Latex for fog seal and scrub seal asphalt emulsions

Abstract

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

Description

Technical Field

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

[0002] Asphalt compositions have a wide range of applications, including but not limited to the production of aggregate pavements. Asphalt pavement is a composite material that includes mineral aggregates and asphalt binder, which hardens to form a robust surface.

[0003] Over time, asphalt pavements deteriorate due to oxidation of the asphalt binder, heavy loading, and weathering. These conditions can lead to problems such as cracking, potholes, rutting, and surface degradation. One method for repairing deteriorated asphalt pavements is to simply excavate, remove the old pavement, and replace it with newly prepared or recycled pavement. However, these repaving procedures can be expensive, time-consuming, and wasteful.

[0004] An alternative to asphalt replacement is asphalt recycling. Asphalt recycling processes are designed to restore and extend the life of deteriorated asphalt pavements. This offers several advantages, such as extending the life of existing pavements and minimizing disruption to traffic flow and business operations. Summary of the Invention

[0005] This article discloses polymer latexes for use in modified fog seal, scrub seal, and tack coat asphalt emulsions. These asphalt emulsion compositions can be used to regenerate deteriorated asphalt surfaces. The asphalt emulsions can also be used as non-stick wheel tack coats.

[0006] In one form, this disclosure provides a bitumen recycling emulsion composition comprising: (i) bitumen; (ii) a latex composition comprising a styrene-modified polymer; (iii) a regenerator; (iv) one or more emulsifiers; and (v) water.

[0007] In another form, this disclosure provides a method for recycling asphalt, the method comprising: (i) providing an asphalt recycling emulsion composition comprising: asphalt; a latex composition comprising a styrene-modified polymer; a regenerator; one or more emulsifiers; and water; and (ii) applying the asphalt recycling emulsion composition to a deteriorated asphalt pavement surface. Detailed Implementation

[0008] I. Definition

[0009] As used herein, the term "comprising" and variations thereof are used synonymously with the term "including" and variations thereof, and are open-ended and 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 "a / 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.

[0010] 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.

[0011] "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.

[0012] 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.

[0013] The term “(meth)acryl…” includes “acryl…”, “methacryl…”, or a mixture thereof.

[0014] The term "polymer" includes homopolymers, copolymers, or mixtures thereof.

[0015] 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.

[0016] 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.

[0017] As used in this article, the phrase “any range covering any two of these 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.

[0018] II. Latex polymer compositions for asphalt modification

[0019] This document describes latex polymer compositions for asphalt modification. Advantageously, incorporating the latex polymers of this disclosure into asphalt emulsions improves their adhesion, ductility, tensile strength, and durability, and makes the polymer-modified asphalt emulsions suitable for recycling applications such as scrub seal and fog seal.

[0020] In some embodiments, the latex comprises a styrene-modified polymer. In a preferred embodiment, the latex comprises a terpolymer of styrene, butadiene, and acrylate monomers. In another preferred embodiment, the latex comprises a quaternary copolymer of styrene, butadiene, acrylate, and acrylonitrile monomers.

[0021] The acrylate monomers in polymer latex can be, for example, based on (meth)acrylic acid, esters of (meth)acrylic acid, (meth)acrylamide, (meth)acrylonitrile, and derivatives of these acrylate monomers. Exemplary esters of (meth)acrylic acid include, but are not limited to, alkyl esters and hydroxyalkyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, and longer-chain alkyl esters of (meth)acrylate, such as ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, and stearyl (meth)acrylate. Derivatives of (meth)acrylamide include, but are not limited to, alkyl-substituted (meth)acrylamides, such as N,N-dimethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, tert-butyl (meth)acrylamide, N-octyl (meth)acrylamide, and longer-chain alkyl (meth)acrylamides, such as N-lauryl (meth)acrylamide and N-stearyl (meth)acrylamide. Acrylic polymers also include polymers commonly referred to as acrylics, acrylate polymers, polyacrylates, or acrylic elastomers. Acrylate polymers belong to a group of polymers that are commonly referred to as plastics, while acrylic elastomers are a general term for a class of synthetic rubbers whose main component is alkyl acrylate (e.g., ethyl acrylate or butyl acrylate).

[0022] As described above, the latex copolymers of the present invention can be derived from styrene and other monomers such as acrylates, methacrylates, butadiene, acrylonitrile, and acrylamide. The copolymers can be derived from other monomers. For example, the 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), and copolymerizable surfactant monomers (e.g., those sold under the trademark ADEKA REASOAP). The copolymers 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 comprise at least one (meth)acrylate. For example, methyl, ethyl, n-butyl, isobutyl, and ethylhexyl 2-acrylate and methacrylate can be used.

[0023] 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 1 The 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.

[0024] Any of the aforementioned monomers may be present in the 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 within 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.

[0025] The latex compositions disclosed herein can be prepared by any polymerization method known in the art. In some embodiments, the compositions disclosed herein are prepared by 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 continuously, gradually, or in a concentration gradient fed into the polymerization zone. As will be readily understood by those skilled in the art, this method can use a single reactor or a series of reactors.

[0026] 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).

[0027] 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 or anionic surfactants, or any combination of nonionic and anionic surfactants, can be added as part of the monomer or initiator feed stream, but these surfactants can 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.

[0028] 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).

[0029] 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 alcohol, and aldehydes.

[0030] 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 an azo initiator; ammonium persulfate, potassium persulfate, or sodium persulfate; or a redox system that typically contains an oxidizing agent and a reducing agent. 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.

[0031] In addition to monomers and initiators, anionic or nonionic surfactants (i.e., emulsifiers) or any combination of nonionic and anionic surfactants (such as those described herein) may be fed into the reactor. Surfactants may 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. Surfactants may also be provided to the reactor as a separate, continuous stream. Based on the total weight of the monomers and surfactants, surfactants may be provided in amounts from 1% to 5% by weight. In some embodiments, surfactants are provided in amounts less than 2% by weight.

[0032] 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 Progress 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 may be added. Cationic, anionic, and / or amphoteric surfactants or polyelectrolytes may optionally be added after the stripping step or later in the final product if desired, to provide a cationic or anionic polymer dispersion.

[0033] Once the polymerization reaction is complete and the stripping step is finished, the reactor temperature can be reduced.

[0034] 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, thermal initiators can be mixed with or replaced by redox initiators that contain free radical generators, reducing agents, and activators (e.g., water-soluble metal salts).

[0035] 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 monomer weight, the free radical generator is typically present in amounts between 0.01% by weight and 1% by weight.

[0036] 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 monomer weight. Furthermore, the weight ratio of the reducing agent to the free radical generator may be between 0.2:1 and 1:1.

[0037] 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. Water-soluble metal salts can be present in amounts less than 0.01% by weight, based on the total monomer weight.

[0038] 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. In some embodiments, tert-dodecyl mercaptan is used as a molecular weight regulator. 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.

[0039] Terpinene is a group of isomeric hydrocarbons classified as monoterpenes. Each compound has the same molecular formula and carbon skeleton, but differs in the position of the carbon-carbon double bond. α-Terpinene can be isolated from cardamom and marjoram oil, as well as other natural sources. β-Terpinene has no known natural source but can be prepared from juniperene. γ-Terpinene and δ-Terpinene (also known as terpinene oil, formula (I)) can be isolated from a variety of plant sources. These compounds are all colorless liquids with a turpentine-like odor. In the context of this disclosure, terpinene oil is used as a chain transfer agent and is not included in the total monomer weight. Formula (I) below is 4-isopropylidene-1-methylcyclohexene.

[0040] (I)

[0041] The amount of tert-dodecyl mercaptan used will depend on the desired molecular weight of the copolymer. In some embodiments, the amount of molecular weight regulator is 0.01% to 4% by weight (e.g., 0.1% to 1% by weight) based on the total monomer weight.

[0042] One or more monomer feeds, surfactant feeds, and initiator feeds can be separately fed into the reactor, where the polymerization of styrene monomers and butadiene monomers occurs. The polymer content of the latex composition of the present invention can be in the range of 30% to 75%. Based on the total weight of the composition, the latex solid content can also be in the range of 30% to 75% by weight.

[0043] As described above, the latex polymer of this disclosure can also be produced using a batch process. In the batch process, the monomer, surfactant, free radical generator, and water are all added to a 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 polymerization.

[0044] 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 time intervals. Preferably, the styrene-butadiene copolymer polymerized at high temperatures is allowed to complete monomer conversion, i.e., greater than 99%.

[0045] 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.

[0046] Suitable nonionic surfactants include, but are not limited to, redoote ® E-47, 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; sorbitol 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) ®The surfactant comprises: 85 polyoxyethylene dehydrated sorbitan trioleate (purchased from Lirkema); 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 monostearate and polyoxyethylene monooleate); polyoxyethylene fatty acid esters (e.g., polyethylene glycol monolaurate and polyethylene glycol monooleate); polyoxyethylene alkylamines; and acetylene glycol. In some embodiments, the nonionic surfactant may have an HLB (hydrophilic-lipophilic balance) at room temperature, such that 8 < HLB < 15. In some embodiments, the HLB is 14 or less. In some embodiments, the nonionic surfactant 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.

[0047] Based on the total weight of the latex, nonionic surfactants may be present in the latex composition in amounts from 0.01 wt% to 30 wt%. For example, nonionic emulsifiers may account for 0.01 wt% to 3 wt%, 0.01 wt% to 5 wt%, 0.01 wt% to 10 wt%, 0.01 wt% to 15 wt%, 0.01 wt% to 20 wt%, 0.01 wt% to 25 wt%, or 0.01 wt% to 30 wt% of the latex polymer.

[0048] 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.

[0049] Antioxidants can be added to latex compositions to prevent the oxidation of double bonds in the polymer, and can be added before or after latex vulcanization. The antioxidant can be a substituted phenol or a secondary aromatic amine.

[0050] 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 Ester; 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-bis(2,6 -Dimethyl-4-tert-butyl-3-hydroxybenzyl sulfide); 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-hydroxycinnamoamide); 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 copolymer.

[0051] Typically, in the presence of a vulcanizing agent, vulcanization accelerator, anti-reversion agent, and optionally a crosslinking agent, the SBR dispersion can be vulcanized or cured by heating to crosslink with the SBR polymer, thereby increasing the tensile strength and elongation of the rubber. Exemplary vulcanizing agents include various sulfurs, 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, 4,4'-methylenebis-o-chloroaniline; alkylphenol resins having hydroxymethyl groups; and mixtures thereof. In some examples, the vulcanizing agent includes a sulfur dispersion or a sulfur donor. Based on the weight of the SBR polymer, the vulcanizing agent may be present in amounts of 0.1 wt% to 15 wt%, 0.3 wt% to 10 wt%, or 0.5 wt% to 5 wt%.

[0052] 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)-disulfides); 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-sulfur compounds; 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.

[0053] 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 dicarboxylate, selenium diethyldithiocarboxylate, cadmium diethyldithiocarboxylate, copper dimethyldithiocarboxylate, iron dimethyldithiocarboxylate, diethylamine diethyldithiocarboxylate, piperidinium pentamethyldithiocarboxylate, and piperidinium pentamethyldithiocarboxylate; 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 wt% to 15 wt%, 0.3 wt% to 10 wt%, or 0.5 wt% to 5 wt%.

[0054] 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.

[0055] 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 it is used in the modified 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.

[0056] III. Asphalt Emulsion Composition

[0057] The latex polymers described in Part II above can be used in asphalt recycling emulsion compositions to improve their properties. When the latex polymers are mixed with asphalt and other optional additives, the resulting compositions can be used as recycling agents, scrub seals, fog seals, sand seals, chip seals, tack coats, bonding coats, or crack filler asphalt compositions.

[0058] In one embodiment, the asphalt recycling emulsion composition comprises:

[0059] (i) Asphalt;

[0060] (ii) a latex composition comprising a styrene-modified polymer;

[0061] (iii) Regenerant;

[0062] (iv) one or more emulsifiers; and

[0063] (v) Water.

[0064] 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. A recycled asphalt emulsion composition may contain as low as 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, or as high as 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 99 wt%, or any range within any two of the aforementioned values ​​as endpoints, in amounts of asphalt. For example, based on the total weight of the asphalt emulsion composition, a recycled asphalt emulsion may contain 60 wt% to 99 wt% asphalt.

[0065] Based on the total weight of the asphalt emulsion composition, the latex composition comprising the styrene-modified polymer as described in Part II above may be present in the asphalt composition in amounts as low as 0.01 wt%, 0.1 wt%, 1 wt%, 5 wt%, or as high as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or in any range covered by any two of the aforementioned values ​​as endpoints. For example, the latex composition comprising the styrene-modified polymer may be present in amounts from 1 wt% to 20 wt%.

[0066] Asphalt compositions may also contain regenerators. Regenerators, sometimes referred to as recycling agents, can be petroleum-based or bio-based. Regenerators are designed to replenish the basic components of the asphalt binder, such as oils and resins, which may be lost over time due to weathering or oxidation. Suitable regenerators include soft asphalt, a non-asphalt fraction of the asphalt, called deasphalted / deasphaltened oil. Regenerators of types such as RA-1, RA-5, RA-25, and RA-75, as defined by ASTM D4552, may also be used. Exemplary regenerators include HYDROLENE. ™ The branded asphalt oil was purchased from Holly Frontier, under the name KENDEX. ™ The brand was acquired from American Refining Group, Inc., or through Golden Bear Preservation's RECLAMITE product. ™The brand is sourced from Tricor Refining, LLC. Asphalt oils conforming to ASTM standard D4552 and classified as RA-1 are suitable for harder asphalts, such as PG 64 asphalt. RA-5, RA-25, and RA-75 oils can also be used with lower viscosity asphalts, such as PG 52 asphalt.

[0067] The regenerator used in this invention can be a bio-based regenerator, or it can be a blend of petroleum-based and bio-based regenerators. The bio-based regenerator can be a bio-renewable oil or ester, comprising oils isolated from plants and animals. A suitable plant-based regenerator is RHEOPHALT, sold by BASF. Non-limiting examples of plant-based oils include soybean oil, linseed oil, canola oil, cottonseed oil, sunflower oil, palm oil, peanut oil, and blends thereof, and non-limiting examples of animal-based oils can include animal fats, such as lard and tallow, and lecithin and blends thereof, as set forth in WO2016 / 138384, which is incorporated herein by reference. Furthermore, non-limiting examples of bio-based regenerators can include oils or esters from natural or biological sources, as set forth in WO2017 / 011747, which is incorporated herein by reference.

[0068] The bitumen composition may optionally contain water. If present, water may be present in amounts as low as 0.01 wt%, 0.1 wt%, 1 wt%, 5 wt%, 10 wt%, or as high as 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or within any range covered by any two of the aforementioned values ​​as endpoints, based on the total weight of the bitumen emulsion composition. For example, water may be present in amounts from 1 wt% to 20 wt%.

[0069] The asphalt composition may further contain an emulsifier to aid in the dispersion and suspension of the asphalt binder. The emulsifier may be cationic, anionic, or nonionic, or a blend of emulsifiers, such as a blend of cationic and nonionic emulsifiers or a blend of anionic and nonionic emulsifiers.

[0070] Exemplary cationic emulsifiers include polyamines, fatty amines, fatty amides, ethoxylated amines, diamines, imidazolines, quaternary ammonium salts, and mixtures thereof. Commercially available cationic emulsifiers include, for example, REDICOTE. ™The brands (including REDICOTE 4819, REDICOTE E-64R, REDICOTE E16, REDICOTE E-9, REDICOTE EM-44, REDICOTE C-346, REDICOTE E-7000, and REDICOTE E-70) were purchased from Nouryon Surface Chemistry, and also from INDULIN. ™ Brands (including INDULIN F-80, INDULIN DF-60, INDULIN DF-40, INDULIN DF-42, INDULIN DF-30, INDULIN R-20, INDULIN AA 56, INDULIN AA 57) and AROSURF ™ The brands (including AROSURF AA-54, AROSURF AA-71, AROSURF AA-78, AROSURF AA-83, AROSURF AA-86, and AROSURF AA-89) were purchased from Ingeaffinity.

[0071] Exemplary anionic emulsifiers include alkali metal or ammonium salts of fatty acids, alkali metal polyalkoxycarboxylates, alkali metal N-acylsarcosine salts, alkali metal hydrocarbon sulfonates (e.g., sodium alkyl sulfonate, sodium aryl sulfonate, sodium alkyl aryl sulfonate, sodium alkyl aromatic sulfonate, sodium lignin sulfonate, sodium dialkyl sulfosuccinate, and sodium alkyl sulfate), long-chain carboxylic acids and sulfonic acids, their salts, and mixtures thereof.

[0072] Exemplary nonionic emulsifiers include ethoxylated compounds and esters, such as ethoxylated fatty alcohols, ethoxylated fatty acids, sorbitan esters, ethoxylated sorbitan esters, ethoxylated alkylphenols, ethoxylated fatty amides, glycerol fatty acid esters, alcohols, alkylphenols, and mixtures thereof.

[0073] Based on the total weight of the asphalt emulsion composition, any of the aforementioned emulsifiers may be present in the asphalt emulsion composition in amounts as low as 0.01 wt%, 0.1 wt%, 1 wt%, 5 wt%, 10 wt%, or as high as 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or in any range covered by any two of the aforementioned values ​​as endpoints. For example, the emulsifier may be present in amounts from 1 wt% to 20 wt%.

[0074] 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.

[0075] 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.

[0076] The latex composition can also be used in asphalt adhesive layers, and the asphalt adhesive composition using the polymer of the present invention can have a de-tack time of 20 minutes or less.

[0077] IV. Methods for applying recycled bitumen emulsions

[0078] This disclosure also provides a method for regenerating bitumen using the polymer latex composition and bitumen composition described herein.

[0079] In one implementation, the method includes:

[0080] (i) Providing a recycled bitumen emulsion composition, the recycled bitumen emulsion composition comprising:

[0081] •asphalt;

[0082] • Latex compositions containing styrene-modified polymers;

[0083] • Regenerant;

[0084] • One or more emulsifiers; and

[0085] • Water; and

[0086] (ii) Apply the asphalt recycling emulsion composition to the deteriorated asphalt pavement surface.

[0087] Reclaimed bitumen emulsions can be applied by manual paving, conventional paving, spraying, or other techniques. Recommended application rates can be, for example, from about 0.045 liters / m² to about 2.7 liters / m² (about 0.01 gallons / yard square to about 0.60 gallons / yard square) or from about 0.14 liters / m² to about 2.0 liters / m² (about 0.03 gallons / yard square to about 0.45 gallons / yard square). The emulsion can be applied multiple times to the substrate at a lower rate to obtain a comparable product, wherein the total application rate is equal to the sum of the multiple applications and is from about 0.045 liters / m² to about 2.7 liters / m² (about 0.01 gallons / yard square to about 0.60 gallons / yard square). For example, the emulsion can be applied three times to the substrate at a single application rate of 0.04 liters / m² (about 0.01 gallons / yard square) or a total application rate of about 0.12 liters / m² (0.03 gallons / yard square). The emulsion application rate can also vary depending on the specific application conditions, emulsion composition, the surface to which it is applied, the properties of the permanent material or substrate (i.e., pavement structure), and other similar factors.

[0088] The emulsion temperature during application can be, for example, from about 4°C (40℉) to about 99°C (210℉), from about 49°C (120℉) to about 77°C (170℉), or from about 38°C (100℉) to about 71°C (160℉). Alternatively, the emulsion can be applied at ambient temperature (e.g., from about 20°C to 25°C (68℉ to 77℉)), but if applied in this way, a longer curing time may be required. The emulsion is typically placed on top of the deteriorated surface and allowed to cure before vehicles pass over the coated surface or before another pavement layer is applied to it.

[0089] The compositions of the present invention also include the tack coat asphalt composition as described herein. A method for applying a tack coat comprising the asphalt composition is also disclosed. This method may include applying the tack coat to a surface, wherein the temperature of the tack coat is from ambient temperature to 130°C, such as 20°C to 130°C, 60°C to 130°C, or ambient temperature to 100°C. The application step may be performed using a brush, rubber roller, or spray equipment. The surface may be selected from soil, gravel, mud seal pavement, chip seal pavement, hot-mix asphalt, warm-mix asphalt, micro-surfaced pavement, and concrete pavement. The methods disclosed herein may further include applying the asphalt composition to the tack coat once the tack coat becomes non-sticky to the wheels.

[0090] 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.

[0091] By way of non-limiting description, some embodiments of the present disclosure are given below.

[0092] Example

[0093] 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.

[0094] Preparation of non-carboxylated styrene-butadiene-acrylate latex

[0095] The following method was used to prepare a non-carboxylated styrene-butadiene-butyl acrylate latex. A copolymer derived from 43.41 parts by weight of styrene, 4.88 parts by weight of acrylamide, 46.83 parts by weight of n-butyl acrylate, and 4.88 parts by weight of butadiene was prepared. Styrene feed, acrylamide feed, n-butyl acrylate feed, and an initiator feed containing an aqueous solution of sodium persulfate initiator (1.15 parts by weight of total monomers) and tert-dodecyl mercaptan (0.75 parts by weight of total monomers) were added over 4 hours to a preheated reactor (85°C) containing water, polystyrene seed latex (0.63 parts by weight of total monomers), and TRILON BX (0.02 parts by weight of total monomers) (ethylenediaminetetraacetic acid, commercially available from BASF (Florom Park, NJ)). Latex particle stabilization during polymerization was achieved by feeding a 10-molar aqueous solution of the ethylene oxide adduct of the tridecaneol surfactant (2.0 parts by weight of the total monomer) during the polymerization process. Butadiene feeding was initiated two hours after monomer feeding. Additionally, 0.12 parts of tetrasodium pyrophosphate were fed into the reactor during polymerization. The temperature was maintained at 85°C throughout the polymerization process. After polymerization, the latex dispersion was vaporized from the residual monomer to provide an aqueous dispersion with a residual styrene level of less than 400 ppm and an acrylonitrile level of less than 100 ppm (if used). The following examples were prepared according to the same general procedure described above. The pH was adjusted using sodium hydroxide as needed.

[0096] Table 1

[0097] Mass balance in Examples 1-3

[0098]

[0099] Example 4 is a commercially available aqueous dispersion of styrene-acrylate copolymer: 48.0% by weight solids content, pH=7.0, viscosity at 23°C (Brookfield RV, #5 rotor, at 50 rpm) of 100cp-500cp, and Tg=12°C as measured by DSC.

[0100] Example 5 is Showa Denko Chloroprene 115, which is a copolymer of chloroprene and methacrylic acid, stabilized with polyvinyl alcohol, with a solid content of 47% by weight, pH=7.0, a viscosity of 350cp-500cp at 23°C (Brookfield RV, #1 rotor, at 30 rpm), and a Tg of -37°C as measured by DSC.

[0101] Table 2

[0102] Mass balance in Examples 6-9

[0103]

[0104] ND = Not measured

[0105] Table 3

[0106] Mass balance in Examples 10-12

[0107]

[0108] Table 4

[0109] Mass balance in Examples 13-15

[0110]

[0111] Swelling resistance of asphalt recycling agents

[0112] The swelling resistance of reclaimers from various latexes in embodiments of the present invention was tested by immersing polymer films made from latex compositions in asphalt reclaimers. According to ASTM D487, 1”×1” polymer films were cut into triplicate, weighed, and placed in aluminum cans. Reclamite Base asphalt reclaimers were added to each can until the polymer film was completely submerged. The sealed cans were placed in an oven at 50°C for 48 hours. After cooling to room temperature, the films were removed from the asphalt reclaimers, gently rinsed with acetone, blotted dry, and then reweighed. The results are summarized in Table 5 below:

[0113] Table 5

[0114] Mass changes after immersion in Reclamite Base at 50°C for 48 hours

[0115]

[0116] The polymer-modified scrubbing and sealing emulsion of the present invention

[0117] Emulsifier solution, latex polymer, and molten bitumen from Midwestern refineries with a range of performance grades (PG) of 64-22 PG or 58-28 PG of hydrocarbon regenerator content are pumped into a colloid mill, where high-shear mixing produces a scrub seal emulsion with 69% by weight of residue.

[0118] Table 6

[0119] Cleanse the top coat emulsion

[0120]

[0121] Particle size determination

[0122] According to ISO 13321:1996, the particle size distribution of asphalt emulsions is determined by quasi-elastic light scattering (QELS), also known as dynamic light scattering (DLS). Measurements are 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 are diluted, and the dilution is 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 7 are the z-mean of the cumulative evaluation of the measured values ​​of the autocorrelation function.

[0123] Table 7

[0124] Scrub the particle size of the sealing emulsion

[0125]

[0126] Example 16: Recovery Percentage Test

[0127] The percentage recovery of the latex of the present invention at various temperatures was measured using a multi-stress creep recovery test according to AASHTO T-350 or ASTM D7405.

[0128] Table 8

[0129] Recovery percentage at 100 Pa

[0130]

[0131] Table 9

[0132] Recovery percentage at 3200 Pa

[0133]

[0134] The results in Tables 8 and 9 show that the bituminous scrub seal emulsion containing acrylonitrile copolymer compositions exhibits the highest recovery percentage at 100 Pa and 3200 Pa.

[0135] In some embodiments, the asphalt composition can be used as a tack coat or coating. A tack coat 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 tack coat serves to provide a degree of adhesion or bonding between asphalt layers and, in some cases, can fuse the layers together. The tack coat 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 of the present invention can be applied to existing paving layers (such as hot-mixed layers) as a tack coat, and new layers containing asphalt (such as hot-mixed layers) can be applied to the tack coat. As those skilled in the art will understand, the tack coat typically does not contain aggregate, but sand can be applied to the tack coat after application.

[0136] The tack coat compositions of the present invention have been shown to be low-tracking or “non-tracking” coatings and conform to ASTM-D-977. Specifically, the asphalt composition cures / dries rapidly. For example, when the asphalt composition is used as a tack coat, the coating cures rapidly, allowing the pavement layer to be applied to the coating shortly after the asphalt composition of the present invention has been applied to the substrate. In some embodiments, the applied asphalt composition can become non-tracking (non-tacking) in less than 20 minutes, such as less than 19 minutes, less than 18 minutes, less than 17 minutes, less than 16 minutes, less than 15 minutes, or less than 10 minutes. In some embodiments, the applied asphalt composition can cure in 15 to 30 minutes and can cure rapidly in less than 10 to 20 minutes after the composition has been 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.

[0137] A method for applying a tack coat comprising the asphalt composition of the present invention may include applying the tack coat to a surface, wherein the temperature of the tack coat is from ambient temperature to 130°C, such as 20°C to 130°C, 60°C to 130°C, or ambient temperature to 100°C. The application step may be performed using a brush, rubber roller, or spray equipment. Surfaces may be selected from soil, gravel, mud seal pavement, chip seal pavement, hot-mix asphalt, warm-mix asphalt, micro-surfaced pavement, and concrete pavement. The methods disclosed herein may also include applying the asphalt composition to the tack coat once the tack coat becomes non-sticky to the wheel.

[0138] The asphalt emulsion composition was applied to a substrate at ambient temperature with a film thickness of 15 mils, and the time it took for the asphalt composition to become non-sticky was measured. The results are summarized in Table 10. Compared with unmodified tack coat asphalt emulsions, the addition of the polymer of the present invention showed an improvement in stickiness reflected by a shorter drying time.

[0139] Table 10

[0140] Non-stick wheel tack coat asphalt emulsion composition .

[0141]

[0142] + Time (minutes) - refers to the time it takes for the coating to become non-sticky on the wheel.

[0143] Example 17: Swelling resistance of terpolymer samples in kerosene

[0144] To further test the swelling resistance of the terpolymer of the present invention, the sample was immersed in kerosene at 50°C for 48 hours. The results are shown in Table 11 below.

[0145] Table 11

[0146] Change in mass after immersion in kerosene, weight %

[0147]

[0148] Example 18: Swelling resistance of terpolymer samples in diesel fuel

[0149] To further test the swelling resistance of the terpolymer of the present invention, the sample was immersed in diesel fuel at 50°C for 48 hours. The results are shown in Table 12 below.

[0150] Table 12

[0151] Change in mass after immersion in diesel fuel, weight %

[0152]

[0153] Example 19: Tensile strength and elongation of terpolymer samples

[0154] The tensile strength and elongation at break of the terpolymer of the present invention were tested. The test results are shown in Table 13 below.

[0155] Table 13

[0156] Strength and elongation

[0157]

[0158] Example 20: Water absorption properties of polymer-modified asphalt

[0159] The water absorption rate was tested in polymer-modified bitumen to determine the effect of the terpolymer of the present invention on the water absorption rate of bitumen. The results are shown in Table 14 below.

[0160] Table 14

[0161] Water absorption properties of polymer-modified bitumen

[0162]

[0163] 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. A bitum regeneration emulsion composition, said bitumen regeneration emulsion composition comprising: (i) Asphalt; (ii) a latex composition comprising a styrene-modified polymer; (iii) Regenerant; (iv) one or more emulsifiers; and (v) Water.

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

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

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

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

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

7. The asphalt emulsion composition according to claim 1, wherein the asphalt is an asphalt binder for scrub seal applications.

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

9. The asphalt emulsion composition according to claim 1, wherein the regenerator is present in an amount of 1% to 99% by weight based on the total weight of the asphalt emulsion composition.

10. The asphalt emulsion composition according to claim 1, wherein the regenerator is present in an amount of 1% to 40% by weight based on the total weight of the asphalt emulsion composition.

11. The asphalt emulsion composition according to claim 1, wherein the regenerator is a hydrocarbon-based regenerator.

12. The asphalt emulsion composition according to claim 1, wherein the rejuvenator is selected from the group consisting of RA-1, RA-5, RA-25 or RA-75 rejuvenators.

13. The asphalt emulsion composition according to claim 1, wherein the regenerator is a bio-based regenerator.

14. The asphalt emulsion composition according to claim 1, wherein the regenerator is a blend of a hydrocarbon-based regenerator and a bio-based regenerator.

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

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

17. The asphalt emulsion composition according to claim 1, wherein the composition is substantially free of emulsifiers and water.

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

19. The asphalt emulsion composition according to claim 1, wherein the regenerator is a bio-based regenerator.

20. The asphalt emulsion composition according to claim 1, wherein the regenerator is a blend of a hydrocarbon-based regenerator and a bio-based regenerator.

21. A recycled asphalt pavement, said recycled asphalt pavement comprising the asphalt recycling emulsion composition according to claim 1.

22. A non-stick wheel adhesive layer comprising the composition according to claim 1.

23. The composition of claim 22, wherein the non-stick wheel adhesive layer is cationic.

24. The composition of claim 22, wherein the non-stick wheel adhesive layer is anionic.

25. The composition of claim 22, wherein the non-stick wheel adhesive layer is nonionic.

26. The composition according to any one of claims 21 to 25, wherein the asphalt composition has a detack time of 20 minutes or less.

27. A scrub seal coat comprising the composition according to claim 1.

28. A fog sealing layer comprising the composition according to claim 1.

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

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

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

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

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

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

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

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

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

38. A method for recycling bitumen, the method comprising: (i) Providing a recycled bitumen emulsion composition, the recycled bitumen emulsion composition comprising: asphalt; Latex compositions containing styrene-modified polymers; Regenerant; One or more emulsifiers; Water; and (ii) Apply the asphalt recycling emulsion composition to the deteriorated asphalt pavement surface.

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

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

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

42. The method of claim 38, wherein the bitumen regeneration emulsion composition further comprises a terpene oil olefin chain transfer agent.

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

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

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

46. ​​The method of claim 38, wherein the regenerator is present in an amount of 1% to 40% by weight, based on the total weight of the asphalt emulsion composition.

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

48. The method of claim 38, wherein the emulsifier is present in an amount of 0.1% to 5% by weight based on the total weight of the asphalt emulsion composition.

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