WO2025117784A1 - Latex pour émulsions d'asphalte pour fog seal et scrub seal - Google Patents

Latex pour émulsions d'asphalte pour fog seal et scrub seal Download PDF

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Publication number
WO2025117784A1
WO2025117784A1 PCT/US2024/057803 US2024057803W WO2025117784A1 WO 2025117784 A1 WO2025117784 A1 WO 2025117784A1 US 2024057803 W US2024057803 W US 2024057803W WO 2025117784 A1 WO2025117784 A1 WO 2025117784A1
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Prior art keywords
asphalt
composition
rejuvenating
emulsion composition
styrene
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English (en)
Inventor
Kostas S Avramidis
William J Kirk
Arlis A. Kadrmas
Titus David DR. LEMAN
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BASF SE
BASF Corp
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BASF SE
BASF Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C08L95/005—Aqueous compositions, e.g. emulsions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/30—Environmental or health characteristics, e.g. energy consumption, recycling or safety issues
    • C08L2555/34—Recycled or waste materials, e.g. reclaimed bitumen, asphalt, roads or pathways, recycled roof coverings or shingles, recycled aggregate, recycled tires, crumb rubber, glass or cullet, fly or fuel ash, or slag
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C08L2555/80—Macromolecular constituents
    • C08L2555/84—Polymers comprising styrene, e.g., polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers

Definitions

  • This disclosure relates generally to asphalt compositions for fog and scrub seal applications, and more particularly to fog and scrub seal asphalt compositions that include polymer latex, and to methods of making and using the polymer-modified asphalt compositions.
  • Asphalt compositions have a wide number of applications, including but not limited to the production of aggregate pavement.
  • Asphalt pavement is a composite material that include mineral aggregate and an asphalt (bitumen) binder which hardens to form a robust surface.
  • asphalt pavement deteriorates from oxidation of the asphalt binder, heavy loads, and weathering. These conditions can result in issues such as cracking, potholes, rutting, and surface deterioration.
  • One method for fixing deteriorated asphalt pavement is to simply excavate, remove, and replace old pavement with newly prepared or recycled pavement. These repaving procedures, however, can be expensive, timeconsuming, and wasteful.
  • Asphalt rejuvenation procedures aim to restore and extend the life of deteriorating asphalt pavements. This provides several advantages such as extending the life of existing pavement and minimization of disruption of traffic flow and business operations.
  • Asphalt emulsion compositions can be used to rejuvenate a deteriorating asphalt surface.
  • the asphalt emulsions can also be used as trackless tack coats.
  • the present disclosure provides an asphalt rejuvenating emulsion composition comprising: (i) asphalt; (ii) a latex composition comprising an styrene-modified polymer; (iii) a rejuvenating agent; (iv) one or more emulsifying agents; and (v) water.
  • the present disclosure provides a method for rejuvenating asphalt comprising: (i) providing an asphalt rejuvenating emulsion composition comprising: asphalt; a latex composition comprising a styrene-modified polymer; a rejuvenating agent; one or more emulsifying agents; water; and (ii) applying the asphalt rejuvenating emulsion composition to a deteriorated asphalt pavement surface.
  • (meth)acryl. includes “acryl. “methacryl. . or mixtures thereof.
  • copolymer includes homopolymers, copolymers, or mixtures thereof.
  • surfactant emulsifier
  • dispersant emulsifier
  • the term “substantially free” means that the composition as a whole contains no more than about 1 % by weight of the species in question. For example, if a product composition is substantially free of water, it contains no more than about 1 wt.% of water.
  • any range encompassing any two of these values as endpoints literally means that any range may be selected from any two of the values listed prior to such phrase regardless of whether the values are in the lower part of the listing or in the higher part of the listing. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.
  • Described herein are latex polymer compositions for use in asphalt modification.
  • the incorporation of the latex polymers of the present disclosure into asphalt emulsions improves their adhesion, ductility, tensile strength, durability, and makes the polymer-modified asphalt emulsions suitable for rejuvenation applications such as scrub seals and fog seals.
  • the latex comprises a styrene-modified polymer.
  • the latex comprises a terpolymer of styrene, butadiene, and acrylate monomers.
  • the latex comprises a quadripolymer of styrene, butadiene, acrylate, and acrylonitrile monomers.
  • the acrylate monomers in the polymer latex may, for example, be based on (meth)acrylic acid, esters of (meth)acrylic acid, (meth)acrylamide, (meth)acrylonitrile and derivatives of these acrylate monomers.
  • esters of (meth)acrylic acids include, but are not limited to, alkyl and hydroxyalkyl esters, e.g., methyl (meth)acrylates, ethyl (meth)acrylates, butyl (meth) acrylates, hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, and longer chain alkyl (meth) acrylates such as ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, and stearyl (meth)acrylate.
  • alkyl and hydroxyalkyl esters e.g., methyl (meth)acrylates, ethyl (meth)acrylates, butyl (meth) acrylates, hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, and longer chain alkyl (meth) acrylates such as ethylhex
  • (meth)acrylamide examples include, but are not limited to, alkyl substituted (meth) acrylamides, e.g., N,N-dimethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, t-butyl (meth)acrylamide, N-octyl (meth) acrylamide, and longer chain alkyl (meth)acrylamides such as N-lauryl (meth)acrylamide and N-stearyl (meth)acrylamide.
  • the acrylic polymers also include polymers commonly known as acrylics, acrylate polymers, poly acrylates or acrylic elastomers.
  • Acrylate polymers belong to a group of polymers which could be referred to generally as plastics while acrylic elastomer is a general term for a type of synthetic rubber whose main component is an acrylic acid alkyl ester (for example, an ethyl or butyl ester).
  • the latex copolymers of the present invention can be derived from styrene along with other monomers such as acrylates, methacrylates, butadiene, acrylonitrile and acrylamide.
  • the copolymer can be derived from other monomers.
  • the copolymer can be derived from vinyl esters of branched monocarboxylic acids having a total of 8 to 12 carbon atoms in the acid residue moiety and 10 to 14 total carbon atoms such as, vinyl 2-ethylhexanoate, vinyl neo-nonanoate, vinyl neodecanoate, vinyl neo-undecanoate, vinyl neo-dodecanoate and mixtures thereof, and copolymerizable surfactant monomers (e.g., those sold under the trademark ADEKA REASOAP).
  • the copolymer can also include at least one additional vinyl aromatic monomer such as alpha. -methylstyrene or o-chlorostyrene.
  • Suitable monomers include acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.
  • the one or more additional monomers can include at least one (meth)acrylic acid ester.
  • methyl, ethyl, n-butyl, isobutyl and 2-ethylhexyl acrylates and methacrylates can be used.
  • the copolymer may also be derived from or further include an organosilane.
  • the organosilane can be represented by the formula (R 1 ) — (Si) — (OR 2 ) 3 , wherein R 1 is a Ci-Cs substituted or unsubstituted alkyl or a Ci-Cs substituted or unsubstituted alkene and R 2 , which are the same or different, each is a Ci-Cs substituted or unsubstituted alkyl group.
  • the organosilane includes a vinyl silane.
  • Exemplary organosilanes can include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2-methoxyethoxysilane), vinyl triisopropoxysilane, (meth)acryloyloxypropyltrimethoxysilane, gamma-(meth)acryloxypropyltrimethoxysilane, gamma-(meth)acryloxypropyltriethoxysilane, or a mixture thereof.
  • any of the foregoing monomers may be present in the latex in an amount as low as 1 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, or as high as 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, 99 wt.%, or within any range encompassed by any two of the foregoing values as endpoints.
  • the latex may comprise styrene monomers in an amount of from 20 wt.% to 70 wt.%, or from 30 wt.% to 60 wt.%.
  • the latex compositions disclosed herein can be prepared by any polymerization method known in the art.
  • the compositions disclosed herein are prepared by a dispersion, a mini-emulsion, or an emulsion polymerization.
  • the compositions disclosed herein can be prepared, for instance, by polymerizing the styrene, butadiene, and optionally other monomers using free -radical emulsion polymerization.
  • the polymerization medium is an aqueous medium. Solvents other than water can be used in the emulsion.
  • the emulsion polymerization can be carried out either as a batch, semi-batch, or continuous process.
  • a portion of the monomers can be heated to the polymerization temperature and partially polymerized, and the remainder of the polymerization batch can be subsequently fed to the polymerization zone continuously, in steps or with superposition of a concentration gradient.
  • the process can use a single reactor, or a series of reactors as would be readily understood by those skilled in the art.
  • the polymer dispersion can be prepared by first charging a reactor with a seed latex, water, the monomers, and optionally at least one nonionic surfactant.
  • the seed latex although optional, helps initiate polymerization and helps produce a polymer having a consistent particle size. Any seed latex appropriate for the specific monomer reaction can be used such as a polystyrene seed.
  • the initial charge can also include a chelating or complexing agent such as ethylenediamine tetraacetic acid (EDTA).
  • EDTA ethylenediamine tetraacetic acid
  • Other compounds such as buffers can be added to the reactor to provide the desired pH for the emulsion polymerization reaction.
  • bases or basic salts such as KOH or tetrasodium pyrophosphate can be used to increase the pH whereas acids or acidic salts can be used to decrease the pH.
  • the initial charge can then be heated to a temperature at or near the reaction temperature.
  • the reaction temperature can be, for example, from 5°C to 100°C (e.g., from 40°C to 90°C, from 50°C to 85°C, or from 55°C to 80°C).
  • the monomers that are to be used in the polymerization can be continuously fed to the reactor in one or more monomer feed streams.
  • the monomers can be supplied as a pre-emulsion in an aqueous medium, particularly if acrylate monomers are used in the polymerization.
  • An initiator feed stream can be also continuously added to the reactor at the time the monomer feed stream is added although it may also be desirable to include at least a portion of the initiator solution to the reactor before adding a monomer pre-emulsion if one is used in the process.
  • the monomer and initiator feed streams are typically continuously added to the reactor over a predetermined period of time (e.g., 1.5-15 hours) to cause polymerization of the monomers and to thereby produce the polymer dispersion.
  • a nonionic or anionic surfactant, or any combination of non-ionic and anionic, surfactants can be added at this time as part of either the monomer stream or the initiator feed stream although they can be provided in a separate feed stream.
  • one or more buffers can be included in either the monomer or initiator feed streams or provided in a separate feed stream to modify or maintain the pH of the reactor.
  • the monomers can be fed in one or more feed streams with each stream including one or more of the monomers being used in the polymerization process.
  • styrene and butadiene when used can be provided in separate monomer feed streams or can be added as a pre-emulsion. It can also be advantageous to delay the feed of certain monomers to provide certain polymer properties or to provide a layered or multiphase structure (e.g., a core/shell structure).
  • the molecular weight of the copolymers can be adjusted by adding a small amount of molecular weight regulators, for example, 0.01 to 4% by weight, based on the monomers being polymerized.
  • Particular regulators which can be used include organic thio compounds (e.g., Zert-dodecylmercaptan), terpinolene, allyl alcohols and aldehydes.
  • the initiator feed stream can include at least one initiator or initiator system that is used to cause the polymerization of the monomers in the monomer feed stream.
  • the initiator stream can also include water and other desired components appropriate for the monomer reaction to be initiated.
  • the initiator can be any initiator known in the art for use in emulsion polymerization such as azo initiators; ammonium, potassium or sodium persulfate; or a redox system that typically includes an oxidant and a reducing agent.
  • exemplary initiators include azo initiators and aqueous solutions of sodium persulfate.
  • the initiator stream can optionally include one or more buffers or pH regulators.
  • an anionic, or nonionic surfactant i.e. , emulsifier
  • any combination of non-ionic and anionic surfactants such as those described herein can be fed to the reactor.
  • the surfactant can be provided in the initial charge of the reactor, provided in the monomer feed stream, provided in an aqueous feed stream, provided in a pre -emulsion, provided in the initiator stream, or a combination thereof.
  • the surfactant can also be provided as a separate continuous stream to the reactor.
  • the surfactant can be provided in an amount of l%-5% by weight, based on the total weight of monomer and surfactant. In some embodiments, the surfactant is provided in an amount less than 2% by weight.
  • the polymer dispersion can be chemically stripped thereby decreasing its residual monomer content.
  • This stripping process can include a chemical stripping step and/or a physical stripping step.
  • the polymer dispersion is chemically stripped by continuously adding an oxidant such as a peroxide (e.g., t-butylhydroperoxide) and a reducing agent (e.g., sodium acetone bisulfite), or another redox pair to the reactor at an elevated temperature and for a predetermined period of time (e.g., 0.5 hours). Suitable redox pairs are described by A.S. Sarac in Progress in Polymer Science 24, 1149-1204 (1999).
  • An optional defoamer can also be added if needed before or during the stripping step.
  • a water or steam flush can be used to further eliminate the non-polymerized monomers in the dispersion.
  • the pH of the polymer dispersion can be adjusted and a biocide or other additives can be added.
  • Cationic, anionic, and/or amphoteric surfactants or polyelectrolytes may optionally be added after the stripping step or at a later time if desired in the end product to provide a cationic or anionic polymer dispersion.
  • a thermal initiator can be used in the reactor such as ammonium persulfate, potassium persulfate, or sodium persulfate.
  • the thermal initiator can be combined with or replaced by a redox initiator comprising a free radical generator, a reducing agent and an activator (e.g., a water-soluble metal salt).
  • Suitable free radical generators include organic peroxygen compounds such as benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,4- dichlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, a-pinene hydroperoxide, t-butyl hydroperoxide, acetyl acetone peroxide, methyl ethyl ketone peroxide, succinic acid peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxymaleic acid, t- butyl peroxybenzoate, and the like; and alkyl perketals, such as 2,2-bis-(t- butylperoxy)butane, ethyl 3,3-
  • Suitable reducing agents for use in the initiator stream include sulfur dioxide; alkali metal disulfites; alkali metal and ammonium hydrogen sulfites; thiosulfate, dithionite and formaldehyde sulfoxylates; hydroxylamine hydrochloride; hydrazine sulfate; glucose and ascorbic acid.
  • the reducing agent can include sodium formaldehyde sulfoxylate dihydrate (SFS), sodium metabisulfite, or a mixture thereof.
  • the reducing agent can be present in an amount between 0.01 and 1% by weight based on total monomer weight.
  • the weight ratio of reducing agent to free radical generator can be between 0.2:1 and 1:1.
  • the water-soluble metal salt can be aniron, copper, cobalt, nickel, tin, titanium, vanadium, manganese, chromium or silver salt and can be chosen from a wide variety of water-soluble metal salts.
  • Suitable water-soluble metal salts include copper (II) amine nitrate, copper (II) metaborate, copper (II) bromate, copper (II) bromide, copper perchlorate, copper (II) dichromate, copper (II) nitrate hexahydrate, iron (II) acetate, iron (III) bromide, iron (III) bromide hexahydrate, iron (II) perchlorate, iron (III) dichromate, iron (III) formate, iron (III) lactate, iron (III) malate, iron (III) nitrate, iron (III) oxalate, iron (II) sulfate pentahydrate, cobalt (II) acetate, cobalt (
  • the metal can also be complexed with a compound, such as ethylenediaminetetraacetic acid (EDTA) to increase its solubility in water.
  • EDTA ethylenediaminetetraacetic acid
  • iron/EDTA complexes or cobalt/EDTA complexes can be used.
  • the water-soluble metal salt can be present in an amount less than 0.01% by weight based on total monomer weight.
  • the polymerization reaction can be conducted in the presence of molecular weight regulators to reduce the molecular weight of the copolymer. Suitable molecular weight regulators include Cs to C12 mercaptans, such as octyl, nonyl, decyl or dodecyl mercaptans.
  • tert-dodecyl mercaptan is used as a molecular weight regulator.
  • terpinolene is used as a molecular weight regulator.
  • a blend of tert-dodecyl mercaptan and terpinolene is used as a molecular weight regulator.
  • Terpinenes are a group of isomeric hydrocarbons that are classified as monoterpenes. Each compound has the same molecular formula and carbon framework but differs in the position of carbon-carbon double bonds.
  • a-Terpinene can be isolated from cardamom and marjoram oils, and from other natural sources. [3-Terpinene has no known natural source but can been prepared from sabinene.
  • y-Terpinene and 5-terpinene also known as terpinolene, Formula (I)
  • terpinolene is used as a chain transfer agent and does not enter into the total monomer weight.
  • Formula (I) below is 4-isopropylidene- 1 -methylcyclohexene.
  • the amount of tert-dodecyl mercaptan used will depend upon the molecular weight that is desired for the copolymer. In some embodiments, the amount of molecular weight regulator is from 0.01 and 4% by weight (e.g., 0.1 to 1% by weight) based on total monomer weight.
  • the one or more monomer feeds, surfactant feed and initiator feed can be separately fed to a reactor where polymerization of the styrene and butadiene monomers occurs.
  • the polymer content of the latex compositions of the present invention can be in the 30% to 75% range.
  • the latex solids may also be in the range of 30 wt.% to 75 wt.%, based on the total weight of the composition.
  • latex polymers of the present disclosure can also be produced using a batch process.
  • the monomers, the surfactant, the free radical generator and water are all added to a reactor and agitated.
  • an activator solution if desired, that includes the reducing agent and the water-soluble metal salt if desired can be added to initiate polymerization.
  • the monomers, the surfactant in an aqueous solution, and the free radical generator in an aqueous solution are all fed to a reactor over a period of time, usually from 3 to 20 hours.
  • an activator solution that includes a reducing agent and/or a water-soluble metal salt can also be added in the reactor prior to commencing the other feeds or can be fed over a time interval to the reactor.
  • the high temperature polymerized styrene-butadiene copolymer is preferably allowed to complete monomer conversion, i.e., greater than 99%.
  • non-ionic emulsifiers such as those typically used for the manufacture of asphalt emulsions may be directly added or post-added to the latex composition.
  • Suitable nonionic surfactants include, but are not limited to, REDICOTE® E-47, polyoxyalkylene alkyl ethers and polyoxyalkylene alkylphenyl ethers (e.g., diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene nonylphenyl ether); oxy ethyleneoxypropylene block copolymers; sorbitan fatty acid esters (e.g., sorbitan monolaurate available as SPAN® 20 from Merck Schuchardt OHG, sorbitan monooleate available as SPAN® 80 from Merck Schuchardt OHG, and sorbitan trioleate available as SPAN® 85 from Merck Schuchardt OHG); polyoxyethylene sorbitan fatty acid esters (e.g., polyoxyethylene sorbitan monolaurate available as TWEEN® 20 and T
  • the nonionic surfactant can have a HLB (hydrophilic lipophilic balance) at room temperature such that 8 ⁇ HLB ⁇ 15. In some embodiments, the HLB is 14 or less.
  • the nonionic surfactant includes an ethylene oxide (EO) m and/or propylene oxide (PO) n adduct of an alkyl, alkylbenzene or dialkylbenzene alcohol wherein (m+n) ⁇ 14, (m+n) ⁇ 12, or (m+n) ⁇ 10 (e.g., 6 ⁇ (m+n) ⁇ 10), such as those available from BASF under the LUTENSOLTM trademark.
  • the non-ionic surfactant may be present in the latex composition in an amount of from 0.01 wt.% to 30 wt.%, based on the total weight of the latex.
  • the non-ionic emulsifier may comprise 0.01 wt.% to 3 wt.%, 0.01 wt.% to 5 wt.%, 0.01 wt.% to 10 wt.%, 0.01 wt.% to 15 wt.%, 0.01 wt.% to 20 wt.%, 0.01 wt.% to 25 wt.%, or 0.01 wt.% to 30 wt.% of the latex polymer.
  • the unreacted monomers can be removed from the latex dispersion.
  • butadiene monomers can be removed by flash distillation at atmospheric pressure and then at reduced pressure.
  • the styrene monomers can be removed by steam stripping in a column.
  • An antioxidant can be added latex composition to prevent oxidation of the double bonds of the polymer and can either be added before or after vulcanization of the latex.
  • the antioxidants can be substituted phenols or secondary aromatic amines.
  • Exemplary substituted phenols include 2,6-di-t-butyl-p-cresol (DBT); 4,4'- thiobis(6-t-butyl-m-cresol); 3-t-butyl-4-hydroxyanisole (3-BHT); 2-t-butyl-4- hydroxyanisole (2-BHT); 2,2-methylenebis(4-methyl-6-t-butylphenol) (MBMBP); 2,2- methylenebis(4-ethyl-6-t-butylphenol) (MB EBP); 4,4'-butylidenebis(3-methyl-6-t- butylphenol) (SBMBP); 2,2-ethylidenebis(4,6-di-t-butylphenol); 2,6-di-t-butyl-4-sec- butylphenol; styrenated phenol; styrenated-p-cresol; l,l,3-tris(2-methyl-4-hydroxy-5-t- butylphenol)butan
  • Exemplary secondary aromatic amines include N-phenyl-N'-isopropyl-p-phenylenediamine; N-phenyl N'-(l,3- dimethylbutyl)-p-phenylenediamine; N,N'-diphenyl-p-phenylenediamine; dioctyl- diphenylamine; dibetanaphthyl-p-phenylenediamine; 2,2,4-trimethyl- 1 ,2-dihydroquinoline polymer and diaryl-p-phenylenediamine.
  • sulfur containing antioxidants such as dilauryl thiodipropionate, distearyl thiodipropionate and 2-mercapto-benzimidazole; phosphorus containing antioxidants such as distearylpentaerythritol diphosphite; nickel containing antioxidants such as nickel diisobutyldithiocarbamate, nickel dimethyldithiocarbamate and nickel di-n-butyldithiocarbamate; 2-mercaptotoluimidazole; zinc 2-mercaptotoluimidazole; and 1,1 l-(3,6,9-trioxaundecyl)bis-3-(dodecylthio)propionate can be used.
  • the antioxidant can be provided in an amount from 0.1 to 5.0 percent or from 0.5 to 2.0 percent by weight based on the weight of the copolymer.
  • the SBR dispersion can be vulcanized or cured to crosslink the SBR polymer thereby increasing the tensile strength and elongation of the rubber by heating the SBR, typically in the presence of vulcanizing agents, vulcanization accelerators, antireversion agents, and optionally crosslinking agents.
  • Exemplary vulcanizing agents include various kinds of sulfur such as sulfur powder, precipitated sulfur, colloidal sulfur, insoluble sulfur and high-dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; sulfur donors such as 4,4’-dithiodimorpholine; selenium; tellurium; organic peroxides such as dicumyl peroxide and di-tert-butyl peroxide; quinone dioximes such as p- quinone dioxime and p,p'-dibenzoylquinone dioxime; organic polyamine compounds such as triethylenetetramine, hexamethylenediamine carbamate, 4,4'- methylenebis(cyclohexylamine) carbamate and 4,4'-methylenebis-o-chloroaniline; alkylphenol resins having a methylol group; and mixtures thereof.
  • the vulcanizing agents include sulfur dispersions or sulfur donors.
  • the vulcanizing agent can be present from
  • Prevulcanization inhibitors can also be added to the latex composition to prevent premature vulcanization or scorching of the polymer.
  • the prevulcanization inhibitor is N-cyclohexylthio-phthalimide (SANTOGARDTM PVI commercially available from Flexsys) or N-phenyl-N- (trichloromethyl sulfenyl)benzene sulfonamide (VULKALENTTM E commercially available from Bayer).
  • the prevulcanization inhibitor is typically provided in an amount from 1 and 5 percent or from 1.5 to 3 percent by weight based on the weight of the latex polymer.
  • Exemplary vulcanization accelerators include sulfenamide-type vulcanization accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide, N-t-butyl-2- benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N-oxydiethylene- 2-benzothiazole sulfenamide, N-oxydiethylene-thiocarbamyl-N-oxydiethylene sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide and N,N'-diisopropyl-2-benzothiazole sulfenamide; guanidine-type vulcanization accelerators such as diphenylguanidine, di-o- tolylguanidine and di-o-tolylbiguanidine; thiourea-type vulcanization accelerators such as thiocarboanilide, di-o-
  • Antireversion agents can also be included in the vulcanization system to prevent reversion, i.e., an undesirable decrease in crosslink density.
  • Suitable antireversion agents include zinc salts of aliphatic carboxylic acids, zinc salts of monocyclic aromatic acids, bismaleimides, biscitraconimides, bisitaconimides, aryl bis-citraconamic acids, bissuccinimides, and polymeric bis succinimide polysulfides (e.g., N,N'- xylenedicitraconamides).
  • the antireversion agent can be present in a range of from 0 to 5%, from 0.1 to 3%, or from 0.1 to 2% by weight based on the weight of the latex polymer.
  • the above additives can be mixed with the latex dispersion before it is used to modify an asphalt composition.
  • Crosslinking agents can also be included in the vulcanization system in small amounts to facilitate crosslinking of the polymer chains and are typically organic peroxides.
  • the latex dispersion can be vulcanized at an elevated temperature and pressure and the vulcanization process is well understood by those skilled in the art. III. Asphalt Emulsion Compositions
  • the latex polymers described in Section II above may be used in asphalt rejuvenation emulsion compositions to improve their characteristics.
  • the resulting composition may be used as a rejuvenator, scrub seal, fog seal, sand seal, chip seal, tack coat, bond coat, or crack filler asphalt composition.
  • the asphalt rejuvenating emulsion composition comprises:
  • asphalt as used herein, includes the alternative term “bitumen.”
  • bitumen compositions can be termed bitumen compositions.
  • asphalt composition as used herein, include asphalt emulsions and hot-mix asphalt compositions.
  • the asphalt can be molten asphalt.
  • the asphalt rejuvenating emulsion compositions may comprise asphalt in an amount as low as 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, or as high as 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, 99 wt.%, or within any range encompassed by any two of the foregoing values as endpoints.
  • the asphalt rejuvenating emulsion may comprise from 60 wt.% to 99 wt.% of asphalt, based on the total weight of the asphalt emulsion composition.
  • the latex composition comprising styrene-modified polymers as described in Section II above may be present in asphalt compositions in an amount of as low as 0.01%, 0.1 wt.%, 1 wt.%, 5 wt.%, or as high as 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the asphalt emulsion composition.
  • the latex composition comprising the styrene-modified polymer may be present in an amount of from 1 wt.% to 20 wt.%.
  • the asphalt compositions may also comprise a rejuvenating agent.
  • Rejuvenating agents are sometimes referred to as recycling agents, may be petroleum- or bio-based. Rejuvenating agents are designed to replenish the essential components of the asphalt binder such as oils and resins, which may have been lost over time due to weathering or oxidation.
  • Suitable rejuvenating agents include maltenes which are the nonasphaltene fraction of asphalt, referred to as deasphalted or deasphaltened oil.
  • Rejuvenating agents which are classified into types such as RA-1, RA-5, RA-25, and RA-75 as defined by ASTM D4552 may also be used.
  • Exemplary rejuvenating agents are available from Holly Frontier under their HYDROLENETM brand asphalt oils, from American Refining Group, Inc. under their KENDEXTM brand or from Tricor Refining, LLC under their Golden Bear Preservation products RECLAMITETM brand.
  • Asphalt oils meeting ASTM standard D4552, and classified as RA-1 are suitable for harder asphalts, such as PG 64 asphalts.
  • RA-5, RA- 25 and RA-75 oils may also be used with lower viscosity asphalts, such as PG 52 asphalts.
  • the rejuvenating agent used in the present invention can be a biobased rejuvenating agent or it can be a blend of a petroleum- and a bio-based rejuvenating agents.
  • Biobased rejuvenating agents may be bio-renewable oils or esters that include oils isolated from plants and animals.
  • An example of a suitable plant based rejuvenation agent is RHEOPHALT marketed by BASF.
  • plant-based oils include soybean oil, linseed oil, canola oil, cottonseed oil, sunflower oil, palm oil, peanut oil and blends thereof and non-limiting examples of animal-based oils may include animal fat such as lard and tallow, and lecithin and blends thereof as listed in WO2016/138384 which is incorporated herein by reference.
  • non-limited examples of biobased rejuvenating agents may include oils or esters from natural or biological sources as listed in W02017/011747 which is incorporated herein by reference.
  • the asphalt compositions may also optionally comprise water. If present, the water may be present in an amount of as low as 0.01%, 0.1 wt.%, 1 wt.%, 5 wt.%, 10 wt.%, or as high as 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the asphalt emulsion composition.
  • the water may be present in an amount of from 1 wt.% to 20 wt.%.
  • the asphalt compositions may also further comprise an emulsifying agent to aid the dispersion and suspension of the asphalt binder.
  • the emulsifying agent may be cationic, anionic, or non-ionic or a blend of emulsifying agents such as a blend of cationic and non-ionic or a blend of anionic and non-ionic emulsifying agents.
  • Exemplary cationic emulsifying agents include polyamines, fatty amines, fatty amido-amines, ethoxylated amines, diamines, imidazolines, quaternary ammonium salts, and mixtures thereof.
  • cationic emulsifying agents include, for example, those available from Nouryon Surface Chemistry under the REDICOTETM brand (including REDICOTE 4819, REDICOTE E-64R, REDICOTE E16, REDICOTE E-9, REDICOTE EM-44, REDICOTE C-346, REDICOTE E-7000 and REDICOTE E-70), and from Ingevity under the INDULINTM brand (including INDULIN F-80, INDULIN DF-60, INDULIN DF- 40, INDULIN DF-42, INDULIN DF-30, INDULIN R-20, INDULIN AA 56, INDULIN AA 57), and the AROSURFTM brand (including AROSURF AA-54, AROSURF AA-71, AROSURF AA-78, AROSURF AA-83, AROSURFAA-86 and AROSURF AA-89).
  • REDICOTETM brand including REDICOTE 4819, REDICOTE E-64
  • Exemplary anionic emulsifying agents include alkali metal or ammonium salts of fatty acids, alkali metal polyalkoxycarboxylates, alkali metal N-acylsarcosinates, alkali metal hydrocarbylsulphonates, for example, sodium alkylsulphonates, sodium arylsulphonates, sodium alkylarylsulphonates, sodium alkylarenesulphonates, sodium lignosulphonates, sodium dialkylsulphosuccinates and sodium alkyl sulphates, long chain carboxylic and sulphonic acids, their salts and mixtures thereof.
  • non-ionic emulsifying agents include ethoxylated compounds and esters, for example ethoxylated fatty alcohols, ethoxylated fatty acids, sorbitan esters, ethoxylated sorbitan esters, ethoxylated alkylphenols, ethoxylated fatty amides, glycerine fatty acid esters, alcohols, alkyl phenols, and mixtures thereof.
  • any of the foregoing emulsifying agents may be present in the asphalt emulsion composition in an amount as low as 0.01%, 0.1 wt.%, 1 wt.%, 5 wt.%, 10 wt.%, or as high as 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the asphalt emulsion composition.
  • the emulsifying agent may be present in an amount of from 1 wt.% to 20 wt.%.
  • the asphalt compositions can further include one or more additional additives.
  • Suitable additional additives include chloride salts, thickeners, and fillers.
  • Chloride salts can be added, for example to improve emulsifyability, in an amount of up to 1 part by weight.
  • Suitable chloride salts include sodium chloride, potassium chloride, calcium chloride, aluminum chloride, or mixtures thereof.
  • Thickeners can be added in an amount of 0.5 parts by weight or greater and can include associative thickeners, polyurethanes, alkali swellable latex thickeners, cellulose, cellulose derivatives, modified cellulose products, plant and vegetable gums, starches, alkyl amines, polyacrylic resins, carboxyvinyl resins, polyethylene maleic anhydrides, polysaccharides, acrylic copolymers, hydrated lime (such as cationic and/or nonionic lime), or mixtures thereof.
  • the asphalt compositions described herein do not include a thickener.
  • Mineral fillers and/or pigments can include calcium carbonate (precipitated or ground), kaolin, clay, talc, diatomaceous earth, mica, barium sulfate, magnesium carbonate, vermiculite, graphite, carbon black, alumina, silicas (fumed or precipitated in powders or dispersions), colloidal silica, silica gel, titanium oxides (e.g., titanium dioxide), aluminum hydroxide, aluminum trihydrate, satine white, magnesium oxide, hydrated lime, limestone dust, Portland cement, silica, alum, fly ash, or mixtures thereof.
  • Fillers such as mineral fillers and carbon black can be included in an amount of up to 5 parts by weight or up to 2 parts by weight.
  • the asphalt compositions can also include an aggregate.
  • the aggregate can be of varying sizes as would be understood by those of skill in the art. Any aggregate that is traditionally employed in the production of bituminous paving compositions can be used, including dense-graded aggregate, gap-graded aggregate, open-graded aggregate, reclaimed asphalt pavement, and mixtures thereof.
  • the asphalt compositions can include an aggregate in an amount of 1 % to 90% by weight, based on the weight of the asphalt composition.
  • the asphalt compositions can include an aggregate in an amount of 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, or 45% or less by weight, based on the weight of the asphalt composition. In some embodiments, the asphalt compositions can include an aggregate in an amount of 5% or greater, 10% or greater, 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 40% or greater, 45% or greater, or 50% or greater by weight, based on the weight of the asphalt composition.
  • the latex compositions can also be used in asphalt tack coats and the asphalt tack compositions using the polymers of the invention can have a tack-free time of 20 minutes or less.
  • the method comprises:
  • a latex composition comprising a styrene-modified polymer; a rejuvenating agent; one or more emulsifying agents; and water;
  • the asphalt rejuvenating emulsion may be applied by hand spreading, conventional spreading, spraying, or other techniques.
  • a recommended application rate may be, for example, about 0.045 to about 2.7 liters/sq. meter (about 0.01 to about 0.60 gal/sq. yd.) or about 0.14 to about 2.0 liters/sq. meter (about 0.03 to about 0.45 gal/sq. yd.).
  • the emulsion can be applied in multiple passes over the substrate layers at lower rates to achieve a comparable product, where the total application rate is equal to the sum of the multiple passes and is from about 0.045 liters/sq. meter to about 2.7 liters/sq. meter (about 0.01 to about 0.60 gal/sq.
  • an emulsion may be applied in three passes over the substrate layer at application rates of 0.04 liters/sq. meter (about 0.01 gal/sq. yd.) each, or a total application rate of about 0.12 liters/sq. meter (0.03 gal/sq. yd.).
  • the emulsion application rate may also vary depending on the specified application conditions, emulsion composition, the surface to which it is applied, and the nature of the permanent materials or base (viz., the pavement structure), and other similar factors.
  • the emulsion temperature during application may, for example, be from about 4° C. (40° F.) to about 99° C. (210° F.), from about 49° C. (120° F.) to about 77° C. (170° F.), or from about 38° C. (100° F.) to about 71° C. (160° F.).
  • the emulsion may be at ambient temperature (e.g. about 20° C. to 25° C. (68° F. to 77° F.), but if so applied may require a longer curing time.
  • the emulsion typically is placed on top of a deteriorated surface and is allowed to cure before traffic passes over the coated surface or additional pavement layer(s) are applied to the coated surface.
  • the present composition also encompasses a tack coat asphalt composition as described herein.
  • Methods for applying tack coats comprising the asphalt compositions are also disclosed.
  • the method can include applying the tack coat to a surface, wherein the tack coat is at a temperature of from ambient temperature to 130°C, such as from 20°C to 130°C, from 60°C to 130°C, or from ambient temperature to 100°C.
  • the applying step can be carried out using a brush, a squeegee, or a spray equipment.
  • the surface can be selected from dirt, gravel, slurry seal pavement, chip seal pavement, hot mix asphalt, warm mix asphalt, microsurfaced pavements, and concrete pavements.
  • the methods disclosed herein can further include applying an asphalt composition to the tack coat once the tack coat has become trackless.
  • compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims.
  • Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims.
  • a non-carhoxylated styrene-butadiene-hutyl acrylate latex was prepared as follows. A copolymer derived from 43.41 parts by weight styrene, 4.88 parts by weight acrylamide, 46.83 parts of n-butyl acrylate, and 4.88 parts by weight butadiene was produced.
  • a styrene feed, an acrylamide feed, an n-butyl acrylate feed, and an initiator feed comprising an aqueous solution of sodium persulfate initiator (1.15 parts by weight of the total monomers) and /e/y -dodecyl mercaptan (0.75 parts by weight of the total monomers) were added over 4 hours to a pre-heated reactor (85 °C) containing water, a polystyrene seed latex (0.63 parts by weight of the total monomers), and TRILON BX (0.02 parts by weight of the total monomers), an ethylenediaminetetraacetic acid commercially available from BASF Corporation (Florham Park, NJ).
  • the stabilization of the latex particles during polymerization was accomplished by feeding an aqueous solution of a 10-mole ethylene oxide adduct of tridecyl alcohol surfactant (2.0 parts by weight of the total monomers) over the course of the polymerization. Two hours into the monomer feed, a butadiene feed was started. In addition, 0.12 parts of tetrasodium pyrophosphate were fed into the reactor over the course of the polymerization. The temperature was maintained at 85 °C throughout the polymerization reaction.
  • the latex dispersion was stripped of the residual monomers to provide an aqueous dispersion with residual styrene levels of less than 400 ppm and acrylonitrile levels of less than 100 ppm, if used.
  • the following examples were prepared. Sodium hydroxide was used to adjust pH as needed.
  • the asphalt compositions can be used as a tack coat or coating.
  • the tack coat is a very light spray application of diluted asphalt emulsion that can be used to promote a bond between an existing surface and the new asphalt application.
  • the tack coat acts to provide a degree of adhesion or bonding between asphalt layers, and in some instances, can fuse the layers together.
  • the tack coat also acts to reduce slippage and sliding of the layers relative to other layers in the pavement structure during use or due to wear and weathering of the pavement structure.
  • the asphalt compositions of the present invention can be applied to an existing paved layer (such as a hot-mix layer) as a tack coat, and a new layer comprising asphalt such as a hot-mix layer can be applied to the tack coat.
  • a new layer comprising asphalt such as a hot-mix layer
  • the tack coat typically does not include aggregate, although sand may be applied to the tack coat after application.
  • the tack coat compositions of the present invention have been shown to be low-tracking or “trackless” coatings and meet an ASTM-D-977 standard.
  • the asphalt compositions cure/dry quickly.
  • the coating cures quickly such that a pavement layer may be applied to the coating, soon after the asphalt composition of the present invention is applied to the substrate.
  • the applied asphalt composition can become trackless (tack-free) in less than 20 minutes, such as less than 19 minutes, less than 18 minutes, less than 17 minutes, less than 16 minutes, less than 15 minutes, or less than 10 minutes.
  • the applied asphalt composition can cure in 15 minutes to 30 minutes, and may cure as rapidly as less than 10 minute to 20 minutes after the composition is applied to the exposed surface.
  • the cure rate will depend on the application rate, the dilution ratios used, the base course conditions, the weather, and other similar considerations. If the prepared pavement surface or base course contains excess moisture, the curing time of the asphalt compositions may be increased.
  • Methods for applying tack coats comprising the asphalt compositions of the present invention can include applying the tack coat to a surface, wherein the tack coat is at a temperature of from ambient temperature to 130°C, such as from 20°C to 130°C, from 60°C to 130°C, or from ambient temperature to 100°C.
  • the applying step can be carried out using a brush, a squeegee, or spray equipment.
  • the surface can be selected from dirt, gravel, slurry seal pavement, chip seal pavement, hot mix asphalt, warm mix asphalt, microsurfaced pavements, and concrete pavements.
  • the methods disclosed herein can further include applying an asphalt composition to the tack coat once the tack coat has become trackless.
  • Time (min) - refers to the time for the coatings to become trackless.
  • Example 18 Swelling Resistance of Terpolymer Samples in Diesel Fuel [00087] In order to test the swelling resistance of the inventive terpolymer further, samples were immersed in diesel fuel for 48 hours at 50°C. The results are included in Table 12 below.
  • compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims.
  • Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims.

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Abstract

L'invention concerne des émulsions d'asphalte pour fog seal et scrub seal modifiées par un polymère de latex pour régénérer ou réparer des revêtements en asphalte détériorés. L'invention concerne également des procédés de formation et d'application des compositions d'émulsion d'asphalte pour fog seal et scrub seal.
PCT/US2024/057803 2023-11-27 2024-11-27 Latex pour émulsions d'asphalte pour fog seal et scrub seal Pending WO2025117784A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016138384A1 (fr) 2015-02-27 2016-09-01 Cargill, Incorporated Émulsions comprenant des huiles polymérisées et procédés de fabrication correspondants
WO2017011747A1 (fr) 2015-07-15 2017-01-19 Ergon Asphalt & Emulsions, Inc. Émulsion de régénération de bitume d'origine biologique
US20230183135A1 (en) * 2020-05-11 2023-06-15 Vinci Construction Cationic latex modified hydrocarbon binder emulsions and their use in the preparation of bituminous products

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016138384A1 (fr) 2015-02-27 2016-09-01 Cargill, Incorporated Émulsions comprenant des huiles polymérisées et procédés de fabrication correspondants
WO2017011747A1 (fr) 2015-07-15 2017-01-19 Ergon Asphalt & Emulsions, Inc. Émulsion de régénération de bitume d'origine biologique
US20180209102A1 (en) * 2015-07-15 2018-07-26 Ergon Asphalt & Emulsions, Inc. Biobased asphalt rejuvenating emulsion
US20230183135A1 (en) * 2020-05-11 2023-06-15 Vinci Construction Cationic latex modified hydrocarbon binder emulsions and their use in the preparation of bituminous products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A.S. SARAC, PROGRESS IN POLYMER SCIENCE, vol. 24, 1999, pages 1149 - 1204

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