stated. As used herein, the term “comprising” and variations thereof are used synonymously with the term “including” and variations thereof and are open-ended, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consistently consisting of” and “consisting of” may be used in place of “comprising” and “including” to provide more specific embodiments of the invention and are also disclosed. Except where indicated in the examples or elsewhere, all figures used in the specification and claims to represent quantities of ingredients, reaction conditions, etc., should be understood, rather than attempting to limit the application of the equivalence principle to the scope of the claims, and should be interpreted in accordance with the number of significant figures and common rounding methods.

Claims

1. An asphalt emulsion composition, said asphalt emulsion composition comprising: (i) Asphalt; (ii) a non-carboxylated latex, wherein the non-carboxylated latex comprises 0.01 to 20% by weight of one or more nonionic surfactants based on the total weight of the latex; (iii) one or more emulsifiers; and (v) Water.

2. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants comprise: Nonionic surfactants according to formula (I): Where G is hydrogen or C1-C 18 Alkyl groups, or C1-C groups substituted with one or more OH groups. 18 Alkyl, C1-C 18 Alkoxy, C5-C 12 Cycloalkoxy, allyloxy, halogen, =O, -COOH, -COOG8, -CONH2, -CONHG9, -CON(G9)(G 10 ), -NH2, -NHG9, =NG9, -N(G9)(G 10 ), -NHCOG 11 -CN, -OCOG 11 , phenoxy; or G is a C3-C that is separated by -O- and can be substituted by OH. 100 Alkyl; or G is C3-C6 alkenyl; glycidyl, C5-C 12 Cycloalkyl groups, C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkyl, -OCOG 11 C7-C that is unsubstituted or substituted with OH 11 Phenylalkyl, C1-C 18 Alkoxy, C1-C 18 Alkyl, -CO-G 12 or -SO2-G 13 G8 is C1-C 18 Alkyl, C3-C 18 Alkenyl groups, C3-C segments spaced by O, NH, NG9, or S, or substituted with OH 50 Alkyl, -P(O)(OG 14 )2、-N(G9)(G 10 ) or -OCOG 11 C1-C4 alkyl groups, glycidyl groups, or C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkylcyclohexyl, phenyl, C7-C 14 Alkylphenyl, C6-C 15 Bicycloalkyl, C6-C 15 Bicycloalkenyl, C6-C 15 Tricycloalkyl, C6-C 15 Dicycloalkyl alkyl or C7-C 11 Phenylalkyl; G9 and G 10 C1-C are independent of each other. 12 Alkyl, C3-C 12 Alkoxyalkyl, C2-C 18 Alkyl group, C4-C 16 Dialkylaminoalkyl or C5-C 12 cycloalkyl, or G9 and G 10 Together they are C3-C9 alkylene or oxaalkylene or azaalkylene; G 11 It is C1-C 18 Alkyl, C1-C 18 Alkoxy, C2-C 18 It is alkenyl, C7-C 11 Phenylalkyl, C7-C 11 Phenylalkoxy, C6-C 12 cycloalkyl, C6-C 12 Cycloalkoxy, phenoxy, or phenyl; or C3-C separated by -O- and potentially substituted with OH. 50 Alkyl; G 12 It is C1-C 18 It is alkenyl, C2-C 18 alkenyl, phenyl, C1-C 18 Alkyl group; C3-C 18 Alkenyl groups, C3-C atoms spaced by O, NH, NG9 or S, or substituted with OH 50 Alkoxy, cyclohexyloxy, phenoxy, C7-C 14 Alkylphenoxy, C7-C 11 Phenylalkoxy, C1-C 12 Alkylamino, phenylamino, tolylamino, or naphthylamino; G 13 It is C1-C 12 Alkyl, phenyl, naphthyl or C7-C 14 Alkylphenyl; G 14 It is C1-C 12 Alkyl, methylphenyl, or phenyl; n is 1-200; and R is C1-C 18 Alkyl, phenyl, C1-C 18 Alkyl-substituted phenyl groups, or C1-C substituted with one or more OH groups. 18 Alkyl, C1-C 18 Alkoxy, C5-C 12 Cycloalkoxy, allyloxy, halogen, =O, -COOH, -COOG8, -CONH2, -CONHG9, -CON(G9)(G 10 ), -NH2, -NHG9, =NG9, -N(G9)(G 10 ), -NHCOG 11 -CN, -OCOG 11 , phenoxy; or R is a C3-C that is separated by -O- and can be substituted by OH. 100 Alkyl, or R is C3-C6 alkenyl, glycidyl, C5-C 12 Cycloalkyl groups, C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkyl, -OCOG 11 Unsubstituted or replaced by OH, Cl, Cl-C 18 Alkoxy or C1-C 18 Alkyl-substituted C7-C 11 Phenylalkyl, -CO-G 12 or -SO2-G 13 ;as well as Polyoxyethylene alkylamine.

3. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants comprise: Surfactants according to formula (I): Where G is hydrogen or C1-C 18 Alkyl groups, or C1-C groups substituted with OH. 18 Alkyl, C1-C 18 Alkoxy, C5-C 12 Cycloalkoxy, =O, -COOH, -COOG8, -CONHG9, -NH2, -NHG9, -N(G9)(G 10 ), -NHCOG 11 C1-C 18 Alkyl-, C1-C 18 alkoxy group; or G is a C3-C group separated by -O- and substituted with OH. 100 Alkyl; or G is C5-C 12 Cycloalkyl groups, C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkyl, -OCOG 11 G8 is C1-C 18 Alkyl groups, C3-C atoms spaced by O, NH, NG9, or S, or substituted with OH 50 Alkyl, -P(O)(OG 14 )2、-N(G9)(G 10 ) or -OCOG 11 C1-C4 alkyl groups, glycidyl groups, or C5-C groups substituted with OH 12 Cycloalkyl, C1-C4 alkylcyclohexyl, phenyl, C7-C 14 Alkylphenyl, C6-C 15 Bicycloalkyl, C6-C 15 Bicycloalkenyl, C6-C 15 Tricycloalkyl or C6-C 15 Bicycloalkylalkyl; G9 and G 10 C1-C are independent of each other. 12 Alkyl, C2-C 18 Alkyl group; or C5-C 12 cycloalkyl, or G9 and G 10 Together they are C3-C9 alkylene or oxaalkylene or azaalkylene; G 11 It is C1-C 18 Alkyl, C1-C 18 Alkoxy, C6-C 12 cycloalkyl, C6-C 12 Cycloalkoxy groups; or C3-C groups separated by -O- and potentially substituted with OH. 50 Alkyl; G 12 It is C1-C 18 It is an alkyl group, C1-C 18 Alkyl group; C3-C 18 Alkenyl group; C3-C substituted with O, NH, NG9 or S, or OH. 50 Alkyloxy; cyclohexyloxy, phenoxy, C7-C 14 Alkylphenoxy; C7-C 11 Phenylacetoxy; C1-C 12 Alkylamino; G 13 It is C1-C 12 Alkyl; G 14 It is C1-C 12 alkyl; n is 1-100; and R is C1-C 18 Alkyl, phenyl, C1-C 18 Alkyl-substituted phenyl or C1-C substituted with one or more OH groups 18 Alkyl groups, or C3-C groups separated by -O-. 50 Alkyl groups; and Polyoxyethylene alkylamine.

4. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants comprise: Nonionic surfactants according to formula (I): Where G is hydrogen or C1-C 18 Alkyl groups, or C1-C groups substituted with OH. 18 Alkyl group; or G is a C3-C group separated by -O- and potentially substituted with OH. 100 alkyl; n is 1-100; and R is C1-C 18 Alkyl, phenyl, C6-C 18 Alkyl-substituted phenyl or C1-C substituted with one or more OH groups 18 Alkyl groups; and Polyoxyethylene alkylamine.

5. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants comprise: Nonionic surfactants according to formula (I): Where G is hydrogen; n is 25-75; and R is C1-C 18 Alkyl or C6-C 12 Alkyl-substituted phenyl; and Polyoxyethylene alkylamine.

6. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants have a molecular weight of 200 g / mol to 15000 g / mol.

7. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants have a molecular weight of 300 g / mol to 10000 g / mol.

8. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants have a molecular weight of 500 g / mol to 8000 g / mol.

9. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants have a molecular weight of 1000 g / mol to 6000 g / mol.

10. The asphalt emulsion composition according to claim 1, wherein the one or more nonionic surfactants have a molecular weight of 1500 g / mol to 3000 g / mol.

11. The composition of claim 1, wherein the uncarboxylated latex is substantially free of cationic reverse surfactant.

12. The composition of claim 1, wherein the noncarboxylated latex comprises a blend of a nonionic reverse surfactant and a cationic reverse surfactant.

13. The composition according to claim 1, wherein the uncarboxylated latex is substantially free of anionic reverse surfactant.

14. The composition of claim 1, wherein the noncarboxylated latex comprises a blend of a nonionic reverse surfactant and an anionic reverse surfactant.

15. The composition of claim 1, wherein the non-carboxylated latex comprises 0.01% to 10% by weight of a nonionic emulsifier based on the total weight of the latex.

16. The composition of claim 1, wherein the asphalt emulsion composition has residual solids in the range of 30% to 75% by weight based on the total weight of the composition.

17. The composition of claim 1, wherein the uncarboxylated latex comprises a styrene-butadiene copolymer.

18. The composition of claim 17, wherein the ratio of styrene to butadiene, based on weight, is in the range of 80 / 20 to 20 / 80.

19. The composition of claim 17, wherein the ratio of styrene to butadiene is 25 / 75 based on weight.

20. The composition of claim 17, wherein the ratio of styrene to butadiene is 50 / 50 based on weight.

21. The composition of claim 1, wherein the uncarboxylated latex comprises styrene-butadiene latex polymerized at a temperature of -5°C to 40°C.

22. The composition of claim 1, wherein the uncarboxylated latex comprises styrene-butadiene latex polymerized at a temperature of 40°C to 100°C.

23. The composition of claim 1, wherein the non-carboxylated latex comprises styrene-butadiene latex, the styrene-butadiene latex being a blend of styrene-butadiene latex polymerized at a temperature of 40°C to 100°C and styrene-butadiene latex polymerized at a temperature of -5°C to 40°C.

24. The composition of claim 1, wherein the non-carboxylated latex comprises a styrene-butadiene-acrylate terpolymer.

25. The composition of claim 1, wherein the non-carboxylated latex copolymer comprises a styrene-butadiene-acrylonitrile copolymer.

26. The composition of claim 1, wherein the non-carboxylated latex comprises a styrene-butadiene-acrylamide copolymer.

27. The composition of claim 1, wherein the non-carboxylated latex copolymer comprises a styrene-butadiene-acrylate-acrylonitrile copolymer.

28. The composition of claim 1, wherein the non-carboxylated latex copolymer comprises a styrene-butadiene-methacrylamide copolymer.

29. The composition of claim 1, wherein the non-carboxylated latex copolymer comprises a styrene-butadiene-N-hydroxymethylacrylamide copolymer.

30. The composition of claim 1, wherein the non-carboxylated latex copolymer comprises a styrene-butadiene-N-hydroxymethylmethacrylamide copolymer.

31. The composition according to claim 1, wherein the uncarboxylated latex copolymer is vulcanized or cured.

32. The composition according to claim 31, wherein the vulcanizing agent is selected from the group consisting of: sulfur powder, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.

33. The composition of claim 32, wherein the vulcanizing agent is copolymerized with the latex polymer and then added to the latex polymer, or copolymerized with the latex polymer and then added to the latex polymer.

34. The composition of claim 1, wherein the non-carboxylated latex copolymer comprises a plasticizer.

35. The composition of claim 1, wherein the uncarboxylated latex comprises a styrene-butadiene copolymer.

36. The composition of claim 35, wherein the styrene-butadiene copolymer is carboxylated.

37. The composition of claim 1, wherein the uncarboxylated latex comprises an acrylic polymer.

38. The composition of claim 37, wherein the acrylic polymer is carboxylated.

39. The composition of claim 37, wherein the acrylic polymer comprises acrylonitrile.

40. The composition of claim 1, wherein the uncarboxylated latex comprises a styrene-acrylic copolymer.

41. The composition of claim 40, wherein the styrene-acrylic polymer is carboxylated.

42. The composition of claim 40, wherein the styrene-acrylic polymer comprises acrylonitrile.

43. The composition of claim 1, wherein the non-carboxylated latex copolymer comprises an ethylene-acrylic acid copolymer.

44. The composition of claim 1, wherein the uncarboxylated latex comprises a natural latex polymer.

45. An adhesive layer comprising the composition according to claim 1.

46. ​​A brush sealant comprising the composition according to claim 1.

47. A fog seal comprising the composition according to claim 1.

48. A gravel seal comprising the composition according to claim 1.

49. A paving asphalt comprising the composition according to claim 1.

50. A micro-surface treated bitumen composition comprising the composition according to claim 1.

51. A waterproof composition comprising the composition according to claim 1.

52. A fiber bonding composition comprising the composition according to claim 1.

53. A hot-mixed bitumen composition comprising the latex composition according to claim 1.

54. A thermomixed bitumen composition comprising the latex composition of claim 1, wherein the latex composition comprises a nonionic surfactant.

55. The hot-mixed bitumen composition according to claim 54, wherein the particle size of the uncarboxylated latex is from 200 nm to 1 micrometer.

56. A method for forming an asphalt emulsion composition, the method comprising: (i) Polymerize monomers to form non-carboxylated latex; (ii) Add one or more nonionic surfactants to the noncarboxylated latex; as well as (iii) Contact the latex, asphalt, one or more emulsifiers and water to form an asphalt emulsion.

57. The method of claim 56, wherein the monomer is selected from the group consisting of styrene, butadiene, (meth)acrylate and acrylonitrile.

58. The method of claim 56, wherein the monomer is selected from the group consisting of styrene, butadiene, (meth)acrylate and acrylonitrile.

59. The method of claim 56, wherein the uncarboxylated latex, asphalt, one or more emulsifiers, and water comprising one or more nonionic surfactants are co-milled in a colloid mill to form a cationic asphalt emulsion.

60. The method of claim 56, wherein the uncarboxylated latex, asphalt, one or more emulsifiers, and water comprising one or more nonionic surfactants are co-milled in a colloid mill to form an anionic asphalt emulsion.

61. The method of claim 56, wherein the non-carboxylated latex, asphalt, one or more emulsifiers, and water comprising one or more nonionic surfactants are co-milled in a colloid mill to form a nonionic asphalt emulsion.

62. The method of claim 56, wherein the noncarboxylated latex comprising one or more of the nonionic surfactants is subsequently added to the asphalt emulsion.

63. The method of claim 56, wherein the monomer is cold polymerized at a temperature of -5°C to 40°C to form the latex.

64. The method of claim 56, wherein the monomer is thermally polymerized at a temperature of 40°C to 100°C to form the latex.

65. The method of claim 56, wherein the resulting non-carboxylated latex comprises styrene-butadiene latex, said styrene-butadiene latex being a blend of styrene-butadiene latex polymerized at a high polymerization temperature and styrene-butadiene latex polymerized at a low polymerization temperature.

66. The method of claim 56, wherein the contact of the latex, asphalt, and optionally the cationic emulsifier does not produce coagulation.

67. A method for forming an asphalt emulsion composition, the method comprising: (i) Polymerize monomers to form carboxylated latex; (ii) Add one or more nonionic surfactants to the carboxylated latex; as well as (iii) Contact the latex, asphalt, one or more emulsifiers and water to form an asphalt emulsion.

68. The method of claim 67, wherein the carboxylated latex, asphalt, one or more emulsifiers and water comprising the one or more nonionic surfactants are co-milled in a colloid mill to form a cationic asphalt emulsion.

69. The method of claim 67, wherein the carboxylated latex, asphalt, one or more emulsifiers, and water comprising the one or more nonionic surfactants are co-milled in a colloid mill to form an anionic asphalt emulsion.

70. The method of claim 67, wherein the carboxylated latex, asphalt, one or more emulsifiers, and water comprising the one or more nonionic surfactants are co-milled in a colloid mill to form a nonionic asphalt emulsion.

71. The method of claim 67, wherein the carboxylated latex comprising one or more of the nonionic surfactants is subsequently added to the asphalt emulsion.

72. The asphalt emulsion composition according to claim 1, wherein the pH of the composition is 10 to 11.

73. The asphalt emulsion composition according to claim 1, wherein the pH of the composition is from 1.0 to 12.

0.

74. The bitumen composition according to claim 1, wherein the one or more nonionic surfactants comprise: Straight-chain or branched-chain or fatty alcohol ethoxylates or alkoxylates, and Polyoxyethylene alkylamine.

75. The asphalt composition according to claim 1, wherein the one or more nonionic surfactants comprise linear or branched or fatty alcohol ethoxylates or alkoxylates.

76. The composition according to claim 1, wherein the composition further comprises natural latex.

77. A slurry seal comprising the composition according to claim 1.

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